Method for manufacturing a patterned cured product, patterned cured product, partition wall, black matrix, color filter, image display panel, image display device, and positive-type photosensitive composition

Abstract

To provide a method for producing patterned cured products using a positive-type photosensitive composition that exhibits excellent sensitivity and developability, and that can form cured products with excellent light-shielding and heat-resistant properties. [Solution] A method for producing a patterned cured product, comprising the steps of: applying a positive-type photosensitive composition containing a specific compound onto a substrate to form a coating film; exposing the coating film to light; developing the exposed coating film; and heating the pattern after development.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a patterned cured product, a patterned cured product, a partition wall, a black matrix, a color filter, an image display panel, an image display device, and a positive-type photosensitive composition. [Background technology]

[0002] In display devices, patterned light-shielding components such as black matrices and black banks are typically formed. Various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator have been proposed as materials for forming such light-shielding components.

[0003] For example, there are known negative-type photosensitive compositions containing black agents such as benzofuranone-based black pigments, perylene-based black pigments, and azo-based black pigments that are highly sensitive and can form patterns of a desired shape (e.g., Patent Document 1), and photosensitive resin compositions containing black colorants (e.g., Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2018 / 181311 [Patent Document 2] Japanese Patent Publication No. 2023-80993 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Step-shaped patterns can be formed by using multi-tone masks such as gray-tone masks or half-tone masks when exposing a photosensitive composition. However, the negative-type photosensitive composition described in Patent Document 1 was not suitable for forming intricate patterns using multi-tone masks. Furthermore, the black coloring agent used in Patent Document 2 sometimes had poor heat resistance.

[0006] Furthermore, the black pigments used in conventional photosensitive compositions typically have poor solubility and dispersibility in the solvents contained in the photosensitive composition, making their use in combination with dispersants common. In addition, they often have insufficient developability, and there are problems such as the formation of residues (foreign matter) in areas that were removed by development after development.

[0007] The present invention has been made in view of the above problems, and aims to provide a method for producing a patterned cured product using a positive-type photosensitive composition that is excellent in sensitivity and developability, and that can form a cured product with excellent light-shielding and heat-resistant properties. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved according to the following configuration example. That is, the present invention provides a method for manufacturing a patterned cured product, a patterned cured product, a partition wall, a black matrix, a color filter, an image display panel, an image display device, and a positive-type photosensitive composition. An example of the configuration of this disclosure is shown below.

[0009] In one embodiment, the present invention is A step of forming a coating film by applying a positive-type photosensitive composition containing a compound represented by the following formula (1) onto a substrate, The process of exposing the coating film, The process of developing the exposed coating film, Includes a step of heating the developed pattern. This relates to a method for manufacturing patterned cured products. [ka] (In formula (1), R 1 and R 2 Each of these is independently a hydrogen atom or a leaving group. However, R 1 and R 2 At least one of them is a leaving group. R 3 , R 4 , and R5 Each is independently a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxy group, or a sulfo group. n1 and n2 are each independently an integer of 0 to 4. n3 is an integer of 0 to 2.)

[0010] In another embodiment, the present invention relates to a positive photosensitive composition containing a compound represented by the following formula (1).

Chemical formula

[0011] In another embodiment, the present invention relates to a patterned cured product formed from the above positive photosensitive composition, a partition wall or a black matrix made of the cured product, a color filter including the black matrix, an image display panel including the color filter, an image display device including the image display panel, and an image display device including the partition wall.

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a method for producing patterned cured products using a positive-type photosensitive composition that is excellent in sensitivity and developability (particularly alkali solubility), while also forming a cured product with excellent light-shielding and heat-resistant properties. The cured product obtained by the manufacturing method of the present invention has excellent light-shielding and heat-resistant properties.

[0013] Furthermore, the positive-type photosensitive composition used in the manufacturing method of the present invention has excellent sensitivity and developability (especially alkali solubility), making it suitable for exposure using multi-tone masks such as gray tone masks and halftone masks. By using a multi-tone mask, stepped patterns can be formed, and for example, spacers can be formed collectively on a black partition. By providing spacers on the black partition, the contact area with the deposition mask when forming the light-emitting layer can be reduced, thereby suppressing a decrease in panel yield due to particle generation and suppressing degradation of the light-emitting element.

[0014] Furthermore, according to the present invention, it is possible to provide a positive-type photosensitive composition that is excellent in sensitivity and developability (especially alkali solubility), while also being able to form a cured product with excellent light-shielding properties and heat resistance. [Modes for carrying out the invention]

[0015] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0016] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the numbers indicated before and after "~" as the lower and upper limits, respectively.

[0017] In this specification, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Linear hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in its main chain and consists only of a linear structure. However, linear hydrocarbon groups may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain an aromatic ring structure. However, an alicyclic hydrocarbon group does not have to consist only of the structure of an alicyclic hydrocarbon; it may also include a linear structure as part of it. "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure. However, an aromatic hydrocarbon group does not have to consist only of an aromatic ring structure; it may also include a linear structure or an alicyclic hydrocarbon structure as part of it. The ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may have substituents consisting of hydrocarbon structures.

[0018] In this specification, "(meth)acryloyl group" encompasses both "acryloyl group" and "methacryloyl group," and "(meth)acrylic" encompasses both "acrylic" and "methacrylic." "(meth)acrylate" encompasses both "acrylate" and "methacrylate."

[0019] The positive-type photosensitive composition of the present invention will be described below.

[0020] <Positive-type photosensitive composition> The positive-type photosensitive composition according to this embodiment (hereinafter also referred to as "this composition") contains a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)"). [ka] (In formula (1), R 1 and R 2 Each of these is independently a hydrogen atom or a leaving group. However, R 1 and R 2 At least one of them is a leaving group. R 3, R 4 , and R 5 These are, independently, a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfo group. n1 and n2 are independent integers between 0 and 4. n3 is an integer between 0 and 2.

[0021] This composition is excellent in sensitivity and developability (especially alkali solubility), and can form a cured product with excellent light-shielding and heat-resistant properties. As represented by formula (1) above, this composition has a thermally leaving group that has excellent solvent solubility, which allows the lactam compound to be dissolved in the solvent at the molecular level, and can significantly suppress the generation of residue during development.

[0022] Furthermore, by introducing thermally leaving groups, the absorption spectrum changes, making it possible to increase the radiation transmittance compared to lactam pigments represented by the following formula (2), thereby increasing sensitivity. In addition, by heating (calcination, post-bake) at a temperature at which thermally leaving groups are released, the thermally leaving groups contained in compound (1) decompose and gasify, and compound (1) can be changed from a dye to a solvent-insoluble or insoluble lactam pigment. As a result, this heating allows the lactam pigment to exhibit its inherent light-shielding properties. Another advantage is that because the thermally leaving groups decompose and lose their solubility in the solvent, color transfer (leaching of dye into the luminescent layer, etc.), which is a problem with dyes, is less likely to occur. Furthermore, this composition does not use a dispersant, or if one is used, only a small amount is needed compared to conventional methods, which has the advantage of suppressing the generation of fumes and decomposition products derived from the dispersant during heating.

[0023] Compound (1) will be described below.

[0024] <Compound (1)> Compound (1) is a compound having a γ-lactam ring represented by the above formula (1), and can be used as a black coloring agent. Compound (1) is classified as a "dye" among coloring agents because it has excellent solubility in solvents at room temperature.

[0025] In this specification, a "leaving group" refers to a group that leaves the body due to heat, light, etc., and is replaced by a hydrogen atom. Leaving groups also include those that are replaced by hydrogen atoms in a stepwise manner, such as the BOC group described later, where a part of the group leaves first, followed by decarboxylation, and as a result is replaced by a hydrogen atom. In other words, compound (1) undergoes a leaving group elimination due to heat, light, etc., and becomes the compound represented by the following formula (2) (hereinafter also referred to as "compound (2)"). [ka] (In formula (2), R 3 , R 4 , R 5 n1, n2, and n3 are equivalent to those in equation (1) above.

[0026] The leaving group in compound (1) is preferably a group that is removed by heat and replaced by a hydrogen atom (hereinafter also referred to as a "thermally leaving group"), more preferably a thermally leaving group that is removed at a heating temperature of 250°C or lower, even more preferably a thermally leaving group that is removed at a heating temperature of 230°C or lower, and particularly preferably a thermally leaving group that is removed at a heating temperature of 200°C or lower.

[0027] Examples of leaving groups include alkoxyalkyl groups such as methoxymethyl groups (MOM groups), alkyloxycarbonyl groups having linear or branched alkyl groups with 1 to 10 carbon atoms, and linear or branched alkenyloxycarbonyl groups having 1 to 10 carbon atoms. The alkyl groups and alkenyl groups may also have alkoxy groups with 1 to 3 carbon atoms. More specifically, examples include methoxymethyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, allyloxycarbonyl group, n-butoxycarbonyl group, isobutyloxycarbonyl group, tert-butoxycarbonyl group (Boc group), n-pentyloxycarbonyl group, methoxyethyloxycarbonyl group, heptyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, allyloxycarbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, and 9-fluorenylmethyloxycarbonyl group (F-moc group). Among these, alkoxyalkyl groups and alkyloxycarbonyl groups are preferred because they have excellent solubility in solvents and allow for easy acquisition of compounds (1) in which the leaving group is removed by heating at low temperatures (e.g., 230°C). More preferably, alkyloxycarbonyl groups having alkoxyalkyl groups with 1 to 5 carbon atoms or branched alkyl groups with 1 to 10 carbon atoms are preferred, and methoxymethyl groups and tert-butoxycarbonyl groups are even more preferred.

[0028] The above R 1 and R 2 It is preferable that the leaving group is such that a compound (1) with excellent solubility in solvents can be easily obtained.

[0029] The above R 3 , R 4 , and R 5Examples of monovalent organic groups in this context include monovalent hydrocarbon groups having 1 to 20 carbon atoms, groups having a divalent heteroatom-containing group between carbon atoms or at the end of the carbon chain of the hydrocarbon group, groups in which some or all of the hydrogen atoms of the hydrocarbon group are replaced with a monovalent heteroatom-containing group, or combinations thereof.

[0030] Examples of the above-mentioned monovalent hydrocarbon groups having 1 to 20 carbon atoms include chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0031] Examples of monovalent linear hydrocarbon groups having 1 to 20 carbon atoms include monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, or monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, isopentyl, and neopentyl groups. Examples of monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl groups; and alkynyl groups such as ethynyl, propynyl, and butynyl groups.

[0032] Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups, or monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl groups. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norborneyl, tricyclodecenyl, and tetracyclododecenyl groups. A bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other are bonded together by a linking group containing one or more carbon atoms.

[0033] Examples of the above-mentioned monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xyl, naphthyl, and anthyl groups; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl groups.

[0034] Examples of the monovalent heteroatom-containing groups mentioned above include hydroxyl groups, carboxyl groups, sulfanyl groups, cyano groups, nitro groups, halogen atoms, and the like.

[0035] Examples of the above-mentioned divalent heteroatom-containing groups include -CO-, -C(=O)O-, -CS-, -NR'-, -O-, -S-, -SO-, -SO2-, or combinations thereof. R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0036] Among these, R 3 , R 4 , and R 5The monovalent organic group in is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, even more preferably a methyl group or a methoxy group, and particularly preferably a methyl group.

[0037] The above n1 and n2 are each an integer between 0 and 4, preferably 0 or 1, and more preferably 0. When n1 or n2 is an integer of 1 or more, that is, when compound (1) has substituents at positions 4 to 7 of the dihydroindorone ring, it is preferable to have substituents at positions 4 or 6 from the viewpoint of ease of manufacture and availability.

[0038] The above n3 is an integer between 0 and 2, preferably 0 or 1, and more preferably 0.

[0039] Compound (1) has geometric isomers EE, ZZ, and EZ, but it may be any single compound of these or a mixture of these geometric isomers.

[0040] The above compound (1) can be synthesized, for example, by synthesizing compound (2) using the method described in International Publication No. 2000 / 24736, and then protecting the amine in the dihydroindorone ring of compound (2) using a known amine protection method or alcohol protection method. For compound (2), a commercially available product may be used. Furthermore, the compound represented by formula (1) can also be obtained by adding dialkyl dicarbonate, dialkenyl dicarbonate, dialkoxyalkyl dicarbonate, etc. to isatin in the presence of a base such as 4-dimethylaminopyridine to obtain N-carbonyloxyalkyl isatin, etc., and then reacting it with 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione under acid or base catalysis, as described in Japanese Patent Publication No. 2016-84425, Japanese Patent Publication No. 2015-121753, International Publication No. 2014 / 071524, J.Am.Chem.Soc., 2013, 135, 12168, J.Am.Chem.Soc., 2015, 137, 15947, etc. Regarding acid catalysts, examples include hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, or organic carboxylic acids such as benzoic acid. Regarding base catalysts, examples include organic amines such as n-butyllithium, lithium diisopropylamide, and triethylamine, organic bases such as pyridines, and inorganic bases such as sodium hydride, sodium hydroxide, and potassium carbonate. The isatin can be synthesized by condensing chloral hydrate, aniline, and hydroxyamine in sulfuric acid, but the cohesiveness and solubility can be adjusted by introducing organic groups into compound (1) using aniline having organic groups such as alkyl groups and alkoxy groups instead of aniline. Furthermore, the cohesiveness and solubility can also be adjusted by mixing multiple compounds (1) with asymmetric structures or compounds (1) with different structures. Depending on the manufacturing method, the introduction rate of leaving groups in the compound represented by formula (1) is all R 1 and R 2 With the total amount being 100 mol%, 50 mol% or more is preferred, 75 mol% or more is more preferred, and 90 mol% or more is even more preferred.

[0041] Compound (2) is a commonly known lactam pigment used as a black pigment, and cured films containing compound (2) exhibit excellent light-shielding properties. Therefore, cured products containing compound (2), which is produced by the detachment of a leaving group from compound (1), have excellent light-shielding properties. Compound (2) is classified as a "pigment" among colorants because it has poor solubility in solvents at room temperature. Due to its low solubility, cured products containing compound (2) as a colorant can suppress elution (color transfer) to the light-emitting layer, etc., when the cured product is used.

[0042] The following structure is a specific example of the above compound (1).

[0043] [ka]

[0044] [ka]

[0045] The lower limit of the content of compound (1) in the positive-type photosensitive composition is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 5 parts by mass, per 100 parts by mass of the alkali-soluble polymer (A) blended into the composition. The upper limit of the content of compound (1) in the positive-type photosensitive composition is preferably 70 parts by mass, more preferably 60 parts by mass, and even more preferably 50 parts by mass. By having the content of compound (1) within the above range, excellent radiation (especially g-rays, h-rays, and i-rays) transmission is obtained, making it easy to obtain a photosensitive composition with excellent sensitivity, and also easy to form a cured product with excellent light-shielding properties.

[0046] The positive-type photosensitive composition used in this manufacturing method may contain the above compound (1), and its other components are not particularly limited, but it is preferable to include, for example, an alkali-soluble polymer (A) and a radiation-sensitive compound (B). Unless otherwise specified, each component may be used alone or in combination of two or more.

[0047] <Alkali-soluble polymer (A)> The alkali-soluble polymer (A) is not particularly limited as long as it is an alkali-soluble polymer or a polymer whose alkali solubility increases with acid or heat, but polymers having acidic groups such as carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, aromatic thiol groups, silanol groups, and fluorinated hydroxyalkyl groups (hydroxyalkyl groups in which some of the hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms) are preferred.

[0048] In this specification, "alkali soluble" means dissolving in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. A polymer is considered alkali soluble if 1 g or more of the polymer dissolves in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. Whether or not a polymer dissolves can be determined by the presence or absence of precipitate.

[0049] Examples of the polymers mentioned above include polymers containing a structural unit (I) having an acid group (A1), siloxane polymers (A2), polyamic acid or polyamic acid esters (A3), novolac resins (A4), cardo resins (A5), and the like.

[0050] (polymer (A1)) A polymer (A1) containing a structural unit (I) having an acidic group (hereinafter also referred to as "polymer (A1)") is an aggregate of polymerization chains containing the structural unit (I) having an acidic group (hereinafter this aggregate is also referred to as the "base polymer"). The structural unit (I) only needs to be included in at least one polymerization chain constituting the base polymer. Polymer (A1) may also contain structural units other than structural unit (I). The following describes each structural unit included in polymer (A1).

[0051] [Structural Unit (I)] Polymer (A1) can have its solubility (alkali solubility) in an alkaline developer enhanced or its curing reactivity improved by the presence of acidic structural units (I).

[0052] Structural unit (I) is not particularly limited as long as it has an acid group, but it is preferably at least one selected from the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. In this specification, "phenolic hydroxyl group" means a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, anthracene ring, etc.).

[0053] Structural unit (I) is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having an acid group include: Examples of monomers constituting structural units having a carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, crotonic acid, and 4-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Examples of monomers constituting structural units having a sulfonic acid group include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc. Examples of monomers constituting structural units having phenolic hydroxyl groups include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc. Each of these can be listed.

[0054] Furthermore, maleimide can be used as the monomer constituting the structural unit (I).

[0055] Among these, (meth)acrylic acid, hydroxyphenyl (meth)acrylate, isopropenylphenol, and 2-(meth)acryloyloxyethyl succinic acid are preferred.

[0056] The base polymer may contain one or more structural units (I) in combination.

[0057] The lower limit of the content of structural unit (I) (total content if multiple types are included) is preferably 1% by mass, more preferably 2% by mass, and still more preferably 5% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass. Setting the content of structural unit (I) within the above range is preferable because it allows for good solubility in alkaline developing solutions.

[0058] [Structural Units (II)] Polymer (A1) is preferable because it contains structural units (II) having crosslinkable groups, which can further improve the resolution and adhesion of the film. The crosslinkable group can be any group that undergoes a curing reaction by heat treatment and is not particularly limited, but in terms of high thermosetting properties, the crosslinkable group is preferably at least one selected from the group consisting of oxyranyl groups, oxetanyl groups, and ethylenically unsaturated groups, with oxyranyl groups or oxetanyl groups being more preferable.

[0059] (Structural unit having an oxetanyl group and an oxyranyl group (II-1)) It is preferable that polymer (A1) contains structural units (II-1) having one or more groups selected from the group consisting of oxetanyl groups and oxyranyl groups, as this can further improve the resolution and adhesion of the film. Furthermore, the oxetanyl and oxyranyl groups act as crosslinking groups, enabling the formation of a cured product with high heat resistance and suppressed degradation over a long period of time. Structural units (II-1) are preferably structural units derived from an unsaturated monomer having oxetanyl and oxyranyl groups, and specifically, are preferably structural units represented by the following formula (4-1). [ka] (In formula (4-1), R 21 This is a monovalent group having an oxyranyl group or an oxetanyl group. R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 1 (This is a single bond or a divalent linking group.)

[0060] In the above equation (4-1), R 21 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups, 3-methyloxetanyl groups, and 3-ethyloxetanyl groups.

[0061] X 1 As the divalent linking group, methylene groups, ethylene groups, and alkanediyl groups such as 1,3-propanediyl groups are preferred.

[0062] Specific examples of monomers that give structural unit (II) represented by the above formula (4-1) include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate. Among these, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred.

[0063] (Structural unit having an ethylenically unsaturated group (II-2)) Structural unit (II-2) preferably has an ethylenically unsaturated group in its side chain, and more preferably has a side chain structure with 3 to 20 carbon atoms having an ethylenically unsaturated group at its terminal. A specific example of structural unit (II-2) is the structural unit represented by the following formula (4-2). [ka] (In formula (4-2), R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 3 This is a divalent linking group having 1 to 12 carbon atoms. R 22 (This is either a hydrogen atom or a methyl group.)

[0064] In the above equation (4-2), X 3 Examples of divalent linking groups represented by include divalent hydrocarbon groups having 1 to 12 carbon atoms, divalent groups in which any methylene group in a divalent hydrocarbon group is replaced with -O-, -COO-, -OCO-, -NHCO-, -CONH-, -OCONH-, or -NHCOO-, and divalent groups in which any hydrogen atom in a divalent hydrocarbon group or a divalent heteroatom-containing group is replaced with a hydroxyl group, a carboxyl group, etc.

[0065] The base polymer may contain one or more structural units (II) in combination.

[0066] When polymer (A1) contains structural unit (II), the lower limit of the content of structural unit (II) (total content if multiple types are included) is preferably 5% by mass, more preferably 15% by mass, and even more preferably 25% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. Setting the content of structural unit (II) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured product to have sufficiently high heat resistance.

[0067] [Structural Unit (III)] In the case of the photosensitive composition of the present invention, if it is a chemically amplified composition, it is preferable that the polymer (A1) contains a structural unit (III) having one or more groups selected from the group consisting of a group represented by the following formula (7) and an acid-dissociable group, from the viewpoint of being able to form a coating film with excellent adhesion between the substrate and the unexposed area during development (development adhesion). [ka] (In formula (7), R A1 , R A2 and R A3 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. However, R A1 , R A2 and R A3 At least one of them is an alkoxy group having 1 to 6 carbon atoms. The asterisk (*) indicates a bonding operation.

[0068] R A1 ~R A3 Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, and tert-butoxy groups. Of these, R A1 ~R A3 The alkoxy group is preferably a methoxy group or an ethoxy group.

[0069] R A1 ~R A3 The C1-C10 alkyl group may be linear or branched. Examples of C1-C10 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and tert-butyl groups. Of these, methyl, ethyl, or propyl groups are preferred.

[0070] From the viewpoint of obtaining a cured product with excellent heat resistance by forming a cross-linked structure, and from the viewpoint of improving the storage stability of the photosensitive composition, RA1 ~R A3 Preferably, at least one of them is an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all are alkoxy groups.

[0071] Among the above, R A1 The group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy group or an ethoxy group. A2 and R A3 The group is preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0072] In structural unit (III), the group represented by formula (7) is preferably bonded to an aromatic ring group or a linear hydrocarbon group. In this specification, "aromatic ring group" means a group obtained by removing n (where n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of such aromatic rings include benzene rings, naphthalene rings, and anthracene rings. The ring may have substituents such as alkyl groups. Examples of linear hydrocarbon groups to which the group represented by formula (7) is bonded include alkanediyl groups and alkenediyl groups.

[0073] The group represented by formula (7) above is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. That is, structural unit (III) preferably has at least one selected from the group consisting of the group represented by formula (7-1), the group represented by formula (7-2), and the group represented by formula (7-3). [ka] (In equations (7-1), (7-2), and (7-3), A 1 and A 2Each of these is independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. m1 is an integer between 0 and 4. m2 is an integer between 0 and 6. However, if m1 is 2 or greater, multiple A 1 These are either the same group or different groups. If m2 is 2 or more, there are multiple A 2 These are either identical or different groups. R 31 This is an alkanediyl group. R A1 , R A2 and R A3 This is equivalent to equation (7) above. The asterisk (*) indicates a bonding operation.

[0074] A 1 and A 2 As an alkoxy group having 1 to 6 carbon atoms, R in formula (7) above is an example. A1 ~R A3 The alkoxy groups with 1 to 6 carbon atoms listed above can be preferably used. Also, A 1 and A 2 As an alkyl group having 1 to 6 carbon atoms, R in formula (7) above is A1 ~R A3 Among the alkyl groups having 1 to 10 carbon atoms, groups corresponding to 1 to 6 carbon atoms can be suitably adopted.

[0075] Group that bonds to aromatic rings "-SiR" A1 R A2 R A3 The position of " is A 1 and A 2 It may be in any position with respect to the other groups except for . For example, in the case of formula (7-1) above, the group "-SiR A1 R A2 R A3 The position of " can be the ortho, meta, or para position, and is preferably the para position.

[0076] m1 is preferably 0 or 1, and more preferably 0. m2 is preferably 0 to 2, and more preferably 0.

[0077] In the above formula (7-3), R 31 is preferably linear. From the viewpoint of increasing the heat resistance of the resulting cured film, R 31 preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

[0078] The structural unit (III) preferably has at least one selected from the group consisting of the group represented by the above formula (7-1) and the group represented by the above formula (7-2) among the above formulas (7-1) to (7-3). Further, when the group “-SiR A1 R A2 R A3 ” is directly bonded to the aromatic ring, it becomes possible to stabilize the silanol group generated with the presence of water. Thereby, it is preferable in that the solubility of the exposed portion in the alkaline developer can be increased and a good pattern can be formed. Among these, the structural unit (III) is particularly preferably a structural unit having the group represented by the above formula (7-1).

[0079] The structural unit (III) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as “unsaturated monomer”), and specifically, at least one selected from the group consisting of the structural unit represented by the following formula (7a-1) and the structural unit represented by the following formula (7a-2) is preferable.

Chemical formula

[0080] In the above equations (7a-1) and (7a-2), R 32 , R 33 The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

[0081] In terms of obtaining a cured product with higher heat resistance and hardness, and increasing the solubility of the exposed area in alkaline developing solution, R 32 , R 33 Among the above, it is preferable that it be a divalent aromatic ring group, and particularly preferable that it be a substituted or unsubstituted phenylene group.

[0082] Specific examples of structural units represented by the above formula (7a-1) include the structural units represented by the following formulas (7a-1-1) and (7a-1-2). Furthermore, specific examples of structural units represented by the above formula (7a-2) include the structural units represented by the following formulas (7a-2-1) and (7a-2-2). [ka] (In equations (7a-1-1), (7a-1-2), (7a-2-1), and (7a-2-2), R 34 and R 35 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 36 These are alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, or hydroxyl groups. m3 is an integer between 1 and 4. A 1 , A 2 m1 and m2 are equivalent to those in equations (7-1) and (7-2) above. R α1 This is equivalent to equations (7a-1) and (7a-2) above.

[0083] Specific examples of monomers constituting structural unit (III) include, for example, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethyldimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinyl naphthyl Examples include (1) silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, etc. Among these, styryltrimethoxysilane and 3-(meth)acryloxypropyltrimethoxysilane are preferred.

[0084] The above-mentioned "acid-dissociable group" refers to a group in which a hydrogen atom in an acidic functional group, such as a phenolic hydroxyl group, carboxyl group, or sulfonic acid group, has been substituted, and which dissociates upon the action of an acid. For example, the acid generated from a photoacid generator upon exposure dissociates the acid-dissociable group, generating a carboxyl group, etc. This creates a difference in solubility in the developer between the exposed and unexposed areas of the coating film, enabling pattern formation.

[0085] The above acid-dissociable group is preferably a group represented by the following formula (8-1) or a group represented by the following formula (8-2). [ka] (In formula (8-1), R A4 and R A5Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least some of the hydrogen atoms of the hydrocarbon group are substituted with a hydroxyl group, a halogen atom, or a cyano group. However, R A4 and R A5 It is impossible for both to be hydrogen atoms. R A6 This refers to a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom or a sulfur atom between carbon atoms or at the end of the bond of this hydrocarbon group, or a group in which at least some of the hydrogen atoms of these groups are substituted with a hydroxyl group, a halogen atom, or a cyano group. R A7 It is a carbon atom or a silicon atom. In formula (8-2), R A8 ~R A14 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. m is either 1 or 2. If m is 2, there are multiple R A11 and R A12 These may be the same or different. In equations (8-1) and (8-2), "*" indicates the site of connection.

[0086] R A4 ~R A6 As a hydrocarbon group having 1 to 30 carbon atoms, R in formula (1) above is 3 and R 4 In this material, a monovalent hydrocarbon group with 1 to 20 carbon atoms can be suitably adopted, with the number of carbon atoms extended up to 30.

[0087] R in the above equation (8-1) A4 ~R A6 As for each of these, alkyl groups having 1 to 30 carbon atoms are preferred, alkyl groups having 1 to 20 carbon atoms are more preferred, alkyl groups having 1 to 10 carbon atoms are even more preferred, and alkyl groups having 1 to 5 carbon atoms are particularly preferred.

[0088] R A8 ~R A14 As for the hydrocarbon group having 1 to 12 carbon atoms, the above R A4 ~RA6 Of the hydrocarbon groups having 1 to 30 carbon atoms, groups corresponding to those with 1 to 12 carbon atoms can be suitably adopted.

[0089] m is either 1 or 2. If m is 2, there are multiple R A11 and R A12 These may be the same or different.

[0090] As structural units having the above-mentioned acid-dissociable group, for example, structural units represented by the following formulas (8-1-1) and (8-1-2) are preferred. [ka]

[0091] In the above equations (8-1-1) and (8-1-2), R α1 This is R in equations (7a-1) and (7a-2) above. α1 This is synonymous with R. A4 ~R A14 ,m is R in the above equations (8-1) and (8-2). A4 ~R A14 It is synonymous with m.

[0092] In the above equations (8-1-1) and (8-1-2), L 1 , L 2 These are, independently, single-bonded and divalent linking groups.

[0093] The above L 1 , L 2 Examples of divalent linking groups in this compound include alkanediyl groups, cycloalkanediyl groups, alkenediyl groups, and arenediyl groups.

[0094] The above alkanediyl group is X in formula (4-1). 1 The same divalent linking group as in the above can be listed.

[0095] Examples of the above-mentioned cycloalkanediyl groups include monocyclic cycloalkanediyl groups such as cyclopentanediyl and cyclohexanediyl groups, and polycyclic cycloalkanediyl groups such as norbornanediyl and adamantanediyl groups.

[0096] Examples of the alkenediyl groups mentioned above include ethendiyl groups, propenediyl groups, and butenediyl groups.

[0097] Examples of the above-mentioned arenediyl group include a phenylene group, a torylene group, a naphthylene group, and the like. A preferred arenediyl group is one having 6 to 15 carbon atoms.

[0098] The above m1 is either 0 or 1.

[0099] The monomers that give the above-mentioned acid-dissociable structural unit are not limited to those listed below. [ka] (R in the above formula) α1 This is R in the above equations (8-1-1) and (8-1-2). α1 (This is synonymous with...)

[0100] The base polymer may contain one or more structural units (III) in combination.

[0101] When polymer (A1) contains structural unit (III), the lower limit of the content of structural unit (III) (or the total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. Setting the content of structural unit (III) within the above range is preferable in that the coating film exhibits better resolution.

[0102] [Structural Units (IV)] The polymer (A1) described above may further contain structural units (IV) (excluding those corresponding to structural unit (III)) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic rings, aromatic vinyl compounds, N-substituted maleimide compounds, heterocyclic vinyl compounds, conjugated dienes, nitrogen-containing vinyl compounds, and unsaturated dialkyl dicarboxylic acid compounds. Introducing these structural units (IV) into the polymer is preferable because it allows for adjusting the glass transition temperature of the polymer (A1) components and improving the pattern shape of the resulting cured film.

[0103] Examples of the alkyl (meth)acrylate esters mentioned above include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0104] Examples of (meth)acrylic acid esters having the above alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo(meth)acrylate [5.2.1.0 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5 Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate.

[0105] Examples of (meth)acrylic acid esters having the above aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0106] Examples of the above aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, and the like.

[0107] Examples of the above N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide.

[0108] Examples of vinyl compounds having the above heterocyclic structure include tetrahydrofurfurylmethyl (meth)acrylate, tetrahydropyranylmethyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) (meth)acrylate, glycerin carbonate (meth)acrylate, (γ-lactam-2-yl) (meth)acrylate, and N-(meth)acryloxyethylhexahydrophthalimide.

[0109] Examples of the above-mentioned conjugated diene compounds include 1,3-butadiene and isoprene; examples of the above-mentioned nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of the above-mentioned unsaturated dicarboxylate dialkyl ester compounds include diethyl itaconate. In addition to the above, other monomers constituting the structural units include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0110] The monomer giving the above structural unit (IV) preferably includes at least one selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, vinyl compounds having a heterocyclic structure, and N-substituted maleimide compounds, and preferably includes at least one selected from the group consisting of methyl (meth)acrylate, styrene, and N-cyclohexyl maleimide.

[0111] The base polymer may contain one or more structural units (IV).

[0112] When polymer (A1) contains structural unit (IV), the lower limit of the content of structural unit (IV) (or the total content if multiple types are included) is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 50% by mass, and more preferably 45% by mass. Setting the content of structural unit (IV) within the above range is preferable because it allows the glass transition temperature of polymer (A1) to be raised to a moderate level.

[0113] [Method for synthesizing polymer (A1)] Polymer (A1) can be produced, for example, by using an unsaturated monomer into which each of the above-mentioned structural units can be introduced, in a suitable solvent, in the presence of a polymerization initiator, according to known methods such as radical polymerization.

[0114] Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl, as well as polymerization initiators of organic peroxides.

[0115] The lower limit of the amount of polymerization initiator used is preferably 0.01 parts by mass, more preferably 1 part by mass, even more preferably 3 parts by mass, and particularly preferably 5 parts by mass, based on 100 parts by mass of the total amount of monomer used in the reaction. The upper limit of the amount of polymerization initiator used is preferably 30 parts by mass, more preferably 25 parts by mass, even more preferably 20 parts by mass, and particularly preferably 15 parts by mass. Using the above range for the amount of polymerization initiator is preferable because it allows for the appropriate polymerization of polymers whose terminal structures have specific structures.

[0116] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass of the total volume of the reaction solution.

[0117] The upper limit of the polymerization reaction temperature is preferably 90°C, more preferably 80°C, and even more preferably 75°C. The lower limit of the reaction temperature is not particularly limited and can be any temperature at which polymerization occurs, but for example, 40°C is preferred, 50°C is more preferred, 60°C is even more preferred, and 65°C is particularly preferred. Setting the polymerization reaction temperature within the above range is preferable because it can suppress the crosslinking reaction between the acid group contained in structural unit (I) and the group contained in structural unit (II) during polymerization.

[0118] The polymerization reaction time varies depending on the type of polymerization initiator and monomer, as well as the reaction temperature, but is usually around 0.5 to 10 hours.

[0119] In the polymerization reaction for producing the above polymer (A1), molecular weight modifiers can be used to adjust the molecular weight. Examples of molecular weight modifiers include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; and terpinolene and α-methylstyrene dimer.

[0120] The polymer (A1) obtained by the polymerization reaction may be used in the preparation of the photosensitive composition while still dissolved in the reaction solution, or it may be isolated from the reaction solution before being used in the preparation of the photosensitive composition. The polymer can be isolated by known isolation methods, such as pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator.

[0121] The polymer (A1) described above has a polystyrene-based weight-average molecular weight (Mw) of preferably 2,000, more preferably 4,000, even more preferably 5,000, and particularly preferably 6,000, determined by gel permeation chromatography (GPC) using THF as a solvent. The upper limit of Mw is preferably 30,000, and more preferably 20,000. It is preferable that Mw be within the above range because it allows for the formation of a cured film with good film-forming properties and good developability.

[0122] Furthermore, in the polymer (A1) described above, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and even more preferably 1.0 to 2.5. When the base polymer consists of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above range.

[0123] The lower limit of the content of the polymer (A1) in the photosensitive composition is preferably 60% by mass, and more preferably 65% ​​by mass, relative to the amount of other substances in the photosensitive composition. The upper limit of the above content is preferably 99% by mass, and more preferably 95% by mass.

[0124] (Polysiloxane (A2)) Specific examples of alkali-soluble polysiloxanes (A2) include copolymers disclosed in, for example, International Publication No. 2017 / 188047, International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, Japanese Patent Publication No. 2020-184010, Japanese Patent Publication No. 2013-114238, Japanese Patent Publication No. 2012-53381, and Japanese Patent Publication No. 2010-32977.

[0125] As the alkali-soluble polysiloxane (A2), silsesquioxane having a first structural unit represented by the following formula (a) and a second structural unit represented by the following formula (b) is preferred. [ka] (In formula (a), X is a monovalent organic group having an unsaturated double bond. In formula (b), Y is a monovalent organic group having a carboxyl group, a carboxylic acid anhydride group, a phenolic hydroxyl group, or a combination thereof.

[0126] In addition, formula (a) above has an average of 1.5 oxygen atoms and 1 X group per silicon atom, and silsesquioxane is represented by the first structural unit (XSiO) in which 1 X group and 3 oxygen atoms are bonded to 1 silicon atom, as shown in formula (i) below. 1.5 This includes (b). The same applies to equation (b). [ka] (In equation (i), * represents a bond with a silicon atom of another structural unit.)

[0127] The group represented by X above is preferably a group having a carbon-carbon double bond, more preferably a group having a vinyl group or a (meth)acryloyl group, even more preferably a group having a (meth)acryloyl group, and even more preferably an acryloyl group. The lower limit of the number of carbon atoms in X is preferably 2, more preferably 4, and even more preferably 6. The upper limit of the number of carbon atoms is preferably 20, and even more preferably 10.

[0128] The above X is a (meth)acryloyloxy group (CH2=CR 1 COO-:R 1 A group consisting of a hydrogen atom or a methyl group and a divalent hydrocarbon group bonded to this (meth)acryloyloxy group is preferred. Specifically, the above X is more preferably a group represented by the following formula (a-1).

[0129] In formula (b) above, Y is a monovalent organic group having a carboxyl group, a carboxylic acid anhydride group, a phenolic hydroxyl group, or a combination thereof. As an organic group, R in formula (1) above. 3 and R 4 A monovalent organic group can be suitably adopted in this material.

[0130] The group represented by Y above is preferably a group having a carboxyl group or a phenolic hydroxyl group, and more preferably a group having a carboxyl group. The lower limit of the number of carbon atoms in Y is preferably 2, more preferably 4, and still more preferably 8. The upper limit of the number of carbon atoms is preferably 30, and more preferably 20.

[0131] As for Y, a group represented by formula (b-1) or formula (b-2) below is preferred. Among these, the group represented by formula (b-1) is more preferred.

[0132] [ka] (In equations (a-1), (b-1), and (b-2), R 51 Each of these is independently either a hydrogen atom or a methyl group. R 52 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. R 53 It is a divalent organic group. R 54 This is a single bond or a divalent organic group. The asterisk (*) indicates a bonding site with Si.

[0133] The above R 52 Examples of C2-C10 alkanediyl groups include ethanediyl, propanediyl, butanediyl, hexanediyl, octanediyl, nonanediyl, and decanediyl groups. Furthermore, some or all of the hydrogen atoms in the alkanediyl group may be substituted with substituents such as halogen atoms (e.g., fluorine, chlorine, bromine, iodine), hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups, acyl groups, acyloxy groups, or groups in which the hydrogen atoms of these groups are substituted with halogen atoms.

[0134] R 53 , R 54The divalent organic group in is R in formula (1) above. 3 and R 4 A group obtained by removing one hydrogen atom from a monovalent organic group can be suitably adopted.

[0135] For siloxane polymers, the weight-average molecular weight (Mw) in polystyrene equivalent, calculated by GPC, is preferably 500 or more. An Mw of 500 or more is preferable because it allows for the acquisition of patterns (cured products) that exhibit sufficiently high heat resistance and good developability. More preferably, Mw is 1000 or more. Furthermore, from the viewpoint of improving film formation and suppressing a decrease in radiation sensitivity, Mw is preferably 10000 or less, and more preferably 5000 or less. In addition, the molecular weight distribution (Mw / Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0136] (Polyamic acid or polyamic acid ester (A3)) The above polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[0137] Examples of the above-mentioned tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include: Examples of aliphatic tetracarboxylic dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc. Examples of aromatic tetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-carbonyl diphthalic anhydride, 4,4'-oxydiphthalic anhydride, propane-1,3-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), and others. In addition, tetracarboxylic dianhydrides described in Japanese Patent Application Publication No. 2010-97188 can be used. The above tetracarboxylic dianhydrides can be used individually or in combination of two or more.

[0138] Among these, the tetracarboxylic dianhydride preferably includes an aromatic tetracarboxylic dianhydride, and more preferably includes 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0139] The above-mentioned diamines are not particularly limited and include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.

[0140] Examples of the above-mentioned aliphatic diamines include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine.

[0141] Examples of the above-mentioned alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine).

[0142] Aromatic diamines include, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]hexanediacid, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl Phenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4,4'-diaminostilbene, 1,4-bis(4-aminophenyl)-piperazine, formula (S-1): [ka] (In formula (S-1), X is -O-, -S-, -CO-, -SO2-, -CH2-, -C(CH3)2-, -C(CH3)(C2H5)-, or -C(CF3)2-. Main-chain diamines such as compounds represented by: Dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-di Cholestanyl aminobenzoate, 3,5-Cholestenyl diaminobenzoate, 3,5-Lanostanyl diaminobenzoate, 3,6-Bis(4-aminobenzoyloxy)cholestane, 3,6-Bis(4-aminophenoxy)cholestane, 4-(4'-Trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-Bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-Diaminobenzoate=5ξ-Cholestan-3-yl, formula (S-2): [ka] (In formula (S-2), X I and X II These are, independently, single bond, -O-, *-COO-, or *-OCO -(However, "*" is R I This shows the combination with ). R I This is an alkanediyl group having 1 to 3 carbon atoms. R II This is a single bond or an alkanediyl group having 1 to 3 carbon atoms. R III This includes alkyl groups, alkoxy groups, fluoroalkyl groups, or C1-C20 alkyl groups. It is a fluoroalkoxy group. a is either 0 or 1. b is an integer between 0 and 3. c is an integer between 0 and 2. d is either 0 or 1, where 1 ≤ a + b + c ≤ 3. Side-chain diamines, etc., of compounds represented by; Examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. In addition, other examples of diaminoorganosiloxanes that can be used include X-22-161-A, PAM-E, KF-8010, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and X-22-9409 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, diamines described in Japanese Patent Publication No. 2010-97188 can be used.

[0143] Among these, the above-mentioned diamine preferably contains a diaminoorganosiloxane, and more preferably contains X-22-161-A (both manufactured by Shin-Etsu Chemical Co., Ltd.).

[0144] The above-mentioned diamines can be used individually or in combination of two or more types.

[0145] Polyamic acids can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine, along with a molecular weight modifier as needed. The preferred ratio of tetracarboxylic dianhydride to diamine used in the synthesis reaction of polyamic acids is such that the acid anhydride groups of the tetracarboxylic dianhydride are 0.2 to 2 equivalents per 1 equivalent of the amino groups of the diamine. Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The preferred ratio of molecular weight modifier is 20 parts by mass or less per 100 parts by mass of the total amount of tetracarboxylic dianhydride and diamine used.

[0146] The synthesis reaction of polyamic acids is preferably carried out in an organic solvent. The reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 to 24 hours. Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenol, or a mixture of one or more of these and other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of organic solvent used (a) is preferably such that the total amount of tetracarboxylic dianhydride and diamine (b) is 0.1 to 50% by mass of the total amount of the reaction solution (a + b).

[0147] As described above, a reaction solution is obtained by dissolving polyamic acid. This reaction solution may be used as is to prepare the photosensitive composition, or the polyamic acid contained in the reaction solution may be isolated before being used to prepare the photosensitive composition.

[0148] The above polyamic acid esters can be obtained, for example, by [I] reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] reacting a tetracarboxylic acid diester with a diamine, [III] reacting a tetracarboxylic acid dihalide with a diamine, etc. The polyamic acid ester to be contained in the photosensitive composition of the present invention may have only an amic acid ester structure, or it may be a partially esterified product in which both an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as is to prepare the photosensitive composition, or the polyamic acid ester contained in the reaction solution may be isolated before being used to prepare the photosensitive composition.

[0149] (Novolac resin (A4)) The novolac resin (A4) can be obtained by polycondensing phenols with aldehydes such as formaldehyde using a known method.

[0150] Examples of the above-mentioned phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis-p-cresol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, and the like. These may be used individually, or two or more may be used in combination.

[0151] In addition to formaldehyde, other examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde. These may be used individually or in combination of two or more.

[0152] The novolac resin preferably has a group containing an unsaturated double bond, such as a (meth)acryloyl group or vinyl, and preferably has a side chain represented by the following formula (5). In this case, it is even more preferable that it has an aromatic ring in the main chain. Among these, a resin having a side chain represented by the following formula (5) and a phenolic novolac main chain is more preferable.

[0153] Examples of resins having a side chain represented by the following formula (5) and a phenolic novolac main chain include acid-modified cresol novolac type epoxy (meth)acrylate resins and acid-modified phenol novolac type epoxy (meth)acrylate resins.

[0154] [ka]

[0155] In the above equation (5), R 61 R is a hydrogen atom or a methyl group. 62 and R 63 These are each independently divalent organic groups. "*" indicates a binding site to the main chain.

[0156] The above R 61 A hydrogen atom is preferred as the element.

[0157] The above R 62 and R 63 As the divalent organic group represented by the above formula (b), a group obtained by removing one hydrogen atom from the monovalent organic group in Y can be suitably adopted.

[0158] The above R 62 and R 63 The number of carbon atoms in the divalent organic group represented by is not particularly limited, and the lower limit may be 1. On the other hand, the upper limit of these carbon atoms may be, for example, 20 or 10.

[0159] The above R 62 As such, divalent hydrocarbon groups are preferred, and divalent linear hydrocarbon groups and divalent alicyclic hydrocarbon groups are more preferred. 63 Preferably, the group is one in which an oxygen atom (-O-) is bonded to the main chain end of a divalent hydrocarbon group, such as -CH2-O-*.

[0160] Examples of acid-modified cresol novolac type epoxy (meth)acrylate resins include polymers represented by the following formula (6). Acid-modified cresol novolac type epoxy (meth)acrylate resins can be obtained, for example, by reacting an epoxy (meth)acrylate resin obtained by reacting a cresol novolac type epoxy resin with (meth)acrylic acid, and then reacting that resin with an acid anhydride such as phthalic anhydride or 1,2,3,6-tetrahydrophthalic anhydride.

[0161] [ka]

[0162] In equation (6) above, p and q are each independent integers between 1 and 30.

[0163] (Cardo resin (A5)) As the above alkali-soluble cardo resin (A5), there is no particular limitation as long as it can be dissolved in an alkali developer, but a resin containing one or more anionic groups such as a carboxy group, a sulfonic acid group, and a phosphonic acid group is preferable. A cardo resin refers to a resin having a cardo skeleton, and a cardo skeleton refers to a skeleton in which two aromatic groups are connected by a single bond to a quaternary carbon atom which is a ring carbon atom constituting a cyclic structure. The cardo resin is preferably a radically polymerizable one, and can be obtained, for example, by reacting a cardo structure-containing epoxy resin, (meth)acrylic acid, and a tetracarboxylic dianhydride. Further, a dicarboxylic anhydride or the like may be reacted as necessary. Commercially available products of radically polymerizable cardo resins include, for example, "WR-301" manufactured by ADEKA Corporation; "V-259ME" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "Ogazol CR-TR1", "Ogazol CR-TR2", "Ogazol CR-TR3", "Ogazol CR-TR4", "Ogazol CR-TR5", "Ogazol CR-TR6" manufactured by Osaka Gas Chemical Co., Ltd., etc. These may be used alone or in combination of two or more. From the viewpoint of alkali developability, the acid value of the alkali-soluble cardo resin is preferably 10 mgKOH / g or more and 300 mgKOH / g or less, and more preferably 20 mgKOH / g or more and 200 mgKOH / g or less.

[0164] (Other alkali-soluble polymers) As the alkali-soluble polymer, in addition to the above, an alkali-soluble polyimide or polybenzoxazole can be used. Specific examples thereof include, for example, the copolymers disclosed in International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, International Publication No. 2017 / 057281, International Publication No. 2017 / 159476, International Publication No. 2017 / 073481, International Publication No. 2017 / 038828, International Publication No. 2016 / 148176, Japanese Patent Application Laid-Open No. 2015-114355, Japanese Patent Application Laid-Open No. 2013-164432, Japanese Patent Application Laid-Open No. 2010-72143, etc.

[0165] The lower limit of the content ratio of the above polymer (A) is preferably 20% by mass, more preferably 30% by mass, and still more preferably 50% by mass with respect to the total amount of solids contained in the present composition (that is, the total mass of components other than the solvent in the photosensitive composition). Further, the upper limit of the content ratio of the polymer (A) is preferably 99% by mass, more preferably 95% by mass with respect to the total amount of solids contained in the photosensitive composition. By setting the content ratio of the polymer (A) within the above range, the pattern formability and the substrate adhesion can be sufficiently increased.

[0166] (Radiation-sensitive compound (B)) Examples of the radiation-sensitive compound (B) include a quinonediazide compound (B1) and a photoacid generator (B2).

[0167] (Quinonediazide compound (B1)) The present composition may contain a quinonediazide compound (B1) as the radiation-sensitive compound (B).

[0168] When using a quinonediazide compound (B1) as the radiation-sensitive compound (B), as the above polymer (A), it is preferable to use a polymer (A1) containing a structural unit (I) having an acid group, or a polymer (A1) containing a structural unit (I) having an acid group and a structural unit (II) having a crosslinkable group, or a polymer different from the above polymer (A1) and further containing a polymer containing a structural unit having a crosslinkable group is preferable.

[0169] The quinonediazide compound (B1) is a compound that generates a carboxylic acid upon irradiation with radiation. Examples of the quinonediazide compound (B1) include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as "parent nucleus") and an orthonaphthoquinonediazide compound. Among these, the quinonediazide compound to be used is preferably a condensate of a compound having a phenolic hydroxyl group as the parent nucleus and an orthonaphthoquinonediazide compound. Specific examples of the parent nucleus include, for example, the compounds described in paragraphs

[0065] to

[0070] of JP-A-2014-186300.

[0170] Specific examples of quinone diazide compounds (B1) include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, and 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene. Examples of ester compounds include those of a phenolic hydroxyl group-containing compound selected from [ethylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, the condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride is preferred as the quinone diazide compound (B1).

[0171] These quinone diazide compounds (B1) may be used alone or in combination of two or more. When quinone diazide compounds (B1) are included, the lower limit of the quinone diazide compound (B1) content is preferably 1 part by mass, more preferably 2 parts by mass, and even more preferably 3 parts by mass, per 100 parts by mass of the polymer (A). The upper limit of the quinone diazide compound (B1) content is preferably 50 parts by mass, more preferably 30 parts by mass, and even more preferably 20 parts by mass, per 100 parts by mass of the polymer (A). It is preferable to have a quinone diazide compound (B1) content of 1 part by mass or more because sufficient carboxylic acid is generated by irradiation of the composition with radiation, the difference in solubility between the irradiated and unirradiated parts in the developer can be sufficiently large, and good patterning can be achieved. In addition, the amount of carboxylic acid that participates in the reaction with polymer components having epoxy groups can be increased, and sufficient heat resistance can be ensured. On the other hand, by limiting the quinone diazide compound content to 50 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, which is preferable in that it can suppress the decrease in developability due to residual quinone diazide compound.

[0172] (Photoacid generator (B2)) The photoacid generator (B2) can be any compound that generates acid in response to radiation (i.e., a radiation-sensitive acid generator), and is not particularly limited. Examples of photoacid generators (B2) include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like.

[0173] When a photoacid generator (B2) is used as the radiation-sensitive compound (B), the polymer (A) is preferably at least one polymer selected from the group consisting of polymers (A1) containing structural unit (III) and siloxane polymers (A2).

[0174] Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include, for example, the compounds described in paragraphs

[0078] to

[0106] of Japanese Patent Publication No. 2014-157252 and the compounds described in International Publication No. 2016 / 124493. From the viewpoint of radiation sensitivity, at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds can be preferably used as the photoacid generator.

[0175] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (b2). [ka] (In formula (b2), R 40 This refers to a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with substituents. The asterisk (*) indicates a bond with another atom in the oximesulfonate compound described above.

[0176] In the above equation (b2), R 40 Examples of monovalent hydrocarbon groups include C1-C20 alkyl groups, C4-C12 cycloalkyl groups, and C6-C20 aryl groups. Examples of substituents include C1-C5 alkyl groups, C1-C5 alkoxy groups, oxo groups, and halogen atoms.

[0177] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylphenylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493. Examples of commercially available oximesulfonate compounds include Irgacure PAG121 from BASF.

[0178] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphasulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphasulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphasulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide (naphthalimidyltrifluoromethanesulfonate).

[0179] These photoacid generators (B2) may be used alone or in combination of two or more. When photoacid generators (B2) are included, the lower limit of the photoacid generator (B2) content is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, and even more preferably 2 parts by mass, per 100 parts by mass of the polymer (A). The upper limit of the photoacid generator (B2) content is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass, per 100 parts by mass of the polymer (A) incorporated into this composition. A photoacid generator (B2) content of 0.01 parts by mass or more is preferable because it allows for good patterning and ensures sufficient heat resistance. Furthermore, a photoacid generator (B2) content of 30 parts by mass or less is preferable because it sufficiently reduces the amount of unreacted photoacid generator after exposure, thereby suppressing a decrease in developability due to residual photoacid generator.

[0180] In addition to the above-mentioned compound (1), alkali-soluble polymer (A), and radiation-sensitive compound (B), this composition may further contain other components to the extent that the effects of the present invention are not impaired. Examples of other components include solvents, colorants other than compound (1), dispersants, dispersing aids, surfactants, polymers other than alkali-soluble polymer (A), polymerization inhibitors, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, ultraviolet absorbers, dissolution accelerators, etc. Among these, it is preferable to include an adhesion aid (C), a dissolution accelerator (D), a surfactant (E), a solvent (S), and a colorant other than compound (1).

[0181] (Adhesion enhancer (C)) This composition, by containing an adhesion aid (C), improves the adhesion between the formed cured product and the substrate (adherent), thereby suppressing the peeling of the cured product from the substrate during the developing process and other steps.

[0182] Examples of the adhesion promoter (C) include a functional silane coupling agent having a reactive functional group or functional acidic phosphates. Examples of the reactive functional group of the functional silane coupling agent include a carboxy group, an acid anhydride group, a (meth)acryloyl group, an epoxy group, a vinyl group, an isocyanate group, etc. Examples of the reactive functional group of the functional acidic phosphates include a (meth)acryloyl group.

[0183] Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. These can be used alone or in combination of two or more. Among these, 3-glycidyloxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferable.

[0184] As the above functional silane coupling agent, commercially available products can also be used. Examples of the commercially available products include KBM-403, KBM-5103, KBM-302, KBM-303, KBM-402, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-967C, etc. (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0185] Specific examples of the functional acidic phosphates include 2-(meth)acryloyloxyethyl acid phosphate, etc.

[0186] Commercially available functional acidic phosphate esters can be used as described above. Examples of commercially available products include Light Ester P-1M and Light Ester P-2M (both manufactured by Kyoeisha Chemical Co., Ltd.).

[0187] The above adhesion aid (C) can be used alone or in a mixture of two or more types.

[0188] When an adhesion aid (C) is incorporated into the photosensitive composition, the lower limit of its content is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, and even more preferably 1 part by mass, per 100 parts by mass of the polymer (A). The upper limit of the content of the adhesion aid (C) is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 3 parts by mass, per 100 parts by mass of the polymer (A) incorporated into the composition. It is preferable that the content ratio of the adhesion aid (C) be within the above range, as this allows for the formation of a cured film with excellent developability adhesion.

[0189] (Dissolution accelerator (D)) The dissolution accelerator (D) can be any compound that promotes solubility in the developer, and examples include low molecular weight compounds with a molecular weight of 1,000 or less that have two or more phenolic hydroxyl groups or one or more carboxyl groups.

[0190] The above low molecular weight compound may have only a carboxyl group, only a phenolic hydroxyl group, or both a carboxyl group and a phenolic hydroxyl group.

[0191] Such phenol compounds with a molecular weight of 1000 or less can be easily synthesized by those skilled in the art by referring to methods described in, for example, Japanese Patent Publication No. 4-122938, Japanese Patent Publication No. 2-28531, U.S. Patent No. 4916210, European Patent No. 219294, etc.

[0192] Specific examples of the above phenol compounds include, for example, resorcinol, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, 2,4,2',4'-biphenyltetrol, 4,4'-thiobis(1,3-dihydroxy)benzene, 2,2',4,4'-tetrahydroxydiphenyl ether, 2,2',4,4'-tetrahydroxydiphenyl sulfoxide, 2,2',4,4'-tetrahydroxydiphenyl sulfone, tris(4-hydroxyphenyl)methane, and 1,1-bis(4-hydroxyphenyl)cyclohexyl Examples include san, 4,4-(α-methylbenzylidene)bisphenol, α,α',α''-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α,α'',α''-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1,2,2-tris(hydroxyphenyl)propane, 1,1,2-tris(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2,5,5-tetrakis(4-hydroxyphenyl)hexane, 1,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,3-tris(hydroxyphenyl)butane, and para[α,α,α',α'-tetrakis(4-hydroxyphenyl)]-xylene.

[0193] Examples of low molecular weight compounds with one or more carboxyl groups and a molecular weight of 1,000 or less include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, and tetramethyl Examples include aliphatic dicarboxylic acids such as chilcuccinic acid and citraconic acid; aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimelitic acid, and mesitylene acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid; and polyfunctional (meth)acrylates having a carboxylic acid.

[0194] Examples of polyfunctional (meth)acrylates having the above-mentioned carboxylic acid include compounds in which trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate have been modified with carboxylic acid. Commercially available products can also be suitably used, such as Aronics M-520 (manufactured by Toagosei Co., Ltd.).

[0195] The above-mentioned dissolution accelerator (D) can be used alone or in a mixture of two or more types.

[0196] When the photosensitive composition used in this manufacturing method contains a dissolution accelerator (D), the lower limit of the content of the dissolution accelerator (D) (total amount if there are multiple types) is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, and still more preferably 1 part by mass, per 100 parts by mass of the polymer (A). The upper limit of the content of the dissolution accelerator (D) is preferably 15 parts by mass, more preferably 10 parts by mass, and still more preferably 8 parts by mass, per 100 parts by mass of the polymer (A) blended into this composition. It is preferable that the content ratio of the dissolution accelerator (D) be within the above range, as this allows for sufficient solubility in the developer solution.

[0197] (Surfactant (E)) Surfactants (E) can be used to further improve the applicability of the composition (specifically, wettability and reduction of uneven application). Examples of surfactants (E) include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

[0198] Specific examples of surfactants include fluorine-based surfactants such as MEGAFACE F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Florard FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.); Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); and F-Top EF301, EF303, and EF352 (manufactured by Shin Akita Chemical Co., Ltd.).

[0199] Examples of silicone-based surfactants include the following product names: SH200-100cs, SH28PA, SH30PA, SH89PA, SH190, SH8400, SH193, SZ6032, SF8428, DC57, DC190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (manufactured by Toray Dow Corning); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BIC Chemie Japan).

[0200] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0201] The above-mentioned surfactant (E) can be used alone or in combination of two or more types.

[0202] When surfactant (E) is incorporated into this composition, the lower limit of the surfactant (E) content is preferably 0.05 parts by mass, more preferably 0.08 parts by mass, per 100 parts by mass of polymer (A). The upper limit of the surfactant (E) content is preferably 1 part by mass, more preferably 0.5 parts by mass, and even more preferably 0.3 parts by mass, per 100 parts by mass of polymer (A) incorporated into this composition.

[0203] (Solvent (S)) This composition is a liquid composition in which compound (1), alkali-soluble polymer (A), radiation-sensitive compound (B), and other components as needed are dissolved or dispersed in a solvent (S). The solvent (S) is preferably an organic solvent that dissolves each component incorporated into the photosensitive composition and does not react with each component.

[0204] Specific examples of solvents (S) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, dimethyl glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, ethers and ketones are preferred as solvents, and propylene glycol monomethyl ether acetate, cyclopentanone, and propylene glycol monomethyl ether are more preferred.

[0205] (Colorants other than compound (1)) In this composition, only compound (1) may be used as the coloring agent, but using coloring agents other than compound (1) (hereinafter also referred to as "other coloring agents") tends to improve the light-shielding properties of the cured product obtained from this composition.

[0206] Other colorants include, for example, organic pigments such as lactam pigments, benzofuranone pigments, azo pigments, and perylene pigments, inorganic black pigments such as carbon black and titanium black, and dyes other than compound (1). Among these, black pigments are preferred, and carbon black is more preferred.

[0207] Furthermore, as described in Japanese Patent Publication No. 2017-226821, for example, a combination of pigments capable of absorbing light in the visible light region may be selected by combining black organic pigments, black inorganic pigments, and specific colored organic pigments. The pigments to be combined are selected from red organic pigments, blue organic pigments, and purple organic pigments. In a preferred embodiment, the red organic pigment is at least one selected from group (a) below, the blue organic pigment is at least one selected from group (b) below, and the purple organic pigment is at least one selected from group (c) below. (a) Group: CI Pigment Red 149, 179, 254, 255, (b) Group: CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 60 (c) Group: CI Pigment Violet 23, 29.

[0208] Examples of dyes other than compound (1) include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, and leuco dyes.

[0209] When other colorants are incorporated into this composition, a composition with excellent sensitivity, developability, and radiation (especially g-rays, h-rays, and i-rays) transmittance can be easily obtained, and a cured product with excellent light-shielding properties can be easily formed. Therefore, the amount of other colorants incorporated is preferably 1 to 70 parts by mass, and more preferably 5 to 60 parts by mass, per 100 parts by mass of the polymer (A).

[0210] When pigments are used as other colorants, their form of use is not particularly limited; they may be used as powders or as dispersions. Among these, it is preferable to prepare the composition by forming a pigment masterbatch and using it as a pigment masterbatch dispersion, from the viewpoint of solvent solubility and solvent dispersibility. It is preferable to use a polymer for the pigment masterbatch, and although the polymer is not particularly limited, it is preferable that it be a polymer similar to the alkali-soluble polymer (A). Dispersants described later may be added to the pigment masterbatch to improve dispersibility.

[0211] As a dispersion medium in a pigment masterbatch dispersion, organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate 3-ethoxyethyl propionate, propylene glycol monomethyl ether propionate, and propylene glycol monomethyl ether can be used; water can also be used.

[0212] (Dispersant) When pigments are used as other colorants, it is preferable to use a dispersant to finely disperse the pigments and stabilize their dispersion state, as this is desirable from the standpoint of ensuring the stability of the composition's quality. Dispersion aids may also be used in conjunction with the dispersant. Furthermore, even when no pigment is applied, if the solubility of compound (1) is poor, a dispersant can be applied to maintain a stable dispersion state.

[0213] As a dispersant, a polymeric dispersant having a functional group is preferred, and moreover, from the viewpoint of dispersion stability, polymeric dispersants having functional groups such as carboxyl groups, phosphate groups, sulfonic acid groups, their bases, primary, secondary, or tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, and pyrazine are preferred. Among these, polymeric dispersants having basic functional groups such as primary, secondary, or tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, and pyrazine are particularly preferred because they can disperse pigments with the use of a small amount of dispersant.

[0214] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants obtained using monomers and macromonomers having amino groups, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants.

[0215] When a dispersant is added to this composition, the amount of dispersant added is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of pigment. Also, when a dispersant is added to this composition even when no pigment is used, the amount of dispersant added is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of compound (1).

[0216] Furthermore, from the viewpoint of ease of manufacture and manufacturing cost, it is preferable that the number of other components that may be included in this composition be as small as possible, and it is also preferable that the composition does not contain a dispersant, as gases and other substances caused by the dispersant may be generated from the cured film.

[0217] (Dispersing agent) When a dispersant is used in this composition, a dispersing aid may also be used together with the dispersant.

[0218] Examples of dispersing agents include pigment derivatives.

[0219] Examples of pigments used in pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolon, quinophthalone, isoindolinone, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments.

[0220] Examples of pigment derivatives include compounds in which sulfonic acid groups, sulfonamide groups, quaternary salts of sulfonamide groups, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., are directly bonded to the pigment skeleton or via alkyl groups, aryl groups, heterocyclic groups, etc.

[0221] (Antioxidant) By using an antioxidant in this composition, the cleavage and degradation of the polymer molecules in this composition can be suppressed, thereby improving durability and other properties.

[0222] Examples of antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0223] (Method for preparing this composition) This composition can be prepared by uniformly stirring, mixing, and dissolving or dispersing compound (1) and other optionally added components. For mixing, known stirrers such as roll mills, ball mills, and sand mills can be used. After mixing each component, the resulting mixture may, if necessary, be filtered through a filter with a pore size of, for example, 2 μm or less.

[0224] The solid content concentration of this composition (i.e., the ratio of the total mass of components other than the solvent (S) in this composition to the total mass of this composition) is appropriately selected considering viscosity, volatility, etc. The solid content concentration of this composition is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and even more preferably 5 to 40% by mass. A solid content concentration above the lower limit is preferable in that it is possible to ensure a sufficient film thickness when this composition is applied to a substrate (adhesion surface). Furthermore, a solid content concentration below the upper limit is preferable in that the viscosity of this composition can be increased to a moderate level, ensuring good coatability.

[0225] This composition can be suitably used to form cured products having light-shielding properties, such as partitions or black matrices. Cured products obtained from this composition, especially partitions and black matrices with excellent light-shielding properties, are particularly useful for liquid crystal display elements, solid-state image sensors, color sensors, organic EL display elements, electronic paper, and the like.

[0226] ≪Method for manufacturing patterned cured products≫ The method for manufacturing a cured product according to this embodiment (hereinafter also referred to as "this manufacturing method") is: A step of forming a coating film by applying a positive-type photosensitive composition containing a compound represented by the following formula (1) onto a substrate, The process of exposing the coating film, The process of developing the exposed coating film, This includes a step of heating the developed pattern. [ka] (In formula (1), R 1 and R 2Each of these is independently a hydrogen atom or a leaving group. However, R 1 and R 2 At least one of them is a leaving group. R 3 , R 4 , and R 5 These are, independently, a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfo group. n1 and n2 are independent integers between 0 and 4. n3 is an integer between 0 and 2.

[0227] <Process (I): Coating process> Step (I) is a step of forming a coating film (organic film) on a substrate by applying a positive-type photosensitive composition containing the compound represented by formula (1) above onto the substrate.

[0228] The present composition can be suitably used as a positive-type photosensitive composition containing the compound represented by the above formula (1).

[0229] Examples of substrates to which the above-mentioned photosensitive composition is applied include glass substrates, silicon wafers, plastic substrates, and substrates on which a colored resist, overcoat, anti-reflective film, various metal thin films, sealing films, etc., are formed on their surfaces.

[0230] Examples of plastic substrates include plastic resin substrates (resin films) made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, polyimide, etc. Various elements (for example, light-receiving elements such as photodiodes, or light-emitting elements such as organic light-emitting diodes) may be pre-installed on the substrate.

[0231] As for the coating method of the above-mentioned photosensitive composition, suitable methods such as spray coating, roll coating, rotary coating (spin coating), slit die coating, bar coating, and inkjet coating can be used. Of these coating methods, spin coating, bar coating, and slit die coating are preferred.

[0232] After applying the above photosensitive composition to a substrate, the composition may be preheated (pre-baked) to prevent dripping, etc. The pre-baking conditions can be appropriately set depending on the type and proportion of each component used in the composition, but for example, conditions of 60 to 130°C for 30 seconds to 10 minutes can be used. It is preferable to heat the pre-baked mixture at a temperature at which the leaving group in compound (1) does not leave the mixture.

[0233] The thickness of the coating film formed, as the thickness after pre-baking, is preferably 0.2 μm or more, more preferably 0.3 to 5 μm, and even more preferably 0.4 to 3 μm.

[0234] <Process (II): Exposure process> Step (II) involves irradiating at least a portion of the coating film formed in step 1 with radiation.

[0235] In step (II), position-selective radiation irradiation of the coating film is usually performed via a mask having a pattern for obtaining a cured product with a desired shape. The mask is preferably a multi-tone mask such as a halftone mask or a graytone mask. The graytone mask has slits formed below the resolution of the exposure machine, and intermediate exposure is achieved by blocking a portion of the light with these slits. In the case of a halftone mask, intermediate exposure is achieved by using a semi-permeable film. By using such a multi-tone mask, stepped patterns can be formed, for example, spacers can be formed collectively on a black partition.

[0236] Examples of radiation used to irradiate the coating include ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. Examples of ultraviolet light include g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). Examples of X-rays include synchrotron radiation. Examples of charged particle beams include electron beams. Of these, ultraviolet light is preferred, and ultraviolet light including g-rays, h-rays, and i-rays is more preferred.

[0237] Examples of light sources used for radiation irradiation include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and LED lamps.

[0238] The radiation exposure dose is 100 to 50,000 J / m². 2 (10-5,000 mJ / cm²) 2 ) is preferred, and 100 to 6,000 J / m 2 (10-600 mJ / cm 2 ) is preferable.

[0239] <Step (III): Development step> Step (III) is a step in which a pattern is formed on the substrate by developing the coating film and cured product obtained in step (II). In this manufacturing method, a positive-type photosensitive composition is used, so positive-type development is performed on the coating film that was irradiated with radiation in step (II) by developing it with a developer to remove the irradiated areas, and a patterned cured product (e.g., an uneven pattern formed by a large number of regularly arranged linear cured products) can be formed on the substrate.

[0240] Examples of developing solutions include aqueous solutions of alkali (basic compounds). Examples of alkalis include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. In addition, an appropriate amount of water-soluble organic solvents such as methanol or ethanol, or surfactants may be added to the aqueous alkali solution, or a small amount of various organic solvents capable of dissolving this composition may be added.

[0241] The concentration of the developer can be appropriately determined according to the composition of the mixture, but is usually 0.01 to 10% by mass, preferably 0.5 to 5% by mass.

[0242] As for the development method, appropriate methods such as the liquid-filling method, dipping method, agitation immersion method, and shower method can be employed.

[0243] The development time can be adjusted as appropriate depending on the composition of this composition, but for example, it is 20 to 120 seconds.

[0244] After the development process, if necessary, a step may be taken to wash the developed patterned substrate using pure water or the like.

[0245] Furthermore, a drying step may be performed on the patterned substrate after development or the cleaning described above. The drying conditions are not particularly limited, but for example, the same conditions as those for pre-baking described above may be used.

[0246] Because this composition has excellent ultraviolet (especially g-ray, h-ray, and i-ray) transmittance, it exhibits superior sensitivity during exposure. As a result, the patterned cured product obtained from this composition adheres well to the substrate, and even fine-line patterns can be formed.

[0247] <Process (IV): Post-bake process> Step (IV) involves heating the coating developed in step (III) (post-bake). Post-bake can be performed using a heating device such as an oven or a hot plate. Regarding post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when heating on a hot plate, and 10 to 80 minutes when heating in an oven. In this way, a cured film having the desired pattern can be formed on the substrate. The shape of the pattern on the cured film is not particularly limited and examples include line-and-space patterns, dot patterns, hole patterns, and grid patterns.

[0248] Step (IV) can also be performed using a step-baking method involving multiple heat treatments.

[0249] <Process (V): Post-exposure process> Step (V) is a step of further irradiating the cured product obtained in step (III) and / or the cured product obtained in step (IV) with radiation. Among these, the step of further irradiating the cured product obtained in step (IV) with radiation is preferred because it allows for the easy formation of a cured product of a desired shape.

[0250] By irradiating with radiation in process (V) (hereinafter also referred to as "post-exposure"), heat resistance, chemical resistance, etc., can be further improved, and highly reliable cured products can be easily formed.

[0251] Of these, the type of radiation and exposure conditions in post-exposure can be the same as those in process (II). The wavelength and dose of the irradiation light, the light source, and other conditions during post-exposure may be the same as or different from those in process (II).

[0252] ≪Cured material, partition, black matrix≫ The cured product of the present invention (hereinafter also referred to as "the cured product") can be formed by curing the positive-type photosensitive composition prepared as described above. The cured product obtained from the positive-type photosensitive composition has excellent developability, optical density (OD value), and heat resistance. Therefore, the patterned cured product can be preferably used as, for example, a color filter (color pattern or black matrix), or a light-shielding partition material (bank). The black matrix refers to a black component that separates each cell such as red, green, and blue (RGB) in a color filter. In addition, partitions are formed on a substrate, and an organic EL light-emitting layer is formed in the recessed space partitioned by the partitions using an inkjet method or the like. A blackened partition to prevent light leakage between pixels is called a light-shielding partition material (black bank). Furthermore, it can also be suitably used as an interlayer insulating film, a planarization film, etc.

[0253] When a cured product formed by curing the curable composition of the present invention is used as a light-shielding partition material, the optical density (OD value) of the cured product is preferably 0.5 to 4.0, and more preferably 0.7 to 3.8. Having an optical density within this range is preferable because it allows the product to exhibit sufficient light-shielding properties as a light-shielding partition material.

[0254] ≪Color Filters≫ The color filter of the present invention comprises the above-mentioned cured material as a black matrix.

[0255] ≪Image Display Panel≫ The image display panel of the present invention only needs to include the above-mentioned color filter, and other configurations are not particularly limited. Furthermore, this cured product can also be used as a color filter or light-shielding partition material in an organic EL panel with a structure that does not have a polarizing plate (POL-LESS) on which a TFT drive circuit layer, a light-shielding partition material (bank), a primary color light-emitting layer having a light-emitting layer, a sealing layer, a touch sensor, a black matrix and a color filter including a color pattern having each color (RGB), and a cover glass are laminated on a substrate.

[0256] Image display device The image display device of the present invention comprises the cured material and the image display panel. The cured material can be used as a light-shielding partition material or a color filter. Examples of such display devices include liquid crystal display devices, organic EL display devices, micro-LED (Light Emitting Diode) display devices, and quantum dot light-emitting display devices. Furthermore, an organic EL display device having an organic EL panel with a polarizing plate-less (POL-LESS) structure is also preferably mentioned. [Examples]

[0257] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0258] Synthesis Example 1: Synthesis of Bk-Dye-1 In a reaction vessel fitted with a condenser, 2.00 g of lactam pigment (Irgaphor Black S0100CF, BASF) was added to 10.00 g of N-methylpyrrolidone and dispersed. Next, 1.95 g of di-tert-butyl dicarbonate, 0.11 g of 4-dimethylaminopyridine, and 1.32 g of triethyl orthoformate were added. The resulting solution was heated to 50°C under a nitrogen stream with stirring and stirred for 5 hours. After the resulting reaction solution was cooled to room temperature, it was added dropwise to 200 mL of hexane. The precipitate was filtered and dissolved in 200 mL of dichloromethane. The resulting dichloromethane solution was washed three times with 200 mL of deionized water, and the organic layer was concentrated under reduced pressure using a rotary evaporator. After drying under reduced pressure at room temperature, 0.50 g of the target Bk-Dye-1 was obtained. The synthesis was repeated as needed.

[0259] [ka]

[0260] Synthesis Example 2: Synthesis of Bk-Dye-2 In a reaction vessel fitted with a condenser, 2.00 g of lactam pigment (Irgaphor Black S0100CF, BASF) was added to 10.00 g of N,N-dimethylformamide and dispersed. Next, 0.79 g of chloromethyl methyl ether and 0.21 g of sodium hydride were added, and the resulting solution was heated to 40°C under a nitrogen stream with stirring for 16 hours. After the resulting reaction solution was cooled to room temperature, 40 mL of saturated sodium bicarbonate aqueous solution was added, and the mixture was stirred for 1 hour. The resulting solution was extracted three times with 100 mL of dichloromethane. The dichloromethane solution after the three extractions was washed three times with 200 mL of deionized water, and the organic layer was concentrated under reduced pressure using a rotary evaporator. The organic layer was then dried under reduced pressure at room temperature to obtain 0.56 g of the target Bk-Dye-2. The synthesis was repeated as needed.

[0261] [ka]

[0262] Synthesis Example 3: Synthesis of Bk-Dye-3 In a reaction vessel fitted with a condenser, 5 g of isatin and 7.5 g of ethylhexyl chloroformate were dissolved in 100 mL of benzene. Then, 10 g of pyridine was added and the mixture was stirred at 50°C for 5 hours. Next, the reaction solution was concentrated under reduced pressure using a rotary evaporator and dissolved in 200 mL of ethyl acetate. This ethyl acetate solution was washed three times with 200 mL of deionized water, and the organic layer was concentrated under reduced pressure using a rotary evaporator and then dried under reduced pressure at room temperature to obtain the desired 2EH-isatin.

[0263] [ka]

[0264] In a reaction vessel fitted with a condenser, 3.3 g of 2EH-isatin and 0.95 g of 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione were dispersed in 100 mL of acetic acid. Next, 0.5 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 115°C for 11 hours. After the resulting reaction solution was cooled to room temperature, it was poured into 500 mL of isopropanol. A precipitate was then obtained by filtration and washed twice with 50 mL of isopropanol. The resulting solid was dried under reduced pressure to obtain the target Bk-Dye-3.

[0265] [ka]

[0266] Synthesis Example 4: Synthesis of the polymer (A1-1) Eight parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Two parts by mass of phenyl methacrylate, 32 parts by mass of cyclomer M100 (manufactured by Daicel Corporation), eight parts by mass of methacrylic acid, 28 parts by mass of N-phenylmaleimide, 20 parts by mass of p-isopropenylphenol, 10 parts by mass of 4-hydroxyphenyl methacrylate, and 2.7 parts by mass of dodecyl mercaptan were then charged into the flask, and the mixture was purged with nitrogen. The mixture was then gently stirred to raise the temperature of the reaction solution to 70°C, and this temperature was maintained for 3 hours for polymerization. Subsequently, the temperature of the reaction solution was raised to 80°C, and polymerization was carried out for a further 1 hour to obtain a solution containing 33.3% by mass of an alkali-soluble polymer (referred to as polymer (A1-1)). The alkali-soluble polymer (A1-1) had an Mw of 9,700.

[0267] Synthesis Example 5: Synthesis of Polymer (A1-2) 220 parts by mass of cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) was placed in a four-necked flask equipped with a stirrer and reflux condenser, and 214 parts by mass of propylene glycol monomethyl ether acetate was added and heated until dissolved. Next, 0.1 parts by mass of hydroquinone was added as a polymerization inhibitor and 2.0 parts by mass of dimethylbenzylamine was added as a reaction catalyst. This mixture was heated to 95-105°C, and 72 parts by mass of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90°C, 106 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours. After cooling, the product was removed to obtain a cresol novolac type epoxy (meth)acrylate resin (A1-2) having acryloyl groups and carboxyl groups (solid content concentration: 50% by mass). The weight-average molecular weight (Mw) of the polymer (A1-2) thus obtained was approximately 3,500.

[0268] Synthesis Example 6: Synthesis of Polymers (A1-3) In a 200 mL three-necked flask equipped with a thermometer and nitrogen inlet tube, 15 g of silsesquioxane (AC-SQ TA-100, manufactured by Toagosei Co., Ltd.) (100 mol% in terms of (meth)acryloyl groups), 15 g of acetonitrile, and 4.8 g (25 mol%) of 3-mercaptopropionic acid were added. Then, 9.2 g (50 mol%) of triethylamine was slowly added, and the mixture was reacted at 50°C for 2 hours. At this point, GPC was checked and the weight-average molecular weight was 4,400, and the 3-mercaptopropionic acid content was less than 0.1%, confirming that Michael addition was proceeding quantitatively. After the reaction was complete, the mixture was transferred to a separatory funnel, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1 M hydrochloric acid solution and three times with 50 mL of water. Next, 40 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the mixture was concentrated to a volume of 40 g. Then, another 40 g of PGMEA was added and the mixture was concentrated again. Subsequently, the solid content was adjusted to 50% by mass using PGMEA to obtain a solution of silsesquioxane (A1-3). The weight-average molecular weight of the obtained silsesquioxane (A1-3) was 4,400.

[0269] Synthesis Example 7: Synthesis of Polymers (A1-4) In a reaction vessel equipped with a condenser, 0.40 g of 3,3',4,4'-biphenyltetracarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 17.0 g of N-methylpyrrolidone. 2.60 g of X-22-161-A (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and the mixture was stirred at 25°C for 10 hours to obtain the target polyamic acid resin (A1-4) (solid content concentration: 15% by mass). The weight-average molecular weight (Mw) of the polymer (A1-4) obtained in this way was approximately 13,200.

[0270] Synthesis Example 8: Synthesis of Polymer (A2-1) Ten parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, ten parts by mass of methacrylic acid, twenty parts by mass of styryltrimethoxysilane, thirty parts by mass of glycidyl methacrylate, thirty parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and ten parts by mass of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A2-1). The solid content concentration of this polymer solution was 34% by mass, the Mw of polymer (A2-1) was 10,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[0271] Synthesis Example 9: Synthesis of Polymer (A2-2) Ten parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, ten parts by mass of methacrylic acid, twenty parts by mass of 3-methacryloxypropyltrimethoxysilane, thirty parts by mass of glycidyl methacrylate, thirty parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and ten parts by mass of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A2-2). The solid content concentration of this polymer solution was 34% by mass, the Mw of polymer (A2-2) was 10,100, and the molecular weight distribution (Mw / Mn) was 2.1.

[0272] Synthesis Example 10: Synthesis of Polymer (A2-3) Ten parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, ten parts by mass of methacrylic acid, fifteen parts by mass of 2-tetrahydropyranylacrylic acid, 35 parts by mass of glycidyl methacrylate, 30 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and ten parts by mass of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A2-3). The solid content concentration of this polymer solution was 33% by mass, the Mw of polymer (A2-3) was 9,500, and the molecular weight distribution (Mw / Mn) was 2.2.

[0273] <Measurement of weight-average molecular weight> The weight-average molecular weight (Mw) and number-average molecular weight (Mw) of the prepared polymers are polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) under the following conditions. Column: TSKgelGRCXLII, manufactured by Tosoh Corporation. Solvent: Tetrahydrofuran Temperature: 40℃ Pressure: 68 kgf / cm² 2

[0274] Preparation Example 1: Preparation of Pigment Dispersion (Bk-MB-1) A pigment dispersion (Bk-MB-1), which is a coloring agent, was prepared by mixing and dispersing a mixture consisting of 12 parts by mass of a lactam pigment (Irgaphor Black S0100CF, manufactured by BASF) as a coloring agent, 11.8 parts by mass of a solution of BYK-LPN21116 (manufactured by Bic Chemie Japan Co., Ltd., solids content concentration 40.0% by mass) as a dispersant, 13.0 parts by mass of a polymer solution (solids content concentration: 33.3% by mass) of polymer (A1-1) as a binder, and 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a dispersion medium, using a bead mill for 12 hours.

[0275] Preparation Example 2: Preparation of Pigment Dispersion (Bk-MB-2) A pigment dispersion (Bk-MB-2), which is a coloring agent, was prepared by mixing and dispersing a mixture consisting of 12 parts by mass of carbon black (TPX1227R, manufactured by Cabot Corporation) as a coloring agent, 11.8 parts by mass of BYK-LPN21116 (manufactured by Bic Chemie Japan Co., Ltd., solid content concentration: 40.0% by mass) as a dispersant in solution, 13.0 parts by mass of polymer (A1-1) as a binder in polymer solution (solid content concentration: 33.3% by mass), and 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a dispersion medium, using a bead mill for 12 hours.

[0276] The details of the components used in the preparation of the photosensitive compositions in the examples and comparative examples are shown below.

[0277] <Coloring agent> Bk-Dye-1, Bk-Dye-2, and Bk-Dye-3 synthesized in synthesis examples 1-3 Bk-MB-1 and Bk-MB-2 prepared in Preparation Examples 1 and 2 ODB-2 (manufactured by Yamamoto Chemical Co., Ltd., 3-dibutylamino-6-methyl-7-anilinofluorane)

[0278] <Alkali-soluble polymer (A1)> A1-1~A1-4: Polymers (A1-1)~(A1-4) synthesized in the above synthesis examples 4~7. A1-5: "WR-301" manufactured by ADEKA Corporation (PGMEA solution with a solid content of 44%), resins obtained by modifying cardo resins with acid anhydrides, and resins having acrylates and carboxylic acid groups. A2-1~A2-3: Polymers synthesized in the above synthesis examples 8~10 (A2-1)~(A2-3)

[0279] <Quinone diazide compound (B1)> B1-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)

[0280] <Photoacid Generator (B2)> B2-1: Irgacure PAG121 (manufactured by BASF) B2-2: Naphthalemidyltrifluoromethanesulfonate

[0281] <Adhesion enhancer (C)> C-1:3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) C-2:2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0282] <Dissolution accelerator (D)> D-1: Compound represented by the following formula [ka] D-2: Arronix M-520 (manufactured by Toagosei Co., Ltd.)

[0283] <Surfactant (E)> E-1: Megafuck F-554 (manufactured by DIC Corporation, fluorine-based surfactant) E-2: DOWSIL SH 8400 Fluid (manufactured by Toray Dow Ltd., silicone-based surfactant)

[0284] [Example 1] As a coloring agent, 3.60 parts by mass of BK-Dye-1, 32.0 parts by mass of alkali-soluble polymer (A1-1), 2.13 parts by mass of quinone diazide compound (B1-1), 0.53 parts by mass of adhesion aid (C-1), 1.06 parts by mass of dissolution accelerator (D-1), and 0.04 parts by mass of surfactant (E-1) were mixed, and then a solvent was added so that the solid content concentration of the final composition was 18.0% by mass. The solvent was propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone (CPN) added in equal mass ratios (PGMEA: 30.3 parts by mass, CPN: 30.3 parts by mass), and the mixture was stirred to prepare a photosensitive composition.

[0285] [Examples 2-24 and Comparative Examples 1-6] A photosensitive composition was prepared in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 1. In Table 1, the values ​​in the column for each component represent parts by mass, and "-" indicates that the corresponding component was not used.

[0286] [Table 1]

[0287] [evaluation] The photosensitive compositions prepared in Examples 1-24 and Comparative Examples 1-6 were evaluated for the following items using the method described below. The evaluation results are shown in Table 3.

[0288] <Evaluation of developability> Each prepared photosensitive composition was applied to a soda glass substrate with an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating with a thickness of 4.0 μm. Next, using a Canon MPA-600FA, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating at a rate of 300 mJ / cm² via a photomask capable of forming a 20 μm wide line pattern. 2 The substrate was exposed to the specified exposure. Subsequently, the exposed coated glass substrate was placed on the horizontal rotating table of a spin-shower developer (AD-2000 model, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C for 60 seconds. After development, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to form a line pattern. The resulting substrates with line patterns were observed using an optical microscope to assess the appearance of the formed line patterns and the presence or absence of residue in the resolution areas. The evaluation criteria are as follows: If there are no defects in the line patterns and no residue in the resolution areas, the substrate is judged to have excellent developability. <Evaluation Criteria> ○: The line pattern is free of defects, and no residue can be observed in the resolution area. ×: Missing line pattern or residual image in the resolution area is visible.

[0289] <Measurement of optical density (OD value) and heat resistance> Each prepared photosensitive composition was applied to a soda glass substrate, which had an SiO2 film formed on its surface to prevent sodium ion elution, using a spin coater. The coating was then dried under reduced pressure at room temperature to form a 3.0 μm thick film. Next, using a Canon MPA-600FA, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the obtained coating film via a photomask at a rate of 300 mJ / cm². 2 The sample was exposed to light at the specified exposure level. Subsequently, an evaluation substrate was formed by post-baking in a clean oven at 230°C for 30 minutes. The optical density (OD value) of the obtained evaluation substrate was measured using an X-rite 361T monochrome transmission densitometer (initial OD value). A higher OD value indicates better light shielding. Furthermore, a heat resistance evaluation substrate was fabricated by post-baking the evaluation substrate for another 60 minutes in a clean oven at 230°C. The optical density (OD value) of the obtained evaluation substrate was measured using an X-rite 361T monochrome transmission densitometer (OD value after heat resistance evaluation). The retention rate compared to the initial OD value was calculated to determine the heat resistance. The criteria for judgment are described below. A higher retention rate indicates superior heat resistance. <Evaluation Criteria> ○: Retention rate ≧90% ×: Retention rate <90%

[0290] <Evaluation of absorbance before and after post-baking at 230°C> The photosensitive composition prepared in Example 1 was applied to a soda glass substrate, on which a SiO2 film for preventing sodium ion elution was formed, using a spin coater. The coating was then dried under reduced pressure at room temperature to form a 1.0 μm thick film. Next, using a Canon MPA-600FA, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the resulting coating via a photomask at a rate of 35 mJ / cm². 2The substrate was exposed to light at the specified exposure level. The evaluation substrate was then prepared by heating it on a 100°C hot plate for 5 minutes. The ultraviolet-visible absorption spectrum of the evaluation substrate was measured using a UV-Vis-Near-Infrared spectrophotometer (Shimadzu Corporation, UV-1900i), and the UV-Vis absorption spectrum was further measured after firing the evaluation substrate at 230°C for 30 minutes. Table 2 shows the absorbance values ​​at 365nm, 405nm, and 436nm before and after firing at 230°C. The results in Table 2 show that the absorbances of the g-line, h-line, and i-line before firing at 230°C were significantly lower compared to after firing at 230°C, demonstrating that sufficient light shielding and improved exposure sensitivity could be achieved simultaneously. [Table 2]

[0291] <Halftone pattern formation> The photosensitive composition prepared in Example 1 was applied to a soda glass substrate with an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating with a thickness of 4.0 μm. Next, using a Canon MPA-600FA, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating at a rate of 300 mJ / cm² via a quartz gray tone photomask (having a 10 μm wide line pattern with 100% transmittance on the inside and a pattern of 15 μm wide intermediate exposure lines with slits with a light transmission area of ​​35% on both ends). 2The substrate was exposed to the specified exposure dose. The exposed coated glass substrate was then placed on a horizontal rotating table of a spin-shower developer (AD-2000 model, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C for 60 seconds. Afterward, the developed substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to form a stepped pattern with a film thickness of 3.0 μm. The resulting substrate with the line pattern was observed using an optical microscope to confirm that there were no defects in the formed line pattern and no residue in the resolution areas. Furthermore, the step width corresponding to the intermediate exposure area was measured using a stylus-type profiler Alpha-Step D500 (ULVAC, Inc.). The result showed a step width of 1.4 μm, confirming that a stepped pattern with a step of approximately half the total film thickness had been formed.

[0292] [Table 3]

[0293] As shown in Table 3, the photosensitive compositions of Examples 1 to 24 were photosensitive compositions with excellent sensitivity and developability, and were able to form cured products with excellent light-shielding and heat-resistant properties. On the other hand, the comparative examples were inferior to the examples.

Claims

1. A step of forming a coating film by applying a positive-type photosensitive composition containing a compound represented by the following formula (1) onto a substrate, The process of exposing the coating film, The process of developing the exposed coating film, Includes a step of heating the developed pattern. A method for manufacturing patterned cured products. 【Chemistry 1】 (In formula (1), R １ and R ２ Each of these is independently a hydrogen atom or a leaving group. However, R １ and R ２ At least one of them is a leaving group. R ３ , R ４ , and R ５ These are, independently, a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfo group. n1 and n2 are independent integers between 0 and 4. n3 is an integer between 0 and 2.

2. The manufacturing method according to claim 1, wherein the step of exposing the coating film is performed using a halftone mask or a graytone mask.

3. The manufacturing method according to claim 1, wherein the leaving group is a methoxymethyl group or a tert-butoxycarbonyl group.

4. The manufacturing method according to claim 1, wherein the positive-type photosensitive composition further comprises a black pigment.

5. The positive-type photosensitive composition further comprises A polymer (A1) containing a structural unit (I) having an acid group, A quinone diazide compound (B1) is included, The manufacturing method according to claim 1.

6. The manufacturing method according to claim 5, wherein the polymer (A1) further comprises a structural unit having a crosslinkable group, or further comprises a polymer different from the polymer (A1) that comprises a structural unit having a crosslinkable group.

7. The manufacturing method according to claim 6, wherein the crosslinkable group is at least one selected from the group consisting of an oxyranyl group, an oxetanyl group, and an ethylenically unsaturated group.

8. The positive-type photosensitive composition further comprises A polymer that is at least one selected from the group consisting of a polymer (A1) containing a structural unit (III) having a group represented by the following formula (7) or an acid-dissociable group, and a siloxane polymer (A2), Including a photoacid generator (B2), The manufacturing method according to claim 1. 【Chemistry 2】 (In formula (7), R Ａ１ , R Ａ２ and R Ａ３ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. However, at least one of R Ａ１ , R Ａ２ and R Ａ３ is an alkoxy group having 1 to 6 carbon atoms. The asterisk (*) indicates a bonding operation.

9. The method for producing the product according to claim 8, wherein the photoacid generator (B2) comprises at least one selected from the group consisting of oximesulfonate compounds and sulfonimide compounds.

10. The manufacturing method according to claim 1, wherein the patterned cured product is a black matrix or a partition.

11. A positive-type photosensitive composition comprising a compound represented by the following formula (1). 【Transformation 3】 (In formula (1), R １ and R ２ Each of these is independently a hydrogen atom or a leaving group. However, R １ and R ２ At least one of them is a leaving group. R ３ , R ４ , and R ５ These are, independently, a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfo group. n1 and n2 are independent integers between 0 and 4. n3 is an integer between 0 and 2.

12. A patterned cured product formed from the positive-type photosensitive composition according to claim 11.

13. A partition made of the cured material according to claim 12.

14. An image display device comprising a partition wall as described in claim 13.

15. A black matrix comprising the cured product described in claim 12.

16. A color filter comprising the black matrix described in claim 15.

17. An image display panel comprising the color filter described in claim 16.

18. An image display device comprising the image display panel described in claim 17.

Images