Photosensitive composition, cured product, electronic component, and method for manufacturing cured product

Abstract

The purpose of the present invention is to provide: a cured product which is included in an electronic component and which has excellent mechanical properties and excellent migration resistance, while achieving both residue suppression in a pattern hem and excellent halftone characteristics; and an electronic component having excellent migration resistance. The present invention is a photosensitive composition containing (A) a binder resin and (C1-C1) an oxime ester compound, and further containing (B) a radical polymerizable compound and / or (F) a cross-linking agent, the (C1-C1) oxime ester compound having a structure (Ia): a condensed polycyclic heterocyclic structure comprising two rings; or a condensed polycyclic heterocyclic structure which comprises a naphthalene structure, a piperidine structure, a tetrahydropyridine structure, a dihydropyridine structure, a pyrrolidine structure or a pyrroline structure and is composed of three rings; the structure (Ib) is an oxime ester carbonyl structure; and structure (Ic): aromatic structure.

Description

Technical Field

[0001] This invention relates to a photosensitive composition, a cured product, an electronic component, and a method for manufacturing the cured product. Background Technology

[0002] In recent years, semiconductor devices with multilayered metal rewiring have attracted attention, aiming to reduce costs and achieve high integration through efficiency improvements in semiconductor manufacturing processes. The materials used in the interlayer insulating layers of such multilayered metal rewiring require high mechanical properties to withstand the stresses associated with multilayering. Furthermore, it is necessary to also suppress development residues during the formation of positive or negative patterns via photolithography. In addition, the miniaturization of wiring accompanying the high integration of semiconductor devices demands reliability related to electrical insulation, thus requiring high migration resistance.

[0003] Furthermore, in the manufacture of organic electroluminescence (hereinafter, "organic EL") displays, the following process is also applied: using a halftone photomask, a step shape is formed in the pixel segmentation layer, which has a region with a thick film thickness (hereinafter, "thick film portion") that serves as a support stage for the evaporation mask used when depositing the light-emitting material, and a thin film portion with a thinner film thickness (hereinafter, "thin film portion"). Therefore, for the materials used in the pixel segmentation layer, etc., excellent halftone characteristics are required in order to reduce process time and improve yield.

[0004] Examples of photosensitizing compositions include, for example, negative photosensitizing compositions containing polyimide and a photopolymerization initiator with a specific structure (see, for example, Patent Document 1).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2018 / 173840 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, the composition described in Patent Document 1 does not simultaneously achieve residue suppression, halftone properties, mechanical properties, and migration resistance at the pattern hem, and further improvements in these properties are desired. The object of this invention is to provide a cured product comprising an electronic component that simultaneously achieves residue suppression at the pattern hem and excellent halftone properties, while also possessing excellent mechanical properties and excellent migration resistance. Furthermore, another object of this invention is to provide an electronic component with excellent migration resistance.

[0010] Technical means to solve the problem

[0011] To solve the aforementioned problems, the photosensitive composition and electronic component of the present invention have the following structures [1] to

[20] .

[0012] [1] A photosensitive composition comprising (A) an adhesive resin and a (C1-1) oxime ester compound, and further comprising any one or both of (B) a free radical polymerizable compound and (F) a crosslinking agent, wherein the (C1-1) oxime ester compound has all of the following (Ia), (Ib) and (Ic) structures in its molecular structure.

[0013] (Ia) Structure: A condensed polycyclic heterocyclic structure consisting of two rings, or a condensed polycyclic heterocyclic structure consisting of three rings, including naphthalene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, or dihydropyrrole structures. (Ib) Structure: Oxime ester carbonyl structure.

[0014] (Ic) Structure: Aromatic structure.

[0015] [2] According to the photosensitive composition of [1], all or part of the (A) adhesive resin is a resin having the following (WA) weak acid groups in its structure (hereinafter referred to as "(A1) resin").

[0016] (WA) Weak acidic group: selected from one or more groups in the group consisting of phenolic hydroxyl, hydroxyimide, hydroxyamide, silanol, 1,1-bis(trifluoromethyl)hydroxymethyl, and mercapto.

[0017] [3] The photosensitive composition according to [1] or [2] further contains one or more of the group consisting of benzene, toluene, xylene and naphthalene, and satisfies the following condition (1).

[0018] Condition (1): The total content of benzene, toluene, xylene and naphthalene in the photosensitive composition is more than 0.010 ppm by mass and less than 1,000 ppm by mass.

[0019] [4] The photosensitive composition according to any one of [1] to [3], wherein the (Ia) structure is an indole structure, a benzoindole structure, an indolin structure, a benzoindolin structure, a benzofuran structure, a naphthofuran structure, a benzothiophene structure, a naphthothiophene structure, a benzodihydrofuran structure, a naphthodihydrofuran structure, a benzodihydrothiophene structure, or a naphthodihydrothiophene structure, and

[0020] The (Ic) structure is an aromatic structure bonded with aryl carbonyl, alkyl carbonyl, nitro, cyano, halogen atom, or heterocyclic group.

[0021] [5] The photosensitive composition according to any one of [1] to [4], wherein the (C1-1) oxime ester compound further has the following (Id) structure in its molecular structure.

[0022] (Id) Structure: any one or two of the following groups: an aliphatic group with 1 to 20 carbon atoms and an alicyclic group with 4 to 20 carbon atoms.

[0023] [6] According to the photosensitive composition described in [2] to [5], wherein the (A1) resin comprises the following (A1x) resin.

[0024] (A1x) resin: a resin having one or more of the following structural units: an imide structure, an amide structure, an oxazole structure, and a siloxane structure.

[0025] [7] According to the photosensitive composition of [6], all or part of the (A1x) resin is selected from one or more of the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamide imides, polyamide imides, polyamides, and copolymers thereof, all having a weak acidic group in their structure, and the (A1x) resin has either or both of an amine residue containing the (WA) weak acidic group and a carboxylic acid residue containing the (WA) weak acidic group.

[0026] [8] The photosensitive composition according to any one of [2] to [7], wherein the (A) adhesive resin comprises (A1) resin, the (A1) resin comprises (A1y) resin, all or part of the (A1y) resin being selected from one or more of the group consisting of phenolic resin, polyhydroxystyrene, phenolic epoxy resin, and phenolic acrylic resin.

[0027] (A1y) Resin: A resin that has phenolic hydroxyl groups in its structural units.

[0028] [9] The photosensitive composition according to any one of [1] to [8], wherein the (A) adhesive resin contains (A1) resin and a resin that does not have a (WA) weak acid group in its structure (hereinafter referred to as "(A2) resin"), the (A1) resin comprising any one or both of the following (A1x) resin and (A1y) resin, and

[0029] The (A2) resin includes any or both of the following (A2x) and (A2y) resins.

[0030] (A1x) resin: a resin having one or more of the following structural units: an imide structure, an amide structure, an oxazole structure, and a siloxane structure.

[0031] (A1y) Resin: A resin that has phenolic hydroxyl groups in its structural units.

[0032] (A2x) resin: A resin that has free radical polymerizable groups in its structure.

[0033] (A2y) resin: A resin that does not have free radical polymerizable groups in its structure.

[0034]

[10] The photosensitive composition according to any one of [1] to [9], wherein the (A) adhesive resin satisfies the following condition (P1α).

[0035] Condition (P1α): In the structure of (A) adhesive resin, the fluorine content is less than 10,000 ppm by mass.

[0036]

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

[10] further comprises an organic black pigment, all or part of which is selected from one or more of the group consisting of benzofuranone black pigments, perylene black pigments, and azobenzene black pigments.

[0037] All or part of the benzofuranone-based black pigments are compounds having at least two benzofuran-2(3H)-one structures or at least two benzofuran-3(2H)-one structures having at least two shared benzene rings, their geometric isomers, their salts, or salts of their geometric isomers.

[0038] All or part of the perylene-based black pigment is a compound having a 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole structure, its geometric isomers, its salts, or salts of its geometric isomers.

[0039] All or part of the azomethyl base-based black pigment is a compound or its salt having an azomethyl base structure and a carbazole structure.

[0040]

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

[11] further comprises an inorganic black pigment, all or part of which is selected from one or more of the group consisting of nitrides containing a metal element, carbides containing a metal element, and oxynitrides containing a metal element, wherein the metal element is selected from one or more of the group consisting of zirconium, vanadium, niobium, hafnium, and tantalum.

[0041]

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

[12] satisfies the following condition (1α).

[0042] Condition (1α): The fluorine content in the total solids of the photosensitive composition is less than 1,000 ppm by mass.

[0043]

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

[13] satisfies either or both of the following conditions (2) and (3).

[0044] Condition (2): It also contains one or more of the group consisting of acetic acid, propionic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, benzoic acid, methyl benzoic acid and trimethyl benzoic acid, wherein the proportion of these relative to the total solids of the photosensitive composition is 0.010 ppm by mass or more and 500 ppm by mass or less.

[0045] Condition (3): It also contains one or both of an aldehyde oxime compound and a ketoxime compound, which account for more than 0.010 ppm by mass and less than 500 ppm by mass relative to the total solids content of the photosensitive composition.

[0046]

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

[14] satisfies the following condition (4).

[0047] Condition (4): It also contains water, and the water content in the photosensitive composition is more than 0.010% by mass and less than 3.0% by mass.

[0048]

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

[15] , wherein a portion of the (C1-1) oxime ester compound is a compound (cis isomer) in which a group containing a carbonyl structure and a group containing an oxygen atom of an oxime structure have a cis structure relative to the C=N bond of the oxime structure within the (Ib) structure, and another portion of the (C1-1) oxime ester compound is a compound (trans isomer) in which a group containing a carbonyl structure and a group containing an oxygen atom of an oxime structure have a trans structure relative to the C=N bond of the oxime structure within the (Ib) structure, and when the total of the cis isomer and the trans isomer is set to 100% by mass, the content ratio of the cis isomer or the trans isomer is 90.0% to 99.9% by mass.

[0049]

[17] A cured product formed by curing the photosensitive composition according to any one of [1] to

[16] .

[0050]

[18] An electronic component comprising the cured material according to

[17] .

[0051]

[19] A method for manufacturing a cured product includes: (1) a step of forming a coating film of the photosensitive composition according to any one of [1] to

[16] on a substrate; (2) a step of irradiating the coating film of the photosensitive composition with active chemical rays using a photomask; (3) a step of developing the photosensitive composition using a developing solution to form a pattern of the photosensitive composition; and (4) a step of heating the pattern to obtain a cured pattern of the photosensitive composition.

[0052]

[20] An electronic component includes a cured product, wherein the cured product comprises a carbonyl compound ((C1x-DL) carbonyl compound) comprising the following (XIa) and (XIc) structures.

[0053] (XIa) Structure: A carbonyl group is bonded to a condensed polycyclic heterocyclic structure consisting of two rings, or a carbonyl group is bonded to a condensed polycyclic heterocyclic structure consisting of three rings, including naphthalene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, or dihydropyrrole structures.

[0054] (XIc) Structure: Aromatic structure.

[0055] The effects of the invention

[0056] The photosensitive composition of the present invention provides a cured product that balances residue suppression at the bottom edge of a pattern with excellent halftone properties and superior mechanical properties. Furthermore, it provides a cured product for use in electronic components with excellent migration resistance. Additionally, the electronic component of the present invention provides an electronic component with excellent migration resistance. Attached Figure Description

[0057] [ Figure 1 This is a schematic diagram illustrating the arrangement and dimensions of the light-transmitting, light-blocking, and semi-transparent portions in a halftone mask used for halftone characteristic evaluation. Detailed Implementation

[0058] The photosensitive composition of the present invention will now be described. The present invention is not limited to the embodiments described below, and various modifications can be made within the scope of achieving the inventive objective without departing from the spirit of the invention. Furthermore, the term "resin main chain" refers to the longest chain among the chains constituting the resin containing structural units. The term "resin side chain" refers to a chain among the chains constituting the resin containing structural units that branches off from or is bonded to the main chain and is shorter than the main chain. The term "resin end" refers to a structure that seals the main chain, for example, a structure derived from an end-capping agent. The term "resin structural unit" refers to a unit constituting a repeating structure in the main chain of the resin. Additionally, the term "hydrocarbon group or alkylene group containing 'XX bond' or 'XX group'" refers to a hydrocarbon group or alkylene group bonded with 'XX bond' or 'XX group', or at least two hydrocarbon groups or at least two alkylene groups linked by 'XX bond' or 'XX group'. The so-called ZZ group containing "XX structure" or "XX atom" refers to a ZZ group that is bonded with "XX structure" or "XX atom", or a ZZ group that contains "XX structure" or "XX atom" in any of its structures.

[0059] In addition, in the following description, the meanings of (Ia) structure, (Ib) structure, (Ic) structure and (Id) structure, as well as condition (1), condition (2), condition (3), condition (P1α), condition (p2α), condition (1α), condition (2α), condition (X1α) and condition (X2α), and (A1) resin, (A2) resin, (A1x) resin, (A1y) resin, (A2x) resin and (A2y) resin and (WA) weak acid group are as follows.

[0060] (Ia) Structure: A condensed polycyclic heterocyclic structure consisting of two rings, or a condensed polycyclic heterocyclic structure consisting of three rings, including naphthalene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, or dihydropyrrole structures. (Ib) Structure: Oxime ester carbonyl structure.

[0061] (Ic) Structure: Aromatic structure.

[0062] (Id) Structure: any one or two of the following groups: an aliphatic group with 1 to 20 carbon atoms and an alicyclic group with 4 to 20 carbon atoms.

[0063] Condition (1): The total content of benzene, toluene, xylene and naphthalene in the photosensitive composition is more than 0.010 ppm by mass and less than 1,000 ppm by mass.

[0064] Condition (2): It also contains one or more of the group consisting of acetic acid, propionic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, benzoic acid, methyl benzoic acid and trimethyl benzoic acid, wherein the proportion of these relative to the total solids of the photosensitive composition is 0.010 ppm by mass or more and 500 ppm by mass or less.

[0065] Condition (3): It also contains one or both of an aldehyde oxime compound and a ketoxime compound, which account for more than 0.010 ppm by mass and less than 500 ppm by mass relative to the total solids content of the photosensitive composition.

[0066] Condition (4): It also contains water, and the water content in the photosensitive composition is more than 0.010% by mass and less than 3.0% by mass.

[0067] Condition (P1α): In the structure of the (A) adhesive resin, the fluorine content is less than 10,000 ppm by mass. Furthermore, here, the fluorine content is the sum of the amount present in the ionic state and the amount present in the nonionic state (the same as in conditions (1α) and (X1α)).

[0068] Condition (P2α): The content of fluoride ions in the structure of (A) adhesive resin is less than 10,000 ppm by mass.

[0069] Condition (1α): The fluorine content in the total solids of the photosensitive composition is less than 1,000 ppm by mass.

[0070] Condition (2α): The content of fluoride ions in the total solids of the photosensitive composition is less than 1,000 ppm by mass.

[0071] Condition (X1α): The fluorine content in the cured product is less than 1,000 ppm by mass.

[0072] Condition (X2α): The content of fluoride ions in the cured product is less than 1,000 ppm by mass.

[0073] (A1) Resin: A resin whose structure contains a (WA) weak acid group.

[0074] (A2) Resin: A resin whose structure does not contain (WA) weak acid groups.

[0075] (A1x) resin: a resin having one or more of the following structural units: an imide structure, an amide structure, an oxazole structure, and a siloxane structure.

[0076] (A1y) Resin: A resin that has phenolic hydroxyl groups in its structural units.

[0077] (A2x) resin: A resin that has free radical polymerizable groups in its structure.

[0078] (A2y) resin: A resin that does not have free radical polymerizable groups in its structure.

[0079] (WA) Weak acidic group: selected from one or more groups in the group consisting of phenolic hydroxyl, hydroxyimide, hydroxyamide, silanol, 1,1-bis(trifluoromethyl)hydroxymethyl, and mercapto.

[0080] <Photosensitive Composition>

[0081] The photosensitive composition of the present invention has the structure described in [1]. By providing the structure described, the photosensitive composition of the present invention can provide a cured product that can simultaneously achieve residue suppression at the hem of the pattern and excellent halftone properties, and excellent mechanical properties. In addition, it can provide a cured product included in electronic components with excellent migration resistance. It is inferred that by containing a (C1-1) oxime ester compound having the specific structure in the photosensitive composition, the compound is compatible throughout the film, and the ultraviolet (UV) transmittance and photobleaching properties of the compound allow for UV-induced curing to the depths of the film with relatively low exposure. As a result, the amount of free radicals generated in the depths of the film can be controlled, and the reflection of UV light caused by the substrate of the substrate is also reduced, thereby suppressing excessive polymerization of free radicals, and thus it is believed to have the effect of suppressing residue at the hem of the pattern. In addition, since UV-induced curing is carried out to the depths of the film, it is inferred that it has the effect of excellent halftone properties. Furthermore, the π electrons in the carbonyl structure of the (Ib) structure and the π electrons in the (Ic) structure, or the hydrophobic structure of the (Ic) structure, interact with the residual organic matter in the opening (which is the unexposed portion in the case of negative photosensitivity and the exposed portion in the case of positive photosensitivity), promoting dissolution relative to the developer, and thus are also considered to have the effect of suppressing residue in the lower part of the pattern.

[0082] It is inferred that (C1-1) oxime ester compounds with the specific structure described above can efficiently cure the film from its surface to its depths using UV-induced curing. As a result, the degree of crosslinking in the film is increased, and the gradient of crosslinking degree within the film becomes more uniform, thus resulting in excellent mechanical properties. Furthermore, it is inferred that (C1-1) oxime ester compounds with the specific structure described above not only generate free radicals during exposure or thermal curing, but also, after bond cleavage during exposure or thermal curing, act as crosslinking agents to form crosslinked structures with resins, etc. Therefore, it is believed that the (Ia) structure contributes to the control of polarization structures or charge balance in the cured product. As a result, it is inferred that excellent migration resistance is achieved by suppressing ion migration or electromigration caused by metallic or ionic impurities that adversely affect electrical insulation. Additionally, it is inferred that high reliability is achieved in electronic components, semiconductor devices, display devices, or metal-clad laminates by suppressing metal migration or agglomeration in wiring.

[0083] <(A) Adhesive Resin>

[0084] The photosensitive composition of the present invention contains (A) a binder resin. The (A) binder resin is a heat-resistant resin that remains at least partially in the cured product obtained by curing the composition. The (A) binder resin is preferably a resin that cures by forming a cross-linked structure through a reaction. The reaction is not particularly limited to reactions carried out by heating, reactions carried out by irradiation with energy rays, etc., and a cross-linked structure can also be formed by the (F) cross-linking agent described later. The (A) binder resin is preferably a thermosetting resin.

[0085] (A) The adhesive resin is preferably an alkali-soluble resin having an acidic group or an organic solvent-soluble resin having an organic solvent-soluble structure. Here, the acidic group refers to a group with an acid dissociation constant of 23.0 or less in dimethyl sulfoxide, and the organic solvent-soluble structure is a structural unit in the resin having an organic group with 1 or more carbon atoms. The acid dissociation constant of the acidic group in dimethyl sulfoxide is preferably 21.0 or less, more preferably 20.0 or less, and even more preferably 19.0 or less. On the other hand, the acid dissociation constant of the acidic group in dimethyl sulfoxide is preferably 0.1 or more, more preferably 5.0 or more, and even more preferably 10.0 or more. The structural unit in the resin with the organic solvent-soluble structure is preferably a structural unit having an organic group with 3 or more carbon atoms, and even more preferably a structural unit having an organic group with 6 or more carbon atoms.

[0086] (A) The adhesive resin is preferably a resin with the following solubility: that is, by means of the photosensitizer (C) described later, the composition is given positive or negative photosensitivity, and positive or negative patterns can be formed. (A) The adhesive resin is more preferably an acidic group in the structural unit of the resin. From the viewpoint of pattern processing in alkaline developing solution, the acidic group is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a 1,1-bis(trifluoromethyl)hydroxymethyl group, a mercapto group, a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group. Furthermore, from the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group is more preferably a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group.

[0087] As the adhesive resin (A), a resin having a free radical polymerizable group is preferred, and more preferably, a resin having a free radical polymerizable group in its structural unit. The free radical polymerizable group is preferably an vinyl unsaturated double bond group, more preferably a photoreactive group, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms. The photoreactive group is preferably styryl, cinnamyl, maleimide, nadicimide, or (meth)acryloyl, and (meth)acryloyl is more preferred from the viewpoint of improving sensitivity during exposure and improving mechanical properties. On the other hand, an alkenyl group or an alkynyl group with 2 to 5 carbon atoms is preferably vinyl, allyl, 2-methyl-2-propenyl, crotonyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, ethynyl, or 2-propynyl, and vinyl or allyl is more preferred from the viewpoint of improving sensitivity during exposure and improving mechanical properties.

[0088] <(A1) resin, (A2) resin>

[0089] From the viewpoint of improving halftone properties, the (A) adhesive resin is preferably (A1) resin. Furthermore, the (A1) resin is more preferably provided with a (WA) weak acidic group in its structural unit. From the viewpoint of suppressing residue at the hem of the pattern and improving halftone properties, the (WA) weak acidic group is preferably a phenolic hydroxyl group, a silanol group, or a 1,1-bis(trifluoromethyl)hydroxymethyl group, more preferably a phenolic hydroxyl group. Moreover, when the (A) adhesive resin satisfies condition (P1α) or condition (P2α), or when the photosensitive composition of the present invention satisfies condition (1α) or condition (2α), the acidic group of the (A) adhesive resin is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a mercapto group, a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group, and the (WA) weak acidic group is preferably one or more groups selected from the group consisting of phenolic hydroxyl groups, hydroxyimide groups, hydroxyamide groups, silanol groups, and mercapto groups.

[0090] The moderate acidity of the (WA) weak acid group in the (A1) resin reduces the amount of developing film that is moderately developed in the halftone exposure area, thus significantly improving halftone properties by controlling solubility. The phenolic hydroxyl groups in the (WA) weak acid group significantly suppress residue at the pattern hem by promoting alkali dissolution. Furthermore, when the composition has negative photosensitivity, the phenolic hydroxyl groups in the (WA) weak acid group control excessive UV-induced curing in the exposure area and moderate the gradient of curing degree relative to the exposure amount caused by UV, thus significantly suppressing residue at the pattern hem and improving halftone properties.

[0091] From the viewpoint of suppressing residue at the bottom edge of the pattern, the (A) adhesive resin preferably includes the (A2) resin. The (A2) resin may have an acidic group different from the (WA) weak acidic group, and more preferably, it has an acidic group different from the (WA) weak acidic group in the structural unit of the resin. From the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the acidic group different from the (WA) weak acidic group is more preferably a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group.

[0092] From the viewpoint of improving sensitivity during exposure and enhancing mechanical properties, the (A) binder resin is preferably a (A1) resin having a free radical polymerizable group within its structure. Examples and preferences regarding the free radical polymerizable group are described in the description of the (A) binder resin.

[0093] Furthermore, as the (A1) resin, it is preferred to include either or both of the (A1x) resin and the (A1y) resin, and as the (A2) resin, it is preferred to include either or both of the (A2x) resin and the (A2y) resin.

[0094] From the viewpoint of improving halftone characteristics and suppressing residue at the bottom of the pattern, the (A) adhesive resin is preferably containing (A1) resin and (A2) resin, (A1) resin including either or both of (A1x) resin and (A1y) resin, and (A2) resin including either or both of (A2x) resin and (A2y) resin.

[0095] Furthermore, when (A1x) resin, (A1y) resin, (A2x) resin, and (A2y) resin have structures or groups that constitute different resins, they are classified as any one of them using the classification method shown in Table 1-1 below. When a resin can be equivalent to two or more of (A1x) resin, (A1y) resin, (A2x) resin, and (A2y) resin, the classification method determines which resin it is equivalent to.

[0096] [Table 1-1]

[0097]

[0098] Furthermore, in Table 1-1, the term "imide structure, etc." is a general term for imide structure, amide structure, oxazole structure, and siloxane structure.

[0099] (A) The adhesive resin is preferably composed of either or both of (A1x) resin and (A1y) resin, more preferably composed of (A1x) resin, and even more preferably composed of both (A1x) resin and (A1y) resin. Furthermore, (A) the adhesive resin is preferably composed of either or both of (A1x) resin and (A1y) resin, and also contains (A2x) resin, more preferably composed of (A1x) resin, (A1y) resin, and (A2x) resin. Additionally, (A) the adhesive resin is also preferably composed of (A1x) resin, (A1y) resin, and (A2x) resin, and also contains (A2y) resin. Furthermore, from the viewpoint of improving the properties of each resin, (A) the adhesive resin is also preferably composed of two or more resins selected from the group consisting of (A1x) resin, (A1y) resin, (A2x) resin, and (A2y) resin.

[0100] <(A1x) resin>

[0101] From the viewpoint of improving halftone properties, improving mechanical properties, and improving migration resistance, the (A1) resin is preferably containing the (A1x) resin. From the viewpoint of improving halftone properties, improving mechanical properties, and improving migration resistance, the (A1x) resin is preferably containing a polyimide (hereinafter, sometimes referred to as "(A1x-1) resin"), a polyimide precursor (hereinafter, sometimes referred to as "(A1x-2) resin"), a polybenzoxazole (hereinafter, sometimes referred to as "(A1x-3) resin"), a polybenzoxazole precursor (hereinafter, sometimes referred to as "(A1x-4) resin"), or a polyimide precursor selected from those having weakly acidic groups in their structure. The resin comprises one or more of the group consisting of amine imides (hereinafter, sometimes referred to as "(A1x-5) resin"), polyamide imide precursors (hereinafter, sometimes referred to as "(A1x-6) resin"), polyamides (hereinafter, sometimes referred to as "(A1x-7) resin"), polysiloxanes (hereinafter, sometimes referred to as "(A1x-8) resin"), maleimide resins, maleimide-styrene resins, maleimide-triazine resins, maleimide-oxazine resins, and copolymers thereof. In particular, it is more preferred to contain one or more of the group consisting of (A1x-1) resins, (A1x-2) resins, (A1x-3) resins, (A1x-4) resins, (A1x-5) resins, (A1x-6) resins, (A1x-7) resins, and copolymers thereof (hereinafter, these are sometimes collectively referred to as "polyimide-based resins having weakly acidic groups"). From the viewpoint of improving mechanical properties, it is preferable to use one or more resins selected from the group consisting of (A1x-1) resin, (A1x-3) resin, and copolymers thereof. From the viewpoint of improving sensitivity during exposure, it is preferable to use one or more resins selected from the group consisting of (A1x-2) resin, (A1x-4) resin, and copolymers thereof. The (A1x) resin can be a single resin or any of these copolymers.

[0102] The (A1x) resin has imide, amide, oxazole, or siloxane structures in its structural units, thereby improving its mechanical properties. Furthermore, since these structures trap metallic or ionic impurities that adversely affect electrical insulation, it is inferred that they can suppress ion migration or electromigration, thus improving migration resistance.

[0103] On the other hand, from the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, improving halftone properties, and improving mechanical properties, the (A2x) resin and (A2y) resin are preferably composed of one or more of the group consisting of polyimides, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyamide-imides, polyamide-imide precursors, polyamides, maleimide resins, maleimide-styrene resins, maleimide-triazine resins, maleimide-oxazine resins, and copolymers thereof, none of which have weakly acidic groups in their structure. In particular, it is more preferable that they are composed of one or more of the group consisting of polyimides, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyamide-imides, polyamide-imide precursors, polyamides, and copolymers thereof (hereinafter, these are sometimes collectively referred to as "polyimide-based resins without weakly acidic groups").

[0104] From the viewpoint of suppressing residue at the hem of the pattern and improving halftone properties, mechanical properties, and migration resistance, the (A1x) resin is preferably one or more of the group consisting of (A1x-1) resin, (A1x-2) resin, (A1x-3) resin, (A1x-4) resin, (A1x-5) resin, (A1x-6) resin, and copolymers thereof, and the (A1x) resin has either or both of an amine residue containing a (WA) weak acid group and a carboxylic acid residue containing a (WA) weak acid group.

[0105] More preferably, it is selected from the group consisting of (A1x-1) resin, (A1x-2) resin, (A1x-3) resin, (A1x-4) resin, (A1x-5) resin, (A1x-6) resin, and copolymers thereof, and has one or more of the group consisting of amine residues selected from general formula (11) and amine residues selected from general formula (13), and one or more of the group consisting of carboxylic acid residues selected from general formula (11), general formula (12), and general formula (14).

[0106] [Chemistry 1]

[0107]

[0108] In general formulas (11) to (14), R 31 ~R 38 Each of these groups independently represents 1,1-bis(trifluoromethyl)hydroxymethyl or mercapto. 39 ~R 42 Each of the following can be independently represented: a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a alkyl halide having 1 to 6 carbon atoms. R 61 ~R 68Each of the following can be independently represented: a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms. 11 X 12 and X 16 Each can be independently represented as a direct bond, a hydrocarbon group, a hydrocarbon group containing an ether bond, or an amide group bonded to a hydrocarbon group. X 13 ~X 15 Each can be represented independently as a hydrocarbon group, a hydrocarbon group containing an ether bond, or an amide group bonded to a hydrocarbon group. 11 ~Y 14 Each of the following groups independently represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a hydrocarbon group, a hydrocarbon group containing an ether bond, a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, a hydrocarbon group containing a carbonyloxy group, or a hydrocarbon group containing a carbonyl amide group. a, b, c, d, e, and f independently represent integers from 0 to 4. g, h, i, j, m, and n independently represent integers from 0 to 4. k and l independently represent integers from 0 to 3. o, p, q, r, s, t, u, and v independently represent integers from 0 to 3. w, x, y, and z independently represent integers from 0 to 6. Furthermore, 1 ≦ a + g ≦ 4, and 1 ≦ b + h ≦ 4. Additionally, 1 ≦ c + i ≦ 4, and 1 ≦ d + j ≦ 4. Furthermore, 1 ≦ e + m ≦ 4, and 1 ≦ f + n ≦ 4. This represents the bond nodes in the resin. In the resin molecule, the locations of structures of general formula (11) to general formula (14) are not restricted.

[0109] In general formulas (11) to (14), the halogen atom is preferably a fluorine atom. The alkyl halide is preferably a fluorinated alkyl halide. In X 11 ~X 16 In this context, the hydrocarbon group, the hydrocarbon group containing an ether bond, and the amide group to which the hydrocarbon group is bonded are preferably alkylene groups having 1 to 10 carbon atoms, cycloalkylene groups having 4 to 10 carbon atoms, arylene groups having 6 to 15 carbon atoms, or arylalkylene groups having 10 to 20 carbon atoms. In Y 11 ~Y 14 In the presence of hydrocarbon groups and hydrocarbon groups containing ether bonds, the hydrocarbon groups are preferably alkylene groups having 1 to 10 carbon atoms, cycloalkylene groups having 4 to 10 carbon atoms, or arylene groups having 6 to 15 carbon atoms. In Y 11 ~Y 14In the resin, the hydrocarbon group containing the carbonyl group and the hydrocarbon group containing the carbonyl amide group preferably have 1 to 15 carbon atoms, and the hydrocarbon group is preferably an aliphatic structure, an alicyclic structure, an aromatic structure, a condensed polycyclic structure, or a condensed polycyclic heterocyclic structure. The substituents and structures may have heteroatoms, and may be either unsubstituted or substituted. In addition, the amine residue represented by general formula (13) is preferably capable of forming a benzoxazole ring. That is, preferably in resins having a benzoxazole ring in the structural unit of the resin, the benzoxazole ring has an amine residue represented by general formula (13). In addition, it is also preferred that the phenolic hydroxyl group in the amine residue represented by general formula (11) reacts with any or both of the structure and the group in the resin to form a benzoxazole ring.

[0110] From the viewpoint of improving the aforementioned properties, the total percentage of amine residues represented by general formulas (11) and (13) in all amine residues of each resin, and the total percentage of carboxylic acid residues represented by general formulas (11), (12), and (14) in all carboxylic acid residues, either or both, are preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more. On the other hand, from the viewpoint of improving the aforementioned properties, the total percentage of amine residues represented by general formulas (11) and (13), and the total percentage of carboxylic acid residues represented by general formulas (11), (12), and (14), either or both, are preferably 100 mol% or less, more preferably 90 mol% or less, and even more preferably 70 mol% or less.

[0111] From the viewpoint of improving sensitivity during exposure and enhancing mechanical properties, the (A1x) resin is preferably one having a free radical polymerizable group. Examples and preferences of free radical polymerizable groups are described in the description of the (A) adhesive resin. The free radical polymerizable group is preferably one or more selected from the group consisting of general formulas (51) to (55). The free radical polymerizable group is preferably obtained by reacting any one or a portion of either or both of the phenolic hydroxyl and carboxyl groups present in the resin with a compound having a free radical polymerizable group.

[0112] [Chemistry 2]

[0113]

[0114] In general formulas (51) to (55), X 21 ~X 24 Each can be independently represented as an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. X 25 This represents an organogroup with a divalent to hexavalent oxidation state. X 26 Represents a direct bond or a divalent to hexavalent organic group. R181 ~R 202 Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a, b, c, d, and e can independently represent 0 or 1. f and g can independently represent integers from 1 to 5.

[0115] In general formulas (51) to (55), X 25 Preferably, it is an aliphatic group with a divalent to hexavalent valence, and more preferably, it is a hydrocarbon group with a divalent to hexavalent valence and 1 to 10 carbon atoms. X 26 Preferably, it is a direct bond or an aliphatic group with divalent to hexavalent valence, more preferably a hydrocarbon group with divalent to hexavalent valence and 1 to 10 carbon atoms. The substituent and structure may have heteroatoms, and may be either unsubstituted or substituted.

[0116] From the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, improving mechanical properties, and improving migration resistance, (A1x) resin is preferably an (A1x) resin containing either a (A1x) resin without free radical polymerizable groups or a (A1x) resin containing free radical polymerizable groups. It is believed that by adopting the aforementioned structure, the (A1x) resin without free radical polymerizable groups can effectively suppress residue at the bottom edge of the pattern due to its acidic or organic solvent-soluble structure, as well as capture the metal or ionic impurities. On the other hand, the (A1x) resin containing free radical polymerizable groups can improve sensitivity during exposure and increase the degree of cross-linking of the film by promoting free radical polymerization. Through this functional separation in the (A1x) resin, the effect of improving multiple properties becomes significant.

[0117] From the viewpoint of improving sensitivity during exposure, the acid equivalent of the (Alx) resin is preferably 200 g / mol or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern, the acid equivalent of the (Alx) resin is preferably 600 g / mol or less. Here, "exposure" refers to irradiation by reactive chemical rays (radiation), such as visible light, ultraviolet light, electron beams, or X-rays. Hereinafter, "exposure" refers to irradiation by reactive chemical rays (radiation). From the viewpoint of suppressing residue at the bottom edge of the pattern, the double bond equivalent of the (Alx) resin is preferably 200 g / mol or more. On the other hand, from the viewpoint of improving sensitivity during exposure, the double bond equivalent of the (Alx) resin is preferably 3,000 g / mol or less.

[0118] <Polyimide resins with weakly acidic groups, and polyimide resins without weakly acidic groups>

[0119] The following is a summary of polyimide-based resins having weakly acidic groups as (A1x) resins, and polyimide-based resins not having weakly acidic groups as (A2x) or (A2y) resins. These resins will sometimes be collectively referred to as polyimide-based resins. Examples of polyimide precursors include: polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide. Examples of polyimides include resins obtained by dehydrating and ring-closing a polyimide precursor. Examples of polybenzoxazole precursors include: polyhydroxyamide. Examples of polybenzoxazole precursors include: resins obtained by dehydrating and ring-closing a polybenzoxazole precursor. Examples of polyamide-imide precursors include resins obtained by reacting tricarboxylic anhydrides, etc., with diamines, etc. Examples of polyamide-imides include: resins obtained by dehydrating and ring-closing a polyamide-imide precursor. Examples of polyamides include resins obtained by reacting dicarboxylic acid chlorides with diamines.

[0120] From the viewpoint of improving mechanical properties, the polyimide precursor is preferably having either or both of ammonium ester and ammonium acid amide structural units. Alternatively, the polyimide precursor may also have an imide ring-closed structural unit formed by ring-closing a portion of an ammonium acid amide structural unit, an ammonium ester structural unit, or an imide ring-closed structural unit. The polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, and polyamide-imide precursor may also be copolymers with polyamides.

[0121] From the viewpoint of improving sensitivity during exposure, polyimide-based resins are preferably those containing either or both of carboxylic acid residues having fluorine atoms and amine residues having fluorine atoms. The combined percentage of carboxylic acid residues having fluorine atoms and amine residues having fluorine atoms in all carboxylic acid residues and all amine residues in each resin is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%. The preferred ranges for the combined percentage of amine residues having fluorine atoms in all amine residues and the combined percentage of carboxylic acid residues having fluorine atoms in all carboxylic acid residues are also the same as described above.

[0122] From the viewpoint of improving storage stability, polyimide-based resins are preferably structured with a structure in which the ends of the resin are sealed using a monoamine, dicarboxylic anhydride, or a monocarboxylic acid derivative. From the viewpoint of improving sensitivity during exposure and improving mechanical properties, polyimide-based resins are preferably those having free radical polymerizable groups or crosslinking groups at the ends of the resin that can react with the resin, etc., more preferably having maleimide groups or nadicimide groups. Examples of acidic monomers having these groups include maleic anhydride or nadic anhydride.

[0123] <(A) Fluorine content and fluoride ion content in the structure of the adhesive resin>

[0124] From the viewpoint of suppressing residue at the hem of the pattern and improving migration resistance, the adhesive resin (A) is preferably satisfied (P1α). The adhesive resin (A) is more preferably satisfied (P2α). Similarly, when the adhesive resin (A) is a polyimide-based resin, from the viewpoint of suppressing residue at the hem of the pattern and improving migration resistance, it is also preferable to satisfy condition (P1α), and more preferably to satisfy condition (P2α).

[0125] From the viewpoint of the effects of the invention, relative to the mass of the adhesive resin (A), the fluorine content in the structure of the adhesive resin (A) is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, further preferably 0.030 ppm by mass or more, further preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of the effects of the invention, relative to the mass of the adhesive resin (A), the fluorine content is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, further preferably 1,000 ppm by mass or less, further preferably 500 ppm by mass or less, particularly preferably 300 ppm by mass or less, and most preferably 100 ppm by mass or less. Furthermore, the fluorine content is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, further preferably 10 ppm by mass or less, further preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.

[0126] The preferred range of the content of fluoride ions in the structure of adhesive resin (A) is also the same as the preferred range of the fluorine content in the structure of adhesive resin (A).

[0127] In the structure of adhesive resin (A), the fluorine content can also be 0 ppm by mass. The content of fluoride ions in the structure of adhesive resin (A) can also be 0 ppm by mass.

[0128] By including (A) adhesive resins with a fluorine content below a specific value in the photosensitive composition, and by ensuring that the content of nonionic fluorine atoms or fluoride ions or fluorine-containing anions derived from these resins is below a specific value, it is inferred that protons in the photosensitive composition are locally activated through interactions such as hydrogen bonds among the components. Therefore, it is believed that the effect of suppressing residue at the bottom edge of the pattern becomes significant through its solubility-promoting effect relative to the developer. Furthermore, it is believed that by intentionally setting the content of the aforementioned component in the resin below a specific value, the content of the aforementioned component in the cured product of the photosensitive composition can also be reduced, thereby controlling the polarization structure or charge balance in the cured product. As a result, it is inferred that migration resistance is improved by suppressing ion migration or electromigration caused by metallic or ionic impurities that adversely affect electrical insulation.

[0129] <Polysiloxanes and other resins>

[0130] The following is a summary of (A1x) resins other than polyimide-based resins with weakly acidic groups, and (A2x) or (A2y) resins other than polyimide-based resins without weakly acidic groups. Furthermore, polysiloxanes have silanol groups and contain siloxane structures in their structural units, thus they can be considered resins with weakly acidic groups.

[0131] From the viewpoint of pattern processing properties in alkaline developing solutions, polysiloxanes are preferably organosilane units containing acidic groups, and from the viewpoint of improving halftone properties, organosilane units containing (WA) weakly acidic groups are more preferred. Examples and preferences of acidic groups and (WA) weakly acidic groups are described in the description of adhesive resin (A). From the viewpoint of improving sensitivity during exposure and improving mechanical properties, polysiloxanes are preferably those containing free radical polymerizable groups, and more preferably organosilane units containing free radical polymerizable groups. Examples and preferences of free radical polymerizable groups are described in the description of adhesive resin (A). From the viewpoint of improving halftone properties, improving mechanical properties, and improving migration resistance, polysiloxanes are preferably those having a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure, and more preferably organosilane units containing naphthyl, anthracene, biphenyl, phenyl, tolyl, or methoxyphenyl.

[0132] Maleimide resin is a resin having at least two maleimide groups. Maleimide-styrene resin is a resin having maleimide groups and units derived from styrene derivatives. Maleimide-triazine resin is a resin having maleimide groups and units comprising a triazine structure. Maleimide-oxazine resin is a resin having maleimide groups and units comprising an oxazine structure. These are resins different from polyimide-based resins.

[0133] <(A1y) resin>

[0134] From the viewpoints of suppressing residue at the hem of the pattern, improving halftone properties, and improving mechanical properties, the (A1) resin is preferably a resin comprising (A1y), wherein all or part of the (A1y) resin is selected from one or more of the group consisting of phenolic resin, polyhydroxystyrene, phenolic epoxy resin, and phenolic acrylic resin. The (A1y) resin may be a single resin or any copolymer thereof.

[0135] From the viewpoints of suppressing residue at the hem of the pattern, improving halftone properties, and improving migration resistance, the (A1y) resin is preferably one or more of the group consisting of structural units selected from (y1) and (y2) described below, or preferably satisfies the following condition (y3). Furthermore, it is more preferable that it satisfies the following condition (y3) and has either or both of the (y1) and (y2) structural units. Additionally, from the viewpoints of suppressing residue at the hem of the pattern, improving halftone properties, improving mechanical properties, and improving migration resistance, the (A1y) resin is preferably one having the (y1) structural unit.

[0136] (y1) Structural unit: A structural unit containing at least two phenolic hydroxyl groups.

[0137] (y2) Structural unit: a structural unit containing phenolic hydroxyl groups and aromatic groups.

[0138] Condition (y3): includes structural units containing phenolic hydroxyl groups and structural units containing second aromatic groups.

[0139] In structural unit (y1), at least two phenolic hydroxyl groups are bonded to the same or different aromatic rings, preferably to different aromatic rings, and also preferably to different aromatic rings in a condensed polycyclic structure. Here, the aromatic group in structural unit (y2) is an aromatic group different from the aromatic ring bonded to the phenolic hydroxyl group. Furthermore, the second aromatic group in condition (y3) is an aromatic group other than the aromatic ring bonded to the phenolic hydroxyl group. The term "second aromatic group" is used to distinguish it from the aromatic group in structural unit (y2) (which refers to an aromatic group different from the aromatic ring bonded to the phenolic hydroxyl group).

[0140] The phenolic resin is preferably a phenolic varnish resin, a soluble phenolic resin, or a phenolic alkyl resin. The phenolic resin is preferably one with a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, an aromatic structure, or a heterocyclic structure.

[0141] Polyhydroxystyrene is preferably a unit derived from a (meth)acrylate derivative comprising a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure, or a unit derived from a styrene derivative.

[0142] Examples of phenol-containing epoxy resins include resins obtained by reacting polyfunctional epoxy compounds with phenolic compounds having epoxy reactive groups, preferably phenol-containing calomel resins or phenol-containing epoxy-modified resins. Phenolic-containing epoxy-modified resins are preferably phenol-containing epoxy ester resins. Phenolic-containing calomel resins are preferably those having a condensed polycyclic structure or a condensed polycyclic heterocyclic structure. Phenolic-containing epoxy resins are preferably those having a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure.

[0143] Examples of phenol-containing acrylic resins include resins obtained by further reacting the acrylic resin described below with a phenolic compound having an addition-reactive group. Additionally, resins obtained by free-radical copolymerization of a copolymer component having phenolic hydroxyl groups with other copolymer components such as (meth)acrylic acid derivatives are also examples. Furthermore, phenol-containing acrylic resins are different from polyhydroxystyrene resins. Phenolic-containing acrylic resins are preferably those having units derived from (meth)acrylic ester derivatives containing condensed polycyclic structures, condensed polycyclic heterocyclic structures, or aromatic structures, or units derived from styrene derivatives.

[0144] These resins contain condensed polycyclic structures, condensed polycyclic heterocyclic structures, aromatic structures, or heterocyclic structures, preferably fluorene, anthracene, naphthalene, or tricyclic [5.2.1.0]. 2,6 Decane structure, adamantane structure, xanthane structure, isoindolinetone structure, biphenyl structure, benzene structure, bisphenol A structure, bisphenol F structure, bisphenol AF structure, isocyanuric acid structure, or triazine structure.

[0145] <(A2x) resin and (A2y) resin>

[0146] From the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, and improving mechanical properties, the (A2) resin preferably contains (A2x) resin, and from the viewpoints of suppressing residue at the bottom edge of the pattern and improving halftone properties, it is preferable to also contain (A2y) resin. From the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, and improving mechanical properties, the (A2x) resin preferably contains one or more resins selected from the group consisting of resins containing polycyclic side chains, acid-modified epoxy resins, and acrylic resins. The (A2x) resin can be a single resin or any copolymer of these. On the other hand, from the viewpoints of suppressing residue at the bottom edge of the pattern and improving halftone properties, the (A2y) resin preferably contains one or more resins selected from the group consisting of resins containing polycyclic side chains, acid-modified epoxy resins, and acrylic resins. The (A2y) resin can be a single resin or any copolymer of these.

[0147] In cases where (A) adhesive resin contains (A1) resin and (A2) resin, (A1) resin contains either or both of (A1x) resin and (A1y) resin, and (A2) resin contains either or both of (A2x) resin and (A2y) resin, examples and preferred formulations of (A2x) resin and (A2y) resin are described as follows.

[0148] From the viewpoint of improving migration resistance, resins containing polycyclic side chains are preferably carboxylate resins having a condensed polycyclic structure or a condensed polycyclic heterocyclic structure. From the viewpoint of improving migration resistance, acid-modified epoxy resins are preferably epoxy (meth)acrylate resins having a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure. From the viewpoint of improving migration resistance, acrylic resins are preferably resins having units derived from (meth)acrylate derivatives containing a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure, or units derived from styrene derivatives. Additionally, resins having units derived from (meth)acrylate derivatives having an epoxy group are also preferred. The condensed polycyclic structure, condensed polycyclic heterocyclic structure, or aromatic structure in these resins is preferably a fluorene structure, anthracene structure, naphthalene structure, or tricyclic [5.2.1.0]. 2,6 [Decane structure, adamantane structure, xanthane structure, isoindolineone structure, biphenyl structure, or benzene structure.]

[0149] From the viewpoint of improving halftone properties, improving mechanical properties, and improving migration resistance, the total content of (A1x) resin in 100% by mass of (A) adhesive resin is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and particularly preferably 70% by mass or more. On the other hand, from the viewpoint of suppressing residue at the hem of the pattern, the total content of (A1x) resin relative to 100% by mass of (A) adhesive resin is preferably 100% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less. In addition, from the viewpoint of suppressing residue at the hem of the pattern, improving halftone properties, and improving mechanical properties, the total content of (A1y) resin relative to 100% by mass of (A) adhesive resin is preferably 5.0% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. On the other hand, from the viewpoint of improving mechanical properties, the total content ratio of (A1y) resin relative to 100% by mass of (A) adhesive resin is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. Furthermore, from the viewpoint of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, improving halftone characteristics, and improving mechanical properties, the total content ratio of (A2x) resin and (A2y) resin relative to 100% by mass of (A) adhesive resin is preferably 5.0% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more. On the other hand, from the viewpoint of improving mechanical properties, the total content ratio of (A2x) resin and (A2y) resin relative to 100% by mass of (A) adhesive resin is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0150] From the viewpoint of improving the properties of each resin, the content of (A) binder resin in the total solids content of the photosensitive composition of the present invention is preferably 10% by mass or more. On the other hand, from the viewpoint of improving the properties of each resin, the content of (A) binder resin is preferably 75% by mass or less. Furthermore, the total solids content of the composition refers to the total mass of all components except the solvent in the composition. In addition, the solids content concentration can be calculated by heating 1 g of the composition at 150°C for 30 minutes to evaporate and dry it, measuring the mass remaining after heating, and calculating the solids content concentration based on the mass before and after heating.

[0151] <(B) Free radical polymerizable compounds>

[0152] The photosensitive composition of the present invention contains either or both of a (B) radical polymerizable compound (hereinafter, sometimes referred to as "(B) compound") and a (F) crosslinking agent. The (B) compound refers to a compound having a radical polymerizable group. Examples and preferred embodiments of the radical polymerizable group are described in the description of the (A) adhesive resin. From the viewpoint of promoting radical polymerization, improving sensitivity during exposure, and improving mechanical properties, the radical polymerizable group is preferably (meth)acryloyl. From the viewpoint of improving sensitivity during exposure and improving mechanical properties, the number of radical polymerizable groups in the (B) compound is preferably two or more in one molecule, more preferably three or more, and even more preferably four or more. On the other hand, from the viewpoint of improving mechanical properties and improving migration resistance, the number of radical polymerizable groups is preferably twelve or less, more preferably ten or less, even more preferably eight or less, and particularly preferably six or less.

[0153] When the photosensitive composition of the present invention contains (A) a binder resin and (B) a compound, when the total amount of (A) a binder resin and (B) a compound is 100 parts by mass, from the viewpoint of improving halftone properties, improving mechanical properties, and improving migration resistance, the content of (A) a binder resin is preferably 25 parts by mass or more, more preferably 35 parts by mass or more, and even more preferably 45 parts by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the content of (A) a binder resin is preferably 85 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less. Furthermore, when the total amount of (A) a binder resin and (B) a compound is 100 parts by mass, from the viewpoint of improving the aforementioned properties, the content of (B) a compound is preferably 15 parts by mass or more. On the other hand, from the viewpoint of improving the aforementioned properties, the content of (B) a compound is preferably 75 parts by mass or less.

[0154] <Compound (B1) ~ Compound (B5)>

[0155] From the viewpoint of improving sensitivity during exposure and improving mechanical properties, the photosensitive composition of the present invention preferably satisfies the following conditions ( ),condition( ), and conditions ( At least one of the following.

[0156] condition( ): (B) compound contains (B1) compound and (B2) compound.

[0157] condition( ): (B) compound contains (B3) compound and (B4) compound.

[0158] condition( ): (B) Compound contains (B1) or (B2) compound, and also contains (B3) or (B4) compound.

[0159] Furthermore, the compounds (B1) to (B4) refer to the following compounds, and the (I-b1) structure, (I-b2) structure, (I-b3) structure, and (I-b4) structure refer to the following structures respectively.

[0160] (B1) Compounds: Compounds having an (I-b1) structure and having at least two free radical polymerizable groups.

[0161] (B2) Compound: A compound having an (I-b2) structure, having a structure including an aliphatic structure, and having at least two free radical polymerizable groups.

[0162] (B3) Compounds: Compounds having at least two (meth)acryloyl groups and also having an (I-b3) structure.

[0163] (B4) Compounds: Compounds having at least two (meth)acryloyl groups and also having an (I-b4) structure.

[0164] (I-b1) Structure: includes condensed polycyclic alicyclic structures, alicyclic structures, or heterocyclic structures.

[0165] (I-b2) Structure: Structures that include condensed polycyclic structures, condensed polycyclic heterocyclic structures, or aromatic structures.

[0166] (I-b3) structure: a structure in which at least two (meth)acryloyl groups are linked by a minimum of 4 to 10 atoms and contain an aliphatic structure.

[0167] (I-b4) structure: a structure in which at least two (meth)acryloyl groups are linked by a minimum number of 11 to 45 atoms and contains an aliphatic structure.

[0168] From the viewpoint of improving mechanical properties, the (I-b1) structure in the (B1) compound is preferably a condensed polycyclic alicyclic structure, more preferably a tricyclic [5.2.1.0]. 2,6 The (I-b1) structure is preferably a decane or adamantane structure. Furthermore, from the viewpoint of improving mechanical properties and migratory resistance, the (I-b1) structure is preferably a heterocyclic structure, more preferably a nitrogen-containing cyclic structure, and even more preferably a cyclic structure having at least two nitrogen atoms, particularly preferably an isocyanuric acid structure or a triazine structure. The heterocyclic structure in the (I-b1) structure preferably has one or more nitrogen atoms, more preferably two or more, and even more preferably three or more. On the other hand, the number of nitrogen atoms is preferably six or less, more preferably four or less.

[0169] (B1) The compound is preferably a structure that also includes an aliphatic structure.

[0170] From the viewpoint of improving sensitivity during exposure and improving migration resistance, the aliphatic structures that may be included in compounds (B1) to (B4) are preferably alkylene, oxoalkylene, alkylene containing a hydroxyl group, oxoalkylene containing a hydroxyl group, alkylene carbonyl, oxoalkylene carbonyl, or aminoalkylene carbonyl, respectively. These aliphatic structures are preferably derived from aliphatic polyfunctional alcohols. Furthermore, compounds (B3) and (B4) are compounds different from compounds (B1) and (B2) and do not have any of the following structures: alicyclic polycyclic, alicyclic, heterocyclic, condensed polycyclic, condensed polycyclic heterocyclic, or aromatic.

[0171] From the viewpoint of improving halftone properties and mechanical properties, the condensed polycyclic structure in the (I-b2) structure of compound (B2) is preferably a fluorene structure, a dihydroindene structure, or a naphthalene structure. Furthermore, from the viewpoint of improving mechanical properties, the condensed polycyclic heterocyclic structure in the (I-b2) structure is preferably an xanthracene structure, an indolinone structure, or an isoindolinone structure. Additionally, from the viewpoint of improving halftone properties and mechanical properties, the aromatic structure in the (I-b2) structure is preferably a benzene structure or a biphenyl structure.

[0172] In the case of compounds (B3) or (B4) having two (meth)acryloyl groups, the minimum number of atoms in the (I-b3) or (I-b4) structure refers to the minimum number of carbon atoms and heteroatoms between the carbonyl carbons containing the two (meth)acryloyl groups. Furthermore, atoms bonded to the carbon atoms and heteroatoms between the carbonyl carbons are not included in the calculation of the minimum number of atoms. For example, if an oxygen atom, an propylene group, and an oxygen atom are present between the carbonyl carbons, the minimum number of atoms is five. Additionally, in the case of compounds (B3) or (B4) having three or more (meth)acryloyl groups, the minimum number of atoms refers to the minimum number of carbon atoms and heteroatoms including the carbonyl carbons connecting all the (meth)acryloyl groups. Similarly, atoms bonded to the carbon atoms and heteroatoms connecting the carbonyl carbons are not included in the calculation of the minimum number of atoms.

[0173] It is inferred that by setting the minimum number of atoms in the (I-b3) structure within a specific range, the (B3) compound can further reduce the low molecular weight of the (B) compound in the cured product and improve migration resistance. The minimum number of atoms in the (I-b3) structure is preferably five or more, more preferably six or more. On the other hand, the minimum number of atoms in the (I-b3) structure is preferably nine or less, more preferably eight or less. On the other hand, by setting the minimum number of atoms in the (I-b4) structure within a specific range, the (B4) compound significantly improves the sensitivity during exposure by increasing the probability of collisions between (meth)acryloyl groups or between (meth)acryloyl groups and other free radical polymerizable groups due to increased molecular mobility. The minimum number of atoms in the (I-b4) structure is preferably thirteen or more, more preferably fifteen or more, further preferably seventeen or more, and particularly preferably twenty or more. On the other hand, the minimum number of atoms in the (I-b4) structure is preferably forty or less, more preferably thirty-five or less, further preferably thirty or less, and particularly preferably twenty-five or less.

[0174] The (B) compound, generated by free radicals during exposure or heating, can improve the crosslinking degree of the cured product. Furthermore, it can achieve an increased crosslinking degree due to the reaction with the free radical polymerizable groups of the resin's side chains or ends, thus significantly improving mechanical properties. Additionally, it is inferred that the (B) compound having the aliphatic structure, through the reduction of low-molecular-weight components derived from the (B) compound in the cured product, can suppress ion migration or electromigration, thereby improving migration resistance.

[0175] From the viewpoint of improving halftone properties and mechanical properties, compound (B) is preferably a compound containing one or more compounds selected from the group consisting of compounds (B1), (B2), (B3), and (B4), and also containing a compound having a structure comprising a condensed polycyclic structure or a condensed polycyclic heterocyclic structure, and having at least two free radical polymerizable groups (the compound in question is referred to as "compound (B5)"). Furthermore, compound (B5) is a compound different from compound (B2) and does not have a structure comprising an aliphatic structure. The condensed polycyclic structure in compound (B5) is preferably a fluorene structure, a dihydroindene structure, or a naphthalene structure. Additionally, the condensed polycyclic heterocyclic structure in compound (B5) is preferably an xanthracene structure, an indolinone structure, or an isoindolinone structure.

[0176] (B) Compound is also preferably one or more of the group consisting of compounds (B1), (B2), (B3), (B4), and (B5). The preferred content of these (B) compounds is also the same as the content of (B) compound when the total of (A) adhesive resin and (B) compound is set to 100 parts by mass.

[0177] <(C) Photosensitive agent>

[0178] The photosensitive composition of the present invention contains a (C) photosensitizer, with the (C1-1) oxime ester compound described below as an essential component. The (C) photosensitizer refers to a compound that, through exposure, undergoes bond cleavage, reaction, or structural change to generate other compounds, thereby imparting positive or negative photosensitivity to the composition. The (C) photosensitizer preferably contains one or more compounds selected from the group consisting of (C1) photopolymerization initiators (hereinafter, "(C1) compounds"), (C2) naphthoquinone diazide compounds (hereinafter, "(C2) compounds"), (C3) photoacid generators (hereinafter, "(C3) compounds"), and (C4) photobase generators (hereinafter, "(C4) compounds"). When imparting negative photosensitivity to the composition, the (C1) compound is preferred. When imparting positive photosensitivity to the composition, the (C2) compound is preferred. A (C2) compound is a compound that undergoes a structural change upon exposure to produce either or both of indenecarboxylic acid and sulfonated indenecarboxylic acid. A (C3) compound is a compound that produces an acid upon exposure to produce either or both of bond cleavage and reactions. A (C4) compound is a compound that produces a base upon exposure to produce either or both of bond cleavage and reactions.

[0179] When the total amount of (A) adhesive resin and (B) compound is set to 100 parts by mass, from the viewpoint of improving sensitivity during exposure, the content of (C) photosensitizer is preferably 1.0 parts by mass or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern, the content of (C) photosensitizer is preferably 30 parts by mass or less.

[0180] <(C1) Photopolymerization Initiator>

[0181] The term "(C1) photopolymerization initiator" refers to a compound that generates free radicals through bond cleavage and one or both of the reactions that occur during exposure. For negative patterning, a (C1) photopolymerization initiator is preferred, as it significantly improves the sensitivity during exposure.

[0182] The photosensitive composition of the present invention requires the use of (C1-1) oxime ester compounds (hereinafter, "(C1-1) compounds"), which are well-known as (C1) photopolymerization initiators. A (C1-1) compound is a compound having an oxime ester structure in its molecule that generates free radicals through bond cleavage and any or both of the reactions that occur during exposure. By containing (C1-1) compounds, the effects of improving sensitivity during exposure and enhancing mechanical properties become significant.

[0183] When the total amount of (A) adhesive resin and (B) compound is set to 100 parts by mass, from the viewpoint of improving sensitivity during exposure and improving mechanical properties, the content of compound (C1-1) is preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern, the content of compound (C1-1) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[0184] <(C1-1) compounds; compounds with a specific structure>

[0185] In this invention, the (C1-1) compound used in the photosensitive composition has all of the (Ia), (Ib) and (Ic) structures within its molecular structure (hereinafter, the (C1-1) compound involved is sometimes referred to as "a (C1-1) compound having a specific structure").

[0186] In (C1-1) compounds with specific structures, from the viewpoints of suppressing residue at the bottom edge of the pattern, improving halftone properties, improving mechanical properties, and improving migration resistance, the (Ia) structure is preferably an indole structure, a benzoindole structure, an indoline structure, a benzoindoline structure, a benzofuran structure, a naphthofuran structure, a benzothiophene structure, a naphthothiophene structure, a benzodihydrofuran structure, a naphthodihydrofuran structure, a benzodihydrothiophene structure, or a naphthodihydrothiophene structure. Furthermore, as a condensed polycyclic heterocyclic structure consisting of two rings in the (Ia) structure, an indole structure, an indoline structure, a benzofuran structure, a benzothiophene structure, a benzodihydrofuran structure, or a benzodihydrothiophene structure is preferred. Furthermore, the condensed polycyclic heterocyclic structure consisting of three rings, including a naphthalene structure, piperidine structure, tetrahydropyridine structure, dihydropyridine structure, pyrrolidine structure, or dihydropyrrole structure in structure (Ia), is preferably a benzoindole structure, a benzoindoline structure, a naphthofuran structure, a naphthothiophene structure, a naphthodihydrofuran structure, or a naphthodihydrothiophene structure. Moreover, for the condensed polycyclic heterocyclic structure consisting of three rings, including the naphthalene structure, piperidine structure, tetrahydropyridine structure, dihydropyridine structure, pyrrolidine structure, and dihydropyrrole structure, it means that the structure of the parent skeleton (carbon skeleton) as part of the structure is observed in the condensed ring, and does not imply a uniform number of hydrogen atoms.

[0187] For example, (X-52) is a compound having a condensed polycyclic heterocyclic structure consisting of three rings containing a naphthalene structure, (X-56) is a compound having a condensed polycyclic heterocyclic structure consisting of three rings containing a pyrrolidine structure, and (X-57) is a compound having a condensed polycyclic heterocyclic structure consisting of three rings containing a piperidine structure.

[0188] [Chemistry 3]

[0189]

[0190] In (C1-1) compounds with specific structures, from the viewpoint of photobleaching properties, the (Ia) structure is preferably an indole, benzoindole, indoline, or benzoindoline structure. From the viewpoint of photobleaching properties, the (Ib) structure is preferably directly bonded to the (Ia) structure. Photobleaching properties achieved by (C1-1) compounds with specific structures significantly improve sensitivity during exposure, suppress residue at the bottom edge of the pattern, and enhance halftone characteristics. Furthermore, it is inferred that reducing the low-molecular-weight components derived from the (C1-1) compounds in the cured product can suppress ion migration or electromigration, thereby improving migration resistance. Moreover, photobleaching properties refer to a reduction in either or both of the absorbance in the ultraviolet region (e.g., below 400 nm) and the absorbance in the visible light region (380 nm to 780 nm) due to bond cleavage and reactions occurring during exposure.

[0191] In (C1-1) compounds with a specific structure, from the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the (Ia) structure is preferably substituted with a nitro group, cyano group, halogen atom, hydroxyl group, alkoxy group with 1 to 6 carbon atoms, hydroxyalkyl group with 1 to 6 carbon atoms, hydroxyalkoxy group with 1 to 6 carbon atoms, alkoxyalkyl group with 1 to 10 carbon atoms, alkoxyalkoxy group with 1 to 10 carbon atoms, heterocyclic carbonyl group with 5 to 10 carbon atoms, heterocyclic group with 4 to 10 carbon atoms, heterocyclic group with 4 to 10 carbon atoms, or alkyl group containing a heterocycle with 5 to 20 carbon atoms. Here, the heterocyclic group is preferably a heterocyclic group containing an oxygen atom, a sulfur atom, or a nitrogen atom, more preferably a furanyl, dihydrofuranyl, phenylthio, dihydrophenylthio, pyrroleyl, or dihydropyrroleyl.

[0192] In (C1-1) compounds with a specific structure, the oxime ester skeleton in the oxime ester carbonyl structure of the (Ib) structure preferably has an acyl group. From the viewpoint of improving sensitivity during exposure, the acyl group is preferably an acyl group containing an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, or an aryl group with 6 to 10 carbon atoms, and more preferably an acetyl or propionyl group. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern, the acyl group is preferably an acyl group containing an aryl group with 6 to 10 carbon atoms, and more preferably a benzoyl group.

[0193] In (C1-1) compounds with a specific structure, from the viewpoint of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, and improving halftone characteristics, the (Ic) structure is preferably an aromatic structure bonded with an aryl carbonyl group, an alkyl carbonyl group, a nitro group, a cyano group, a halogen atom, or a heterocyclic group. Furthermore, from the viewpoint of the effects of the invention, the (Ic) structure is preferably directly bonded to the (Ia) structure. On the other hand, the (Ic) structure is also preferably bonded to the (Ia) structure via a carbonyl group. The aromatic structure in the (Ic) structure is preferably an aromatic structure with 6 to 15 carbon atoms, more preferably a benzene structure or a naphthalene structure. Here, the aryl carbonyl group is preferably a carbonyl group bonded with aryl groups having 6 to 15 carbon atoms, a carbonyl group bonded with arylalkyl groups having 7 to 20 carbon atoms, a carbonyl group bonded with alkylaryl groups having 7 to 20 carbon atoms, a carbonyl group bonded with dialkylaryl groups having 8 to 20 carbon atoms, or a carbonyl group bonded with trialkylaryl groups having 9 to 20 carbon atoms. More preferably, it is a carbonyl group bonded with aryl groups having 6 to 10 carbon atoms, a carbonyl group bonded with arylalkyl groups having 7 to 15 carbon atoms, a carbonyl group bonded with alkylaryl groups having 7 to 15 carbon atoms, a carbonyl group bonded with dialkylaryl groups having 8 to 15 carbon atoms, or a carbonyl group bonded with trialkylaryl groups having 9 to 15 carbon atoms. Among these, phenyl carbonyl, naphthyl carbonyl, or anthracene carbonyl are preferred. Furthermore, the alkyl carbonyl group is preferably a carbonyl group with an alkyl group having 1 to 20 carbon atoms or a carbonyl group with a haloalkyl group having 1 to 20 carbon atoms, more preferably a carbonyl group with an alkyl group having 1 to 10 carbon atoms or a carbonyl group with a haloalkyl group having 1 to 10 carbon atoms, and even more preferably a carbonyl group with an alkyl group having 1 to 6 carbon atoms or a carbonyl group with a haloalkyl group having 1 to 6 carbon atoms. Additionally, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom. Furthermore, the heterocyclic group is preferably a heterocyclic carbonyl group having 5 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxygen group having 4 to 10 carbon atoms, or an alkyl group containing a heterocycle having 5 to 20 carbon atoms. On the other hand, as a specific heterocyclic group, it is preferred to be a heterocyclic group that contains an oxygen atom, a sulfur atom, or a nitrogen atom in the ring structure, and more preferably furanyl, dihydrofuranyl, phenylthio, dihydrophenylthio, pyrroleyl, or dihydropyrroleyl.

[0194] From the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the (C1-1) compound preferably also has an (Id) structure. Furthermore, from the viewpoint of the effects of the invention, the (Id) structure is preferably directly bonded to the (Ia) or (Ib) structure. (C1-1) compounds having a specific structure are also preferably further having an (Id) structure. From the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the aliphatic and alicyclic groups in the (Id) structure are preferably 4 or more carbon atoms, more preferably 6 or more carbon atoms, and even more preferably 8 or more carbon atoms. On the other hand, from the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the aliphatic and alicyclic groups in the (Id) structure are preferably 18 or less carbon atoms, more preferably 15 or less carbon atoms, and even more preferably 12 or less carbon atoms. The aliphatic group is preferably a straight-chain or branched alkyl, alkenyl, or alkynyl group. The alicyclic group is preferably a straight-chain or branched cycloalkyl, cycloalkenyl, or cycloalkynyl group. From the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, and improving halftone characteristics, the aliphatic and alicyclic groups in the (Id) structure are preferably groups substituted with halogen atoms, more preferably groups substituted with fluorine atoms. The halogen-substituted groups are preferably trifluoromethyl, trifluoropropyl, trichloropropyl, tetrafluoropropyl, fluorocyclopentyl, fluorophenyl, or pentafluorophenyl. When the polyimide-based resin contains either or both of a carboxylic acid residue having a fluorine atom and an amine residue having a fluorine atom, the (C1-1) compound is preferably a group substituted with a halogen atom.

[0195] In (C1-1) compounds with a specific structure, from the viewpoint of improving the properties based on each structure, the (Ib) structure and the (Ic) structure are preferably directly bonded to the (Ia) structure, and more preferably the (Ib) structure, the (Ic) structure, and the (Id) structure are directly bonded to the (Ia) structure.

[0196] The (C1-1) compound having a specific structure is preferably one or more of the group consisting of compounds selected from those represented by general formula (15), general formula (16) and general formula (17).

[0197] [Chemistry 4]

[0198]

[0199] In general formulas (15) to (17), the dashed part represents a carbon-carbon single bond or a carbon-carbon double bond. 1 ~X 3 Each can be independently represented by an arylene group or a direct bond with 6 to 15 carbon atoms. X 4 ~X 7Each can be independently represented by a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. X 8 Y represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. 1 ~Y 3 Each atom can be represented independently as a carbon atom, nitrogen atom, oxygen atom, or sulfur atom. In X 1 X 2 、 or X 3 In the case of an arylene group having 6 to 15 carbon atoms, the corresponding R 101 R 102 、or R 103 Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a carbonyl group with an aryl group having 6 to 15 carbon atoms, a carbonyl group with an arylalkyl group having 7 to 20 carbon atoms, or an alkyl aryl group having 7 to 20 carbon atoms. Carbonyl groups containing 8-20 carbon atoms, carbonyl groups containing 9-20 carbon atoms, carbonyl groups containing 1-20 carbon atoms, carbonyl groups containing 1-20 carbon atoms, carbonyl groups containing 1-20 carbon atoms of haloalkyl groups, heterocyclic carbonyl groups containing 5-10 carbon atoms, heterocyclic groups containing 4-10 carbon atoms, heterocyclic oxygen groups containing 4-10 carbon atoms, alkyl groups containing 5-20 carbon atoms, nitro groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. In X 1 X 2 、 or X 3 In the case of a direct key, the corresponding R 101 R 102 、or R 103 Each of the bases forming the ring is represented independently. Furthermore, in R... 101 In the case of forming a ring base, through R 101 and R 110 or R 101 and R 111 A ring is formed. In R 101 In the case of forming a basis for a ring, f or g represents an integer from 1 to 3, where there are multiple R... 110 or multiple R 111 In the case of R, at least one of them is in relation to R 101 A loop is formed between them. In R 102 In the case of forming a ring base, through R 102 and R 112 or R 102 and R 113 A ring is formed. In R 102In the case of forming a basis for a ring, h or i represents an integer from 1 to 3, where there are multiple R... 112 or multiple R 113 In the case of R, at least one of them is in relation to R 102 A loop is formed between them. In R 103 In the case of forming a ring base, through R 103 and R 114 or R 103 and R 115 A ring is formed. In R 103 In the case of forming a basis for a ring, j or k represents an integer from 1 to 3, where there are multiple R... 114 or multiple R 115 In the case of R, at least one of them indicates that in relation to R 103 The bases that form a ring between them. Furthermore, based on R... 101 and R 110 or R 101 and R 111 The number of atoms in the ring members ranges from 4 to 10. Based on R 102 and R 112 or R 102 and R 113 The number of atoms in the ring members ranges from 4 to 10. Based on R 103 and R 114 or R 103 and R 115 The number of atoms in the ring members ranges from 4 to 10. Furthermore, the so-called R... 101 R 102 R 103 R 110 R 111 R 112 R 113 R 114 and R 115 The group that forms the ring is an alkylene or alkenylene group, etc., which constitutes the ring in a manner that satisfies the atomic number of ring members and the degree of unsaturation of the ring to be formed. R 104 ~R 107 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 108 and R 109Each of the following can be independently represented as a carbonyl group bonded to an aryl group of 6–15 carbons, a carbonyl group bonded to an arylalkyl group of 7–20 carbons, a carbonyl group bonded to an alkylaryl group of 7–20 carbons, a carbonyl group bonded to a dialkylaryl group of 8–20 carbons, a carbonyl group bonded to a trialkylaryl group of 9–20 carbons, a carbonyl group bonded to an alkyl group of 1–20 carbons, a carbonyl group bonded to a haloalkyl group of 1–20 carbons, a heterocyclic carbonyl group of 5–10 carbons, a heterocyclic group of 4–10 carbons, a heterocyclic oxygen group of 4–10 carbons, an alkyl group containing a heterocycle of 5–20 carbons, a nitro group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, an alkoxy group of 1–6 carbons, a hydroxyalkyl group of 1–6 carbons, a hydroxyalkoxy group of 1–6 carbons, an alkoxyalkyl group of 1–10 carbons, or an alkoxyalkoxy group of 1–10 carbons. R 110 ~R 115 Each of these can independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a group forming a ring. Furthermore, based on multiple R... 110 or multiple R 111 The number of carbon atoms in the ring members ranges from 4 to 10. Based on multiple R... 112 or multiple R 113 The number of carbon atoms in the ring members ranges from 4 to 10. Based on multiple R... 114 or multiple R 115 The number of carbon atoms in the ring members ranges from 4 to 10. Furthermore, the so-called multiple R... 110 Multiple R 111 Multiple R 112 Multiple R 113 Multiple R 114 and multiple R 115 The group that forms the ring is an alkylene or alkenylene group, etc., which constitutes the ring in a manner that satisfies the atomic number of ring members and the degree of unsaturation of the ring to be formed. R 116 ~R 119 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 4 to 20 carbon atoms, an aryl group with 6 to 15 carbon atoms, a (cycloalkyl)alkyl group with 4 to 20 carbon atoms, an arylalkyl group with 7 to 20 carbon atoms, an alkylaryl group with 7 to 20 carbon atoms, a dialkylaryl group with 8 to 20 carbon atoms, a trialkylaryl group with 9 to 20 carbon atoms, a haloalkyl group with 1 to 20 carbon atoms, a haloalkoxy group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an alkoxyalkyl group with 2 to 20 carbon atoms, an alkoxycarbonyl group with 3 to 20 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a carbonyl group with 6 to 15 carbon atoms, a carbonyl group with 1 to 20 carbon atoms, or a nitro group. In Y 1 Y 2 , or Y 3 In the case of carbon atoms, the corresponding a, b, or c is 2. In Y... 1 Y 2, or Y 3 In the case of nitrogen atoms, the corresponding a, b, or c is 1. In Y... 1 Y 2 , or Y 3 In the case of oxygen or sulfur atoms, the corresponding a, b, or c is 0. d and e independently represent integers from 0 to 4. f, g, h, i, j, and k independently represent integers from 0 to 3 (where 0 < d + f ≦ 4, 0 < e + h ≦ 4). l, m, n, and o independently represent integers from 1 to 10. t and v independently are 0 or 1, and t + v is 0 or 1. When t + v is 0, w is 0. When t + v is 1, w is 1. When t is 0, y is 1. When t is 1, y is 0. When v is 0, b is as described. When v is 1, b is 0. x represents integers from 0 to 4. α, β, and γ independently represent integers from 0 to 4. and Indicates and The key node.

[0200] Furthermore, among the compounds represented by general formulas (15), (16), and (17), X is particularly preferred. 1 ~X 3 The arylene group with 6 to 15 carbon atoms corresponds to the (Ic) structure in a (C1-1) compound having a specific structure; additionally, R is preferred. 108 and R 109 The carbonyl group in R is bonded with an aryl group having 6 to 15 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a dialkylaryl group having 8 to 20 carbon atoms, or a trialkylaryl group having 9 to 20 carbon atoms; 116 ~R 119 The aryl group having 6 to 15 carbon atoms or a carbonyl group bonded with 6 to 15 carbon atoms; or X 4 ~X 7 The arylene groups with 6 to 15 carbon atoms correspond to the (Ic) structure in (C1-1) compounds with specific structures. Composed of multiple R... 110 or multiple R 111 Multiple R 112 or multiple R 113 or multiple R 114 or multiple R 115 The formed ring having 4 to 10 carbon atoms is preferably a benzene ring, a cyclohexane ring, or a cyclopentane ring. In R 101 and R 110 or R 101 and R 111 R 102 and R 112 or R102 and R 113 Or R 103 and R 114 or R 103 and R 115 In this process, the ring with 4 to 10 atoms is preferably a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, a pyrrolidine ring, or a dihydropyrrole ring. The substituents and structure may have heteroatoms, or may be either unsubstituted or substituted.

[0201] The (C1-1) compound is preferably all or part of an isomer that has a cis structure relative to the C=N bond of the oxime structure (cis isomer) or a trans structure (trans isomer) within the (Ib) structure, comprising a group containing a carbonyl structure and a group containing an oxygen atom of an oxime structure. When the total percentage of the cis isomer and the trans isomer is set to 100% by mass, from the viewpoint of improving the aforementioned properties, the content ratio of the cis isomer or trans isomer is preferably 90.0% by mass or more, more preferably 95.0% by mass or more, further preferably 97.0% by mass or more, and particularly preferably 99.0% by mass or more. On the other hand, from the viewpoint of improving the aforementioned properties, the content ratio of the cis isomer (Z-isomer) or the trans isomer (E-isomer) is preferably 100.0% by mass or less, more preferably 99.9% by mass or less, and further preferably 99.5% by mass or less. The preferred ratio of the trans isomer is the ratio found in (C1-1) compounds with a specific structure.

[0202] The (C1-1) compounds with specific structures can improve the crosslinking degree of the cured product or promote the ring-closing reaction of the resin through the free radical generation during heating or the interaction between the carbonyl structure of the oxime ester and the phenolic hydroxyl or carboxyl groups in the polyimide resin, thus significantly improving the mechanical properties. Furthermore, since the π electrons in the carbonyl structures of the (Ib) and (Ic) structures help control the polarization structure or charge balance in the cured product, it is inferred that they improve migration resistance.

[0203] <Compounds other than those with a specific structure>

[0204] The photosensitive compositions of the present invention may use (C1-1) compounds other than (C1-1) compounds having a specific structure as (C1-1) compounds (hereinafter, (C1-1) compounds other than (C1-1) compounds having a specific structure are sometimes referred to as "(C1-1) compounds having other structures").

[0205] From the viewpoint of improving mechanical properties, (C1-1) compounds with other structures are preferably those with the following (Ca) structure, and from the viewpoint of improving sensitivity during exposure, compounds with the following (Cb) structure are preferably those with the following (Cb) structure.

[0206] (Ca) Structure: A structure in which at least one oxime ester structure or at least one oxime ester carbonyl structure is bonded to a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, a diaryl sulfide structure or a benzene structure.

[0207] (Cb) Structure: A structure with a nitro group, a halogen-substituted group, a naphthyl carbonyl structure, a trimethylbenzoyl structure, a phenylthiocarbonyl structure, a furanyl carbonyl structure, at least two oxime ester structures, or at least two oxime ester carbonyl structures.

[0208] Furthermore, from the viewpoint of improving sensitivity during exposure, improving halftone properties, and improving mechanical properties, (C1-1) compounds having other structures are more preferably having (Ca) structures and (Cb) structures, and even more preferably having a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, a diaryl sulfide structure, or a benzene structure bonded to a (Cb) structure in the (Ca) structure.

[0209] From the viewpoint of suppressing residue at the bottom edge of the pattern, improving halftone properties, and enhancing mechanical properties, the condensed polycyclic structure in the (Ca) structure is preferably a fluorene structure, a benzo[a]fluorene structure, a dibenzo[a]fluorene structure, an indene structure, a dihydroindene structure, a benzo[a]indene structure, or a benzo[a]dihydroindene structure. From the viewpoint of suppressing residue at the bottom edge of the pattern, improving halftone properties, enhancing mechanical properties, and enhancing migration resistance, the condensed polycyclic heterocyclic structure in the (Ca) structure is preferably a carbazole structure, a dibenzofuran structure, a dibenzothiophene structure, a benzo[a]carbazole structure, a phenothiazine structure, or a phenothiazine oxide structure. From the viewpoint of suppressing residue at the bottom edge of the pattern and enhancing halftone properties, the diaryl sulfide structure in the (Ca) structure is preferably a diphenyl sulfide structure, a naphthylphenyl sulfide structure, or a dinaphthyl sulfide structure.

[0210] From the viewpoint of improving sensitivity during exposure and enhancing mechanical properties, (C1-1) compounds with other structures are preferably those having halogen-substituted groups, more preferably those having fluorine-substituted groups. The halogen-substituted groups are preferably trifluoromethyl, trifluoropropyl, trichloropropyl, tetrafluoropropyl, fluorocyclopentyl, fluorophenyl, or pentafluorophenyl.

[0211] From the viewpoint of photobleaching properties, (C1-1) compounds with other structures are preferably those having a fluorene structure, a benzo[a]fluorene structure, a dibenzo[a]fluorene structure, a phenothiazine structure, a phenothiazine oxide structure, or a diphenyl sulfide structure. They are also preferably those having at least one oxime ester carbonyl group bonded to a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, a diphenyl sulfide structure, or a benzene structure. By enabling (C1-1) compounds with other structures to exhibit photobleaching properties, the effects of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, and improving halftone characteristics become significant.

[0212] The (C1-1) compounds with other structures can improve the crosslinking degree of the cured product or promote the ring-closing reaction of the resin through the free radical generation during heating or the interaction between the phenolic hydroxyl or carboxyl groups in the polyimide resin brought about by the oxime ester structure, thus significantly improving the mechanical properties.

[0213] When the total amount of (A) adhesive resin and (B) compound is set to 100 parts by mass, from the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, improving halftone properties, improving mechanical properties, and improving migration resistance, the content of the (C1-1) compound with a specific structure is preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more. On the other hand, from the viewpoints of suppressing residue at the bottom edge of the pattern and improving halftone properties, the content of the (C1-1) compound with a specific structure is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[0214] When the total amount of (A) adhesive resin and (B) compound is set to 100 parts by mass, from the viewpoint of improving sensitivity during exposure, improving halftone characteristics, and improving mechanical properties, the content of (C1-1) compound having other structures is preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern and improving halftone characteristics, the content of (C1-1) compound having other structures is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[0215] From the viewpoints of improving sensitivity during exposure, suppressing residue at the bottom edge of the pattern, improving halftone properties, improving mechanical properties, and improving migration resistance, the content ratio of the (C1-1) compound with a specific structure in 100% by mass of the total (C1-1) compounds is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more. On the other hand, from the viewpoints of improving sensitivity during exposure and improving halftone properties, the content ratio of the (C1-1) compound with a specific structure is preferably 100% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.

[0216] From the viewpoint of improving the aforementioned properties, the content ratio of (C1-1) compounds having other structures in the total 100% by mass of (C1-1) compounds is preferably more than 0% by mass. On the other hand, from the viewpoint of improving the aforementioned properties, the content ratio of (C1-1) compounds having other structures is preferably 90% by mass or less.

[0217] <Other Photopolymerization Initiators>

[0218] The photosensitizing composition of the present invention preferably also contains other photopolymerization initiators. These other photopolymerization initiators are preferably benzoyl ketal compounds, α-hydroxy ketal compounds, α-amino ketal compounds, biimidazole compounds, phosphine oxide compounds, acridine compounds, dicene compounds, benzophenone compounds, acetophenone compounds, aromatic ketone ester compounds, or benzoic acid ester compounds. From the viewpoint of improving sensitivity during exposure and improving mechanical properties, α-hydroxy ketal compounds, α-amino ketal compounds, biimidazole compounds, or phosphine oxide compounds are preferred. The preferred amounts of these other photopolymerization initiators are also the same as the amounts of the (C1-1) compounds having other structures.

[0219] The α-hydroxy ketone compounds, α-amino ketone compounds, biimidazole compounds, and phosphine oxide compounds can improve the crosslinking degree of the cured product or promote the ring-closing reaction of the resin through the generation of free radicals during heating or the interaction brought about by the hydroxyl, amino, imidazole, or phosphine oxide structures, thus significantly improving the mechanical properties.

[0220] <(D) Colorant>

[0221] The photosensitive composition of the present invention preferably also contains a (D) colorant. A (D) colorant is a compound that colors light by absorbing wavelengths of visible light. The (D) colorant is preferably a pigment or dye. From the viewpoint of suppressing external light reflection, the (D) colorant is preferably a black agent or a mixture of two or more colorants. As a black agent, either or both of organic black pigments and inorganic black pigments are preferably used. The black colorant is as described in paragraphs

[0284] to

[0285] of International Publication No. 2019 / 087985.

[0222] From the viewpoint of suppressing external light reflection and improving the reliability of the element, the content of colorant (D) in the total solids of the photosensitive composition of the present invention is preferably 5.0% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and suppressing residue at the bottom edge of the pattern, the content of colorant (D) in the total solids of the photosensitive composition of the present invention is preferably 70% by mass or less, more preferably 50% by mass or less.

[0223] From the viewpoint of suppressing residue at the hem of the pattern, halftone characteristics, and improving migration resistance, the photosensitive composition of the present invention preferably further contains an organic black pigment. The organic black pigment contains one or more selected from the group consisting of benzofuranone black pigments, perylene black pigments, and azomethyl black pigments. More preferably, the benzofuranone black pigment comprises a compound having at least two benzofuran-2(3H)-one structures or at least two benzofuran-3(2H)-one structures having at least two shared benzene rings, their geometric isomers, salts, or salts of these geometric isomers. The perylene black pigment comprises a compound having a 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole structure, its geometric isomers, salts, or salts of these geometric isomers. The azomethyl black pigment comprises a compound having an azomethyl base and a carbazole structure, or a salt thereof. Because the organic black pigment has high transmittance in the ultraviolet region, its effect on improving sensitivity during exposure becomes significant.

[0224] Organic black pigments are preferably anthraquinone-based black pigments, aniline-based black pigments, azo-based black pigments, or carbon black. Carbon black is preferably treated with resin coating, dye coating, oxidation treatment, surface modification with organic groups having ionic groups, or surface treatment with sulfonic acid groups.

[0225] From the viewpoint of suppressing residue and halftone characteristics at the hem of the pattern, the photosensitive composition of the present invention preferably contains either or both of a mixture of two or more coloring pigments and a mixture of two or more coloring dyes. As for the two or more colors, either or both of blue and purple, and red and orange are preferred. Examples of preferably usable coloring pigments include: anthraquinone pigments, diketopyrrolopyrrole pigments, perylene pigments, isoindoline pigments, isoindolineone pigments, imidazolinone pigments, quinacrine pigments, pinanthrone pigments, phthalocyanine pigments, indanone pigments, and dioxazine pigments. Examples of preferably usable coloring dyes include: squaric acid monazine salt dyes, xanthracene dyes, triarylmethane dyes, and phthalocyanine dyes.

[0226] From the viewpoint of improving the reliability of the component, the average primary particle size of the pigment is preferably set to 20 nm or more. On the other hand, from the viewpoint of suppressing external light reflection and improving the reliability of the component, the average primary particle size of the pigment is preferably 150 nm or less.

[0227] From the viewpoint of suppressing residue and halftone characteristics at the bottom edge of the pattern, the photosensitive composition of the present invention preferably also contains an inorganic black pigment. The inorganic black pigment is selected from one or more of the group consisting of nitrides containing a metal element, carbides containing a metal element, and oxides containing a metal element (hereinafter, the inorganic black pigment referred to is sometimes called a "specific inorganic black pigment"). Here, the metal element contained in the specific inorganic black pigment is preferably selected from one or more of the group consisting of zirconium, vanadium, niobium, hafnium, and tantalum. From the viewpoint of improving sensitivity during exposure, the specific inorganic black pigment is more preferably selected from one or more of the group consisting of zirconium nitrides, zirconium carbides, and zirconium oxides. Zirconium nitrides, zirconium carbides, and zirconium oxides have high transmittance in the ultraviolet region, thus significantly improving sensitivity during exposure.

[0228] The specific inorganic black pigment preferably contains zirconium, vanadium, niobium, hafnium, or tantalum as its main component elements. Furthermore, the term "main component element" refers to the element that constitutes the most abundant element by mass. The main component element is an element different from H, B, C, N, O, F, P, S, or Cl. From the viewpoint of suppressing external light reflection and improving component reliability, the specific inorganic black pigment preferably contains elements different from the main component elements, more preferably B, Al, Si, Mn, Co, Ni, Fe, Cu, Zn, or Ag.

[0229] The crystallite size of the zirconium nitride particles and other compound particles contained in a specific inorganic black pigment can be calculated based on the half-width of the peak originating from the (111) plane in an X-ray diffraction spectrum using CuKα rays as the X-ray source. From the viewpoint of suppressing external light reflection and improving the reliability of the device, the crystallite size is preferably 5.0 nm or more. On the other hand, from the viewpoint of improving sensitivity during exposure and suppressing external light reflection, the crystallite size is preferably 60 nm or less. Furthermore, the crystallite size of the particle powder, the crystallite size of the particles in the dispersion, and the crystallite size of the particles in the film can be determined based on the methods described in paragraphs

[0172] to

[0179] of International Publication No. 2021 / 182499.

[0230] The photosensitive composition of the present invention is preferably a pigment having a coating layer. A coating layer refers to a layer that coats the surface of the pigment, such as a layer formed by surface treatment using a silane coupling agent or by coating treatment using a resin. By having a coating layer on the pigment, the effects of suppressing residue at the bottom edge of the pattern, halftone characteristics, and improving migration resistance become significant. The coating layer is preferably one or more selected from the group consisting of silica coating layers, metal oxide coating layers, and metal hydroxide coating layers.

[0231] <(E) Dispersant>

[0232] The photosensitive composition of the present invention preferably also contains an (E) dispersant. An (E) dispersant refers to a compound having a structure that interacts with the pigment surface and a structure that prevents pigments from approaching each other. From the viewpoint of improving the dispersion stability of the pigment, the (E) dispersant is preferably a basic group, an acidic group, or a salt structure of the like, and more preferably a basic group or a salt structure thereof.

[0233] <(F) Crosslinking agent>

[0234] The photosensitive composition of the present invention contains either or both of a compound (B) and a crosslinking agent (F). The crosslinking agent (F) refers to a compound having a crosslinking group, a cationic polymerizable group, or an anionic polymerizable group capable of reacting with resins, etc. From the viewpoint of improving sensitivity during exposure and improving mechanical properties, the crosslinking agent (F) preferably has one or more groups selected from the group consisting of alkoxyalkyl, hydroxyalkyl, epoxy, oxetyl, and block isocyanate groups (hereinafter, the groups involved are sometimes referred to as "specific crosslinking groups"). Alkoxyalkyl is preferably alkoxymethyl or alkoxyethyl, more preferably methoxymethyl or methoxyethyl. Hydroxyalkyl is preferably hydroxymethyl or hydroxyethyl. From the viewpoint of improving sensitivity during exposure and improving mechanical properties, the number of specific crosslinking groups in one molecule of the crosslinking agent (F) is preferably two or more, more preferably three or more, and even more preferably four or more, particularly preferably six or more. On the other hand, from the viewpoint of improving mechanical properties, the number of specific crosslinking groups is preferably twelve or less, more preferably ten or less, and even more preferably eight or less.

[0235] When the total amount of (A) adhesive resin and (B) compound is set to 100 parts by mass (and (B) compound is sometimes not included in the photosensitive composition), from the viewpoint of improving sensitivity during exposure and improving mechanical properties, the content of (F) crosslinking agent is preferably 1.0 parts by mass or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern and improving mechanical properties, when the total amount of (A) adhesive resin and (B) compound is set to 100 parts by mass (as above), the content of (F) crosslinking agent is preferably 30 parts by mass or less.

[0236] From the viewpoint of suppressing residue at the hem of the pattern and improving mechanical properties, all or part of the (F) crosslinking agent is preferably the following (F1) compound or (F2) compound. Furthermore, (F1) compound and (F2) compound can be used together. The preferred amounts of these (F) crosslinking agents are also the same as described above.

[0237] (F1) Compound: A compound having at least two phenolic hydroxyl groups and at least two specific crosslinking groups.

[0238] (F2) Compound: A compound having a structure including a heterocyclic structure and at least two specific crosslinking groups.

[0239] From the viewpoint of improving mechanical properties, compound (F1) is preferably a structure having at least two phenolic hydroxyl groups and specific crosslinking groups bonded to one aromatic structure, more preferably a structure having at least two phenolic hydroxyl groups and at least two specific crosslinking groups bonded to one aromatic structure. The aromatic structure in compound (F1) is preferably an aromatic structure with 6 to 15 carbon atoms, more preferably a benzene structure or a naphthalene structure. From the viewpoint of improving mechanical properties, the heterocyclic structure in compound (F2) is preferably a nitrogen-containing cyclic structure, more preferably a cyclic structure having at least two nitrogen atoms, and even more preferably an isocyanuric acid structure, a triazine structure, a glycourea structure, an imidazoline structure, a pyrazole structure, an imidazoline structure, a triazole structure, a tetrazolium structure, or a purine structure. The number of nitrogen atoms in the heterocyclic structure of compound (F2) is preferably one or more in one molecule, more preferably two or more, and even more preferably three or more. On the other hand, the number of nitrogen atoms is preferably six or less, more preferably four or less.

[0240] <(G) Inorganic Particles>

[0241] From the viewpoint of improving migration resistance, the photosensitive composition of the present invention preferably also contains (G) inorganic particles. (G) inorganic particles refer to particles that contain elements selected from the group consisting of metallic elements, half-metallic elements, and semiconductor elements in their main components. Furthermore, the term "main component" refers to the component that is present in the largest quantity by mass among the constituent components. From the viewpoint of improving migration resistance, the (G) inorganic particles preferably have either or both hydroxyl and silanol groups on their particle surface. From the viewpoint of improving migration resistance, the (G) inorganic particles preferably contain one or more of the group consisting of silica particles, alumina particles, titanium oxide particles, vanadium oxide particles, chromium oxide particles, iron oxide particles, cobalt oxide particles, copper oxide particles, zinc oxide particles, zirconium oxide particles, niobium oxide particles, tin oxide particles, and cerium oxide particles; from the viewpoint of further suppressing external light reflection, it is more preferable to contain silica particles.

[0242] From the viewpoint of improving halftone properties and improving migration resistance, silica particles preferably have free radical polymerizable groups, thermally reactive groups, hydroxyl groups, silanol groups, alkoxysilyl groups, alkylsilyl groups, dialkylsilyl groups, trialkylsilyl groups, phenylsilyl groups, or diphenylsilyl groups on the particle surface. From the viewpoint of further improving halftone properties, it is more preferable that the particles have free radical polymerizable groups or thermally reactive groups on the particle surface. Examples and preferences of free radical polymerizable groups are described as described in the adhesive resin described in (A).

[0243] From the viewpoint of improving migration resistance, the average primary particle size of the silica particles is preferably 5.0 nm or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern and suppressing external light reflection, the average primary particle size of the silica particles is preferably 200 nm or less. Furthermore, from the viewpoint of high elastic coefficient and low coefficient of thermal expansion, the average primary particle size of the silica particles is preferably more than 0.20 μm. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern, the average primary particle size of the silica particles is preferably 100 μm or less.

[0244] The so-called primary particle diameter of the pigment and silica particles refers to the major axis diameter of the primary particles. The average primary particle diameter of the pigment and silica particles in the film can be calculated as the average value obtained by photographing and analyzing the cross-section of the film using a transmission electron microscope (hereinafter "TEM") and measuring 30 primary particles. Furthermore, the preferred range of the average primary particle diameter in the pigment dispersion and the silica particle dispersion is the same as the preferred range of the average primary particle diameter in the film. The average primary particle diameter in the pigment dispersion and the silica particle dispersion is determined by measuring the particle size distribution using dynamic light scattering. For example, the SZ-100 manufactured by Horiba Corporation can be used for dynamic light scattering, and the SLD3100 manufactured by Shimadzu Corporation or the LA-920 manufactured by Horiba Corporation or equivalent products can be used for laser diffraction-scattering.

[0245] It is believed that the silica particles capture metallic or ionic impurities that adversely affect electrical insulation through the acidity or negative charge of either or both of the hydroxyl and silanol groups on the particle surface. Furthermore, due to the robust structure of the particles, the captured impurities are retained even after heat treatment or the application of voltage, thus improving migration resistance. Additionally, it is believed that the silica particles, which are biased towards the surface of the cured material, reduce the reflection and scattering of incident external light.

[0246] From the viewpoint of improving migration resistance, the sodium content in the silica particles is preferably 1.0 ppm by mass or more. On the other hand, from the viewpoint of improving migration resistance, the sodium content in the silica particles is preferably 1,000 ppm by mass or less. Examples of sodium forms include, for instance, Na+ ions. + ) or salts with silanol groups (Si-ONa).

[0247] From the viewpoint of improving migration resistance, the content of (G) inorganic particles in the total solids composition of the photosensitive composition of the present invention is preferably 5.0% by mass or more. On the other hand, from the viewpoint of suppressing residue at the bottom edge of the pattern, the content of (G) inorganic particles is preferably 90% by mass or less.

[0248] <Other Additives and Solvents>

[0249] The photosensitive composition of the present invention preferably also contains a thermal color developer, an oxidative color developer, a solubility promoter, an ink repellent, a sensitizer, a chain transfer agent, a polymerization inhibitor, a silane coupling agent, or a surfactant. Known additives may also be used. The photosensitive composition of the present invention preferably also contains a solvent. When the photosensitive composition of the present invention contains a pigment and also contains a dispersant, from the viewpoint of improving the dispersion stability of the pigment, the solvent is preferably a compound having an acetate bond, a propionate bond, or a butyrate bond.

[0250] <Content of specific aromatic compounds>

[0251] From the viewpoint of suppressing residue at the bottom of the pattern, improving mechanical properties, and improving migration resistance, the photosensitive composition of the present invention preferably contains one or more of the group consisting of benzene, toluene, xylene, and naphthalene (hereinafter, the aromatic compound involved is sometimes referred to as "specific aromatic compound"), and satisfies condition (1).

[0252] From the viewpoint of suppressing residue at the hem of the pattern, improving mechanical properties, and enhancing migration resistance, the content of the specific aromatic compound in the photosensitive composition is preferably 0.030 ppm by mass or more, more preferably 0.050 ppm by mass or more, even more preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of suppressing residue at the hem of the pattern, improving mechanical properties, and enhancing migration resistance, the content of the specific aromatic compound is preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, and even more preferably 100 ppm by mass or less. Furthermore, it is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5.0 ppm by mass or less, particularly preferably 3.0 ppm by mass or less, and most preferably 1.0 ppm by mass or less.

[0253] Furthermore, from the viewpoints of suppressing residue at the hem of the pattern, improving mechanical properties, and enhancing migration resistance, the content of the specific aromatic compound is preferably 0.010 parts by mass or more, more preferably 0.030 parts by mass or more, and even more preferably 0.050 parts by mass or more, and even more preferably 0.070 parts by mass or more, and particularly preferably 0.10 parts by mass or more, relative to 10,000 parts by mass of the (C1-1) compound with the specific structure. On the other hand, from the viewpoints of suppressing residue at the hem of the pattern, improving mechanical properties, and enhancing migration resistance, the content of the specific aromatic compound is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less, and particularly preferably 100 parts by mass or less, relative to 10,000 parts by mass of the (C1-1) compound with the specific structure. Furthermore, it is preferable to use 50 parts by weight or less, more preferably 30 parts by weight or less, even more preferably 10 parts by weight or less, even more preferably 5.0 parts by weight or less, particularly preferably 3.0 parts by weight or less, and most preferably 1.0 parts by weight or less.

[0254] By containing trace amounts of the specific aromatic compound, the surface of the opening is modified during pattern formation of the photosensitive composition, thus preventing residue from adhering to the wiring surface and significantly suppressing residue at the bottom edge of the pattern. Furthermore, through the π-electron interaction between the specific aromatic compound and resins having aromatic rings, such as polyimide, polybenzoxazole, and their precursors, or through coordination bonding with resins containing silicon atoms with empty atomic orbitals (i.e., 3d orbitals), such as polysiloxane, these resins become locally oriented, efficiently undergoing cross-linking reactions or ring-closing reactions between resins, thus significantly improving mechanical properties. Additionally, since the specific aromatic compound helps control the polarization structure or charge balance in the cured product, it is inferred that migration resistance is improved.

[0255] When the photosensitive composition of the present invention has negative photosensitivity, from the viewpoint of suppressing residue at the bottom edge of the pattern, the photosensitive composition of the present invention preferably satisfies condition (1). When the photosensitive composition of the present invention satisfies condition (1), the photosensitive composition of the present invention is more preferably containing a (C1) photopolymerization initiator and a (B) compound. The specific aromatic compound is stabilized by interacting with active free radicals, or active species in cationic or anionic polymerization, using π electrons on the aromatic ring, thereby significantly suppressing residue at the bottom edge of the pattern. In particular, the specific aromatic compound significantly suppresses residue at the bottom edge of the pattern by capturing active free radicals from the (C1) photopolymerization initiator and the (B) compound, resulting in controlled free radical polymerization during exposure.

[0256] Furthermore, in cases where the storage stability of the photosensitive composition is poor, the formation of foreign matter after storage at room temperature can sometimes become a problem. When foreign matter forms during the storage of the photosensitive composition, it can remain in the cured product or at pattern openings during the formation of the cured product of the photosensitive composition, such as in the electronic components of the present invention. Such foreign matter can, for example, reduce the reliability of the light-emitting elements in a display device or reduce the migration resistance of electronic components. The photosensitive composition of the present invention, by setting the content of specific aromatic compounds within a specific range, can significantly suppress the formation of foreign matter during storage and improve storage stability.

[0257] <Content of specific nitrogen-containing compounds>

[0258] From the viewpoint of improving mechanical properties and improving migration resistance, the photosensitive composition of the present invention preferably contains one or more of the group consisting of cyclic amide compounds represented by general formula (20), amide compounds represented by general formula (21), cyclic urea compounds represented by general formula (22), urea compounds represented by general formula (23), oxazolidinone compounds represented by general formula (24), and isoxazolidinone compounds represented by general formula (25) (hereinafter, the compounds involved are referred to as "specific nitrogen-containing compounds"), and satisfies the following condition (5).

[0259] Condition (5): When the total solid content of the photosensitive composition is set to 100% by mass, the content of a specific nitrogen-containing compound is 0.010% by mass or more and 5.0% by mass or less.

[0260] [Chemistry 5]

[0261]

[0262] In general formulas (20) to (25), R 46 ~R 56 Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. R 130 R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a monoalkylamino group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. 131 ~R 142Each of the following groups independently represents an alkyl group having 1 to 6 carbon atoms. α, β, and γ each independently represent an integer from 0 to 6. a, b, c, e, f, g, h, i, j, k, l, and m each independently represent an integer from 0 to 2. When α is 0, a is 0. When β is 0, b is 0. When γ is 0, c is 0. The substituents and structure may have heteroatoms and may be either unsubstituted or substituted.

[0263] Specific nitrogen-containing compounds include, for example: N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutylamide, N,N-dimethyl-3-methoxypropionamide, N,N-dimethyl-3-butoxypropionamide, 1,3-dimethyl-2-imidazolium ketone, 1,3-diethyl-2-imidazolium ketone, N,N'-dimethylpropylene urea, 1,1,3,3-tetramethylurea, or 1,1,3,3-tetraethylurea.

[0264] When the total solids content of the photosensitive composition is set to 100% by mass, from the viewpoint of improving mechanical properties and migratory resistance, the content of the specific nitrogen-containing compound is preferably 0.030% by mass or more, more preferably 0.050% by mass or more, further preferably 0.070% by mass or more, and particularly preferably 0.10% by mass or more. On the other hand, from the viewpoint of improving mechanical properties and migratory resistance, when the total solids content of the photosensitive composition is set to 100% by mass, the content of the specific nitrogen-containing compound is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, and further preferably 3.0% by mass or less. More preferably, it is 2.5% by mass or less, more preferably 2.0% by mass or less, further preferably 1.5% by mass or less, further preferably 1.0% by mass or less, particularly preferably 0.70% by mass or less, and most preferably 0.50% by mass or less. Furthermore, the mass of the total solids in the composition can be calculated in the same way as the concentration of the solids, by heating 1 g of the composition at 150°C for 30 minutes to evaporate it to dryness and measuring the mass remaining after heating.

[0265] It is inferred that by containing trace amounts of the specific nitrogen-containing compound, the nitrogen-containing structure with non-covalent electron pairs captures metallic or ionic impurities that adversely affect electrical insulation, thus suppressing ion migration or electromigration and improving migration resistance. Furthermore, the specific nitrogen-containing compound functions as a catalyst to promote cross-linking reactions on aromatic rings in resins containing aromatic rings, such as polyimides, polybenzoxazoles, and their precursors, or ring-closing reactions in resins containing silanol groups, such as polysiloxanes, thus significantly improving mechanical properties.

[0266] When the photosensitive composition of the present invention contains the polyimide-based resin, from the viewpoint of improving migration resistance, the photosensitive composition of the present invention preferably satisfies condition (5). When the photosensitive composition of the present invention satisfies condition (5), the polyimide-based resin is more preferably a polyimide-based resin containing a weakly acidic group.

[0267] <Content of specific carboxylic acids and specific oxime compounds>

[0268] The photosensitive composition of the present invention preferably satisfies either or both of conditions (2) and (3). Here, either or both of the aldehyde oxime and ketoxime compounds involved in condition (3) (hereinafter, the oxime compounds involved are sometimes referred to as "specific oxime compounds") are more preferably having a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, a diaryl sulfide structure, or a benzene structure. The condensed polycyclic structure is preferably a fluorene structure, a benzo[a]fluorene structure, a dibenzo[a]fluorene structure, an indene structure, a dihydroindene structure, a benzo[a]indene structure, or a benzo[a]dihydroindene structure. The condensed polycyclic heterocyclic structure is preferably a carbazole structure, a dibenzofuran structure, a dibenzothiophene structure, a benzo[a]carbazole structure, an indole structure, an indoline structure, a benzo[a]indole structure, a benzo[a]indoline structure, a phenothiazine structure, or a phenothiazine oxide structure. The preferred diaryl sulfide structure is a diphenyl sulfide structure, a naphthylphenyl sulfide structure, or a dinaphthyl sulfide structure.

[0269] Furthermore, from the viewpoint of improving sensitivity during exposure and improving migration resistance, the content of one or more of the group consisting of acetic acid, propionic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, benzoic acid, methylbenzoic acid, and trimethylbenzoic acid involved in condition (2) relative to the total solids content of the photosensitive composition is preferably 0.030 ppm by mass or more, more preferably 0.050 ppm by mass or more, even more preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and improving migration resistance, the content of the specific carboxylic acid relative to the total solids content of the photosensitive composition is preferably 300 ppm by mass or less, more preferably 200 ppm by mass or less, and even more preferably 100 ppm by mass or less. Furthermore, it is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5.0 ppm by mass or less, particularly preferably 3.0 ppm by mass or less, and most preferably 1.0 ppm by mass or less.

[0270] From the viewpoint of improving sensitivity during exposure and enhancing migration resistance, the content of the specific oxime compound in the total solids component of the photosensitive composition is preferably 0.030 ppm by mass or more, more preferably 0.050 ppm by mass or more, even more preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and enhancing migration resistance, the content of the specific oxime compound in the total solids component of the photosensitive composition is preferably 300 ppm by mass or less, more preferably 200 ppm by mass or less, and even more preferably 100 ppm by mass or less. Furthermore, it is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5.0 ppm by mass or less, particularly preferably 3.0 ppm by mass or less, and most preferably 1.0 ppm by mass or less.

[0271] It is inferred that by containing trace amounts of the specific carboxylic acid or oxime compound, the acidity or negative charge of the carboxyl and oxime groups can capture metallic or ionic impurities that adversely affect electrical insulation, thereby inhibiting ion migration or electromigration and improving migration resistance. Furthermore, it is inferred that because the specific carboxylic acid and oxime compound capture moisture in the cured product, ion migration or electromigration can be inhibited, thus improving migration resistance.

[0272] When the photosensitive composition of the present invention contains the (C1-1) compound, from the viewpoint of improving sensitivity during exposure and improving migration resistance, the photosensitive composition of the present invention preferably satisfies either or both of the conditions (2) and (3). It is believed that by containing trace amounts of the specific carboxylic acid or the specific oxime compound, the free radicals generated from the (C1-1) compound are prolonged, and the effect of improving sensitivity during exposure becomes significant.

[0273] <Content of chlorine, bromine, and sulfur>

[0274] From the viewpoint of improving sensitivity during exposure and improving migration resistance, the photosensitizing composition of the present invention preferably contains one or more components selected from the group consisting of a component containing chlorine, a component containing bromine, and a component containing sulfur, and satisfies the following condition (6).

[0275] Condition (6): The total chlorine and bromine content in the total solids of the photosensitive composition is 0.010 ppm by mass or more and 500 ppm by mass or less, or the sulfur content in the total solids of the photosensitive composition is 0.010 ppm by mass or more and 500 ppm by mass or less.

[0276] The components containing chlorine and bromine are preferably chlorinated alkyl compounds, chlorinated cycloalkyl compounds, chlorinated aryl compounds, brominated alkyl compounds, brominated cycloalkyl compounds, or brominated aryl compounds. The components containing sulfur are preferably thiols, thioethers, dithioethers, sulfoxides, sulfones, sulfonates, sulfonyl compounds, or thiophenes.

[0277] From the viewpoint of improving sensitivity during exposure and improving migration resistance, the photosensitive composition of the present invention is more preferably to satisfy the following condition (6I).

[0278] Condition (6I): When chlorine, bromine and sulfur are present in the total solids of the photosensitive composition in the form of ions, the total content of chlorine present in the form of ions and the total content of bromine present in the form of ions in the total solids of the photosensitive resin composition is 0.010 ppm by mass or more and 500 ppm by mass or less, or the content of sulfur present in the form of ions in the total solids of the photosensitive composition is 0.010 ppm by mass or more and 500 ppm by mass or less.

[0279] Chlorine and bromine, both present as ions, are preferably present as chloride or bromide ions. Sulfur, present as ions, is preferably present as sulfide ions, hydrogen sulfide ions, sulfate ions, hydrogen sulfate ions, or sulfite ions.

[0280] From the viewpoint of improving sensitivity during exposure and improving migration resistance, the total content of chlorine and bromine, and the content of sulfur in the total solids composition of the photosensitive composition are preferably 0.030 ppm by mass or more, more preferably 0.050 ppm by mass or more, even more preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and improving migration resistance, the total content of chlorine and bromine, and the content of sulfur are preferably 300 ppm by mass or less, more preferably 200 ppm by mass or less, and even more preferably 100 ppm by mass or less. Furthermore, it is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5.0 ppm by mass or less, particularly preferably 3.0 ppm by mass or less, and most preferably 1.0 ppm by mass or less.

[0281] It is inferred that by using trace amounts of chlorine, bromine, or sulfur, non-covalent electron pairs or empty atomic orbitals (i.e., 3d orbitals) can capture metallic or ionic impurities that adversely affect electrical insulation, thereby suppressing ion migration or electromigration and improving migration resistance.

[0282] When the photosensitive composition of the present invention satisfies any one or both of conditions (2) and (3), from the viewpoint of improving migration resistance, the photosensitive composition of the present invention preferably satisfies any one or both of conditions (6) and (6I). When the photosensitive composition of the present invention satisfies conditions (6) or (6I), by containing trace amounts of the chlorine, bromine, or sulfur elements, the storage stability of the (Cl-1) compound is improved. Therefore, it is preferable in terms of controlling the content of specific carboxylic acids and specific oxime compounds, and the effect of improving sensitivity during exposure becomes significant. In addition, by containing trace amounts of the chlorine, bromine, or sulfur elements, the generation of foreign matter during storage can be suppressed, and the effect of improving storage stability becomes significant.

[0283] <Water content>

[0284] From the viewpoint of improving sensitivity during exposure and improving migration resistance, the photosensitive composition of the present invention preferably satisfies condition (4).

[0285] From the viewpoint of improving sensitivity during exposure and improving migration resistance, the water content in the photosensitizing composition is preferably 0.030% by mass or more, more preferably 0.050% by mass or more, further preferably 0.070% by mass or more, and particularly preferably 0.10% by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and improving migration resistance, the water content is preferably 2.5% by mass or less, more preferably 2.2% by mass or less, and further preferably 2.0% by mass or less. More preferably, it is 1.7% by mass or less, more preferably 1.5% by mass or less, further preferably 1.2% by mass or less, further preferably 1.0% by mass or less, particularly preferably 0.70% by mass or less, and most preferably 0.50% by mass or less.

[0286] It is inferred that the water, through the interaction of water molecules such as dipole moments or hydrogen bonds, captures metallic or ionic impurities that adversely affect electrical insulation, thus inhibiting ion migration or electromigration and improving migration resistance.

[0287] When the photosensitive composition of the present invention satisfies condition (2) or condition (3), from the viewpoint of improving migration resistance, the photosensitive composition of the present invention preferably satisfies condition (4). The photosensitive composition of the present invention improves the storage stability of the (C1-1) compound by setting the water content within a specific range, thus it is preferable in terms of controlling the content of specific carboxylic acids and specific oxime compounds, and the effect of significantly improving sensitivity during exposure becomes significant. Furthermore, by setting the water content within a specific range, the photosensitive composition of the present invention can suppress the generation of foreign matter during storage, and the effect of significantly improving storage stability becomes significant.

[0288] <Fluoride content>

[0289] From the viewpoint of suppressing residue at the hem of the pattern and improving migration resistance, the photosensitive composition of the present invention preferably satisfies condition (1α). More preferably, the photosensitive composition of the present invention satisfies condition (2α).

[0290] From the viewpoint of the effectiveness of the invention, the fluorine content in the total solids component of the photosensitive composition is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of the effectiveness of the invention, the fluorine content is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 300 ppm by mass or less, and particularly preferably 100 ppm by mass or less. Furthermore, the fluorine content is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, even more preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.

[0291] The preferred range of the content of fluoride ions in the total solids of the photosensitive composition is the same as the preferred range of the content of fluorine in the total solids of the photosensitive composition.

[0292] In the total solids composition of the photosensitive composition, the fluorine content may also be 0 ppm by mass. The content of fluoride ions in the total solids composition of the photosensitive composition may also be 0 ppm by mass. When the fluorine content or fluoride ion content in the total solids composition of the photosensitive composition exceeds 0 ppm by mass, the photosensitive composition of the present invention preferably contains (A) an adhesive resin, (C) a photosensitizer, (B) a compound, or (F) a crosslinking agent having fluorine atoms or fluoride ions in its structure, or further contains any one or both of the components containing nonionic fluorine atoms and components containing fluoride ions.

[0293] The component containing nonionic fluorine atoms is preferably a phenolic compound, a fluorinated alkyl compound, a fluorinated cycloalkyl compound, or a fluorinated aryl compound having a substituent containing a fluorinated alkyl group. The component containing fluoride ions is preferably a cation containing ammonium ions, primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, or quaternary ammonium ions. Quaternary ammonium ions are preferably hydrocarbon groups having a straight chain or branches. The hydrocarbon group is preferably an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0294] By setting the content of compounds containing nonionic fluorine atoms or components containing fluoride ions in the photosensitive composition to a specific amount or less, and the content of nonionic fluorine atoms or fluoride ions or fluorine-containing anions derived from these components to a specific amount or less, it is inferred that protons in the photosensitive composition are locally activated through the interactions of hydrogen bonds and the like among the components. Therefore, it is believed that the effect of suppressing residue at the bottom edge of the pattern becomes significant through its solubilizing effect relative to the developer. Furthermore, it is believed that by intentionally setting the content of the aforementioned components to a specific amount or less, the polarization structure or charge balance in the cured product can be controlled. As a result, it is inferred that migration resistance is improved by suppressing ion migration or electromigration caused by metallic or ionic impurities that adversely affect electrical insulation.

[0295] <Content of carbonyl-containing compounds with specific structures>

[0296] From the viewpoint of improving mechanical properties and migratory resistance, the photosensitive composition of the present invention preferably contains a specific (C1x-DL) compound described later. Examples and preferences of the specific (C1x-DL) compound are described as described later in the description of the specific (C1x-DL) compound in the cured product.

[0297] <Photosensitive composition coating and photosensitive composition film of the present invention>

[0298] The photosensitive composition film of the present invention is a semi-cured (B-stage) film formed by forming the photosensitive composition of the present invention. The term "semi-cured" refers to a state in which no cross-linked structure has been formed, or a state in which a cross-linked structure has been formed through a partial reaction but the film remains fluid. Examples include a state in which the coating is dried under reduced pressure and the solvent is removed by distillation after coating on a substrate, or a state in which the coating is dried by heating at 40°C to 150°C; and a state in which it is soluble in alkaline solutions or organic solvents. The photosensitive composition film of the present invention preferably comprises a photosensitive composition film formed by forming the photosensitive composition of the present invention and a support. From an operability point of view, this structure is preferred. The photosensitive composition film has positive or negative photosensitivity. The photosensitive composition film is also preferably capable of forming a self-supporting film from a single film. The photosensitive composition film preferably has adhesiveness, and is also preferably capable of bonding multiple components. The ability to form a self-supporting film using a single film refers to the ability to form a film with a width of 1.5 cm or more, a length of 5.0 cm or more, and a thickness of 5.0 μm or more without a support. That is, the photosensitive composition film is preferably a photosensitive composition film capable of forming a self-supporting film using a single film. The support is preferably a flexible substrate, but a rigid substrate may also be used. The surface of the photosensitive film side of the support may also be surface-treated with a silane coupling agent or the like. From an operability point of view, the thickness of the support is preferably 10 μm to 200 μm.

[0299] <Curated product of the photosensitive composition of the present invention>

[0300] The cured product of the present invention is formed by curing the photosensitive composition of the present invention. Curing refers to the loss of film fluidity or the formation of the aforementioned state through the formation of a cross-linked structure by a reaction. The reaction used for curing is not particularly limited to reactions carried out by heating, reactions carried out by irradiation with energy rays, etc., but reactions carried out by heating are preferred. The loss of film fluidity through the formation of a cross-linked structure by heating is called thermal curing. Heating conditions include, for example, heating at 150°C to 500°C for 5 minutes to 300 minutes. The cured product of the present invention may also be formed by curing the photosensitive film of the present invention.

[0301] From the viewpoint of suppressing external light reflection and improving the reliability of the device, the optical concentration at the wavelength of visible light per 1 μm of film thickness of the cured material of the present invention is preferably 0.20 or more, more preferably 0.50 or more, and even more preferably 1.0 or more. On the other hand, from the viewpoint of improving sensitivity during exposure and improving the reliability of the device, the optical concentration is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. Furthermore, the optical concentration is preferably the optical concentration in the cured material formed by heating and curing the composition. When the optical concentration is within the above range, incident external light can be blocked, and thus the effect of suppressing external light reflection becomes significant. In addition, since the light degradation of the cured material itself or the layers located inside it can be suppressed, the effect of improving the reliability of the device becomes significant.

[0302] From the viewpoint of improving component reliability and reducing transmission loss, the dielectric loss tangent of the cured material of the present invention is preferably 0.00010 to 0.0100 at a frequency of 1 GHz. Furthermore, the dielectric loss tangent is a value obtained by measuring using a resonator method with a split post dielectric resonator (SPDR). Additionally, from the viewpoint of improving component reliability and reducing transmission loss, the dielectric constant of the cured material of the present invention is preferably 2.0 to 3.5 at a frequency of 1 GHz. The preferred ranges for the dielectric loss tangent and dielectric constant of the cured material of the present invention at frequencies of 10 GHz, 30 GHz, and 70 GHz are also the same as described above.

[0303] From the viewpoint of improving migration resistance, the water absorption rate of the cured product of the present invention is preferably 0.10% by mass or more, more preferably 0.30% by mass or more. On the other hand, from the viewpoint of improving migration resistance, the water absorption rate is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, further preferably 0.80% by mass or less, more preferably 0.60% by mass or less, and particularly preferably 0.50% by mass or less.

[0304] <Including solidified components and articles>

[0305] The elements of this invention include the cured product of this invention. Additionally, the articles of this invention include the cured product of this invention. Examples of articles include: electronic components, electronic devices, mobile bodies, buildings, or windows. Examples of electronic components include: semiconductor devices, antennas, display devices, metal-clad laminates, wiring boards, semiconductor packages, active components containing semiconductor devices, or passive components. The photosensitive composition of this invention is preferably used to form electronic components. Examples of semiconductor devices include: semiconductor devices having a fan-out wafer-level package structure, a fan-out panel-level package structure, or an antenna-in-package structure. Examples of antennas include: microstrip antennas or stripline antennas. Examples of display devices include: organic EL displays, quantum dot displays, micro-light-emitting diode (LED) displays, micro-LED displays, or liquid crystal displays. Examples of metal-clad laminates include: printed circuit boards.

[0306] The electronic components of the present invention include the cured products of the present invention. The cured products of the present invention possess both excellent mechanical properties and high migration resistance. Therefore, the photosensitive composition of the present invention is preferably used for forming an insulating layer, a protective layer, or an interlayer insulating layer for metal wiring in electronic components. Furthermore, the photosensitive composition of the present invention is also preferably used for forming an interlayer insulating layer for rewiring in semiconductor devices, and is also preferably used for forming an insulating layer, a protective layer, or an interlayer insulating layer between metal wiring and ground wiring in antennas. It is also preferably used for forming pixel partitioning layers, planarization layers, protective layers, interlayer insulating layers, or gate insulating layers in organic EL displays, quantum dot displays, or micro-LED displays, and is also preferably used for forming insulating layers, protective layers, or solder resist layers for metal wiring in metal-clad laminates.

[0307] <Hollow Structure>

[0308] The cured product of the present invention can be used as a material for hollow structures, and the electronic components of the present invention preferably have the hollow structure involved. The hollow structure has a hollow structure support material and a hollow structure roof material. From the viewpoint of improving heat resistance and reliability, the hollow structure support material and the hollow structure roof material are preferably resins containing the polyimide system described above. The film thickness of the hollow structure support material is preferably 5 μm to 20 μm. The film thickness of the hollow structure roof material is preferably 10 μm to 50 μm. The photosensitive composition of the present invention is preferably used to form a hollow structure. The photosensitive film of the present invention is preferably used to form a hollow structure. Examples of electronic components having a hollow structure include microelectromechanical systems (MEMS).

[0309] <Electronic Components>

[0310] The electronic components of the present invention will now be described. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of achieving the purpose of the invention without departing from its spirit.

[0311] The electronic component of the present invention has the structure described in

[20] . By adopting the structure described, the electronic component of the present invention can provide an electronic component with excellent migration resistance. It is believed that the (XIa) structure helps to control the polarization structure or charge balance in the cured material. In addition, it is believed that the π electrons in the aromatic structure of the (XIc) structure capture metallic impurities or ionic impurities that have an adverse effect on electrical insulation. Furthermore, it is inferred that the hydrophobic structure in the (XIc) structure inhibits the penetration of moisture into the cured material. It is inferred that the result of these effects is to achieve excellent migration resistance by suppressing ion migration or electromigration caused by metallic impurities or ionic impurities that have an adverse effect on electrical insulation. In addition, it is inferred that by suppressing the migration or agglomeration of metals in the wiring, high reliability is also achieved in electronic components, semiconductor devices, display devices, and metal-clad laminates.

[0312] In the electronic components of the present invention, the (C1x-DL) carbonyl-containing compound in the cured material is a compound having the following (XIa) structure and the following (XIc) structure within its molecular structure (hereinafter, the (C1x-DL) carbonyl-containing compound involved is sometimes referred to as a "specific (C1x-DL) compound").

[0313] (XIa) Structure: A carbonyl group is bonded to a condensed polycyclic heterocyclic structure consisting of two rings, or a carbonyl group is bonded to a condensed polycyclic heterocyclic structure consisting of three rings, including naphthalene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, or dihydropyrrole structures.

[0314] (XIc) Structure: Aromatic structure.

[0315] From the viewpoint of improving migration resistance, the specific (C1x-DL) compound, when the (XIc) structure has a carbonyl group, preferably has a carbonyl group in the (XIa) structure that is different from the carbonyl group. The carbonyl group in the (XIa) structure is preferably a carbonyl group in a ketone, aldehyde, carboxylic acid, carboxylic ester, or carboxylic amide structure. The specific (C1x-DL) compound in the cured product is preferably the specific (C1x-DL) compound in the photosensitive composition, or a compound having a structure derived from a (C1-1) compound having a specific structure. Examples and preferences regarding the (XIa) and (XIc) structures in the specific (C1x-DL) compound in the cured product are described as follows regarding examples and preferences regarding the (Ia) and (Ic) structures in the (C1-1) compound having a specific structure.

[0316] From the viewpoint of improving migration resistance, the cured material in the electronic component of the present invention preferably satisfies the following condition (Xπ).

[0317] Condition (Xπ): The content of a specific (C1x-DL) compound in the cured product is 0.0010% by mass or more and 5.0% by mass or less.

[0318] From the viewpoint of improving migration resistance, the content of the specific (C1x-DL) compound in the cured product is preferably 0.0050% by mass or more, more preferably 0.010% by mass or more, even more preferably 0.050% by mass or more, and particularly preferably 0.10% by mass or more. On the other hand, from the viewpoint of improving migration resistance, the content of the specific (C1x-DL) compound is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, even more preferably 3.0% by mass or less. Furthermore, it is preferably 2.5% by mass or less, more preferably 2.0% by mass or less, even more preferably 1.5% by mass or less, even more preferably 1.0% by mass or less, particularly preferably 0.70% by mass or less, and most preferably 0.50% by mass or less.

[0319] <Resins and compounds in cured products>

[0320] The electronic component of the present invention includes a cured product. The cured product in the electronic component of the present invention is preferably a cured product of a photosensitive composition, more preferably containing a resin. The resin in the cured product is preferably either or both of a resin containing a weakly acidic group (XA1) and a resin not containing a weakly acidic group (XA2). The resin containing a weakly acidic group (XA1) in the cured product is preferably the (A1) resin or a resin having a structure derived from the resin. The resin not containing a weakly acidic group (XA2) is preferably the (A2) resin or a resin having a structure derived from the resin. Examples and preferences regarding the resin in the cured product are described as in the examples and preferences regarding the (A) adhesive resin. The resin in the cured product may be either the (A) adhesive resin in the composition or a resin having a structure derived from the resin.

[0321] <Content of specific nitrogen-containing compounds in the solidified product>

[0322] From the viewpoint of improving migration resistance, the cured material in the electronic component of the present invention preferably also contains one or more selected from the group consisting of the specific nitrogen-containing compounds, and satisfies the following condition (X5). Examples and preferences of the specific nitrogen-containing compounds are described as described in the description of the specific nitrogen-containing compounds in the photosensitive composition.

[0323] Condition (X5): When the mass of the cured product is set to 100% by mass, the content of a specific nitrogen-containing compound in the cured product is 0.010% by mass or more and 5.0% by mass or less.

[0324] <Fluorine content in the solidified product>

[0325] From the viewpoint of improving migration resistance, the cured material in the electronic component of the present invention preferably satisfies condition (X1α). More preferably, the cured material in the electronic component of the present invention satisfies condition (X2α).

[0326] From the viewpoint of the effectiveness of the invention, the fluorine content in the cured product is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, further preferably 0.030 ppm by mass or more, further preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of the effectiveness of the invention, the fluorine content is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, further preferably 300 ppm by mass or less, and particularly preferably 100 ppm by mass or less. Furthermore, the fluorine content is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, further preferably 10 ppm by mass or less, further preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.

[0327] The preferred range of fluoride ion content in the cured product is also the same as the preferred range of fluorine content in the cured product.

[0328] The fluorine content in the cured product can be 0 ppm by mass. The fluoride ion content in the cured product can also be 0 ppm by mass. When either or both of the fluorine content and the fluoride ion content in the cured product exceed 0 ppm by mass, the cured product in the electronic component of the present invention preferably has fluorine atoms or fluoride ions in its structure, or further contains either or both of the components containing nonionic fluorine atoms and the components containing fluoride ions.

[0329] Examples and preferred embodiments of the cured material containing nonionic fluorine atoms and fluoride ions are described as described in the descriptions of the components in the photosensitive composition.

[0330] It is believed that by intentionally setting the fluorine content or fluoride ion content in the cured product below a certain value, the polarization structure or charge balance in the cured product can be controlled. As a result, it is inferred that migration resistance can be improved by suppressing ion migration or electromigration caused by metallic or ionic impurities that adversely affect electrical insulation.

[0331] <Method for manufacturing solidified products>

[0332] The method for manufacturing the cured product of the present invention comprises: (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate; (2) a step of irradiating the coating film of the photosensitive composition with active chemical rays using a photomask; (3) a step of developing the photosensitive composition using a developing solution to form a pattern of the photosensitive composition; and (4) a step of heating the pattern to obtain a cured pattern of the photosensitive composition. Furthermore, the methods described in paragraphs

[0453] to

[0481] of International Publication No. 2019 / 087985 may also be applied in these steps. The step of forming the coating film is preferably performed by pre-baking after coating to form the film. The step of obtaining the cured pattern is preferably performed by heating the pattern to thermally cure it.

[0333] Example

[0334] The present invention will be described in more detail below with examples, reference examples, and comparative examples, but the present invention is not limited to these scopes. Furthermore, for compounds used in the following descriptions or tables with abbreviations, the corresponding names are summarized in Tables 1-2.

[0335] [Table 1-2]

[0336]

[0337] <Synthesis Examples of Various Resins>

[0338] As the adhesive resin (A), the compositions of the resins obtained in Synthesis Examples 1 to 25 are summarized in Tables 1-3 to 1-5. Each resin was synthesized using known methods, with appropriate modifications to the monomeric compounds or copolymerization ratios as described in known literature. The copolymerization ratios of the monomers are as shown in Tables 1-3 to 1-5.

[0339] The hydroxyl-containing diamine (HA) used in Synthesis Example 8 is synthesized using the method described in Synthesis Example 1 of International Publication No. 2016 / 056451, paragraphs

[0374] to

[0376] , and by a known method. Furthermore, the resin obtained in Synthesis Example 5 using the hydroxyl-containing diamine (HA) is a polyimide precursor having an amide ester structural unit, an amide acid structural unit, and an imide closed-ring structure.

[0340] [Chemistry 6]

[0341]

[0342] In Synthesis Example 19, based on the synthesis methods described in Synthesis Example 3 and Synthesis Example 5 in paragraphs

[0109] to

[0122] of International Publication No. 2012 / 141165, a phenolic compound with the following structure was synthesized as the condensation product of XLN and SAD instead of the condensation reaction product of XLN and 4-hydroxybenzaldehyde. The obtained phenolic compound was used for the condensation reaction with an aldehyde compound.

[0343] [Chemistry 7]

[0344]

[0345] In Synthesis Example 8, DFA, as an esterifying agent, was reacted with the amic acid structural unit in the resin to convert its structure into an amic acid ester structural unit with a methyl group.

[0346] In Synthesis Examples 9 and 10, HEMA or GDMA was reacted with ODPA, which is a tetracarboxylic acid dianhydride, to perform ring-opening addition of all the anhydride groups of ODPA. Then, BAHF, which is a diaminophenol compound, and EtOH, which is a capping agent, were reacted with carboxyl groups derived from ODPA.

[0347] In Synthesis Example 18, GMA having epoxy groups was reacted with carboxyl groups derived from MAA in the resin to achieve ring-opening addition of all epoxy groups in GMA.

[0348] In Synthesis Example 24, DHBA with a carboxyl group was reacted with epoxy groups derived from GMA in the resin to induce a ring-opening addition of all the epoxy groups in GMA.

[0349] In Synthesis Example 25, GMA with epoxy groups was reacted with phenolic hydroxyl groups derived from HPMA in the resin to achieve ring-opening addition of all epoxy groups in GMA.

[0350] [Table 1-3]

[0351]

[0352] [Table 1-4]

[0353]

[0354] [Table 1-5]

[0355]

[0356] The structural units and structures of the resins obtained in each synthesis example, as well as those used in each example, reference example, and comparative example, are summarized in Table 2-1. Furthermore, the resins in polyimide (PI-1) to polyimide (PI-4), polyimide precursor (PIP-1) to polyimide precursor (PIP-3), polybenzoxazole (PB-1), polybenzoxazole precursor (PBP-1), and polyamide-imide (PAI-1) have a fluorine content exceeding 10,000 ppm by mass. The resins in polyimide (PI-5) to polyimide (PI-7), polyimide precursor (PIP-4), and other synthesis examples have a fluorine content of 0 ppm by mass.

[0357] [Table 2-1]

[0358]

[0359] A summary and description of the (D) colorant and (E) dispersant used in each embodiment, reference example, and comparative example are shown in Table 2-2. In addition, “AR52-BB7” shown in Table 3-8 is a dye obtained by mixing AR52 and BB7 at a 1 / 1 (mol ratio), stirring, filtering the precipitated salt, washing it three times with water, and then drying it.

[0360] [Table 2-2]

[0361]

[0362] <Examples of preparation of various pigment dispersions>

[0363] As pigment dispersions, the compositions of each dispersion obtained in Preparation Examples Bk-1 to Bk-7 are summarized in Table 2-3. Each pigment dispersion in Preparation Examples Bk-1 to Bk-7 was prepared using the following method.

[0364] Preparation of Pigment Dispersions (Bk-1) to (Bk-7) - Examples Bk-1

[0365] Based on paragraphs

[0138] to

[0140] of International Publication No. 2022 / 196261, and the method described in Preparation Example 1, the colorant described in Tables 2-3 and the polyalkylene amine-polyoxyalkylene ether dispersant ADP as a dispersant were used to perform wet media dispersion treatment in a cyclic manner, with the average primary particle size of the pigment being the value described in Tables 2-3. Afterwards, the dispersion was filtered using a 0.80 μmø filter to obtain pigment dispersions (Bk-1) to (Bk-7) with a solid content concentration of 15% by mass and a colorant / dispersant ratio of 100 / 35 (mass ratio). The average primary particle size of the pigment in the obtained pigment dispersions is shown in Tables 2-3. Additionally, the average primary particle size of the pigment in the cured film, the crystallite size of the pigment in the pigment dispersion, and the crystallite size of the pigment in the cured film are also shown in Tables 2-3.

[0366] [Table 2-3]

[0367]

[0368] <Example of Synthesis of Silica Particle Dispersion>

[0369] A summary and description of the inorganic particles, namely silica particles, used in each embodiment, reference example, and comparative example are shown in Tables 2-4.

[0370] Synthesis of dispersions of silica particles (SP-1) to (SP-3) in Examples 26 to 28

[0371] Based on paragraphs

[0132] to

[0134] of International Publication No. 2022 / 196261 and the method described in Synthesis Example 3, dispersions of silica particles (SP-1) to silica particles (SP-3) were obtained using the silica particle dispersions, surface modifiers and polymerization inhibitors described in Tables 2-4.

[0372] [Table 2-4]

[0373]

[0374] <Evaluation methods in various embodiments, reference examples, and comparative examples>

[0375] The evaluation methods in each embodiment, reference example, and comparative example are shown below. Furthermore, a glass substrate (manufactured by Geomatec Corporation; hereinafter, "ITO / Ag substrate") formed by sputtering APC (silver / palladium / copper = 98.07 / 0.87 / 1.06 (mass ratio)) to a 100 nm layer on glass, followed by sputtering ITO to a 10 nm layer on top of the APC layer, was used after UV-O3 cleaning for 100 seconds using a desktop optical surface treatment apparatus (PL16-110; manufactured by SEN Special Light Sources). Tempax glass substrates (manufactured by AGC Techno Glass) or other substrates were used without pretreatment. In addition, regarding film thickness measurement, a surface roughness / profile shape measuring machine (SURFCOM 1400D; manufactured by Tokyo Seimitsu Co., Ltd.) was used to measure the film thickness under the conditions of a measurement magnification of 10,000x, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm / s.

[0376] (1) Weight average molecular weight of resin

[0377] For the aforementioned polyimides (PI-1) to (PI-7), polyimide precursors (PIP-1) to (PIP-4), polybenzoxazole (PB-1), polybenzoxazole precursor (PBP-1), and polyamide-imide (PAI-1), 0.10% by mass N-methyl-2-pyrrolidone solutions of each resin were prepared for use. The molecular weight was determined by measuring the weight-average molecular weight of polystyrene using a gel permeation chromatography (GPC) apparatus (Waters 2690; manufactured by Waters Corporation), with N-methyl-2-pyrrolidone containing 0.050 mol / L dissolved lithium chloride and phosphoric acid as the mobile layer. For other resins, the weight-average molecular weight of polystyrene was determined and calculated using a GPC analytical apparatus (HLC-8220; manufactured by Tosoh Corporation) with tetrahydrofuran or N-methyl-2-pyrrolidone as the flow layer, based on Japanese Industrial Standards (JIS) K7252-3 (2008), by a method near room temperature.

[0378] (2) The content of specific aromatic compounds, specific nitrogen-containing compounds, specific carboxylic acids, specific oxime compounds, and specific (C1x-DL) compounds in the composition or cured film.

[0379] The contents of specific aromatic compounds, specific nitrogen-containing compounds, specific carboxylic acids, specific oxime compounds, and specific (C1x-DL) compounds in the composition or cured film were determined by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry using calibration curves based on standard substances. Furthermore, the content of these compounds in the total solids of the composition was calculated from the obtained measurements using the following formula.

[0380] (The content of the target compound in the total solids of the composition) = (The content of the target compound in the composition) × 100 / (The concentration of the solids of the composition [mass%]).

[0381] (3) The content of a specific element in the resin, the composition, or the cured film.

[0382] Under the following test conditions, the contents of fluorine, chlorine, bromine, and sulfur in the resin, composition, or cured film are determined by combustion ion chromatography (represented as "fluorine content," "chlorine content," "bromine content," and "sulfur content," respectively). Each resin is used after being separated by GPC. Furthermore, even when the resin contains resins with different structural units constituting the resin, each resin is used after being separated by GPC. Additionally, in cases where the composition contains either a single resin or resins with different structural units constituting the resin, the resin is used after being extracted with dichloromethane, ultracentrifuged, and then separated from the dichloromethane-insoluble matter by GPC. The resin, composition, or cured film is burned and decomposed in the combustion tube of the analytical apparatus, and the generated gas is absorbed into the absorbent. A portion of the absorbent is analyzed by ion chromatography. The absence of an element content indicates that the element was not detected. Furthermore, the content in the total solids of the composition is calculated from the obtained measured value using the following formula.

[0383] (The percentage of the target compound in the total solids of the composition) = (The percentage of the target compound in the composition) × 100 / (The concentration of the solids in the composition [mass%])

[0384] Combustion-Absorption Conditions

[0385] System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation)

[0386] Electric furnace temperature: Inlet 900℃, Outlet 1000℃

[0387] Gases: Ar / O2 200 mL / min, O2 400 mL / min

[0388] Absorbent: H2O2 0.1% by mass

[0389] Absorption liquid volume: 5 mL

[0390] <Ion Chromatography - Anion Analysis Conditions>

[0391] System: ICS1600 (manufactured by Dionex)

[0392] Shift phase: 2.7 mmol / L Na₂CO₃, 0.3 mmol / L NaHCO₃

[0393] Flow rate: 1.50 mL / min

[0394] Detector: Conductivity detector

[0395] Injection volume: 100 μL.

[0396] (4) The content of fluoride ions in the composition or the cured film

[0397] The content of fluoride ions in the composition or the cured membrane was determined by ion chromatography under the following conditions. The composition or cured membrane was added to ultrapure water, and the mixture was shaken at room temperature to extract the ionic components. After processing the extract using a solid-phase extraction cartridge, the anionic components were analyzed by ion chromatography. For anionic components, if they could not be determined using ion chromatography analysis condition 1 described below, they were determined using ion chromatography analysis condition 2 described below. The absence of ion content in the table indicates that the ion was not detected. Furthermore, the content of the fluoride ions in the total solids of the composition was calculated from the obtained measured value using the following formula.

[0398] (Content in the total solids of the composition) = (Content in the composition) × 100 / (Concentration of solids in the composition [mass%])

[0399] <Ion Chromatography Analysis Conditions 1 (Anionic Components)>

[0400] Device: IC-2010 (manufactured by Tosoh Corporation)

[0401] Separation string: 4.6 mmø × 100 mm, TSKgel Super IC-Anion HS

[0402] Eluent: Sodium bicarbonate

[0403] Column temperature: 40℃

[0404] Detector: Conductivity meter

[0405] Sample injection volume: 250 μL

[0406] <Ion Chromatography Analysis Conditions 2 (Anionic Components)>

[0407] Device: IC-2010 (manufactured by Tosoh Corporation)

[0408] Separation string: 4.6 mmø × 100 mm, TSKgel Super IC-Anion HS

[0409] Eluent: Sodium carbonate / Sodium bicarbonate

[0410] Column temperature: 40℃

[0411] Detector: Conductivity meter

[0412] Sample injection volume: 250 μL.

[0413] (5) Water content in the composition

[0414] The water content in the composition was determined by volumetric titration using a Karl Fischer moisture meter (MKS-520; manufactured by Kyoto Electronics Co., Ltd.) and Karl Fischer reagent as the titrant, based on "JIS K0113 (2005)".

[0415] (6) Sensitivity

[0416] The analytical pattern of the developed film was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon). As an indicator of sensitivity, the exposure (value from an i-ray radiometer) required to form a spatial pattern with a width equivalent to an opening of 18 μm within a 20 μm line and spatial pattern was defined as the sensitivity. A sensitivity of 90 mJ / cm² was determined as follows. 2 The following values ​​A+, A, B+, B, C+, and C are considered qualified.

[0417] A+: Sensitivity is 30 mJ / cm 2 the following

[0418] A: Sensitivity exceeds 30 mJ / cm 2 And it is 40 mJ / cm 2 the following

[0419] B+: Sensitivity exceeding 40 mJ / cm 2 And it is 50 mJ / cm 2 the following

[0420] B: Sensitivity exceeds 50 mJ / cm 2 And it is 60 mJ / cm 2 the following

[0421] C+: Sensitivity exceeds 60 mJ / cm 2 And it is 75 mJ / cm 2 the following

[0422] C: Sensitivity exceeds 75 mJ / cm 2 And it is 90 mJ / cm 2 the following

[0423] D: Sensitivity exceeds 90 mJ / cm 2 And it is 150 mJ / cm 2 the following

[0424] E: Sensitivity exceeds 150 mJ / cm 2 .

[0425] (7) Developing residue at the bottom edge of the pattern

[0426] The analytical pattern of the developed film was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon). As an indicator of development residue at the bottom edge of the pattern, the presence of residue was observed in the bottom edge of a 20 μm opening pattern, and the percentage of the outer perimeter of the opening with residue at the bottom edge was calculated. As described below, A+, A, B+, B, C+, and C, where the percentage of the outer perimeter of the opening with residue was 20% or less, were considered acceptable.

[0427] A+: No residue at the bottom of the pattern.

[0428] A: The percentage of residue on the outer periphery of the opening is less than 3%.

[0429] B+: The percentage of residue on the outer periphery of the opening exceeds 3% but is less than 6%.

[0430] B: The percentage of residue on the outer periphery of the opening exceeds 6% but is less than 10%.

[0431] C+: The percentage of residue on the outer periphery of the opening exceeds 10% but is less than 15%.

[0432] C: The percentage of residue on the outer periphery of the opening exceeds 15% but is less than 20%.

[0433] D: The percentage of residue on the outer periphery of the opening exceeds 20% but is less than 50%.

[0434] E: The percentage of residue on the outer periphery of the opening exceeds 50% but is less than 100%.

[0435] (8) Halftone characteristics

[0436] A pre-baked film of the composition was formed on an ITO / Ag substrate with a film thickness of 5 μm. A sample of the pre-baked film was formed using the method described in Example 1 (wherein the composition used in each example or comparative example). A halftone photomask for halftone characteristic evaluation was used, and the exposure was varied. The film was then patterned and exposed to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from an ultra-high pressure mercury lamp, followed by development to produce a developed film of the composition. The transmittance (%T) of the halftone photomask with semi-transparent portions is... HT The transmittance of the light-transmitting part (%T) is respectively. FT The halftone mask used will be applied to 20%, 25%, 30%, 35%, 40%, or 50% of the area. A schematic diagram of the halftone mask used will be provided. Figure 1 The developed film, with its stepped shape, was analyzed, and the developed film thickness (T) of the thick film portion formed by the light-transmitting portion was measured. FT ) μm. The film thickness (T) after development is measured at locations with different transmittance formed by the halftone exposure section, i.e., the semi-transparent section. HT ) μm, calculate the minimum film thickness (T) of the residual film portion after development. HT / min ) μm. As an indicator of halftone characteristics, the maximum step difference film thickness ((T)) was calculated. FT )-(T HT / min )) μm. As described below, A+, A, B+, B, C+ and C with a maximum step difference film thickness of 0.4 μm or more are considered qualified.

[0437] A+: Maximum step difference film thickness is 2.5 μm or more.

[0438] A: The maximum step difference film thickness is greater than 2.0 μm but less than 2.5 μm.

[0439] B+: Maximum step thickness is 1.5 μm or more but less than 2.0 μm.

[0440] B: Maximum step thickness is greater than 1.0 μm but less than 1.5 μm

[0441] C+: Maximum step difference film thickness is 0.7 μm or more but less than 1.0 μm

[0442] C: The maximum step difference film thickness is greater than 0.4 μm but less than 0.7 μm.

[0443] D: The maximum step difference film thickness is greater than 0.1 μm but less than 0.4 μm.

[0444] E: The maximum step difference film thickness is less than 0.1 μm, or there is no residual film after development, so it cannot be measured.

[0445] (9) Opacity (Optical Density Value (hereinafter referred to as "OD value"))

[0446] Samples were obtained by forming cured films using the method described in Example 1, except that a Tempax glass substrate (manufactured by AGC Techno Glass) was used as the substrate (wherein the composition used in each example or comparative example was used. Furthermore, exposure-development was not performed). The incident light intensity (I0) and transmitted light intensity (I) at three in-plane locations of the cured film were measured using a transmittance meter (X-Rite 361T(V); manufactured by X-Rite). As an indicator of light-shielding properties, the OD value per 1 μm of film thickness was calculated using the following formula, and the average OD value at the three in-plane locations was calculated.

[0447] OD value = log 10 (I0 / I).

[0448] (10) Mechanical properties (elongation at break)

[0449] Samples were obtained by forming a cured film using the method described in Example 1, except that a 6-inch diameter SiO2 / Si wafer was used as the substrate (the composition used in each example or comparative example was used; exposure-development was not performed). The cured film was peeled off from the SiO2 / Si wafer using dilute hydrofluoric acid. The peeled cured film was cut into strips with a width of 1.5 cm and a length of 9.0 cm. Tensile tests were performed using a Tensilon (RTM-100; manufactured by Orientec) at a room temperature of 23.0°C and a humidity of 45.0%RH at a tensile speed of 50 mm / min, and the elongation at break was measured. In addition, 10 strips were measured for one sample. As an indicator of mechanical properties, the average of the top 5 results was calculated. As described below, A+, A, B+, B, C+, and C with an elongation at break of 5.0% or more were deemed acceptable.

[0450] A+: Elongation at break is 30% or more.

[0451] A: The elongation at the breaking point is 20% or more but less than 30%.

[0452] B+: Elongation at break is 15% or more but less than 20%.

[0453] B: The elongation at the breaking point is 10% or more but less than 15%.

[0454] C+: Elongation at break is 7.5% or more but less than 10%.

[0455] C: Elongation at break is 5.0% or more but less than 7.5%

[0456] D: Elongation at break is 1.0% or more but less than 5.0%

[0457] E: The elongation at the breaking point is less than 1.0% or cannot be determined.

[0458] (11) Migration resistance (insulation reliability)

[0459] A sample of a cured film was obtained by forming a cured film using the method described in Example 1, except that a migration evaluation substrate (WALTS-TEG ME0102JY; manufactured by Walts Corporation) was used as the substrate and the film thickness of the cured film was set to 1.5 μm. (The composition used in each example or comparative example was the same. Exposure-development was not performed.) Next, wires were soldered to the measurement terminals at 15 μm in the line and 10 μm in the space of the copper wiring of the comb teeth to fabricate an evaluation element. The insulation reliability of the fabricated evaluation element under high temperature and high humidity was evaluated using an insulation degradation characteristic evaluation system (ETAC SIR13; manufactured by Kusumoto Chemical Co., Ltd.). The evaluation element was placed in a high temperature and high humidity bath with test conditions set to 85°C and 85%RH, and a voltage of 5.0 V was applied. The change in resistance over time was measured at 5-minute intervals. The resistance value reached 1.0 × 10⁻⁶. 6 If the resistance is below Ω, it is considered poor insulation. As an indicator of migration resistance, the test time is measured. As follows, A+, A, B+, B, C+, and C with a test time of 200 hours or more are considered qualified.

[0460] A+: Test duration of 1,000 hours or more

[0461] A: The test duration is more than 800 hours but less than 1,000 hours.

[0462] B+: The test duration is more than 600 hours but less than 800 hours.

[0463] B: The test duration is more than 400 hours but less than 600 hours.

[0464] C+: The test duration is more than 300 hours but less than 400 hours.

[0465] C: The test duration is more than 200 hours but less than 300 hours.

[0466] D: The test duration is more than 50 hours but less than 200 hours.

[0467] E: The test time is less than 50 hours or cannot be measured.

[0468] <Compounds used in the various embodiments, reference examples, and comparative examples>

[0469] The structures of the compounds used in the various examples, reference examples, and comparative examples are shown below. Regarding the minimum number of atoms between the two (meth)acryloyl groups in the (I-b3) structure, (b-5) has 4. Regarding the minimum number of atoms between the two (meth)acryloyl groups in the (I-b4) structure, (b-6) has 13, (b-7) has 23, (b-8) has 31, and (b-9) has 17. (Cb-1) to (Cb-3) correspond to the specific (C1x-DL) compounds. These compounds were synthesized by known methods.

[0470] [Chemistry 8]

[0471]

[0472] Additionally, in the table, the ratio of E-body to Z-body (E / Z) in "x-1a" is E / Z = 99 / 1 (mass ratio). In "x-1b" it is E / Z = 90 / 10 (mass ratio). In "x-1c" it is E / Z = 1 / 99 (mass ratio). "x-1 (E)" and "x-1 (Z)" represent that E-body and Z-body are 100%, respectively. These are obtained by synthesizing the cis isomer (Z-body) and trans isomer (E-body) separately, separating the isomers by recrystallization and column chromatography (either or both), and then mixing the isomers at the stated mass ratio.

[0473] [Chemistry 9]

[0474]

[0475] [Chemistry 10]

[0476]

[0477] [Chemistry 11]

[0478]

[0479] [Chemistry 12]

[0480]

[0481] [Chemistry 13]

[0482]

[0483] [Chemistry 14]

[0484]

[0485] [Chemistry 15]

[0486]

[0487] [Chemistry 16]

[0488]

[0489] In addition, the specific aromatic compounds, specific nitrogen-containing compounds, specific carboxylic acids, specific oxime compounds, compounds containing fluorine, chlorine, bromine, or sulfur (hereinafter, "compounds containing specific elements") used in each embodiment, reference example, and comparative example are summarized in Tables 2-5.

[0490] [Table 2-5]

[0491]

[0492] <Preparation of Photosensitive Compositions>

[0493] Compositions 1 to 166 were prepared using the compositions described in Tables 3-1 to 3-10. The values ​​in parentheses in Tables 3-1 to 3-10 represent the mass parts of the solid components of each ingredient. When the composition contains pigment, a blending solution without pigment dispersion was first prepared, and then the pigment dispersion was mixed with the blending solution to prepare the composition. As a solvent, PGMEA / EL / GBL = 50 / 40 / 10 (mass ratio) was used to prepare the composition with a solid component concentration of 20% by mass. The resulting solution of the composition was filtered using a 0.45 μmø filter before use.

[0494] <Example 1>

[0495] Composition 1 was coated onto an ITO / Ag substrate using a spin coater (MS-A100; manufactured by Mikasa). A pre-baked film with a thickness of approximately 1.8 μm was then pre-baked at 120°C for 120 seconds using an alarm buzzer heating plate (HPD-3000BZN; manufactured by ASONE). The pre-baked film was then spray-developed using a small photolithography developing apparatus (AD-1200; manufactured by Takizawa Sangyo) with a 2.38% (w / w) TMAH aqueous solution or cyclopentanone. The time for complete dissolution of the unexposed portion of the pre-baked film (Breaking Point; hereinafter "BP") was measured.

[0496] The pre-baked film was prepared using the same method. For the pre-baked film, a double-sided aligned single-sided exposure apparatus (PEM-6M mask alignment exposure machine; manufactured by United Optics Co., Ltd.) and a grayscale mask for dielectric sensitivity measurement (MDRMMODEL 4000-5-FS; manufactured by Opto-Line International Co., Ltd.) were used for patterning exposure with i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from an ultra-high pressure mercury lamp. After exposure, development was performed using a small photolithography developing apparatus (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) with a 2.38% (w / w) TMAH aqueous solution, followed by a 30-second water rinse to prepare the developed film. The development time was set to 1.3 times the measured BP. Furthermore, when a pattern could not be formed after development with a 2.38% (w / w) TMAH aqueous solution, an exposed film was prepared using the same method as described above. After exposure, a small photolithography developing apparatus (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) was used for development with cyclopentanone, followed by rinsing with water for 30 seconds to prepare a developed film. The development time was set to 1.3 times the measured BP. The developed pattern was observed, and the optimal exposure (i-ray irradiance meter value) was determined to form a spatial pattern with a width of 18 μm corresponding to the opening within a 20 μm line and spatial pattern. After exposure at the optimal exposure, the developed pattern was thermally cured at 220°C for 60 minutes using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermosystem Co., Ltd.) to prepare a cured film with a thickness of approximately 1.2 μm. Regarding the thermosetting conditions, the temperature was increased to 220°C at a rate of 3.5°C / min in a nitrogen environment with an oxygen concentration of less than 20 ppm by mass, and then heated at 220°C for 60 minutes before cooling to 50°C.

[0497] The cured membrane was analyzed using methods such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, gas chromatography, liquid chromatography, and time-of-flight secondary ion mass spectrometry to analyze the structural units of the resin contained in the cured membrane and the structure of the compounds contained in the cured membrane.

[0498] Furthermore, the cured film of Composition 1 contains the following resins and compounds, including resins having structures derived from the resins included in Composition 1, and compounds having structures derived from the compounds included in Composition 1. (XA1x) resin: a resin having phenolic hydroxyl groups and an imide structure in its structural units; resin-specific (C1x-DL) compounds having phenolic hydroxyl groups and having an amide ester structure, an amide acid structure, and an imide structure in their structural units; compounds having an indole structure, a structure with a carbonyl group bonded at the 3-position of the indole, and a benzoyl group bonded at the 4-position and a phenyl group bonded at the 1-position of the indole.

[0499] <Examples 2 to 158 and Comparative Examples 1 to 8>

[0500] The compositions shown in Tables 3-1 to 3-10 were subjected to the same procedures and evaluations as in Example 1. These evaluation results are summarized in Tables 3-1 to 3-10. Furthermore, in Examples 1 to 150 and Comparative Examples 1 to 8, the fluorine content in the total solids of the compositions and the fluorine content in the cured products exceeded 1,000 ppm by mass. In Examples 151 to 153, the fluorine content in the total solids of the compositions and the fluorine content in the cured products were 0 ppm by mass. In Examples 154 to 158, the fluorine content in the total solids of the compositions was as described in Table 3-9, and the fluorine content in the cured products was the same as the fluorine content in the total solids of the compositions. Furthermore, regarding the thermosetting conditions of Example 148, the temperature was increased to 200°C at a heating rate of 3.5°C / min in a nitrogen environment with an oxygen concentration of 20 ppm by mass or less, and then heated at 200°C for 60 minutes, followed by cooling to 50°C. In addition, in each embodiment, when using a composition with positive photosensitivity, the photomask is a photomask with the light-transmitting and light-blocking portions reversed. The development time is set to 60 seconds, 90 seconds, or 120 seconds. Using a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), the optimal exposure (i-ray lux meter value) is determined to form a spatial pattern with a 20 μm width corresponding to an opening in a 20 μm line and spatial pattern. Based on these results, the optimal development time (60 seconds, 90 seconds, or 120 seconds) and the optimal exposure at that development time are determined. After exposure at the optimal exposure, the pattern developed at the optimal development time is heat-cured at 200°C for 60 minutes. Regarding the heat-curing conditions, the temperature is increased to 200°C at a rate of 3.5°C / min in a nitrogen environment with an oxygen concentration of less than 20 ppm by mass, and then heat-treated at 200°C for 60 minutes, followed by cooling to 50°C.

[0501] [Table 3-1]

[0502]

[0503] [Table 3-2]

[0504]

[0505] [Table 3-3]

[0506]

[0507] [Table 3-4]

[0508]

[0509] [Table 3-5]

[0510]

[0511] [Table 3-6]

[0512]

[0513] [Table 3-7]

[0514]

[0515] [Table 3-8]

[0516]

[0517] [Table 3-9]

[0518]

[0519] [Table 3-10]

[0520]

[0521] Comparative Examples 1 through 8, lacking a (C1-1) compound with a specific structure, exhibited poor properties. Furthermore, in Comparative Example 6, the content of a specific aromatic compound in the composition exceeded the preferred range. In Comparative Example 7, the excessive content of a sulfur-containing compound resulted in the sulfur content in the total solids of the composition deviating from the preferred range. In Comparative Example 8, the water content in the composition exceeded the preferred range. Consequently, sensitivity, mechanical properties, and migration resistance decreased.

[0522] <Storage stability of photosensitive compositions>

[0523] The compositions prepared in Examples 1 to 158 were stored at 25°C for one week. After storage, the compositions were deposited on a substrate in the same manner as in Example 1, and no foreign matter was generated, indicating good storage stability. On the other hand, compositions 164 to 166 prepared in Comparative Examples 6 to 8, whose content of specific aromatic compounds, sulfur content in sulfur-containing ions, or water content deviated from the preferred range, were also stored at 25°C for one week. After storage, the compositions were deposited on a substrate in the same manner, and the results showed that more foreign matter was generated, indicating poor storage stability.

[0524] Explanation of icon numbers

[0525] 41: Light-transmitting section

[0526] 42: Shading part

[0527] 43: Semi-transparent section

Claims

1. A photosensitive composition comprising (A) an adhesive resin and a (C1-1) oxime ester compound, and further comprising any one or both of (B) a free radical polymerizable compound and (F) a crosslinking agent, wherein the (C1-1) oxime ester compound has all of the following (Ia), (Ib) and (Ic) structures within its molecular structure. (Ia) Structure: A condensed polycyclic heterocyclic structure consisting of two rings, or a condensed polycyclic heterocyclic structure consisting of three rings including naphthalene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, or dihydropyrrole structures; (Ib) Structure: Oxime ester carbonyl structure. (Ic) Structure: Aromatic structure.

2. The photosensitizing composition according to claim 1, wherein, All or part of the (A) adhesive resin is a resin having the following (WA) weak acid groups in its structure (hereinafter referred to as "(A1) resin"). (WA) Weak acidic group: selected from one or more groups in the group consisting of phenolic hydroxyl, hydroxyimide, hydroxyamide, silanol, 1,1-bis(trifluoromethyl)hydroxymethyl, and mercapto.

3. The photosensitive composition according to claim 1 further comprises one or more of the group consisting of benzene, toluene, xylene and naphthalene, and satisfies the following condition (1). Condition (1): The total content of benzene, toluene, xylene and naphthalene in the photosensitive composition is more than 0.010 ppm by mass and less than 1,000 ppm by mass.

4. The photosensitizing composition according to claim 1, wherein, The (Ia) structure is an indole structure, a benzoindole structure, an indoleline structure, a benzoindoleline structure, a benzofuran structure, a naphthofuran structure, a benzothiophene structure, a naphthothiophene structure, a benzodihydrofuran structure, a naphthodihydrofuran structure, a benzodihydrothiophene structure, or a naphthodihydrothiophene structure, and The (Ic) structure is an aromatic structure bonded with aryl carbonyl, alkyl carbonyl, nitro, cyano, halogen atom, or heterocyclic group.

5. The photosensitizing composition according to claim 1, wherein, The (C1-1) oxime ester compounds also have the following (Id) structure within their molecular structure. (Id) Structure: any one or two of the following groups: an aliphatic group with 1 to 20 carbon atoms and an alicyclic group with 4 to 20 carbon atoms.

6. The photosensitizing composition according to claim 2, wherein, The (A1) resin includes the following (A1x) resin. (A1x) resin: a resin having one or more of the following structural units: an imide structure, an amide structure, an oxazole structure, and a siloxane structure.

7. The photosensitizing composition according to claim 6, wherein, The (A1x) resin is selected from one or more of the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamide-imides, polyamide-imide precursors, polyamides, and copolymers thereof, all of which have weakly acidic groups in their structure. The (A1x) resin has either or both of an amine residue containing the (WA) weak acid group and a carboxylic acid residue containing the (WA) weak acid group.

8. The photosensitive composition according to any one of claims 2 to 7, wherein, The (A) adhesive resin comprises (A1) resin, which comprises (A1y) resin, all or part of which is selected from one or more of the group consisting of phenolic resins, polyhydroxystyrene, phenolic epoxy resins, and phenolic acrylic resins. (A1y) Resin: A resin that has phenolic hydroxyl groups in its structural units.

9. The photosensitive composition according to any one of claims 1 to 7, wherein, The (A) adhesive resin contains (A1) resin and a resin that does not have a (WA) weak acid group in its structure (hereinafter referred to as "(A2) resin"), wherein the (A1) resin contains any or both of the following (A1x) resin and (A1y) resin, and The (A2) resin includes any or both of the following (A2x) and (A2y) resins. (A1x) resin: a resin having one or more of the following structural units: an imide structure, an amide structure, an oxazole structure, and a siloxane structure. (A1y) Resin: A resin that has phenolic hydroxyl groups in its structural units. (A2x) resin: A resin that has free radical polymerizable groups in its structure. (A2y) resin: A resin that does not have free radical polymerizable groups in its structure.

10. The photosensitive composition according to any one of claims 1 to 7, wherein, The adhesive resin (A) satisfies the following condition (P1α). Condition (P1α): In the structure of (A) adhesive resin, the fluorine content is less than 10,000 ppm by mass.

11. The photosensitive composition according to any one of claims 1 to 7, further comprising an organic black pigment, wherein all or part of the organic black pigment is one or more selected from the group consisting of benzofuranone black pigments, perylene black pigments, and azobenzene black pigments. All or part of the benzofuranone-based black pigments are compounds having at least two benzofuran-2(3H)-one structures or at least two benzofuran-3(2H)-one structures having at least two shared benzene rings, their geometric isomers, their salts, or salts of their geometric isomers. All or part of the perylene-based black pigment is a compound having a 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole structure, its geometric isomers, its salts, or salts of its geometric isomers. All or part of the azomethyl base-based black pigment is a compound or its salt having an azomethyl base structure and a carbazole structure.

12. The photosensitive composition according to any one of claims 1 to 7, further comprising an inorganic black pigment, all or part of said inorganic black pigment being selected from one or more of the group consisting of nitrides containing a metal element, carbides containing a metal element, and oxynitrides containing a metal element, said metal element being selected from one or more of the group consisting of zirconium, vanadium, niobium, hafnium, and tantalum.

13. The photosensitive composition according to any one of claims 1 to 7, satisfying the following condition (1α). Condition (1α): The fluorine content in the total solids of the photosensitive composition is less than 1,000 ppm by mass.

14. The photosensitive composition according to any one of claims 1 to 7, further satisfying any one or both of the following conditions (2) and (3). Condition (2): It also contains one or more of the group consisting of acetic acid, propionic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, benzoic acid, methyl benzoic acid and trimethyl benzoic acid, wherein the proportion of these relative to the total solids of the photosensitive composition is 0.010 ppm by mass or more and 500 ppm by mass or less. Condition (3): It also contains one or both of an aldehyde oxime compound and a ketoxime compound, which account for more than 0.010 ppm by mass and less than 500 ppm by mass relative to the total solids content of the photosensitive composition.

15. The photosensitive composition according to any one of claims 1 to 7, satisfying the following condition (4). Condition (4): It also contains water, and the water content in the photosensitive composition is more than 0.010% by mass and less than 3.0% by mass.

16. The photosensitive composition according to any one of claims 1 to 7, wherein, A portion of the (C1-1) oxime ester compounds are compounds (cis isomers) in which a group containing a carbonyl structure and a group containing an oxygen atom of an oxime structure have a cis structure relative to the C=N bond of the oxime structure within the (Ib) structure. Another portion of the (C1-1) oxime ester compounds are compounds (trans isomers) in which a group containing a carbonyl structure and a group containing an oxygen atom of an oxime structure have a trans structure relative to the C=N bond of the oxime structure within the (Ib) structure. When the total of the cis isomers and the trans isomers is set to 100% by mass, the content ratio of the cis isomers or trans isomers is 90.0% to 99.9% by mass.

17. A cured product formed by curing the photosensitive composition as described in any one of claims 1 to 7.

18. An electronic component comprising the cured material as described in claim 17.

19. A method for manufacturing a cured product, comprising: (1) a step of forming a coating film of a photosensitive composition as described in any one of claims 1 to 7 on a substrate; (2) a step of irradiating the coating film of the photosensitive composition with active chemical rays using a photomask; (3) a step of developing the photosensitive composition using a developing solution to form a pattern of the photosensitive composition; and (4) a step of heating the pattern to obtain a cured pattern of the photosensitive composition.

20. An electronic component comprising a cured product, wherein the cured product comprises a carbonyl-containing compound ((C1x-DL) carbonyl-containing compound), the carbonyl-containing compound ((C1x-DL) carbonyl-containing compound) comprising the following (XIa) and (XIc) structures. (XIa) Structure: A carbonyl group is bonded to a condensed polycyclic heterocyclic structure consisting of two rings, or a carbonyl group is bonded to a condensed polycyclic heterocyclic structure consisting of three rings, including naphthalene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, or dihydropyrrole structures. (XIc) Structure: Aromatic structure.

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