Photosensitive composition, transfer film, cured film, semiconductor package, pattern forming method, and semiconductor package manufacturing method

Abstract

To provide a photosensitive composition that can form a pattern having excellent heat resistance and also excellent insulation reliability, and a transfer film, a cured film, a semiconductor package, a patterning method and a method for producing a semiconductor package.SOLUTION: A photosensitive composition comprises a compound A having acid radicals, and a compound β configured to reduce the number of acid radicals of the compound A by light exposure. The compound A comprises at least one selected from the group consisting of a carboxylic acid modified epoxy methacrylate resin, an acid radical-bearing modified phenolic resin, and a compound bearing an acid radical and a bisphenol structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition, a transfer film, a cured film, a semiconductor package, a pattern forming method, and a method for manufacturing a semiconductor package.

[0002] In a display device equipped with a touch panel such as a capacitance-type input device (specifically, examples of the display device include an organic electroluminescence (EL) display device and a liquid crystal display device), conductive patterns such as an electrode pattern corresponding to the sensor of the visible area, and wiring of the peripheral wiring portion and the extraction wiring portion are provided inside the touch panel.

[0003] Generally, a photosensitive composition is used to form a patterned layer (hereinafter also simply referred to as a "pattern"). For example, Patent Document 1 discloses a photosensitive resin composition (photosensitive composition) having a predetermined structure. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 01-032255 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have conducted an investigation into forming a pattern using a photosensitive composition having the configuration described in Patent Document 1, and have found that at least one of the heat resistance and insulating reliability of the formed pattern is reduced. When the insulation resistance is measured over time under certain conditions, the insulation resistance is less likely to decrease, which is also referred to as excellent insulation reliability.

[0006] Therefore, an object of the present invention is to provide a photosensitive composition capable of forming a pattern having excellent heat resistance and insulating reliability, and also to provide a transfer film, a cured film, a semiconductor package, a pattern forming method, and a semiconductor package manufacturing method related to the photosensitive composition. [Means for solving the problem]

[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 compound A having an acid group; and a compound β having a structure that reduces the amount of the acid group contained in the compound A upon exposure to light, The photosensitive composition, wherein the compound A comprises at least one selected from the group consisting of a carboxylic acid-modified epoxy (meth)acrylate resin, a modified phenolic resin having an acid group, and a compound having an acid group and a bisphenol structure. [2] The photosensitive composition according to [1], wherein the compound β is a compound B having a structure capable of accepting electrons from the acid group of the compound A in a photoexcited state. [3] The photosensitive composition according to [2], wherein the total number of the electron-accepting structures contained in the compound B is 3 mol % or more relative to the total number of the acid groups contained in the compound A. [4] The photosensitive composition according to any one of [1] to [3], wherein the acid value of the compound A is 30 to 400 mgKOH / g. [5] The photosensitive composition according to any one of [1] to [4], wherein the compound β includes at least one selected from the group consisting of acridine, 9-methylacridine, and 9-phenylacridine. [6] The photosensitive composition according to any one of [1] to [5], wherein the compound β has a molar absorption coefficient at a wavelength of 365 nm of more than 1000 L / (mol·cm). [7] The photosensitive composition according to any one of [1] to [6], further comprising a filler. [8] The photosensitive composition according to [7], wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates. [9] The photosensitive composition according to [7] or [8], wherein the content of the filler is 10 to 80 mass % based on the total solid content of the photosensitive composition.

[10] The photosensitive composition according to any one of [7] to [9], wherein the filler has an average primary particle size of 10 to 300 nm.

[11] The photosensitive composition according to any one of [7] to

[10] , wherein the filler has a refractive index of 1.2 to 1.8.

[12] The photosensitive composition according to any one of [7] to

[11] , wherein the filler is surface-treated.

[13] the content of the compound A is 20 to 98 mass% based on the total solid content of the photosensitive composition, the content of the compound β is 1 to 30 mass % based on the total solid content of the photosensitive composition, the content of the filler is 10 to 80 mass% based on the total solid content of the photosensitive composition, the mass ratio of the content of the filler to the content of the compound A is 0.5 or more; the mass ratio of the content of the compound β to the content of the compound A is 0.7 or less; The photosensitive composition according to any one of [7] to

[12] , wherein the mass ratio of the content of the compound β to the content of the filler is 0.5 or less.

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

[13] , further comprising an epoxy compound.

[15] The photosensitive composition according to

[14] , wherein the epoxy compound comprises at least one selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenyl epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, and urethane epoxy epoxy resins.

[16] The photosensitive composition according to

[14] or

[15] , wherein the epoxy compound has two or more epoxy groups in one molecule.

[17] The photosensitive composition according to any one of

[14] to

[16] , wherein the epoxy compound has an epoxy value of 90 to 290 g / eq.

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

[17] , which does not contain a polymerizable compound having a molecular weight of 2000 or less, which has an ethylenically unsaturated group, and which does not contain an acid group, or, if it contains the polymerizable compound, the content of the polymerizable compound is 5 mass % or less based on the total solid content of the photosensitive composition.

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

[18] , which can form a photosensitive layer capable of forming a pattern by exposure and development using a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C.

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

[19] . 〔twenty one〕 A cured film obtained by curing the photosensitive composition according to any one of [1] to

[19] . 〔twenty two〕 A semiconductor package comprising the cured film according to

[21] . 〔twenty three〕 A step of forming a photosensitive layer on a substrate using the photosensitive composition according to any one of [1] to

[19] or the transfer film according to

[20] ; patternwise exposing the photosensitive layer; and developing the exposed photosensitive layer with an alkaline developer to form a pattern. 〔twenty four〕 A step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive composition according to any one of [1] to

[20] or the transfer film according to

[21] ; patternwise exposing the photosensitive layer; developing the exposed photosensitive layer with an alkaline developer to form a pattern having vias; forming a circuit pattern on the pattern; A method for manufacturing a semiconductor package, comprising the steps of: [Effects of the Invention]

[0009] According to the present invention, there is provided a photosensitive composition that can form a pattern having excellent heat resistance and insulating reliability. In addition, there are also provided a transfer film, a cured film, a semiconductor package, a pattern forming method, and a semiconductor package manufacturing method related to the photosensitive composition. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film. DETAILED DESCRIPTION OF THE INVENTION

[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. Furthermore, in the numerical ranges described in stages in this specification, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[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, the temperature when performing each of the above steps may be 25° C. unless otherwise specified.

[0014] In this specification, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0015] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, such as g-rays, h-rays, and i-rays, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). Furthermore, in the present invention, light refers to actinic rays or radiation.

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

[0017] In this specification, unless otherwise specified, the content ratio of each repeating unit in a polymer is a molar ratio. 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 is present, the molecular weight is a weight average molecular weight. In this specification, the weight average molecular weight is a value 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 composition refers to components that form a composition layer (e.g., a photosensitive layer) formed using the composition (e.g., a photosensitive composition), and when the composition contains a solvent (e.g., an organic solvent and water), 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 layer thickness (film thickness) 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 comprises a compound A having an acid group and a compound β having a structure that reduces the amount of acid groups in the compound A upon exposure to light, The compound A includes at least one selected from the group consisting of a carboxylic acid-modified epoxy (meth)acrylate resin, a modified phenolic resin having an acid group, and a compound having an acid group and a bisphenol structure. Although the detailed mechanism of action of the photosensitive composition of the present invention is not clear, the present inventors speculate as follows: It is speculated that the pattern (cured film) obtained by exposing and developing a photosensitive layer formed using the photosensitive composition of the present invention has excellent heat resistance and insulating reliability due to the inclusion of Compound A and the reduction in the content of acid groups in Compound A by Compound β. Hereinafter, the achievement of at least one of the effects of better heat resistance and better insulation reliability will also be referred to as "the effect of the present invention being better."

[0024] An example of an embodiment of the photosensitive composition will be described below. Embodiment X-1-a1: A photosensitive composition comprising a compound A and a compound β, and substantially free of a polymerizable compound and a photopolymerization initiator. Embodiment X-1-a2: A photosensitive composition comprising a compound A and a compound β, and substantially free of a photopolymerization initiator. Embodiment X-1-a3: A photosensitive composition comprising a compound A and a compound β, and further comprising a polymerizable compound and a photopolymerization initiator.

[0025] In embodiment X-1-a1, "substantially free of polymerizable compounds" means that the content of polymerizable compounds is 5% by mass or less, preferably less than 3% by mass, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, based on the total solid content of the photosensitive composition. In Embodiment X-1-a1 and Embodiment X-1-a2, "substantially free of a photopolymerization initiator" means that the content of the photopolymerization initiator is less than 0.1 mass %, preferably 0 to 0.05 mass %, and more preferably 0 to 0.01 mass %, based on the total solid content of the photosensitive composition. In Embodiments X-1-a1 to X-1-a3, the "polymerizable compound" is a polymerizable compound that does not have an acid group but has an ethylenically unsaturated group, as described below. Embodiment X-1-a1 or embodiment X-1-a2 is preferred, and embodiment X-1-a1 is more preferred.

[0026] In addition, preferred ranges for each component in the photosensitive composition are: Compound A content is 20 to 98% by mass relative to the total solid content of the photosensitive composition; Compound β content is 1 to 30% by mass relative to the total solid content of the photosensitive composition; Filler content is 10 to 80% by mass relative to the total solid content of the photosensitive composition; the mass ratio of the filler content to Compound A content is 0.5 or more; the mass ratio of the compound β content to the compound A content is 0.7 or less; and the mass ratio of the compound β content to the filler content is 0.5 or less. Note that suitable contents and mass ratios of the various components described above are as described below.

[0027] An example of a mechanism by which the content of acid groups derived from compound A is reduced by exposure is decarboxylation when the acid groups are carboxy groups. A reduction in the content of carboxy groups in compound A by decarboxylation refers to the elimination of carboxy groups as CO (carbon dioxide), and does not include the conversion of carboxy groups to other groups such as esterification. It is believed that when a photosensitive layer formed using a photosensitive composition is exposed to light, a decarboxylation reaction of the carboxy groups in compound A may occur.

[0028] Hereinafter, the estimated mechanism by which the content of carboxy groups in compound A is reduced by exposure will be described in detail, taking as an example a modified phenolic resin having carboxy groups as compound A and quinoline as compound β. As shown in the diagram below, the carboxyl group of the modified phenolic resin and the nitrogen atom of the quinoline form a hydrogen bond when they coexist. When exposed to light, quinoline becomes more electron-accepting and receives electrons from the carboxyl group of the modified phenolic resin (step 1: photoexcitation). When the carboxyl group of the modified phenolic resin receives electrons from the quinoline, it becomes unstable and carbon dioxide is released (step 2: decarboxylation). After the decarboxylation, radicals are generated in the residues of the modified phenolic resin, and a radical reaction proceeds. Radical reactions can occur between residues of the modified phenolic resin, between the residues of the modified phenolic resin and an optional polymerizable compound (monomer (M)), or between hydrogen atoms in the atmosphere (step 3: polarity conversion, crosslinking, and polymerization reaction). After the radical reaction is complete, compound β is regenerated and can once again contribute to the decarboxylation process of compound A (step 4: compound β (catalyst) regeneration).

[0029] [ka]

[0030] Due to the above mechanism, the photosensitive layer formed using the photosensitive composition has a change in polarity due to a decrease in the content of carboxy groups in compound A in the exposed area, and the solubility in the developer changes. That is, the solubility in the alkaline developer decreases in the exposed area, and the solubility in the organic solvent developer increases. On the other hand, the solubility in the developer remains almost unchanged in the unexposed area. As a result, the photosensitive layer is considered to have excellent pattern-forming properties.

[0031] Various components that may be contained in the photosensitive composition of the present invention will be described in detail below.

[0032] [Compound A] The photosensitive composition includes Compound A. Compound A includes at least one selected from the group consisting of a carboxylic acid-modified epoxy (meth)acrylate resin, a modified phenolic resin having an acid group, and a compound having an acid group and a bisphenol structure, and preferably includes a modified phenolic resin having an acid group.

[0033] The carboxylic acid-modified epoxy (meth)acrylate resin and the acid group-containing modified phenolic resin are polymeric compounds (hereinafter also referred to as "polymers" or "resins"), and the weight-average molecular weight of the carboxylic acid-modified epoxy (meth)acrylate resin and the acid group-containing modified phenolic resin is preferably 4,500 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, in terms of excellent photosensitive layer formability. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, in terms of excellent adhesion (lamination adhesion) when attached to any substrate. The compound having an acid group and a bisphenol structure may be either a low molecular weight compound or a high molecular weight compound, and is preferably a polymer. When the compound having an acid group and a bisphenol structure is a low molecular weight compound, the molecular weight of the compound having an acid group and a bisphenol structure is preferably less than 4,500, more preferably 2,000 or less, even more preferably 1,000 or less, particularly preferably 500 or less, and most preferably 400 or less. When the compound having an acid group and a bisphenol structure is a polymer compound, the weight-average molecular weight of the compound having an acid group and a bisphenol structure is preferably 4,500 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, from the viewpoint of excellent photosensitive layer formability. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, from the viewpoint of excellent adhesion (lamination adhesion) when attached to any substrate.

[0034] Examples of the acid group contained in the compound A include a carboxy group, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group, with a carboxy group being preferred. When compound A has a carboxy group as an acid group, some or all of the carboxy groups (—COOH) of compound A may be anionized or not in the photosensitive composition. In this specification, the expression “carboxy group” means an anionized carboxy group (—COOH - This concept includes both anionized carboxyl groups (-COOH) and non-anionized carboxyl groups (-COOH).

[0035] Compound A may contain a structure (hereinafter also referred to as "specific structure S0") that reduces the amount of acid groups contained in compound A upon exposure to light. Hereinafter, compound A not having specific structure S0 will also be referred to as "compound Aa," and compound A having specific structure S0 will also be referred to as "compound Ab." Compound Ab is preferably a polymer. In other words, compound Ab is preferably a polymer having specific structure S0. The phrase "compound A does not have the specific structure S0" means that compound A does not substantially have the specific structure S0. For example, the content of the specific structure S0 in compound Aa may be less than 1% by mass, preferably 0 to 0.5% by mass, and more preferably 0 to 0.05% by mass, relative to the total mass of compound Aa. The content of the specific structure S0 in the compound Ab is preferably 1% by mass or more, more preferably 1 to 50% by mass, and even more preferably 5 to 40% by mass, based on the total mass of the compound Ab. When compound A contains compound Ab, the content of compound Ab is preferably 5 to 100 mass % based on the total mass of compound A. The specific structure S0 is preferably the specific structure S1 described below.

[0036] As described above, the compound A may have a specific structure S0 (preferably a specific structure S1). When the compound A has the specific structure S0 (preferably a specific structure S1), the compound A is preferably a polymer having the specific structure S0 (preferably a specific structure S1).

[0037] <Carboxylic acid modified epoxy (meth)acrylate resin> Carboxylic acid-modified epoxy (meth)acrylate resins are resins obtained by introducing a (meth)acryloyl group by ring-opening addition of the carboxy group of a carboxylic acid having a (meth)acryloyl group to the epoxy group of a parent epoxy resin, and then introducing a carboxy group by adding a polybasic carboxylic acid or an anhydride thereof to at least one of the hydroxyl groups generated by ring-opening of the epoxy group. That is, the carboxylic acid-modified epoxy (meth)acrylate resin is a resin having a carboxy group as the acid group.

[0038] A carboxylic acid having a (meth)acryloyl group is a compound having one or more carboxy groups and one or more (meth)acryloyl groups. The number of the carboxy groups is preferably 1 to 3, and more preferably 1. The number of the (meth)acryloyl groups is preferably 1 to 3, and more preferably 1. Examples of carboxylic acids having a (meth)acryloyl group include acrylic acid and methacrylic acid.

[0039] The base epoxy resin preferably has a ring such as an aromatic ring or an alicyclic ring, more preferably has an aromatic ring, and further preferably has an aromatic hydrocarbon ring. The aromatic ring may be either a monocyclic ring or a polycyclic ring. The aromatic ring preferably has 6 to 30 carbon atoms, and more preferably has 6 to 15 carbon atoms. Examples of the aromatic ring include a benzene ring, a biphenyl ring, a naphthalene ring, and an anthracene ring. The aromatic ring may further have a substituent, such as a hydroxyl group or an alkyl group. Examples of the base epoxy resin include epoxy resins having a biphenyl structure, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins.

[0040] Examples of polybasic carboxylic acids or anhydrides thereof include maleic acid, maleic anhydride, succinic acid, succinic anhydride, tetrahydrophthalic acid, and tetrahydrophthalic anhydride.

[0041] The carboxylic acid-modified epoxy (meth)acrylate resin preferably has a group represented by formula (D).

[0042] [ka]

[0043] In formula (D), L D represents a single bond or a divalent linking group. D represents a hydrogen atom or an alkyl group.

[0044] L D represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -(R N represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), hydrocarbon groups (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups such as phenylene groups, etc.), and linking groups combining these. The divalent linking group is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms.

[0045] R D represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 carbon atom.

[0046] The carboxylic acid-modified epoxy (meth)acrylate resin may have a repeating unit that may be contained in other compounds described below.

[0047] Examples of carboxylic acid-modified epoxy (meth)acrylate resins include the KAYARAD CCR series (e.g., 1171, etc.), ZAR series (e.g., 1494H, 2001H, and 2051H, etc.), ZFR series (e.g., 1491H and 1569H, etc.), ZCR series (e.g., 1569H, 1797H, 1798H, and 1761H, etc.), and UXE series (e.g., 3000, etc.) (all manufactured by Nippon Kayaku Co., Ltd.).

[0048] <Modified phenolic resin with acid groups> The modified phenolic resin having an acid group is a resin into which an acid group has been introduced by reacting a compound having an acid group with a phenolic hydroxyl group of the base phenolic resin. The modified phenolic resin having an acid group is a resin different from the various components described above.

[0049] Examples of the acid group contained in the compound having an acid group include a carboxy group, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group, with a carboxy group being preferred. The compound having an acid group has one or more acid groups, preferably one to three acid groups. The acid group of the compound having an acid group may be protected by a protecting group and may be an acid group generated by a deprotection reaction, specifically, a compound having a methyl ester group in which a carboxy group is protected by a methyl group. The compound having an acid group may have other groups in addition to the acid group, such as functional groups capable of reacting with a phenolic hydroxyl group, such as halogen atoms (e.g., chlorine atoms and iodine atoms). The compound having an acid group may be either a low molecular weight compound or a high molecular weight compound, and is preferably a low molecular weight compound. Specifically, the molecular weight of the compound having an acid group is preferably less than 4,500, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0050] Examples of compounds having an acid group include methyl acetate, methyl chloroacetate, methyl 3-chloropropionate, and methyl 2-chloropropionate. Examples of the phenolic resin that serves as the base include phenol novolac resin, cresol novolac resin, biphenyl aralkyl type phenolic resin, naphthol aralkyl resin, and naphthol novolac resin.

[0051] The modified phenolic resin having an acid group preferably has a group represented by formula (E), and more preferably has a repeating unit represented by formula (E1).

[0052] [ka]

[0053] In formula (E), Ar E represents an aromatic ring group. E represents a divalent linking group. nE represents an integer of 1 or more. * represents the bonding position.

[0054] Ar E represents an aromatic ring group. Examples of the aromatic ring group include the aromatic ring groups that the above-mentioned epoxy resins can have.

[0055] L E represents a divalent linking group. Examples of the divalent linking group include L D Examples of the divalent linking group include a divalent linking group represented by the following formula: The divalent linking group is preferably a hydrocarbon group, more preferably an alkylene group.

[0056] nE represents an integer of 1 or more. nE is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

[0057] [ka]

[0058] In formula (E1), R E represents a substituent. E1represents a divalent linking group. nE1 represents an integer of 0 to 3.

[0059] R E represents a substituent. R E The substituent represented by the formula (I) is preferably an alkyl group or a hydroxyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. R E If there are multiple, R E They may be the same or different.

[0060] L E1 represents a divalent linking group. L E1 is the L mentioned above. E The same definition and preferred embodiments are also the same.

[0061] nE1 represents an integer of 0 to 3. nE1 is preferably an integer of 0 to 2.

[0062] The modified phenolic resin having a carboxy group may have a repeating unit that may be contained in other compounds described below.

[0063] <Compound having an acid group and a bisphenol structure> The compound having an acid group and a bisphenol structure is a compound having one or more acid groups and one or more bisphenol structures in the molecule. The compound having an acid group and a bisphenol structure is a compound different from the various components described above. The compound having an acid group and a bisphenol structure may be either a low molecular weight compound or a high molecular weight compound, and is preferably a high molecular weight compound. The suitable molecular weights of the low molecular weight compound and the high molecular weight compound are as described above.

[0064] Examples of the acid group include the acid group contained in the modified phenolic resin having the acid group described above, and a carboxy group is preferred.

[0065] Examples of the bisphenol structure include a structure derived from bisphenol A, a structure derived from bisphenol AP, a structure derived from bisphenol AF, a structure derived from bisphenol B, a structure derived from bisphenol BP, a structure derived from bisphenol C, a structure derived from bisphenol C, a structure derived from bisphenol E, a structure derived from bisphenol F, a structure derived from bisphenol G, a structure derived from bisphenol M, a structure derived from bisphenol S, and a structure derived from bisphenol P.

[0066] The compound having an acid group and a bisphenol structure may have other groups in addition to the acid group, such as acid groups other than carboxy groups (e.g., phenolic hydroxyl groups, phosphate groups, sulfonic acid groups, etc.) and halogen atoms (e.g., chlorine atoms, iodine atoms, etc.). The compound having an acid group and a bisphenol structure may have a repeating unit that can be contained in other compounds described below.

[0067] The acid value of compound A is preferably from 10 to 600 mgKOH / g, more preferably from 30 to 500 mgKOH / g, from the viewpoint of developability. The acid value can be measured in accordance with JIS K0070 (1992).

[0068] The compound A may be used alone or in combination of two or more. When the photosensitive composition contains compound A, which is a polymer compound, the content of compound A is preferably 75 to 100 mass %, more preferably 85 to 100 mass %, still more preferably 90 to 100 mass %, and particularly preferably 95 to 100 mass %, based on the total mass of compound A. When the photosensitive composition contains compound A, which is a low molecular weight compound, the content of compound A, which is a low molecular weight compound, is preferably 0 to 25 mass %, more preferably 0 to 10 mass %, and even more preferably 0 to 5 mass %, based on the total mass of compound A. Compound A of the polymer compound means at least one selected from the group consisting of carboxylic acid-modified epoxy (meth)acrylate resin, modified phenol resin having an acid group, and a compound of a polymer compound having an acid group and a bisphenol structure. The low molecular weight compound A means a compound having an acid group of a low molecular weight compound and a bisphenol structure.

[0069] The lower limit of the content of compound A is often 1% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total solid content of the photosensitive composition. The upper limit is preferably 100% by mass or less, more preferably 99% by mass or less, even more preferably 97% by mass or less, and particularly preferably 95% by mass or less, based on the total solid content of the photosensitive composition. In the photosensitive composition of embodiment X-1-a1, the content of compound A is preferably from 45 to 98 mass %, more preferably from 50 to 95 mass %, based on the total solid content of the photosensitive composition.

[0070] [Compound β] The photosensitive composition contains the compound β. Compound β is a compound having a structure (specific structure S0) that reduces the amount of acid groups contained in compound A upon exposure to light.

[0071] The specific structure S0 is a structure that, upon exposure, exhibits the effect of reducing the amount of acid groups contained in the compound A. The specific structure S0 is preferably a structure that transitions from the ground state to an excited state upon exposure and exhibits the effect of reducing the amount of acid groups contained in the compound A in the excited state. An example of the specific structure S0 is a structure that can accept electrons from the acid group of the compound A in a photoexcited state (hereinafter, also referred to as "specific structure S1").

[0072] The specific structure S0 of the compound β may be the entire structure constituting the entire compound β, or may be a partial structure constituting a part of the compound β. The compound β may be either a low molecular weight compound or a high molecular weight compound, and is preferably a low molecular weight compound. When compound β is a low molecular weight compound, the molecular weight of compound β is preferably less than 5,000, more preferably less than 1,000, further preferably 65 to 300, and particularly preferably 75 to 250.

[0073] The specific structure S0 is preferably a structure (specific structure S1) that can accept electrons from the acid group of compound A in a photoexcited state. That is, compound β is preferably compound B that has a structure (specific structure S1) that can accept electrons from the acid group of compound A in a photoexcited state. For example, when compound A has a carboxy group, compound B is thought to be able to eliminate the carboxy group as CO (decarboxylation).

[0074] Compound β (preferably Compound B) will be described in detail below. In terms of more excellent pattern forming ability, the compound β (preferably the compound B) is preferably an aromatic compound having an aromatic ring as the specific structure S. That is, the specific structure S is preferably an aromatic ring, and more preferably a heteroaromatic ring as described later. The compound β (preferably the compound B) may have only one aromatic ring or may have a plurality of aromatic rings. When a plurality of aromatic rings are present, the aromatic rings may be present, for example, in the side chain of the resin. In compound β (preferably compound B), the aromatic ring can be used as a structure (specific structure S0 (preferably specific structure S1)) that reduces the amount of acid groups in compound A upon exposure to light. The aromatic ring may be monocyclic or polycyclic, and is preferably polycyclic. The polycyclic aromatic ring is, for example, an aromatic ring formed by condensing a plurality of (e.g., 2 to 5) aromatic ring structures, and it is preferred that at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. The aromatic ring may be a heteroaromatic ring, which preferably has one or more (e.g., 1 to 4) heteroatoms (e.g., nitrogen atoms, oxygen atoms, sulfur atoms, etc.) as ring member atoms, and more preferably has one or more (e.g., 1 to 4) nitrogen atoms as ring member atoms. The aromatic ring preferably has 5 to 15 ring atoms.

[0075] The aromatic ring of compound β (preferably compound B) is preferably a polycyclic ring (a polycyclic aromatic ring) in terms of a higher molar absorption coefficient at a wavelength of 365 nm. The number of monocyclic aromatic rings (number of condensed rings) in the polycyclic aromatic ring is preferably 2 or more, and more preferably 3 or more in terms of a higher molar absorption coefficient at a wavelength of 365 nm. The upper limit may be 6 or less. The polycyclic aromatic ring preferably has a heteroatom (such as a nitrogen atom, an oxygen atom, or a sulfur atom) as a ring member (in other words, it is a polycyclic heteroaromatic ring).

[0076] Examples of the aromatic ring contained in compound β (preferably compound B) include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; aromatic rings fused with two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings fused with three rings such as an acridine ring, a benzo[f]quinoline ring, a benzo[h]quinoline ring, a phenanthridine ring (benzo[c]quinoline ring), a benzo[h]isoquinoline ring, a phenanthroline ring, and a phenazine ring.

[0077] The aromatic ring may have one or more (e.g., 1 to 5) substituents, and examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. When the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring. It is also preferred that the aromatic ring is directly bonded to a carbonyl group to form an aromatic carbonyl group in compound β (preferably compound B).It is also preferred that a plurality of aromatic rings are bonded via a carbonyl group. It is also preferred that the aromatic ring is bonded to an imide group to form an aromatic imide group in compound β (preferably compound B). The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring. In addition, when a series of aromatic ring structures is formed by a plurality of aromatic rings (e.g., 2 to 5 rings) being bonded via a structure selected from the group consisting of a single bond, a carbonyl group, and a multiple bond (e.g., an optionally substituted vinylene group, -C≡C-, -N=N-, etc.), the entire series of aromatic ring structures is regarded as one specific structure. In addition, it is preferable that at least one of the plurality of aromatic rings constituting the series of aromatic ring structures is the heteroaromatic ring.

[0078] In terms of achieving superior pattern forming ability, compound β (preferably compound B) is preferably a compound that satisfies one or more (e.g., 1 to 4) of requirements (1) to (4), more preferably satisfies at least one of requirements (1) and (2), and even more preferably satisfies at least requirements (1) and (2) (i.e., is a polycyclic heteroaromatic ring). The heteroaromatic ring preferably contains at least a nitrogen atom as a heteroatom. Requirement (1): Having a polycyclic aromatic ring. Requirement (2): Having a heteroaromatic ring. Requirement (3): Having an aromatic carbonyl group. Requirement (4): The compound has an aromatic imide group.

[0079] Compound β (preferably compound B) includes monocyclic aromatic compounds such as pyridine, pyrazine, pyrimidine, and triazine; compounds in which two rings are fused to form an aromatic ring, such as quinoline, isoquinoline, quinoxaline, and quinazoline; and compounds in which three or more rings are fused to form an aromatic ring, such as acridine, benzo[f]quinoline, benzo[h]quinoline, phenanthridine, benzo[h]isoquinoline, phenanthroline, and phenazine. These compounds may further have a substituent, which is preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group.

[0080] Compound β (preferably compound B) is preferably one or more selected from the group consisting of acridine, benzo[f]quinoline, benzo[h]quinoline, phenanthridine, benzo[h]isoquinoline, phenanthroline, and phenazine, because they have a higher molar absorption coefficient at a wavelength of 365 nm and excellent photosensitivity at a wavelength of 365 nm. These compounds may further have a substituent, and the substituent is preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group.

[0081] When compound β (preferably compound B) is a polymer, it may be a polymer in which the specific structure is bonded to the polymer main chain via a single bond or a linking group. The polymer compound β (preferably compound B) can be obtained, for example, by polymerizing a monomer having a polycyclic heteroaromatic ring (specifically, a vinyl polycyclic heteroaromatic ring and / or a (meth)acrylate monomer having a specific structure (preferably a polycyclic heteroaromatic ring)). If necessary, it may be copolymerized with other monomers.

[0082] In terms of achieving superior pattern forming ability, the molar absorption coefficient of compound β (preferably compound B) at a wavelength of 365 nm is preferably 100 L / (mol cm) or more, more preferably 500 L / (mol cm) or more, even more preferably more than 1,000 L / (mol cm), and particularly preferably 4,000 L / (mol cm) or more. The upper limit of the molar absorption coefficient may be 20,000 L / (mol cm). The molar absorption coefficient at a wavelength of 365 nm is measured by dissolving compound β (preferably compound B) in acetonitrile. When compound β (preferably compound B) is not soluble in acetonitrile, the solvent for dissolving compound β (preferably compound B) may be changed as appropriate. The fact that the molar absorption coefficient of compound β (preferably compound B) is within the above range is particularly advantageous when the photosensitive layer is exposed through a temporary support (preferably a PET film). That is, because the absorption coefficient is appropriately low, it is possible to control the generation of bubbles due to decarbonation even when exposure is performed through a temporary support, and it is possible to prevent deterioration of the pattern shape. Examples of compounds having a high molar absorption coefficient at a wavelength of 365 nm include compounds in which three or more aromatic rings are fused to form an aromatic ring. Examples of compounds in which three or more aromatic rings are fused to form an aromatic ring include the compounds described above.

[0083] Examples of compound β (preferably compound B) include 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, quinoline, benzo[f]quinoline, benzo[h]quinoline, isoquinoline, benzo[h]isoquinoline, 1-methylisoquinoline, 1-phenylisoquinoline, acridine, 9-methylacridine, phenanthridine, phenanthroline, and phenazine. The compound β preferably includes at least one selected from the group consisting of acridine, 9-methylacridine, and 9-phenylacridine.

[0084] The compound β (preferably compound B) may be used alone or in combination of two or more. In terms of achieving better pattern forming ability, the lower limit of the content of compound β (preferably compound B) is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total solid content of the photosensitive composition, and the upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the photosensitive composition. In the photosensitive composition for forming the photosensitive layer of embodiment X-1-a1, the content of compound β (preferably compound B) is preferably 1 to 30 mass %, more preferably 1 to 20 mass %, based on the total solid content of the photosensitive composition.

[0085] In terms of achieving better pattern forming ability, the total number of specific structures S0 (preferably specific structures S1) possessed by compound β (preferably compound B) is preferably 1 mol % or more, more preferably 3 mol % or more, even more preferably 5 mol % or more, and particularly preferably 10 mol % or more, relative to the total number of acid groups possessed by compound A. The upper limit of the total number of specific structures S0 (preferably specific structures S1) possessed by compound β (preferably compound B) is preferably 200 mol % or less, more preferably 100 mol % or less, and even more preferably 80 mol % or less, relative to the total number of acid groups possessed by compound A, in terms of the quality of the resulting film.

[0086] The mass ratio of the content of compound β to the content of compound A is preferably 0.7 or less, more preferably 0.5 or less. There is no particular lower limit, but it is preferably 0.05 or more.

[0087] [Filler] The photosensitive composition includes a filler. Examples of the filler include organic fillers and inorganic fillers, with inorganic fillers being preferred. Examples of fillers include silicon dioxide (e.g., silica, etc.); 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, boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide.

[0088] The shape of the filler may be either spherical or non-spherical (for example, crushed or fibrous), with spherical being preferred. The filler may be surface-treated, for example, by introducing a functional group or by using a known surface modifier. Examples of the surface modifier include a silane coupling agent, a titanate coupling agent, and a silazane compound.

[0089] Examples of fillers include SC-2050MB (manufactured by Admatechs Co., Ltd., silicon dioxide, epoxy silane surface treatment, MEK (methyl ethyl ketone) slurry with a solid content of 70% by mass), SO-C2 (manufactured by Admatechs Co., Ltd., silicon dioxide), Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, no surface treatment, solid content of 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, trimethylsilyl surface treatment, solid content of 100% by mass), and YA050C-MJE (manufactured by Admatechs Co., Ltd.). Silicon dioxide (manufactured by Tex Co., Ltd., acrylic surface treatment product, solid content concentration 50% by mass MEK slurry), MEK-EC-2430Z (manufactured by Nissan Chemical Co., Ltd., epoxy silane surface treatment, solid content concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., no surface treatment, solid content concentration 100% by mass), AZ filler (manufactured by AGC Co., Ltd., no surface treatment, solid content concentration 100% by mass), spherical alumina (manufactured by Showa Denko K.K., CB-P02 (average particle size 2 μm), CB-P05 (average particle size 4 μm)), talc (manufactured by Hayashi Kasei Co., Ltd., MW Examples include HS-T (average particle size 4.75 μm), KHP-25 (average particle size 4.75 μm)), clay (Kaolin clay RC-1 (average particle size 0.4 μm) manufactured by Takehara Chemical Industry Co., Ltd.), mica powder (A-11 (average particle size 3 μm) manufactured by Yamaguchi Mica Co., Ltd.), and boron nitride (UHP-S1 (average particle size 0.5 μm) manufactured by Showa Denko KK). Examples of fillers include those described in paragraphs 0032 to 0042 of JP 2019-104941 A.

[0090] The average primary particle size of the filler is preferably from 1 to 5000 nm, more preferably from 5 to 1000 nm, and even more preferably from 10 to 300 nm. The average primary particle size can be measured, for example, using a dynamic scattering analyzer.

[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 fillers may be used alone or in combination of two or more. The content of the filler is often 1% by mass or more, preferably 10 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 35 to 70% by mass, based on the total solid content of the photosensitive composition.

[0093] The mass ratio of the content of the filler to the content of compound A is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. There is no particular upper limit, but it is preferably 10 or less. The mass ratio of the content of compound β to the content of the filler is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less. There is no particular lower limit, but it is preferably 0.0005 or more.

[0094] [Epoxy Compound] The photosensitive composition preferably contains an epoxy compound, as this will provide better effects of the present invention. The epoxy compound is a compound having an epoxy group, and is a compound different from the various components described above.

[0095] The epoxy compound may be either a low molecular weight compound or a high molecular weight compound, and a high molecular weight compound is preferred. When the epoxy compound is a low molecular weight compound, the molecular weight of the epoxy compound is preferably less than 4,500, more preferably 2,000 or less, and even more preferably 1,000 or less. When the epoxy compound is a polymeric compound, the molecular weight of the epoxy compound is preferably 4,500 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. The upper limit is preferably 100,000 or less, and more preferably 50,000 or less.

[0096] The epoxy compound may be a compound having one or more epoxy groups in one molecule, preferably two or more epoxy groups, and the upper limit may be 100 or less. The epoxy compound may have other groups in addition to the epoxy group, and the other groups are preferably aromatic ring groups. The aromatic ring group may be either a monocyclic or polycyclic ring, and may further have a substituent. The aromatic ring group preferably has 6 to 30 carbon atoms, and more preferably has 6 to 12 carbon atoms. Examples of the aromatic ring group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, a biphenyl group, and a fluorenyl group, and a phenyl group or a biphenyl group is preferred.

[0097] Examples of epoxy compounds include TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.), jER (registered trademark) epoxy resins (e.g., 828 and 828EL, etc., manufactured by Mitsubishi Chemical Corporation), EPICLON series (registered trademark) (e.g., N-770, etc., manufactured by DIC Corporation), TECHMORE VG3101L (manufactured by Printec Co., Ltd.), and NC-3000 (manufactured by Nippon Kayaku Co., Ltd.).

[0098] The epoxy compound preferably contains at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and urethane epoxy type epoxy resins, and more preferably contains at least one selected from the group consisting of bisphenol A type epoxy resins, phenol novolac type epoxy resins, and bisphenyl type epoxy resins.

[0099] The epoxy value of the epoxy compound is preferably from 50 to 500 g / eq, more preferably from 90 to 290 g / eq. The epoxy value can be calculated, for example, from the chemical structure of the epoxy compound by dividing the molecular weight of the epoxy compound by the number of epoxy groups per molecule.

[0100] The epoxy compounds may be used alone or in combination of two or more. When the photosensitive composition contains an epoxy compound, the content of the epoxy compound is preferably from 1 to 40 mass %, more preferably from 1 to 20 mass %, based on the total solid content of the photosensitive composition.

[0101] [Surfactant] The photosensitive composition may contain a surfactant. The surfactant is a compound different from the various components described above. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants.

[0102] Examples of nonionic 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, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Japan Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Yushi Co., Ltd.), Olfine E1010, Surfynol 104, 400 and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0103] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0104] Examples of fluorine-based surfactants include 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, 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, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-101, RS-102, RS-718K, RS-72-K, DS-21 (all manufactured by DIC), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS), and U-120E (manufactured by Unichem).

[0105] Furthermore, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferred. Furthermore, as the fluorine-based surfactant, a block polymer is also preferred. As the fluorine-based surfactant, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are also preferred in terms of improving environmental friendliness.

[0106] Examples of surfactants include 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 Toray Dow Corning 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, KP-341, K F-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-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momenty Examples of such acrylic acid esters include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0107] Examples of surfactants include those described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, paragraph 0017 of Japanese Patent No. 4502784, and paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362.

[0108] The surfactants may be used alone or in combination of two or more. When the photosensitive composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 10 mass %, more preferably 0.001 to 5 mass %, and even more preferably 0.005 to 3 mass %, based on the total solid content of the photosensitive composition.

[0109] [Polymerizable Compound Having an Ethylenically Unsaturated Group and No Acid Group] The photosensitive composition may contain a polymerizable compound that has no acid group, an ethylenically unsaturated group, and no acid group (hereinafter, also simply referred to as "polymerizable compound"). The polymerizable compound does not have an acid group and has one or more (for example, 1 to 15) ethylenically unsaturated groups in one molecule, and is a compound different from the various components described above.

[0110] The photosensitive composition does not contain a polymerizable compound having a molecular weight of 2000 or less, having an ethylenically unsaturated group, and not having an acid group, or, if it contains the polymerizable compound, the content of the polymerizable compound is preferably 5% by mass or less, more preferably less than 3% by mass, even more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.1% by mass or less, based on the total solid content of the photosensitive composition.

[0111] Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group.

[0112] Examples of the polymerizable compound include a polymerizable compound having one ethylenically unsaturated group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two ethylenically unsaturated groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more ethylenically unsaturated groups in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound").

[0113] Examples of bifunctional polymerizable compounds include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Specific examples include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0114] Examples of the tri- or higher functional polymerizable compound 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. The term "(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 the term "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0115] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0116] Examples of the polymerizable compound include urethane (meth)acrylate (preferably tri- or higher functional urethane (meth)acrylate). The lower limit of the number of functional groups is preferably 6 or more, more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher 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.); and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0117] The polymerizable compounds may be used alone or in combination of two or more. When the photosensitive composition contains a polymerizable compound, the content of the polymerizable compound may be 6 to 70% by mass based on the total solid content of the photosensitive composition.

[0118] [Photopolymerization initiator] The photosensitive composition may contain a photopolymerization initiator. The photopolymerization initiator is a compound different from the various components described above. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0119] The photosensitive composition preferably contains substantially no photopolymerization initiator. "Substantially free of photopolymerization initiator" is as described above.

[0120] 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, an acylphosphine oxide compound, and a bistriphenylimidazole compound. The photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime ester compound and an aminoacetophenone compound, and more preferably contains an oxime ester compound and an aminoacetophenone compound.

[0121] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, 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]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE 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, DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Powerful 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, 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, Changzhou Powerful Electronic New Materials Co., Ltd.).

[0122] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, the Omnirad series is manufactured by IGM Resins BV), 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.).

[0123] Examples of photopolymerization initiators 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 H) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).

[0124] 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.

[0125] The photopolymerization initiators may be used alone or in combination of two or more. When the photosensitive composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass %, based on the total solid content of the photosensitive composition.

[0126] [Other compounds] The photosensitive composition may contain other compounds having an acid group in addition to the above-mentioned carboxylic acid-modified epoxy (meth)acrylate resin, modified phenolic resin having an acid group, and compound having an acid group and a bisphenol structure. The repeating units that the other compounds may have will be described in detail below.

[0127] <Repeating unit having a carboxy group> The repeating unit having a carboxy group is preferably a repeating unit represented by formula (A).

[0128] [ka]

[0129] In formula (A), R A represents a hydrogen atom, a halogen atom or an alkyl group. A represents a single bond or a divalent linking group.

[0130] The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 carbon atom. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -(R N represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), hydrocarbon groups (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups such as phenylene groups, etc.), and linking groups combining these.

[0131] Examples of monomers from which repeating units having a carboxy group are derived include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, with (meth)acrylic acid being preferred in terms of superior resolution. That is, the repeating units having a carboxy group are preferably repeating units derived from (meth)acrylic acid, and the polymer preferably has repeating units derived from (meth)acrylic acid.

[0132] <Repeating Unit Having a Polymerizable Group> The repeating unit having a polymerizable group is a repeating unit different from the repeating units described above.

[0133] Examples of the polymerizable group include ethylenically unsaturated groups (e.g., (meth)acryloyl group, allyl group, styryl group, etc.) and cyclic ether groups (e.g., epoxy group, oxetanyl group, etc.), with ethylenically unsaturated groups being preferred, and allyl groups or (meth)acryloyl groups being more preferred. The repeating unit having a polymerizable group is preferably a repeating unit represented by formula (B).

[0134] [ka]

[0135] In formula (B), X B1 and X B2 are each independently -O- or -NR N - represents R N represents a hydrogen atom or an alkyl group. L represents an alkylene group or an arylene group. R B1 and R B2 each independently represents a hydrogen atom or an alkyl group.

[0136] X B1 and X B2 are each independently -O- or -NR N - represents R N represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms.

[0137] L represents an alkylene group or an arylene group. The alkylene group may be either linear or branched. The alkylene group preferably has 1 to 5 carbon atoms. The arylene group may be either monocyclic or polycyclic. The arylene group preferably has 6 to 15 carbon atoms. The alkylene group and the arylene group may have a substituent, and the substituent is preferably an acid group.

[0138] R B1 and R B2 each independently represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 carbon atom.

[0139] The repeating unit having a polymerizable group may be a repeating unit derived from a compound having an allyl group, for example, a repeating unit derived from allyl (meth)acrylate.

[0140] <Repeating units having aromatic rings> The repeating unit having an aromatic ring is a repeating unit different from the repeating units described above.

[0141] The aromatic ring is preferably an aromatic hydrocarbon ring. Examples of repeating units having an aromatic ring include repeating units derived from (meth)acrylates having an aromatic ring, and repeating units derived from styrene and polymerizable styrene derivatives. Examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Styrene and polymerizable styrene derivatives include, for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer.

[0142] The repeating unit having an aromatic ring is preferably a repeating unit represented by formula (C).

[0143] [ka]

[0144] In formula (B), R C represents a hydrogen atom, a halogen atom or an alkyl group. C represents a phenyl group or a naphthyl group.

[0145] The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 carbon atom. The phenyl group and naphthyl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryl group, a halogen atom, and a hydroxy group. Ar C As the alkyl group, a phenyl group is preferred.

[0146] Examples of repeating units having an aromatic ring include the following repeating units.

[0147] [ka]

[0148] <Repeating unit having an alicyclic ring> The repeating unit having an alicyclic ring is a repeating unit different from the repeating units described above.

[0149] The alicyclic ring may be either a monocyclic ring or a polycyclic ring. Examples of the alicyclic ring include a dicyclopentanyl ring, a dicyclopentenyl ring, an isobornyl ring, an adamantane ring, and a cyclohexyl ring. Examples of monomers from which repeating units having an alicyclic ring are derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0150] <Repeating Units Derived from (Meth)acrylic Acid Alkyl Esters> The repeating unit derived from a (meth)acrylic acid alkyl ester is a repeating unit different from the repeating units described above.

[0151] The alkyl group in the (meth)acrylic acid alkyl ester is preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may further have a substituent such as a hydroxy group. An example of the alkyl (meth)acrylate is methyl (meth)acrylate.

[0152] <Repeating unit having specific structure S0> The repeating unit having the specific structure S0 is a repeating unit different from the repeating units described above. The specific structure S0 and the specific structure S1 have the same meaning as the specific structure S0 and the specific structure S1 of the compound β, and the preferred embodiments are also the same.

[0153] In the repeating unit having the specific structure S0 (preferably the specific structure S1), the specific structure S0 (preferably the specific structure S1) may be present in the main chain or in the side chain, and is preferably present in the side chain. When the specific structure S0 (preferably the specific structure S1) is present in the side chain, the specific structure S0 (preferably the specific structure S1) is bonded to the polymer main chain via a single bond or a linking group. Examples of the repeating unit having the specific structure S0 (preferably the specific structure S1) include repeating units derived from a monomer having a heteroaromatic ring (for example, a vinyl heteroaromatic ring such as vinylpyridine and vinyl(iso)quinoline, and a (meth)acrylate monomer having a heteroaromatic ring).

[0154] Examples of the repeating unit having the specific structure S0 (preferably the specific structure S1) include the following repeating units.

[0155] [ka]

[0156] [Other additives] The photosensitive composition may contain other additives in addition to the various components described above. Examples of other additives include solvents, impurities, plasticizers, sensitizers, and alkoxysilane compounds. Examples of plasticizers, sensitizers, and alkoxysilane compounds include those described in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0157] As the solvent, any known solvent can be used as long as it can dissolve or disperse various components other than the solvent. Specific examples include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0158] The solvents may be used alone or in combination of two or more. When the photosensitive composition contains a solvent, the content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0159] The photosensitive 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.

[0160] 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 photosensitive composition. The lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or 0.1 ppm by mass or more, based on the total solid content of the photosensitive composition.

[0161] Methods for adjusting the content of impurities include, for example, using raw materials with low impurity contents for the various components of the photosensitive composition, purifying the various components, and preventing the inclusion of impurities during preparation of the photosensitive composition.

[0162] Impurities can be quantitatively determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0163] In the photosensitive composition, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably 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 photosensitive composition. The lower limit of the content may be 10 ppb by mass or more, or 100 ppb by mass or more, based on the total solid content of the photosensitive composition. The content of these compounds can be adjusted in the same manner as for the above-mentioned impurities, and the content of these compounds can be quantified by known measurement methods.

[0164] The photosensitive composition is preferably capable of forming a photosensitive layer that can be patterned by exposure to light and development using a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C. The pattern forming method, such as exposure conditions, may be, for example, the pattern forming method described below.

[0165] [Transfer film] The transfer film has a temporary support and a photosensitive layer formed using the above-described photosensitive composition. When the transfer film is exposed to light, the amount of acid groups contained in the compound A in the photosensitive layer is reduced.

[0166] FIG. 1 is a cross-sectional view showing an example of an embodiment of a transfer film. The transfer film 10 shown in FIG. 1 has a configuration in which a temporary support 12, a photosensitive layer 14, and a cover film 16 are laminated in this order. 1 is in a form in which a cover film 16 is disposed, but the cover film 16 does not have to be disposed. In addition, as will be described later, the transfer film 10 may further have an intermediate layer and / or a thermoplastic resin layer. Each component of the transfer film will be described in detail below.

[0167] [Temporary support] The temporary support is a support that supports the photosensitive layer and is peelable from the photosensitive layer. The temporary support preferably has light transparency, since the photosensitive layer can be exposed through the temporary support when the photosensitive layer is subjected to pattern exposure. The pattern exposure is a form of exposure in a pattern, and refers to an exposure form in which exposed areas and unexposed areas exist. Furthermore, having optical transparency means that the transmittance of the dominant wavelength of the light used for exposure (which may be pattern exposure or full-surface exposure) is 50% or more. The transmittance of the dominant wavelength of the light used for exposure is preferably 60% or more, and more preferably 70% or more, in terms of superior exposure sensitivity. The transmittance can be measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0168] Examples of the temporary support include a glass substrate, a resin film, and paper, with a resin film being preferred because of its superior strength, flexibility, etc. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, with a biaxially stretched polyethylene terephthalate film being preferred.

[0169] In terms of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of particles, foreign matter, and defects contained in the temporary support is small. Specifically, the number of fine particles, foreign matter, and defects with a diameter of 2 μm or more is 50 / 10 mm. 2 Preferably less than 10 pieces / 10mm 2 Less than 3 pieces / 10mm is more preferable. 2 The lower limit is 1 piece / 10 mm. 2 It may be more than that. In order to further improve the handling property, the temporary support has particles with a diameter of 0.5 to 5 μm at a density of 1 particle / mm on the surface opposite to the side on which the photosensitive layer is formed. 2 It is preferable to have a layer in which there are at least 1 to 50 particles / mm 2 It is more preferable that it exists.

[0170] The thickness of the temporary support is preferably from 5 to 200 μm, more preferably from 10 to 150 μm, in terms of ease of handling and versatility. The thickness of the temporary support can be appropriately selected depending on the material, taking into consideration the strength as a support, the flexibility required for bonding to the circuit wiring formation substrate, and the light transmittance required in the initial exposure step.

[0171] Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP 2014-085643 A, paragraphs 0019 to 0026 of JP 2016-027363 A, paragraphs 0041 to 0057 of WO 2012 / 081680 A, and paragraphs 0029 to 0040 of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

[0172] Examples of temporary supports include COSMOSHINE (registered trademark) A4100 (manufactured by Toyobo Co., Ltd.), COSMOSHINE (registered trademark) A4300 (manufactured by Toyobo Co., Ltd.), COSMOSHINE (registered trademark) A4160 (manufactured by Toyobo Co., Ltd.), COSMOSHINE (registered trademark) A4360 (manufactured by Toyobo Co., Ltd.), LUMIRROR (registered trademark) 16FB40 (manufactured by Toray Industries, Inc.), and LUMIRROR (registered trademark) 16QS62 (manufactured by Toray Industries, Inc.), and a 16 μm thick biaxially oriented polyethylene terephthalate film, a 12 μm thick biaxially oriented polyethylene terephthalate film, or a 9 μm thick biaxially oriented polyethylene terephthalate film is preferred. The temporary support may be a recycled product. Examples of recycled products include films made from chips obtained by cleaning used films, etc. Examples of recycled products include the Ecouse (registered trademark) series manufactured by Toray Industries, Inc.

[0173] [Photosensitive layer] The photosensitive layer is a layer formed using the above-mentioned photosensitive composition. The photosensitive layer contains a compound A, and has a mechanism in which the content of acid groups in the compound A decreases upon exposure to light. For example, when compound A has a carboxy group, the reduction rate of the acid group content of compound A in the photosensitive layer can be determined by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure and determining the reduction rate of the acid group content of compound A in the range of 1680 to 1720 cm -1 It can be calculated from the decrease rate of the peak top height of the maximum absorption peak present in the wavelength range of 1680 to 1720 cm. Usually, the maximum absorption peak of the C=O stretching of the acid group is usually in the range of 1680 to 1720 cm. -1 appears in the wavelength range.

[0174] The various components that can be contained in the photosensitive layer have the same meanings as, for example, the various components that can be contained in the photosensitive composition described above, and the preferred embodiments are also the same. However, the preferred ranges of the contents of the various components in the photosensitive layer are the same as the preferred ranges obtained by replacing the above-mentioned "contents (% by mass) of the various components relative to the total solid content of the photosensitive material" with "contents (% by mass) of the various components relative to the total mass of the photosensitive layer." Specifically, the statement "The lower limit of the content of compound A is often 1% by mass or more, and preferably 15% by mass or more, relative to the total solid content of the photosensitive composition" should be replaced with "The lower limit of the content of compound A is often 1% by mass or more, and preferably 15% by mass or more, relative to the total mass of the photosensitive layer."

[0175] <Thickness of photosensitive layer> The average thickness of the photosensitive layer is preferably 0.5 to 40 μm, more preferably 0.5 to 25 μm. When the average thickness of the photosensitive layer is 40 μm or less, the pattern resolution is superior, and when the average thickness of the photosensitive layer is 0.5 μm or more, it is preferable from the viewpoint of reliability. The average thickness of the photosensitive layer is more preferably 3 to 20 μm.

[0176] [Intermediate layer and thermoplastic resin layer] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of intermediate layers and thermoplastic resin layers include those described in paragraphs 0164 to 0204 of International Publication No. 2021 / 166719, the contents of which are incorporated herein by reference.

[0177] [Cover film] The transfer film may have a cover film.

[0178] The cover film contains 5 fish eyes with a diameter of 80 μm or more per m 2 The following is preferable: Fisheyes are foreign matter, unmelted 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.

[0179] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is more preferable: This can suppress defects caused by the transfer of irregularities caused by particles contained in the cover film to the photosensitive layer.

[0180] 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 can be improved. Furthermore, 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.

[0181] Examples of the cover film include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film. Examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0182] 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 films made from used films that have been cleaned and chipped. Examples of recycled products include the Ecouse (registered trademark) series manufactured by Toray Industries, Inc.

[0183] [Others] The transfer film may include other layers in addition to the layers described above. The other layer may be, for example, 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.

[0184] [Transfer film manufacturing method] The transfer film can be produced by a known production method. As a method for producing the transfer film, it is preferable to form a photosensitive layer on a temporary support by a coating method. For example, a method for manufacturing the transfer film 10 shown in Figure 1 includes a process that includes applying a photosensitive composition to the surface of a temporary support to form a coating film, and then drying this coating film to form a photosensitive layer.

[0185] The transfer film 10 shown in Fig. 1 is produced by pressing a cover film onto the photosensitive layer of the transfer film produced by the above-mentioned production method. The transfer film 10 shown in Fig. 1 may also be wound up after production and stored as a roll of transfer film. The roll of transfer film can be provided as is for the lamination step with a substrate in a roll-to-roll system, which will be described later.

[0186] The transfer film may also have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the photosensitive layer. Examples of compositions for forming an intermediate layer, methods for forming an intermediate layer, compositions for forming a thermoplastic resin layer, and methods for forming a thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0187] <Method for forming photosensitive layer> The photosensitive layer can be formed by a known method, for example, by applying and drying a photosensitive composition. As described above, the photosensitive composition contains the compound A and the compound β.

[0188] Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating. The photosensitive composition preferably further contains a solvent. The solvent has the same meaning as the solvent that the photosensitive composition may contain, and the preferred embodiments are also the same.

[0189] <An example of a transfer film manufacturing method> When forming the photosensitive layer of the transfer film, the photosensitive composition may be either a water-based composition or an organic solvent-based composition. In a method for producing a transfer film having an intermediate layer between a thermoplastic resin layer and a photosensitive layer, the photosensitive composition is preferably an organic solvent-based composition, since interlayer mixing with the intermediate layer is suppressed and resolution is improved. On the other hand, in a method for producing a transfer film having no intermediate layer between a thermoplastic resin layer and a photosensitive layer, the photosensitive composition is preferably an aqueous composition, since interlayer mixing with the thermoplastic resin layer is suppressed and resolution is improved.

[0190] By water-based composition it is meant that the solvent comprises water. The solvent in the aqueous composition is preferably water alone or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms, more preferably a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms, because of its superior drying properties, and even more preferably a mixed solvent of methanol and water. In the aqueous composition, the content of water is preferably 30% by mass or more, more preferably 40% by mass or more, relative to the total mass of the solvent, and the upper limit may be 100% by mass or less.

[0191] When the photosensitive composition is an aqueous composition, the compound A in the photosensitive composition is preferably in the form of an ammonium salt, since this has better solubility in the solvent. When the photosensitive composition is applied to a thermoplastic resin layer and dried to form the photosensitive composition, ammonia, which has a boiling point lower than that of water, is likely to volatilize during drying, so that the acid group of the ammonium salt of compound A is regenerated. In other words, even if the ammonium salt of compound A is used as a starting material, it can be contained as compound A in the photosensitive layer of the transfer film.

[0192] When the photosensitive composition contains an ammonium salt of compound A, the drying conditions for the drying treatment of the coating film of the photosensitive composition include, for example, a method of heating to 40 to 150°C.

[0193] When the photosensitive composition is an aqueous composition, the pH of the photosensitive composition is preferably 7.0 to 10.0, more preferably 7.0 to 8.5, in order to provide a more excellent stability of the ammonium salt structure. [Application] The above-described photosensitive composition, the above-described transfer film, and the pattern (cured film) obtained using the above-described photosensitive composition or the photosensitive layer of the above-described transfer film can be used in various applications, such as electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, partition walls, spacers, microlenses, optical filters, antireflection films, etching resists, and plating members. More specifically, examples include protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, color filters, overcoat films for color filters, and etching resists for wiring formation.

[0194] [Pattern formation method] A transfer film may be used in the pattern formation method. The pattern formation method may be any of the above-mentioned pattern formation methods using a transfer film. Specifically, it is preferable that the method includes, in this order, a step of forming a photosensitive layer on a substrate using the above-mentioned photosensitive composition or transfer film, a step of pattern-exposing the photosensitive layer, and a step of developing the exposed photosensitive layer (for example, alkali development or organic solvent development). Examples of the step of forming a photosensitive layer using a photosensitive composition include the method of forming a photosensitive layer in the above-mentioned method for producing a transfer film. Examples of the step of pattern-exposing the photosensitive layer and the step of developing the exposed photosensitive layer (for example, alkali development or organic solvent development) include the respective steps in the pattern formation method described below. When the development is carried out using an organic solvent, it is preferable to further include a step of exposing the resulting pattern to light. Examples of the pattern forming method of the present invention include the pattern forming methods of embodiment 1 and embodiment 2. Each step of the pattern forming method will be described in detail below.

[0195] [Embodiment 1 of the pattern formation method] The pattern formation method according to the first embodiment includes steps X1 to X3. Step X2 corresponds to a step of reducing the content of carboxy groups in Compound A in the photosensitive layer by exposure. However, when the developer in Step X3 is an organic solvent developer, it is preferable to further include Step X4 after Step X3.

[0196] Step X1: A step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with the substrate, thereby laminating the transfer film and the substrate. Step X2: Step of pattern-exposing the photosensitive layer Step X3: A step of developing the photosensitive layer using a developer (e.g., an alkaline developer or an organic solvent developer). Step X4: After the development step of Step X3, a step of exposing the pattern formed by development

[0197] When an alkaline developer is used as the developer in Step X3, the photosensitive layer is preferably the photosensitive layer formed using the photosensitive composition of Embodiment X-1-a1 or X-1-a2. When an organic solvent developer is used as the developer in Step X3, the photosensitive layer is preferably the photosensitive layer of Embodiment X-1-a1. The pattern forming method of embodiment 1 is preferably applied to a transfer film including a photosensitive layer formed using the photosensitive composition of embodiment X-1-a1 and embodiment X-1-a2 described above.

[0198] Furthermore, the pattern formation method of embodiment 1 preferably includes a step of peeling off the temporary support between step X1 and step X2, and between step X2 and step X3.

[0199] <Process X1> The pattern forming method according to the first embodiment includes a step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with the substrate, and laminating the transfer film and the substrate together.

[0200] (base material) Examples of the substrate include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer. Examples of the substrates included in the substrate having a conductive layer include the above-mentioned substrates. The substrate is preferably transparent. The refractive index of the substrate is preferably 1.50 to 1.52. The substrate may be a light-transmitting substrate such as a glass substrate, and may be, for example, tempered glass such as Gorilla Glass manufactured by Corning Inc. In addition, materials used in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492 are also preferred as materials contained in the substrate. When the substrate includes a resin substrate, the resin substrate is preferably a resin film with small optical distortion and / or high transparency, such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0201] The substrate included in the substrate having a conductive layer is preferably a resin substrate, more preferably a resin film, in terms of being produced by a roll-to-roll method.

[0202] The conductive layer may be, for example, any conductive layer used in general circuit wiring or touch panel wiring. As the conductive layer, from the viewpoints of conductivity and fine line formability, one or more layers selected from the group consisting of a metal layer (e.g., metal foil), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer are preferred, a metal layer is more preferred, and a copper layer or a silver layer is even more preferred. The conductive layer in the substrate may be one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, the conductive layers are preferably made of different materials. Examples of materials for the conductive layer include elemental metals and conductive metal oxides. Examples of elemental metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. The conductivity is determined by the volume resistivity of 1×10 6 This means that the volume resistivity is less than 1×10 4 It is preferably less than Ωcm.

[0203] 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.

[0204] (Step X1 procedure) The step X1 is preferably a lamination step that involves applying pressure and heat using a roll, etc. For lamination, a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator can be used. Step X1 is preferably carried out by 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 is 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 (hereinafter also referred to as an "unwinding step") before any of the steps included in the pattern formation method of the present invention, and a step of winding the substrate (hereinafter also referred to as a "winding step") after any of the steps, and at least any of the steps (preferably all of the steps or all of the steps other than the heating step) are performed while the substrate is being transported. As the unwinding method in the unwinding step and the winding method in the winding step, a known method may be used in a manufacturing method that employs a roll-to-roll system.

[0205] <Process X2> The pattern forming method of embodiment 1 includes, after the above-mentioned step X1, a step (step X2) of patternwise exposing the photosensitive layer. Step X2 corresponds to a step of reducing the content of carboxy groups in compound A in the photosensitive layer by exposure. More specifically, it is preferable to patternwise expose the photosensitive layer using light of a wavelength that excites the specific structure in compound β (preferably compound B) and / or the specific structure in compound A in the photosensitive layer.

[0206] In the exposure step, the detailed arrangement and specific size of the pattern are not particularly limited. For example, when the pattern forming method of embodiment 1 is applied to the manufacture of circuit wiring, in order to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring manufactured by the pattern forming method of embodiment 1 and to minimize the area occupied by the lead wiring, it is preferable that at least a portion of the pattern (particularly the portion corresponding to the electrode pattern and lead wiring of the touch panel) be a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less.

[0207] The light source used for exposure can be appropriately selected as long as it irradiates light in a wavelength range capable of reducing the content of carboxy groups in compound A in the photosensitive layer (light having a wavelength that excites the specific structure in compound β (preferably compound B) and / or the specific structure in compound A in the photosensitive layer; examples include light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm). Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light emitting diodes).

[0208] The exposure dose is 10 to 10,000 mJ / cm 2 is preferred, and 50 to 3000 mJ / cm 2 is more preferred.

[0209] In step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. In order to prevent mask contamination due to contact between the photosensitive layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling the temporary support. Note that the pattern exposure may be exposure through a mask or direct exposure using a laser or the like. Before the step X3 described below, the temporary support is peeled off from the photosensitive layer.

[0210] <Process X3> The pattern forming method according to the first embodiment includes, after the step X2, a step (step X3) of developing the patternwise exposed photosensitive layer using a developer (for example, an alkaline developer or an organic solvent developer). In the photosensitive layer that has undergone step X2, the content of carboxy groups in the exposed areas of the photosensitive layer is reduced, resulting in a difference in solubility in a developer (dissolution contrast) between the exposed and unexposed areas. The formation of dissolution contrast in the photosensitive layer makes it possible to form a pattern in step X3. When the developer used in step X3 is an alkaline developer, the unexposed areas are removed by performing step X3, forming a negative pattern. On the other hand, when the developer used in step X3 is an organic solvent developer, the exposed areas are removed by performing step X3, forming a positive pattern. The resulting positive pattern must be subjected to a treatment to reduce the content of carboxy groups in compound A in step X4, which will be described later.

[0211] (alkaline developer) The alkaline developer is not particularly limited as long as it can remove the unexposed areas of the photosensitive resin layer, and known developers such as those described in JP-A No. 5-072724 can be used. The alkaline developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L. The alkaline developer may further contain a water-soluble organic solvent, a surfactant, etc. As the alkaline developer, the developer described in paragraph 0194 of WO 2015 / 093271 is preferred. The concentration of water in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. The upper limit may be less than 100% by mass. Examples of the alkaline developer include an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, and an aqueous solution of tetramethylammonium hydroxide. The concentration of the alkaline developer (the alkaline component constituting the alkaline developer) can be, for example, a 0.1% by mass aqueous solution, a 1.0% by mass aqueous solution, and a 2.38% by mass aqueous solution.

[0212] (organic solvent developer) The organic solvent developer is not particularly limited as long as it can remove the exposed portion of the photosensitive resin layer, and for example, developers containing organic solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents can be used. Organic solvent developers include, for example, cyclopentanone and propylene glycol monomethyl ether acetate. In the organic solvent developer, a plurality of organic solvents may be mixed, or may be mixed with an organic solvent other than those mentioned above or water. However, in order to fully achieve the effects of the present invention, the water content of the organic solvent developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water. The concentration of the organic solvent (total when a plurality of organic solvents are mixed) in the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. The upper limit may be 100% by mass or less.

[0213] 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 exposed photosensitive resin layer in a shower. After development, it is also preferable to spray a detergent or the like in a shower and remove development residues by scrubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0214] The pattern forming method according to the first embodiment may or may not further include a post-baking step of heat-treating the pattern including the photosensitive layer obtained by development. Post-baking is preferably carried out in an environment of 8.1 to 121.6 kPa, more preferably 50.66 kPa or higher, more preferably 111.46 kPa or lower, and even more preferably 101.3 kPa or lower. The post-baking temperature is preferably 80 to 250°C, more preferably 110 to 170°C, and even more preferably 130 to 150°C. The post-baking time is preferably from 1 to 60 minutes, more preferably from 2 to 50 minutes, and even more preferably from 5 to 40 minutes. The post-baking may be carried out in an air environment or in a nitrogen-substituted environment.

[0215] <Process X4> When the developer used in step X3 is an organic solvent developer, step X4 is carried out on the resulting positive pattern. Step X4 corresponds to a step of exposing the positive pattern obtained in step X3 to light to reduce the content of carboxy groups derived from compound A. More specifically, it is preferable to patternwise expose the photosensitive layer using light having a wavelength that excites the specific structure in compound B and / or the specific structure in compound A in the photosensitive layer.

[0216] The light source and exposure dose used for exposure are the same as those described in step X1, and the preferred embodiments are also the same.

[0217] [Embodiment 2 of the pattern formation method] Embodiment 2 of the pattern formation method comprises steps Y1, Y2P, and Y3 in this order, and further comprises step Y2Q (a step of further exposing the photosensitive layer exposed in step Y2P) between step Y2P and step Y3 or after step Y3.

[0218] Step Y1: A step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with a substrate to bond the transfer film to the substrate. Process Y2P: Process of exposing the photosensitive layer Step Y3: Developing the photosensitive layer using a developer

[0219] The pattern formation method of Embodiment 2 corresponds to an aspect applicable when the photosensitive layer further contains a photopolymerization initiator and a polymerizable compound. Therefore, the pattern formation method of Embodiment 2 is preferably applied to a transfer film including a photosensitive layer formed using the photosensitive composition of Embodiment X-1-a3 described above. Hereinafter, the pattern forming method according to the second embodiment will be described, but since steps Y1 and Y3 are similar to steps X1 and X3, respectively, a description thereof will be omitted. It should be noted that the process Y3 only needs to be performed at least after the process Y2P, and the process Y3 may be performed between the process Y2P and the process Y2Q. The pattern formation method of Embodiment 2 may or may not further include a post-bake step of heat-treating the pattern including the photosensitive layer obtained by development after step Y3. The post-bake step can be performed in the same manner as the post-bake step that may be included in the pattern formation method of Embodiment 1 described above. When step Y3 is performed between step Y2P and step Y2Q, the post-bake step may be performed before step Y2Q, or after step Y2Q, as long as it is performed after step Y3.

[0220] Furthermore, the pattern formation method according to the second embodiment preferably includes a step of peeling off the temporary support between the step Y1 and the step Y2P, and between the step Y2P and the step Y3.

[0221] <Process Y2P, Process Y2Q> The pattern formation method according to the second embodiment includes a step (step Y2P) of exposing the photosensitive layer that has been subjected to step Y1, and a step (step Y2Q) of further exposing the exposed photosensitive layer. One of the exposure treatments (step Y2P and step Y2Q) is an exposure treatment mainly for reducing the content of carboxy groups in compound A by exposure, and the other of the exposure treatments (step Y2P and step Y2Q) is an exposure treatment mainly for inducing a polymerization reaction of the polymerizable compound based on a photopolymerization initiator. Furthermore, each of the exposure treatments (step Y2P and step Y2Q) may be either a full-surface exposure or a patterned exposure, but one of the exposure treatments is a patterned exposure. For example, when step Y2P is patternwise exposure for reducing the content of carboxy groups in compound A by exposure, the developer used in step Y3 may be an alkaline developer or an organic solvent developer. However, when development is performed with an organic solvent developer, step Y2Q is usually performed after step Y3, and a polymerization reaction of the polymerizable compound based on the photopolymerization initiator is caused in the developed photosensitive layer (pattern), and the content of carboxy groups in compound A is reduced. Furthermore, for example, when step Y2P is patterned exposure for inducing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator, the developer used in step Y3 is typically an alkaline developer. In this case, step Y2Q may be performed either before or after step Y3, and when step Y2Q is performed before step Y3, it is typically patterned exposure.

[0222] In the steps Y2P and Y2Q, the light source used for exposure may be the light source used in the step X2 described above.

[0223] In the exposure for reducing the content of carboxy groups of compound A in the photosensitive layer, the exposure dose is 10 to 10,000 mJ / cm 2 is preferred, and 50 to 3000 mJ / cm 2 is more preferred. In the exposure for inducing a reaction of the polymerizable compound based on the photopolymerization initiator in the photosensitive layer, the exposure dose is 5 to 200 mJ / cm 2 is preferred, and 10 to 150 mJ / cm 2 is more preferred.

[0224] In steps Y2P and Y2Q, similar to step X2 described above, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off.

[0225] In the exposure step, the detailed arrangement and specific size of the pattern may be, for example, the embodiment in step X2.

[0226] [Preferred embodiment] The pattern formation method preferably includes Step Y1, Step Y2A, and Step Y3 in this order. It is also preferable to further include Step Y2B in this order after Step Y3. It is also preferable that one of Step Y2A and Step Y2B is an exposure step for reducing the content of carboxy groups derived from Compound A by exposure, and the other is an exposure step for initiating a polymerization reaction of the polymerizable compound based on a photopolymerization initiator.

[0227] Step Y1: A step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with a substrate to bond the transfer film to the substrate. Process Y2A: Process of pattern-exposing the photosensitive layer Step Y3: developing the photosensitive layer with an alkaline developer to form a patterned photosensitive layer. Step Y2B: Step of exposing the patterned photosensitive layer

[0228] The pattern forming method preferably includes a step of peeling off the temporary support between step Y1 and step Y2A, and between step Y2A and step Y3.

[0229] The above-mentioned step Y2A is preferably an exposure step for inducing a polymerization reaction of the polymerizable compound based on a photopolymerization initiator, and the above-mentioned step Y2B is preferably an exposure step for reducing the content of carboxy groups derived from compound A by exposure.

[0230] [Optional steps that may be included in the pattern formation method] The pattern formation method (such as the pattern formation method of embodiment 1, embodiment 2, or the preferred embodiment described above) may include any steps other than those described above (for example, other steps). For example, the following steps may be included, but the present invention is not limited to these steps.

[0231] <Cover film peeling process> When the transfer film has a cover film, the pattern forming method preferably includes a step of peeling off the cover film from the transfer film (hereinafter also referred to as a "cover film peeling step"). A known method can be used as the method of peeling off the cover film.

[0232] <Step of reducing visible light reflectance> When the substrate has a conductive layer, the pattern formation method may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer. When the substrate has a plurality of conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. An example of a treatment for reducing the visible light reflectance is oxidation treatment. For example, copper is oxidized to form copper oxide, which blackens the conductive layer, thereby reducing the visible light reflectance of the conductive layer. Suitable embodiments of the treatment for reducing 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.

[0233] <Etching process> When the substrate is a substrate having a conductive layer, the pattern forming method preferably includes 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) and step Y3 (or step Y2B) as an etching resist film. As the etching method, a wet etching method as described in paragraphs 0048 to 0054 of JP-A No. 2010-152155, or a known dry etching method such as plasma etching can be used.

[0234] For example, the etching method may be a commonly used wet etching method in which the substrate is immersed in an etching solution. The etching solution used for wet etching may be an acidic or alkaline etching solution selected appropriately depending on the target to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and aqueous solutions of mixtures of acidic components with salts such as ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines such as tetramethylammonium hydroxide, as well as aqueous solutions of mixtures of alkaline components with salts such as potassium permanganate. The alkaline component may be a combination of multiple alkaline components.

[0235] The temperature of the etching solution is preferably 45° C. or less. In the circuit wiring manufacturing method of the present invention, the pattern formed by step X3 (or step X4) and step Y3, which is used as an etching resist film, preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45° C. or less. With the above-mentioned configuration, peeling of the etching resist film is prevented during the etching step, and portions where no etching resist film is present are selectively etched. After the etching step, a cleaning step for cleaning the etched substrate and a drying step for drying the cleaned substrate may be carried out as necessary to prevent contamination of the process line.

[0236] <Other embodiments> In the above pattern forming method, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces thereof, and to form patterns on the conductive layers formed on both surfaces thereof sequentially or simultaneously. With this configuration, the first conductive pattern can be formed on one surface of the substrate and the second conductive pattern on the other surface. It is also preferable to form the patterns on both sides of the substrate using a roll-to-roll process.

[0237] [Circuit wiring manufacturing method] The transfer film may be used in the production of circuit wiring. The method for manufacturing circuit wiring may be any method for manufacturing circuit wiring using the above-mentioned transfer film, and preferably includes the steps of: contacting the surface of the photosensitive layer in the above-mentioned transfer film opposite the temporary support side with a conductive layer in a substrate having a conductive layer, and bonding the transfer film to the substrate having a conductive layer (bonding step); exposing the photosensitive layer in the bonded transfer film to a pattern (first exposure step); developing the exposed photosensitive layer using an alkaline developer to form a patterned etching resist film (etching resist film formation step); etching the conductive layer in areas where the etching resist film is not located (etching step); and peeling off the pattern (peeling step).

[0238] In the circuit wiring manufacturing method of the present invention, the laminating step, the first exposure step, and the alkali development step can all be carried out in the same procedures as steps X1, X2, and X3 in the pattern formation method according to embodiment 1 described above. Furthermore, the circuit wiring manufacturing method of the present invention preferably further includes a temporary support peeling step between the laminating step and the first exposure step or between the first exposure step and the etching resist film forming step.

[0239] Furthermore, when the photosensitive layer is formed using the photosensitive composition of embodiment X-1-a3, the etching resist film formation step may further include a second exposure step (after the development step) in which the pattern obtained through the first exposure step and the development step is exposed to light. The second exposure step can be performed in the same manner as step Y2Q of embodiment 2 of the pattern formation method described above.

[0240] The substrate having a conductive layer used in the circuit wiring manufacturing method of the present invention is the same as the substrate having a conductive layer used in the above-mentioned step X1. The circuit wiring manufacturing method of the present invention may also include other steps in addition to the above-mentioned steps. Examples of other steps include any steps that may be included in the pattern formation methods of embodiments 1 and 2.

[0241] In the method for producing circuit wiring of the present invention, it is also preferable that the steps from the laminating step to the etching step are regarded as one set and are repeated multiple times. The film used as an etching resist film can also be used as a protective film (permanent film) for the formed circuit wiring.

[0242] [Semiconductor package manufacturing method] Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as a build-up substrate manufacturing method. Specifically, the manufacturing method includes steps Z1 to Z4 in this order. Step Z1: forming a photosensitive layer on a substrate having a conductive layer using a photosensitive composition or a transfer film; Step Z2: Step of pattern-exposing the photosensitive layer Step Z3: developing the exposed photosensitive layer with an alkaline developer to form a pattern having vias Step Z4: forming a circuit pattern on the pattern

[0243] The methods for forming the substrate having a conductive layer, the photosensitive composition, the transfer film, and the photosensitive layer in step Z1 are as described above. An example of step Z2 is step X2.

[0244] [Process Z3] Step Z3 is a step of developing the exposed photosensitive layer with an alkaline developer to form a pattern having vias. An example of a method for developing using an alkaline developer is the method for developing using an alkaline developer in step X3.

[0245] The shape of the vias in the above pattern may be, for example, a square, a trapezoid, or an inverted trapezoid in cross section; or a circle or a square in front view (the shape of the via when observed from the direction in which the via bottom is visible). The shape of the vias in the pattern is preferably an inverted trapezoid in cross section, as this increases 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 10 μm or less, and most preferably 5 μm or less. The lower limit is preferably 15 μm or more, more preferably 20 μm or more. The number of vias may be one or two or more, and is preferably two or more.

[0246] [Process Z4] Step Z4 is a step of forming a circuit pattern on the pattern. As a method for forming a circuit pattern, a semi-additive process is preferred because it allows the formation of fine wiring. In the semi-additive process, first, a seed layer is formed by electroless copper plating using a palladium catalyst or the like on the via bottom, via wall surface, and the entire surface of the pattern after step Z3. The seed layer is for forming a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 μm. If the thickness of the seed layer is 0.1 μm or more, it tends to be possible to suppress a decrease in connection reliability during electrolytic copper plating, and if the thickness of the seed layer is 2.0 μm or less, it is not necessary to increase the etching amount when flash etching the seed layer between wirings, and it tends to be possible to suppress damage to the wiring during etching. Electroless copper plating is carried out by reacting copper ions with a reducing agent to deposit metallic copper on the surface of a pattern having vias. Examples of the electroless plating method and the electrolytic plating method include known plating methods. The catalyst for the electroless plating process is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating composition for the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Examples of commercially available electroless copper plating solutions include "MSK-DK" manufactured by Atotech Japan and "ThruCup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0247] After the electroless copper plating treatment, it is preferable to heat-press the surface of the photosensitive layer of the transfer film opposite to the temporary support onto the electroless copper plating using a roll laminator. The thickness of the photosensitive layer is preferably 5 to 30 μm, since this allows the thickness to be greater than the height of the wiring after electrolytic copper plating. After the transfer film is thermocompression bonded, the photosensitive layer is exposed to light, for example, through a mask on which a desired wiring pattern is drawn. Examples of the exposure method include the exposure method in step X2. After the exposure, the support of the transfer film is peeled off, and the exposed photosensitive layer is developed using an alkaline developer to form a pattern. After the pattern is formed, development residues of the photosensitive layer may be removed using plasma or the like. After development, copper electroplating is carried out to form a copper circuit layer and fill vias. After the copper electroplating, the pattern is stripped using an alkaline aqueous solution or an amine-based stripper. After the pattern is peeled off, the seed layer between the wirings is removed (flash etching). Flash etching is performed using, for example, sulfuric acid, an acidic solution such as hydrogen peroxide, and an oxidizing solution. Specific examples 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.

[0248] After the pattern peeling or flash etching step, a post-baking treatment is preferably carried out to sufficiently cure any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The heat curing conditions are preferably a curing temperature of 150 to 240° C. and a curing time of 15 to 500 minutes.

[0249] The method for manufacturing a semiconductor package may include a roughening step of roughening the pattern having vias, which is preferably performed after step Z3 and before step Z4. By carrying out the roughening step, the surface of the pattern can be roughened to improve adhesion to the circuit wiring, and smears can also be removed at the same time. The roughening step may be, for example, a known desmear treatment, and is preferably a treatment in which a roughening solution is brought into contact with the surface. Examples of the roughening solution include a roughening solution containing chromium and sulfuric acid, a roughening solution containing alkaline permanganate (for example, a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.

[0250] 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.

[0251] [Touch panel manufacturing method] The transfer film may be used in the manufacture of a touch panel. The method for manufacturing a touch panel may be any method for manufacturing a touch panel using the above-mentioned transfer film, and preferably includes the steps of contacting the surface of the photosensitive layer in the above-mentioned transfer film opposite the temporary support side 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) to bond the transfer film to the substrate having the conductive layer (bonding step), exposing the photosensitive layer in the bonded transfer film to a pattern (first exposure step), and developing the exposed photosensitive layer using an alkaline developer to form a patterned protective film or insulating film on the conductive layer (protective film or insulating film formation step).

[0252] [Method of manufacturing a semiconductor device] A known manufacturing method can be applied to the manufacturing method of the semiconductor device. Specifically, examples include a method for manufacturing a semiconductor device including the above-described pattern forming method 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, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0253] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes a pattern (cured film) obtained using the above-mentioned photosensitive composition or the above-mentioned photosensitive layer of the transfer film. The cured film may be used as an insulating film, or may be used as an insulating film in a so-called build-up substrate. [Example]

[0254] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment 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 construed 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.

[0255] [Preparation of Photosensitive Composition] The various components were mixed as shown in the table below to obtain a mixed solution. The mixed solution was then diluted to a solids ratio of MEK (methyl ethyl ketone):PGMEA (propylene glycol monomethyl ether acetate) = 36% by mass: 50% by mass: 14% by mass. When the silica was not in a slurry form, it was dispersed in a 20% by mass MEK solution to form a slurry, and then mixed.

[0256] The resulting mixture was diluted 100 times (by mass) with PGMEA to prepare a sample for particle size measurement. Using the prepared sample for particle size measurement, the particle size of the filler was confirmed to be within ±5% of the particle size listed in Table 1 using a Zetasizer Nano ZS (particle size measurement range: 0.3 nm to 10 μm, peak mode range: 0.6 nm to 8.9 μm, measurement principle: dynamic light scattering). If the desired granular shape was not obtained, the filler was dispersed using an ultrasonic homogenizer (Sonifier 450, output: 400 W, frequency: 20 Hz) to prepare a sample for particle size measurement.

[0257] [Compound A] ZFR-1491H: KAYARAD ZFR-1491H, bisphenol F type carboxylic acid modified epoxy (meth)acrylate resin (Mw=12000, acid value 98 mgKOH / g, viscosity 50 Pa·s, solid content concentration 67.5 mass% PGMEA solution), manufactured by Nippon Kayaku Co., Ltd. CCR-1171: KAYARAD CCR-1171, a cresol novolac-type carboxylic acid-modified epoxy (meth)acrylate resin (Mw=7500, acid value 99 mgKOH / g, viscosity 39 Pa·s, solids concentration 65% by mass in PGMEA solution), manufactured by Nippon Kayaku Co., Ltd. ZCR-1569H: KAYARAD ZCR-1569H, biphenyl-type carboxylic acid-modified epoxy (meth)acrylate resin (Mw=4500, acid value 99 mg KOH / g, viscosity 37 Pa·s, solids concentration 69 mass% PGMEA solution), manufactured by Nippon Kayaku Co., Ltd. ZCR-1797H: KAYARAD ZCR-1797H, biphenyl-type carboxylic acid-modified epoxy (meth)acrylate resin (Mw=8000, acid value 101 mgKOH / g, viscosity 10 Pa·s, solids concentration 61% by mass in PGMEA solution), manufactured by Nippon Kayaku Co., Ltd. ZAR-2051H: KAYARAD ZAR-2051H, bisphenol A type carboxylic acid modified epoxy (meth)acrylate resin (Mw=9500, acid value 71 mgKOH / g, viscosity 37 Pa·s, solid content 67.5 mass% PGMEA solution), manufactured by Nippon Kayaku Co., Ltd. Resin X1: The resin shown below, a modified phenolic resin with acid groups (Mw=7000, acid value 342mgKOH / g) Resin X1 was synthesized by reacting "H4" (phenol novolac resin, manufactured by Lignite Corporation, molecular weight 5000 to 8000) with methyl chloroacetate under basic conditions to hydrolyze the ester bond. The resulting resin X was diluted with PGMEA to prepare a 40% by mass PGMEA solution, which was used to prepare a photosensitive composition. Resin X2: The resin shown below, a modified phenolic resin with acid groups (Mw=12000, acid value 315mgKOH / g) Resin X2 was synthesized by reacting "TR4020G" (cresol novolac resin, manufactured by Lignite Corporation) with methyl chloroacetate under basic conditions to hydrolyze the ester bond. The resulting resin X2 was diluted with PGMEA to prepare a 40% by mass PGMEA solution, which was used to prepare the photosensitive composition. Resin X2 is a mixture of structures that can have the repeating units shown below.

[0258] [ka]

[0259] [Compound for comparison] Resin C1: Resin of methacrylic acid / methyl methacrylate / ethyl acrylate = 12% by mass / 58% by mass / 30% by mass (Mw = 65,000, acid value 78 mg KOH / g) Resin C2: the compound shown below (Mw=55,000, acid value 67 mgKOH / g, described in JP-A-01-032255)

[0260] [ka]

[0261] [Compound β] 9-Methylacridine: manufactured by Tokyo Chemical Industry Co., Ltd. Acridine: manufactured by Tokyo Chemical Industry Co., Ltd. 9-phenylacridine: manufactured by Tokyo Chemical Industry Co., Ltd.

[0262] [Filler] KE-S30: Seahoster KE-S30, spherical silica, no surface treatment, solid content 100% by mass, manufactured by Nippon Shokubai Co., Ltd. NHM-3N: Spherical silica, trimethylsilyl surface treatment, solid content 100% by mass, manufactured by Tokuyama Corporation YA050C-MJE: Spherical silica slurry, methacrylic surface treatment product, solid content concentration 50% by mass MEK slurry, manufactured by Admatechs Co., Ltd. MEK-EC-2430Z: Spherical silica slurry, epoxy silane surface treatment, solid content 30% by mass, manufactured by Nissan Chemical Industries, Ltd. ASA: Barium sulfate, no surface treatment, solids concentration 100% by mass, manufactured by Japan Solvay AZ: AZ filler, titanium-doped spherical glass filler, no surface treatment, solid content 100% by mass, manufactured by AGC

[0263] [Epoxy Compound] jER828EL: Bisphenol A epoxy compound, manufactured by Mitsubishi Chemical Corporation EPICLON N-770: Phenol novolac epoxy compound, manufactured by DIC TETRAD-X: tetrafunctional epoxy compound, manufactured by Mitsubishi Gas Chemical Company, Inc. NC-3000: Difunctional bisphenyl epoxy compound, manufactured by Nippon Kayaku Co., Ltd. TECHMORE VG3101L: Bisphenol A trifunctional epoxy compound, manufactured by Printec

[0264] [Other ingredients] DPHA: Dipentaerythritol hexaacrylate, manufactured by Tokyo Chemical Industry Co., Ltd. Irgacure OXE01: Molar absorption coefficient at 365 nm is 2400 (L / (mol cm), manufactured by BASF

[0265] [Creating transfer film] The photosensitive composition thus obtained was applied to a temporary support (PET film, Lumirror 16FB40, thickness 16 μm, manufactured by Toray Industries, Inc.) and dried to form a photosensitive layer. The thickness of the photosensitive layer was adjusted to the film thickness shown in the table below. Next, a cover film (polypropylene film, FG-201, thickness 30 μm, manufactured by Oji F-Tex Co., Ltd.) was placed on the photosensitive layer to obtain each transfer film.

[0266] [Various evaluations] [Molar absorption coefficient of compound β] The molar absorption coefficient of compound β at a wavelength of 365 nm was measured by the following procedure. Compound β (10 mg) was added to acetonitrile (500 mL) and stirred at 500 rpm for 20 minutes to obtain a measurement solution. An appropriate amount of the measurement solution was used and absorbance measurement was performed using a UV-2400PC spectrophotometer (Shimadzu Corporation). From the obtained absorbance at a wavelength of 365 nm, the molar absorption coefficient at a wavelength of 365 nm was calculated according to the Beer-Lambert law. The absorbance of acetonitrile alone was measured as a blank, and this was subtracted from the absorbance at a wavelength of 365 nm of the measurement solution to calculate the molar absorption coefficient of compound β at a wavelength of 365 nm. If compound β is not soluble in acetonitrile, the solvent used to dissolve compound β may be changed as appropriate.

[0267] [Heat resistance] The photosensitive composition was applied to a glass sheet (Corning glass, 5 cm length x 5 cm width x 1.1 mm thickness) to a dry thickness of 10 μm, and then dried to form a photosensitive layer. The resulting photosensitive layer was exposed to light using an ultra-high pressure mercury lamp. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 500 mJ / cm. 2 It was. After exposure, the sample was left to stand for 30 minutes and then developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) as the developer. After development, the sample was rinsed with pure water for 20 seconds and then air was blown to remove moisture. The developed sample was exposed to light from the opposite side of the temporary support using a high-pressure mercury lamp. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 1000 mJ / cm. 2 It was. After exposure, the sample was heat-treated at 160°C for 240 minutes. After the heat treatment, the sample was scraped off with a single-edged knife, and a total of 500 mg of evaluation samples was collected. The evaluation samples were evaluated using a TG-DTA device (TG / DTA6200, manufactured by Seiko Instruments Inc.). The final thermal weight loss rate was measured in the range from room temperature to 300°C (held at 300°C for 30 minutes) (heating rate of 10°C / min, in a nitrogen atmosphere). The measurement was repeated three times and the average value was calculated. The obtained thermal weight loss rate was evaluated according to the following criteria.

[0268] (Heat resistance evaluation criteria) A: Thermogravimetric reduction rate is 5.0% or less B: Thermogravimetric reduction rate is more than 5.0% and less than 10.0% C: Thermogravimetric reduction rate is over 10.0%

[0269] [Insulation reliability] A silicon wafer was coated with a photosensitive composition to a thickness of 10 μm on which comb-shaped wiring with a copper line / space ratio of 10 μm / 10 μm was formed. The photosensitive composition was then applied to a silicon wafer with a thickness of 5 μm and dried to form a photosensitive layer. The resulting photosensitive layer was exposed to light using an ultra-high pressure mercury lamp. The cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 500 mJ / cm. 2 It was. After exposure, the sample was left to stand for 30 minutes and then developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) as the developer. After development, the sample was rinsed with pure water for 20 seconds and then air was blown to remove moisture. The developed sample was exposed to light from the entire surface of the photosensitive layer opposite the silicon wafer using a high-pressure mercury lamp. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 1000 mJ / cm. 2 It was. After exposure, the sample was heat-treated for 240 minutes at 160° C. A voltage of 3.3 V was applied to the heat-treated sample for a certain period of time under conditions of 130° C. and 85% RH, and the insulation resistance was measured under the same conditions. The insulation resistance when a voltage of 3.3 V was first applied was compared with the insulation resistance after a certain period of time had passed, and the results were evaluated according to the following criteria.

[0270] (Insulation reliability) A: The insulation resistance did not decrease even after 200 hours. B: The insulation resistance did not decrease until 120 hours, but then decreased before 200 hours had elapsed. C: The insulation resistance did not decrease until 70 hours, but then decreased before 120 hours had elapsed. D: The insulation resistance decreased before 70 hours had elapsed.

[0271] [Decarboxylation reaction] The photosensitive composition was applied to a silicon wafer substrate to a dry thickness of 10.0 μm and dried at 75° C. for 150 seconds to form a photosensitive layer. The photosensitive layer was then exposed to light from the entire surface using an ultra-high pressure mercury lamp on the side opposite the substrate, and developed with a 0.9% by mass aqueous sodium carbonate solution at 25° C. for 40 seconds. The cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm during exposure was 500 mJ / cm. 2 It was. At this time, the IR spectra of the photosensitive layer before exposure and the cured film after development were measured, and the IR spectra of the photosensitive layer before exposure and the cured film after development were measured. -1 The rate of change when comparing the two peaks located close to each other was evaluated based on the following criteria.

[0272] (Decarboxylation reaction evaluation criteria) A: The change rate of the peak after development relative to the peak before exposure is 10% or more B: The rate of change in the peak after development relative to the peak before exposure is 5% or more and less than 10% C: The change rate of the peak after development relative to the peak before exposure is less than 5%

[0273] [Photolithography] Photolithography properties were evaluated using a 1% by mass aqueous solution of sodium carbonate. The photosensitive composition was applied to a glass sheet (Corning glass, 5 cm length x 5 cm width x 1.1 mm thickness) so as to have a dry thickness of 10 μm, and then dried to form a photosensitive layer. The obtained photosensitive layer was subjected to pattern exposure using an ultra-high pressure mercury lamp. At this time, an exposure mask having a plurality of circular light-shielding portions of φ10 μm was used. The interval between the circular light-shielding portions of the exposure mask (the distance from the center of the circle to the center of the circle) was 300 μm. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 200 mJ / cm. 2 It was. After exposure, the film was left to stand for 30 minutes and then developed for 40 seconds using a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 30°C) as the developer. After development, the film was rinsed with pure water for 20 seconds and then air was blown to remove moisture, forming holes (unexposed areas). For the obtained sample, the film thickness of the unexposed areas and the film thickness of the exposed areas were measured at three points each, and the average of the differences (corresponding to the hole depth) was calculated and evaluated according to the following criteria.

[0274] (Photolithography evaluation criteria) A: The difference in film thickness between the non-exposed area and the exposed area is 7 μm or more and 10 μm or less B: The difference in film thickness between the non-exposed area and the exposed area is 4 μm or more and less than 7 μm C: The difference in film thickness between the unexposed and exposed areas is less than 4 μm

[0275] The contents of various components and the evaluation results are shown below. The column "Solid content concentration (mass %)" indicates the solid content concentration (mass %) of each component relative to the total solid content in the photosensitive composition. The "Molar absorption coefficient (365 nm)" column indicates the molar absorption coefficient (L / (mol·cm)) of compound β at a wavelength of 365 nm. "Particle size" indicates the average primary particle size of the filler. The column "mol % relative to acid groups" indicates the total number (mol %) of structures capable of accepting electrons that compound B has relative to the total number of acid groups that compound A has.

[0276] [Table 1]

[0277] [Table 2]

[0278] It was confirmed that when compound A contains a modified phenolic resin having an acid group, the insulation reliability is more excellent (Examples 1 to 14, etc.). It was confirmed that when the photosensitive composition contained a filler and an epoxy compound, the insulation reliability was superior (Examples 1 to 8 and 15 to 19, etc.). It was confirmed that when the average primary particle size of the filler is 10 to 300 nm, the decarboxylation reaction proceeds more rapidly and the photolithography properties are also excellent (Examples 30 to 34, etc.).

[0279] [Examples 1A to 42A] Each transfer film was produced in the same manner as in Examples 1 to 42, except that the temporary support and cover film used in producing the transfer film were changed to the following materials. Temporary support: Product name "Cosmoshine (registered trademark) A4160", manufactured by Toyobo Co., Ltd., thickness 50 μm, PET film Cover film: Product name: Alphan (registered trademark) E-210F, manufactured by Oji F-Tex Co., Ltd., 50 μm thick, polypropylene film

[0280] [Examples 1B to 42B] Each transfer film was produced in the same manner as in Examples 1 to 42, except that the temporary support and cover film used in producing the transfer film were changed to the following materials. Temporary support: Product name "Cosmoshine (registered trademark) A4360", manufactured by Toyobo Co., Ltd., thickness 38 μm, PET film Cover film: Product name: Alphan (registered trademark) FG-201, manufactured by Oji F-Tex Co., Ltd., 30 μm thick, polypropylene film

[0281] [Examples 1C to 42C] Each transfer film was produced in the same manner as in Examples 1 to 42, except that the temporary support and cover film used in producing the transfer film were changed to the following materials. Temporary support: Product name "Lumirror (registered trademark) #38-U48", manufactured by Toray Industries, Inc., thickness 38 μm, PET film Cover film: Product name: Alphan (registered trademark) E-210F, manufactured by Oji F-Tex Co., Ltd., 50 μm thick, polypropylene film

[0282] [Examples 1D to 42D] Each transfer film was produced in the same manner as in Examples 1 to 42, except that the temporary support and cover film used in producing the transfer film were changed to the following materials. Temporary support: Product name "Lumirror (registered trademark) #75-U34", manufactured by Toray Industries, Inc., thickness 75 μm, PET film Cover film: Product name: Alphan (registered trademark) FG-201, manufactured by Oji F-Tex Co., Ltd., 30 μm thick, polypropylene film

[0283] [Examples 1E to 42E] Each transfer film was produced in the same manner as in Examples 1 to 42, except that the temporary support and cover film used in producing the transfer film were changed to the following materials. Temporary support: Product name "Lumirror (registered trademark) 16KS40", manufactured by Toray Industries, Inc., thickness 16 μm, PET film Cover film: Product name: Alphan (registered trademark) E-210F, manufactured by Oji F-Tex Co., Ltd., 50 μm thick, polypropylene film

[0284] [Example 101] The transfer film of Example 1 was 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, and photosensitive layers were formed 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 the following conditions: substrate temperature: 40°C, rubber roller temperature: 100°C, linear pressure: 3 N / cm, and conveying speed: 2 m / min. A pattern (φ60 μm) with vias at predetermined positions was formed on the formed photosensitive layer using the same method as in the above [Photolithography] except that the via diameter was different. The residue was then removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed. Next, a pattern was formed at predetermined positions using a known dry film resist, and electrolytic plating was performed. Next, a seed layer etching process was performed. Finally, the resist was stripped using a stripping solution, and copper wiring was formed on the cured film by heat treatment (160°C, 1 hour). The above process from lamination to heat treatment was repeated three times, and finally a solder resist was formed as the outermost layer. A semiconductor element was then sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted in a predetermined position on a printed wiring board to obtain a semiconductor package substrate. The resulting semiconductor package substrate was confirmed to operate normally.

[0285] In Example 101, semiconductor packages were produced and semiconductor package substrates were obtained in the same manner as in Example 1, except that the transfer film of Example 1 was replaced with the transfer films of Examples 2 to 42, Examples 1A to 42A, Examples 1B to 42B, Examples 1C to 42C, Examples 1D to 42D, and Examples 1E to 42E. It was confirmed that all of the obtained semiconductor package substrates operated normally. [Explanation of symbols]

[0286] 12: Temporary support 14: Photosensitive layer 16: Cover film 100: Transfer film

Claims

1. a compound A having an acid group; and a compound β having a structure that reduces the amount of the acid group contained in the compound A upon exposure to light, the compound A includes at least one selected from the group consisting of a carboxylic acid-modified epoxy (meth)acrylate resin, a modified phenolic resin having an acid group, and a compound having an acid group and a bisphenol structure, the compound β is a compound B having a structure capable of accepting electrons from the acid group of the compound A in a photoexcited state, a total number of the electron-accepting structures contained in the compound B being 3 mol % or more relative to the total number of the acid groups contained in the compound A;

2. 2. The photosensitive composition according to claim 1, wherein the compound A has an acid value of 30 to 400 mgKOH / g.

3. 3. The photosensitive composition according to claim 1, wherein the compound B comprises at least one selected from the group consisting of acridine, 9-methylacridine, and 9-phenylacridine.

4. 4. The photosensitive composition according to claim 1, wherein the compound B has a molar absorption coefficient at a wavelength of 365 nm of more than 1,000 L / (mol cm).

5. The photosensitive composition according to any one of claims 1 to 4, further comprising a filler.

6. 6. The photosensitive composition of claim 5, wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

7. 7. The photosensitive composition according to claim 5, wherein the content of the filler is 10 to 80% by mass based on the total solid content of the photosensitive composition.

8. 8. The photosensitive composition according to claim 5, wherein the filler has an average primary particle size of 10 to 300 nm.

9. 9. The photosensitive composition according to claim 5, wherein the filler has a refractive index of 1.2 to 1.

8.

10. The photosensitive composition according to any one of claims 5 to 9, wherein the filler is surface-treated.

11. the content of the compound A is 20 to 98 mass % based on the total solid content of the photosensitive composition, the content of the compound β is 1 to 30 mass % based on the total solid content of the photosensitive composition, the content of the filler is 10 to 80% by mass based on the total solid content of the photosensitive composition, a mass ratio of the content of the filler to the content of the compound A is 0.5 or more; a mass ratio of the content of the compound β to the content of the compound A is 0.7 or less; 11. The photosensitive composition according to claim 5, wherein the mass ratio of the content of the compound β to the content of the filler is 0.5 or less.

12. The photosensitive composition according to any one of claims 1 to 11, further comprising an epoxy compound.

13. 13. The photosensitive composition according to claim 12, wherein the epoxy compound comprises at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and urethane epoxy type epoxy resins.

14. 14. The photosensitive composition according to claim 12, wherein the epoxy compound has two or more epoxy groups in one molecule.

15. 15. The photosensitive composition according to claim 12, wherein the epoxy compound has an epoxy value of 90 to 290 g / eq.

16. The photosensitive composition according to any one of claims 1 to 15, wherein the photosensitive composition does not contain a polymerizable compound having a molecular weight of 2000 or less, having an ethylenically unsaturated group, and not having an acid group, or, if the photosensitive composition contains the polymerizable compound, the content of the polymerizable compound is 5 mass% or less based on the total solid content of the photosensitive composition.

17. The photosensitive composition according to any one of claims 1 to 16, which can form a photosensitive layer capable of forming a pattern by exposure to light and development using a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C.

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

19. A cured film obtained by curing the photosensitive composition according to any one of claims 1 to 17.

20. A semiconductor package comprising the cured film of claim 19.

21. forming a photosensitive layer on a substrate using the photosensitive composition according to any one of claims 1 to 17 or the transfer film according to claim 18; patternwise exposing the photosensitive layer; and developing the exposed photosensitive layer with an alkaline developer to form a pattern.

22. forming a photosensitive layer on a substrate having a conductive layer using the photosensitive composition according to any one of claims 1 to 17 or the transfer film according to claim 18; patternwise exposing the photosensitive layer; developing the exposed photosensitive layer with an alkaline developer to form a pattern having vias; forming a circuit pattern on the pattern; A method for manufacturing a semiconductor package, comprising the steps of:

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