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

Abstract

The present invention aims to provide a positive-type photosensitive composition that exhibits excellent developability, such as sensitivity, suppression of developing residue, and developing film rate, and to provide a method for producing a patterned cured product using the positive-type photosensitive composition. [Solution] A method for producing a patterned cured product, comprising the steps of: applying a positive-type photosensitive composition onto a substrate to form a coating film; exposing the coating film to light; developing the exposed coating film; and heating the pattern after development, wherein the positive-type photosensitive composition contains a silsesquioxane having a structural unit (I) represented by the following formula (1). JPEG2026093369000060.jpg32170 (In equation (1) above, X is a base represented by a specific equation.)

Description

[Technical Field]

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

[0002] In display devices, patterned light-shielding components such as black matrices and black banks are typically formed. Various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator have been proposed as materials used to form such light-shielding components. As such photosensitive compositions, for example, a photosensitive resin composition containing a black coloring agent (for example, Patent Document 1) is known. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-80993 [Overview of the project] [Problems that the invention aims to solve]

[0004] When exposing a photosensitive composition, a stepped pattern can be formed by using a multi-tone mask such as a gray-tone mask or a half-tone mask. By using such a multi-tone mask, a stepped pattern can be formed, for example, by forming spacers on a black partition all at once. However, when forming all at once using a multi-tone mask, the film thickness increases, and in some cases, the bottom of the film is not sufficiently exposed. In the photosensitive composition containing a coloring agent such as a black pigment described in Patent Document 1, when formed all at once using a multi-tone mask, the bottom of the film was not exposed, and as a result, residue was generated during development.

[0005] Furthermore, if the positive-type photosensitive composition has high solubility in alkaline developer, developing may sometimes reduce the residual film percentage in the unexposed areas.

[0006] The present invention has been made in view of the above problems, and aims to provide a positive-type photosensitive composition that exhibits excellent developability, such as sensitivity, development residue suppression, and development residue rate, and a method for producing a patterned cured product using the positive-type photosensitive composition. [Means for solving the problem]

[0007] The present inventors have found that the above-mentioned problems can be solved according to the following configuration example. That is, the present invention provides a method for manufacturing a patterned cured product, a patterned cured product, a partition wall, a black matrix, a color filter, an image display panel, an image display device, and a positive-type photosensitive composition. An example of the configuration of this disclosure is shown below.

[0008] In one embodiment, the present invention is A process of applying a positive-type photosensitive composition onto a substrate to form a coating film, The process of exposing the coating film, The process of developing the exposed coating film, Includes a step of heating the developed pattern. A method for manufacturing a patterned cured product, The present invention relates to a method for producing the positive-type photosensitive composition, which contains a silsesquioxane having a structural unit (I) represented by the following formula (1). [ka] (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). [ka] (In the above equations (1a) to (1c), R 1 This is either a hydrogen atom or a methyl group. R2 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

[0009] In another embodiment, the present invention is This invention relates to a positive-type photosensitive composition containing a silsesquioxane having a structural unit (I) represented by the following formula (1). [ka] (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). [ka] (In the above equations (1a) to (1c), R 1 This is either a hydrogen atom or a methyl group. R 2 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

[0010] In another embodiment, the present invention relates to a patterned cured product formed from the positive-type photosensitive composition, a partition or black matrix made of the cured product, a color filter having the black matrix, an image display panel having the color filter, an image display device having the image display panel, and an image display device having the partition. [Effects of the Invention]

[0011] According to the present invention, a positive-type photosensitive composition can be provided that has silsesquioxane having structural unit (I), thereby reducing development residue even when batch formation is performed using a multi-gradation mask. Furthermore, since the silsesquioxane having structural unit (I) is unevenly distributed on the upper part of the resist film, the reduction in film thickness during development can be suppressed. In addition, a method for producing patterned cured products using this photosensitive composition can be provided.

[0012] Furthermore, the photosensitive composition used in the manufacturing method of the present invention has excellent sensitivity and developability (development residue suppression, development film rate), making it suitable for exposure using multi-tone masks such as gray tone masks and halftone masks. By using a multi-tone mask, stepped patterns can be formed, and for example, spacers can be formed all at once on a black partition. [Modes for carrying out the invention]

[0013] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0014] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the numbers indicated before and after "~" as the lower and upper limits, respectively.

[0015] In this specification, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Linear hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in its main chain and consists only of a linear structure. However, linear hydrocarbon groups may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain an aromatic ring structure. However, an alicyclic hydrocarbon group does not have to consist only of the structure of an alicyclic hydrocarbon; it may also include a linear structure as part of it. "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure. However, an aromatic hydrocarbon group does not have to consist only of an aromatic ring structure; it may also include a linear structure or an alicyclic hydrocarbon structure as part of it. The ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may have substituents consisting of hydrocarbon structures.

[0016] In this specification, "(meth)acryloyl group" encompasses both "acryloyl group" and "methacryloyl group," and "(meth)acrylic" encompasses both "acrylic" and "methacrylic." "(meth)acrylate" encompasses both "acrylate" and "methacrylate."

[0017] The positive-type photosensitive composition of the present invention will be described below.

[0018] <Positive-type photosensitive composition> The positive-type photosensitive composition according to this embodiment (hereinafter also referred to as "this composition") contains a silsesquioxane (A) having a structural unit (I) represented by the following formula (1). [ka] (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). [ka] (In the above equations (1a) to (1c), R 1 This is either a hydrogen atom or a methyl group. R 2 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

[0019] This composition, by containing the above-mentioned silsesquioxane (A), can significantly suppress the generation of residue during development and also improve the residual film rate after development.

[0020] The following describes each component contained in this composition.

[0021] <Silsesquioxane (A)> The above silsesquioxane (A) contains structural unit (I) represented by formula (1) above. It may also contain structural units other than structural unit (I).

[0022] [Structural Unit (I)] The above silsesquioxane (A) contains the structural unit (I) represented by the following formula (1). [ka] (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). [ka] (In the above equations (1a) to (1c), R 1 This is either a hydrogen atom or a methyl group. R 2 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

[0023] The above formula (1) has an average of 1.5 oxygen atoms and one X group per silicon atom, and the silsesquioxane (A) has a structural unit (XSiO 1.5 ) in which one X group and three oxygen atoms are bonded to one silicon atom, as represented by the following formula (i). [Chemical formula] (In formula (i), * represents a bond with a silicon atom of another structural unit.)

[0024] The above R 1 is a hydrogen atom or a methyl group.

[0025] The above R 2 is an alkanediyl group having 2 to 10 carbon atoms. Examples of the alkanediyl group include an ethanediyl group, a propanediyl group, a butanediyl group, a hexanediyl group, an octanediyl group, a nonanediyl group, and a decanediyl group. Also, some or all of the hydrogen atoms of the alkanediyl group may be substituted with substituents such as halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxy groups; carboxy groups; cyano groups; nitro groups; alkyl groups; alkoxy groups; alkoxycarbonyl groups; alkoxycarbonyloxy groups; acyl groups; acyloxy groups or groups in which the hydrogen atoms of these groups are substituted with halogen atoms. Further, some of the carbon atoms of the alkanediyl group may be substituted with substituents such as oxygen atoms, sulfur atoms, amino groups, amide groups, urethane groups, urea groups, and ester groups.

[0026] Among the above alkanediyl groups having 2 to 10 carbon atoms, an alkanediyl group having 2 to 8 carbon atoms is preferable, an alkanediyl group having 2 to 6 carbon atoms is more preferable, and an alkanediyl group having 2 to 5 carbon atoms is even more preferable.

[0027] p is 1 or 2, and 1 is preferable.

[0028] Cy is an alicyclic hydrocarbon ring having 3 to 20 carbon atoms. R 3 and R4 Examples of rings corresponding to monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms can be given. Among these, cyclopentane, cyclohexane, norbornane, or fused ring structures thereof are preferred.

[0029] The group represented by formula (1c) above is preferably the group represented by the following formulas (1c-1) and (1c-2). [ka] (In formulas (1c-1) and (1c-2), R 2 This is equivalent to equation (1c). q is an integer between 1 and 3. Cy1 is an alicyclic hydrocarbon ring with 3 to 15 carbon atoms.

[0030] q is an integer between 1 and 3, preferably 1 or 2.

[0031] As the alicyclic hydrocarbon ring having 3 to 15 carbon atoms in Cy1, those with 3 to 15 carbon atoms listed above for Cy can be preferably used. Among these, norbornane is preferred.

[0032] While there are no particular limitations on specific examples of structural units (I), one example is the structure represented by the following formula. In the following formula, R 1 This is equivalent to equation (1) above. m is an integer between 2 and 4.

[0033] [ka]

[0034] The silsesquioxane (A) described above may contain silanol groups (-SiOH), but the amount of silanol groups is preferably less than 0.3, more preferably less than 0.25, and even more preferably 0.2 or less, in terms of a molar ratio (moles of silanol groups / total molars of structural units constituting silsesquioxane (A)) relative to the total amount of structural units constituting silsesquioxane (A). A molar ratio of less than 0.3 is preferable because it results in a high degree of condensation and a strong tendency for silsesquioxane (A) to have a cage-like or ladder-like structure. As a result, this composition can produce a cured product (cured film) with excellent developability. The lower limit of the above molar ratio is not particularly limited and may be 0, 0.01, or 0.05.

[0035] [Structural Units (II)] Preferably, the silsesquioxane (A) has, in addition to the structural unit (I) represented by formula (1) above, a structural unit (II) represented by the following formula (2). [ka] (In the above formula (2), Y is a group represented by the following formulas (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), or (2i). [ka] [ka] [ka] (In the above formulas (2a) to (2i), R 1 Each of these is independently either a hydrogen atom or a methyl group. R 2 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. R 21 Each of these is independently either a single bond or a methylene group. R3 These are, independently, divalent organic groups. R 4 Each of these is independently a single-bonded or divalent organic group. X 1 Each of these is independently a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, or an alkoxy group. n is an independent integer between 0 and 4. If n is 2 or greater, multiple X 1 They are either identical or different from one another. Each Cy element is an independent alicyclic hydrocarbon ring with 3 to 20 carbon atoms. * indicates the binding site.

[0036] The above formula (2) has an average of 1.5 oxygen atoms and 1 Y group per silicon atom, and silsesquioxane (A) is a structural unit in which 1 Y group and 3 oxygen atoms are bonded to 1 silicon atom (YSiO2), as shown in the following formula (ii). 1.5 It is preferable that it includes ). [ka] (In formula (ii), * represents a bond with a silicon atom of another structural unit.)

[0037] The above R 1 , R 2 Cy is equivalent to equation (1) above.

[0038] R 21 This is either a single bond or a methylene group.

[0039] R 3 , R 4 Examples of divalent organic groups represented by this formula include groups obtained by removing one hydrogen atom from a monovalent organic group.

[0040] Examples of monovalent organic groups include monovalent hydrocarbon groups having 1 to 20 carbon atoms, groups having a divalent heteroatom-containing group between carbon atoms or at the end of the carbon chain of the hydrocarbon group, groups in which some or all of the hydrogen atoms of the hydrocarbon group are replaced with a monovalent heteroatom-containing group, or combinations thereof.

[0041] Examples of the above-mentioned monovalent hydrocarbon groups having 1 to 20 carbon atoms include chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0042] Examples of monovalent linear hydrocarbon groups having 1 to 20 carbon atoms include monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, or monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, isopentyl, and neopentyl groups. Examples of monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl groups; and alkynyl groups such as ethynyl, propynyl, and butynyl groups.

[0043] Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups, or monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl groups. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norborneyl, tricyclodecenyl, and tetracyclododecenyl groups. A bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other are bonded together by a linking group containing one or more carbon atoms.

[0044] Examples of the above-mentioned monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xyl, naphthyl, and anthyl groups; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl groups.

[0045] Examples of the monovalent heteroatom-containing groups mentioned above include hydroxyl groups, carboxyl groups, sulfanyl groups, cyano groups, nitro groups, halogen atoms, and the like.

[0046] Examples of the above-mentioned divalent heteroatom-containing groups include -CO-, -C(=O)O-, -CS-, -NR'-, -O-, -S-, -SO-, -SO2-, or combinations thereof. R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0047] The above X 1 Examples of halogen atoms represented by this formula include fluorine, chlorine, bromine, and iodine atoms.

[0048] The above X 1Examples of alkyl groups represented by the above include the chain-like hydrocarbon groups having 1 to 20 carbon atoms.

[0049] The above X 1 Examples of the alkyl group portion of the alkoxy group represented by the above alkyl group include the alkyl group mentioned above.

[0050] The above value of n is an integer between 0 and 4, and is preferably 0 or 1.

[0051] Furthermore, the above formulas (2g) to (2i) are preferably groups represented by the following formulas (2g-1) to (2i-1) and (2g-2) to (2i-2). [ka] [ka] (Formula (2g-1) to formula (2i-1), formula (2g-2) to formula (2i-2), R 2 ~R 4 , X 1 n is equivalent to equations (2g) to (2i). q is an integer between 1 and 3. Cy1 is an alicyclic hydrocarbon ring with 3 to 15 carbon atoms.

[0052] q is an integer between 1 and 3, preferably 1 or 2.

[0053] As the alicyclic hydrocarbon ring having 3 to 15 carbon atoms in Cy1, those with 3 to 15 carbon atoms listed above for Cy can be preferably used. Among these, norbornane is preferred.

[0054] While there are no particular limitations on specific examples of structural unit (II), one example is the structure represented by the following formula. In the following formula, R 1 This is equivalent to equation (2) above, where m is an integer between 2 and 4.

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] The lower limit of the content of structural unit (I) relative to the total content of structural unit (I) and structural unit (II) in the above-mentioned silsesquioxane (A) is preferably 10 mol%, more preferably 30 mol%, even more preferably 50 mol%, and particularly preferably 60 mol%. The upper limit of the content is preferably 100 mol%, more preferably 95 mol%, and even more preferably 90 mol%. It is preferable to set the content of structural unit (I) within the above range because it can improve lithography performance.

[0060] The above silsesquioxane (A) may have structural units other than structural unit (I) and structural unit (II). Other structural units include structural units having a silanol group (-SiOH) or -(R a SiO 1.5 )-(R a Examples include structural units represented by a monovalent hydrocarbon group (excluding those corresponding to structural unit (I) or structural unit (II)).

[0061] The lower limit of the total content of structural unit (I) and structural unit (II) relative to the total structural units of the above silsesquioxane (A) is preferably 60 mol%, more preferably 70 mol%, and even more preferably 80 mol%. The upper limit of the above total content is not particularly limited and may be 100 mol%.

[0062] The lower limit of the weight-average molecular weight (Mw) of the above silsesquioxane (A) is preferably 1,000, more preferably 2,000, and even more preferably 3,000. The upper limit of the weight-average molecular weight is preferably 20,000, more preferably 10,000, and even more preferably 6,000.

[0063] The lower limit of the silsesquioxane (A) content in this composition is preferably 1% by mass, more preferably 3% by mass, and still more preferably 5% by mass, relative to the total solids content (100% by mass) of the composition. On the other hand, the upper limit of this content is preferably 90% by mass, more preferably 80% by mass, still more preferably 70% by mass, and particularly preferably 60% by mass. Total solids refer to all components other than the solvent (S). Setting the silsesquioxane (A) content within the above range is preferable from the viewpoint of residue suppression and residual film rate.

[0064] The method for producing the above-mentioned silsesquioxane (A) is not particularly limited, but for example, the following synthesis method It can be synthesized by [method].

[0065] (synthesis method) The synthesis scheme (M-1) is shown below.

[0066] [ka]

[0067] In the above scheme (M-1), R 11 is an alkyl group having 1 to 6 carbon atoms. k, m, and n are natural numbers satisfying k = m + n. X and Y are the same as X and Y in equations (1) and (2).

[0068] Starting with the trialkoxysilane represented by formula (1A) above, hydrolysis and condensation in the presence of a base yields silsesquioxane represented by formula (1B). Subsequently, silsesquioxane (A) can be obtained by adding an SH compound to this silsesquioxane.

[0069] Examples of trialkoxysilanes represented by the above formula (1A) include acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, acryloxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, acryloxyoctyltriethoxysilane, methacryloxyoctyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-oxetanylpropyltrimethoxysilane, 3-oxetanylpropyltriethoxysilane, 2-(2,3-epoxycyclopentyl)ethyltrimethoxysilane, 2-(2,3-epoxycyclopentyl)ethyltriethoxysilane, [ka] These are some examples. Among these, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are more preferred.

[0070] In addition to the trialkoxysilane represented by formula (1A) above, other trialkoxysilanes can also be used. Examples of other trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, 4-vinylphenyltrimethoxysilane, and 4-vinylphenyltriethoxysilane.

[0071] Examples of bases used in hydrolysis condensation reactions include trimethylamine, triethylamine, tripropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, sodium hydroxide, and potassium hydroxide. Among these, triethylamine is preferred.

[0072] Examples of SH compounds in the above scheme (M-1) include monovalent thiol compounds having a carboxyl group, a carboxylic acid anhydride group, a phenolic hydroxyl group, or a combination thereof. Methods for the addition reaction of the SH compound include the Michael addition reaction and the enthiol reaction, but the Michael addition reaction is preferred. Specifically, examples of SH compounds include those represented by the following formulas (SH-1) to (SH-20), with compounds represented by the following formulas (SH-1) to (SH-4) being preferred, and the compound represented by the following formula (SH-1) being even more preferred.

[0073] [ka]

[0074] Examples of bases used in the Michael addition reaction include trimethylamine, triethylamine, tripropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, sodium hydroxide, and potassium hydroxide. Among these, triethylamine is preferred.

[0075] An example of a synthesis method is shown in the following scheme (M-1-1).

[0076] [ka]

[0077] <Alkali-soluble polymer (B)> In addition to the silsesquioxane (A) described above, this composition may contain an alkali-soluble polymer (B). The alkali-soluble polymer (B) is not particularly limited as long as it is an alkali-soluble polymer, but polymers having acidic groups such as a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an aromatic thiol group, a silanol group, and a fluorinated hydroxyalkyl group (a hydroxyalkyl group in which some of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms) are preferred.

[0078] In this specification, "alkali soluble" means dissolving in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. A polymer is considered alkali soluble if 1 g or more of the polymer dissolves in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. Whether or not a polymer dissolves can be determined by the presence or absence of precipitate.

[0079] Examples of the polymer (B) mentioned above include polymers (B1) containing a structural unit (III) having an acid group, polymers (B2) containing a structural unit (VI) having a group represented by formula (7) described later or an acid-dissociable group, siloxane polymers (B3), polyamic acid or polyamic acid esters (B4), novolac resins (B5), cardo resins (B6), and the like.

[0080] (Polymer (B1)) A polymer (B1) containing a structural unit (III) having an acid group (hereinafter also referred to as "polymer (B1)") is an aggregate of polymerization chains containing a structural unit (III) having an acid group (hereinafter this aggregate is also referred to as the "base polymer"). Structural unit (III) only needs to be included in at least one polymerization chain constituting the base polymer. Polymer (B1) may also contain structural units other than structural unit (III). The following describes each structural unit included in polymer (B1).

[0081] [Structural Unit (III)] Polymer (B1) can have its solubility (alkali solubility) in alkaline developers increased or its curing reactivity enhanced by the presence of acidic structural units (III).

[0082] Structural unit (III) is not particularly limited as long as it has an acid group, but it is preferably at least one selected from the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. In this specification, "phenolic hydroxyl group" means a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, naphthalene ring, anthracene ring, etc.).

[0083] Structural unit (III) is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having an acid group include: Examples of monomers constituting structural units having a carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, crotonic acid, and 4-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Examples of monomers constituting structural units having a sulfonic acid group include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc. Examples of monomers constituting structural units having phenolic hydroxyl groups include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc. Each of these can be listed.

[0084] Furthermore, maleimide can be used as the monomer constituting structural unit (III).

[0085] Among these, (meth)acrylic acid is preferred.

[0086] The base polymer may contain one or more structural units (III) in combination.

[0087] The lower limit of the content of structural unit (III) (total content if multiple types are included) is preferably 1% by mass, more preferably 2% by mass, and still more preferably 5% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass. Setting the content of structural unit (III) within the above range is preferable because it allows for good solubility in alkaline developing solutions.

[0088] [Structural Unit (IV)] Polymer (B1) is preferable because it contains structural units (IV) having crosslinkable groups, which can further improve the resolution and adhesion of the film. The crosslinkable group can be any group that undergoes a curing reaction by heat treatment and is not particularly limited, but in terms of high thermosetting properties, the crosslinkable group is preferably at least one selected from the group consisting of oxyranyl groups, oxetanyl groups, and ethylenically unsaturated groups, with oxyranyl groups or oxetanyl groups being more preferable.

[0089] (Structural unit having an oxetanyl group and an oxyranyl group (IV-1)) It is preferable that polymer (B1) contains structural units (IV-1) having one or more groups selected from the group consisting of oxetanyl groups and oxyranyl groups, as this can further improve the resolution and adhesion of the film. Furthermore, the oxetanyl and oxyranyl groups act as crosslinking groups, enabling the formation of a cured product with high heat resistance and suppressed degradation over a long period of time. Structural units (IV-1) are preferably derived from unsaturated monomers having oxetanyl and oxyranyl groups, and specifically, are preferably structural units represented by the following formula (4-1). [ka] (In formula (4-1), R B1 This is a monovalent group having an oxyranyl group or an oxetanyl group. R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X A1 (This is a single bond or a divalent linking group.)

[0090] In the above equation (4-1), R B1 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups, 3-methyloxetanyl groups, and 3-ethyloxetanyl groups.

[0091] X A1 As the divalent linking group, methylene groups, ethylene groups, and alkanediyl groups such as 1,3-propanediyl groups are preferred.

[0092] Specific examples of monomers that give structural unit (IV) represented by the above formula (4-1) include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6Examples include decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate. Among these, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred.

[0093] (Structural unit having an ethylenically unsaturated group (IV-2)) Structural unit (IV-2) preferably has an ethylenically unsaturated group in its side chain, and more preferably has a side chain structure with 3 to 20 carbon atoms having an ethylenically unsaturated group at its terminal. A specific example of structural unit (IV-2) is the structural unit represented by the following formula (4-2). [ka] (In formula (4-2), R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X A3 This is a divalent linking group having 1 to 12 carbon atoms. R B2 (This is either a hydrogen atom or a methyl group.)

[0094] In the above equation (4-2), X A3 Examples of divalent linking groups represented by include divalent hydrocarbon groups having 1 to 12 carbon atoms, divalent groups in which any methylene group in a divalent hydrocarbon group is replaced with -O-, -COO-, -OCO-, -NHCO-, -CONH-, -OCONH-, or -NHCOO-, and divalent groups in which any hydrogen atom in a divalent hydrocarbon group or a divalent heteroatom-containing group is replaced with a hydroxyl group, a carboxyl group, etc.

[0095] The base polymer may contain one or more structural units (IV).

[0096] When polymer (B1) contains structural unit (IV), the lower limit of the content of structural unit (IV) (total content if multiple types are included) is preferably 5% by mass, more preferably 15% by mass, and even more preferably 25% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. Setting the content of structural unit (IV) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured product to have sufficiently high heat resistance.

[0097] [Structural Unit (V)] The polymer (B1) described above may further contain structural units (V) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic rings, aromatic vinyl compounds, N-substituted maleimide compounds, heterocyclic vinyl compounds, conjugated dienes, nitrogen-containing vinyl compounds, and unsaturated dialkyl dicarboxylate compounds. Introducing these structural units (V) into the polymer is preferable because it allows for adjusting the glass transition temperature of the polymer (B1) components and improving the pattern shape of the resulting cured film.

[0098] Examples of the alkyl (meth)acrylate esters mentioned above include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0099] Examples of (meth)acrylic acid esters having the above alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo(meth)acrylate [5.2.1.0 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.02,5 Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate.

[0100] Examples of (meth)acrylic acid esters having the above aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0101] Examples of the above aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, and the like.

[0102] Examples of the above N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide.

[0103] Examples of vinyl compounds having the above heterocyclic structure include tetrahydrofurfurylmethyl (meth)acrylate, tetrahydropyranylmethyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) (meth)acrylate, glycerin carbonate (meth)acrylate, (γ-lactam-2-yl) (meth)acrylate, and N-(meth)acryloxyethylhexahydrophthalimide.

[0104] Examples of the above-mentioned conjugated diene compounds include 1,3-butadiene and isoprene; examples of the above-mentioned nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of the above-mentioned unsaturated dicarboxylate dialkyl ester compounds include diethyl itaconate. In addition to the above, other monomers constituting the structural units include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0105] The monomer that gives the above structural unit (V) preferably includes at least one selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, vinyl compounds having a heterocyclic structure, and N-substituted maleimide compounds, and preferably includes at least one selected from the group consisting of methyl (meth)acrylate, styrene, tetrahydropyranylmethyl (meth)acrylate, and N-cyclohexylmaleimide.

[0106] The base polymer may contain one or more structural units (V).

[0107] When polymer (B1) contains structural units (V), the lower limit of the content of structural units (V) (or the total content if multiple types are included) is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 70% by mass, and more preferably 60% by mass. Setting the content of structural units (V) within the above range is preferable because it allows the glass transition temperature of polymer (B1) to be raised to an appropriate level.

[0108] [Method for synthesizing polymer (B1)] Polymer (B1) can be produced, for example, by using unsaturated monomers into which each of the above-mentioned structural units can be introduced, in a suitable solvent, in the presence of a polymerization initiator, according to known methods such as radical polymerization.

[0109] Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl.

[0110] The lower limit of the amount of polymerization initiator used is preferably 0.01 parts by mass, more preferably 1 part by mass, even more preferably 3 parts by mass, and particularly preferably 5 parts by mass, based on 100 parts by mass of the total amount of monomer used in the reaction. The upper limit of the amount of polymerization initiator used is preferably 30 parts by mass, more preferably 25 parts by mass, even more preferably 20 parts by mass, and particularly preferably 15 parts by mass. Using the above range for the amount of polymerization initiator is preferable because it allows for the appropriate polymerization of polymers whose terminal structures have specific structures.

[0111] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass of the total volume of the reaction solution.

[0112] The upper limit of the polymerization reaction temperature is preferably 90°C, more preferably 80°C, and even more preferably 75°C. The lower limit of the reaction temperature is not particularly limited and can be any temperature at which polymerization occurs, but for example, 40°C is preferred, 50°C is more preferred, 60°C is even more preferred, and 65°C is particularly preferred. Setting the polymerization reaction temperature within the above range is preferable because it can suppress the crosslinking reaction between the acid group contained in structural unit (III) and the group contained in structural unit (IV) during polymerization.

[0113] The polymerization reaction time varies depending on the type of polymerization initiator and monomer, as well as the reaction temperature, but is usually around 0.5 to 10 hours.

[0114] In the polymerization reaction for producing the above polymer (B1), molecular weight modifiers can be used to adjust the molecular weight. Examples of molecular weight modifiers include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; and terpinolene and α-methylstyrene dimer.

[0115] The polymer (B1) obtained by the polymerization reaction may be used in the preparation of the photosensitive composition while still dissolved in the reaction solution, or it may be isolated from the reaction solution before being used in the preparation of the photosensitive composition. The polymer can be isolated by known isolation methods, such as pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator.

[0116] The polymer (B1) described above has a polystyrene-based weight-average molecular weight (Mw) of preferably 2,000, more preferably 3,000, and even more preferably 4,000, determined by gel permeation chromatography (GPC) using THF as a solvent. The upper limit of Mw is preferably 30,000, and more preferably 20,000. It is preferable that Mw be within the above range because it allows for the formation of a cured film with good film-forming properties and good developability.

[0117] Furthermore, in the polymer (B1) described above, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and even more preferably 1.0 to 2.5. When the base polymer consists of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above range.

[0118] The lower limit of the content of the polymer (B1) in the photosensitive composition is preferably 60% by mass, and more preferably 65% ​​by mass, relative to the amount of other substances in the photosensitive composition. The upper limit of the above content is preferably 99% by mass, and more preferably 95% by mass.

[0119] (Polymer (B2)) Polymer (B2) (hereinafter also referred to as "polymer (B2)") is an aggregate of polymerization chains containing a structural unit (VI) having a group represented by the following formula (7) or an acid-dissociable group (hereinafter this aggregate is also referred to as the "base polymer"). Polymer (B2) can be suitably used in chemically amplified compositions. Structural unit (VI) only needs to be included in at least one polymerization chain constituting the base polymer. Polymer (B2) may also contain structural units other than structural unit (VI). The following describes each structural unit included in polymer (B2).

[0120] [Structural Unit (VI)] From the viewpoint of forming a coating film with excellent developability, it is preferable that the photosensitive composition of the present invention contains a structural unit (VI) having one or more groups selected from the group consisting of a group represented by the following formula (7) and an acid-dissociable group. [ka] (In formula (7), R A1 , R A2 and R A3 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. However, R A1 , R A2 and R A3 At least one of them is an alkoxy group having 1 to 6 carbon atoms. The asterisk (*) indicates a bonding operation.

[0121] R A1 ~R A3 Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, and tert-butoxy groups. Of these, R A1 ~R A3 The alkoxy group is preferably a methoxy group or an ethoxy group.

[0122] R A1 ~R A3 The C1-C10 alkyl group may be linear or branched. Examples of C1-C10 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and tert-butyl groups. Of these, methyl, ethyl, or propyl groups are preferred.

[0123] From the viewpoint of obtaining a cured product with excellent heat resistance by forming a cross-linked structure, and from the viewpoint of improving the storage stability of the photosensitive composition, R A1 ~R A3 Preferably, at least one of them is an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all are alkoxy groups.

[0124] Among the above, R A1The group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy group or an ethoxy group. A2 and R A3 The group is preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0125] In structural unit (VI), the group represented by formula (7) is preferably bonded to an aromatic ring group or a linear hydrocarbon group. In this specification, "aromatic ring group" means a group obtained by removing n (where n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of such aromatic rings include benzene rings, naphthalene rings, and anthracene rings. The ring may have substituents such as alkyl groups. Examples of linear hydrocarbon groups to which the group represented by formula (7) is bonded include alkanediyl groups and alkenediyl groups.

[0126] The group represented by formula (7) above is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. That is, structural unit (VI) preferably has at least one selected from the group consisting of the group represented by formula (7-1), the group represented by formula (7-2), and the group represented by formula (7-3). [ka] (In equations (7-1), (7-2), and (7-3), A 1 and A 2 Each of these is independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. m1 is an integer between 0 and 4. m2 is an integer between 0 and 6. However, if m1 is 2 or greater, multiple A 1 These are either the same group or different groups. If m2 is 2 or more, there are multiple A 2 These are either identical or different groups. R31 is an alkanediyl group. R A1 , R A2 and R A3 are synonymous with the above formula (7). “*” represents a bond. )

[0127] A 1 and A 2 As the alkoxy group having 1 to 6 carbon atoms of A A1 ~R A3 of the alkoxy group having 1 to 6 carbon atoms, those exemplified above can be preferably employed. Also, as the alkyl group having 1 to 6 carbon atoms of A 1 and A 2 among the alkyl groups having 1 to 10 carbon atoms of the above formula (7) for R A1 ~R A3 groups corresponding to 1 to 6 carbon atoms can be preferably employed.

[0128] The position of the group “-SiR A1 R A2 R A3 ” bonded to the aromatic ring may be at any position with respect to other groups excluding A 1 and A 2 . For example, in the case of the above formula (7-1), the position of the group “-SiR A1 R A2 R A3 ” may be any of the ortho position, meta position, and para position, and preferably the para position.

[0129] m1 is preferably 0 or 1, and more preferably 0. m2 is preferably 0 to 2, and more preferably 0.

[0130] In the above formula (7-3), R 31 is preferably linear. From the viewpoint of increasing the heat resistance of the resulting cured film, R 31 preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0131] The structural unit (VI) preferably has at least one selected from the group consisting of the group represented by the above formula (7-1) and the group represented by the above formula (7-2) among the above formulas (7-1) to (7-3). Further, when the group "-SiR A1 R A2 R A3 " is directly bonded to the aromatic ring, it becomes possible to stabilize the silanol group generated with the presence of water. Thereby, it is preferable in that the solubility of the exposed portion in an alkaline developer can be increased and a good pattern can be formed. Among these, the structural unit (VI) is particularly preferably a structural unit having the group represented by the above formula (7-1).

[0132] The structural unit (VI) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "unsaturated monomer"), and specifically, at least one selected from the group consisting of the structural unit represented by the following formula (7a-1) and the structural unit represented by the following formula (7a-2) is preferable.

Chemical formula

[0133] In the above formulas (7a-1) and (7a-2), the divalent aromatic ring group of R 32 、R 33 is preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalenediyl group. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

[0134] In terms of obtaining a cured product with higher heat resistance and hardness, and increasing the solubility of the exposed area in alkaline developing solution, R 32 , R 33 Among the above, it is preferable that it be a divalent aromatic ring group, and particularly preferable that it be a substituted or unsubstituted phenylene group.

[0135] Specific examples of structural units represented by the above formula (7a-1) include the structural units represented by the following formulas (7a-1-1) and (7a-1-2). Furthermore, specific examples of structural units represented by the above formula (7a-2) include the structural units represented by the following formulas (7a-2-1) and (7a-2-2). [ka] (In equations (7a-1-1), (7a-1-2), (7a-2-1), and (7a-2-2), R 34 and R 35 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 36 These are alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, or hydroxyl groups. m3 is an integer between 1 and 4. A 1 , A 2 m1 and m2 are equivalent to those in equations (7-1) and (7-2) above. R α1 This is equivalent to equations (7a-1) and (7a-2) above.

[0136] Specific examples of monomers constituting structural unit (VI) include, for example, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethyldimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinyl naphthyl Examples include (1) silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, etc. Among these, styryltrimethoxysilane and 3-(meth)acryloxypropyltrimethoxysilane are preferred.

[0137] The above-mentioned "acid-dissociable group" refers to a group in which a hydrogen atom in an acidic functional group, such as a phenolic hydroxyl group, carboxyl group, or sulfonic acid group, has been substituted, and which dissociates upon the action of an acid. For example, the acid generated from a photoacid generator upon exposure dissociates the acid-dissociable group, generating a carboxyl group, etc. This creates a difference in solubility in the developer between the exposed and unexposed areas of the coating film, enabling pattern formation.

[0138] The above acid-dissociable group is preferably a group represented by the following formula (8-1) or a group represented by the following formula (8-2). [ka] (In formula (8-1), R A4 and R A5Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least some of the hydrogen atoms of the hydrocarbon group are substituted with a hydroxyl group, a halogen atom, or a cyano group. However, R A4 and R A5 It is impossible for both to be hydrogen atoms. R A6 This refers to a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom or a sulfur atom between carbon atoms or at the end of the bond of this hydrocarbon group, or a group in which at least some of the hydrogen atoms of these groups are substituted with a hydroxyl group, a halogen atom, or a cyano group. R A7 It is a carbon atom or a silicon atom. In formula (8-2), R A8 ~R A14 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. m is either 1 or 2. If m is 2, then multiple R A11 and R A12 These may be the same or different. In equations (8-1) and (8-2), "*" indicates the site of connection.

[0139] R A4 ~R A6 As a hydrocarbon group having 1 to 30 carbon atoms, R in formula (1) above is 3 and R 4 In this material, a monovalent hydrocarbon group with 1 to 20 carbon atoms can be suitably adopted, with the number of carbon atoms extended up to 30.

[0140] R in the above formula (8-1) A4 ~R A6 Independently, alkyl groups having 1 to 30 carbon atoms are preferred, alkyl groups having 1 to 20 carbon atoms are more preferred, alkyl groups having 1 to 10 carbon atoms are even more preferred, and alkyl groups having 1 to 5 carbon atoms are particularly preferred.

[0141] R A8 ~R A14 As for the hydrocarbon group having 1 to 12 carbon atoms, the above R A4 ~RA6 Of the hydrocarbon groups having 1 to 30 carbon atoms, groups corresponding to those with 1 to 12 carbon atoms can be suitably adopted.

[0142] m is either 1 or 2. If m is 2, then multiple R A11 and R A12 These may be the same or different.

[0143] As structural units having the above-mentioned acid-dissociable group, for example, structural units represented by the following formulas (8-1-1) and (8-1-2) are preferred. [ka]

[0144] In the above equations (8-1-1) and (8-1-2), R α1 This is R in equations (7a-1) and (7a-2) above. α1 This is synonymous with R. A4 ~R A14 ,m is R in the above equations (8-1) and (8-2). A4 ~R A14 It is synonymous with m.

[0145] In the above equations (8-1-1) and (8-1-2), L 1 , L 2 These are, independently, single-bonded and divalent linking groups.

[0146] The above L 1 , L 2 Examples of divalent linking groups in this compound include alkanediyl groups, cycloalkanediyl groups, alkenediyl groups, and arenediyl groups.

[0147] The above alkanediyl group is X in formula (4-1). A1 The same divalent linking group as in the above can be listed.

[0148] Examples of the cycloalkanediyl group include monocyclic cycloalkanediyl groups such as a cyclopentanediyl group and a cyclohexanediyl group; polycyclic cycloalkanediyl groups such as a norbornanediyl group and an adamantanediyl group.

[0149] Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, and a butenediyl group.

[0150] Examples of the arenediyl group include a phenylene group, a tolylene group, and a naphthylene group. The arenediyl group is preferably an arenediyl group having 6 to 15 carbon atoms.

[0151] The above m1 is 0 or 1.

[0152] Examples of the monomer that gives the structural unit having the acid dissociable group include, but are not limited to, those shown below. [Chemical formula] (In the above formula, R α1 is synonymous with R in the above formulas (8-1-1) and (8-1-2).) α1

[0153] The base polymer may contain one or a combination of two or more of the structural units (VI).

[0154] When the polymer (B2) contains the structural unit (VI), the lower limit of the content ratio of the structural unit (VI) (when a plurality of types are included, the total content ratio) is preferably 5% by mass, more preferably 10% by mass, and still more preferably 15% by mass with respect to all the structural units constituting the base polymer. The upper limit of the above content ratio is preferably 50% by mass, more preferably 40% by mass, and still more preferably 30% by mass. Setting the content ratio of the structural unit (VI) within the above range is preferable in that the coating film exhibits better resolution.

[0155] ​The polymer (B2) described above may contain structural units (III) to (V) of polymer (B1), and the content ratio can preferably be within the same range as that of polymer (B1). Furthermore, the synthesis method, Mw, Mw / Mn, content, etc., of polymer (B2) can preferably be within the same range as those of polymer (B1).

[0156] (Siloxane polymer (B3)) Examples of siloxane polymers include hydrolysis condensates of hydrolyzable silane compounds. Here, "hydrolyzable silane compound" refers to a compound containing a group that can be hydrolyzed to produce a silanol group or a group that can form a siloxane condensate, and "hydrolysis condensate" refers to a condensate formed when the silanol groups of a hydrolyzed silane compound are condensed together. Examples of such siloxane polymers include those described in Japanese Patent Publication No. 2017-048355.

[0157] (Polyamic acid or polyamic acid ester (B4)) The above polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[0158] Examples of the above-mentioned tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include: Examples of aliphatic tetracarboxylic dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc. Examples of aromatic tetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, propane-1,3-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), and the tetracarboxylic dianhydride described in Japanese Patent Application Publication No. 2010-97188 can also be used. The above tetracarboxylic dianhydrides can be used individually or in combination of two or more.

[0159] Among these, the tetracarboxylic dianhydride preferably includes an aromatic tetracarboxylic dianhydride, and more preferably includes 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0160] The above-mentioned diamines are not particularly limited and include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.

[0161] Examples of the above-mentioned aliphatic diamines include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine.

[0162] Examples of the above-mentioned alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine).

[0163] 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]hexanediacid, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl Nyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4,4'-diaminosylbenzene, 1,4-bis(4-aminophenyl)-piperazine, formula (S-1): [ka] (In formula (S-1), X is -O-, -S-, -CO-, -SO2-, -CH2-, -C(CH3)2-, -C(CH3)(C2H5)-, or -C(CF3)2-. Main-chain diamines such as compounds represented by: Dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl 3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid 5ξ-cholestan-3-yl, the following formula (S-2): [Chemical formula] (In formula (S-2), X I and X II are each independently a single bond, -O-, *-COO- or *-OCO -(However, "*" represents the bond to the phenyl group adjacent to X I or the bond to R I .). R<000,0154>is an alkanediyl group having 1 to 3 carbon atoms. R II is a single bond or an alkanediyl group having 1 to 3 carbon atoms. R III is an alkyl group, an alkoxy group, a fluoroalkyl group, or a fluoroalkoxy group having 1 to 20 carbon atoms. a is 0 or 1. b is an integer from 0 to 3. c is an integer from 0 to 2. d is 0 or 1. However, 1 ≦ a + b + c ≦ 3.) Side-chain diamines, etc., of compounds represented by; Examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. In addition, other examples of diaminoorganosiloxanes that can be used include X-22-161-A, PAM-E, KF-8010, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and X-22-9409 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, diamines described in Japanese Patent Publication No. 2010-97188 can be used.

[0164] Among these, the above-mentioned diamine preferably contains a diaminoorganosiloxane, and more preferably contains X-22-161-A (both manufactured by Shin-Etsu Chemical Co., Ltd.).

[0165] The above-mentioned diamines can be used individually or in combination of two or more types.

[0166] Polyamic acids can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine, along with a molecular weight modifier as needed. The preferred ratio of tetracarboxylic dianhydride to diamine used in the synthesis reaction of polyamic acids is such that the acid anhydride groups of the tetracarboxylic dianhydride are 0.2 to 2 equivalents per 1 equivalent of the amino groups of the diamine. Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The preferred ratio of molecular weight modifier is 20 parts by mass or less per 100 parts by mass of the total amount of tetracarboxylic dianhydride and diamine used.

[0167] The synthesis reaction of polyamic acids is preferably carried out in an organic solvent. The reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 to 24 hours. Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenol, or a mixture of one or more of these and other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of organic solvent used (a) is preferably such that the total amount of tetracarboxylic dianhydride and diamine (b) is 0.1 to 50% by mass of the total amount of the reaction solution (a + b).

[0168] As described above, a reaction solution is obtained by dissolving polyamic acid. This reaction solution may be used as is to prepare the photosensitive composition, or the polyamic acid contained in the reaction solution may be isolated before being used to prepare the photosensitive composition.

[0169] The above polyamic acid esters can be obtained, for example, by [I] reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] reacting a tetracarboxylic acid diester with a diamine, [III] reacting a tetracarboxylic acid dihalide with a diamine, etc. The polyamic acid ester to be contained in the photosensitive composition of the present invention may have only an amic acid ester structure, or it may be a partially esterified product in which both an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as is to prepare the photosensitive composition, or the polyamic acid ester contained in the reaction solution may be isolated before being used to prepare the photosensitive composition.

[0170] (Novolac resin (B5)) The novolac resin (B5) can be obtained by polycondensing phenols with aldehydes such as formaldehyde using a known method.

[0171] Examples of the above-mentioned phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis-p-cresol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, and the like. These may be used individually, or two or more may be used in combination.

[0172] In addition to formaldehyde, other examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde. These may be used individually or in combination of two or more.

[0173] The novolac resin preferably has a (meth)acryloyl group, a group containing an unsaturated double bond such as vinyl, and a side chain represented by the following formula (5). In this case, it is even more preferable that it has an aromatic ring in the main chain. Among these, a resin having a side chain represented by the following formula (5) and a phenolic novolac main chain is more preferable.

[0174] [ka] (In formula (5), X 12 This is either a hydroxyl group or a carboxyl group. X 11 These are halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups, or alkoxy groups. n is an integer from 0 to 4. If n is 2 or greater, multiple X 1 They are either identical or different from one another. R 41 This is a single bond or a divalent organic group. R 63 It is a divalent organic group. * indicates a bond to the main chain.

[0175] The above X 11 The alkyl and alkoxy groups represented by the above formulas (2d) to (2f) are X 1 Alkyl and alkoxy groups can be suitably used in this.

[0176] The above R 41 , R 63 The divalent organic group in is R in the above formulas (2d) to (2f). 4 A divalent organic group can be suitably used in this.

[0177] The above R 41 A single bond is preferred.

[0178] The above R 63 Preferably, the group is one in which an oxygen atom (-O-) is bonded to the main chain end of a divalent hydrocarbon group, such as -CH2-O-*.

[0179] (Cardo resin (B6)) The alkali-soluble cardo resin (B6) described above is not particularly limited as long as it can be dissolved in an alkaline developer, but a resin containing one or more anionic groups such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group is preferred. A cardo resin is a resin having a cardo skeleton, which is a skeleton in which two aromatic groups are connected by single bonds to a quaternary carbon atom, which is a ring carbon atom constituting a cyclic structure. Cardo resins that are radically polymerizable are preferred, and can be obtained, for example, by reacting a cardo-type structure-containing epoxy resin, (meth)acrylic acid, and a tetracarboxylic dianhydride. Dicarboxylic anhydrides may also be reacted as needed. Examples of commercially available radical polymerizable cardo resins include "WR-301" from ADEKA Corporation, "V-259ME" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "Ogzol CR-TR1," "Ogzol CR-TR2," "Ogzol CR-TR3," "Ogzol CR-TR4," "Ogzol CR-TR5," and "Ogzol CR-TR6" from Osaka Gas Chemical Co., Ltd. These may be used individually or in combination of two or more types. From the viewpoint of alkali-soluble cardo resin, the acid value is preferably 10 mg KOH / g or more and 300 mg KOH / g or less, and more preferably 20 mg KOH / g or more and 200 mg KOH / g or less.

[0180] (Other alkali-soluble polymers) In addition to the above, alkali-soluble polyimides or polybenzoxazoles can be used as alkali-soluble polymers. Specific examples of these include copolymers disclosed in, for example, International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, International Publication No. 2017 / 057281, International Publication No. 2017 / 159476, International Publication No. 2017 / 073481, International Publication No. 2017 / 038828, International Publication No. 2016 / 148176, Japanese Patent Publication No. 2015-114355, Japanese Patent Publication No. 2013-164432, Japanese Patent Publication No. 2010-72143, and others.

[0181] The lower limit of the content of polymer (B) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass, based on the total amount of solids contained in the composition (i.e., the total mass of components other than the solvent in the photosensitive composition). The upper limit of the content of polymer (B) is preferably 99% by mass, and more preferably 95% by mass, based on the total amount of solids contained in the photosensitive composition. By setting the content of polymer (B) within the above range, the pattern-forming properties and substrate adhesion can be sufficiently high.

[0182] (Radiation sensitive compound (C)) This composition may contain a radiation-sensitive compound (C). Examples of radiation-sensitive compound (C) include a quinone diazide compound (C1) and a photoacid generator (C2).

[0183] (Quinone diazide compound (C1)) This composition may contain a quinone diazide compound (C1) as the radiation-sensitive compound (C).

[0184] When a quinone diazide compound (C1) is used as the radiation-sensitive compound (C), it is preferable to use a polymer (B1) containing a structural unit (III) having an acid group as the polymer (B), and it is preferable to further include a polymer (B1) containing a structural unit (III) having an acid group and a structural unit (IV) having a crosslinking group, or a polymer different from the polymer (B1) that contains a structural unit having a crosslinking group.

[0185] The quinone diazide compound (C1) is a compound that generates a carboxylic acid upon irradiation with radiation. Examples of quinone diazide compounds (C1) include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as the "nucleus") and an orthonaphthoquinone diazide compound. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the nucleus and an orthonaphthoquinone diazide compound. Specific examples of the nucleus include, for example, the compounds described in paragraphs

[0065] to

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

[0186] Specific examples of quinone diazide compounds (C1) include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, and 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene. Examples of ester compounds include those of a phenolic hydroxyl group-containing compound selected from [ethylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, the condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride is preferred as the quinone diazide compound (B1).

[0187] These quinone diazide compounds (C1) may be used alone or in combination of two or more. When quinone diazide compounds (C1) are included, the lower limit of the quinone diazide compound (C1) content is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 15 parts by mass, per 100 parts by mass of the polymer (B). The upper limit of the quinone diazide compound (C1) content is preferably 80 parts by mass, more preferably 70 parts by mass, and even more preferably 60 parts by mass, per 100 parts by mass of the polymer (B). It is preferable to have a quinone diazide compound (C1) content of 1 part by mass or more because sufficient carboxylic acid is generated by irradiation of the composition with radiation, the difference in solubility between the irradiated and unirradiated parts in the developer can be sufficiently large, and good patterning can be achieved. In addition, the amount of carboxylic acid involved in the reaction with the polymer components can be increased, and sufficient heat resistance can be ensured. On the other hand, by limiting the quinone diazide compound content to 80 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, which is preferable because it suppresses the decrease in developability due to residual quinone diazide compound.

[0188] (Photoacid generator (C2)) The photoacid generator (C2) can be any compound that generates acid in response to radiation (i.e., a radiation-sensitive acid generator), and is not particularly limited. Examples of photoacid generators (B2) include oximesulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like.

[0189] When a photoacid generator (C2) is used as the radiation-sensitive compound (C), the polymer (B) is preferably at least one polymer selected from the group consisting of polymers (B2) containing structural unit (VI) and siloxane polymers (B3).

[0190] Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include, for example, the compounds described in paragraphs

[0078] to

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

[0191] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (b2). [ka] (In formula (b2), R 40 This refers to a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with substituents. The asterisk (*) indicates a bonding operation.

[0192] In the above equation (b2), R 40 Examples of monovalent hydrocarbon groups include C1-C20 alkyl groups, C4-C12 cycloalkyl groups, and C6-C20 aryl groups. Examples of substituents include C1-C5 alkyl groups, C1-C5 alkoxy groups, oxo groups, and halogen atoms.

[0193] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, {2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene}-2-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493. Examples of commercially available oximesulfonate compounds include Irgacure PAG121 from BASF.

[0194] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphasulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphasulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphasulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide (naphthalimidyltrifluoromethanesulfonate).

[0195] These photoacid generators (C2) may be used alone or in combination of two or more. When photoacid generators (C2) are included, the lower limit of the photoacid generator (C2) content is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 10 parts by mass, per 100 parts by mass of the polymer (B). The upper limit of the photoacid generator (C2) content is preferably 50 parts by mass, more preferably 40 parts by mass, and even more preferably 35 parts by mass, per 100 parts by mass of the polymer (B) incorporated into this composition. A photoacid generator (C2) content of 1 part by mass or more is preferable because it allows for good patterning and ensures sufficient heat resistance. Furthermore, a photoacid generator (C2) content of 50 parts by mass or less is preferable because it sufficiently reduces the amount of unreacted photoacid generator after exposure, thereby suppressing a decrease in developability due to residual photoacid generator.

[0196] In addition to silsesquioxane (A), alkali-soluble polymer (B), and radiation-sensitive compound (C), this composition may further contain other components to the extent that the effects of the present invention are not impaired. Examples of other components include solvents, colorants, dispersants, dispersion aids, surfactants, polymers other than alkali-soluble polymer (B), polymerization inhibitors, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, UV absorbers, and dissolution accelerators. Among these, it is preferable to include adhesion aids (D), dissolution accelerators (E), surfactants (F), solvents (S), and colorants.

[0197] (Adhesion enhancer (D)) This composition, by containing an adhesion aid (D), improves the adhesion between the formed cured product and the substrate (adherent), thereby suppressing the peeling of the cured product from the substrate during the developing process and other steps.

[0198] Examples of adhesion promoters (D) include functional silane coupling agents having reactive functional groups, or functional acidic phosphate esters. Examples of reactive functional groups in functional silane coupling agents include carboxyl groups, acid anhydride groups, (meth)acryloyl groups, epoxy groups, vinyl groups, and isocyanate groups. Examples of reactive functional groups in functional acidic phosphate esters include (meth)acryloyl groups.

[0199] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. These can be used individually or in combination of two or more. Among these, 3-glycidyloxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred.

[0200] Commercially available functional silane coupling agents can also be used. Examples of commercially available products include KBM-403, KBM-5103, KBM-302, KBM-303, KBM-402, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-967C, etc. (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0201] Specific examples of functional acidic phosphate esters include 2-(meth)acryloyloxyethyl acid phosphate.

[0202] Commercially available functional acidic phosphate esters can be used as described above. Examples of commercially available products include Light Ester P-1M and Light Ester P-2M (both manufactured by Kyoeisha Chemical Co., Ltd.).

[0203] The above adhesion aid (D) can be used alone or in a mixture of two or more types.

[0204] When an adhesion aid (D) is incorporated into the photosensitive composition, the lower limit of its content is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 10 parts by mass, per 100 parts by mass of the polymer (B). The upper limit of the content of the adhesion aid (D) is preferably 60 parts by mass, more preferably 50 parts by mass, and even more preferably 45 parts by mass, per 100 parts by mass of the polymer (B) incorporated into the composition. It is preferable that the content ratio of the adhesion aid (D) be within the above range, as this allows for the formation of a cured film with excellent developability adhesion.

[0205] (Dissolution accelerator (E)) The dissolution accelerator (E) can be any compound that promotes solubility in the developer, and examples include low molecular weight compounds with a molecular weight of 1,000 or less that have two or more phenolic hydroxyl groups or one or more carboxyl groups.

[0206] The above low molecular weight compound may have only a carboxyl group, only a phenolic hydroxyl group, or both a carboxyl group and a phenolic hydroxyl group.

[0207] Such phenol compounds with a molecular weight of 1000 or less can be easily synthesized by those skilled in the art by referring to methods described in, for example, Japanese Patent Publication No. 4-122938, Japanese Patent Publication No. 2-28531, U.S. Patent No. 4916210, European Patent No. 219294, etc.

[0208] Specific examples of the above phenol compounds include, for example, resorcinol, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, phloroglucoside, 2,4,2',4'-biphenyltetrol, 4,4'-thiobis(1,3-dihydroxy)benzene, 2,2',4,4'-tetrahydroxydiphenyl ether, 2,2',4,4'-tetrahydroxydiphenyl sulfoxide, 2,2',4,4'-tetrahydroxydiphenyl sulfone, tris(4-hydroxyphenyl)methane, and 1,1-bis(4-hydroxyphenyl)sulfate. Examples include crohexane, 4,4-(α-methylbenzylidene)bisphenol, α,α',α''-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α,α'',α''-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1,2,2-tris(hydroxyphenyl)propane, 1,1,2-tris(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2,5,5-tetrakis(4-hydroxyphenyl)hexane, 1,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,3-tris(hydroxyphenyl)butane, and para[α,α,α',α'-tetrakis(4-hydroxyphenyl)]-xylene.

[0209] Examples of low molecular weight compounds with one or more carboxyl groups and a molecular weight of 1,000 or less include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, and tetramethyl Examples include aliphatic dicarboxylic acids such as chilcuccinic acid and citraconic acid; aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimelitic acid, and mesitylene acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid; and polyfunctional (meth)acrylates having a carboxylic acid.

[0210] Examples of polyfunctional (meth)acrylates having the above-mentioned carboxylic acid include compounds in which trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate have been modified with carboxylic acid. Commercially available products can also be suitably used, such as Aronics M-520 (manufactured by Toagosei Co., Ltd.).

[0211] The above-mentioned dissolution accelerator (E) can be used alone or in a mixture of two or more types.

[0212] When the photosensitive composition used in this manufacturing method contains a dissolution accelerator (E), the lower limit of the content of the dissolution accelerator (E) (total amount if there are multiple types) is preferably 1 part by mass, more preferably 5 parts by mass, and still more preferably 10 parts by mass, per 100 parts by mass of the polymer (B). The upper limit of the content of the dissolution accelerator (E) is preferably 65 parts by mass, more preferably 60 parts by mass, and still more preferably 50 parts by mass, per 100 parts by mass of the polymer (B) blended into this composition. It is preferable that the content ratio of the dissolution accelerator (E) be within the above range, as this allows for sufficient solubility in the developer solution.

[0213] (Surfactant (F)) Surfactants (F) can be used to further improve the applicability of the composition (specifically, wettability and reduction of uneven application). Examples of surfactants (F) include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

[0214] Specific examples of surfactants include fluorine-based surfactants such as Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Florard FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); and Ftop EF301, EF303, and EF352 (manufactured by Shin Akita Chemical Co., Ltd.).

[0215] Examples of silicone-based surfactants include the following product names: SH200-100cs, SH28PA, SH30PA, SH89PA, SH190, SH8400, SH193, SZ6032, SF8428, DC57, DC190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (manufactured by Toray Dow Corning); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BIC Chemie Japan).

[0216] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0217] The above-mentioned surfactant (F) can be used alone or in combination of two or more types.

[0218] When a surfactant (F) is incorporated into this composition, the lower limit of the surfactant (F) content is preferably 0.1 parts by mass, and more preferably 0.5 parts by mass, per 100 parts by mass of the polymer (B). The upper limit of the surfactant (F) content is preferably 5 parts by mass, and more preferably 3 parts by mass, per 100 parts by mass of the polymer (B) incorporated into this composition.

[0219] (Coloring agent) This composition may contain a coloring agent. The presence of a coloring agent allows for the imparting of a desired color depending on the application of the photosensitive composition.

[0220] The coloring agent is not particularly limited and may be an organic pigment, an inorganic pigment, or a dye.

[0221] Examples of the above-mentioned organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyersand Colourists), specifically those assigned the following Color Index (CI) numbers.

[0222] Yellow pigments such as CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211, etc. Orange pigments such as CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74, etc. CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red Red pigments such as Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272, etc. Purple pigments such as CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38; Blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, CI Pigment Blue 80, etc. Green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, and CI Pigment Green 59; Brown pigments such as CI Pigment Brown 23 and CI Pigment Brown 25; Black pigments such as CI Pigment Black 1, CI Pigment Black 7, CI Pigment Black 31, CI Pigment Black 32, lactam-based black pigments, and perylene-based black pigments.

[0223] In the present invention, organic pigments can also be purified and used by methods such as recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof.

[0224] Examples of the inorganic pigments mentioned above include titanium dioxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

[0225] These colorants may be used after their particle surfaces have been modified with polymers, if desired. Examples of polymers for modifying the particle surface of pigments include the polymers described in Japanese Patent Publication No. 8-259876, and various commercially available polymers or oligomers for pigment dispersion. Methods for polymer coating the surface of carbon black are disclosed, for example, in Japanese Patent Publication Nos. 9-71733, 9-95625, and 9-124969.

[0226] As for the black colorant, either a single black colorant or a black colorant obtained by mixing it with other colorants such as red, green, and blue can be used. These black colorants can be appropriately selected from inorganic or organic pigments and dyes, and can be used individually or in combination of multiple types.

[0227] Examples of individual black pigments include organic and inorganic pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, perylene black, lactam black, cyanine black, and titanium black.

[0228] Dyes used are those that produce the desired color, and specific structural parts (chromophores) that are the source of color include triarylmethane-based cationic chromophores, methine-based cationic chromophores, azo-based cationic chromophores, diarylmethane-based cationic chromophores, quinone imine-based cationic chromophores, anthraquinone-based cationic chromophores, cyanine-based cationic chromophores, squarylium-based cationic chromophores, and xanthene-based cationic chromophores.

[0229] When this composition is used to form a light-shielding partition, black organic pigment, titanium black, or carbon black is preferably used as the coloring agent, from the viewpoint of preventing light leakage from adjacent light-emitting layers.

[0230] When using a pigment as the coloring agent, it is preferable to perform a dispersion treatment using a pigment dispersant so that the composition can be obtained in a state in which the pigment is uniformly dispersed. In this case, although the pigment and pigment dispersant may be used when preparing the composition, it is preferable to prepare a pigment dispersion liquid by mixing the pigment, pigment dispersant and dispersion medium in advance before preparing the composition, and then prepare the composition using the prepared pigment dispersion liquid.

[0231] Examples of the above-mentioned pigment dispersants include cationic pigment dispersants, anionic pigment dispersants, nonionic pigment dispersants, and amphoteric pigment dispersants. Specifically, examples include polyester pigment dispersants, polyamine pigment dispersants, and acrylic pigment dispersants. One or more types of pigment dispersants may be used.

[0232] When using the aforementioned pigment dispersant, it is preferable that the amount used be 100 parts by mass or less, and more preferably 5 to 50 parts by mass, per 100 parts by mass of pigment, in order to easily obtain a pigment dispersion in which the pigment is uniformly dispersed.

[0233] The above colorants can be used individually or in combination of two or more.

[0234] The lower limit of the content of the above-mentioned colorants (total amount in the case of multiple types) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass, relative to the total solid content (100% by mass) of the composition. On the other hand, the upper limit of the above-mentioned content is preferably 60% by mass, more preferably 50% by mass, and even more preferably 45% by mass. It is preferable to set the content of the above-mentioned colorants within the above range because it is possible to achieve both developability and a suitable degree of coloration.

[0235] (Solvent (S)) This composition is a liquid composition in which silsesquioxane (A), an alkali-soluble polymer (B), a radiation-sensitive compound (C), and other components as may be added are preferably dissolved or dispersed in a solvent (S). As the solvent (S), an organic solvent that dissolves each component added to the photosensitive composition and does not react with each component is preferred.

[0236] Specific examples of solvents (S) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethyl 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. Of these, ethers and ketones are preferred as solvents, and propylene glycol monomethyl ether acetate, cyclopentanone, and propylene glycol monomethyl ether are more preferred.

[0237] (Method for preparing this composition) This composition can be prepared by uniformly stirring, mixing, and dissolving or dispersing compound (1) and other optionally added components. For mixing, known stirrers such as roll mills, ball mills, and sand mills can be used. After mixing each component, the resulting mixture may, if necessary, be filtered through a filter with a pore size of, for example, 2 μm or less.

[0238] The solid content concentration of this composition (i.e., the ratio of the total mass of components other than the solvent (S) in this composition to the total mass of this composition) is appropriately selected considering viscosity, volatility, etc. The solid content concentration of this composition is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and even more preferably 5 to 40% by mass. A solid content concentration above the lower limit is preferable in that it is possible to ensure a sufficient film thickness when this composition is applied to a substrate (adhesion surface). Furthermore, a solid content concentration below the upper limit is preferable in that the viscosity of this composition can be increased to a moderate level, ensuring good coatability.

[0239] This composition can be suitably used to form cured products having light-shielding properties, such as partitions or black matrices. Cured products obtained from this composition, especially partitions and black matrices with excellent light-shielding properties, are particularly useful for liquid crystal display elements, solid-state image sensors, color sensors, organic EL display elements, electronic paper, and the like.

[0240] ≪Method for manufacturing patterned cured products≫ The method for manufacturing a cured product according to this embodiment (hereinafter also referred to as "this manufacturing method") is: A process of applying a positive-type photosensitive composition onto a substrate to form a coating film, The process of exposing the coating film, The process of developing the exposed coating film, This includes a step of heating the developed pattern, A method for producing the positive-type photosensitive composition, comprising a silsesquioxane having a structural unit (I) represented by the following formula (1). [ka] (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). [ka] (In the above formulas (1a) to (1c), R 1 Each of these is independently either a hydrogen atom or a methyl group. R 2 These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is independently either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

[0241] <Process (I): Coating process> Step (I) is a step of forming a coating film (organic film) on a substrate by applying the above-mentioned positive-type photosensitive composition onto the substrate.

[0242] The present composition can be suitably used as the positive-type photosensitive composition described above.

[0243] Examples of substrates to which the above-mentioned photosensitive composition is applied include glass substrates, silicon wafers, plastic substrates, and substrates on which a colored resist, overcoat, anti-reflective film, various metal thin films, sealing films, etc., are formed on their surfaces.

[0244] Examples of plastic substrates include plastic resin substrates (resin films) made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, polyimide, etc. Various elements (for example, light-receiving elements such as photodiodes, or light-emitting elements such as organic light-emitting diodes) may be pre-installed on the substrate.

[0245] As for the coating method of the above-mentioned photosensitive composition, suitable methods such as spray coating, roll coating, rotary coating (spin coating), slit die coating, bar coating, and inkjet coating can be used. Of these coating methods, spin coating, bar coating, and slit die coating are preferred.

[0246] After applying the above photosensitive composition to a substrate, the composition may be preheated (pre-baked) to prevent dripping, etc. The pre-baking conditions can be appropriately set depending on the type and proportion of each component used in the composition, but for example, conditions of 60 to 130°C for 30 seconds to 10 minutes can be used.

[0247] The thickness of the coating film formed, as the thickness after pre-baking, is preferably 0.2 μm or more, more preferably 0.3 to 5 μm, and even more preferably 0.4 to 4 μm.

[0248] <Process (II): Exposure process> Step (II) involves irradiating at least a portion of the coating film formed in step (I) with radiation.

[0249] In step (II), position-selective radiation irradiation of the coating film is usually performed via a mask having a pattern for obtaining a cured product with a desired shape. The mask is preferably a multi-tone mask such as a halftone mask or a graytone mask. The graytone mask has slits formed below the resolution of the exposure machine, and intermediate exposure is achieved by blocking a portion of the light with these slits. In the case of a halftone mask, intermediate exposure is achieved by using a semi-permeable film. By using such a multi-tone mask, stepped patterns can be formed, for example, spacers can be formed collectively on a black partition.

[0250] Examples of radiation used to irradiate the coating include ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. Examples of ultraviolet light include g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). Examples of X-rays include synchrotron radiation. Examples of charged particle beams include electron beams. Of these, ultraviolet light is preferred, and ultraviolet light including g-rays, h-rays, and i-rays is more preferred.

[0251] Examples of light sources used for radiation irradiation include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and LED lamps.

[0252] The radiation exposure dose is 100 to 50,000 J / m². 2 (10-5,000 mJ / cm²) 2 ) is preferred, and 100 to 6,000 J / m 2 (10-600 mJ / cm 2 ) is preferable.

[0253] <Step (III): Development step> Step (III) is a step in which a pattern is formed on the substrate by developing the coating film and cured product obtained in step (II). In this manufacturing method, a positive-type photosensitive composition is used, so positive-type development is performed on the coating film that was irradiated with radiation in step (II) by developing it with a developer to remove the irradiated areas, and a patterned cured product (e.g., an uneven pattern formed by a large number of regularly arranged linear cured products) can be formed on the substrate.

[0254] Examples of developing solutions include aqueous solutions of alkali (basic compounds). Examples of alkalis include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. In addition, an appropriate amount of water-soluble organic solvents such as methanol or ethanol, or surfactants may be added to the aqueous alkali solution, or a small amount of various organic solvents capable of dissolving this composition may be added.

[0255] The concentration of the developer can be appropriately determined according to the composition of the mixture, but is usually 0.01 to 10% by mass, preferably 0.5 to 5% by mass.

[0256] As for the development method, appropriate methods such as the liquid-filling method, dipping method, agitation immersion method, and shower method can be employed.

[0257] The development time can be adjusted as appropriate depending on the composition of this composition, but for example, it is 20 to 120 seconds.

[0258] After the development process, if necessary, a step may be taken to wash the developed patterned substrate using pure water or the like.

[0259] Furthermore, a drying step may be performed on the patterned substrate after development or the cleaning described above. The drying conditions are not particularly limited, but for example, the same conditions as those for pre-baking described above may be used.

[0260] Because this composition has excellent ultraviolet (especially g-ray, h-ray, and i-ray) transmittance, it exhibits superior sensitivity during exposure. As a result, the patterned cured product obtained from this composition adheres well to the substrate, and even fine-line patterns can be formed.

[0261] <Process (IV): Post-bake process> Step (IV) involves a heating process (post-bake) of the coating developed in step (III). Post-bake can be performed using a heating device such as an oven or a hot plate. Regarding post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when heating on a hot plate, and 10 to 80 minutes when heating in an oven. In this way, a cured film having the desired pattern can be formed on the substrate. The shape of the pattern on the cured film is not particularly limited and examples include line-and-space patterns, dot patterns, hole patterns, and grid patterns.

[0262] Step (IV) can also be performed using a step-baking method involving multiple heat treatments.

[0263] <Process (V): Post-exposure process> Step (V) is a step of further irradiating the cured product obtained in step (III) and / or the cured product obtained in step (IV) with radiation. Among these, the step of further irradiating the cured product obtained in step (IV) with radiation is preferred because it allows for the easy formation of a cured product of a desired shape.

[0264] By irradiating with radiation in process (V) (hereinafter also referred to as "post-exposure"), heat resistance, chemical resistance, etc., can be further improved, and highly reliable cured products can be easily formed.

[0265] Of these, the type of radiation and exposure conditions in post-exposure can be the same as those in process (II). The wavelength, dose, and light source conditions of the irradiation light during post-exposure may be the same as or different from those in process (II).

[0266] ≪Cured material, partition, black matrix≫ The cured product of the present invention (hereinafter also referred to as "the cured product") can be formed by curing the positive-type photosensitive composition prepared as described above. The cured product obtained from the positive-type photosensitive composition exhibits excellent sensitivity and developability. Therefore, the patterned cured product can be preferably used as, for example, a color filter (color pattern or black matrix), or a light-shielding partition material (bank). The black matrix refers to a black component that separates each cell, such as red, green, and blue (RGB), in a color filter. In addition, partitions are formed on a substrate, and an organic EL light-emitting layer is formed in the recessed space partitioned by the partitions using an inkjet method or the like. A blackened partition to prevent light leakage between pixels is called a light-shielding partition material (black bank). Furthermore, it can also be suitably used as an interlayer insulating film, a planarization film, and the like.

[0267] When a cured product formed by curing the curable composition of the present invention is used as a light-shielding partition material, the optical density (OD value) of the cured product is preferably 0.5 to 5.0, and more preferably 0.7 to 4.5. Having an optical density within this range is preferable because it allows the product to exhibit sufficient light-shielding properties as a light-shielding partition material.

[0268] ≪Color Filters≫ The color filter of the present invention comprises the above-mentioned cured material as a black matrix.

[0269] ≪Image Display Panel≫ The image display panel of the present invention only needs to include the above-mentioned color filter, and other configurations are not particularly limited. Furthermore, this cured product can also be used as a color filter or light-shielding partition material in an organic EL panel with a structure that does not have a polarizing plate (POL-LESS) on which a TFT drive circuit layer, a light-shielding partition material (bank), a primary color light-emitting layer having a light-emitting layer, a sealing layer, a touch sensor, a black matrix and a color filter including a color pattern having each color (RGB), and a cover glass are laminated on a substrate.

[0270] Image display device The image display device of the present invention comprises the cured material and the image display panel. The cured material can be used as a light-shielding partition material or a color filter. Examples of such display devices include liquid crystal display devices, organic EL display devices, micro-LED (Light Emitting Diode) display devices, and quantum dot light-emitting display devices. Furthermore, an organic EL display device having an organic EL panel with a polarizing plate-less (POL-LESS) structure is also preferably mentioned. [Examples]

[0271] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0272] [Weight average molecular weight (Mw)] Mw was measured by gel permeation chromatography (GPC) under the following conditions. Equipment: Showa Denko Co., Ltd.'s "GPC-101" Column: A combination of Showa Denko Corporation's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803", and "GPC-KF-804". Mobile phase: tetrahydrofuran Column temperature: 40℃ Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0273] <Compounds used in synthesis> The compounds used in the synthesis are listed below. • Silsesquioxane (AC-SQ): "AC-SQ TA-100" manufactured by Toagosei Co., Ltd.: Silsesquioxane having the following structural units. [ka]

[0274] • SH compounds: The following compounds (SH-1) to (SH-4) [ka]

[0275] • Silane compounds: The following compounds (TAS-1) to (TAS-8) [ka]

[0276] [Synthesis Example 1] Synthesis of Silsesquioxane (A-1) In a 300 mL three-necked flask equipped with a thermometer, 50.0 g (210 mmol) of compound (TAS-1), 50 mL of ethyl acetate, and 0.2 g (0.1 mmol) of 4-methoxyphenol were added, and the mixture was heated to 30°C while stirring. Then, 4.8 g (47.4 mmol%) of triethylamine and 12.7 g of ultrapure water were slowly added, and the mixture was heated to 60°C and stirred for 3 hours. After that, the mixture was cooled to 30°C while stirring, and 2.3 g (21.7 mmol) of compound (SH-1) was added, and the reaction was carried out at 50°C for 2 hours. At this point, GPC was checked and the weight-average molecular weight (Mw) was 4400, and the remaining amount of compound (SH-1) was less than 0.1 mol%, confirming that Michael addition was proceeding quantitatively. After the reaction was complete, the mixture was transferred to a separatory funnel, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1 M hydrochloric acid solution and three times with 50 mL of water. Next, 80 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the solution was concentrated to 100 g. Then, another 80 g of PGMEA was added and the solution was concentrated again. After that, the solid content was adjusted to 50% by mass with PGMEA to obtain a solution of silsesquioxane (A-1). The weight-average molecular weight (Mw) of the obtained silsesquioxane (A-1) was 4400.

[0277] The obtained silsesquioxane (A-1) was reprecipitation with hexane and dried to form dimethyl sulfoxide-d 6 Dissolve in 1¹H-NMR measurements revealed the following peaks: δ 12.2 ppm (broad), 6.3 ppm (s, 0.75H), 6.1 ppm (s, 0.75H), 5.9 ppm (s, 0.75H), 4.0 ppm (d, 2H), 2.5~2.7 ppm (m, 2H), 1.6 ppm (m, 2H), and 0.6 ppm (m, 2H). This indicates that compound (SH-1) underwent quantitative Michael addition. Furthermore, ¹H-NMR measurements of silsesquioxane (A-1) showed multiple peaks at -55~-58 ppm for component T2 (component with a silanol group) and -65~-70 ppm for component T3 (component without a silanol group). In this synthesis example 1, the component without a silanol group corresponds to either structural unit (I) or structural unit (II) in the above embodiment. Based on the intensities of components T2 and T3, the molar ratio of silanol groups (SiOH content ratio) to the total content (100 mol%) of structural units (I) and (II) in silsesquioxane (A-1) was 0.2. From these findings, it was inferred that the obtained silsesquioxane (A-1) primarily has a highly condensed cage-like structure. Furthermore, based on the amount of raw materials used, the molar ratio of structural units (I) without compound (SH-1) to structural units (II) with compound (SH-1) attached in the obtained silsesquioxane (A-1) was calculated to be 90:10.

[0278] [Synthesis Examples 2-5, 10-14] Silsesquioxanes (A-2) to (A-5) and (A-10) to (A-14) were synthesized using the same method as in Synthesis Example 1, in the combinations shown in Table 1. The weight-average molecular weight and silanol group content of each obtained silsesquioxane were measured in the same manner as in Synthesis Example 1, and the molar ratio of structural unit (I) to structural unit (II) was calculated. The measurement results are shown in Table 1.

[0279] [Synthesis Example 6] The polymerization of silsesquioxane (A-6) was carried out with reference to paragraphs

[0050] to

[0051] of Japanese Patent No. 4734832. During the distillation removal of isopropanol, an appropriate amount of PGMEA was added to achieve a solid content concentration of 50% by mass.

[0280] [Synthesis Example 7] In a 300 mL three-necked flask equipped with a thermometer, 52.5 g (210 mmol) of compound (TAS-3), 50 mL of ethyl acetate, and 0.2 g (0.1 mmol) of 4-methoxyphenol were added, and the mixture was heated to 30°C while stirring. Then, 4.8 g (47.4 mmol%) of triethylamine and 12.7 g of ultrapure water were slowly added, and the mixture was heated to 60°C and stirred for 3 hours. After the reaction was complete, the mixture was transferred to a separatory funnel, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1 M hydrochloric acid solution and three times with 50 mL of water. Next, 80 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the solution was concentrated to 100 g. Then, another 80 g of PGMEA was added and the solution was concentrated again. Finally, the solid content was adjusted to 50% by mass with PGMEA to obtain a solution of silsesquioxane (A-7). The weight-average molecular weight (Mw) of the obtained silsesquioxane (A-7) was 3600.

[0281] [Synthesis Example 8] In a 300 mL three-necked flask equipped with a thermometer, 50 g of silsesquioxane (A-6), 25 g of isopropanol, and 1.5 g (11.9 mmol) of compound (SH-1) were added, and the mixture was heated to 30°C while stirring. Then, 0.2 g (0.6 mmol) of tetrabutylammonium bromide was added, and the mixture was heated to 50°C and stirred for 3 hours. After the reaction was complete, the isopropanol was removed by distillation, and the mixture was transferred to a separatory funnel. 100 mL of ethyl acetate was added, and the mixture was washed three times with 100 mL of water. Next, 50 g of PGMEA was added, and the solution was concentrated to 50 g. Then, another 50 g of PGMEA was added and the solution was concentrated again. Finally, the solid content was adjusted to 50% by mass with PGMEA to obtain a solution of silsesquioxane (A-8). The weight-average molecular weight (Mw) of the obtained silsesquioxane (A-8) was 4300.

[0282] [Synthesis Example 9] In a 300 mL three-necked flask equipped with a thermometer, 50 g of silsesquioxane (A-7), 25 g of isopropanol, and 1.5 g (11.9 mmol) of compound (SH-1) were added, and the mixture was heated to 30°C while stirring. Then, 0.2 g (0.6 mmol) of tetrabutylammonium bromide was added, and the mixture was heated to 50°C and stirred for 3 hours. After the reaction was complete, the isopropanol was removed by distillation, and the mixture was transferred to a separatory funnel. 100 mL of ethyl acetate was added, and the mixture was washed three times with 100 mL of water. Next, 50 g of PGMEA was added, and the solution was concentrated to 50 g. Then, another 50 g of PGMEA was added and the solution was concentrated again. Finally, the solid content was adjusted to 50% by mass with PGMEA to obtain a solution of silsesquioxane (A-9). The weight-average molecular weight (Mw) of the obtained silsesquioxane (A-9) was 3400.

[0283] [Table 1]

[0284] [Comparative Synthesis Example 1] Synthesis of linear polysiloxanes containing acryloyl groups In a 500 mL separable flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux tube, 23.4 g (99.8 mmol) of compound (TAS-1), 211 g of 1-methoxy-2-propanol, 1.8 g of water, and 0.12 g of phosphoric acid were added and the mixture was stirred at 60°C for 4 hours. After the reaction was complete, 211 g of 1-methoxy-2-propanol was added to concentrate the solution to 160 g, and then another 211 g of 1-methoxy-2-propanol was added to concentrate it to 75 g. Finally, 1-methoxy-2-propanol was added to obtain a solution of polysiloxane (RS-1) having an acryloyl group with a solid content of 20% by mass. Si-NMR of polysiloxane (RS-1) showed multiple peaks at -55 to -58 ppm for the T2 component and -65 to -70 ppm for the T3 component. Based on the intensities of components T2 and T3, the molar ratio of silanol groups to the total content of structural units (I) and (II) in polysiloxane (RS-1) (SiOH content ratio) was 1.1. This suggests that polysiloxane (RS-1) has a structure that contains a large amount of linear structures.

[0285] [Comparative Synthesis Example 2] Addition of Michael to Polysiloxane In a 500 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 117 g of polysiloxane (RS-1) (a polycondensate of 99.8 mol of TAS-1), 1.1 g (10.4 mmol) of compound (SH-1), and 174 g of tetrahydrofuran were added. Then, 2.3 g (22.7 mmol) of triethylamine was slowly added, and the temperature was raised to 50°C, at which point gelation occurred.

[0286] [Synthesis Example 15] Polymerization of a polymer (B-1) obtained by introducing side-chain phenols into a cresol novolac type epoxy resin. 220 parts of cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) were placed in a four-necked flask equipped with a stirrer and reflux condenser, and 214 parts of PGMEA were added and heated until dissolved. Next, 63.1 parts (500 mmol) of compound (SH-1) and 8.0 parts (25 mmol) of tetrabutylammonium bromide as a reaction catalyst were added. After the reaction was complete, the mixture was transferred to a separatory funnel, 200 mL of ethyl acetate was added, and the mixture was washed three times with 200 mL of water. Next, 200 g of PGMEA was added, and the mixture was concentrated to a volume of 500 g. Then, another 200 g of PGMEA was added and the mixture was concentrated again. Subsequently, the solid content concentration was adjusted to 50% by mass with PGMEA to obtain polymer (B-1) in which a phenol side chain was introduced to the cresol novolac type epoxy resin (solid content concentration: 50% by mass). The weight-average molecular weight (Mw) of the polymer (B-1) obtained in this way was approximately 4,000.

[0287] [Synthesis Example 16] Polymerization of a polymer (B-2) obtained by introducing side-chain benzoic acid into a cresol novolac type epoxy resin. 220 parts of cresol novolac epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) were placed in a four-necked flask equipped with a stirrer and reflux condenser, and 214 parts of PGMEA were added and heated until dissolved. Next, 77.1 parts (500 mmol) of compound (SH-4) and 8.0 parts (25 mmol) of tetrabutylammonium bromide as a reaction catalyst were added. After the reaction was complete, the mixture was transferred to a separatory funnel, 200 mL of ethyl acetate was added, and the mixture was washed three times with 200 mL of water. Next, 200 g of PGMEA was added, and the mixture was concentrated to a volume of 500 g. Then, another 200 g of PGMEA was added and the mixture was concentrated again. Subsequently, the solid content concentration was adjusted to 50% by mass with PGMEA to obtain polymer (B-2) in which a benzoic acid side chain was introduced to the cresol novolac epoxy resin (solid content concentration: 50% by mass). The weight-average molecular weight (Mw) of the polymer (B-2) obtained in this way was approximately 4,200.

[0288] [Synthesis Example 17] Polymerization of alkali-soluble poly(meth)acrylic polymer (B-3) In a 200 mL flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux tube, a solution prepared by dissolving 3.8 g of acrylic acid, 9.6 g of cyclomer M100 (manufactured by Daicel Corporation), 3.2 g of phenylmaleimide, 2.6 g of styrene, and 12.8 g of methyl methacrylate in 68 g of PGMEA, along with 4.2 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.8 g of n-dodecyl mercaptan, was added. The mixture was heated to 70°C while stirring and stirred for 5 hours. After the reaction was complete, the mixture was cooled to room temperature to obtain a poly(meth)acrylic polymer (B-3) solution with a solid content of 32% by mass. The weight-average molecular weight (Mw) of the poly(meth)acrylic polymer (B-3) was 4,000.

[0289] Synthesis Example 18: Synthesis of Polymer (B-5) Ten parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, ten parts by mass of methacrylic acid, twenty parts by mass of styryltrimethoxysilane, thirty parts by mass of glycidyl methacrylate, thirty parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and ten parts by mass of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (B-5). The solid content concentration of this polymer solution was 34% by mass, the Mw of polymer (B-5) was 10,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[0290] Synthesis Example 19: Synthesis of Polymer (B-6) Ten parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, ten parts by mass of methacrylic acid, twenty parts by mass of 3-methacryloxypropyltrimethoxysilane, thirty parts by mass of glycidyl methacrylate, thirty parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and ten parts by mass of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (B-6). The solid content concentration of this polymer solution was 34% by mass, the Mw of polymer (B-6) was 10,100, and the molecular weight distribution (Mw / Mn) was 2.1.

[0291] Synthesis Example 20: Synthesis of Polymer (B-7) Ten parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, ten parts by mass of methacrylic acid, fifteen parts by mass of 2-tetrahydropyranylacrylic acid, 35 parts by mass of glycidyl methacrylate, 30 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and ten parts by mass of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (B-7). The solid content concentration of this polymer solution was 33% by mass, the Mw of polymer (B-7) was 9,500, and the molecular weight distribution (Mw / Mn) was 2.2.

[0292] [Preparation Example 1] Preparation of Pigment Dispersion (BK-MB-1) A pigment dispersion (BK-MB-1), which is a coloring agent, was prepared by mixing and dispersing a mixture consisting of 12.0 parts by mass of lactam pigment [Irgaphor Black S0100CF (manufactured by B ASF Japan)] as a coloring agent, 11.8 parts by mass of BYK-LPN21116 (manufactured by Bic Chemie Japan Co., Ltd., solid content concentration 40.0% by mass) as a dispersant in solution, 13.0 parts by mass of alkali-soluble resin (B-4) as a binder in polymer solution (solid content concentration 32% by mass), and 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a dispersion medium, using a bead mill for 12 hours.

[0293] [Preparation Example 2] Preparation of Pigment Dispersion (BK-MB-2) A pigment dispersion (BK-MB-2) was prepared using the same procedure as in Preparation Example 1, except that the type of colorant was changed to carbon black (TPX1227R, manufactured by Cabot).

[0294] [Preparation Example 3] Preparation of Pigment Dispersion (BK-MB-3) A pigment dispersion (BK-MB-3) was prepared using the same procedure as in Preparation Example 1 above, except that the type of coloring agent was changed to a perylene-based pigment (Irgaphor Black FK4280, manufactured by BASF).

[0295] [Preparation Example 4] Preparation of Pigment Dispersion (BK-MB-4) A pigment dispersion (BK-MB-4) was prepared using the same procedure as in Preparation Example 1 above, except that the type of coloring agent was changed to titanium black (titanium nitride, manufactured by Gemco).

[0296] <Preparation of photosensitive composition> The components used in the preparation of the photosensitive compositions of the examples and comparative examples are shown.

[0297] <Silsesquioxane (A), etc.> • (A-1)~(A-14): Silsesquioxanes (A-1)~(A-14) synthesized in the above synthesis examples 1~14. • (RS-1): Polysiloxane (RS-1) synthesized in the above comparative synthesis example 1. • (AC-SQ): "AC-SQ TA-100" manufactured by Toagosei Co., Ltd.

[0298] <Alkali-soluble polymer (B)> • (B-1)~(B-2): Acid-modified cresol novolac type epoxy resin synthesized in the above synthesis examples 15~16 • (B-3): Poly(meth)acrylic polymer synthesized in the above synthesis example 17 • (B-4): ADEKA's "WR-301" (PGMEA solution with a solid content of 44%), a resin modified from cardo resin to acid anhydride, and a resin having acrylate and carboxylic acid groups. • (B-5)~(B-7): Polymers synthesized in the above synthesis examples 18~20

[0299] <Pigment dispersion (BK-MB-1~4)> • (BK-MB-1)~(BK-MB-4): Pigment dispersions obtained in Preparation Examples 1~4

[0300] <Quinone diazide compound (C1)> • (C1-1): Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.2 mol)

[0301] <Photoacid Generator (C2)> • (C2-1): Irgacure PAG121 (manufactured by BASF)

[0302] <Adhesion enhancer (D)> • (D-1): 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) • (D-2): Light Ester P-1M (EO-modified methacrylate phosphate, manufactured by Kyoeisha Chemical Co., Ltd.)

[0303] <Dissolution accelerator (E)> • (E-1): Compound represented by the following formula [ka]

[0304] <Surfactant (F)> • (F-1): DOWSIL SH 8400 Fluid (manufactured by Toray Dow Ltd., silicone-based surfactant) • (F-2): Megafac F-554 (manufactured by DIC Corporation, fluorine-based surfactant)

[0305] <Solvent (S)> • (S-1) Propylene glycol monomethyl ether acetate (PGMEA)

[0306] [Example 1] A colored composition was prepared by adding PGMEA to 37.5 parts by mass of pigment dispersion (BK-MB-1), 7.0 parts by mass of (A-1) as silsesquioxane, 7.0 parts by mass of (B-1) as alkali-soluble polymer, 1.0 part by mass of (C1-1) as naphthoquinone diazide, 0.70 parts by mass of (D-1) as adhesion aid, 1.0 part by mass of (E-1) as dissolution accelerator, and 0.036 parts by mass of silicone-based surfactant (F-1) as surfactant, so that the final solid content was 18.0% by mass.

[0307] [Examples 2-62, Comparative Examples 1-4] The compositions for Examples 2-62 and Comparative Examples 1-4 were prepared in the same manner as for Example 1, except that the compositions were changed as shown in Tables 2-1 and 2-2.

[0308] [Table 2-1]

[0309] [Table 2-2]

[0310] [Evaluation Method] The above photosensitive compositions were evaluated for the following items using the method described below. The evaluation results are shown in Tables 3-1 and 3-2.

[0311] <Halftone pattern formation> The photosensitive composition prepared in Example 1 was applied to a soda glass substrate with an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating with a thickness of 4.0 μm. Next, using a Canon MPA-600FA, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating via a quartz halftone photomask (having a line pattern with 10 μm width and 100% transmittance on the inside and a line pattern with 15 μm width intermediate exposure areas with slits with a light transmission area of ​​35% on both ends) at a rate of 300 mJ / cm². 2The substrate was exposed to the specified exposure dose. The exposed coated glass substrate was then placed on a horizontal rotating table of a spin-shower developer (AD-2000 model, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C for 60 seconds. Afterward, the developed substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to form a stepped pattern with a film thickness of 3.0 μm. The resulting substrate with the line pattern was observed using an optical microscope to confirm that there were no defects in the formed line pattern and no residue in the resolution areas. Furthermore, the step width corresponding to the intermediate exposure area was measured using a stylus-type profiler Alpha-Step D500 (ULVAC, Inc.). The result showed a step width of 1.4 μm, confirming that a stepped pattern with a step of approximately half the total film thickness had been formed.

[0312] <Evaluation of developability> Each prepared photosensitive composition was applied to a soda glass substrate with an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating with a thickness of 3.5 μm. Next, using a Canon MPA-600FA, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating at a rate of 50 mJ / cm² through a photomask capable of forming a hole pattern with an inner diameter of 10 μm. 2 50 mJ / cm² at intervals 2 ~300 mJ / cm 2 The substrate was exposed to the specified exposure. Subsequently, the exposed coated glass substrate was placed on the horizontal rotating table of a spin-shower developer (AD-2000 model, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C for 60 seconds. After development, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to form a 10 μm hole pattern. The resulting hole-patterned substrates were observed using an optical microscope to check for the presence or absence of residue in the resolved areas of the formed hole patterns. The exposure level at which no residue was observed was determined. The residual film rate was calculated by evaluating the coating film thickness and the film thickness after development. Higher sensitivity is indicated by a lower exposure level required to form a residue-free hole pattern and a higher residual film rate after development. <Evaluation Criteria> ○: Resolution exposure (sensitivity) 150 mJ / cm 2 The following, and with a residual film rate of 70% or more: ×: Resolution exposure (sensitivity) 150 mJ / cm 2 Higher and less than 70% residual film rate

[0313] <Measurement of optical density (OD value)> Each prepared photosensitive composition was coated onto a soda glass substrate, which had an SiO2 film formed on its surface to prevent sodium ion elution, using a spin coater. The composition was then dried under reduced pressure at room temperature. Next, using a Canon MPA-600FA, the resulting coating was exposed to radiation at 300 mJ / cm², including wavelengths of 365 nm, 405 nm, and 436 nm, via a photomask. 2 The substrates were exposed to light at the specified exposure level. Subsequently, a 3.0 μm thick evaluation substrate was formed by post-baking in a clean oven at 230°C for 30 minutes. The optical density (OD value) of the obtained evaluation substrates was measured using an X-rite 361T monochrome transmission densitometer. A higher OD value indicates higher light shielding. In comparative examples 1 to 4, surface roughness and cracks occurred across the entire surface, making it impossible to measure the optical density.

[0314] [Table 3-1]

[0315] [Table 3-2]

[0316] As shown in Tables 3-1 and 3-2, the photosensitive compositions of Examples 1 to 62 were excellent in terms of sensitivity, residual film rate, developer residue suppression, and light shielding properties. On the other hand, the comparative examples were inferior to the examples.

Claims

1. A process of applying a positive-type photosensitive composition onto a substrate to form a coating film, The process of exposing the coating film, The process of developing the exposed coating film, Includes a step of heating the developed pattern. A method for manufacturing a patterned cured product, A method for producing the positive-type photosensitive composition, comprising a silsesquioxane having a structural unit (I) represented by the following formula (1). 【Chemistry 1】 (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). 【Chemistry 2】 (In the above formulas (1a) to (1c), R １ This is either a hydrogen atom or a methyl group. R ２ These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

2. The manufacturing method according to claim 1, wherein the content of silanol groups relative to the total content of structural units constituting the silsesquioxane is less than 0.3 in molar ratio.

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

4. The method for producing a positive-type photosensitive composition, wherein the positive-type photosensitive composition comprises a silsesquioxane having a structural unit (II) represented by the following formula (2) in addition to the structural unit (I) represented by the above formula (1). 【Transformation 3】 (In the above formula (2), Y is a group represented by the following formulas (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), or (2i). 【Chemistry 4】 【Transformation 5】 【Transformation 6】 (In the above formulas (2a) to (2i), R １ Each of these is independently either a hydrogen atom or a methyl group. R ２ These are, independently, alkanediyl groups having 2 to 10 carbon atoms. R ２１ Each of these is independently either a single bond or a methylene group. R ３ These are, independently, divalent organic groups. R ４ Each of these is independently a single bond or a divalent organic group. X １ Each of these is independently a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, or an alkoxy group. n is, independently of each other, an integer from 0 to 4. When n is 2 or more, the plurality of Xs １ are the same as or different from each other. Each Cy element is an independently alicyclic hydrocarbon ring with 3 to 20 carbon atoms. * indicates the binding site.

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

6. The positive-type photosensitive composition further comprises A polymer (B1) containing a structural unit (III) having an acid group, A quinone diazide compound (C1) is included, The manufacturing method according to claim 1.

7. The manufacturing method according to claim 6, wherein the polymer (B1) further comprises a structural unit (IV) having a crosslinkable group, or the positive-type photosensitive composition further comprises a polymer different from the polymer (B1) and comprising a structural unit (IV) having a crosslinkable group.

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

9. The positive-type photosensitive composition further comprises A method for producing a polymer according to claim 1, comprising a polymer (B2) containing a structural unit (VI) having a group represented by the following formula (7) or an acid-dissociable group, and a polymer (B3) which is at least one selected from the group consisting of these polymers, and a photoacid generator (C2). 【Transformation 7】 (In formula (7), R Ａ１ , R Ａ２ and R Ａ３ Each of these is independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. However, R Ａ１ , R Ａ２ and R Ａ３ At least one of these is an alkoxy group having 1 to 6 carbon atoms. The asterisk (*) indicates a bonding operation.

10. The production method according to claim 9, wherein the photoacid generator (C2) comprises at least one selected from the group consisting of oximesulfonate compounds and sulfonimide compounds.

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

12. A positive-type photosensitive composition comprising a silsesquioxane having a structural unit (I) represented by the following formula (1). 【Transformation 8】 (In the above formula (1), X is a group represented by the following formulas (1a), (1b), or (1c). 【Chemistry 9】 (In the above formulas (1a) to (1c), R １ This is either a hydrogen atom or a methyl group. R ２ These are, independently, alkanediyl groups having 2 to 10 carbon atoms. p is either 1 or 2. Cy is an alicyclic hydrocarbon ring with 3 to 20 carbon atoms.

13. The positive-type photosensitive composition according to claim 12, wherein the content of silanol groups relative to the total content of structural units constituting the silsesquioxane is less than 0.3 in molar ratio.

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

15. A partition wall made of the cured material according to claim 14.

16. An image display device comprising a partition wall as described in claim 15.

17. A black matrix comprising the cured product described in claim 14.

18. A color filter comprising the black matrix described in claim 17.

19. An image display panel comprising the color filter described in claim 18.

20. An image display device comprising the image display panel described in claim 19.

Images