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

Abstract

The present invention addresses the problem of providing a photosensitive composition having excellent photolithographic properties and a small linear expansion coefficient in an obtained cured film. The photosensitive composition according to the present invention contains a polybenzoxazole precursor resin having a polymerizable group, and a photopolymerization initiator.

Description

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

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

[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] JP 2009-282491 A

[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 CTE equivalent 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, and also to provide a transfer film, a method for producing a laminate, a laminate, and a semiconductor package 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 polybenzoxazole precursor resin having a polymerizable group and a photopolymerization initiator. [2] The photosensitive composition according to [1], wherein the precursor resin has a phenolic hydroxyl group protected by a protecting group that is deprotected by the action of acid or heat, and the protecting group has a polymerizable group. [3] The photosensitive composition according to [1], wherein the precursor resin has a repeating unit represented by formula (1) described below. [4] The photosensitive composition according to [3], wherein at least one of Z represents a group represented by formula (2) described below. [5] The photosensitive composition according to any one of [1] to [4], further comprising a filler. [6] The photosensitive composition according to [5], wherein the content of the filler is 50 mass% or more based on the total solid content of the photosensitive composition. [7] The photosensitive composition according to [5] or [6], wherein the average particle size of the filler is 300 nm or less. [8] The photosensitive composition according to any one of [1] to [4], further comprising a filler, the content of the filler being 50 mass% or more relative to the total solid content of the photosensitive composition, and the average particle size of the filler being 300 nm or less. [9] A transfer film having a temporary support and a composition layer formed using the photosensitive composition according to any one of [1] to [8].

[10] A method for producing a laminate, comprising the steps of: forming a composition layer on a substrate using the photosensitive composition according to any one of [1] to [8]; patternwise exposing the composition layer; developing the exposed composition layer with a developer to form a pattern; and heat-treating the pattern.

[11] The method for producing a laminate according to

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

[12] The method for producing a laminate according to

[10] or

[11] , wherein the developer is an organic solvent developer.

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

[10] to

[12] .

[14] A semiconductor package comprising the laminate according to

[13] .

[15] A method for producing a laminate, comprising the steps of: forming a composition layer on a substrate using the transfer film according to [9]; pattern-exposing the composition layer; developing the exposed composition layer with a developer to form a pattern; and heat-treating the pattern.

[16] A method for producing a laminate according to

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

[17] A method for producing a laminate according to

[15] or

[16] , wherein the developer is an organic solvent developer.

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

[15] to

[17] .

[19] A semiconductor package comprising the laminate according to

[18] .

[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, and a semiconductor package, all of which relate 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 of the above steps 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, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp such as g-line, h-line, and i-line, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In addition, in the present invention, light means 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 of a polymer is a molar ratio. Furthermore, in this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0018] 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.

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

[0020] 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.

[0021] 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., an 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.

[0022] 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.

[0023] [Photosensitive Composition] The photosensitive composition of the present invention (hereinafter also simply referred to as "composition") contains a polybenzoxazole precursor resin having a polymerizable group (hereinafter also referred to as "resin A") and a photopolymerization initiator.

[0024] Although the detailed mechanism of action of the composition of the present invention is not clear, the present inventors speculate as follows: When the composition of the present invention is used, it is speculated that the resin A has a polymerizable group and the composition contains a photopolymerization initiator, thereby providing excellent photolithography properties and reducing the linear expansion coefficient of the cured film obtained from the polybenzoxazole derived from the resin A. Hereinafter, obtaining at least one of the effects of excellent photolithography properties and a smaller linear expansion coefficient of the cured film formed is also referred to as "excellent effects of the present invention."

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

[0026] [Resin A] The composition contains Resin A. Resin A is a polybenzoxazole precursor resin having a polymerizable group. Resin A is a compound different from the various components (e.g., polymerizable compounds) described below. The polybenzoxazole precursor resin is a resin that is converted into polybenzoxazole by heat treatment or chemical treatment. Resin A is preferably a resin obtained from a divalent carboxylic acid derivative (a compound having two carboxy groups, which may have a substituent) and a divalent aminophenol derivative (a dimer of aminophenol, which may have a substituent).

[0027] Resin A has a polymerizable group. The position of the polymerizable group in Resin A is not particularly limited, but is preferably a side chain of Resin A, and more preferably the terminal portion of the specific protecting group described below. Examples of the polymerizable group include known polymerizable groups such as radically polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups. The radically polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the ethylenically unsaturated bond include vinyl groups, styryl groups, (meth)acrylamide groups, and (meth)acryloyl groups, with (meth)acrylamide groups or (meth)acryloyl groups being preferred, and (meth)acryloyl groups being more preferred. The number of polymerizable groups in Resin A is 1 or more, preferably 2 or more. The upper limit is preferably 1,000 or less. It is also preferable that Resin A has a polymerizable group polymerizable with a polymerizable group in the polymerizable compound described below.

[0028] Resin A preferably has a phenolic hydroxyl group (hereinafter also referred to as "specific group A") protected with a protecting group (hereinafter also referred to as "specific protecting group") that is deprotected by the action of acid or heat, and more preferably has a polymerizable group and a phenolic hydroxyl group protected with a protecting group that is deprotected by the action of acid or heat (hereinafter also referred to as "specific group A having a polymerizable group"). In other words, resin A preferably has a group that generates a phenolic hydroxyl group by the action of acid or heat. Note that the specific protecting group may be deprotected by the action of both acid and heat. The position of the specific group A is not particularly limited, but is preferably a side chain of resin A. The number of specific groups A is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 1,000 or less. The specific protecting group possessed by specific group A is a group that is deprotected by the action of acid or heat. The specific protecting group is not particularly limited, but is preferably a group that is deprotected in step X4 or step X4' in the method for producing a laminate described below. It is also preferable that the specific protecting group has a polymerizable group. The above-mentioned polymerizable group has the same meaning as the polymerizable group contained in the resin A, and the preferred embodiments are also the same. Furthermore, when the specific protecting group is deprotected by heat, the specific protecting group is preferably a group that is deprotected by 90 mol% or more within 1 hour at a temperature of 300°C or less, more preferably a group that is deprotected by 250°C or less, and even more preferably a group that is deprotected by 200°C or less. Examples of groups that satisfy the above temperature requirement include a protecting group having an acetal group.

[0029] When the resin A has the specific group A, polybenzoxazole can be easily obtained even if the temperature during synthesis of polybenzoxazole from the resin A is relatively low (for example, the temperature of the heat treatment in step X4 (preferably 200 to 250° C.)).

[0030] The specific group A is preferably a group having a partial structure represented by formula (H1), and more preferably a group having a partial structure represented by formula (H2). ｈ１ ~R ｈ３ It is preferable that the main chain portion of the resin A is constituted by the copolymer (i.e., ...

[0031]

[0032] In formula (H1), R ｈ１ ~R ｈ３ R each independently represents a hydrogen atom or a monovalent organic group. ｈ２ and R ｈ３ may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group, with an alkyl group being preferred. The alkyl group may be linear, branched, or cyclic, with a linear group being preferred. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 15, and even more preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group, the aryl group, and the aralkyl group may contain a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, in the alkyl group, the aryl group, and the aralkyl group, one or more methylene groups may be replaced with a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. Further, examples of the monovalent organic group include the monovalent organic group U described below. R ｈ１ and R ｈ２ Preferably, one of R represents a hydrogen atom and the other represents a monovalent organic group. ｈ３ is preferably a monovalent organic group, more preferably a monovalent organic group having a polymerizable group. In addition, the polymerizable group constituting the monovalent organic group having a polymerizable group preferably has a polymerizable group at the terminal of the monovalent organic group. Examples of the polymerizable group include polymerizable groups that can be contained in resin A.

[0033]

[0034] In formula (H2), L ｈ１ and L ｈ２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a combination thereof; M represents a single bond or a divalent linking group; Q represents a polymerizable group.

[0035] In formula (H2), L ｈ１ and L ｈ２each independently represents a hydrogen atom, an alkyl group, an aryl group, or a group combining these. The alkyl group and the aryl group can be, for example, R ｈ１ ~R ｈ３ Examples of the monovalent organic groups represented by the formula (I) include alkyl groups and aryl groups. Examples of the groups combining these include groups combining an aryl group and an alkyl group. ｈ１ and L ｈ２ Preferably, one of the groups represents a hydrogen atom, and the other represents an alkyl group, an aryl group, or a group in which an alkyl group and an aryl group are combined.

[0036] In formula (H2), M represents a single bond or a divalent linking group. Examples of the divalent linking group include —O—, —S—, —CO—, —COO—, and —CONR Ｎ -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, and a divalent linking group formed by combining these groups. Ｎ represents a hydrogen atom or a substituent. As the divalent linking group, a group represented by formula (M1) is also preferred.

[0037] *-(alkylene group -O) ｍ - * (M1)

[0038] In formula (M1), m represents an integer of 1 to 3. * represents a bonding position. m is preferably 1 or 2. The alkylene group may be linear, branched, or cyclic, and is preferably linear. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group.

[0039] In formula (H2), Q represents a polymerizable group. The polymerizable group has the same meaning as the polymerizable group contained in resin A, and preferred embodiments are also the same.

[0040] Resin A preferably has a repeating unit represented by formula (1).

[0041]

[0042] In formula (1), X represents a divalent linking group, Y represents a tetravalent linking group having an aromatic ring, and Z each independently represents -OH, -OL, １ -T １ or a phenolic hydroxyl group having a polymerizable group and protected with a protecting group that can be deprotected by the action of an acid or heat (specific group A having a polymerizable group). １ represents a divalent linking group. １ represents a polymerizable group, provided that at least one of Z's is -OL １ -T １ or a phenolic hydroxyl group (specific group A having a polymerizable group) protected with a protecting group that is deprotected by the action of an acid or heat.

[0043] In formula (1), X represents a divalent linking group. Examples of the divalent linking group include a divalent linking group having an aromatic ring, a divalent aliphatic group, and a divalent linking group formed by combining these groups, and a divalent linking group having an aromatic ring is preferred.

[0044] 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 or polycyclic 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 -O-, -CO-, -S-, and -SO ２ - and -NHCO-.

[0045] Examples of the divalent linking group having an aromatic ring include the following divalent linking groups.

[0046]

[0047] 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 -O-, -CO-, -S-, and -SO. ２ - and -NHCO-. As the divalent aliphatic group, an alkylene group having 2 to 12 carbon atoms or an aralkylene group having 7 to 15 carbon atoms is preferred. The alkylene group may be linear, branched, or cyclic.

[0048] X is preferably a group represented by formula (X).

[0049] *-Ar ０ - (L ０ -Ar ０ ) ｎｘ -* (X)

[0050] In formula (X), Ar ０ represents an aromatic hydrocarbon group. 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 represents -, -NHCO-, a group formed by combining these, or a single bond. nx represents an integer of 0 to 3. * represents the bonding position.

[0051] Multiple Ar ０ may be the same or different. ０ If there are multiple L ０ They may be the same or different.

[0052] In formula (X), Ar ０ The number of carbon atoms in the aromatic hydrocarbon group represented by the formula (I) is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenyl group. ０ The aromatic hydrocarbon group represented by the formula (I) is preferably a divalent aromatic hydrocarbon group.

[0053] In formula (X), L ０The 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 combination thereof is more preferred, and -O-, -C(CF ３ ) ２ - or -C(CH ３ ) ２ - is more preferred.

[0054] In formula (1), the tetravalent linking group having an aromatic ring represented by Y is preferably a group represented by any one of formulas (Y1) to (Y3), and more preferably a group represented by formula (Y1) or a group represented by formula (Y2).

[0055]

[0056] In formula (Y1), L ｙ represents an alkynylene group, 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—, or —SO ２ represents -, -NHCO-, or a combination thereof, or a single bond. * represents a bonding position. In formula (Y2), * represents a bonding position. In formula (Y3), * represents a bonding position.

[0057] Examples of the tetravalent linking group having an aromatic ring include the following tetravalent linking groups.

[0058]

[0059] In formula (1), each Z is independently —OH, —OL １ -T １ or a phenolic hydroxyl group having a polymerizable group and protected with a protecting group that can be deprotected by the action of an acid or heat.１ represents a divalent linking group. １ represents a polymerizable group. １ -T １ does not include a phenolic hydroxyl group protected with a protecting group that has the above polymerizable group and is deprotected by the action of acid or heat. Z is preferably —OH or a specific group A that has a polymerizable group. １ Examples of the divalent linking group represented by the formula: include a divalent linking group represented by the formula: M. １ The polymerizable group represented by the formula (I) has the same meaning as the polymerizable group that the resin A may have, and the preferred embodiments are also the same. As described above, a phenolic hydroxyl group that has a polymerizable group and is protected with a protecting group that is deprotected by the action of an acid or heat is the specific group A having a polymerizable group. When Z represents the specific group A having a polymerizable group, the hydroxyl group constituting the specific group A having a polymerizable group is directly bonded to the aromatic ring constituting the group represented by Y and is protected with a specific protecting group having a polymerizable group.

[0060] However, at least one of Z is -OL １ -T １ or a specific group A having a polymerizable group. At least one of Z's preferably represents a specific group A having a polymerizable group, and it is preferred that one of Z's represents a specific group A having a polymerizable group and the other represents —OH or a specific group A having a polymerizable group. Multiple Z's may be the same or different.

[0061] The specific group A having a polymerizable group is preferably a group represented by formula (2).

[0062]

[0063] In formula (2), R ｘ represents a group represented by formula (X1) or a group represented by formula (X2). １ represents a divalent linking group. ２ represents —O— or —NH—. ３ represents a hydrogen atom or a methyl group. * represents a bonding position.

[0064] In formula (2), R ｘrepresents a group represented by formula (X1) or a group represented by formula (X2). ｘ is preferably a group represented by formula (X1).

[0065] *-C(R ｘ１ ) (R ｘ２ )-O-* (X1)

[0066] In formula (X1), R ｘ１ and R ｘ２ each independently represents a hydrogen atom or a monovalent organic group. * represents a bonding position. Examples of the monovalent organic group include R ｈ１ ~R ｈ３ Examples of the monovalent organic group include a monovalent organic group represented by the formula: R ｘ１ and R ｘ２ Preferably, at least one of R represents an alkyl group, ｘ１ and R ｘ２ It is more preferable that at least one of these groups represents an alkyl group and the other represents a hydrogen atom.

[0067] *-CO-OC(R ｘ３ ) (R ｘ４ ) - * (X2)

[0068] In formula (X2), R ｘ３ and R ｘ４ each independently represents a monovalent organic group. * represents a bonding position. Examples of the monovalent organic group include R ｈ１ ~R ｈ３ Examples of the monovalent organic group include a monovalent organic group represented by the following formula:

[0069] In formula (2), R １ represents a divalent linking group. Examples of the divalent linking group include a divalent linking group represented by M.

[0070] In formula (2), R ２ represents —O— or —NH—. ２ As the group, —O— is preferred.

[0071] 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 the repeating units described in paragraphs 0150 to 0154 of JP 2020-154205 A.

[0072] The weight average molecular weight of Resin A is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 7,000 to 30,000. 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.

[0073] 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 99.0 mass% or less, more preferably 70.0 mass% or less, even more preferably 50.0 mass% or less, and particularly preferably 30.0 mass% or less, based on the total solid content of the composition.

[0074] The content of the specific group A in the resin A is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more, based on the total content of the specific group A and the phenolic hydroxyl group in the resin A. The upper limit is preferably 100 mol% or less, based on the total content of the specific group A and the phenolic hydroxyl group in the resin A. The content of the specific group A can be, for example, １ It can be measured using H-NMR.

[0075] Resin A can be synthesized, for example, by reacting a divalent carboxylic acid derivative with a divalent aminophenol derivative to synthesize a polybenzoxazole precursor resin, and then reacting the phenolic hydroxyl group of the precursor resin with a vinyl ether compound having a polymerizable group in the presence of an acid catalyst.

[0076] (Monovalent Organic Group U) The monovalent organic group U is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent, and more preferably an alkyl group which may have an aromatic ring group. The alkyl group may be linear, branched, or cyclic. The cyclic group may be monocyclic or polycyclic. The linear or branched alkyl group preferably has 1 to 30 carbon atoms. The cyclic alkyl group (cycloalkyl group) preferably has 3 to 30 carbon atoms. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, campholoyl, dicyclohexyl, and pinenyl. The substituent that the alkyl group may have is preferably an aromatic ring group, as described below.

[0077] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring group may be either a monocyclic or polycyclic ring. Examples of rings constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring; a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyridine ... Examples of aromatic heterocyclic groups include an imidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring. As the substituent that the aromatic ring group may have, the above-mentioned alkyl group is preferred.

[0078] [Photopolymerization initiator] The composition contains 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.

[0079] Examples of the photopolymerization initiator include an oxime ester compound (a photopolymerization initiator having an oxime ester structure), an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure), a hydroxyacetophenone compound (a photopolymerization initiator having a hydroxyacetophenone structure), an acylphosphine oxide compound (a photopolymerization initiator having an acylphosphine oxide structure), and a bistriphenylimidazole compound (a photopolymerization initiator having a bistriphenylimidazole structure). As the photopolymerization initiator, an oxime ester compound or an aminoacetophenone compound is preferred, and an oxime ester compound is more preferred.

[0080] 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.).

[0081] 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.).

[0082] 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).

[0083] Examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0084] 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.

[0085] [Filler] The composition preferably contains a filler. When the composition contains a filler, the linear expansion coefficient and average dielectric tangent of a cured film obtained using the composition are superior.

[0086] 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).

[0087] 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.

[0088] 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).

[0089] 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.

[0090] 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.

[0091] The refractive index of the filler is preferably 0.5 to 3.0, more preferably 1.2 to 1.8. The refractive index can be measured by the method described above.

[0092] The filler may be used alone or in combination of two or more. The content of the filler is preferably 10.0 mass% or more, more preferably 30.0 mass% or more, even more preferably 50.0 mass% or more, particularly preferably 60.0 mass% or more, and most preferably 65.0 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.

[0093] [Polymerizable Compound] The composition preferably contains a polymerizable compound, which is a compound different from the various components described above.

[0094] 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, with a (meth)acryloyl group being preferred and a methacryloyl group being more preferred.

[0095] 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.

[0096] Examples of bifunctional polymerizable compounds include polyethylene glycol dimethacrylate, 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.).

[0097] 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.

[0098] 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.).

[0099] 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.).

[0100] 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, still more preferably 20.0 mass% or less, and particularly preferably 15.0 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.

[0101] [Thermal Base Generator] The composition may contain a thermal base generator. When the composition contains a thermal base generator, the ring-closing reaction of the resin A is accelerated, and polybenzoxazole is easily produced. When the composition contains a thermal base generator, it is also preferable that the composition does not contain a thermal acid generator.

[0102] 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: are shown below. The temperature at which the acidic compound and the onium salt compound generate a base is preferably the temperature of the heat treatment 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, and using this peak temperature as the base generation temperature.

[0103] 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.

[0104] The acidic compound is preferably a compound represented by formula (A1) or a compound represented by formula (A2).

[0105]

[0106] 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.

[0107] In formula (A1), A ａ１ represents a p-valent organic group. Examples of the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with an aromatic ring group being preferred. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group and an alkenyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, 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, and even more preferably 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group. Examples of p-valent aliphatic hydrocarbon groups (where p is an integer of 2 or greater) include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may further have a substituent.

[0108] The aromatic ring group may be either a monocyclic or polycyclic ring. The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group, a phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, a pyridinium ring group, a benzophenone ... Examples of aromatic ring groups include a benzene ring group, an indolizine ring group, an indole ring group, a benzofuran ring group, a benzothiophene ring group, an isobenzofuran ring group, a quinolizine ring group, a quinoline ring group, a phthalazine ring group, a naphthyridine ring group, a quinoxaline ring group, a quinoxazoline ring group, an isoquinoline ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxathiin ring group, a phenothiazine ring group, and a phenazine ring group, and a benzene ring group is preferred. The aromatic ring group may further have a substituent.

[0109] 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.

[0110] In formula (A1), L ａ１ represents an (m+1)-valent linking group. Examples of the (m+1)-valent linking group include an ether group (—O—), a carbonyl group (—CO—), an ester group (—COO—), a thioether group (—S—), and —SO ２ -, -NR Ｎ - (R Ｎrepresents a hydrogen atom or a substituent), divalent linking groups such as alkylene groups (preferably having 1 to 10 carbon atoms) and alkenylene groups (preferably having 2 to 10 carbon atoms); trivalent linking groups having a group represented by "-N<" and trivalent linking groups having a group represented by "-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.

[0111] In formula (A1), m represents an integer of 1 or greater. m is preferably 1 or 2, and more preferably 1.

[0112] In formula (A1), p represents an integer of 1 or greater. p is preferably 1 or 2, and more preferably 1.

[0113] (HOOC-L ａ２ ) ｎａ１ -A ａ２ - (L ａ３ -N(R ａ２ ) (R ａ３ )) ｎａ２ (A2)

[0114] In formula (A2), A ａ２ represents an aromatic ring group. 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.

[0115] A ａ２ Examples of the aromatic ring group represented by the formula: ａ１ Among the p-valent organic groups represented by the formula (I), aromatic ring groups are exemplified, and a benzene ring group 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, with monovalent aliphatic hydrocarbon groups being preferred. ａ２ and L ａ３ Examples of the divalent linking group represented by the formula: ａ１Examples 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.

[0116] 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).

[0117]

[0118] 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.

[0119] R １ ~R ４ , and R ５ ~R ７The aliphatic group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the aliphatic group is preferably 1 to 10. The aliphatic group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. The aliphatic group may have a substituent. Examples of the substituent include an arylcarbonyl group. The aliphatic group may have a substituent such that the methylene group (-CH ２ -) may be replaced with a heteroatom (for example, an oxygen atom, a sulfur atom, or -NR-, where R represents a hydrogen atom or a substituent). ５ ~R ７ At least one of the R is preferably an aliphatic group having —NR—, and more preferably an alkyl group having —NR—. ５ ~R ７ At least two of R may be bonded to each other to form a ring; ５ and R ７ , and R ６ and R ７ are preferably bonded to each other to form a ring. In other words, the ring formed is preferably a polycyclic heterocycle, more preferably a bicyclic heterocycle.

[0120] Examples of the thermal base generator include the thermal base generators described in WO 2018 / 038002.

[0121] 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.

[0122] [Thermal Acid Generator] The composition preferably contains a thermal acid generator. When the composition contains a thermal acid generator, it is also preferable that the composition does not contain a thermal base generator. The thermal acid generator is preferably a compound that does not generate acid in any of steps X1 to X3 in the laminate manufacturing method described below. That is, it is preferable that the thermal acid generator is stable to any of the heat treatments in steps X1 to X3, and more preferably a compound in which the decomposition rate of the thermal acid generator is 5 mol % or less upon any of the heat treatments in steps X1 to X3. Also preferred are compounds in which, when heated at a rate of 10°C / min using a thermogravimetric differential thermal analyzer (TG / DTA), the decomposition rate at 120°C is 5% or less and the decomposition rate at 230°C is 50% or more. The thermal acid generator preferably does not generate acid even during the exposure step for pattern formation (exposure treatment in step X2), and more preferably a compound in which the molar extinction coefficient for light with a wavelength of 365 nm is 1000 or less. The acid generated by the thermal acid generator upon heating is preferably sulfonic acid. Preferred thermal acid generators include onium salt compounds (compounds having an onium salt structure) such as iodonium salts and sulfonium salts, and sulfonate ester compounds (compounds having a sulfonate ester structure) such as oxime sulfonates, sulfonate esters of hydroxyimides, and alkyl sulfonate esters. Examples of thermal acid generators include cyclohexyl p-toluenesulfonate, N-hydroxyphthalimide-p-toluenesulfonate, and di(t-butylphenyl)iodonium-p-toluenesulfonate. One or more thermal acid generators may be used alone, or two or more may be used in combination. The content of the thermal acid generator is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 1.0% by mass or less, based on the total solid content of the composition. The lower limit is preferably greater than 0% by mass, more preferably 0.1% by mass or more, based on the total solid content of the composition.

[0123] [Photoacid Generator] The composition may contain a photoacid generator. The photoacid generator is a compound that generates an acid when exposed to light (for example, exposure light).

[0124] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators. Examples of ionic photoacid generators include compounds having a sulfonium structure, onium salt compounds having a diaryliodonium or triarylsulfonium structure, and ammonium salt compounds having a quaternary ammonium structure. Examples of ionic photoacid generators include the ionic photoacid generators described in paragraphs

[0114] to

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

[0083] to

[0088] of JP 2011-221494 A.

[0125] The content of the photoacid generator is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total solid content of the composition.

[0126] [Surfactant] The composition may contain a surfactant. Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0127] Examples of surfactants include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental friendliness, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant. 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).

[0128] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound. The fluorosurfactant may be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group having an ethylenically unsaturated group in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0129] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0130] 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.).

[0131] 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.

[0132] 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).

[0133]

[0134] 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.

[0135]

[0136] 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.

[0137] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0138]

[0139] 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.

[0140] 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).

[0141] The surfactant also includes a nonionic surfactant.

[0142] The surfactant content is preferably 0.01 to 3.0 mass%, more preferably 0.01 to 1.0 mass%, and even more preferably 0.05 to 0.8 mass%, based on the total solid content of the composition.

[0143] [Other Additives] In addition to the various components described above, the composition may contain other additives. Examples of other additives include heterocyclic compounds (e.g., 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 heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds include the various components described in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds include those described in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0144] 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 solvents containing two or more of these. Solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] The content of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0149] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, and hexane in the composition is preferably low. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, based on the total solid content of the composition. The lower limit of each of these compounds 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 using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0150] [Transfer Film] The transfer film has a temporary support and a composition layer formed using the above-described composition.

[0151] 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.

[0152] [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.

[0153] 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 film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0154] 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. 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:

[0155] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope).

[0156] 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.

[0157] 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.).

[0158] 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.

[0159] 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.).

[0160] [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."

[0161] <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.

[0162] [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.

[0163] [Cover Film] The transfer film may have a cover film.

[0164] The number of fish eyes with a diameter of 80 μm or more contained in the cover film is 5 / m ２ Preferably, 0 pieces / m ２ Fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is introduced into the film when the material is thermally melted and then kneaded, extruded, and / or biaxially stretched, cast, or other methods are used to produce the film.

[0165] 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 ２More preferably, 5 or less pieces / mm ２ More 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.

[0166] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more.If Ra is within this range, for example, when the transfer film is long, the winding property of the transfer film is excellent.In addition, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0167] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film, and examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0168] 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.).

[0169] [Other Layers] The transfer film may include other layers in addition to the above-described 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.

[0170] [Method for Producing Transfer Film] The method for producing the transfer film can be a known method, and is preferably a method for producing the transfer film in which a composition is applied onto a temporary support to form a composition layer.

[0171] For example, a method for manufacturing the transfer film 100 shown in Fig. 1 includes a process including the steps of applying a composition to the surface of a temporary support 12 to form a coating film, and then drying this coating film to form a composition layer 14. Furthermore, the transfer film 100 shown in Fig. 1 is manufactured by pressing a cover film onto the composition layer of the transfer film manufactured by the above manufacturing process. Furthermore, the transfer film 100 shown in Fig. 1 may be wound up after manufacturing and stored as a roll-form transfer film 100. The roll-form transfer film 100 can be provided in its current form for the lamination step with a substrate in a roll-to-roll system, which will be described later.

[0172] As described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the composition layer. Examples of the intermediate layer-forming composition, the method for forming the intermediate layer, the thermoplastic resin layer-forming composition, and the method for forming the thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0173] <Method for forming composition layer> A known method can be used to form the composition layer, for example, a method of forming the composition layer by applying and drying a composition. As described above, the composition contains Resin A and a photopolymerization initiator.

[0174] Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating. The composition preferably further 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.

[0175] [Applications] The pattern (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. More specifically, it can be used as 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.

[0176] [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. Specifically, the method for producing a laminate preferably includes steps X1 to X4. A laminate having a pattern is produced by the following procedures: Step X1: A step of forming a composition layer on a substrate using a composition or a transfer film; Step X2: A step of pattern-exposing the composition layer; Step X3: A step of developing the exposed composition layer using a developer (e.g., an organic solvent developer, etc.) to form a pattern; Step X4: A step of heat-treating the pattern. The method for producing a laminate may include a step X4' of exposing the pattern to light with a wavelength different from the exposure wavelength in step X2 after step X3 and before step X4.

[0177] Each step of the method for producing the laminate will be described in detail below.

[0178] <Step X1> Step X1 is a step of forming a composition layer on a substrate using a composition or a transfer film. 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 a method for applying the composition include the method for forming a composition layer in the above-mentioned method for producing a transfer film. 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 can be used. Examples of lamination methods include known transfer methods and lamination methods, and preferred are methods 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. Examples of the lamination method include known laminators such as vacuum laminators and auto-cut laminators. The lamination temperature is preferably 70 to 130°C. Step X1 is preferably performed using a roll-to-roll system. The substrate to which the transfer film is attached is preferably a resin film or a resin film having a conductive layer.The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate before any step included in the method for producing a laminate of the present invention, and a step of winding the substrate after any step, and at least any step (preferably all steps or all steps other than the heating step) is carried out while transporting the substrate.As the unwinding method in the unwinding step and the winding method in the winding step, known methods may be used in production methods that apply the roll-to-roll method.

[0179] (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, and tempered glass, such as Corning Gorilla Glass, can also be used. Materials contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. When the substrate includes a resin substrate, a resin film with low optical distortion and / or high transparency is more preferred. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0180] 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, in terms of being manufactured 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.

[0181] Examples of the conductive layer include any conductive layer used in general circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. 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, it is preferable that each conductive layer is made of a different material. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO２ The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４ It is preferably less than Ωcm.

[0182] When the substrate has two or more conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0183] <Step X2> Step X2 is a step of patternwise exposing the composition layer after the above-mentioned step X1. Note that "patternwise exposure" refers to a form of patternwise exposure, that is, exposure in a form in which exposed areas and unexposed areas exist. The positional relationship between the exposed areas and unexposed areas in the patternwise exposure is not particularly limited and may be adjusted as appropriate. Exposure may be performed from the side opposite the substrate of the composition layer, or from the substrate side of the composition layer.

[0184] The light source used for exposure can be appropriately selected as long as it irradiates light in a wavelength range (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, 405 nm, etc.) to which various photosensitive components (e.g., photopolymerization initiators, etc.) in the composition layer are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0185] The exposure dose is 5 to 500 mJ / cm ２ is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0186] When the composition layer is formed using a transfer film having a temporary support, in step X2, the patterned exposure may be performed after peeling the temporary support from the composition layer, or the patterned exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. To prevent contamination of the photomask due to contact between the composition layer and the photomask and to avoid the influence of foreign matter attached to the photomask on the exposure, it is preferable to perform the patterned exposure without peeling off the temporary support. The patterned exposure may be performed through a photomask or may be performed by direct exposure using a laser or the like. When exposure is performed through a photomask, examples of the photomask include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified. It is preferable to peel the temporary support from the composition layer before step X3, which will be described later.

[0187] <Step X3> Step X3 is a step of forming a pattern by developing the composition layer exposed after Step X2 using a developer (e.g., an alkaline developer or an organic solvent developer). Examples of the developer include an alkaline developer or an organic solvent developer, and an organic solvent developer is preferred.

[0188] 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, cyclohexanone, butyl acetate, pentyl acetate, and propylene glycol monomethyl ether acetate, with cyclopentanone being preferred. In the organic solvent developer, a mixture of organic solvents may be used, or the organic solvent may be mixed with an organic solvent other than those mentioned above or with water. The water content of the organic solvent developer is preferably less than 10% by mass, and more preferably substantially free of water, based on the total mass of the organic solvent developer. The organic solvent content of the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer. The upper limit is preferably 100% by mass or less, based on the total mass of the organic solvent developer.

[0189] Examples of development methods include puddle development, shower development, spin development, and dip development. In shower development, unnecessary portions can be removed by spraying a developer onto the composition layer after exposure. It is also preferable to spray a detergent or the like onto the layer after development and remove development residues by rubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0190] <Step X4> Step X4 is a step of heat-treating the pattern obtained in Step X3. Step X4 converts resin A into polybenzoxazole. When resin A has specific group A, the specific protecting group contained in specific group A is deprotected to generate a phenolic hydroxyl group, and the phenolic hydroxyl group then initiates a ring-closing reaction to produce polybenzoxazole. Step X4 also improves the purity of the pattern. The purity of the pattern means that the various components contained in the pattern are essentially composed of polybenzoxazole alone. Specifically, the total content of polybenzoxazole is preferably 90% by mass or more, more preferably 95% by mass or more, relative to the total mass of the pattern. The upper limit is preferably 100% by mass or less, relative to the total mass of the pattern. For example, the pattern obtained in Step X3 may contain a polymer derived from resin A and a polymerizable compound, etc., produced in Step X2. In contrast, when the heat treatment in step X4 is performed, the heat treatment depolymerizes the polymer and removes the depolymerized product. Furthermore, by-products produced by the ring-closing reaction of resin A (e.g., compounds produced by decomposition of some groups in the precursor) can also be removed, and polybenzoxazole is produced, presumably resulting in improved pattern purity. Furthermore, when the composition or the composition layer of the transfer film contains a thermal base generator, the heat treatment in step X4 deprotects the specific protecting group contained in specific group A, generating a phenolic hydroxyl group. Meanwhile, the heat generates a base from the thermal base generator, which accelerates the ring-closing reaction, allowing polybenzoxazole to be obtained efficiently and / or under more lenient conditions (e.g., a lower heating temperature). Furthermore, when the composition or the composition layer of the transfer film contains a thermal acid generator, the heat treatment in step X4 deprotects the specific protecting group contained in specific group A, generating a phenolic hydroxyl group, either by the heat or by the acid generated from the thermal acid generator. The heat then drives the ring-closure reaction to produce polybenzoxazole.

[0191] The temperature and time of the heat treatment are not particularly limited, as long as they are sufficient to deprotect the specific protecting group or promote the ring-closure reaction of Resin A. 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 carried out in either an air environment or a nitrogen-substituted environment. The 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.

[0192] <Step X4'> Step X4' is a step of exposing the pattern with light at a wavelength different from the exposure wavelength in step X2, performed after step X3 and before step X4. When step X4' is performed, it is preferable that resin A has a specific group A and the composition or composition layer contains a photoacid generator. For example, when step X4' is performed on a pattern formed using the composition or composition layer, an acid is generated from the photoacid generator, and the specific protecting group contained in the specific group A is deprotected by the acid, resulting in a phenolic hydroxyl group. The exposure method in step X4' may be the same as the exposure method in step X2, except for the different exposure wavelength. As described above, step X4' exposes the pattern with light at a wavelength different from the exposure wavelength in step X2. In other words, step X2 exposes the pattern with light at a wavelength to which the photopolymerization initiator contained in the composition or composition layer is sensitive but the photoacid generator is not sensitive, and step X4' exposes the pattern with light at a wavelength to which the photoacid generator is sensitive. This may enable deprotection of the specific protecting group while forming a pattern.

[0193] [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.

[0194] <Cover film peeling step> In the case where the composition layer is formed using a transfer film in the above-mentioned laminate manufacturing method, if the transfer film has a cover film, it is preferable to include a step of peeling off the cover film of the transfer film. As the method for peeling off the cover film, a known method can be applied.

[0195] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the method for producing the laminate may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer. When the substrate is a substrate having a plurality of conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. Examples of treatments to reduce the visible light reflectance include oxidation treatments. Specifically, the visible light reflectance of the conductive layer can be reduced by oxidizing copper to blacken it into copper oxide. Suitable embodiments of treatments to reduce the visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, the contents of which are incorporated herein by reference.

[0196] <Etching Step> When the substrate is a substrate having a conductive layer, the method for producing a laminate may include a step (etching step) of etching the conductive layer in an area where the etching resist film is not disposed, using the pattern 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.

[0197] In the method for producing the laminate, a substrate having a plurality of conductive layers on each of its two surfaces is preferably used, and patterns are formed sequentially or simultaneously on the conductive layers formed on both surfaces. With this configuration, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. Formation from both surfaces of the substrate by roll-to-roll is also preferred.

[0198] [Laminate] The laminate is not particularly limited as long as it is a laminate produced by the above-described laminate production method.

[0199] [Method for producing circuit wiring] The method for producing circuit wiring is not particularly limited as long as it is a method for producing 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 heat-treating the pattern, and a step of etching the conductive layer in an area where the pattern is not arranged.

[0200] Examples of the steps in the method for producing circuit wiring of the present invention include the steps in the method for producing the laminate. The method for producing circuit wiring of the present invention also preferably has a configuration in which a plurality of sets of steps, each set consisting of the laminating step or the step of forming a composition layer using a composition to the etching step, are repeated. The film used as the etching resist film can also be used as a protective film (insulating film) for the formed circuit wiring.

[0201] [Method for Manufacturing Semiconductor Package] Examples of methods for manufacturing semiconductor packages include known manufacturing methods such as methods for manufacturing build-up substrates. Specifically, examples include manufacturing methods including Steps Z1 to Z5 in this order. 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: heat-treating the pattern; Step Z5: forming a circuit pattern on the pattern. The method for manufacturing a semiconductor package may include, after Step Z3 and before Step Z4, Step Z4' of exposing the pattern to light with a wavelength different from the exposure wavelength in Step Z2.

[0202] Steps Z1, Z2, Z4, and Z4' in the method for manufacturing a semiconductor package include step X1, step X2, step X4, and step X4', respectively.

[0203] [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.

[0204] 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.

[0205] [Step Z5] Step Z5 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming a circuit pattern, as it allows for the formation of fine wiring. In the semi-additive process, a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via walls, and the entire surface of the pattern after Step Z3. The seed layer serves to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, thereby suppressing damage to the wiring during etching. The electroless copper plating process is performed by depositing metallic copper on the surface of a pattern having vias through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst used in the electroless plating process is preferably a palladium-tin mixed catalyst. The average particle size of the mixed catalyst is preferably 10 nm or less. The plating composition used in the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Commercially available electroless copper plating solutions include, for example, "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0206] After electroless copper plating, it is preferable to thermocompress the surface of the composition layer of the transfer film opposite the temporary support onto the electroless copper plating using a roll laminator. The thickness of the composition layer is preferably 5 to 30 μm, since it can be made thicker than the wiring height after electrolytic copper plating. After thermocompression bonding of the transfer film, the composition layer is exposed to light, for example, through a photomask on which a desired wiring pattern is drawn. Examples of the exposure method include the exposure method in step X2. After exposure, the temporary support of the transfer film is peeled off, and the exposed composition layer is developed using an alkaline developer to form a pattern. After forming the pattern, development residues of the composition may be removed using plasma or the like. After development, electrolytic copper plating is performed to form a copper circuit layer and via filling. After electrolytic copper plating, the pattern is peeled off using an alkaline aqueous solution or an amine-based stripper, and after peeling the pattern, the seed layer between the wiring is removed (flash etching). Flash etching is performed, for example, using an oxidizing solution containing sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of oxidizing solutions include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium can be removed using an acidic solution such as nitric acid and hydrochloric acid.

[0207] After the pattern is removed or after the flash etching step, a post-baking treatment is preferably performed. 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.

[0208] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z4 and before step Z5. By performing the roughening step, the surface of the pattern is roughened to improve adhesion to the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of roughening liquids include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid, etc.), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.

[0209] The above-described steps are repeated depending on the number of layers required to manufacture a semiconductor package. It is preferable to form a solder resist on the outermost layer.

[0210] [Method of manufacturing a touch panel] The method of manufacturing a touch panel is not particularly limited as long as it is a method of manufacturing a touch panel using a composition or a transfer film.Preferably, the method comprises the steps of: bringing the surface of the composition layer in the transfer film opposite to the temporary support side into contact with a conductive layer in a substrate having a conductive layer (preferably a patterned conductive layer, specifically a conductive pattern such as a touch panel electrode pattern or wiring), and laminating the transfer film and the substrate having a conductive layer; or applying a composition to the substrate to form a composition layer, exposing the composition layer to a pattern, and developing the exposed composition layer using a developer to form a protective film or insulating film patterned on the conductive layer.

[0211] [Method for Manufacturing Semiconductor Device] A known manufacturing method can be applied to the method for manufacturing a semiconductor device. Specific examples include a method for manufacturing a semiconductor device that includes the above-described method for manufacturing a laminate or the above-described method for manufacturing a semiconductor package. Examples of semiconductor devices include various semiconductor devices such as semiconductor packages used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0212] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes the laminate described above. The pattern (cured film) may be used as an insulating film or as an organic interposer in a so-called build-up base material.

[0213] 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.

[0214] [Preparation of Composition] Various components were mixed to obtain the solid content ratios shown in the table below, and then further diluted to obtain a solid concentration of 30% by mass, a MEK (methyl ethyl ketone) concentration of 20% by mass, and an NMP (N-methylpyrrolidone) concentration of 50% by 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% by mass MEK solution to form a slurry, and then finally mixed to prepare the composition.

[0215] [Resin] Resins A-1 to A-5 are all resins that fall under the category of Resin A.

[0216] <Resin A-1> Under a nitrogen stream, 2,2'-diamino-4,4'-(perfluoropropane-2,2-diyl)diphenol (16.75 g) and N-methylpyrrolidone (30 mL) were mixed and cooled to 0°C. To the resulting mixture, a solution of 4,4'-oxybis(benzoyl chloride) (15 g) dissolved in N-methylpyrrolidone (100 mL) was added dropwise over 1 hour. After stirring at room temperature for 1 hour, aniline (0.95 g) was added, and the carboxylic acid chloride remaining at the end of the resin was reacted with the aniline to form an amide. After further stirring at room temperature for 1 hour, the mixture was poured into water (1 L). The resulting powder was filtered and dried to obtain a resin. The resulting resin (15 g) was dissolved in tetrahydrofuran (100 mL), and camphorsulfonic acid (0.36 g) was added to the solution. Further, ethylene glycol monovinyl ether methacrylate (15.9 g) was slowly added. After reacting for 4 hours at room temperature, triethylamine (1 g) was added to the reaction solution, and the mixture was poured into hexane (500 mL). The precipitated powder was collected by filtration and dried to obtain Resin A-1 (21 g). Resin A-1 had a weight average molecular weight of 13,000 and a dispersity of 2.8. Furthermore, of the total content of phenolic hydroxyl groups and specific groups A in Resin A-1, 90 mol % was specific group A, and specific group A had a polymerizable group and was composed of a protecting group having an acetal group. Furthermore, when Resin A-1 was heated at 200°C for 1 hour, it was confirmed that the above-mentioned protecting groups had completely disappeared. １ This was confirmed by H-NMR. In other words, it was confirmed that the specific protecting group constituting the specific group A was deprotected, resulting in the generation of a phenolic hydroxyl group. In the following formula, at least one of Z represents a group represented by formula (Z1):

[0217]

[0218] <Resin A-2> Under a nitrogen stream, 2,2'-diamino-4,4'-(perfluoropropane-2,2-diyl)diphenol (20.48 g) and N-methylpyrrolidone (30 mL) were mixed and cooled to 0°C. To the resulting mixture, a solution of 4,4'-oxybis(benzoyl chloride) (15 g) dissolved in N-methylpyrrolidone (100 mL) was added dropwise over 1 hour. After stirring at room temperature for 1 hour, the mixture was cooled again to 0°C, and acetic anhydride (1.04 g) was added to react with the aminophenol remaining at the end of the resin to form an amide. After stirring at room temperature for an additional 1 hour, the mixture was poured into 1 L of water. The resulting powder was filtered and dried to obtain a resin. The resulting resin (15 g) was dissolved in tetrahydrofuran (100 mL), and camphorsulfonic acid (0.36 g) was added to the solution. Further, ethylene glycol monovinyl ether methacrylate (15.9 g) was slowly added. After reacting for 4 hours at room temperature, triethylamine (1 g) was added to the reaction solution, and the mixture was poured into hexane (500 mL). The precipitated powder was collected by filtration and dried to obtain Resin A-2 (22 g). Resin A-2 had a weight average molecular weight of 11,000 and a dispersity of 2.7. Furthermore, of the total content of phenolic hydroxyl groups and specific groups A in Resin A-2, 89 mol % was specific group A, and the specific group A had a polymerizable group and was composed of a protecting group having an acetal group. Furthermore, when Resin A-2 was heated at 200°C for 1 hour, it was confirmed that the above-mentioned protecting groups had completely disappeared. １ This was confirmed by H-NMR. In other words, it was confirmed that the specific protecting group constituting the specific group A was deprotected, resulting in the generation of a phenolic hydroxyl group. In the following formula, at least one of Z represents a group represented by formula (Z2):

[0219]

[0220] <Resin A-3> Resin A-3 was synthesized using the same formulation as Resin A-1, except that in the above <Resin A-1>, terephthalic acid dichloride was used instead of 4,4'-oxybis(benzoyl chloride), and 2-(2-vinyloxyethoxy)ethyl acrylate (BEEA, manufactured by Nippon Shokubai Co., Ltd.) was used instead of ethylene glycol monovinyl ether methacrylate, each in the same molar amounts as Resin A-1. Resin A-3 had a weight average molecular weight of 9,000 and a dispersity of 2.5. Furthermore, of the total content of phenolic hydroxyl groups and specific groups A in Resin A-3, 95 mol % was specific group A, and specific group A had a polymerizable group and was composed of a protecting group having an acetal group. Furthermore, when Resin A-3 was heated at 200°C for 1 hour, it was confirmed that the protecting groups had completely disappeared. １ This was confirmed by H-NMR. In other words, it was confirmed that the specific protecting group constituting the specific group A was deprotected, resulting in the generation of a phenolic hydroxyl group. In the following formula, at least one of Z represents a group represented by formula (Z3):

[0221]

[0222] <Resin A-4> Under a nitrogen stream, 2,2-bis(3-amino-4-hydroxyphenyl)propane (15.27 g) and N-methylpyrrolidone (30 mL) were mixed and cooled to 0°C. To this mixture, a solution of 4,4'-biphenyldicarbonyl chloride (15 g) dissolved in N-methylpyrrolidone (100 mL) was added dropwise over 1 hour. After stirring at room temperature for 1 hour, the mixture was cooled again to 0°C, and maleic anhydride (1.05 g) was added to react with the aminophenol remaining at the resin terminal to form an amide. This was then reacted at 150°C for 1 hour to convert the terminal to maleimide. The mixture was poured into water (1 L), and the resulting powder was filtered and dried to obtain a resin. The resulting resin (15 g) was dissolved in tetrahydrofuran (100 mL), and camphorsulfonic acid (0.36 g) was added to the solution. To this was slowly added 2-(2-vinyloxyethoxy)ethyl methacrylate (BEEM, manufactured by Nippon Shokubai Co., Ltd.) (18 g). After reacting for 4 hours at room temperature, triethylamine (1 g) was added to the reaction solution, and the mixture was poured into hexane (500 mL). The precipitated powder was collected by filtration and dried to obtain 23 g of resin A-4. Resin A-4 had a weight average molecular weight of 20,000 and a dispersity of 2.7. Furthermore, of the total content of phenolic hydroxyl groups and specific groups A in resin A-4, 92 mol % was specific group A, and specific group A had a polymerizable group and was composed of a protecting group having an acetal group. Furthermore, when resin A-4 was heated at 200°C for 1 hour, it was confirmed that the above-mentioned protecting groups had completely disappeared. １ This was confirmed by H-NMR. In other words, it was confirmed that the specific protecting group constituting the specific group A was deprotected, resulting in the generation of a phenolic hydroxyl group. In the following formula, at least one of Z represents a group represented by formula (Z4).

[0223]

[0224] <Resin A-5> Under a nitrogen stream, 2,2'-diamino-4,4'-(perfluoropropane-2,2-diyl)diphenol (16.75 g) and N-methylpyrrolidone (30 mL) were mixed and cooled to 0°C. To this mixture, a solution of 4,4'-oxybis(benzoyl chloride) (15 g) dissolved in N-methylpyrrolidone (100 mL) was added dropwise over 1 hour. After stirring at room temperature for 1 hour, aniline (0.95 g) was added and the carboxylic acid chloride remaining at the end of the resin was reacted with the aniline to form an amide. After stirring at room temperature for another 1 hour, the mixture was poured into water (1 L). The resulting powder was filtered and dried to obtain a resin. γ-Butyrolactone (70 g) was added to the resulting resin (15 g) to redissolve the resin, and dibutyltin dilaurate (0.15 g) was added and heated to 50°C. To this, a solution of 2-isocyanatoethyl methacrylate (7.9 g) dissolved in γ-butyrolactone (30 g) was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at 50°C for 4 hours. Resin A-5 had a weight average molecular weight of 13,000 and a dispersity of 2.8. Furthermore, of the total content of phenolic hydroxyl groups and specific groups A in Resin A-5, 95 mol % was specific group A, and the specific group A had a polymerizable group and was composed of a protecting group having a urethane bond. Furthermore, when Resin A-5 was heated at 200°C for 1 hour, it was confirmed that the above-mentioned protecting groups were not decomposed. １ This was confirmed by H-NMR. In other words, it was confirmed that Resin A-5 does not have the specific group A. In the following formula, at least one of Z represents a group represented by formula (Z5):

[0225]

[0226] <Resin X-1> Under a nitrogen stream, 2,2'-diamino-4,4'-(perfluoropropane-2,2-diyl)diphenol (16.75 g) and N-methylpyrrolidone (30 mL) were mixed and cooled to 0°C. To this was added dropwise a solution of 4,4'-oxybis(benzoyl chloride) (15 g) dissolved in N-methylpyrrolidone (100 mL) over 1 hour. After stirring at room temperature for 1 hour, aniline (0.95 g) was added, and the aniline reacted with the carboxylic acid chloride remaining at the end of the resin to form an amide. After stirring at room temperature for another 1 hour, the mixture was poured into water (1 L). The resulting powder was filtered and dried to obtain Resin X-1. Resin X-1 had a weight average molecular weight of 12,000 and a dispersity of 2.8.

[0227]

[0228] [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.

[0229] [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.

[0230] [Photopolymerization initiator] Oxe01: IRGACURE OXE-01, manufactured by BASF Omn-379EG: Omnirad 379EG, manufactured by IGM Resins B.V.

[0231] [Thermal base generator]

[0232]

[0233] [Thermal acid generator] TsCH: cyclohexyl p-toluenesulfonate TsPhI: N-hydroxyphthalimide-p-toluenesulfonic acid ester TsIS: di(t-butylphenyl)iodonium-p-toluenesulfonate

[0234] [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 with 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.

[0235] [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 distance between the light-shielding sections (distance from center to center of the circle) was 150 μm or more. 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 30 mJ / cm ２The photomask was then removed from the laminate. After exposure, the laminate was left to stand for 30 minutes, and the temporary support and photomask were peeled off from the laminate. The laminate was then developed for 90 seconds at 25°C using cyclopentanone as a developer. After development, the laminate was rinsed for 20 seconds at room temperature using propylene glycol monoethyl ether acetate 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 the vias of each diameter in the sample were observed and evaluated according to the following evaluation criteria. The smallest diameter of the via that could be formed without film loss and without residue at the via bottom was used for evaluation.

[0236] <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.

[0237] <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.

[0238] [Various Measurements and Evaluations] 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 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 dip-developed in cyclopentanone at 25 ° C for 90 seconds, then rinsed at room temperature for 20 seconds using propylene glycol monomethyl ether acetate as a rinse solution, and then air was blown to remove the remaining rinse solution. This was then heated in an oven (250 ° C, 8 hours), immersed in 2 M 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. Note that if the free-standing film could not be peeled by the above peeling treatment, it was further immersed in 2 M hydrochloric acid for about 1 week and peeled. The obtained free-standing film was cut into strips to prepare measurement samples.

[0239] [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).

[0240] <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 and less than 70 ppm / K G: Average value X is 70 ppm / K or more

[0241] [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.

[0242] <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

[0243] <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 and less than 0.015 E: Average dielectric tangent is 0.015 or more

[0244] The contents of various components and the evaluation results are shown below. The "Content in solids" column indicates the solid concentration (% by mass) of various components relative to the total solids 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 composition was completely dissolved during development), and therefore none of the CTE, average relative dielectric constant, and average dielectric loss tangent could be measured.

[0245]

[0246]

[0247] From the evaluation results shown in the table, it was confirmed that the composition of the present invention can achieve the desired effects.

[0248] It was confirmed that when Resin A contained a specific group A, the CTE, average relative dielectric constant, and average dielectric dissipation factor were better (Examples 1-1 to 1-6). It was confirmed that when the composition contained a polymerizable compound, the photolithography properties were better (Examples 1-1 and 1-7 to 1-16). It was confirmed that when the composition contained a bifunctional polymerizable compound, the CTE was better (Examples 1-7 to 1-16). It was confirmed that when the composition contained a filler, the CTE and average dielectric dissipation factor were better (Examples 1-1 and 2-1 to 2-4). 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) relative to the total solids content of the composition, the CTE, average relative dielectric constant, and average dielectric dissipation factor were better (Examples 2-1 and 2-14 to 2-17). It was confirmed that when the average particle size of the filler was 300 nm or less, the photolithography properties were superior (Examples 2-1, 2-18, and 2-19).

[0249] Example 101 The cover film was peeled from the transfer film of Example 1-1, and laminated on both sides of a glass epoxy substrate (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern had been formed, forming composition layers on both sides of the glass epoxy substrate. A vacuum laminator was used for this. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 40°C, a rubber roller temperature of 120°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. A pattern (φ60 μm) with vias at predetermined positions was formed on the formed composition layer using the same method as in the above [Photolithography] except that the via diameter was different. After that, residues were removed using an aqueous sodium permanganate solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions using a known dry film resist, and electrolytic plating was performed. The resist pattern was then stripped using a stripping solution. Finally, a seed layer etching process was performed, followed by a heat treatment (160°C, 1 hour) to form copper wiring on the cured film. The above process from lamination to heat treatment was repeated three times. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted in a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the resulting semiconductor package substrate operated normally.

[0250] In Example 101, semiconductor packages were produced and semiconductor package substrates were obtained in the same manner as in Example 1-1, except that the transfer film of Example 1-1 was changed to the transfer films of Examples 1-2 to 1-20 and Examples 2-1 to 2-25. It was confirmed that all of the obtained semiconductor package substrates operated normally.

[0251] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. A photosensitive composition comprising a polybenzoxazole precursor resin having a polymerizable group and a photopolymerization initiator.

2. the precursor resin has a phenolic hydroxyl group protected by a protecting group that can be deprotected by the action of an acid or heat, The photosensitive composition of claim 1 , wherein the protecting group has a polymerizable group.

3. The photosensitive composition according to claim 1 , wherein the precursor resin has a repeating unit represented by formula (1). 【Chemistry 1】 In formula (1), X represents a divalent linking group, Y represents a tetravalent linking group having an aromatic ring, and Z each independently represents -OH, -OL, １ -T １ or a phenolic hydroxyl group having a polymerizable group and protected with a protecting group which can be deprotected by the action of an acid or heat. １ represents a divalent linking group. １ represents a polymerizable group. However, at least one of Z is -O-L １ -T １ Or it represents a phenolic hydroxyl group having the above-mentioned polymerizable group and protected with a protecting group which can be deprotected by the action of an acid or heat.

4. The photosensitive composition according to claim 3 , wherein at least one of Z represents a group represented by formula (2). 【Chemistry 2】 In formula (2), R ｘ R represents a group represented by formula (X1) or a group represented by formula (X2). １ R represents a divalent linking group. ２ represents -O- or -NH-. ３ represents a hydrogen atom or a methyl group. * represents the bonding position. *-C(R ｘ１ )(R ｘ２ )-O-* (X1) *-C-O-C(R ｘ３ )(R ｘ４ )-* (X2) In formula (X1), R ｘ１ and R ｘ２ each independently represents a hydrogen atom or a monovalent organic group. * represents a bonding position. In formula (X2), R ｘ３ and R ｘ４ each independently represents a monovalent organic group. * represents a bonding site.

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

6. The photosensitive composition according to claim 5 , wherein the content of the filler is 50% by mass or more based on the total solid content of the photosensitive composition.

7. 6. The photosensitive composition according to claim 5, wherein the filler has an average particle size of 300 nm or less.

8. Further, the composition contains a filler. The content of the filler is 50% by mass or more based on the total solid content of the photosensitive composition, 2. The photosensitive composition according to claim 1, wherein the filler has an average particle size of 300 nm or less.

9. The photosensitive composition according to claim 2, wherein the polymerizable group is selected from the group consisting of a group having an ethylenically unsaturated bond, an epoxy group, and an oxetanyl group.

10. The photosensitive composition of claim 1, wherein the precursor resin has a repeating unit represented by formula (1). 【Chemistry 1】 In formula (1), X represents a divalent linking group. Y represents a tetravalent linking group having an aromatic ring. Each Z independently represents -OH, -OL 1 -T 1 , or a group represented by formula (2). L 1 represents a divalent linking group. T 1 represents a polymerizable group. However, at least one of Z's represents a group represented by the above formula (2). 【Chemistry 2】 In formula (2), R x represents a group represented by formula (X1) or a group represented by formula (X2). R 1 represents -S-, -CO-, -COO-, -CONR N -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a divalent linking group formed by combining these. R 2 represents -O- or -NH-. R 3 represents a hydrogen atom or a methyl group. * represents a bonding position. *-C(R x1 )(R x2 )-O-* (X1) *-CO-O-C(R x3 )(R x4 )-* (X2) In formula (X1), R x1 and R x2 each independently represent a hydrogen atom or a monovalent organic group. * represents a bonding position. In formula (X2), R x3 and R x4 each independently represent a monovalent organic group. * represents a bonding site.

11. A transfer film comprising a temporary support and a composition layer formed using the photosensitive composition according to any one of claims 1 to 10.

12. A step of forming a composition layer on a substrate using the photosensitive composition according to any one of claims 1 to 10; patternwise exposing the composition layer; developing the exposed composition layer with a developer to form a pattern; and heat treating the pattern.

13. The method for producing a laminate according to claim 12, wherein the substrate is an organic substrate having a copper pattern.

14. The method for producing a laminate according to claim 12 , wherein the developer is an organic solvent developer.

15. A laminate produced by the method according to claim 12.

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

17. A step of forming a composition layer on a substrate using the transfer film according to claim 11; patternwise exposing the composition layer; developing the exposed composition layer with a developer to form a pattern; and heat treating the pattern.

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

19. The method for producing a laminate according to claim 17 , wherein the developer is an organic solvent developer.

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

21. A semiconductor package comprising the laminate of claim 20.

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