Photosensitive composition, transfer film, laminate manufacturing method, laminate, semiconductor package, and resin

Abstract

The present invention addresses the problem of providing a photosensitive composition wherein photolithography properties are excellent and a cured film obtained therefrom has a low coefficient of linear expansion, as well as a transfer film, a laminate manufacturing method, a laminate, a semiconductor package, and a resin. A photosensitive composition according to the present invention includes: a resin A that includes at least one substance selected from the group consisting of a polyimide that has a carboxy group, a polybenzoxazole that has a carboxy group, a polyimide precursor that has a carboxy group, and a polybenzoxazole precursor that has a carboxy group; and a compound β that has a structure which, when exposed to light, reduces the quantity of carboxy groups in the resin A.

Description

Photosensitive composition, transfer film, laminate manufacturing method, laminate, semiconductor package, resin

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

[0002] Photosensitive materials are used in interlayer insulating films within semiconductor chips, connection layers with printed wiring boards (for example, build-up layers and interposers), and the like.

[0003] For example, Patent Document 1 discloses a photosensitive composition having a predetermined structure.

[0004] Japanese Patent Application Laid-Open No. 2022-091355

[0005] With the advancement of miniaturization of semiconductor wiring, there is a demand for materials capable of forming insulating films with high resolution. Furthermore, if the coefficient of linear expansion (CTE) of an insulating film material is higher than that of copper wiring, peeling is more likely to occur, so a low coefficient of linear expansion comparable to that of copper is required. The present inventors have investigated photosensitive compositions having the configuration described in Patent Document 1 and found that at least one of poor photolithographic properties and a high coefficient of linear expansion of the resulting cured film (pattern) occurs, making it difficult to achieve both photolithographic properties and a high coefficient of linear expansion. Excellent photolithographic properties mean that high-resolution patterns can be obtained with little film loss and residue.

[0006] Therefore, an object of the present invention is to provide a photosensitive composition that has excellent photolithography properties and produces a cured film with a small linear expansion coefficient. Another object of the present invention is to provide a transfer film, a method for producing a laminate, a laminate, a semiconductor package, and a resin related to the photosensitive composition.

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

[0008] [1] A photosensitive composition comprising: a resin A containing at least one selected from the group consisting of a polyimide having a carboxy group, a polybenzoxazole having a carboxy group, a polyimide precursor having a carboxy group, and a polybenzoxazole precursor having a carboxy group; and a compound β having a structure that reduces the amount of carboxy groups in the resin A upon exposure. [2] The photosensitive composition according to [1], wherein the resin A contains the polyimide precursor having a carboxy group. [3] The photosensitive composition according to [1] or [2], wherein the resin A has an aliphatic hydrocarbon group having a carboxy group. [4] The photosensitive composition according to any one of [1] to [3], wherein the resin A has a repeating unit represented by formula (1) described below. [5] Z １ and Z ２The photosensitive composition according to [4], wherein at least one of the following represents a group represented by formula (Z1) described below. [6] The photosensitive composition according to [1], wherein the compound β is compound B having a structure capable of accepting electrons from the carboxy group of the resin A in a photoexcited state. [7] The photosensitive composition according to any one of [1] to [6], wherein the compound β is a nitrogen-containing aromatic compound. [8] The photosensitive composition according to any one of [1] to [7], further comprising a filler. [9] The photosensitive composition according to [8], wherein the content of the filler is 50 mass % or more based on the total solid content of the photosensitive composition.

[10] The photosensitive composition according to [8] or [9], wherein the average particle size of the filler is 300 nm or less.

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

[10] , further comprising a filler, wherein the resin A has a repeating unit represented by formula (2) described below, the compound β is a nitrogen-containing aromatic compound, and the average particle size of the filler is 300 nm or less.

[12] The photosensitive composition according to any one of [1] to

[11] , further comprising a polymerizable compound.

[13] The photosensitive composition according to

[12] , further comprising a photopolymerization initiator.

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

[13] .

[15] A method for producing a laminate, comprising: a step X1 of forming a composition layer on a substrate using the photosensitive composition according to any one of [1] to

[13] ; a step X2 of patternwise exposing the composition layer; and a step X3 of developing the exposed composition layer with a developer to form a pattern.

[16] The method for producing a laminate according to

[15] , wherein the step X2 is a step of reducing the carboxy groups of the resin A to change its solubility in a developer.

[17] The method for producing a laminate according to

[15] or

[16] , further comprising a step X4 of heating the pattern after the step X3.

[18] The method for producing a laminate according to any one of

[15] to

[17] , wherein the substrate is an organic substrate having a copper pattern.

[19] The method for producing a laminate according to any one of

[15] to

[18] , wherein the developer is an alkaline developer.

[20] A laminate produced by the production method according to any one of

[15] to

[19] .

[21] A semiconductor package comprising the laminate according to

[20] .

[22] A resin having a repeating unit represented by formula (3) described below.

[0009] The present invention provides a photosensitive composition that has excellent photolithography properties and produces a cured film with a small linear expansion coefficient. It also provides a transfer film, a method for producing a laminate, a laminate, a semiconductor package, and a resin related to the photosensitive 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. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the numerical ranges described in stages in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, unless otherwise specified, the temperature when performing each step may be 25° C.

[0014] 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.

[0015] In this specification, the terms "actinic rays" and "radiation" refer to bright line spectra of mercury lamps 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). In addition, in the present invention, light refers to actinic rays or radiation.

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

[0017] In this specification, unless otherwise specified, the content ratio of each repeating unit in a resin is a molar ratio.

[0018] In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0019] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight 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 ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0020] In this specification, the term "(meth)acryloyl group" encompasses both acryloyl and methacryloyl groups, and the term "(meth)acrylate" encompasses both acrylate and methacrylate.

[0021] In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0022] The "solid content" of a photosensitive composition refers to components that form a composition layer formed using the photosensitive composition, and when the photosensitive composition contains a solvent (e.g., organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0023] 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.

[0024] [Photosensitive Composition] The photosensitive composition of the present invention (hereinafter also simply referred to as "composition") contains a resin A including at least one selected from the group consisting of a polyimide having a carboxy group, a polybenzoxazole having a carboxy group, a polyimide precursor having a carboxy group, and a polybenzoxazole precursor having a carboxy group, and a compound β having a structure that reduces the amount of carboxy groups in the resin A upon exposure to light.

[0025] Although the detailed mechanism of action of the composition of the present invention is not clear, the inventors speculate as follows. In the composition layer formed using the composition, the polarity changes due to a decrease in the content of carboxy groups in resin A in the exposed area, and the solubility in the developer changes. That is, in the exposed area, the solubility in an alkaline developer decreases, and the solubility in an organic solvent developer increases. On the other hand, in the unexposed area, the solubility in the developer remains largely unchanged. As a result, the composition layer is speculated to have excellent photolithography properties. Furthermore, since the obtained cured film contains a resin derived from resin A (e.g., polyimide and polybenzoxazole), it also has excellent CTE.

[0026] The mechanism by which the content of carboxy groups in resin A is reduced by exposure to light is, for example, a mechanism by decarboxylation. The mechanism by which the content of carboxy groups in resin A is reduced by decarboxylation is, for example, a mechanism by which the carboxy groups are converted to CO ２ This refers to elimination as a carboxyl group (carbon dioxide), and does not include the conversion of a carboxyl group to a group other than a carboxyl group due to esterification, etc. It is presumed that when a composition layer formed using a photosensitive composition is exposed to light, a decarboxylation reaction of the carboxyl group of resin A may occur due to compound β.

[0027] Examples of embodiments of the composition are shown below. - Embodiment X-1: A photosensitive composition containing resin A, compound β, and a filler, and substantially free of a polymerizable compound and a photopolymerization initiator. - Embodiment X-2: A photosensitive composition containing resin A, compound β, a filler, and a polymerizable compound, and substantially free of a photopolymerization initiator. - Embodiment X-3: A photosensitive composition containing resin A, compound β, and a filler, and also containing a polymerizable compound and a photopolymerization initiator.

[0028] In Embodiment X-1, "substantially free of polymerizable compounds" means that the content of polymerizable compounds is less than 1% by mass, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, based on the total solid content of the composition. In Embodiments X-1 and X-2, "substantially free of photopolymerization initiators" means that the content of photopolymerization initiators is less than 0.1% by mass, preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass, based on the total solid content of the composition. As an embodiment of the photosensitive composition, Embodiment X-1 or Embodiment X-3 is preferred, and Embodiment X-3 is more preferred.

[0029] The various components that may be contained in the composition of the present invention are described in detail below.

[0030] [Resin A] The composition contains Resin A. Resin A contains at least one selected from the group consisting of polyimide having a carboxy group, polybenzoxazole having a carboxy group, polyimide precursor having a carboxy group, and polybenzoxazole precursor having a carboxy group. Resin A preferably contains a polyimide precursor having a carboxy group. The polyimide precursor is a resin that can be converted to polyimide by heat treatment or chemical treatment. The polybenzoxazole precursor is a resin that can be converted to polybenzoxazole by heat treatment or chemical treatment. Examples of the heat treatment include step X4 described below and step Z4 described below.

[0031] Resin A preferably has a monovalent aliphatic hydrocarbon group having a carboxy group and optionally having a substituent, or a monovalent aromatic hydrocarbon group having a carboxy group and optionally having a substituent. In particular, Resin A more preferably has a monovalent aliphatic hydrocarbon group having a carboxy group and optionally having a substituent. Examples of the monovalent aliphatic hydrocarbon group and the monovalent aromatic hydrocarbon group include the Z group described below. １ and Z ２ Examples of the carboxyl group-containing groups include monovalent aliphatic hydrocarbon groups and the monovalent aromatic hydrocarbon groups. The number of carboxyl groups contained in the resin A is preferably 1 or 2 or more, and more preferably 10 or more. The upper limit is preferably 1,000 or less.

[0032] <Polyimide having a carboxy group and polyimide precursor having a carboxy group> The polyimide having a carboxy group is a resin having a carboxy group and an imide structure. The polyimide having a carboxy group is preferably a resin having a carboxy group and a cyclic imide structure. The polyimide may have a substituent other than the carboxy group. The polyimide precursor having a carboxy group preferably has a repeating unit represented by formula (1).

[0033]

[0034] In formula (1), X represents a tetravalent linking group. Y represents a divalent linking group. Z １ and Z ２ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group having a carboxy group. １ and Z ２ At least one of the groups represents a hydrogen atom or a group having a carboxy group.

[0035] The tetravalent linking group represented by X is preferably a tetravalent linking group having an aromatic ring or a tetravalent linking group having an alicyclic ring. When X is a tetravalent linking group having an aromatic ring or a tetravalent linking group having an alicyclic ring, -COO-Z １ and -COO-Z ２is preferably directly bonded to the aromatic ring or alicyclic ring constituting the tetravalent linking group, and is preferably -COO-Z as specified in formula (1). １ and —CONH-Y-NH— are at the ortho position relative to each other, and —COO-Z ２ It is more preferable that —CO— and —CO— are directly bonded to the aromatic ring or alicyclic ring constituting the tetravalent linking group at the ortho positions relative to each other. １ and Z ２ It is also preferred that one of the groups represents a group having a carboxy group, and the other represents a monovalent organic group not having a carboxy group or a group having a carboxy group.

[0036] X is preferably a group represented by any one of formulas (X1) to (X6), and more preferably a group represented by any one of formulas (X1) to (X3).

[0037]

[0038] In formula (X1), * represents a bonding position. Ｘ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have an aromatic hydrocarbon ring and which may have a fluorine atom, -O-, -CO-, -COO-, -S-, -SO ２ represents -, -NHCO-, or a combination thereof, or a single bond. In formula (X2), * represents a bonding position. In formula (X3), * represents a bonding position. In formula (X4), * represents a bonding position. Cy １ represents an alicyclic ring. In formula (X5), * represents a bonding position. Cy ２ and Cy ３ each independently represents an alicyclic ring. ｃｙ represents a single bond or a divalent linking group. In formula (X6), * represents a bonding position. Cy ４ and Cy ５ Each of Cy independently represents an alicyclic ring. ６ represents a ring having two or more carbon atoms.

[0039] L Ｘ Examples of the ０ Examples of the group include a group represented by the following formula:

[0040] Cy １The alicyclic ring represented by the formula (I) may be either a monocyclic ring or a polycyclic ring. The number of carbon atoms in the alicyclic ring is preferably 3 to 20, and more preferably 4 to 10. The alicyclic ring may have a crosslinked structure or an unsaturated bond (for example, an alkenylene group). Examples of the alicyclic ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a bornane ring, an isobornane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, an adamantane ring, a bicyclooctane ring, a bicyclooctene ring, a dicyclopentadiene ring, a norbornane ring, and a norbornene ring.

[0041] Cy ２ and Cy ３ is Cy １ The meaning and preferred embodiments are also the same as those of the alicyclic ring represented by the following formula: ｃｙ Examples of the divalent linking group represented by the formula (I) include an alkylene group and an arylene group.

[0042] Cy ４ and Cy ５ is Cy １ The meaning and preferred embodiments are also the same as those of the alicyclic ring represented by the following formula: ６ The ring having two or more carbon atoms represented by Cy ４ and form a spiro ring, and Cy ５ In other words, Cy ６ is a ring having two carbon atoms as spiro atoms. The ring may be either a monocyclic or polycyclic ring. The number of carbon atoms in the ring is preferably 3 to 10, more preferably 4 to 8. The number of ring members in the ring is preferably 3 to 10, more preferably 4 to 8. The ring may have a heteroatom. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of rings having a heteroatom include a cycloalkanone ring and a lactone ring.

[0043] Examples of the tetravalent linking group represented by X include the following tetravalent linking groups: * represents the bonding position.

[0044]

[0045]

[0046] In formula (1), Y represents a divalent linking group. Examples of the divalent linking group include a divalent linking group having an aromatic ring, a divalent linking group having a silicon atom, and a divalent aliphatic group, and a divalent linking group having an aromatic ring or a divalent linking group having a silicon atom is preferred.

[0047] Each aromatic ring constituting the divalent linking group having an aromatic ring may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 6 to 20, more preferably 6 to 8. The number of carbon atoms refers to the number of carbon atoms in each monocyclic aromatic ring constituting the divalent linking group having an aromatic ring, and is not the total number of carbon atoms in the aromatic rings constituting the divalent linking group having an aromatic ring. The number of aromatic rings in the divalent linking group having an aromatic ring is 1 or more, preferably 2 to 5, more preferably 2 or 3. The divalent linking group having an aromatic ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the divalent linking group having an aromatic ring and a heteroatom include a group consisting of an aromatic ring and -O-, -CO-, -S-, -SO ２ and a divalent linking group having at least one selected from the group consisting of - and -NHCO-. Furthermore, the divalent linking group having an aromatic ring may have a substituent on the aromatic ring constituting the divalent linking group having an aromatic ring. The substituent is preferably a halogen atom (preferably a fluorine atom), a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms and a fluorine atom.

[0048] The divalent linking group having a silicon atom is preferably a group represented by formula (S).

[0049] *-L Ｓ１ -Si(R Ｓ１ ) (R Ｓ２ )-L Ｓ２ -Si(R Ｓ３ ) (R Ｓ４ )-L Ｓ３ -* (S)

[0050] In formula (S), * represents a bonding position. Ｓ１ ~LＳ３ R each independently represents —O—, an alkylene group, or an arylene group. Ｓ１ ~R Ｓ４ each independently represents an alkyl group or an aryl group. Ｓ１ ~L Ｓ３ The alkylene group represented by the formula (I) may be linear, branched, or cyclic. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 5 carbon atoms. Ｓ１ ~L Ｓ３ The arylene group represented by the formula (I) may be either a monocyclic or polycyclic ring. The number of carbon atoms in the arylene group is preferably 6 to 20, and more preferably 6 to 12. Ｓ１ and L Ｓ３ is preferably an alkylene group. Ｓ２ is preferably —O— or an arylene group.

[0051] R Ｓ１ ~R Ｓ４ The alkyl group represented by R may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 5. Ｓ１ ~R Ｓ４ The aryl group represented by the formula (I) may be either a monocyclic or polycyclic group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.

[0052] The divalent aliphatic group may be linear, branched, or cyclic. The divalent aliphatic group preferably has 2 to 20 carbon atoms, more preferably 3 to 20 carbon atoms. The divalent aliphatic group may have a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the divalent aliphatic group having a heteroatom include a divalent aliphatic group and -O-, -CO-, -S-, -SO ２ and a divalent aliphatic group having at least one selected from the group consisting of - and -NHCO-. The divalent aliphatic group is preferably an alkylene group having 2 to 12 carbon atoms or an aralkylene group having 7 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic.

[0053] The divalent linking group represented by Y is preferably a group represented by formula (Y).

[0054] *-Ar ０ - (L ０ -Ar ０ ) ｎｙ -* (Y)

[0055] In formula (Y), * represents a bonding position. ０ represents an aromatic hydrocarbon group which may have a substituent. ０ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have an aromatic hydrocarbon ring and which may have a fluorine atom, -O-, -CO-, -COO-, -S-, -SO ２ ny represents an integer of 0 to 3, or represents -, -NHCO-, or a combination thereof, or a single bond.

[0056] Multiple Ar ０ may be the same or different. ０ If there are multiple L ０ They may be the same or different.

[0057] Ar ０ The number of carbon atoms in the aromatic hydrocarbon group, which may have a substituent, represented by the following formula (I), is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. Examples of the substituent that the aromatic hydrocarbon group may have include an alkyl group which may have a fluorine atom. As the aromatic hydrocarbon group, a phenyl group is preferred.

[0058] L ０ The aromatic hydrocarbon ring that the aliphatic hydrocarbon group represented by the formula (I) may have is preferably a fluorene ring. ０ Examples of the alkylene group include an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -COO-, -S-, and -SO ２ - or a combination thereof, or a single bond is preferred, and -CH ２ -, -O-, -COO-, -S-, -SO ２ -, -C(CF ３ ) ２ -, -C(CH ３ )２ - or a group in which these are combined, or a single bond is more preferred, and -O-, -C(CF ３ ) ２ -, -C(CH ３ ) ２ - or a single bond is more preferred.

[0059] Examples of the divalent linking group include the following divalent linking groups: * indicates the bonding position.

[0060]

[0061] In formula (1), Z １ and Z ２ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group having a carboxy group. １ and Z ２ At least one of the groups represents a hydrogen atom or a group having a carboxy group.

[0062] -COOZ as specified in formula (1) １ or -COOZ ２ is directly bonded to the alicyclic ring constituting the tetravalent linking group represented by X, Z １ and Z ２ is preferably a group having a carboxy group. For example, when X is a group represented by any one of formulas (X4) to (X6), Z １ and Z ２ is preferably a group having a carboxy group.

[0063] Z １ and Z ２Examples of the monovalent organic group not having a carboxy group represented by the formula (I) include monovalent aliphatic hydrocarbon groups which may have a substituent other than a carboxy group and monovalent aromatic hydrocarbon groups which may have a substituent other than a carboxy group, with the above monovalent aliphatic hydrocarbon groups being preferred. The monovalent aliphatic hydrocarbon group may be either a monovalent saturated aliphatic hydrocarbon group which may have a substituent other than a carboxy group or a monovalent unsaturated aliphatic hydrocarbon group which may have a substituent other than a carboxy group. The monovalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The monovalent aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. When the monovalent aliphatic hydrocarbon group has a substituent, the carbon number includes the number of carbon atoms of the substituent. Examples of the monovalent aliphatic hydrocarbon group include alkyl groups which may have a substituent other than a carboxy group and alkenyl groups which may have a substituent other than a carboxy group. The monovalent aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the monovalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 8. When the monovalent aromatic hydrocarbon group has a substituent, the number of carbon atoms in the substituent is the same as or includes the number of carbon atoms in the substituent. Examples of the substituent other than the carboxy group that may be possessed by the monovalent aliphatic hydrocarbon group and the monovalent aromatic hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, and a polymerizable group. Examples of the polymerizable group include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred.

[0064] Z １ and Z ２The carboxyl group-containing group represented by the formula (I) is not particularly limited as long as it is a group having a carboxyl group. The number of carboxyl groups contained in the carboxyl group-containing group is preferably 1 or 2 or more, more preferably 1 or 2. Examples of the carboxyl group-containing group include monovalent organic groups having a carboxyl group. A monovalent aliphatic hydrocarbon group having a carboxyl group and optionally having a substituent, or a monovalent aromatic hydrocarbon group having a carboxyl group and optionally having a substituent, is preferred. Of these, the carboxyl group-containing group is more preferably a monovalent aliphatic hydrocarbon group having a carboxyl group and optionally having a substituent. The monovalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The monovalent aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15, in terms of providing a cured film with a better CTE and average dielectric constant. When the monovalent aliphatic hydrocarbon group has a substituent, the number of carbon atoms of the substituent is included in the number of carbon atoms. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group having a carboxy group and optionally having a substituent, and an alkenyl group having a carboxy group and optionally having a substituent. The monovalent aromatic hydrocarbon group may be either monocyclic or polycyclic. The monovalent aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 8 carbon atoms. When the monovalent aromatic hydrocarbon group has a substituent, the number of carbon atoms in the substituent is the same as the number of carbon atoms in the substituent. Examples of the substituent that the monovalent aliphatic hydrocarbon group and the monovalent aromatic hydrocarbon group may have include a carboxy group, an alkyl group, an alkenyl group, an aryl group, and a polymerizable group. Examples of the polymerizable group include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred.

[0065] The group having a carboxy group is preferably a group represented by formula (Z1).

[0066]

[0067] In formula (Z1), * represents a bonding position. Ｚ１ represents a divalent linking group. Ｚ１Examples of the divalent linking group represented by the formula: ２ -, -NR Ｎ - (R Ｎ represents a hydrogen atom or a substituent. ), divalent aliphatic hydrocarbon groups which may have a substituent, divalent aromatic hydrocarbon groups which may have a substituent, and divalent linking groups which are combinations of these can be mentioned, and divalent aliphatic hydrocarbon groups which may have a substituent are preferred. The number of carbon atoms in the divalent linking group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15 in terms of providing a cured film with a better CTE and average dielectric constant. Examples of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group include Z １ and Z ２ Among the monovalent organic groups having a carboxy group represented by the formula (I), examples include a group formed by removing one hydrogen atom from a monovalent aliphatic hydrocarbon group which has a carboxy group and which may have a substituent, and a group formed by removing one hydrogen atom from a monovalent aromatic hydrocarbon group which has a carboxy group and which may have a substituent.

[0068] The polyimide precursor having a carboxy group preferably has a repeating unit represented by formula (2).

[0069]

[0070] In formula (2), X represents a tetravalent linking group. Y represents a divalent linking group. Z ３ and Z ４ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group represented by formula (Z2). ３ and Z ４ At least one of the groups represents a hydrogen atom or a group represented by formula (Z2). X and Y have the same meanings as X and Y in formula (1), respectively, and preferred embodiments are also the same. Z ３ and Z ４ The monovalent organic group having no carboxy group represented by Z １ and Z ２ The meaning and preferred embodiments are also the same as the monovalent organic group having no carboxy group represented by the following formula: ３ and Z ４is preferably a group represented by formula (Z2).

[0071]

[0072] In formula (Z2), * represents a bonding position. Ｚ２ represents a divalent aliphatic hydrocarbon group which may have a substituent. Ｚ２ As the divalent aliphatic hydrocarbon group represented by Ｚ１ Examples of the divalent linking group include a divalent aliphatic hydrocarbon group which may have a substituent, among the divalent linking groups represented by the following formula:

[0073] The polyimide precursor having a carboxy group also preferably has a repeating unit represented by formula (3).

[0074]

[0075] In formula (3), X represents a tetravalent linking group. Y represents a divalent linking group. Z ５ and Z ６ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group represented by formula (Z1). ５ and Z ６ At least one of the groups represents a hydrogen atom or a group represented by formula (Z1). X and Y have the same meanings as X and Y in formula (1), respectively, and preferred embodiments are also the same. Z ５ and Z ６ The monovalent organic group having no carboxy group represented by Z １ and Z ２ The meaning and preferred embodiments are also the same as the monovalent organic group having no carboxy group represented by the following formula: ５ and Z ６ is preferably a group represented by formula (Z1).

[0076]

[0077] In formula (Z1), * represents a bonding position. Ｚ１ represents a divalent linking group. Ｚ１ is as described above.

[0078] 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 all repeating units of the polyimide precursor having a carboxy group. The upper limit is preferably 100 mol % or less.

[0079] <Polybenzoxazole having a carboxy group and polybenzoxazole precursor having a carboxy group> Polybenzoxazole having a carboxy group is a resin having a carboxy group and a benzoxazole ring. The polybenzoxazole having a carboxy group is not particularly limited as long as it is a resin having a carboxy group and a benzoxazole ring. The polybenzoxazole may have a substituent. The polybenzoxazole is preferably a resin synthesized from a polybenzoxazole precursor having a repeating unit represented by formula (P) (for example, a resin obtained by a ring-closing reaction). The polybenzoxazole precursor preferably has a repeating unit represented by formula (P).

[0080]

[0081] In formula (P), X Ｐ represents a tetravalent linking group. Ｐ represents a divalent linking group. Ｐ１ and Z Ｐ２ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group having a carboxy group. Ｐ１ and Z Ｐ２ At least one of the groups represents a hydrogen atom or a group having a carboxy group.

[0082] X Ｐ , Y Ｐ , Z Ｐ１ and Z Ｐ２ are X, Y, and Z, respectively. １ and Z ２ The preferred embodiments are also the same as those of the above. Ｐ is preferably a tetravalent linking group having an aromatic ring, more preferably a group represented by any one of formulas (X1) to (X6), and still more preferably a group represented by any one of formulas (X1) to (X3).

[0083] The content of the repeating unit represented by formula (P) 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 polybenzoxazole precursor having a carboxy group. The upper limit is preferably 100 mol % or less.

[0084] Resin A may contain other repeating units in addition to the repeating unit represented by formula (1). Examples of the other repeating units include repeating units having a siloxane structure. Examples of the other repeating units include those described in paragraphs 0150 to 0154 of JP 2020-154205 A.

[0085] Resin A may contain fluorine atoms. The content of fluorine atoms in Resin A is preferably 1% by mass or more, and more preferably 10% by mass or more, relative to the total mass of Resin A. The upper limit is preferably 50% by mass or less.

[0086] The weight average molecular weight of Resin A is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 8,000 to 50,000. The dispersity of Resin A is preferably 1.0 to 4.0, more preferably 1.5 to 3.5, and even more preferably 1.8 to 3.0.

[0087] The acid value of the resin A is preferably from 50 to 300 mgKOH / g, more preferably from 70 to 250 mgKOH / g, and even more preferably from 90 to 200 mgKOH / g.

[0088] Resin A may be used alone or in combination of two or more. The content of Resin A is preferably 5.0 mass% or more, more preferably 10.0 mass% or more, based on the total solid content of the composition. The upper limit is preferably 50.0 mass% or less, more preferably 30.0 mass% or less, based on the total solid content of the composition.

[0089] [Compound β] The composition contains compound β. Compound β is a compound different from the various components described above. Compound β is a compound having a structure (hereinafter also referred to as "specific structure S0") that reduces the amount of carboxy groups in resin A upon exposure.

[0090] The specific structure S0 is a structure that, when exposed to light, exhibits the effect of reducing the amount of carboxy groups in the resin A. The specific structure S0 is preferably a structure that transitions from a ground state to an excited state upon exposure and, in the excited state, exhibits the effect of reducing the number of carboxy groups in the resin A. An example of the specific structure S0 is a structure that can accept electrons from the carboxy groups in the resin A in a photoexcited state (hereinafter also referred to as "specific structure S1").

[0091] The specific structure S0 of compound β may be the overall structure constituting the entire compound β, or may be a partial structure constituting a part of compound β. Compound β may be either a low molecular weight compound or a high molecular weight compound, and is preferably a low molecular weight compound. Furthermore, when compound β is a low molecular weight compound, it is preferable that the low molecular weight compound does not have a repeating unit. When compound β is a low molecular weight compound, the molecular weight of compound β is preferably less than 5,000, more preferably less than 1,000, even more preferably 65 to 300, and particularly preferably 75 to 250.

[0092] The specific structure S0 is preferably a structure (specific structure S1) that can accept electrons from the carboxy group of the resin A in a photoexcited state. That is, the compound β is preferably a compound B having a structure (specific structure S1) that can accept electrons from the carboxy group of the resin A in a photoexcited state. According to the compound B, the carboxy group of the resin A can be converted into CO ２ It is thought that the carboxyl group can be eliminated (decarboxylated) as

[0093] In terms of superior pattern forming ability, the compound β is preferably an aromatic compound having an aromatic ring as the specific structure S0, more preferably a heteroaromatic compound having a heteroaromatic ring as the specific structure S0, and even more preferably a nitrogen-containing aromatic compound having a heteroaromatic ring as the specific structure S0. That is, the specific structure S0 is preferably an aromatic ring, more preferably a heteroaromatic ring, and even more preferably a nitrogen-containing aromatic ring. The aromatic compound is a compound having one or more aromatic rings. The nitrogen-containing aromatic compound is a compound having a heteroaromatic ring having one or more nitrogen atoms (e.g., 1 to 4) as ring member atoms. Only one aromatic ring may be present in the compound β, or multiple aromatic rings may be present. When multiple aromatic rings are present, for example, the aromatic rings may be present in a side chain of the resin. In the compound β, the aromatic ring can be used as a structure (specific structure S0) that reduces the amount of carboxy groups in the resin A upon exposure. The aromatic ring may be either a monocyclic or polycyclic ring, with polycyclic rings being preferred. The polycyclic aromatic ring is, for example, an aromatic ring formed by condensing a plurality of (e.g., 2 to 5, etc.) aromatic ring structures, and it is preferable that at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. The aromatic ring may be a heteroaromatic ring, and it is preferable that it has one or more (e.g., 1 to 4, etc.) heteroatoms (e.g., nitrogen atoms, oxygen atoms, sulfur atoms, etc.) as ring member atoms, and it is more preferable that it has one or more (e.g., 1 to 4, etc.) nitrogen atoms as ring member atoms. The number of ring member atoms of the aromatic ring is preferably 5 to 15.

[0094] The aromatic ring of compound β is preferably a polycyclic ring (a polycyclic aromatic ring) in that it has a higher molar absorption coefficient for light having a wavelength of 365 nm. The number of monocyclic aromatic rings (number of condensed rings) in the polycyclic aromatic ring is preferably 2 or more, and more preferably 3 or more in that it has a higher molar absorption coefficient for light having a wavelength of 365 nm. The upper limit is preferably 6 or less. In addition, it is also preferable that the polycyclic aromatic ring has a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.) as a ring member atom (in other words, it is a polycyclic heteroaromatic ring).

[0095] Examples of the aromatic ring contained in compound β include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; aromatic rings formed by condensing two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings formed by condensing three rings such as an acridine ring, a benzo[f]quinoline ring, a benzo[h]quinoline ring, a phenanthridine ring (benzo[c]quinoline ring), a benzo[h]isoquinoline ring, a phenanthroline ring, and a phenazine ring.

[0096] The aromatic ring may have one or more (e.g., 1 to 5) substituents. Examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. When the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring. It is also preferable that the aromatic ring is directly bonded to a carbonyl group to form an aromatic carbonyl group in compound β. It is also preferable that multiple aromatic rings are bonded via carbonyl groups. It is also preferable that the aromatic ring is bonded to an imide group to form an aromatic imide group in compound β. The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring. In addition, when a series of aromatic ring structures is formed by a plurality of aromatic rings (e.g., 2 to 5 rings) bonded by a structure selected from the group consisting of a single bond, a carbonyl group, and a multiple bond (e.g., an optionally substituted vinylene group, -C≡C-, and -N=N-), the series of aromatic ring structures as a whole is regarded as one specific structure. In addition, it is preferable that one or more of the plurality of aromatic rings constituting the series of aromatic ring structures is the heteroaromatic ring.

[0097] In terms of achieving superior pattern forming ability, compound β is preferably a compound that satisfies one or more of requirements (1) to (4), more preferably satisfies at least one of requirements (1) and (2), and even more preferably satisfies at least requirements (1) and (2) (is a polycyclic heteroaromatic ring). The heteroatom contained in the heteroaromatic ring preferably contains at least a nitrogen atom. Requirement (1): Contains a polycyclic aromatic ring. Requirement (2): Contains a heteroaromatic ring. Requirement (3): Contains an aromatic carbonyl group. Requirement (4): Contains an aromatic imide group.

[0098] Other suitable embodiments of compound β include, for example, acridinium salts, (iso)quinolinium salts, and iridium complexes. Compound β may also exhibit the function of compound β through the action of two types of compounds. Examples of such two types of compounds include a combination of an aromatic compound (b1) that is unsubstituted or substituted with an electron-donating group (preferably an alkyl group or an alkoxy group) and an aromatic compound (b2) that is substituted with an electron-withdrawing group (preferably a cyano group or an alkoxycarbonyl group). In this combination, electrons are transferred from photoexcited aromatic compound (b1) to aromatic compound (b2), and the resulting cation radical of aromatic compound (b1) accepts electrons from the carboxy group, thereby exhibiting the function of compound β.

[0099] Compound β is preferably at least one selected from the group consisting of acridine, benzo[f]quinoline, benzo[h]quinoline, phenanthridine, benzo[h]isoquinoline, phenanthroline, and phenazine, because they have a higher molar absorption coefficient at 365 nm and excellent photosensitivity to 365 nm light. These compounds may further have a substituent. Preferred examples of the substituent include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group.

[0100] When the compound β is a resin, the specific structure S0 may be bonded to the main chain of the resin via a single bond or a linking group. The compound β as a resin can be obtained, for example, by polymerizing a monomer having a polycyclic heteroaromatic ring (e.g., a vinyl polycyclic heteroaromatic ring and / or a (meth)acrylate monomer having the specific structure S0 (preferably a polycyclic heteroaromatic ring)). If necessary, it may be copolymerized with other monomers.

[0101] In terms of superior pattern-forming ability, the molar absorption coefficient of compound β at light with a wavelength of 365 nm is preferably 100 L / (mol cm) or more, more preferably 500 L / (mol cm) or more, even more preferably more than 1,000 L / (mol cm), and particularly preferably 4,000 L / (mol cm) or more. The upper limit is preferably 20,000 L / (mol cm) or less. The molar absorption coefficient at light with a wavelength of 365 nm is the molar absorption coefficient measured by dissolving compound β in acetonitrile. If compound β is not soluble in acetonitrile, the solvent used to dissolve compound β may be changed as appropriate. Having the molar absorption coefficient of compound β within the above range is particularly advantageous when exposing a photosensitive layer through a temporary support (preferably a PET film). In other words, because the absorption coefficient is appropriately low, the generation of bubbles due to decarbonation can be controlled even when exposed through a temporary support, preventing deterioration of the pattern shape. Examples of compounds having a high molar absorption coefficient for light with a wavelength of 365 nm include compounds in which three or more aromatic rings are condensed to form an aromatic ring. Examples of compounds in which three or more aromatic rings are condensed to form an aromatic ring include the compounds described above.

[0102] Examples of compound β include monocyclic aromatic compounds such as pyridine, 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, pyrazine, pyrimidine, and triazine; compounds in which two rings are fused to form an aromatic ring, such as quinoline, 2,4-dimethylquinoline, quinoline, isoquinoline, 1-methylisoquinoline, 1-phenylisoquinoline, quinoxaline, and quinazoline; and compounds in which three or more rings are fused to form an aromatic ring, such as acridine, 9-methylacridine, benzo[f]quinoline, benzo[h]quinoline, phenanthridine, benzo[h]isoquinoline, phenanthroline, and phenazine. These compounds may further have a substituent. Preferred examples of the substituent include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. Compound β preferably includes at least one selected from the group consisting of acridine, 9-alkylacridine (preferably 9-methylacridine), 9-phenylacridine, quinoline and 2,4-dialkylquinoline (preferably 2,4-dimethylquinoline), isoquinoline and 1-alkylisoquinoline (preferably 2-methylquinoline).

[0103] The compound β may be used alone or in combination of two or more. From the viewpoint of achieving superior pattern-forming ability, the content of the compound β is preferably 0.1% by mass or more, and more preferably 1.0% by mass or more, based on the total solid content of the composition. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the composition.

[0104] In terms of more excellent pattern forming ability, the total number of specific structures S0 in compound β is preferably 1 mol % or more, more preferably 3 mol % or more, even more preferably 5 mol % or more, and particularly preferably 10 mol % or more, relative to the total number of carboxy groups in resin A. In terms of the film quality of the obtained film, the upper limit is preferably 200 mol % or less, more preferably 100 mol % or less, and even more preferably 80 mol % or less, relative to the total number of carboxy groups in resin A.

[0105] [Filler] The composition preferably contains a filler. When the composition contains a filler, the resulting cured film has a better linear expansion coefficient and average dielectric loss tangent.

[0106] 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).

[0107] The shape of the filler may be either spherical or non-spherical (e.g., 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 modifiers. Examples of the functional groups include polymerizable groups (e.g., polymerizable groups contained in polymerizable compounds described below) and hydrophobic groups. Examples of surface modifiers include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.

[0108] Examples of fillers include Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, 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), SO-C series (e.g., SO-C2, etc., manufactured by Admatechs Co., Ltd., silicon dioxide), SO-E series (e.g., SO-E2, etc., manufactured by Admatechs Co., Ltd., silicon dioxide), and PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide). Examples of suitable MEK slurry include MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, 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).

[0109] The average particle diameter of the filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. The lower limit is preferably more than 0 nm, more preferably 5 nm or more. The average particle diameter of the filler is also preferably 5 to 100 nm. The average particle diameter of the filler is calculated by the following particle diameter measurement method. Particle diameter measurement method: A coating liquid containing a filler is applied to a substrate to form a coating film, and a rectangular region of 3 μm x 10 μm in a cross section taken along the normal direction to the surface of the coating film is observed with a scanning electron microscope. The major axes of all fillers observed within the region are measured at five different locations on the coating film, and the average value of the major axes of all fillers measured in each measurement is defined as the average particle diameter of the filler. The coating liquid may be the composition of the present invention.

[0110] The procedure for the particle size measurement method is described in detail below. First, a coating liquid containing a filler is applied to a substrate to form a coating film. The thickness of the coating film is preferably 3 μm or more. A glass substrate is used as the substrate. When forming the coating film, a drying treatment may be performed as necessary. A cross section along the normal direction of the surface of the obtained coating film (the surface opposite the substrate side) is cut out, and a rectangular region of 3 μm x 10 μm on the cross section is observed with a scanning electron microscope, and the major diameters of all fillers observed within the region are measured. As the scanning electron microscope, for example, an S-4800 manufactured by Hitachi High-Tech Corporation is used. The magnification for observation is 50,000 times. The above operation is performed at five different locations on the coating film, and the average (arithmetic mean) of the major diameters of all fillers measured in each operation is taken as the average particle size of the filler. Note that the major diameter refers to the length of the longest line segment connecting any two points on the outline of the filler 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.

[0111] The refractive index of the filler is preferably 0.5 to 3.0, more preferably 1.2 to 1.8.

[0112] The filler may be used alone or in combination of two or more. The content of the filler is often 10.0 mass% or more, preferably 30.0 mass% or more, more preferably 50.0 mass% or more, even more preferably 60.0 mass% or more, particularly preferably 65.0 mass% or more, and most preferably 70.0 mass% or more, based on the total solid content of the composition. The upper limit is preferably 90.0 mass% or less, more preferably 80.0 mass% or less, and even more preferably 75.0 mass% or less, based on the total solid content of the composition.

[0113] [Polymerizable Compound] The composition preferably contains a polymerizable compound. The polymerizable compound is a compound different from the various components described above. The polymerizable compound is preferably a compound having a polymerizable group but no carboxy group.

[0114] The polymerizable compound is a compound having one or more polymerizable groups in one molecule. Examples of the polymerizable group that the polymerizable compound has include a (meth)acryloyl group, a vinyl group, and a styryl group, and a (meth)acryloyl group is preferred.

[0115] Examples of the polymerizable compound include a polymerizable compound having one polymerizable group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two polymerizable groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more polymerizable groups in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound"). As the polymerizable compound, a bifunctional polymerizable compound is preferred.

[0116] Examples of bifunctional polymerizable compounds include polyethylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Commercially available bifunctional polymerizable compounds include diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0117] Examples of trifunctional or higher functional polymerizable compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton. "(Tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0118] Commercially available polymerizable compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.); alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation); and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0119] Examples of the polymerizable compound include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates). The number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, and more preferably 8 or more. The upper limit is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0120] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, even more preferably 20.0 mass% or less, particularly preferably 15.0 mass% or less, and most preferably 10.0 mass% or less, based on the total solid content of the composition. The lower limit is preferably 1.0 mass% or more, more preferably 5.0 mass% or more, based on the total solid content of the composition.

[0121] [Photopolymerization initiator] The composition may contain a photopolymerization initiator. The photopolymerization initiator is a compound different from the various components described above. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0122] Examples of the photopolymerization initiator include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure). As the photopolymerization initiator, oxime ester compounds or aminoacetophenone compounds are preferred.

[0123] 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), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Power Electronic New 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 Powerful Electronic New 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 Powerful Electronic New Materials Co., Ltd.).

[0124] 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.).

[0125] 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).

[0126] Examples of the photopolymerization initiator include those described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0127] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 10.0 mass% or less, more preferably 5.0 mass% or less, and even more preferably 2.0 mass% or less, based on the total solid content of the composition. The lower limit is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, based on the total solid content of the composition.

[0128] [Thermal Base Generator] The composition may contain a thermal base generator. The thermal base generator is a compound different from the various components described above. When the composition contains a thermal base generator and the resin A contains a precursor of a polyimide having a carboxy group or a precursor of a polybenzoxazole having a carboxy group, the ring-closing reaction of these precursors is promoted, and polyimide or polybenzoxazole is likely to be produced.

[0129] The thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base upon heating. The onium salt compound is preferably an ammonium salt compound (a compound consisting of an ammonium cation and an anion), an iminium salt compound (a compound consisting of an iminium cation and an anion), a sulfonium salt compound (a compound consisting of a sulfonium cation and an anion), an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion), and more preferably an ammonium salt compound. The anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion, or a sulfate anion, and more preferably a carboxylate anion. The anion constituting the ammonium salt compound preferably further has an aromatic ring. The aromatic ring may, for example, be A in the formula (A1) described below. ａ１ Examples of the aromatic rings that constitute the aromatic ring group represented by the formula (I) include aromatic rings. The temperature at which the acidic compound and the onium salt compound generate a base is preferably the heating temperature in step X4 in the laminate manufacturing method described below. The temperature at which the thermal base generator generates a base (base generation temperature) can be determined, for example, by using differential scanning calorimetry to heat the compound to be measured in a pressure-resistant capsule to 250°C at 5°C / min, and reading the peak temperature of the lowest exothermic peak. This peak temperature can be used as the base generation temperature.

[0130] 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.

[0131] <Acidic Compound> The acidic compound is preferably a compound represented by formula (A1) or a compound represented by formula (A2).

[0132]

[0133] 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.

[0134] In formula (A1), A ａ１ represents a p-valent organic group. Examples of the p-valent organic group include a p-valent aliphatic hydrocarbon group and a p-valent aromatic ring group, with a p-valent aromatic ring group being preferred. Examples of the monovalent (when p is 1) 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 p-valent aliphatic hydrocarbon groups may further have a substituent.

[0135] The monovalent (when p is 1) aromatic ring group may be either a monocyclic or polycyclic ring. The monovalent aromatic ring group may be either a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group. Examples of the monovalent 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 pyr ... phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a Examples of suitable aromatic ring groups include an aryl ring group, an indolizine ring group, an indole ring group, a benzofuran ring group, a benzothiophene ring group, an isobenzofuran ring group, a quinolizine ring group, a quinoline ring group, a phthalazine ring group, a naphthyridine ring group, a quinoxaline ring group, a quinoxazoline ring group, an isoquinoline ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxathiin ring group, a phenothiazine ring group, and a phenazine ring group, with a benzene ring group being preferred. Examples of p-valent aromatic ring groups (where p is an integer of 2 or more) include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aromatic ring group. The p-valent aromatic ring group may further have a substituent.

[0136] In formula (A1), R ａ１ represents a monovalent organic group. Examples of the monovalent organic group include A ａ１ Examples of the p-valent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group. The monovalent organic group may further have a substituent. The substituent is preferably a carboxy group.

[0137] In formula (A1), L ａ１ represents an (m+1)-valent linking group. Examples of the (m+1)-valent linking group include -O-, -CO-, -COO-, -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 "-CH<"; tetravalent linking groups having a group represented by ">C<"; (m+1)-valent linking groups having a cyclic group such as an aromatic ring group or an alicyclic group; and groups combining these.

[0138] In formula (A1), m represents an integer of 1 or greater. m is preferably 1 or 2, and more preferably 1.

[0139] In formula (A1), p represents an integer of 1 or greater. p is preferably 1 or 2, and more preferably 1.

[0140] (HOOC-L ａ２ ) ｎａ１ -A ａ２ - (L ａ３ -N(R ａ２ ) (R ａ３ )) ｎａ２ (A2)

[0141] In formula (A2), A ａ２ represents an aromatic ring group having a valence of (na1 + na2). ａ２ and R ａ３ each independently represents a monovalent organic group. ａ２ and L ａ３ each independently represents a single bond or a divalent linking group. na1 and na2 each independently represents an integer of 1 to 3.

[0142] A ａ２ Examples of the aromatic ring group represented by the formula: ａ１ Among the p-valent organic groups represented by the formula (R), an aromatic ring group having a valence of (na1+na2) is exemplified, and a benzene ring group having a valence of (na1+na2) is preferred. ａ２ and R ａ３ Examples of the monovalent organic group represented by the formula: ａ１ Among the p-valent organic groups represented by the formula (I), monovalent aliphatic hydrocarbon groups and monovalent aromatic ring groups are exemplified, and monovalent aliphatic hydrocarbon groups are preferred. ａ２ and L ａ３ Examples of the divalent linking group represented by the formula:ａ１ Examples of the divalent linking groups include those having a valence of (m+1) and represented by the formula: ａ２ is preferably a single bond. ａ３ is preferably —CO—. na1 and na2 are preferably 1. L ａ２ If there are multiple L ａ２ They may be the same or different. ａ３ If there are multiple L ａ３ R may be the same or different. ａ２ If there are multiple R ａ２ R may be the same or different. ａ３ If there are multiple R ａ３ They may be the same or different.

[0143] <Ammonium Salt Compound> 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).

[0144]

[0145] 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.

[0146] 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 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.

[0147] Examples of thermal base generators include those described in WO 2018 / 038002.

[0148] The thermal base generator may be used alone or in combination of two or more. The content of the thermal base generator is preferably 10.0 mass% or less, more preferably 5.0 mass% or less, and even more preferably 1.0 mass% or less, based on the total solid content of the composition. The lower limit is preferably more than 0 mass%, more preferably 0.1 mass% or more, based on the total solid content of the composition.

[0149] [Surfactant] The composition may contain a surfactant, which is a compound different from the above-mentioned various components.

[0150] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of nonionic surfactants include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. From the viewpoint of improving environmental compatibility, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon-based surfactant or a silicone-based surfactant.

[0151] 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 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).

[0152] Examples of fluorosurfactants include acrylic compounds that have a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Megafac DS-21, etc., as described in The Chemical Daily (February 22, 2016) and The Nikkei Business Daily (February 23, 2016)). 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 also be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound having 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 having an ethylenically unsaturated group in the side chain. Specific examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). From the viewpoint of improving environmental compatibility, preferred fluorine-based surfactants are 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).

[0153] 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 esters. Examples of hydrocarbon surfactants include 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); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0154] 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.

[0155] 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).

[0156]

[0157] 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. A plurality of R's may be the same or different.

[0158]

[0159] 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.

[0160] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0161]

[0162] 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.

[0163] Examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (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, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-1 25, 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).

[0164] Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0165] The surfactant content is preferably from 0.0001 to 10.0 mass%, more preferably from 0.001 to 5.0 mass%, and even more preferably from 0.005 to 3.0 mass%, based on the total solid content of the composition.

[0166] [Other Additives] In addition to the various components described above, the composition may contain other additives. Examples of other additives include resins other than Resin A, triazole, benzotriazole, tetrazole, and derivatives thereof, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, and alkoxysilane compounds. Examples of triazole, benzotriazole, tetrazole, and derivatives thereof, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds are described, for example, in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds are described, for example, in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0167] The solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the composition. 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., dimethyl sulfoxide and sulfolane), amide solvents, cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone), lactone solvents, and mixed solvents containing two or more of these. The solvents may be used alone or in combination of two or more. 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 solid content of the composition.

[0168] 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 easily mixed in as impurities, so the following contents are preferred.

[0169] The content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, based on the total solid content of the composition. The lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or may be 0.1 ppm by mass or more, based on the total solid content of the composition.

[0170] Methods for adjusting the content of impurities include, for example, a method of using raw materials with low impurity contents as raw materials for various components that may be contained in the composition, a method of purifying various components that may be contained in the composition, and a method of preventing impurities from being mixed in when preparing the composition.

[0171] The content of impurities can be measured by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0172] In the composition, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, and hexane 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, based on the total solid content of the composition. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, based on the total solid content of the composition. The content of these compounds can be adjusted in the same manner as for the above-mentioned impurities. The content of these compounds can be measured using known measurement methods.

[0173] [Transfer Film] The transfer film has a temporary support and a composition layer formed using the above-described composition.

[0174] 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 100 may have a configuration without the 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.

[0175] [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.

[0176] 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 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. It is also preferable that the temporary support is free of deformations such as wrinkles and scratches.

[0177] 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 particularly 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. Specifically, the number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 3 or less per mm ２ More preferably, 0 pieces / mm ２ As a specific example of the number of fine particles, foreign matter and defects having a diameter of 1 μm or more on the temporary support, 2 particles / mm ２ , and 0 pieces / mm ２ Examples include:

[0178] 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 is the average value of any five points measured by cross-sectional observation using a SEM.

[0179] 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 ２Examples 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.

[0180] 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.).

[0181] 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.

[0182] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support in order to provide 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, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0183] [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 preferred embodiments are also the same. However, the preferred ranges of 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 A 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 A is preferably 5.0% by mass or more relative to the total mass of the composition layer."

[0184] <Thickness of Composition Layer> The average thickness of the composition layer is preferably 0.5 to 40 μm, more preferably 0.5 to 25 μm, and even more preferably 3 to 20 μm. When the average thickness of the composition layer is 40 μm or less, it is preferred in terms of excellent pattern resolution, and when the average thickness of the composition layer is 0.5 μm or more, it is preferred in terms of excellent reliability.

[0185] [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.

[0186] [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 Preferably, 0 pieces / m ２ The fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is trapped in the cover film when the cover film is produced by thermally melting the material and then kneading, extrusion and / or biaxial stretching and casting.

[0187] 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 ２More preferably, 0 pieces / mm ２ This makes it possible to suppress defects caused by the transfer of irregularities caused by particles contained in the cover film to the composition layer.

[0188] 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 the above 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, the upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0189] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film. Examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP 2006-259138 A, the contents of which are incorporated herein by reference.

[0190] 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.).

[0191] [Other Layers] The transfer film may include other layers in addition to the above layers. Examples of other layers include a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0192] [Method for producing transfer film] The method for producing the transfer film is not particularly limited as long as it is a production method using a composition. In the method for producing the transfer film, the composition is preferably applied onto a temporary support to form a composition layer.

[0193] For example, a method for manufacturing the transfer film 100 shown in FIG. 1 includes a manufacturing method including a step of applying a composition to the surface of a temporary support 12 to form a coating film, and then drying the coating film to form a composition layer 14. The transfer film 100 shown in FIG. 1 is manufactured by pressing a cover film onto the composition layer of the transfer film manufactured by the above manufacturing method. The transfer film 100 shown in FIG. 1 may also be wound up after manufacturing and stored as a roll of transfer film 100. The roll of transfer film 100 can be used as is in the lamination step with a substrate in a roll-to-roll system, which will be described later.

[0194] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of the composition for forming an intermediate layer, the method for forming an intermediate layer, the composition for forming a thermoplastic resin layer, and the method for forming a thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0195] [Method for Forming Composition Layer] The method for forming the composition layer may be, for example, a known method, such as a method of applying and drying the composition.

[0196] Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating. The composition used in the method for forming the composition layer preferably contains a solvent. The solvent has the same meaning as the solvent that may be contained in the composition, and preferred embodiments are also the same.

[0197] [Applications] The pattern (cured film) obtained from the composition layer formed using the composition or the transfer film can be used in various applications. For example, it can be used 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. Specific examples 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 forming wiring.

[0198] [Method for producing laminate] The method for producing a laminate is not particularly limited as long as it is a method using the composition or the transfer film. The method for producing a laminate preferably includes steps X1 to X3, and more preferably steps X1 to X4. Step X1: forming a composition layer on a substrate using the composition or the transfer film; Step X2: patternwise exposing the composition layer; Step X3: developing the exposed composition layer using a developer to form a pattern; Step X4: heating the pattern; Step X4': exposing the pattern obtained by the development. The composition and the transfer film are as described above. When the developer in step X3 is an organic solvent developer, it is preferable to include step X4' after step X3 or between steps X3 and X4.

[0199] Each step of the method for producing the laminate will be described in detail below.

[0200] [Step X1] Step X1 is a step of forming a composition layer on a substrate using a composition or a transfer film. In other words, step X1 may be a step of forming a composition layer using a composition, or a step of forming a composition layer using a transfer film. In particular, step X1 is preferably a step of forming a composition layer using a composition. When a composition is used, step X1 is preferably a step of applying the composition to a substrate to form a composition layer. Examples of methods for applying the composition include the method of forming a composition layer in the above-mentioned method for producing a transfer film.

[0201] When a transfer film is used, step X1 is preferably a step of contacting the surface of the composition layer in the transfer film opposite the temporary support side with the substrate, and laminating the transfer film and the substrate. For lamination, known laminators such as laminators, vacuum laminators, and auto-cut laminators may be used. Examples of lamination methods include known transfer methods and lamination methods, and a method in which a substrate is placed on the surface of the composition layer and pressure and heat are applied using a roll or the like is preferred. Examples of lamination methods include known laminators such as vacuum laminators and auto-cut laminators. The lamination temperature is preferably 70 to 130°C.

[0202] Process X1 is preferably carried out by a roll-to-roll method. The substrate to which the transfer film is attached is preferably a resin film or a resin film having a conductive layer. The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a process of unwinding the substrate before any of the processes included in the method for producing a laminate, and a process of winding the substrate after any of the processes, and at least one of the processes (preferably all of the processes or all of the processes other than the heating process) is carried out while the substrate is being transported. Examples of the unwinding method and the winding method include known methods.

[0203] <Substrate> Examples of the substrate include glass substrates, glass epoxy substrates, silicon substrates, and resin substrates, as well as substrates 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. Examples of the substrate include tempered glass such as Gorilla Glass (manufactured by Corning Incorporated). Materials that can be contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. Resin substrates are preferably resin films with low optical distortion and / or high transparency. Examples of resin substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0204] As the substrate having a conductive layer, a resin substrate having a conductive layer is preferred, and a resin film having a conductive layer is more preferred, because it can be produced by a roll-to-roll method.As the substrate having a conductive layer, an organic substrate having a copper pattern is also preferred.As the organic substrate, for example, a resin substrate can be mentioned.

[0205] Examples of the conductive layer include a conductive layer used for circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably at least one 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. Furthermore, the conductive layer in the substrate having a conductive layer may be either one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, the conductive layers may be the same or different, and are preferably different. 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 SiO２ Conductivity is defined as a material having a volume resistivity of 1×10 ６ It means that the volume resistivity is less than 1×10 ４ Preferably, the resistivity is less than Ωcm. When the substrate having a conductive layer has two or more conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0206] [Step X2] Step X2 is a step of patternwise exposing the composition layer after the above-mentioned step X1. Step X2 is preferably a step of reducing the content of carboxy groups in the resin A in the composition layer to change the solubility in a developer. "Patternwise exposure" refers to a form of patternwise exposure, i.e., exposure in a form in which exposed areas and unexposed areas are present. The positional relationship between the exposed areas and unexposed areas in the patternwise exposure is not particularly limited. The exposure direction may be from the opposite side of the composition layer to the substrate, or from the substrate side of the composition layer.

[0207] The reduction rate of the carboxyl group content of the resin A in the composition layer was measured by measuring the IR (infrared) spectrum of the composition layer before and after exposure, and the reduction rate was measured by measuring the IR spectrum of the composition layer after exposure. －１ The maximum absorption peak due to the C═O stretching of the carboxyl group can be calculated from the reduction rate of the peak top height of the maximum absorption peak present in the wavelength range of 1680 to 1720 cm －１ appears in the wavelength range.

[0208] The exposure light source is not particularly limited as long as it emits light in a wavelength range that can reduce the content of carboxy groups in resin A (light with a wavelength that excites a specific structure in compound β, for example, light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm). Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes). The exposure dose is 10 to 10,000 mJ / cm. ２ is preferred, and 50 to 3000 mJ / cm ２ is more preferred.

[0209] When the composition layer is formed using a transfer film having a temporary support, step X2 may be a step of performing patternwise exposure after peeling the temporary support from the composition layer, or a step of performing patternwise exposure through the temporary support before peeling the temporary support. Step 2 is preferably a step of performing patternwise exposure through the temporary support before peeling the temporary support, in order to prevent contamination of the photomask due to contact between the composition layer and the photomask and to prevent adverse effects on exposure due to foreign matter attached to the photomask. Furthermore, it is preferable to peel the temporary support from the composition layer before step X3. The patternwise exposure may be either exposure through a photomask or direct exposure using a laser or the like. Examples of photomasks 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. Specifically, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is an example.

[0210] [Step X3] Step X3 is a step of forming a pattern by developing the exposed composition layer using a developer after Step X2. The composition layer exposed in Step X2 has a difference in solubility in the developer between the exposed and unexposed areas (dissolution contrast) due to a decrease in the carboxy group content in the exposed areas of the composition layer. The dissolution contrast in the composition layer allows a pattern to be formed in Step X3. For example, when the developer in Step X3 is an alkaline developer, the unexposed areas are removed by Step X3 to form a negative pattern. On the other hand, when the developer in Step X3 is an organic solvent developer, the exposed areas are removed by performing Step X3 to form a positive pattern. It is preferable to reduce the carboxy group content of Resin A in the obtained positive pattern by Step X4', which will be described later.

[0211] Examples of the developer include an alkaline developer and an organic solvent developer, with an alkaline developer being preferred. The alkaline developer is not particularly limited, as long as it can remove the unexposed portions of the composition layer. An alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferred. The alkaline developer may also contain a water-soluble organic solvent and / or a surfactant. 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. Examples of the alkaline developer include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution. The concentration of the alkaline component constituting the alkaline developer may be, for example, a 0.1% by mass aqueous solution, a 1.0% by mass aqueous solution, or a 2.38% by mass aqueous solution. Examples of alkaline developers include those described in JP-A-5-072724 and paragraph 0194 of WO 2015 / 093271.

[0212] 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. Examples of organic solvent developers include cyclopentanone and propylene glycol monomethyl ether acetate. The organic solvent developer may contain two or more organic solvents, and may also contain water. The content of water in the organic solvent developer is preferably less than 10% by mass, based on the total mass of the organic solvent developer. It is more preferable that the organic solvent developer is substantially free of water. The content of the organic solvent in the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer. The upper limit is preferably 100% by mass or less.

[0213] Examples of the development method include puddle development, shower development, spin development, and dip development. A development method in which a developer is sprayed onto the composition layer after exposure by showering is preferred. After development, development residues may be removed by spraying a detergent or the like by showering and rubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0214] [Step X4] Step X4 is a step of heating the pattern obtained in step X3 or step X4'. In step X4, a polyimide is produced by a ring-closing reaction from a polyimide precursor derived from resin A, or a polybenzoxazole is produced by a ring-closing reaction from a polybenzoxazole precursor derived from resin A.

[0215] Step X4 can improve the purity of the pattern. Pattern purity means that the various components contained in the pattern are substantially composed of only polyimide and / or polybenzoxazole. Specifically, the total content of polyimide and polybenzoxazole is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total mass of the pattern. The upper limit is preferably 100% by mass or less, based on the total mass of the pattern. For example, when the developer in Step X3 is an alkaline developer, the pattern obtained in Step X3 may contain a polymer derived from the polymerizable compound produced in Step X2. When Step X4 is performed, the polymer or the like is depolymerized and removed, and by-products produced by the ring-closing reaction of the polyimide precursor derived from Resin A or the polybenzoxazole precursor derived from Resin A (e.g., compounds produced by decomposition of some groups of the precursor) can also be removed. This is presumably to improve the purity of the pattern. When the composition or the composition layer of the transfer film contains a thermal base generator, carrying out step X4 promotes the ring-closing reaction by the base generated from the thermal base generator by heat, and polyimide and polybenzoxazole are obtained efficiently and / or under more lenient conditions (for example, lower heating temperature, etc.). Furthermore, in step X4, when resin A', which has a reduced carboxy group content compared to resin A in the composition layer by step X3, is derived from a polyimide precursor or polybenzoxazole precursor, carboxy groups that serve as starting points for the ring-closing reaction are generated from resin A', and polyimide and polybenzoxazole are further produced by the ring-closing reaction.

[0216] The temperature and time of the heat treatment are not particularly limited as long as they are sufficient to promote the ring-closure reaction of the polyimide precursor and the polybenzoxazole precursor. The heat treatment temperature is preferably 150 to 400°C, more preferably 200 to 350°C, even more preferably 200 to 300°C, and particularly preferably 200 to 250°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 higher, more preferably 50.66 kPa or higher. The upper limit is preferably 121.6 kPa or lower, more preferably 111.46 kPa or lower, and even more preferably 101.3 kPa or lower.

[0217] [Step X4'] Step X4' is a step of exposing the pattern obtained in Step X3. When the developer in Step X3 is an organic solvent developer, Step X4' is preferably included after Step X3 or between Steps X3 and X4. When the developer in Step X3 is an organic solvent developer, Step X4' is a step of exposing the positive pattern obtained in Step 3 to light to reduce the content of carboxy groups in Resin A. Specifically, it is preferable to pattern-expose the composition layer using light of a wavelength that excites a specific structure in Compound β in the composition layer. The exposure may be either full-surface exposure or pattern-exposure. Examples of the exposure method and exposure conditions include the exposure method and exposure conditions in Step X2.

[0218] The relationship between Step X2 and Step X4' in the case where the composition contains a polymerizable compound and a photopolymerization initiator (for example, composition embodiment X-3) will be described in detail. Step X2 and Step X4' may be Step Xa, in which the content of carboxy groups in Resin A in the composition layer is reduced to change the solubility in the developer, or Step Xb, in which a polymerization reaction of the polymerizable compound based on the photopolymerization initiator is initiated, or both. Step X2 is preferably at least Step Xa. When Step X2 is Step Xa and the developer in Step X3 is an organic solvent developer, Step 4' is preferably Step Xa.

[0219] [Other Steps] The method for producing a laminate may include other steps in addition to the steps described above. Examples of other steps include the following steps.

[0220] <Step of Peeling Off Cover Film> When the composition layer is formed using a transfer film having a cover film, the method for producing a laminate preferably includes a step of peeling off the cover film. Examples of the method for peeling off the cover film include known methods.

[0221] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the method for producing a laminate may 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. Specifically, treatments include a treatment in which copper is oxidized to blacken it as copper oxide, thereby reducing the visible light reflectance of the conductive layer. Suitable embodiments of treatments to reduce the visible light reflectance include those 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.

[0222] <Etching Step> When the substrate is a substrate having a conductive layer, the method for producing a laminate may include a step of etching the conductive layer in an area where the etching resist film is not disposed, using the pattern formed in step X3 or step X4 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.

[0223] A preferred method for manufacturing a laminate is to use a substrate having a plurality of conductive layers on both surfaces thereof, and to sequentially or simultaneously form patterns on the conductive layers formed on both surfaces. With the above 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.

[0224] [Laminate] The laminate is not particularly limited as long as it is a laminate produced by a laminate production method.

[0225] [Method for manufacturing circuit wiring] The method for manufacturing circuit wiring is not particularly limited as long as it is a method for manufacturing circuit wiring using a composition or a transfer film. Preferably, the method includes a step of contacting the surface of the composition layer in the transfer film opposite to the temporary support side with the conductive layer in a substrate having a conductive layer, and laminating the transfer film and the substrate having a conductive layer, or a step of applying a composition to the substrate to form a composition layer, a step of pattern-exposing the composition layer, a step of developing the exposed composition layer with a developer to form a pattern, a step of heating the pattern, and a step of etching the conductive layer in an area where the pattern is not arranged.

[0226] Examples of the steps in the method for producing a circuit wiring include the steps in the method for producing a laminate. The method for producing a circuit wiring is preferably carried out in multiple sets, with each set consisting of the laminating step or the step of forming a composition layer using a composition to the etching step. The film used as an etching resist film can also be used as a protective film (insulating film) for the formed circuit wiring.

[0227] [Method for Manufacturing Semiconductor Package] Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as methods for manufacturing build-up substrates. Specifically, examples of methods for manufacturing semiconductor packages include methods for manufacturing semiconductor packages including steps Z1 to Z5. Step Z1: forming a composition layer on a substrate having a conductive layer using a composition or a transfer film; Step Z2: pattern-exposing the composition layer; Step Z3: developing the exposed composition layer using a developer to form a pattern having vias; Step Z4: heating the pattern; and Step Z5: forming a circuit pattern on the pattern.

[0228] Steps Z1, Z2, and Z4 in the method for manufacturing a semiconductor package include step X1, step X2, and step X4, respectively.

[0229] [Step Z3] Step Z3 is a step of developing the exposed composition layer with a developer to form a pattern having vias. Examples of the method of development with a developer include the method of development with the developer in Step X3.

[0230] The shape of the vias in the pattern may be, for example, a square, trapezoid, inverted trapezoid, or other cross-sectional shape, as well as a circular or square front shape (the shape of the via when observed from the direction in which the via bottom is visible). The cross-sectional shape of the vias in the pattern is preferably an inverted trapezoid, as this improves the adhesion of plated copper to the via wall surface. The via size (diameter) is often 300 μm or less, preferably 200 μm or less, more preferably less than 40 μm, even more preferably 30 μm or less, even more preferably 20 μm or less, particularly preferably 15 μm or less, and most preferably 10 μm or less. The lower limit is preferably 1 μm or more, more preferably 5 μm or more. The number of vias may be 1 or 2 or more, with 2 or more being preferred.

[0231] [Step Z5] Step Z5 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming the circuit pattern, as it allows for the formation of fine wiring. In the semi-additive process, a seed layer is formed by electroless copper plating using a palladium catalyst or the like on the via bottom, via wall, and the entire surface of the pattern after step Z3. The seed layer is used to form a power supply layer for electrolytic copper plating. The seed layer preferably has a thickness of 0.1 to 2.0 μm. When the seed layer has a thickness of 0.1 μm or more, a decrease in connection reliability during electrolytic copper plating can be suppressed. When the seed layer has a thickness of 2.0 μm or less, there is no need to increase the amount of etching when flash etching the seed layer between wirings, and damage to the wiring during etching can also be suppressed.

[0232] 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. A palladium-tin mixed catalyst is preferred as the catalyst used in the electroless plating process. The average particle size of the mixed catalyst is preferably 10 nm or less. Furthermore, the plating composition used in the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Examples of commercially available electroless copper plating solutions include "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0233] 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, it is preferable to expose the composition layer through a photomask on which the desired wiring pattern is drawn. Examples of exposure methods include the exposure method in step X2. Furthermore, 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. Furthermore, after forming the pattern, development residues of the composition may be removed using plasma or the like. After development, electrolytic copper plating may be performed to form a copper circuit layer and via filling. After electrolytic copper plating, the pattern may be peeled off using an alkaline aqueous solution or an amine-based stripper, and the seed layer between the wiring may also be removed (flash etching). Flash etching may be performed using an oxidizing solution containing, for example, 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 Company, Inc. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium may be removed using an acidic solution such as nitric acid or hydrochloric acid.

[0234] After pattern peeling or flash etching, a post-baking treatment is preferably carried out. The post-baking treatment sufficiently heat-cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The curing temperature is preferably 150 to 240°C. The curing time is preferably 15 to 500 minutes.

[0235] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed between step Z4 and step Z5. By performing the roughening step, the surface of the pattern is roughened to improve adhesion to the circuit wiring and also remove smears. Examples of the roughening step include known desmearing treatments, and a treatment involving contact with a roughening liquid is preferred. Examples of the roughening liquid 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.

[0236] Steps Z1 to Z5 may be repeated depending on the number of layers required. In addition, it is preferable to form a solder resist on the outermost layer of the resulting semiconductor package.

[0237] [Method for Manufacturing Semiconductor Device] The method for manufacturing a semiconductor device is not particularly limited as long as it includes a method for manufacturing a semiconductor package. Examples of the semiconductor device include semiconductor devices such as semiconductor packages used in electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0238] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes the laminate. The pattern (cured film) may be used as an insulating film or an organic interposer in a build-up base material.

[0239] The present invention will be described in further 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, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0240] [Preparation of Composition] Various components were mixed to obtain the solid content ratios shown in the table below, and then diluted to a solid concentration of 30 mass %, a MEK (methyl ethyl ketone) concentration of 20 mass %, and an NMP (N-methylpyrrolidone) concentration of 50 mass % to prepare compositions. Note that when the silica was not in a slurry form (when it was in a powder form), the silica was dispersed in a 50 mass % MEK solution to form a slurry, and then the mixture was finally mixed to prepare the composition.

[0241] [Resin] Resins A-1 to A-10 are all resins that fall under the category of Resin A.

[0242] <Resin A-1> Resin A-1 was synthesized according to the following scheme.

[0243]

[0244] 4,4'-Oxydiphthalic dianhydride (15.5 g), γ-butyrolactone (40 mL), and methoxyethoxymethyl-protected 6-hydroxyhexanoic acid (15.1 g) were mixed, and pyridine (7.9 g) was slowly added. The mixture was stirred at room temperature for 10 hours to obtain a reaction mixture. A solution of dicyclohexylcarbodiimide (DCC, 20.6 g) in γ-butyrolactone (18 mL) was slowly added to the resulting reaction mixture under ice cooling, followed by the slow addition of a suspension of 4,4'-oxydianiline (9.3 g) in γ-butyrolactone (35 mL). After further stirring at room temperature for 2 hours, ethanol (5 mL) was added and the mixture was stirred for 1 hour. The resulting reaction mixture was slowly poured into water (2 L), and the resulting precipitate was collected by filtration. The precipitate was dissolved in tetrahydrofuran (200 mL), and 1N hydrochloric acid (5 mL) was added to the mixture, followed by a reaction at 40°C for 1 hour. The reaction mixture was then slowly poured into 2 L of water, and the resulting precipitate was collected by filtration and dried to obtain Resin A-1, which had a weight-average molecular weight of 19,000, a polydispersity of 2.7, and an acid value of 152 mg KOH / g.

[0245] <Resins A-2 to A-10> Resins A-2 to A-10 were synthesized with reference to the synthesis method for resin A-1.

[0246]

[0247]

[0248] [Compound β] 9MeAC: 9-methylacridine 2,4-DMQ: 2,4-dimethylquinoline All of the above compounds fall under Compound B.

[0249] [Filler] YA050C-MJE: Spherical silica slurry, methacrylic surface treated, MEK slurry with a solid content of 50% by mass, manufactured by Admatechs Co., Ltd. SFP-20M: Silica, manufactured by Denka Co., Ltd. SO-C2: Silica, manufactured by Admatechs Co., Ltd.

[0250] [Polymerizable compounds] NK4G: NK ester 4G (bifunctional polyethylene glycol methacrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. A-NOD-N: NK ester A-NOD-N (bifunctional alkyl acrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. DPHA: dipentaerythritol hexaacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0251] [Photopolymerization initiator] Oxe01: IRGACURE OXE-01, manufactured by BASF Omn-379EG: Omnirad 379EG, manufactured by IGM Resins B.V.

[0252] [Thermal base generator]

[0253]

[0254] [Measurement of Average Particle Diameter] Each composition of each Example and Comparative Example was applied to a glass substrate and dried to form a coating film having a thickness of 4.0 μm. A cross section of the obtained coating film was cut out along the normal direction of the surface, and the cross section was observed under a scanning electron microscope. The major axes of all fillers observed within a region having a length of 3 μm in the longitudinal direction parallel to the thickness direction of the coating film and a length of 10 μm in the transverse direction perpendicular to the longitudinal direction were measured. The above operation was performed at five different locations on the coating film, and the average value (arithmetic mean value) of the major axes of all fillers measured in each operation was taken as the average particle diameter of the filler. Note that, for the compositions of each Example and Comparative Example, after measuring the average particle diameter as described above, the coating film was heated at 230° C. for 8 hours, and then the average particle diameter was measured according to the same procedure as described above. The value was the same as the average particle diameter before heat treatment.

[0255] [Photolithography] <Coating Method> The compositions shown in the table were coated and dried on glass (Corning glass, 5 cm length x 5 cm width x 1.1 mm thickness) to a dry thickness of 10 μm to form a composition layer. A temporary support (PET film, Lumirror 16FB40, 16 μm thickness, manufactured by Toray Industries, Inc.) and a photomask were laminated in this order on the obtained composition layer to obtain a laminate. The photomask used had multiple circular light-shielding sections with diameters of 20 μm, 15 μm, and 10 μm, and the spacing between the light-shielding sections (distance from center to center of circle) was 300 μm. The obtained laminate was subjected to pattern exposure using an ultra-high pressure mercury lamp from the side opposite the temporary support side of the photomask. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 500 mJ / cm ２ The photomask was then removed from the laminate. After exposure, the laminate was left to stand for 30 minutes, and the temporary support was peeled off from the laminate. The laminate was then developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) as a developer. After development, the laminate was rinsed for 20 seconds at room temperature using pure water as a rinse solution, and air was blown to remove any remaining rinse solution. This was then heat-treated in an oven (250°C, 8 hours), and vias of each diameter in the sample were observed and evaluated according to the following evaluation criteria. The smallest diameter of vias that could be formed without film loss and without residue at the via bottom was used for evaluation.

[0256] <Evaluation criteria for photolithography> A: A via with a diameter of 10 μm could be formed, with no film loss and no residue at the via bottom. B: A via with a diameter of 15 μm could be formed, with no film loss and no residue at the via bottom. C: A via with a diameter of 20 μm could be formed, with no film loss and no residue at the via bottom. D: The entire surface dissolved during development, and a via could not be formed.

[0257] <Transfer Film Method> The obtained composition was applied to a temporary support (PET film, Lumirror 16FB40, thickness 16 μm, manufactured by Toray Industries, Inc.) and dried to form a composition layer with a thickness of 10 μm. Next, a cover film (polypropylene film, FG-201, thickness 30 μm, manufactured by Oji F-Tex Co., Ltd.) was provided on the composition layer to obtain each transfer film. The cover film was peeled from the prepared transfer film and laminated to a polyimide substrate on which a copper pattern with a line width of 3 μm had been formed, thereby obtaining a laminate having a laminate structure in the order of "temporary support / composition layer / copper pattern / substrate (polyimide)". The lamination conditions were a substrate temperature of 40°C, a rubber roller temperature (lamination temperature) of 120°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. The lamination properties were good. Using each transfer film, the same operation as in the evaluation of the above coating method was performed, and the photolithography properties of each transfer film showed the same results as in the evaluation of the coating method.

[0258] [Preparation of Measurement Samples] For the compositions listed in the tables below, measurement samples were prepared according to the following method X. A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the compositions shown in the tables were applied to the substrate (on the copper surface) and dried to obtain a laminate having a composition layer with a thickness of 10.0 μm on the substrate. The obtained laminate was exposed to light (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 dip-developed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) for 90 seconds. Then, the substrate was rinsed for 20 seconds at room temperature using pure water as a rinse solution, and air was blown to remove any remaining rinse solution. This was then heated in an oven (250°C, 8 hours), immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film derived from the composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week for peeling. The obtained free-standing film was cut into strips to prepare measurement samples.

[0259] [Coefficient of Linear Expansion (CTE)] The measurement sample obtained by Method X was processed to a size of 19 mm x 5 mm, and the CTE was measured using a TMA (thermomechanical analyzer, TMA450EM, manufactured by TA Instruments). The measurement conditions were a heating rate of 10°C / min, a chuck distance of 16 mm, and a load of 49 mN. The measurement was carried out in a temperature range of -60 to 350°C. The CTE was taken as the average value (ppm / K) in the temperature range of 50 to 100°C during heating. Three samples were measured, and the average value was taken as average value X (ppm / K).

[0260] <CTE evaluation criteria> A: Average value X is less than 15 ppm / K B: Average value X is 15 ppm / K or more and less than 20 ppm / K C: Average value X is 20 ppm / K or more and less than 30 ppm / K D: Average value X is 30 ppm / K or more and less than 50 ppm / K E: Average value X is 50 ppm / K or more and less than 60 ppm / K F: Average value X is 60 ppm / K or more

[0261] [Average relative dielectric constant and average dielectric loss tangent] The average relative dielectric constant and average dielectric loss tangent of the measurement samples obtained by Method X were measured using a 28 GHz split cylinder resonator (manufactured by Kanto Electronics Application Development Co., Ltd.) The measurement was carried out on three samples, and the average values ​​were used.

[0262] <Evaluation criteria for average relative dielectric constant> A: Average relative dielectric constant is less than 2.9 B: Average relative dielectric constant is 2.9 or more and less than 3.1 C: Average relative dielectric constant is 3.1 or more

[0263] <Evaluation criteria for average dielectric tangent> A: Average dielectric tangent is less than 0.005 B: Average dielectric tangent is 0.005 or more and less than 0.007 C: Average dielectric tangent is 0.007 or more and less than 0.010 D: Average dielectric tangent is 0.010 or more

[0264] The contents of various components and the evaluation results are shown below. The column "Requirement A" indicates the L Ｚ１ When the carbon number of the group corresponding to the above is 1 to 15, it is designated as "A", and when the carbon number is 16 or more, it is designated as "B". Ｚ１ In the "Requirement B" column, the group corresponding to X in formula (1) is a tetravalent linking group having an alicyclic ring, and Z １and Z ２ is a hydrogen atom, the case where the group corresponding to X in formula (1) is a tetravalent linking group having an alicyclic ring, and Z １ and Z ２ is a hydrogen atom, the result was rated as "B." The "Content in solids" column indicates the solid concentration (% by mass) of each component relative to the total solid content in the composition. Note that "Not measurable" in the evaluation results column for Comparative Example 1-1 means that a pattern could not be formed using the composition of Comparative Example 1-1 (the entire surface was dissolved during development), and therefore none of the CTE, average relative dielectric constant, and average dielectric loss tangent could be measured.

[0265]

[0266]

[0267] The evaluation results shown in the table confirm that the compositions of the present invention achieve the desired effects. When Resin A satisfies Requirement A (when the Requirement A column is marked "A"), the CTE and average dielectric constant were confirmed to be superior (Examples 1-1 to 1-8). When Resin A satisfies Requirement B (when the Requirement B column is marked "A"), the CTE and average dielectric constant were confirmed to be superior (Examples 1-1 to 1-6 and 1-8 to 1-10). When the composition contains a thermal base generator, the CTE was confirmed to be superior (Examples 1-1, 1-14, and 1-15). When the composition contains a filler, the CTE and average dielectric tangent were confirmed to be superior (Examples 1-1 to 1-10 and 2-1 to 2-10). When the average particle size of the filler is 300 nm or less, the photolithography properties were confirmed to be superior (Examples 2-1, 2-11, and 2-12). It was confirmed that when the filler content was 50.0 mass% or more (preferably 60.0 mass% or more, more preferably 65.0 mass% or more, and even more preferably 70.0 mass% or more) relative to the total solids content of the composition, the CTE and average dielectric loss tangent were better (Examples 2-1 and 2-13 to 2-17). It was confirmed that when the polymerizable compound content was 10.0 mass% or less, the CTE and average dielectric loss tangent were better (Examples 2-1 and 2-18 to 2-20). It was confirmed that when the composition contained a bifunctional polymerizable compound, the CTE was better (Examples 2-21 to 2-23).

[0268] In each example, instead of forming a composition layer using a composition, a measurement sample was prepared using a transfer film prepared according to the following procedure. The obtained composition was applied to a temporary support (PET film, Lumirror 16FB40, thickness 16 μm, manufactured by Toray Industries, Inc.) and dried to form a composition layer with a thickness of 10 μm. A cover film (polypropylene film, FG-201, thickness 30 μm, manufactured by Oji F-Tex Co., Ltd.) was then provided on the composition layer to obtain each transfer film. The cover film was peeled from the obtained transfer film, and the exposed composition layer was laminated on the copper surface of a copper-clad polyimide film (Metaloyal, manufactured by Toray Industries, Inc.). The lamination conditions were a substrate temperature of 40°C, a rubber roller temperature (lamination temperature) of 120°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. Lamination properties were good. Furthermore, the temporary support was peeled from the obtained sample to obtain a laminate having a laminate structure in the order of "composition layer / copper / substrate (polyimide)". The obtained laminate was exposed to light from the side opposite to the substrate side of the composition layer (high-pressure mercury lamp, cumulative illuminance of 100 mJ / cm measured with an illuminometer at a wavelength of 365 nm). ２ ), and then dip-developed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) for 90 seconds. The resulting sample was then rinsed at room temperature for 20 seconds using pure water as a rinse solution, and air was blown to remove any remaining rinse solution. The resulting sample was then heated in an oven (250°C, 8 hours), immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (pure water at room temperature for 1 hour), and then peeled from the substrate to obtain a free-standing film derived from the composition layer. If the free-standing film could not be peeled by the peeling treatment, it was further immersed in 2M hydrochloric acid for about a week for peeling. The resulting free-standing film was cut into strips to prepare measurement samples. The obtained measurement sample was evaluated for linear expansion coefficient (CTE), average relative dielectric constant, and average dielectric loss tangent in the same manner as the composition. The evaluation results were the same as those for the measurement sample prepared by Method X.

[0269] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. A resin A including at least one selected from the group consisting of a polyimide precursor having a carboxy group, a polyimide having a carboxy group, a polybenzoxazole having a carboxy group, and a polybenzoxazole precursor having a carboxy group; and a compound β having a structure that reduces the amount of the carboxy groups in the resin A upon exposure to light.

2. The photosensitive composition according to claim 1 , wherein the resin A comprises a polyimide precursor having a carboxy group.

3. The photosensitive composition according to claim 1 , wherein the resin A has an aliphatic hydrocarbon group having a carboxy group.

4. The photosensitive composition according to claim 1 , wherein the resin A has a repeating unit represented by formula (1). 【Chemistry 1】 In formula (1), X represents a tetravalent linking group. Y represents a divalent linking group. Z １ and Z ２ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group having a carboxy group. １ and Z ２ At least one of these represents a hydrogen atom or a group having a carboxy group.

5. Z １ and Z ２ The photosensitive composition according to claim 4 , wherein at least one of the following represents a group represented by formula (Z1): 【Chemistry 2】 In formula (Z1), * represents a bonding position. Ｚ１ represents a divalent linking group.

6. The photosensitive composition according to claim 1 , wherein the compound β is a compound B having a structure capable of accepting electrons from the carboxy group of the resin A in a photoexcited state.

7. The photosensitive composition according to claim 1 , wherein the compound β is a nitrogen-containing aromatic compound.

8. The photosensitive composition of claim 1 further comprising a filler.

9. The photosensitive composition according to claim 8 , wherein the content of the filler is 50% by mass or more based on the total solid content of the photosensitive composition.

10. 9. The photosensitive composition according to claim 8, wherein the filler has an average particle size of 300 nm or less.

11. Further, the composition contains a filler. The resin A has a repeating unit represented by formula (2), the compound β is a nitrogen-containing aromatic compound, 2. The photosensitive composition according to claim 1, wherein the filler has an average particle size of 300 nm or less. 【Chemistry 3】 In formula (2), X represents a tetravalent linking group. Y represents a divalent linking group. Z ３ and Z ４ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group represented by formula (Z2). ３ and Z ４ At least one of these represents a hydrogen atom or a group represented by formula (Z2). 【Chemistry 4】 In formula (Z2), * represents a bonding position. Ｚ２ represents a divalent aliphatic hydrocarbon group which may have a substituent.

12. The photosensitive composition according to claim 1 , further comprising a polymerizable compound.

13. The photosensitive composition of claim 12 further comprising a photopolymerization initiator.

14. The photosensitive composition according to claim 5, wherein the compound β is a nitrogen-containing aromatic compound having a heteroaromatic ring.

15. The structure is a polycyclic aromatic ring group, The photosensitive composition according to claim 5 , wherein the compound β is a nitrogen-containing aromatic compound having a heteroaromatic ring.

16. A transfer film comprising a temporary support and a composition layer formed by using the photosensitive composition according to any one of claims 1 to 15.

17. A step X1 of forming a composition layer on a substrate using the photosensitive composition according to any one of claims 1 to 15; A step X2 of pattern-exposing the composition layer; and a step X3 of developing the exposed composition layer with a developer to form a pattern.

18. The method for producing a laminate according to claim 17 , wherein the step X2 is a step of reducing the carboxy groups of the resin A to change the solubility in a developer.

19. The method for producing a laminate according to claim 17, further comprising a step X4 of heating the pattern after the step X3.

20. The method for producing a laminate according to claim 17, wherein the substrate is an organic substrate having a copper pattern.

21. The method for producing a laminate according to claim 17 , wherein the developer is an alkaline developer.

22. A laminate produced by the method according to claim 17.

23. A semiconductor package comprising the laminate of claim 22.

24. A resin having a repeating unit represented by formula (3): 【Chemistry 5】 In formula (3), X represents a tetravalent linking group. Y represents a divalent linking group. Z ５ and Z ６ each independently represents a hydrogen atom, a monovalent organic group not having a carboxy group, or a group represented by formula (Z1). ５ and Z ６ At least one of these represents a hydrogen atom or a group represented by formula (Z1). 【Chemistry 6】 In formula (Z1), * represents a bonding position. Ｚ１ represents a divalent linking group.

25. The resin according to claim 24, wherein at least one of Z 5 and Z 6 represents a group represented by formula (Z1). 【Chemistry 7】 In formula (Z1), * represents a bonding position, and L Z1 represents a divalent linking group.

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