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

Abstract

The invention provides a manufacturing method of a patterned hardened material, the patterned hardened material, a partition wall, a black matrix, a color filter, an image display panel, an image display device and a positive photosensitive composition. The positive photosensitive composition has excellent sensitivity and developability to form a cured product having excellent light shielding properties. A chemical 9 manufacturing method includes: a step of forming a coating film by applying a positive photosensitive composition containing a compound represented by formula (1) onto a substrate; a step for exposing the coating film; a step for developing the exposed coating film; and a step for heating the developed pattern. (In formula (1), R1 and R2 are each independently a hydrogen atom or a releasable group; in the formula, at least one of R1 and R2 is an abscisic group; r3, R4 and R5 are each independently a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group or a sulfo group; each of n1 and n2 independently represents an integer of 0-4; and n3 represents an integer of 0-2). [Chemical Formula 1]

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a patterned hardened material, the patterned hardened material, a barrier wall, a black matrix, a color filter, an image display panel, an image display device, and a positive photosensitive composition. Background Technology

[0002] In display devices, patterned light-shielding components such as black matrices or black banks are typically formed. Various photosensitive compositions comprising light-shielding black pigments and photopolymerization initiators have been proposed as materials for forming these light-shielding components.

[0003] For example, a negative photosensitive composition containing black agents such as benzofuranone-based black pigments, perylene-based black pigments, and azo-based black pigments is known to be highly sensitive and capable of forming patterns of desired shapes (e.g., Patent Document 1), or a photosensitive resin composition containing black colorants (e.g., Patent Document 2).

[0004] [Existing Technical Documents]

[0005] [Patent Literature]

[0006] [Patent Document 1] International Publication No. 2018 / 181311

[0007] [Patent Document 2] Japanese Patent Application Publication No. 2023-80993 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] When exposing a photosensitive composition, a pattern with varying gradients can be formed by using multi-grayscale masks such as gray-tone masks or halftone masks. However, the negative photosensitive composition of Patent Document 1 is not suitable for forming dense patterns using multi-grayscale masks. In addition, the black colorant used in Patent Document 2 is sometimes poor in terms of heat resistance.

[0010] In addition, the black pigments used in conventional photosensitive compositions usually have low solubility or dispersibility in the solvents contained in the photosensitive composition, and are generally used in conjunction with dispersants. Furthermore, there are problems such as insufficient developability and residues (foreign matter) sometimes being generated at the points removed by development after development.

[0011] The present invention was made in view of the aforementioned problem, and its object is to provide a method for manufacturing patterned cured articles using a positive photosensitive composition, wherein the positive photosensitive composition is a positive photosensitive composition with excellent sensitivity and developability and can form cured articles with excellent light-blocking or heat resistance.

[0012] [Technical means to solve the problem]

[0013] The inventors have discovered that the aforementioned problems can be solved according to the following structural examples. That is, according to the present invention, a method for manufacturing a patterned cured material, a patterned cured material, a partition wall, a black matrix, a color filter, an image display panel, an image display device, and a positive photosensitive composition can be provided. Structural examples of this disclosure are shown below.

[0014] In one embodiment of the present invention

[0015] A method for manufacturing a patterned hardened material includes:

[0016] The process of coating a positive photosensitive composition containing a compound represented by the following formula (1) onto a substrate to form a coating film;

[0017] The process of exposing the coating film;

[0018] The process of developing the exposed coating; and

[0019] The process of heating the developed pattern.

[0020] [Chemistry 1]

[0021]

[0022] (In formula (1),)

[0023] R 1 and R 2 Each is independently a hydrogen atom or a depleted radical; wherein, R 1 and R 2 At least one of them is a detachable base;

[0024] R 3 R 4 and R 5 Each can be independently composed of a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfonyl group;

[0025] n1 and n2 are independent integers from 0 to 4;

[0026] (n3 is an integer between 0 and 2)

[0027] In another embodiment, the present invention relates to a positive photosensitizing composition.

[0028] It includes compounds represented by the following formula (1).

[0029] [Chemistry 2]

[0030]

[0031] (In formula (1),)

[0032] R 1 and R 2 Each is independently a hydrogen atom or a depleted radical; wherein, R 1 and R 2 At least one of them is a detachable base;

[0033] R 3 R 4 and R 5 Each can be independently composed of a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfonyl group;

[0034] n1 and n2 are independent integers from 0 to 4;

[0035] (n3 is an integer between 0 and 2)

[0036] In another embodiment of the invention, the present invention relates to a patterned hardened material formed from the positive photosensitive composition, an isolation wall or black matrix comprising the hardened material, a color filter comprising the black matrix, an image display panel comprising the color filter, an image display device comprising the image display panel, and an image display device comprising the isolation wall.

[0037] [The effects of the invention]

[0038] According to the present invention, a method for manufacturing patterned cured articles using a positive photosensitive composition is provided. The positive photosensitive composition is one with excellent sensitivity and developability (especially alkali solubility), and can simultaneously form cured articles with excellent light-blocking and heat-resistant properties. The cured articles obtained by the manufacturing method of the present invention exhibit excellent light-blocking and heat-resistant properties.

[0039] Furthermore, the positive photosensitive composition used in the manufacturing method of the present invention exhibits excellent sensitivity and developability (especially alkali solubility), making it suitable for exposure using multi-grayscale masks such as grayscale toning masks or halftone masks. By using multi-grayscale masks, a pattern with stepped shapes can be formed, for example, spacers can be formed simultaneously on the black isolation wall. By providing spacers on the black isolation wall, the contact area with the vapor deposition mask during the formation of the light-emitting layer can be reduced, thereby suppressing the reduction in panel yield caused by particle generation and suppressing the deterioration of the light-emitting element.

[0040] Furthermore, according to the present invention, a positive photosensitive composition can be provided, which is a positive photosensitive composition with excellent sensitivity and developability (especially alkali solubility), and can also form a hardened material with excellent light-blocking and heat resistance. Detailed Implementation

[0041] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0042] The following provides a detailed description of matters related to the implementation method. Furthermore, in this specification, the numerical range indicated by “~” means the values ​​before and after the “~” are considered as lower and upper limits.

[0043] In this specification, "hydrocarbon group" has the meaning of including chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain hydrocarbon group" refers to a straight-chain hydrocarbon group or branched hydrocarbon group that consists only of a chain structure and does not contain a ring structure in its main chain. The chain hydrocarbon group can be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as its ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon group does not necessarily need to consist only of an alicyclic hydrocarbon structure; it may also include a group with a chain structure in a portion of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure. The aromatic hydrocarbon group does not necessarily need to consist only of an aromatic ring structure; it may also contain a chain structure or an alicyclic hydrocarbon structure in a portion of it. Furthermore, the ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may also have substituents containing hydrocarbon structures.

[0044] In this specification, "(meth)acryloyl" means including both "acryloyl" and "methacryloyl", "(meth)acrylate" means including both "acrylate" and "methacrylate", and "(meth)acrylate" means including both "acrylate" and "methacrylate".

[0045] The positive photosensitive composition of the present invention will be described below.

[0046] Positive-type photosensitizing compositions

[0047] The positive photosensitive composition of 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)").

[0048] [Chemistry 3]

[0049]

[0050] (In formula (1),)

[0051] R 1 and R2 Each is independently a hydrogen atom or a depleted radical; wherein, R 1 and R 2 At least one of them is a detachable base;

[0052] R 3 R 4 and R 5 Each can be independently composed of a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfonyl group;

[0053] n1 and n2 are independent integers from 0 to 4;

[0054] (n3 is an integer between 0 and 2)

[0055] This composition is a composition with excellent sensitivity and developability (especially alkali solubility) and can form a hardened product with excellent opacity and heat resistance. As represented by the formula (1), this composition has a heat-detaching group with excellent solvent solubility, thereby allowing the lactam compound to dissolve in the solvent at the molecular level and significantly suppressing the formation of residues during development.

[0056] Furthermore, by introducing thermally detachable radicals, the absorption spectrum changes, and compared with the lactam pigment represented by the following formula (2), the transmittance of radiation can be increased, thus improving sensitivity. Moreover, by heating (calcining, post-baking) at the temperature at which the thermally detachable radicals are detached, the thermally detachable radicals contained in compound (1) decompose and vaporize, and compound (1) can change from a dye to a lactam pigment that is poorly soluble or insoluble in solvents. Therefore, the original opacity of the lactam pigment can be utilized through this heating. Additionally, it has the advantage that the loss of solvent solubility due to thermally detachable radical decomposition makes it less prone to migration (dissolution of the dye into the luminescent layer, etc.), which is a problem in dyes. Furthermore, this composition does not use a dispersant, or even if a dispersant is used, only a smaller amount is required than before, thus also having the advantage of suppressing the generation of smoke or decomposition products originating from the dispersant during heating.

[0057] The following describes compound (1).

[0058] <Compound(1)>

[0059] The compound represented by formula (1), which has a γ-lactam ring, can be used as a black colorant. Compound (1) has excellent solubility in solvents at room temperature and is therefore classified as a "dye" among colorants.

[0060] In this specification, the term "disposable group" refers to a group that is disposable and replaced by a hydrogen atom by heat or light. Disposable groups also include groups that are partially disposable, decarbonated, and subsequently replaced by a hydrogen atom in stages, such as the tert-butoxycarbonyl group (Boc(t-Butyloxy carbonyl) group) described later. That is, compound (1) is a compound represented by the following formula (2) by disposable groups being disposable by heat or light (hereinafter also referred to as "compound (2)").

[0061] [Chemistry 4]

[0062]

[0063] (In equation (2), R) 3 R 4 R 5 n1, n2, and n3 have the same meaning as in equation (1).

[0064] The de-detachable group in compound (1) is preferably a group that is de-detached by heat and replaced by a hydrogen atom (hereinafter also referred to as "thermally de-detachable group"), more preferably a thermally de-detachable group that is de-detached at a heating temperature of 250°C or less, and even more preferably a thermally de-detachable group that is de-detached at a heating temperature of 230°C or less, and particularly preferably a thermally de-detachable group that is de-detached at a heating temperature of 200°C or less.

[0065] Examples of dissociative groups include alkoxyalkyl groups such as methoxymethyl (MOM), alkyloxycarbonyl groups containing 1 to 10 carbon atoms with a straight or branched alkyl chain, and alkenyloxycarbonyl groups containing 1 to 10 carbon atoms with a straight or branched chain, wherein the alkyl or alkenyl group may have an alkoxy group with 1 to 3 carbon atoms. More specifically, examples include: methoxymethyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, allyloxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl (Boc group), n-pentyloxycarbonyl, methoxyethyloxycarbonyl, heptyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, and 9-fluorenylmethyloxycarbonyl (F-moc group). Among these, compounds that readily exhibit excellent solubility in solvents and desorbable radicals upon heating at low temperatures (e.g., 230°C) are preferred in terms of alkoxyalkyl or alkyloxycarbonyl groups, more preferably alkoxyalkyl groups with 1 to 5 carbon atoms or alkyloxycarbonyl groups containing 1 to 10 branched alkyl groups, and even more preferably methoxymethyl or tert-butoxycarbonyl groups.

[0066] In terms of readily obtainable compounds with excellent solubility in solvents (1), the R 1 and R 2 Preferably, it is the detachable group.

[0067] As the R 3 R 4 and R 5 Examples of monovalent organic groups include: monovalent hydrocarbon groups with 1 to 20 carbon atoms, groups having divalent heteroatoms between carbon atoms or at the end of the carbon chain of the hydrocarbon group, groups formed by substituting some or all of the hydrogen atoms of the hydrocarbon group with a monovalent heteroatom group, or combinations thereof.

[0068] Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms include: chain hydrocarbon groups with 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0069] Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include monovalent straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, and monovalent straight-chain or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of monovalent straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. Examples of monovalent straight-chain or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as vinyl, propynyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0070] Examples of monovalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups and monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups. Examples of polycyclic saturated hydrocarbon groups include norbornyl, adamantyl, tricyclic decyl, tetracyclic dodecyl, and other bridged alicyclic hydrocarbon groups. Examples of monocyclic unsaturated hydrocarbon groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and other monocyclic cycloalkenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include norbornyl, tricyclic decenyl, tetracyclic dodecenyl, and other polycyclic cycloalkenyl groups. Furthermore, a bridged alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which two non-adjacent carbon atoms constituting the alicyclic ring are bonded by a linker group containing one or more carbon atoms.

[0071] Examples of monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms include: aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl.

[0072] Examples of monovalent heteroatom-containing groups include: hydroxyl, carboxyl, sulfanyl, cyano, nitro, halogen atoms, etc.

[0073] Examples of divalent heteroatom-containing groups include: -CO-, -C(=O)O-, -CS-, -NR'-, -O-, -S-, -SO-, -SO2-, or groups formed by combining these. R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0074] Among these, as R 3 R 4 and R 5 The monovalent organic group in the form is preferably an alkyl group or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methyl or methoxy group, with methyl being particularly preferred.

[0075] The n1 and n2 are each independently an integer from 0 to 4, preferably 0 or 1, more preferably 0. When n1 or n2 is an integer of 1 or more, that is, when there is a substituent at the 4th to 7th position of the dihydroindole ring in compound (1), it is preferable to have a substituent at the 4th or 6th position in terms of ease of manufacture or ease of acquisition.

[0076] The n3 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0077] Regarding compound (1), it has EE, ZZ and EZ as geometric isomers, and can be any single compound or a mixture of these geometric isomers.

[0078] The compound (1) can be synthesized, for example, by synthesizing the compound (2) using the method described in International Publication No. 2000 / 24736, and then protecting the amine within the dihydroindolone ring of the compound (2) using a known amine protection method or alcohol protection method. Commercially available products can also be used for the compound (2). Alternatively, the compound represented by formula (1) can also be obtained by adding dialkyl esters of dicarbonate, dienyl esters of dicarbonate, or dialkoxyalkyl esters of dicarbonate to isatitin in the presence of a base such as 4-dimethylaminopyridine to obtain N-carbonyloxyalkyl indigo, etc., and then following Japanese Patent Application Publication No. 2016-84425, Japanese Patent Application Publication No. 2015-121753, International Publication No. 2014 / 071524, and the Journal of the American Chemical Society. According to records in the Journal of the American Chemical Society (J. Am. Chem. Soc.) (2013, 135, 12168.) and the Journal of the American Chemical Society (J. Am. Chem. Soc.) (2015, 137, 15947.), it reacts with 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione under acid or base catalysts. Examples of acid catalysts include organic carboxylic acids such as hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, or benzoic acid. Examples of base catalysts include organic amines such as n-butyllithium, diisopropylamide lithium, and triethylamine, organic bases such as pyridines, and inorganic bases such as sodium hydride, sodium hydroxide, and potassium carbonate. The indigo can be synthesized by condensing chloral hydrate, aniline, and hydroxylamine in sulfuric acid, but aniline with alkyl or alkoxy groups can be used instead to introduce organic groups into compound (1) to adjust its cohesiveness and solubility. Furthermore, cohesiveness and solubility can also be adjusted by mixing various compounds (1) with non-target structures and compounds (1) with different structures. Although it also depends on the preparation method, the introduction rate of the detachable group in the compound represented by formula (1) is significant when all R are present. 1 and R 2 When the total amount is set to 100 mol%, it is preferably 50 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more.

[0079] The compound (2) is a compound commonly known as a lactam pigment and can be used as a black pigment. The hardened film containing compound (2) has excellent opacity. Therefore, the hardened product containing compound (2), which is generated by removing the detachable group from compound (1), has excellent opacity. In addition, compound (2) has poor solubility in solvents at room temperature, and is therefore classified as a "pigment" among colorants. Due to its low solubility, the hardened product containing compound (2) as a colorant can suppress dissolution (migration) into the luminescent layer, etc., when using the hardened product.

[0080] Specifically, the following structures can be listed as examples of the compound (1).

[0081] [Chemistry 5]

[0082]

[0083] [Chemistry 6]

[0084]

[0085] The lower limit of the content of compound (1) in the positive photosensitive composition is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 5 parts by mass, relative to 100 parts by mass of the alkali-soluble polymer (A) formulated in this composition. Furthermore, the upper limit of the content of compound (1) in the positive photosensitive composition is preferably 70 parts by mass, more preferably 60 parts by mass, and even more preferably 50 parts by mass. With the content of compound (1) within the aforementioned range, radiation transmittance (especially gamma rays, h-rays, and i-rays) is excellent, thus a photosensitive composition with excellent sensitivity can be easily obtained. In addition, a hardened material with excellent light-blocking properties can be easily formed.

[0086] The positive photosensitive composition used in this manufacturing method only needs to contain the compound (1), and other structures are not particularly limited. For example, it is preferred to contain an alkali-soluble polymer (A) and a radiosensitive linear compound (B). In addition, unless otherwise specified, one or more of the components may be used alone.

[0087] <Alkali-soluble polymer (A)>

[0088] As for the alkali-soluble polymer (A), there are no particular limitations as long as it is an alkali-soluble polymer or a polymer whose alkali solubility increases by acid or heat. For example, polymers having acidic groups such as carboxyl, anhydride, phenolic hydroxyl, aromatic thiol, silanol, and fluorinated hydroxyalkyl (hydroxyalkyl in which a portion of the hydrogen atom bonded to the carbon atom is replaced by a fluorine atom) are preferred.

[0089] In this specification, "alkali-soluble" means dissolving in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. Furthermore, a polymer is considered alkali-soluble when more than 1g of the polymer dissolves relative to 100g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. Dissolution can be determined by the presence or absence of precipitate.

[0090] Examples of such polymers include: polymers (A1) containing structural units (I) having acid groups, siloxane polymers (A2), polyamic acid or polyamic acid esters (A3), phenolic varnish resins (A4), cardo resins (A5), etc.

[0091] (Polymer (A1))

[0092] A polymer (A1) containing a structural unit (I) having an acid group (hereinafter also referred to as "polymer (A1)") is an assembly of polymeric chains containing a structural unit (I) having an acid group (hereinafter also referred to as "base polymer"). The structural unit (I) need only be contained in at least one polymeric chain constituting the base polymer. The polymer (A1) may also contain structural units other than the structural unit (I). The structural units contained in the polymer (A1) will be described below.

[0093] [Structural Unit (I)]

[0094] The polymer (A1) can improve its solubility in alkaline developing solutions (alkali solubility) or its curing reactivity by having structural units (I) with acid groups.

[0095] The structural unit (I) is not particularly limited as long as it has an acid group, but is preferably selected from at least one of 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. Furthermore, in this specification, "phenolic hydroxyl group" refers to a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0096] Structural unit (I) is preferably derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having acid groups are provided below.

[0097] Examples of monocarboxylic acids that constitute structural units with carboxyl groups include: (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, crotonic acid, 4-vinylbenzoic acid, and other unsaturated monocarboxylic acids; maleic acid, fumaric acid, citraconic acid, succinic acid, itaconic acid, and other unsaturated dicarboxylic acids.

[0098] Examples of monoisocyanates that constitute structural units having sulfonic acid groups include: vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc.

[0099] Examples of monomers that constitute structural units with phenolic hydroxyl groups include: 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl methacrylate, etc.

[0100] In addition, maleimide can also be used as a monolith that constitutes structural unit (I).

[0101] Among these, (meth)acrylic acid, (meth)acrylic acid hydroxyphenyl ester, isopropenylphenol, and 2-(meth)acryloyloxyethyl succinic acid are preferred.

[0102] The basic polymer may contain one structural unit (I) or a combination of two or more.

[0103] The lower limit of the content ratio (total content ratio in the case of multiple structural units) of structural unit (I) relative to all structural units constituting the base polymer is preferably 1% by mass, more preferably 2% by mass, and even more preferably 5% by mass. Furthermore, the upper limit of the content ratio is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass. By setting the content ratio of structural unit (I) within the aforementioned range, good solubility in alkaline developing solutions can be imparted, and therefore this is preferred.

[0104] [Structural Unit (II)]

[0105] The polymer (A1) is preferred because it contains structural units (II) with crosslinking groups, which can further improve the resolution or adhesion of the film. The crosslinking group is not particularly limited to any group that can be cured by heat treatment; however, in terms of high thermosetting properties, the crosslinking group is preferably at least one selected from the group consisting of oxetyl, oxetyl, and vinyl unsaturated groups, more preferably oxetyl or oxetyl.

[0106] (Structural unit (II-1) containing oxehirobutyl and oxehiropropyl groups)

[0107] The polymer (A1) is preferred because it contains structural units (II-1) having one or more groups selected from the group consisting of oxetyl and oxetylpropyl, which can further improve the resolution or adhesion of the film. Furthermore, the oxetyl and oxetylpropyl groups act as crosslinking groups, enabling the formation of a hardened film with high heat resistance and long-term anti-deterioration properties. The structural unit (II-1) is preferably derived from an unsaturated monomer having oxetyl and oxetylpropyl groups; specifically, it is preferably the structural unit represented by the following formula (4-1).

[0108] [Chemistry 7]

[0109]

[0110] (In equation (4-1),)

[0111] R 21 It is a monovalent group having an oxetine propyl or oxetine butyl group;

[0112] R α It can be a hydrogen atom, methyl group, hydroxymethyl group, cyano group, or trifluoromethyl group;

[0113] X 1 (For single-bond or divalent linkages)

[0114] In the above equation (4-1), R is... 21 Examples include: oxetyl propyl, oxetyl butyl, 3,4-epoxycyclohexyl, 3,4-epoxytricyclic [5.2.1.0] 2,6 Decyl, 3-methyloxetyl, 3-ethyloxetyl, etc.

[0115] As X 1 The divalent linker in it is preferably a alkyl dimethyl group such as methylene, ethylene, or 1,3-propanediyl.

[0116] Specific examples of providing a monolithic form of structural unit (II) represented by formula (4-1) include, for example: glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo (meth)acrylate [5.2.1.0]. 2,6 [Methyl methyl methacrylate, 3-methyloxetane-3-yl methacrylate, 3-ethyloxetane-3-yl methacrylate, methyl methacrylate, 3-ethyloxetane-3-yl methacrylate, etc. Among these, glycidyl methacrylate, 3-ethyloxetane-3-yl methacrylate, and 3,4-epoxycyclohexyl methacrylate are preferred.]

[0117] (Structural unit with vinyl unsaturated group (II-2))

[0118] The structural unit (II-2) is preferably a side chain structure having an ethylene unsaturated group in the side chain, and more preferably a side chain structure containing 3 to 20 carbon atoms having an ethylene unsaturated group at the end. As a specific example of the structural unit (II-2), the structural unit represented by the following formula (4-2) can be cited.

[0119] [Chemistry 8]

[0120]

[0121] (In equation (4-2),)

[0122] R α It can be a hydrogen atom, methyl, hydroxymethyl, cyano, or trifluoromethyl;

[0123] X 3 It is a divalent linker with 1 to 12 carbon atoms;

[0124] R 22 (for hydrogen atoms or methyl groups)

[0125] In the above equation (4-2), X is... 3 The divalent linkages represented can be listed as: divalent hydrocarbon groups with 1 to 12 carbon atoms, divalent groups formed by substituting any methylene group in a divalent hydrocarbon group with -O-, -COO-, -OCO-, -NHCO-, -CONH-, -OCONH- or -NHCOO-, and divalent groups formed by substituting any hydrogen atom in a divalent hydrocarbon group or a divalent group containing heteroatoms with hydroxyl, carboxyl, or other groups.

[0126] The base polymer may contain one structural unit (II) or a combination of two or more.

[0127] When the polymer (A1) contains structural unit (II), the lower limit of the content ratio of structural unit (II) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 15% by mass, and even more preferably 25% by mass. Furthermore, the upper limit of the content ratio is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. By setting the content ratio of structural unit (II) within the aforementioned range, the coating film exhibits better resolution, and the heat resistance of the obtained cured product can be sufficiently improved; in this respect, it is preferred.

[0128] [Structural Unit (III)]

[0129] In the case that the photosensitive composition of the present invention is a chemically amplified composition, when the polymer (A1) contains a structural unit (III) having one or more groups selected from the group consisting of groups represented by the following formula (7) and acid-dissociable groups, a coating film with excellent adhesion (development adhesion) between the substrate and the unexposed portion during development can be formed, which is preferred from the above point of view.

[0130] [Chemistry 9]

[0131]

[0132] (In formula (7),)

[0133] R A1 R A2 and R A3 Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl or phenyl group having 1 to 10 carbon atoms; wherein, R A1 RA2 and R A3 At least one of them is an alkoxy group having 1 to 6 carbon atoms;

[0134] "*" indicates a bond.

[0135] As R A1 ~R A3 Alkoxy groups with 1 to 6 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc. Among these, R... A1 ~R A3 The alkoxy group in the sample is preferably methoxy or ethoxy.

[0136] R A1 ~R A3 The alkyl group having 1 to 10 carbon atoms can be either straight-chain or branched. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among these, methyl, ethyl, or propyl is preferred.

[0137] From the perspective of obtaining a hardened material with excellent heat resistance by forming a cross-linked structure, and from the perspective of improving the storage stability of photosensitive compositions, R A1 ~R A3 At least one of them is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all of them are alkoxy groups.

[0138] In the above, R A1 Preferably, it is 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 or ethoxy group. A2 and R A3 Preferably, it is a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a phenyl group; more preferably, it is a hydroxyl group, an alkoxy group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms.

[0139] In structural unit (III), the group represented by formula (7) is preferably bonded to an aromatic cyclic group or a chain hydrocarbon group. Furthermore, in this specification, "aromatic cyclic group" refers to a group formed by removing n (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 also have substituents such as alkyl groups. Examples of such chain hydrocarbon groups bonded to the group represented by formula (7) include alkyldiyl and alkenediyl groups.

[0140] The group represented by formula (7) is preferably bonded to the benzene ring, naphthalene ring or alkyl chain. That is, the structural unit (III) is preferably composed of at least one group selected from the group represented by formula (7-1), formula (7-2) and formula (7-3).

[0141] [Chemistry 10]

[0142]

[0143] (In equations (7-1), (7-2), and (7-3),

[0144] A 1 and A 2 Each 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;

[0145] m1 is an integer from 0 to 4; m2 is an integer from 0 to 6; where m1 is 2 or higher, multiple A's 1 The bases are either identical or different; when m² is greater than 2, multiple A's are... 2 The bases are either identical or different.

[0146] R 31 It is an alkyl diol;

[0147] R A1 R A2 and R A3 It has the same meaning as the above formula (7);

[0148] "*" indicates a bond.

[0149] As A 1 and A 2 The alkoxy group with 1 to 6 carbon atoms in the formula (7) can preferably be R. A1 ~R A3 Examples include alkoxy groups with 1 to 6 carbon atoms. Additionally, as A... 1 and A 2 The alkyl group having 1 to 6 carbon atoms can preferably be R of formula (7). A1 ~R A3 The alkyl group having 1 to 10 carbon atoms that corresponds to the group having 1 to 6 carbon atoms.

[0150] The group "-SiR" bonded to the aromatic ring A1 R A2 R A3 The position of " relative to A" 1 and A 2 Other than the bases, they can be in any position. For example, in the case of equation (7-1), the base "-SiR" is... A1 R A2 R A3 The position of “” can be any of the following: adjacent, intermediate, or opposite, with opposite being preferred.

[0151] m1 is preferably 0 or 1, more preferably 0. m2 is preferably 0 to 2, more preferably 0.

[0152] In the above formula (7-3), R 31 Preferably, it is linear. From the viewpoint of improving the heat resistance of the obtained hardened film, R... 31 Preferably, it has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

[0153] Structural unit (III) is preferably selected from the group consisting of at least one base represented by formula (7-1) and the base represented by formula (7-2) in formulas (7-1) to (7-3). Additionally, in the base "-SiR..." A1 R A2 R A3 "When directly bonded to an aromatic ring, the silanol group generated in the presence of water can be stabilized. This improves the solubility of the exposure section in the alkaline developer, resulting in the formation of good patterns, which is preferred in this respect. Among these, structural unit (III) is particularly preferred to be a structural unit having the group represented by the formula (7-1)."

[0154] The structural unit (III) is preferably a structural unit derived from a monolith having polymeric carbon-carbon unsaturated bonds (hereinafter also referred to as "unsaturated monolith"), and more specifically, preferably at least one selected from the group consisting of the structural units represented by the following formula (7a-1) and the structural units represented by the following formula (7a-2).

[0155] [Chemistry 11]

[0156]

[0157] (In equations (7a-1) and (7a-2),

[0158] R α1 It can be a hydrogen atom, methyl group, hydroxymethyl group, cyano group, or trifluoromethyl group;

[0159] R 32 and R 33 Each can be independently a divalent aromatic cyclic group or a chain hydrocarbon group;

[0160] R A1 R A2 and R A3 (This has the same meaning as equation (7))

[0161] In equations (7a-1) and (7a-2), R 32 R 33The divalent aromatic cyclic group is preferably a substituted or unsubstituted phenylene or a substituted or unsubstituted naphthylene. The divalent chain hydrocarbon group is preferably an alkyldiyl group having 1 to 6 carbon atoms, more preferably an alkyldiyl group having 1 to 4 carbon atoms.

[0162] In terms of obtaining hardened materials with higher heat resistance and hardness, and in terms of improving the solubility of the exposure section in alkaline developer, R 32 R 33 Preferably, it is a divalent aromatic cyclic group, and particularly preferably a substituted or unsubstituted phenylene group.

[0163] As specific examples of the structural unit represented by equation (7a-1), structural units represented by equations (7a-1-1) and (7a-1-2) can be listed below. Furthermore, as specific examples of the structural unit represented by equation (7a-2), structural units represented by equations (7a-2-1) and (7a-2-2) can be listed below.

[0164] [Chemistry 12]

[0165]

[0166] (In equations (7a-1-1), (7a-1-2), (7a-2-1), and (7a-2-2),)

[0167] R 34 and R 35 Each is independently an alkyl group having 1 to 4 carbon atoms, R 36 It is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group;

[0168] m3 is an integer from 1 to 4;

[0169] A 1 A 2 m1 and m2 have the same meaning as in equations (7-1) and (7-2);

[0170] R α1 (This has the same meaning as equations (7a-1) and (7a-2) mentioned above)

[0171] Specific examples of monomorphs constituting structural unit (III) include: styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloyloxyphenyltrimethoxysilane, (meth)acryloyloxyphenyltriethoxysilane, (meth)acryloyloxyphenylmethyldimethoxysilane, (meth)acryloyloxyphenylethyldiethoxysilane, etc.; trimethoxy (4 (-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloyloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, etc. Among these, styryltrimethoxysilane and 3-(meth)acryloyloxypropyltrimethoxysilane are preferred.

[0172] The term "acid-dissociable group" refers to a group that substitutes for hydrogen atoms in acidic functional groups such as phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups, and specifically to a group that dissociates under the action of an acid. For example, exposure to light can cause the acid-dissociable group to dissociate, producing a carboxyl group, etc., due to the acid generated by the photoacid generator. This creates a difference in the solubility of the developer between the exposed and unexposed areas of the coating, thereby enabling pattern formation.

[0173] The acid dissociative group is preferably the group represented by formula (8-1) or the group represented by formula (8-2).

[0174] [Chemistry 13]

[0175]

[0176] (In equation (8-1),)

[0177] R A4 and R A5 Each group is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least a portion of the hydrogen atoms of the hydrocarbon group is substituted by a hydroxyl group, a halogen atom, or a cyano group; wherein, R is absent. A4 and R A5 The case where all atoms are hydrogen atoms;

[0178] R A6It is a hydrocarbon group having 1 to 30 carbon atoms, a group having an oxygen atom or a sulfur atom at the carbon-carbon inter-carbon or bond side end of the hydrocarbon group, or a group having at least a portion of the hydrogen atoms of these groups substituted by a hydroxyl group, a halogen atom or a cyano group.

[0179] R A7 It consists of carbon atoms or silicon atoms;

[0180] In equation (8-2),

[0181] R A8 ~R A14 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms;

[0182] m is 1 or 2; when m is 2, multiple R A11 and R A12 They can be the same or different;

[0183] In equations (8-1) and (8-2), "*" indicates the location of the bond.

[0184] As R A4 ~R A6 The hydrocarbon group having 1 to 30 carbon atoms can preferably be R of the formula (1). 3 and R 4 The carbon number of monovalent hydrocarbon groups with 1 to 20 carbons is expanded to 30.

[0185] R as in equation (8-1) A4 ~R A6 Preferably, each is an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0186] As R A8 ~R A14 The hydrocarbon group with 1 to 12 carbon atoms in it can preferably be the R group. A4 ~R A6 The groups in hydrocarbon groups with 1 to 30 carbon atoms that correspond to the groups with 1 to 12 carbon atoms.

[0187] m is 1 or 2. When m is 2, multiple R... A11 and R A12 They can be the same or different.

[0188] As a structural unit having the acid dissociative group, the structural unit represented by the following formulas (8-1-1) and (8-1-2) is preferred, for example.

[0189] [Chemistry 14]

[0190]

[0191] R in equations (8-1-1) and (8-1-2) α1 R in equations (7a-1) and (7a-2) α1 They have the same meaning. R A4 ~R A14 , m and R in equations (8-1) and (8-2) A4 ~R A14 、m have the same meaning.

[0192] L in equations (8-1-1) and (8-1-2) 1 L 2 They are independent single-bond and divalent linkage groups, respectively.

[0193] As the L 1 L 2 Divalent linkages in alkyl groups can be listed as: alkyldiyl, cycloalkyldiyl, alkenyl, and aryldiyl.

[0194] As the alkyl diene, examples include X in formula (4-1). 1 The same base as the divalent linker in the matrix.

[0195] Examples of cycloalkyl dimethyl groups include monocyclic cycloalkyl dimethyl groups such as cyclopentadiyl and cyclohexadiyl, and polycyclic cycloalkyl dimethyl groups such as norbornenediyl and adamantanediyl.

[0196] Examples of the alkenyl groups include: ethylenediyl, propylenediyl, butenediyl, etc.

[0197] Examples of the aryl dimethyl group include phenylene, methylphenylene, and naphthylene. Preferably, the aryl dimethyl group has 6 to 15 carbon atoms.

[0198] m1 can be 0 or 1.

[0199] There is no limitation on the single entity that provides the structural unit having the acid dissociative group, and the following examples are provided.

[0200] [Chemistry 15]

[0201]

[0202] (where R is in the formula) α1 R in equations (8-1-1) and (8-1-2) α1 (meaning the same thing)

[0203] The basic polymer may contain one structural unit (III) or a combination of two or more.

[0204] When the polymer (A1) contains structural unit (III), the lower limit of the content ratio of structural unit (III) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. Furthermore, the upper limit of the content ratio is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. Setting the content ratio of structural unit (III) within this range is preferable in terms of exhibiting better resolution of the coating film.

[0205] [Structural Unit (IV)]

[0206] The polymer (A1) may further comprise structural units (IV) (excluding units equivalent to structural unit (III)), said structural unit (IV) being derived from at least one monolith selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and dialkyl dicarboxylic acid compounds. By incorporating these structural units (IV) into the polymer, the glass transition temperature of the polymer (A1) composition can be adjusted, and the pattern shape of the obtained cured film can be improved, which is preferred in this respect.

[0207] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate.

[0208] Examples of (meth)acrylates having an alicyclic structure include: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclohexyl (meth)acrylate [5.2.1.0]. 2,6 ] Decane-8-yl ester, (meth)acrylate tricyclic [5.2.1.0] 2,5 Decane-8-yloxyethyl ester, isobornyl acrylate, etc.

[0209] Examples of (meth)acrylates having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0210] Examples of such aromatic vinyl compounds include: styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc.

[0211] Examples of the 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, N-naphthylmaleimide, etc.

[0212] Examples of vinyl compounds having heterocyclic structures include: tetrahydrofurfuryl methyl methacrylate, tetrahydropyranomethyl methacrylate, 5-ethyl-1,3-dioxane-5-yl methyl methacrylate, 5-methyl-1,3-dioxane-5-yl methyl methacrylate, (2-methyl-2-ethyl-1,3-dioxane-4-yl) methyl methacrylate, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) acrylate, glyceryl carbonate (meth) acrylate, (γ-lactam-2-yl) acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, etc.

[0213] Examples of conjugated diene compounds include 1,3-butadiene and isoprene; examples of nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of unsaturated dialkyl dicarboxylic acid esters include diethyl itaconic acid. In addition to the aforementioned examples, other monomers constituting the structural unit include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0214] As a monolithic entity providing the structural unit (IV), it is preferably composed of at least one selected from the group consisting of alkyl methacrylates, aromatic vinyl compounds, vinyl compounds having heterocyclic structures and N-substituted maleimide compounds, more preferably at least one selected from the group consisting of methyl methacrylate, styrene and N-cyclohexylmaleimide.

[0215] The base polymer may contain one structural unit (IV) or a combination of two or more.

[0216] When the polymer (A1) contains structural units (IV), the lower limit of the content ratio of structural units (IV) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass. Furthermore, the upper limit of the content ratio is preferably 50% by mass, more preferably 45% by mass. By setting the content ratio of structural units (IV) within the aforementioned range, the glass transition temperature of the polymer (A1) can be moderately increased, which is preferable in this respect.

[0217] [Synthesis methods of polymer (A1)]

[0218] The polymer (A1) can be manufactured, for example, using an unsaturated monomer capable of incorporating the structural units, in a suitable solvent, in the presence of a polymerization initiator, by known methods such as free radical polymerization.

[0219] Examples of polymerization initiators include azo compounds and organic peroxides such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and dimethyl 2,2'-azobis(isobutyric acid) ester.

[0220] Relative to the total amount of monomers used in the reaction (100 parts by mass), the lower limit of the amount of polymerization initiator used is preferably 0.01 parts by mass, more preferably 1 part by mass, further preferably 3 parts by mass, and particularly preferably 5 parts by mass. Furthermore, the upper limit of the amount of polymerization initiator used is preferably 30 parts by mass, more preferably 25 parts by mass, further preferably 20 parts by mass, and particularly preferably 15 parts by mass. By setting the amount of polymerization initiator used within the aforementioned range, polymers with specific end structures can be appropriately polymerized, which is therefore preferable.

[0221] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably set to be 0.1% to 60% by mass of the total amount of the monomers used in the reaction relative to the total amount of the reaction solution.

[0222] 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, as long as it is the temperature at which the polymerization reaction occurs; for example, 40°C is preferred, more preferably 50°C, even more preferably 60°C, and particularly preferably 65°C. By setting the polymerization reaction temperature within the aforementioned range, the crosslinking reaction between the acid groups contained in structural unit (I) and the groups contained in structural unit (II) can be suppressed during polymerization, which is therefore preferable.

[0223] The polymerization reaction time varies depending on the type of polymerization initiator and monomer or the reaction temperature, and is usually about 0.5 hours to 10 hours.

[0224] In the polymerization reaction used to manufacture the polymer (A1), molecular weight adjusters can be used to adjust the molecular weight. Examples of molecular weight adjusters include: halogenated hydrocarbons such as chloroform and carbon tetrabromide; thiols such as n-hexylthiol, n-octylthiol, n-dodecylthiol, tert-dodecylthiol, and thioglycolic acid; xanthates such as dimethyl xanthogen sulfide and diisopropyl disulfide; terpinolene and α-methylstyrene dimers.

[0225] The polymer (A1) obtained through polymerization can be used directly in the preparation of photosensitive compositions while dissolved in the reaction solution, or it can be used in the preparation of photosensitive compositions after being separated from the reaction solution. Polymer separation can be carried out by known methods, such as injecting the reaction solution into a large amount of undesirable solvent and drying the resulting precipitate under reduced pressure, or removing the precipitate by vacuum distillation using an evaporator.

[0226] The lower limit of the converted weight average molecular weight (Mw) of polystyrene obtained in the polymer (A1) by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent is preferably 2,000, more preferably 4,000, further preferably 5,000, and particularly preferably 6,000. Furthermore, the upper limit of the Mw is preferably 30,000, more preferably 20,000. If the Mw is within the aforementioned range, a hardened film with good film-forming properties and exhibiting good reproducibility can be obtained, which is preferred in this respect.

[0227] Furthermore, the molecular weight distribution (Mw / Mn) in the polymer (A1) 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 comprises two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer respectively satisfy the aforementioned ranges.

[0228] The lower limit of the content of the polymer (Al) in the photosensitive composition, other than the amount of solvent contained therein, is preferably 60% by mass, more preferably 65% ​​by mass. The upper limit of the content is preferably 99% by mass, more preferably 95% by mass.

[0229] (Polysiloxane (A2))

[0230] Specific examples of alkali-soluble polysiloxanes (A2) include copolymers disclosed in International Publication No. 2017 / 188047, International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, Japanese Patent Application Publication No. 2020-184010, Japanese Patent Application Publication No. 2013-114238, Japanese Patent Application Publication No. 2012-53381, and Japanese Patent Application Publication No. 2010-32977.

[0231] As an alkali-soluble polysiloxane (A2), a silsesquioxane having a first structural unit represented by formula (a) and a second structural unit represented by formula (b) is preferred.

[0232] [Chemistry 16]

[0233]

[0234] (in formula (a),

[0235] X is a monovalent organic group with an unsaturated double bond;

[0236] In equation (b),

[0237] Y is a monovalent organic group having a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof.

[0238] Furthermore, in formula (a), having an average of 1.5 oxygen atoms and one X group relative to one silicon atom, the silsesquioxane comprises a first structural unit (XSiO) with one X group and three oxygen atoms bonded to one silicon atom as shown in formula (i) below. 1.5 The same applies to equation (b).

[0239] [Chemistry 17]

[0240]

[0241] (In equation (i), * represents the bond between silicon atoms and other structural units)

[0242] The group represented by X is preferably a group having a carbon-carbon double bond, more preferably a group having a vinyl or (meth)acryloyl group, and even more preferably a group having a (meth)acryloyl group, and even more preferably a group having an acryloyl group. The lower limit for the number of carbons in X is preferably 2, more preferably 4, and even more preferably 6. Furthermore, the upper limit for the number of carbons is preferably 20, and even more preferably 10.

[0243] X is preferably a (meth)acryloyloxy group (CH2=CR) 1 COO-:R 1 The group consisting of a hydrogen atom or a methyl group and a divalent hydrocarbon group bonded to the (meth)acryloyloxy group. More preferably, the X is a group represented by the following formula (a-1).

[0244] In formula (b), Y is a monovalent organic group having a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof. Preferably, R from formula (1) is used as the organic group. 3 and R 4 Monovalent organic groups in.

[0245] The group represented by Y is preferably a group having a carboxyl group or a phenolic hydroxyl group, more preferably a group having a carboxyl group. The lower limit of the number of carbons in Y is preferably 2, more preferably 4, and even more preferably 8. In addition, the upper limit of the number of carbons is preferably 30, more preferably 20.

[0246] The Y is preferably a basis represented by formula (b-1) or formula (b-2) below. Among these, the basis represented by formula (b-1) is more preferred.

[0247] [Chemistry 18]

[0248]

[0249] (In equations (a-1), (b-1), and (b-2),)

[0250] R 51 Each can be independently a hydrogen atom or a methyl group;

[0251] R 52 Each is independently an alkyldiyl group having 2 to 10 carbon atoms;

[0252] R 53 It is a divalent organic group;

[0253] R 54 It is a single bond or a divalent organic group;

[0254] (* indicates the bonding site with Si)

[0255] As the R 52 Alkadiyl groups having 2 to 10 carbon atoms include, for example, ethanediyl, propanediyl, butanediyl, hexanediyl, octanediyl, nonanediyl, and decanediyl. Furthermore, some or all of the hydrogen atoms in the alkyldiyl group may be substituted with substituents such as halogen atoms (e.g., fluorine, chlorine, bromine, iodine); hydroxyl; carboxyl; cyano; nitro; alkyl; alkoxy; alkoxycarbonyl; alkoxycarbonyloxy; acyl; acyloxy, or groups formed by substituting the hydrogen atoms of these groups with halogen atoms.

[0256] R 53 R 54 The divalent organic group in it can preferably be R from the formula (1). 3 and R 4 A radical formed by removing a hydrogen atom from a monovalent organic radical.

[0257] Regarding the siloxane polymer, the weight-average molecular weight (Mw) of the polystyrene obtained by GPC is preferably 500 or more. If Mw is 500 or more, a pattern (cured product) with sufficiently high heat resistance and good developability can be obtained, which is preferable in this respect. Mw is more preferably 1000 or more. Furthermore, from the viewpoint of good film-forming properties and suppression of reduced radioactivity, Mw is preferably 10000 or less, more preferably 5000 or less. Additionally, 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.

[0258] (Polyamic acid or polyamic ester (A3))

[0259] The polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[0260] Examples of the aforementioned tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include...

[0261] Examples of aliphatic tetracarboxylic dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydrides, etc.

[0262] Examples of alicyclic tetracarboxylic dianhydrides include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxylated cyclopentylacetic 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-tetracarboxylated bicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.

[0263] Examples of aromatic tetracarboxylic dianhydrides include: 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bis(triphenylene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, propane-1,3-dimethylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ester), etc. In addition, the tetracarboxylic dianhydride described in Japanese Patent Application Publication No. 2010-97188 may also be used. As said tetracarboxylic dianhydrides, one or more may be used alone or in combination.

[0264] Among these, the tetracarboxylic dianhydride is preferably an aromatic tetracarboxylic dianhydride, and more preferably a 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0265] There are no particular limitations on the diamines mentioned above, and examples include: aliphatic diamines, alicyclic diamines, aromatic diamines, and diamino organosiloxanes.

[0266] Examples of aliphatic diamines include: m-phenylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc.

[0267] Examples of alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine).

[0268] Examples of aromatic diamines include: 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]adipic acid, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenylmethane. Biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylene diisopropylidene)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)]diphenylamine, 4,4'-diaminobenzoylaniline, 4,4'-diaminostilbene, 1,4-bis(4-aminophenyl)piperazine, and the following formula (S-1):

[0269] [Chemistry 19]

[0270]

[0271] (In formula (S-1),

[0272] X can be -O-, -S-, -CO-, -SO2-, -CH2-, -C(CH3)2-, -C(CH3)(C2H5)-, or -C(CF3)2-.

[0273] The compounds represented are main-chain diamines:

[0274] Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl Esters, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanosteryl ester, 3,6-bis(4-aminobenzoyloxy)cholestan, 3,6-bis(4-aminophenoxy)cholestan, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, and the following formula (S-2):

[0275] [Chemistry 20]

[0276]

[0277] (In formula (S-2),)

[0278] X I and X II Each can be independently a single bond, -O-, *-COO-, or *-OCO- (where "*" indicates a bond with R). I (The bond of the bond);

[0279] R I It is an alkyldiyl group with 1 to 3 carbon atoms;

[0280] R II It is a single bond or an alkyl dienyllium with 1 to 3 carbon atoms;

[0281] R III It is an alkyl, alkoxy, fluoroalkyl, or fluoroalkoxy group having 1 to 20 carbon atoms;

[0282] a is 0 or 1;

[0283] b is an integer between 0 and 3;

[0284] c is an integer from 0 to 2;

[0285] d is 0 or 1; where 1 ≦ a + b + c ≦ 3)

[0286] The compounds represented include side-chain diamines, etc.

[0287] Examples of diamino organosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. Other examples 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.). Additionally, the diamine described in Japanese Patent Application Publication No. 2010-97188 may be used.

[0288] Of these, the diamine is preferably a diamino organosiloxane, more preferably X-22-161-A (both manufactured by Shin-Etsu Chemical Co., Ltd.).

[0289] The diamine can be used alone or in combination of two or more.

[0290] Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride with a diamine and, if desired, a molecular weight adjuster. The ratio of tetracarboxylic dianhydride to diamine used in the synthesis reaction of polyamic acid is preferably 0.2 to 2 equivalents of the anhydride group of the tetracarboxylic dianhydride relative to the amino group of the diamine. Examples of molecular weight adjusters include: maleic anhydride, phthalic anhydride, itaconic anhydride, and other monoanhydrides; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The ratio of the molecular weight adjuster used is preferably 20 parts by mass or less, relative to the total 100 parts by mass of the tetracarboxylic dianhydride and diamine used.

[0291] The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The preferred reaction temperature is -20°C to 150°C, and the preferred reaction time is 0.1 hours 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, hexamethylphosphoric triamine, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these solvents with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount (a) of organic solvent used is preferably set such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1% to 50% by mass relative to the total amount (a+b) of the reaction solution.

[0292] In the above manner, a reaction solution formed by dissolving polyamic acid can be obtained. The reaction solution can be used directly for the preparation of the photosensitive composition, or the polyamic acid contained in the reaction solution can be separated and used for the preparation of the photosensitive composition.

[0293] The polyamic acid ester can be obtained, for example, by the following methods: [I] reacting the polyamic acid obtained by the synthesis reaction with an esterifying agent; [II] reacting a tetracarboxylic acid diester with a diamine; [III] reacting a tetracarboxylic acid diester dihalide with a diamine, etc. The polyamic acid ester contained in the photosensitive composition of the present invention may have only an amide ester structure, or it may be a partial esterification containing both an amide acid structure and an amide ester structure. The reaction solution obtained by dissolving the polyamic acid ester can be directly used in the preparation of the photosensitive composition, or the polyamic acid ester contained in the reaction solution can be separated and used in the preparation of the photosensitive composition.

[0294] (Phenolic varnish resin (A4))

[0295] The phenolic varnish resin (A4) can be obtained by using known methods and by polycondensation of phenols with aldehydes such as formaldehyde.

[0296] Examples of such 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, methylene... Bisphenol, methylene bis-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, etc. These can be used alone or in combination of two or more.

[0297] In addition to formaldehyde, other aldehydes mentioned include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde. These can be used alone or in combination of two or more.

[0298] The phenolic varnish resin is preferably a group containing unsaturated double bonds, such as (meth)acryloyl or vinyl groups, and more preferably a side chain represented by the following formula (5). In this case, it is preferable that the main chain also has an aromatic ring. More preferably, it is a resin having a side chain represented by the following formula (5) and a phenolic varnish main chain.

[0299] Examples of resins having the side chains represented by the formula (5) below and having a phenolic varnish main chain include acid-modified cresol varnish type epoxy (meth) acrylate resin and acid-modified phenol varnish type epoxy (meth) acrylate resin.

[0300] [Chemistry 21]

[0301]

[0302] In equation (5), R 61 It can be a hydrogen atom or a methyl group. R 62 and R 63 Each is an independent divalent organic group. * indicates a bonding site with the main chain.

[0303] As the R 61 Preferably, it contains hydrogen atoms.

[0304] As the R 62 and R 63The divalent organic group represented may preferably be a group formed by removing a hydrogen atom from the monovalent organic group in Y of formula (b).

[0305] As the R 62 and R 63 The number of carbon atoms in the divalent organic groups is not particularly limited; as a lower limit, it can be 1. On the other hand, as an upper limit, it can be, for example, 20 or 10.

[0306] As the R 62 Preferably, it is a divalent hydrocarbon group, more preferably a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group. As the R... 63 Preferably, it is a group such as -CH2-O-* with an oxygen atom (-O-) bonded to the end of the main chain of a divalent hydrocarbon group.

[0307] As an acid-modified cresol varnish-type epoxy (meth)acrylate resin, examples include the polymer represented by formula (6) below. The acid-modified cresol varnish-type epoxy (meth)acrylate resin can be obtained, for example, by reacting anhydrides such as phthalic anhydride and 1,2,3,6-tetrahydrophthalic anhydride with an epoxy (meth)acrylate resin obtained by reacting (meth)acrylate with a cresol varnish-type epoxy resin.

[0308] [Chemistry 22]

[0309]

[0310] In equation (6), p and q are independent integers from 1 to 30.

[0311] (Cardo resin (A5))

[0312] The alkali-soluble calo resin (A5) is not particularly limited as long as it can be dissolved in alkaline developing solution, but preferably contains one or more anionic groups such as carboxyl groups, sulfonic acid groups, and phosphonic acid groups. Calo resin refers to a resin having a calo skeleton, which is a skeleton in which two aromatic groups are connected by single bonds to the quaternary carbon atom of the ring carbon atom constituting the ring structure. Calo resin is preferably free radical polymerizable, and can be obtained, for example, by reacting an epoxy resin containing a calo structure, (meth)acrylic acid, and tetracarboxylic acid dianhydride. Alternatively, dicarboxylic acid anhydride may be reacted as needed. Commercially available calomelting resins with free radical polymerization properties include, for example, "WR-301" manufactured by ADEKA (stock); "V-259ME" manufactured by Nippon Steel & Sumitomo Chemical (stock); and "Ogsol CR-TR1", "Ogsol CR-TR2", "Ogsol CR-TR3", "Ogsol CR-TR4", "Ogsol CR-TR5", and "Ogsol CR-TR6" manufactured by Osaka Gas Chemical (stock). These can be used individually or in combination. From the viewpoint of alkali-developable properties, the acid value of the alkali-soluble calomel resin is preferably 10 mg KOH / g or more and 300 mg KOH / g or less, more preferably 20 mg KOH / g or more and 200 mg KOH / g or less.

[0313] (Other alkali-soluble polymers)

[0314] In addition to the above, alkali-soluble polyimides or polybenzoxazoles can also be used as alkali-soluble polymers. Specific examples of these include copolymers disclosed in International Publications No. 2017 / 169763, 2017 / 159876, 2017 / 057281, 2017 / 159476, 2017 / 073481, 2017 / 038828, 2016 / 148176, Japanese Patent Application Publication No. 2015-114355, Japanese Patent Application Publication No. 2013-164432, and Japanese Patent Application Publication No. 2010-72143.

[0315] The lower limit of the content of polymer (A) relative to the total amount of solid components contained in the composition (i.e., the total mass of components other than solvents in the photosensitive composition) is preferably 20% by mass, more preferably 30% by mass, and even more preferably 50% by mass. Furthermore, the upper limit of the content of polymer (A) relative to the total amount of solid components contained in the photosensitive composition is preferably 99% by mass, more preferably 95% by mass. By setting the content of polymer (A) within the aforementioned range, pattern formation properties and substrate adhesion can be sufficiently improved.

[0316] (Radiosensitive linear compound (B))

[0317] Examples of radiosensitive linear compounds (B) include quinone diazide compounds (B1) and photoacid generators (B2).

[0318] (quinone diazide compound (B1))

[0319] This composition may contain a quinone diazide compound (B1) as a radiosensitive linear compound (B).

[0320] When using a quinone diazide compound (B1) as the radiosensitive linear compound (B), the polymer (A) is preferably a polymer (A1) containing a structural unit (I) having an acid group, and preferably also includes: a polymer (A1) containing a structural unit (I) having an acid group and a structural unit (II) having a crosslinking group, or a polymer different from the polymer (A1) and containing a structural unit having a crosslinking group.

[0321] Quinone diazide compounds (B1) are compounds that produce carboxylic acids through irradiation with radiation. Examples of quinone diazide compounds (B1) include condensates of phenolic or alcoholic compounds (hereinafter also referred to as "cores") with o-naphthoquinone diazide compounds. Among these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the core and an o-naphthoquinone diazide compound. Specific examples of cores include the compounds described in paragraphs

[0065] to

[0070] of Japanese Patent Application Publication No. 2014-186300.

[0322] Specific examples of quinone diazide compounds (B1) include: compounds containing phenolic hydroxyl groups selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and ester compounds with 1,2-naphthoquinone diazide-4-sulfonyl chloride or 1,2-naphthoquinone diazide-5-sulfonyl chloride. Among these, the preferred condensate of 4,4'-[1-[4-[1-[4-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinone diazide-5-sulfonyl chloride is the quinone diazide-5-sulfonyl chloride.

[0323] These quinone diazide compounds (B1) can be used alone or in combination of two or more. When quinone diazide compounds (B1) are included, the lower limit of the content of quinone diazide compound (B1) relative to 100 parts by mass of the polymer (A) is preferably 1 part by mass, more preferably 2 parts by mass, and even more preferably 3 parts by mass. Furthermore, the upper limit of the content of quinone diazide compound (B1) relative to 100 parts by mass of the polymer (A) is preferably 50 parts by mass, more preferably 30 parts by mass, and even more preferably 20 parts by mass. If the content of quinone diazide compound (B1) is set to 1 part by mass or more, carboxylic acid is sufficiently generated by irradiation of the composition, which sufficiently increases the difference in solubility of the irradiated and unirradiated portions relative to the developing solution, allowing for good patterning; this is preferable in this respect. In addition, increasing the amount of carboxylic acid participating in the reaction with epoxy-containing polymer components, etc., sufficiently ensures heat resistance. On the other hand, by setting the content of quinone diazide compound to 50 parts by mass or less, the amount of quinone diazide compound that does not react after exposure can be sufficiently reduced, and the reduction in developability caused by the residue of quinone diazide compound can be suppressed, which is preferred in this respect.

[0324] (Photoacid generator (B2))

[0325] Photoacid generator (B2) is any compound that generates acid in response to radiation (i.e., a radiosensitive acid generator), and there are no particular limitations. Examples of photoacid generators (B2) include: oxime sulfonate compounds, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, etc.

[0326] When using photoacid generator (B2) as radiosensitive linear compound (B), the polymer (A) is preferably a polymer selected from at least one of the group consisting of polymers (A1) containing structural unit (III) and siloxane polymers (A2).

[0327] Specific examples of oxime sulfonate compounds, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylic acid ester compounds include, for example, the compounds described in paragraphs

[0078] to

[0106] of Japanese Patent Application Publication No. 2014-157252, and the compounds described in International Publication No. 2016 / 124493. As a photoacid generator, from the viewpoint of radiation sensitivity, at least one selected from the group consisting of the oxime sulfonate compounds and sulfonylimide compounds described above is preferably used.

[0328] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (b2).

[0329] [Chemistry 23]

[0330]

[0331] (in formula (b2),)

[0332] R 40 It is a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted by a substituent;

[0333] The asterisk (*) indicates a bond with other atoms in the oxime sulfonate compound.

[0334] In the above equation (b2), R is... 40 Monovalent hydrocarbon groups in the group can be exemplified by, for example, alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 4 to 12 carbon atoms, and aryl groups with 6 to 20 carbon atoms. Substituents can be exemplified by, for example, alkyl groups with 1 to 5 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, side oxygen groups, and halogen atoms.

[0335] Examples of oxime sulfonate compounds include: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylphenylsulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493, etc. Commercially available oxime sulfonate compounds include BASF's Irgacure PAG121.

[0336] If sulfonylimide compounds are to be exemplified, the following can be listed: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, etc. Phthalicimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, trifluoromethanesulfonic acid-1,8-naphthalimide (naphthalimide trifluoromethanesulfonate).

[0337] These photoacid generators (B2) can be used alone or in combination of two or more. When photoacid generators (B2) are included, the lower limit of the content of photoacid generators (B2) relative to 100 parts by weight of the polymer (A) is preferably 0.01 parts by weight, more preferably 0.1 parts by weight, and even more preferably 2 parts by weight. Furthermore, the upper limit of the content of photoacid generators (B2) relative to 100 parts by weight of the polymer (A) formulated in this composition is preferably 30 parts by weight, more preferably 20 parts by weight, and even more preferably 10 parts by weight. Setting the content of photoacid generators (B2) to 0.01 parts by weight or more allows for good patterning and sufficiently ensures heat resistance, which is preferable in this respect. Furthermore, setting the content of photoacid generators (B2) to 30 parts by weight or less sufficiently reduces the amount of unreacted photoacid generators after exposure and suppresses the decrease in developability caused by the residue of photoacid generators, which is preferable in this respect.

[0338] In addition to the compound (1), the alkali-soluble polymer (A), and the radiosensitive linear compound (B), this composition may further contain other components without impairing the effects of the present invention. Examples of other components include: solvents, colorants other than the compound (1), dispersants, dispersing aids, surfactants, polymers other than the alkali-soluble polymer (A), polymerization inhibitors, antioxidants, sensitizers, softeners, plasticizers, bonding aids, ultraviolet absorbers, and solubilizers. Among these, bonding aids (C), solubilizers (D), surfactants (E), solvents (S), and colorants other than the compound (1) are preferred.

[0339] (Sealing agent (C))

[0340] This composition, by including a bonding agent (C), can improve the adhesion between the formed hardened material and the substrate (adhesive), and suppress the peeling of the hardened material from the substrate during processes such as development.

[0341] Examples of bonding aids (C) include functionalized silane coupling agents or functionalized acidic phosphate esters possessing reactive functional groups. Examples of reactive functional groups in functionalized silane coupling agents include: carboxyl, anhydride, (meth)acryloyl, epoxy, vinyl, and isocyanate groups. Examples of reactive functional groups in functionalized acidic phosphate esters include (meth)acryloyl.

[0342] Specific examples of functional silane coupling agents include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, etc. These can be used alone or in combination of two or more. Among these, 3-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred.

[0343] Commercially available products can also be used as the aforementioned functional silane coupling agent. 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 Industry Co., Ltd.).

[0344] Specific examples of functional acidic phosphate esters include 2-(meth)acryloyloxyethyl acidic phosphate ester.

[0345] Commercially available products can be used as the aforementioned functional acidic phosphate esters. Examples of commercially available products include LightEster P-1M and LightEster P-2M (both manufactured by Kyoeisha Chemical Co., Ltd.).

[0346] The bonding agent (C) can be used alone or in combination of two or more.

[0347] When the adhesion promoter (C) is incorporated into the photosensitive composition, the lower limit of the content of the adhesion promoter (C) relative to 100 parts by weight of the polymer (A) is preferably 0.1 parts by weight, more preferably 0.5 parts by weight, and even more preferably 1 part by weight. Furthermore, the upper limit of the content of the adhesion promoter (C) relative to 100 parts by weight of the polymer (A) incorporated in this composition is preferably 10 parts by weight, more preferably 5 parts by weight, and even more preferably 3 parts by weight. By having the adhesion promoter (C) contained within the aforementioned range, a hardened film with excellent adhesion can be formed, which is therefore preferable.

[0348] (Solubility accelerator (D))

[0349] Solubility promoter (D) can be any compound that promotes the solubility of the developer, such as low molecular weight compounds with a molecular weight of less than 1,000 that have two or more phenolic hydroxyl groups or one or more carboxyl groups.

[0350] The 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.

[0351] As for such phenolic compounds with a molecular weight of less than 1000, they can be easily synthesized by those skilled in the art by referring to the methods described in, for example, Japanese Patent Application Publication No. 4-122938, Japanese Patent Application Publication No. 2-28531, US Patent No. 4916210, European Patent No. 219294, etc.

[0352] Specific examples of the phenolic compounds include: resorcinol, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, acetone-phloroglucinol 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, 1, 1-Bis(4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzyl)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-tetra(4-hydroxyphenyl)hexane, 1,2-tetra(4-hydroxyphenyl)ethane, 1,1,3-tris(hydroxyphenyl)butane, p-[α,α,α',α'-tetra(4-hydroxyphenyl)]-xylene, etc.

[0353] Examples of low-molecular-weight compounds with a molecular weight of less than 1,000 and having one or more carboxyl groups include: aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pentanoic acid, hexanoic acid, diethylacetic acid, heptanoic acid, and octanoic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, brassylicacid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citralic acid; aliphatic tricarboxylic acids such as tricarboxylic acid, aconitic acid, and norcarbamate; and benzoic acid, benzoic acid, cuminic acid, and hemimellitic acid. Aromatic monocarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellomelanic acid, pyromellitic acid, etc.; and polyfunctional (meth)acrylates containing carboxylic acids.

[0354] Examples of polyfunctional (meth)acrylates having the aforementioned carboxylic acid include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate modified with carboxylic acid. Commercially available products may also be preferred, such as Aronix M-520 (manufactured by Toa Synthetic Co., Ltd.).

[0355] The solubility accelerator (D) can be used alone or in combination of two or more.

[0356] When the photosensitive composition used in this manufacturing method contains a solubility accelerator (D), the lower limit of the content of the solubility accelerator (D) (in the case of multiple components, the total amount) is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, and even more preferably 1 part by mass relative to 100 parts by mass of the polymer (A). Furthermore, the upper limit of the content of the solubility accelerator (D) relative to 100 parts by mass of the polymer (A) formulated in this composition is preferably 15 parts by mass, more preferably 10 parts by mass, and even more preferably 8 parts by mass. Since the content of the solubility accelerator (D) is within the aforementioned range, sufficient solubility in the developer can be achieved, which is therefore preferable.

[0357] (surfactant(E))

[0358] Surfactant (E) can be used to further improve the coatability of this composition (specifically, the reduction of wetting spread or uneven coating). Examples of surfactants (E) include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

[0359] Specific examples of surfactants, as fluorinated surfactants, can be listed by the following trade names: MEGAFAC F-171, MEGAFAC F-172, MEGAFAC F-173, MEGAFAC F-251, MEGAFAC F-430, MEGAFAC F-554, MEGAFAC F-563 (manufactured by DIC); Fluorad FC430, Fluorad FC431 (manufactured by Sumitomo 3M); Asahi Guard) AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103 , Surflon SC-104, Surflon SC-105, Surflon SC-106, Surflon S-611 (AGC Qingmei Chemical (AGC) SEIMIChemical (stock) manufactures; Polyflow No. 75 and Polyflow No. 95 (manufactured by Kyoeisha Chemical (stock)); FTX-218 (manufactured by NEOS (stock)); Eftop EF301, Eftop EF303, and Eftop EF352 (manufactured by Shin-Akita Chemical (stock)), etc.

[0360] As silicone-based surfactants, examples include the following trade names: SH200-100cs, SH28PA, SH30PA, SH89PA, SH190, SH8400, SH193, SZ6032, SF8428, DC57, DC190, PAINTAD 19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (Toray Dow Corning). Corning Corporation (manufactured); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BYK-Chemie Japan).

[0361] Examples of nonionic surfactants include: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0362] The surfactant (E) can be used alone or in combination of two or more.

[0363] When surfactant (E) is incorporated into this composition, the lower limit of the surfactant (E) content relative to 100 parts by weight of polymer (A) is preferably 0.05 parts by weight, more preferably 0.08 parts by weight. Furthermore, the upper limit of the surfactant (E) content relative to 100 parts by weight of polymer (A) incorporated into this composition is preferably 1 part by weight, more preferably 0.5 parts by weight, and even more preferably 0.3 parts by weight.

[0364] (solvent(S))

[0365] This composition is a liquid composition in which compound (I), alkali-soluble polymer (A), radiosensitive linear compound (B), and other components as needed are preferably dissolved or dispersed in a solvent (S). The solvent (S) is preferably an organic solvent that dissolves and does not react with any of the components in the photosensitive composition.

[0366] Specific examples of solvents (S) include: 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, dimethylene glycol dimethyl ether, diethylene 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. Among these, ethers and ketones are preferred solvents, and propylene glycol monomethyl ether acetate, cyclopentanone, and propylene glycol monomethyl ether are more preferred.

[0367] (Coloring agents other than compound (1))

[0368] In this composition, the colorant may be compound (1) alone, but by using colorants other than compound (1) (hereinafter also referred to as "other colorants"), there is a tendency to improve the opacity of the cured material obtained from this composition.

[0369] 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.

[0370] Furthermore, as described in Japanese Patent Application Publication No. 2017-226821, in addition to black organic pigments and black inorganic pigments, a combination of pigments capable of absorbing light in the visible light region can be selected without using black organic pigments or black inorganic pigments, by combining specific colored organic pigments. The pigments used in the combination are selected from red organic pigments, blue organic pigments, and purple organic pigments. In a preferred embodiment, the red organic pigment is selected from at least one of group (a) below, the blue organic pigment is selected from at least one of group (b) below, and the purple organic pigment is selected from at least one of group (c) below.

[0371] (a) Group: Color Index (CI) Pigment Red 149, 179, 254, 255,

[0372] (b) Group: CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 60

[0373] (c) Group: CI Pigment Violet 23, 29.

[0374] Other dyes besides compound (1) include, for example: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, succinyl dyes, anthocyanin dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, phthalocyanine dyes, and leuco dyes.

[0375] When other colorants are incorporated into this composition, a composition with excellent sensitivity, developability, and radiation (especially gamma rays, h rays, and i rays) transmittance can be easily obtained, thereby easily forming a hardened material with excellent light-shielding properties. In terms of these properties, the amount of other colorants incorporated relative to 100 parts by weight of the polymer (A) is preferably 1 to 70 parts by weight, more preferably 5 to 60 parts by weight.

[0376] The form in which the pigment is used as another colorant is not particularly limited; it can be used as a powder or as a dispersion. Among these, in terms of solvent solubility or solvent dispersibility, it is preferable to masterbatch the pigment and use it as a pigment masterbatch dispersion in the preparation of this composition. A polymer is preferably used in the pigment masterbatch; the polymer is not particularly limited, but it is preferably the same polymer as the alkali-soluble polymer (A). To improve dispersibility, a dispersant described later may be incorporated into the pigment masterbatch.

[0377] As a dispersion medium in pigment masterbatch dispersions, organic solvents such as propylene glycol monomethyl ether acetate, cellosol 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.

[0378] (Dispersant)

[0379] When using pigments as other colorants, it is preferable to finely disperse the pigments and stabilize their dispersion state in terms of the quality and stability of the composition; therefore, it is preferable to use a dispersant. Alternatively, a dispersing aid may also be used in conjunction with the dispersant. Furthermore, regarding the case where no pigment is used, when the solubility of compound (1) is poor, a dispersant may be used for the purpose of maintaining a stable dispersion state.

[0380] As a dispersant, a polymeric dispersant with functional groups is preferred. Furthermore, in terms of dispersion stability, polymeric dispersants with functional groups such as carboxyl groups, phosphate groups, sulfonic acid groups, bases of these, primary, secondary, or tertiary amino groups, quaternary ammonium salt groups, or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are preferred. Among these, polymeric dispersants with basic functional groups such as primary, secondary, or tertiary amino groups, quaternary ammonium salt groups, or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are particularly preferred because a small amount of dispersant is needed to disperse the pigment.

[0381] In addition, examples of polymeric dispersants include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants obtained by using monomers with amino groups and macromolecular monomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0382] When a dispersant is incorporated into this composition, the amount of dispersant incorporated relative to 100 parts by weight of pigment is preferably 10 to 100 parts by weight, more preferably 15 to 80 parts by weight, and even more preferably 20 to 60 parts by weight. Furthermore, when a dispersant is incorporated into this composition even when no pigment is used, the amount of dispersant incorporated relative to 100 parts by weight of compound (1) is preferably 10 to 100 parts by weight, more preferably 15 to 80 parts by weight, and even more preferably 20 to 60 parts by weight.

[0383] Furthermore, from the viewpoints of ease of manufacture and manufacturing cost, it is preferable that the composition may contain as few other components as possible. In addition, gases caused by dispersants may sometimes be generated from the hardened film, so it is also preferable that the composition does not contain dispersants.

[0384] (Dispersing agent)

[0385] When a dispersant is used in this composition, a dispersing aid may also be used in conjunction with the dispersant.

[0386] Examples of dispersing aids include pigment derivatives.

[0387] Pigments that are pigment derivatives include, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolineone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, violet-based, and diketopyrrolopyrrole-based pigments.

[0388] As pigment derivatives, examples include compounds that have sulfonic acid groups, sulfonamide groups, quaternary salts of sulfonamide groups, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., directly or via alkyl, aryl, heterocyclic groups, etc., bonded to the pigment skeleton.

[0389] (Antioxidants)

[0390] By using antioxidants in this composition, the degradation of polymer molecules is inhibited, thereby improving durability, etc.

[0391] Examples of antioxidants include: 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodivinylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0392] (Preparation method of this composition)

[0393] This composition can be prepared by uniformly stirring and mixing compound (1) and any other ingredients, and uniformly dissolving or dispersing them. During mixing, known mixers such as roller mills, ball mills, and sand mills can be used. After mixing, the resulting mixture can be filtered, if necessary, using a filter with a pore size of, for example, less than 2 μm.

[0394] The concentration of solids in this composition (i.e., the proportion of the total mass of the components other than the solvent (S) in the composition relative to the total mass of the composition) can be appropriately selected considering factors such as viscosity and volatility. The concentration of solids in 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. If the concentration of solids is above the lower limit, sufficient film thickness can be ensured when the composition is applied to a substrate (adhesive), which is preferable in this respect. Furthermore, if the concentration of solids is below the upper limit, the viscosity of the composition can be moderately increased, and good coatability can be ensured, which is preferable in this respect.

[0395] This composition is preferably used to form light-shielding cured materials such as isolation walls or black matrices. Cured materials obtained from this composition, especially isolation walls or black matrices with excellent light-shielding properties, can be used particularly effectively in liquid crystal display elements, solid-state imaging elements, color sensors, organic electroluminescence (EL) display elements, electronic paper, etc.

[0396] Method for manufacturing patterned hardened materials

[0397] The method for manufacturing the hardened material according to this embodiment (hereinafter also referred to as "this manufacturing method") includes:

[0398] The process of coating a positive photosensitive composition containing a compound represented by the following formula (1) onto a substrate to form a coating film;

[0399] The process of exposing the coating film;

[0400] The process of developing the exposed coating; and

[0401] The process of heating the developed pattern.

[0402] [Chemistry 24]

[0403]

[0404] (In formula (1),)

[0405] R 1 and R2 Each is independently a hydrogen atom or a depleted radical; wherein, R 1 and R 2 At least one of them is a detachable base;

[0406] R 3 and R 4 and R 5 Each can be independently composed of a bromine atom, a chlorine atom, a fluorine atom, a monovalent organic group, a nitro group, a carboxyl group, or a sulfonyl group;

[0407] n1 and n2 are independent integers from 0 to 4;

[0408] (n3 is an integer between 0 and 2)

[0409] <Process (I): Coating Process>

[0410] Step (I) is a process of forming a coating (organic film) on a substrate by applying a positive photosensitive composition containing the compound represented by formula (1) onto the substrate.

[0411] This composition may preferably be used as a positive photosensitive composition comprising the compound represented by formula (1).

[0412] Examples of substrates for coating the photosensitive composition include: glass substrates, silicon wafers, plastic substrates, and substrates on which colored resists, outer coatings, anti-reflective films, various metal films, sealing films, etc., are formed.

[0413] Examples of plastic substrates include resin substrates (resin films) made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. Various components (e.g., light-receiving components such as photodiodes, or light-emitting components such as organic light-emitting diodes) may also be pre-formed into the substrate.

[0414] As a coating method for the photosensitive composition, suitable methods such as spraying, roller coating, spin coating, slot die coating, bar coating, and inkjet coating can be used. Among these coating methods, spin coating, bar coating, or slot die coating are preferred.

[0415] After the photosensitive composition is coated onto a substrate, the composition may be preheated (pre-baked) to prevent dripping. The pre-baking conditions may be appropriately set according to the type or proportion of each component used in the composition, for example, at 60°C to 130°C for about 30 seconds to 10 minutes. Furthermore, the pre-baking is preferably performed at a temperature at which the detachable groups in compound (1) will not detach.

[0416] The thickness of the coating film formed, measured by the pre-baked film thickness, is preferably 0.2 μm or more, more preferably 0.3 μm to 5 μm, and even more preferably 0.4 μm to 3 μm.

[0417] <Process (II): Exposure Process>

[0418] Step (II) involves irradiating at least a portion of the coating film formed in step 1 with radiation.

[0419] In step (II), the position-selective radiation irradiation of the coating is typically performed using a spacer mask with a pattern for obtaining a hardened material with the desired shape. The mask is preferably a multi-grayscale mask, such as a halftone mask or a grayscale mask. Slits below the resolution of the exposure machine are formed on the grayscale mask, and intermediate exposure is achieved by partially blocking light using these slits. In a halftone mask, intermediate exposure is achieved by using a semi-transparent film. Using such a multi-grayscale mask, a pattern with stepped shapes can be formed, for example, spacers can be formed on a black isolation wall.

[0420] Examples of radiation that irradiates the coating include: ultraviolet radiation, far ultraviolet radiation, X-rays, and charged particle beams. Examples of ultraviolet radiation include: gamma 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. Among these radiations, ultraviolet radiation is preferred, and more preferably ultraviolet radiation containing gamma rays, h-rays, and i-rays.

[0421] Examples of light sources used in radiation irradiation include: low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and light-emitting diode (LED) lamps.

[0422] The preferred exposure level for radiation is 100 J / m². 2 ~50,000 J / m 2 (10mJ / m 2~5,000 mJ / cm 2 ), more preferably 100 J / m 2 ~6,000 J / m 2 (10mJ / cm 2 ~600mJ / cm 2 ).

[0423] <Process (III): Development Process>

[0424] Step (III) is a step of forming a pattern on a substrate by developing the coating and hardened material obtained in step (II). In this manufacturing method, in order to use a positive photosensitive composition, the coating film irradiated with radiation in step (II) can be positively developed by developing it with a developing solution to remove the irradiated portion, thereby forming a patterned hardened material (e.g., a raised pattern formed by a plurality of regularly arranged linear hardened materials) on the substrate.

[0425] As a developer, an aqueous solution of an alkali (basic compound) can be included. Examples of such 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, 1,5-diazabicyclo[4.3.0]-5-nonane, etc. Alternatively, a suitable amount of a water-soluble organic solvent or surfactant such as methanol or ethanol, or a small amount of various organic solvents capable of dissolving this composition, can be added to the aqueous solution of the alkali.

[0426] The concentration of the developer can be appropriately determined according to the composition of the composition, and is usually 0.01% to 10% by mass, preferably 0.5% to 5% by mass.

[0427] As a developing method, suitable methods such as liquid coating, immersion, shaking immersion, and spraying can be used.

[0428] The development time can be adjusted appropriately according to the composition of this composition, for example, from 20 seconds to 120 seconds.

[0429] After the development process, if necessary, the patterned substrate can also be cleaned with pure water or similar substances.

[0430] Alternatively, a drying process can be performed on the patterned substrate after development or cleaning. There are no particular limitations on the drying conditions; for example, the same conditions as those used for pre-baking can be cited.

[0431] Because of the excellent ultraviolet (especially gamma, h and i rays) transmittance of this composition and its excellent sensitivity during exposure, the patterned hardened material obtained from this composition adheres well to the substrate and can also form patterns with fine line widths.

[0432] <Process (IV): Post-baking process>

[0433] In step (IV), the developed coating from step (III) is heated (post-baking). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120°C to 250°C. For example, when heating is performed on a hot plate, the heating time is 5 minutes to 40 minutes; when heating is performed in an oven, the heating time is 10 minutes to 80 minutes. By performing this as described above, a hardened film with a target pattern can be formed on the substrate. The shape of the pattern in the hardened film is not particularly limited; examples include line and space patterns, dot patterns, hole patterns, and grid patterns.

[0434] Process (IV) can also use a step baking method that involves multiple heating processes.

[0435] <Process (V): Post-exposure process>

[0436] Step (V) is a step of further irradiating the developed hardened material obtained in step (III) and / or the hardened material obtained in step (IV) with radiation. Among these, the step of further irradiating the hardened material obtained in step (IV) with radiation is preferred in terms of ease of forming a hardened material of the desired shape.

[0437] By irradiating with radiation in process (V) (hereinafter also referred to as "post-exposure"), heat resistance or chemical resistance can be further improved, and highly reliable hardened products can be easily formed.

[0438] Regarding the type of radiation or exposure conditions in the post-exposure, the same type of radiation or exposure conditions as in process (II) can be used. In addition, the wavelength or amount of irradiation light, light source, and other conditions during post-exposure can be the same as or different from those in process (II).

[0439] Hardened Material, Isolation Wall, Black Matrix

[0440] The cured material of the present invention (hereinafter also referred to as "this cured material") can be formed by curing a positive photosensitive composition prepared as described above. The cured material obtained from the positive photosensitive composition has excellent developability, optical density (OD (Optical density) value), and heat resistance. Therefore, the patterned cured material can preferably be used, for example, as a color filter (color pattern or black matrix) or a light-shielding isolation wall material (barrier). The black matrix refers to the black component in a color filter or the like that is used to divide red, green, and blue (RGB) cells. In addition, if an isolation wall is formed on a substrate in advance, and an organic EL light-emitting layer is formed in the recessed space divided by the isolation wall by inkjet printing or the like, the isolation wall that is blackened to prevent light leakage between pixels is called a light-shielding isolation wall material (black barrier). In addition to the above, it can also preferably be used as an interlayer insulating film, a planarization film, etc.

[0441] When the hardened product formed by curing the curable composition of the present invention is used as a light-shielding wall material, the optical density (DO value) of the hardened product is preferably 0.5 to 4.0, more preferably 0.7 to 3.8. With an optical density within this range, it can exert sufficient light-shielding properties as a light-shielding wall material, and is therefore preferred.

[0442] Color Filters

[0443] The color filter of the present invention includes the hardened material as a black matrix.

[0444] Image Display Panel

[0445] The image display panel of the present invention only needs to include the color filter; other structures are not particularly limited. Alternatively, a color filter or light-shielding barrier material of an organic EL panel that is stacked on a substrate, comprising a thin film transistor (TFT) driving circuit layer, a light-shielding barrier material (barrier), a light-emitting layer with three primary colors having a light-emitting layer, a sealing layer, a touch sensor, a color filter containing a black matrix and color patterns having various colors (RGB), a cover glass, and not having a polarizer (POL-LESS) structure, can also be used as the cured material.

[0446] Image Display Devices

[0447] The image display device of the present invention includes the cured material and the image display panel. The cured material may be used as a light-shielding insulating material or a color filter. Examples of such display devices include: liquid crystal display devices, organic EL display devices, light-emitting diode (LED) display devices, and quantum dot light-emitting display devices. Alternatively, organic EL display devices having an organic EL panel without a polarizer (POL-LESS) structure are also preferably included.

[0448] [Example]

[0449] The present invention will be specifically described below through embodiments, but the present invention is not limited to the following embodiments.

[0450] Synthesis Example 1: Synthesis of Bk-Dye-1

[0451] In a reaction vessel equipped with a cooling pipe, 2.00 g of a lactam-based pigment (Irgaphor Black SO100CF, manufactured by BASF) was added to 10.00 g of N-methylpyrrolidone and dispersed. Then, 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 atmosphere with stirring for 5 hours. The resulting reaction solution was then cooled to room temperature and 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. The organic layer was concentrated under reduced pressure using a rotary evaporator and then dried under reduced pressure at room temperature to obtain 0.50 g of the target Bk-Dye-1. The synthesis could be repeated as needed.

[0452] [Chemistry 25]

[0453]

[0454] Synthesis Example 2: Synthesis of Bk-Dye-2

[0455] In a reaction vessel equipped with a cooling pipe, 2.00 g of a lactam-based pigment (Irgaphor Black S0100CF, manufactured by BASF) was added to 10.00 g of N,N-dimethylformamide and dispersed. Then, 0.79 g of chloromethyl 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. The resulting reaction solution was then cooled to room temperature, and 40 mL of a saturated sodium bicarbonate aqueous solution was added, followed by stirring for 1 hour. The resulting liquid 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. The organic layer was concentrated under reduced pressure using a rotary evaporator and 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.

[0456] [Chemistry 26]

[0457]

[0458] Synthesis Example 3: Synthesis of Bk-Dye-3

[0459] In a reaction vessel equipped with a cooling tube, 5 g of indigo 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. The reaction solution was then concentrated under reduced pressure using a rotary evaporator and dissolved in 200 mL of ethyl acetate. The ethyl acetate solution was washed three times with 200 mL of deionized water. The organic layer was then concentrated under reduced pressure using a rotary evaporator and dried under reduced pressure at room temperature to obtain the target 2EH-indigo.

[0460] [Chemistry 27]

[0461]

[0462] In a reaction vessel equipped with a cooling pipe, 3.3 g of 2EH-indigo 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. Then, 0.5 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 115 °C for 11 hours. After cooling the resulting reaction solution to room temperature, it was injected into 500 mL of isopropanol. The precipitate was then obtained by filtration and washed twice with 50 mL of isopropanol. The obtained solid was dried under reduced pressure to obtain the target...

[0463] Bk-Dye-3.

[0464] [Chemistry 28]

[0465]

[0466] Synthesis Example 4: Synthesis of Polymer (A1-1)

[0467] In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. In the same flask, 2 parts by weight of phenyl methacrylate, 32 parts by weight of Cyclomer M100 (manufactured by Daicel), 8 parts by weight of methacrylic acid, 28 parts by weight of N-phenylmaleimide, 20 parts by weight of p-isopropenylphenol, 10 parts by weight of 4-hydroxyphenyl methacrylate, and 2.7 parts by weight of dodecyl mercaptan were added, and the mixture was purged with nitrogen. The mixture was then slowly stirred to raise the temperature of the reaction solution to 70°C, maintained at this temperature for 3 hours, and polymerization was carried out. The temperature of the reaction solution was then raised to 80°C, and polymerization was carried out for 1 hour, thereby obtaining a solution containing 33.3% by weight of an alkali-soluble polymer (designated as polymer (A1-1)). The Mw of the alkali-soluble polymer (A1-1) was 9,700.

[0468] Synthesis Example 5: Synthesis of Polymer (A1-2)

[0469] 220 parts by weight of cresol phenolic varnish-type epoxy resin (manufactured by DIC (stock), trade name: Epiclon N-695, epoxy equivalent: 220) were placed in a four-necked flask equipped with a stirrer and reflux cooler. 214 parts by weight of propylene glycol monomethyl ether acetate were added and heated to dissolve. Next, 0.1 parts by weight of hydroquinone as a polymerization inhibitor and 2.0 parts by weight of dimethyl benzylamine as a reaction catalyst were added. This mixture was heated to 95°C–105°C, and 72 parts by weight of acrylic acid were slowly added dropwise, reacting for 16 hours. This reaction product was cooled to 80°C–90°C, and 106 parts by weight of tetrahydrophthalic anhydride were added, reacting for 8 hours. After cooling, the product was removed to obtain cresol phenolic varnish-type epoxy (meth)acrylate resin (A1-2) (solid content concentration: 50% by weight) with acryloyl and carboxyl groups. The polymer (A1-2) obtained in this way has a weight-average molecular weight (Mw) of about 3,500.

[0470] Synthesis Example 6: Synthesis of Polymer (A1-3)

[0471] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 15 g of silsesquioxane (AC-SQ TA-100 manufactured by Toa Synthetic Co., Ltd., 100 mol%), 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 reaction was carried out at 50 °C for 2 hours. At this time point, the GPC was confirmed, showing a weight-average molecular weight of 4,400 and 3-mercaptopropionic acid content below 0.1%, thus confirming quantitative Michael addition. 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 1M hydrochloric acid solution and three times with 50 mL of water. Next, 40 g of propylene glycol monomethyl ether acetate (PGMEA) was added and concentrated to a volume of 40 g. Then, another 40 g of PGMEA was added and the concentration was increased. The concentration was then adjusted to 50% by mass using PGMEA to obtain a solution of silsesquioxane (A1-3). The obtained silsesquioxane (A1-3) had a weight-average molecular weight of 4,400.

[0472] Synthesis Example 7: Synthesis of Polymer (A1-4)

[0473] In a reaction vessel equipped with a cooling pipe, 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, thereby obtaining the target polyamic acid resin (A1-4) (solids concentration: 15% by mass). The polymer (A1-4) thus obtained has a weight-average molecular weight (Mw) of approximately 13,200.

[0474] Synthesis Example 8: Synthesis of Polymer (A2-1)

[0475] Ten parts by mass of 2,2'-azobis(2,4-dimethylpentanones) and 200 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Then, 10 parts by mass of methacrylic acid, 20 parts by mass of styryltrimethoxysilane, 30 parts by mass of glycidyl methacrylate, 30 parts by mass of methyl methacrylate (3-ethyloxetane-3-yl)methacrylate, and 10 parts by mass of methyl methacrylate were added. After nitrogen purging, the temperature of the solution was raised to 70°C while stirring slowly, and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing polymer (A2-1). The solid content concentration of the 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.

[0476] Synthesis Example 9: Synthesis of Polymer (A2-2)

[0477] Ten parts by mass of 2,2'-azobis(2,4-dimethylpentanones) and 200 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Then, 10 parts by mass of methacrylic acid, 20 parts by mass of 3-methacryloyloxypropyltrimethoxysilane, 30 parts by mass of glycidyl methacrylate, 30 parts by mass of (3-ethyloxecyclobutane-3-yl) methyl methacrylate, and 10 parts by mass of methyl methacrylate were added. After nitrogen purging, the temperature of the solution was raised to 70°C while stirring slowly, and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing polymer (A2-2). The solid content concentration of the 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.

[0478] Synthesis Example 10: Synthesis of Polymer (A2-3)

[0479] In a flask equipped with a cooling tube and a stirrer, 10 parts by mass of 2,2'-azobis(2,4-dimethylpentanonitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were added. Then, 10 parts by mass of methacrylic acid, 15 parts by mass of 2-tetrahydropyranoacrylate, 35 parts by mass of glycidyl methacrylate, 30 parts by mass of (3-ethyloxetane-3-yl)methyl methacrylate, and 10 parts by mass of methyl methacrylate were added. After nitrogen purging, the temperature of the solution was raised to 70°C while slowly stirring, and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing polymer (A2-3). The solid content concentration of the 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.

[0480] <Determination of weight-average molecular weight>

[0481] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the prepared polymer are polystyrene conversion values ​​determined by gel permeation chromatography (GPC) under the following conditions.

[0482] Tube Column: TSKgelGRCXLII manufactured by Tosoh Corporation

[0483] Solvent: Tetrahydrofuran

[0484] Temperature: 40℃

[0485] Pressure: 68 kgf / cm 2

[0486] Preparation Example 1: Preparation of Pigment Dispersion (Bk-MB-1)

[0487] Using a bead mill, 12 parts by weight of a lactam pigment (Irgaphor Black S0100CF, manufactured by BASF) as a colorant and 11.8 parts by weight of BYK as a dispersant were mixed.

[0488] -LPN21116 (manufactured by BYK Chemie Japan, Inc., with a solid content concentration of 40.0% by mass), a polymer (A1-1) as a binder, comprising 13.0 parts by mass of a polymer solution (solid content concentration: 33.3% by mass), and a mixture comprising 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, are mixed and dispersed for 12 hours to prepare a pigment dispersion (Bk-MB-1) as a colorant.

[0489] Preparation Example 2: Preparation of Pigment Dispersion (Bk-MB-2)

[0490] A pigment dispersion (Bk-MB-2) was prepared by mixing and dispersing for 12 hours using a bead mill with 12 parts by weight of carbon black (TPX1227R, manufactured by Cabot Corporation) as a colorant, 11.8 parts by weight of BYK-LPN21116 (manufactured by BYK Chemie Japan Co., Ltd., solid content concentration: 40.0% by weight) as a dispersant (based on the amount of the polymer solution, solid content concentration: 33.3% by weight) as a binder, and a mixture containing 55.0 parts by weight of propylene glycol methyl ether acetate and 8 parts by weight of propylene glycol monomethyl ether as a dispersion medium.

[0491] The following details the components used to prepare the photosensitizing compositions in the examples and comparative examples.

[0492] <Coloring agent>

[0493] Bk-Dye-1, Bk-Dye-2, and Bk-Dye-3 synthesized in Synthesis Examples 1 to 3

[0494] Bk-MB-1 and Bk-MB-2 prepared in Preparation Example 1 and Preparation Example 2

[0495] ODB-2 (manufactured by Yamamoto Kasei Corporation, 3-dibutylamino-6-methyl-7-anilinefluorane)

[0496] <Alkali-soluble polymer (A1)>

[0497] A1-1 to A1-4: Polymers (A1-1) to (A1-4) synthesized in Synthetic Examples 4 to 7.

[0498] A1-5: "WR-301" (a 44% solids concentration PGMEA solution) manufactured by ADEKA (stock), is a resin made by modifying calorie resin into anhydride and a resin containing acrylate and carboxylic acid groups.

[0499] A2-1 to A2-3: Polymers (A2-1) to (A2-3) synthesized in Synthetic Examples 8 to 10.

[0500] <Quinone diazide compound (B1)>

[0501] B1-1: A condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (2.0 mol).

[0502] <Photoacid generator (B2)>

[0503] B2-1: Irgacure PAG121 (manufactured by BASF)

[0504] B2-2: Naphthalimide trifluoromethanesulfonate

[0505] <Seam-Sealing Agent (C)>

[0506] C-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0507] C-2: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

[0508] <Solubility Improver (D)>

[0509] D-1: The compound represented by the following formula

[0510] [Chemistry 29]

[0511]

[0512] D-2: Aronix M-520 (manufactured by Dong-A Synthetic Co., Ltd.)

[0513] <Surfactant (E)>

[0514] E-1: Megafac F-554 (manufactured by DIC, a fluorinated surfactant)

[0515] E-2: DOWSIL SH 8400 Fluid (manufactured by Toray Dow, a silicone surfactant)

[0516] [Example 1]

[0517] A photosensitive composition was prepared by mixing 3.60 parts by weight of BK-Dye-1 (as a colorant), 32.0 parts by weight of an alkali-soluble polymer (A1-1), 2.13 parts by weight of a quinone diazide compound (B1-1), 0.53 parts by weight of a bonding agent (C-1), 1.06 parts by weight of a solubility promoter (D-1), and 0.04 parts by weight of a surfactant (E-1), and further adding solvent to bring the final composition to a solid content of 18.0% by weight. The solvent was added in equal parts by weight of propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone (CPN) (PGMEA: 30.3 parts by weight, CPN: 30.3 parts by weight), and the mixture was stirred.

[0518] [Examples 2 to 24 and Comparative Examples 1 to 6]

[0519] Except for changing the types and amounts of each component as described in Table 1, the photosensitive composition was prepared in the same manner as in Example 1. Furthermore, the values ​​in the component columns of Table 1 represent parts by mass, and "-" indicates that the corresponding component was not used.

[0520]

[0521] [evaluate]

[0522] The photosensitive compositions prepared in Examples 1 to 24 and Comparative Examples 1 to 6 were evaluated using the methods described below. The evaluation results are shown in Table 3.

[0523] <Evaluation of radioactivity>

[0524] The prepared photosensitive compositions were coated onto a sodium glass substrate with an indium tin oxide (ITO) film 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. Subsequently, a photomask capable of forming line patterns 20 μm wide was used, manufactured by Canon, at 300 mJ / cm². 2The exposure levels for the coating included radiation at wavelengths of 365 nm, 405 nm, and 436 nm. The glass substrate with the exposed coating was then placed on the horizontal rotating stage of a rotary / spray developer (AD-2000 type, manufactured by Takizawa Sangyo Co., Ltd.), and developed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C for 60 seconds using a water-pit method. The developed substrate was then rinsed with ultrapure water, air-dried, and subsequently baked in a clean oven at 230°C for 30 minutes, thereby forming a line pattern.

[0525] The obtained substrate with line patterns was observed using an optical microscope to determine the appearance of the formed line patterns and the presence of residue in the resolvable areas. The evaluation criteria are as follows. If the line patterns are free of defects and there is no residue in the resolvable areas, the substrate can be judged to have excellent developability.

[0526] <Evaluation Criteria>

[0527] ○: The line pattern is undamaged, and no residue can be identified in the distinguishing section.

[0528] ×: This indicates that the appearance of the line pattern is damaged or there are residues in the distinguishing parts.

[0529] <Determination of optical density (OD value) and heat resistance>

[0530] Using a spin coater, the prepared photosensitive compositions are coated onto a sodium glass substrate with a SiO2 film formed on its surface to prevent sodium ion leaching. The substrate is then dried under reduced pressure at room temperature to form a coating with a thickness of 3.0 μm.

[0531] Subsequently, using the MPA-600FA photomask manufactured by Canon (stock), at 300mJ / cm 2 The exposure amount for the obtained coating film included radiation at wavelengths of 365nm, 405nm, and 436nm. Then, it was baked in a clean oven at 230°C for 30 minutes to form an evaluation substrate. The optical density (OD value) (initial OD value) of the obtained evaluation substrate was measured using a white-black transmission density meter 361T manufactured by X-rite. A higher OD value indicates higher light-blocking properties. Furthermore, a heat resistance evaluation substrate was prepared by baking the evaluation substrate in a clean oven at 230°C for another 60 minutes. The optical density (OD value) (OD value after heat resistance evaluation) of the obtained evaluation substrate was measured using a white-black transmission density meter 361T manufactured by X-rite. The heat resistance was judged by calculating the retention rate compared to the initial OD value. The judgment criteria are described below. It can be said that a higher retention rate indicates better heat resistance.

[0532] <Evaluation Criteria>

[0533] ○: Retention rate ≥ 90%

[0534] ×: Retention rate < 90%

[0535] <Evaluation of absorbance before and after baking at 230℃>

[0536] Using a spin coater, the photosensitive composition of Example 1 was coated onto a sodium glass substrate with a SiO2 film formed on its surface to prevent sodium ion dissolution. The coating was then dried under reduced pressure at room temperature to form a film with a thickness of 1.0 μm. Subsequently, using an MPA-600FA photomask manufactured by Canon, a photosensitive composition was applied at 35 mJ / cm². 2 The exposure amount for the obtained coating included radiation at wavelengths of 365 nm, 405 nm, and 436 nm. Then, the coating was heated on a hot plate at 100°C for 5 minutes to create an evaluation substrate. The UV-Vis absorption spectrum of the evaluation substrate was measured using a UV-Vis near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-1900i), and the UV-Vis absorption spectrum was further measured after calcining the evaluation substrate at 230°C for 30 minutes. The absorbance values ​​at 365 nm, 405 nm, and 436 nm before and after calcination at 230°C are shown in Table 2. According to the results in Table 2, the absorbance of g-rays, h-rays, and i-rays before calcination at 230°C was significantly reduced compared to after calcination at 230°C, achieving a balance between sufficient light-blocking properties and improved exposure sensitivity.

[0537] [Table 2]

[0538] Absorbance (436nm) Absorbance (405nm) Absorbance (365nm) Before calcination at 230℃ 0.32 0.39 0.40 After calcination at 230℃ 0.84 0.88 0.52

[0539] <Halftone Pattern Formation>

[0540] The photosensitive composition of Example 1 prepared by spin coating was applied onto a sodium 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. Subsequently, using an MPA-600FA manufactured by Canon, a quartz grayscale photomask (with a 10 μm wide line pattern with 100% transmittance on the inner side and a 15 μm wide central exposure area with slits at both ends having a light transmittance of 35%) was applied at 300 mJ / cm². 2The exposure levels for the coating included radiation at wavelengths of 365 nm, 405 nm, and 436 nm. The glass substrate with the exposed coating was then placed on the horizontal rotating stage of a rotary / spray developer (AD-2000 type, manufactured by Takizawa Sangyo Co., Ltd.), and developed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C for 60 seconds using a water-pit method. The developed substrate was then rinsed with ultrapure water, air-dried, and subsequently baked in a clean oven at 230°C for 30 minutes, thereby forming a step pattern with a film thickness of 3.0 μm. The obtained substrate with the line pattern was observed using an optical microscope to check for defects in the formed line pattern and the presence of residue in the resolving areas, confirming that there were no problems. Furthermore, the step width corresponding to the intermediate exposure area was measured using an Alpha-Step D500 profiler (Ulvac Co., Ltd.). As a result, the step width was 1.4 μm, confirming that a step pattern with a step difference of approximately half that of the overall film thickness could be formed.

[0541] [Table 3]

[0542]

[0543] As shown in Table 3, the photosensitive compositions of Examples 1 to 24 are photosensitive compositions with excellent sensitivity and developability, and can form cured products with excellent light-blocking or heat resistance. On the other hand, the comparative examples are inferior to the examples.

Claims

1. A method for producing a patterned hardened substance, comprising: a step of forming a coating film by applying a positive photosensitive composition comprising a compound represented by the following formula (1) on a substrate; a step of exposing the coating film; a step of developing the exposed coating film; and a step of heating the developed pattern, [Chemical Formula 1] (In formula (1), R 1 and R 2 are each independently a hydrogen atom or a leaving group; wherein at least one of R 1 and R 2 is a leaving group; R 3 , R 4 , and R 5 are each 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 each independently an integer of 0 to 4; n3 is an integer of 0 to 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 gray tone 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 photosensitive composition further comprises a black pigment.

5. The production method according to claim 1, wherein the positive photosensitive composition further comprises: a polymer (Al) comprising a structural unit (I) having an acid group; and a quinonediazide compound (Bl).

6. The manufacturing method according to claim 5, wherein, The polymer (Al) further comprises a structural unit having a crosslinkable group, or further comprises a polymer different from the polymer (Al) and comprising 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 oxiranyl group, an oxetanyl group, and an ethylenically unsaturated group.

8. The production method according to claim 1, wherein the positive photosensitive composition further comprises: a polymer selected from at least one of a polymer (Al) comprising a structural unit (III) having a group represented by the following formula (7) or an acid dissociable group, and a siloxane polymer (A2); and a photoacid generator (B2), [Chemical Formula 2] (In formula (7), R A1 , R A2 , and R A3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, an alkyl group having a carbon number of 1 to 10, or a phenyl group; wherein at least one of R A1 , R A2 , and R A3 is an alkoxy group having a carbon number of 1 to 6; "*" represents a bond).

9. The manufacturing method according to claim 8, wherein, The photoacid generator (B2) comprises at least one selected from the group consisting of an oxime sulfonate compound and a sulfonimine compound.

10. The manufacturing method of claim 1, wherein, The patterned hardened substance is a black matrix or a barrier rib.

11. A positive photosensitive composition comprising a compound represented by the following formula (1), [Chemical Formula 3] (In formula (1), R 1 and R 2 are each independently a hydrogen atom or a leaving group; wherein, R 1 and at least one of R 2 is a leaving group; R 3 , R 4 , and R 5 are each 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 each independently an integer of 0 to 4; n3 is an integer of 0 to 2).

12. A patterned hardened substance formed from the positive photosensitive composition according to claim 11.

13. A barrier rib comprising the hardened substance according to claim 12.

14. An image display device comprising the barrier rib according to claim 13.

15. A black matrix comprising the hardened substance according to claim 12.

16. A color filter comprising the black matrix according to claim 15.

17. An image display panel comprising the color filter according to claim 16.

18. An image display device comprising the image display panel according to claim 17.

Images