Radiation-sensitive composition, interlayer insulating film, method for manufacturing the same, and display element

Abstract

The present invention provides a radiation-sensitive composition that can form a cured film with high radiation sensitivity, excellent dry etching resistance, and superior transparency. [Solution] A radiation-sensitive composition containing an alkali-soluble polymer (A), a quinone diazide compound (B), a structural unit (V) represented by the following formula (1), and a structural unit (VI) derived from a compound selected from the group consisting of maleimide, N-substituted maleimide, and maleic anhydride. JPEG2026096193000024.jpg64170

Description

[Technical Field]

[0001] The present invention relates to a radiation-sensitive composition, an interlayer insulating film, a method for manufacturing the same, and a display element. [Background technology]

[0002] The display element is provided with an interlayer insulating film that insulates the space between the wiring and the substrate, and between the wiring itself. In a display element, the interlayer insulating film is generally formed by exposing and developing a coating film made of a radiation-sensitive composition, followed by heat treatment to thermally cure it (see, for example, Patent Document 1).

[0003] Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble resin containing a structural unit having (meth)acrylic acid, and a quinone diazide compound as a photosensitive component, wherein a cured film that is soluble in an alkaline developer, has high resolution, and leaves little developing residue can be obtained by including a compound having two or more five-membered cyclic carbonate groups in the molecule. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-5357 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, with the expansion of applications for display elements, there has been a growing demand for higher-resolution display elements. Against this backdrop, there is a need for technology that can form cured films with even better radiation sensitivity than before.

[0006] Patent Document 1 reports that incorporating a specific compound into a radiation-sensitive composition improves its radiation sensitivity. However, the radiation-sensitive composition described in Patent Document 1 sometimes resulted in film roughness during the dry etching process of the cured film. Therefore, there is a need for a cured film that does not experience problems such as film roughness during dry etching.

[0007] Furthermore, transparency is required for the cured film. When a radiation-sensitive composition contains a quinone diazide compound as a photosensitive agent, the quinone diazide compound is a coloring component, and therefore, reducing the amount of the quinone diazide compound added is considered effective from the standpoint of transparency. However, there was a problem in that the radiation sensitivity decreased with decreasing amounts of the quinone diazide compound added.

[0008] The present invention has been made in view of the above problems, and aims to provide a radiation-sensitive composition that can form a cured film with high radiation sensitivity, excellent dry etching resistance and transparency, an interlayer insulating film formed from the composition, a display element equipped with the interlayer insulating film, and a method for manufacturing the interlayer insulating film. [Means for solving the problem]

[0009] According to the present invention, the following radiation-sensitive composition, interlayer insulating film, method for manufacturing the same, and display element are provided.

[0010] In one embodiment, the present invention is Alkali-soluble polymer (A) (excluding polymer (C) below) and Quinone diazide compound (B) and, A polymer (C) containing a structural unit (V) represented by the following formula (1), and a structural unit (VI) derived from at least one compound selected from the group consisting of maleimide, N-substituted maleimide, and maleic anhydride, wherein the total content of structural unit (V) and structural unit (VI) is 55% by mass or more relative to the total structural units constituting polymer (C), This invention relates to a radiation-sensitive composition containing a solvent (S). [ka] (In formula (1), R A This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ar has an aromatic ring structure. R 1 R is a halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, or a monovalent organic group having 1 to 20 carbon atoms. 1 If multiple R 1 They are either the same or different. n1 is an integer between 0 and 10.

[0011] In another embodiment, the present invention is The present invention relates to an interlayer insulating film formed using the above-mentioned radiation-sensitive composition, and to a display element having the interlayer insulating film.

[0012] In another embodiment, the present invention is A step of forming a coating film using the above-mentioned radiation-sensitive composition, A step of irradiating at least a portion of the coating film with radiation, A step of developing the coating film that has been irradiated with radiation, The present invention relates to a method for manufacturing an interlayer insulating film, which includes a step of heating the developed coating film. [Effects of the Invention]

[0013] The radiation-sensitive composition of the present invention, by using an alkali-soluble polymer (A) and a polymer (C) having a specific structure in combination, can form a cured film with high radiation sensitivity, excellent dry etching resistance, and transparency. Polymer (C) has a rigid and regular helical structure in its main chain and occupies a large volume. Furthermore, the aromatic groups of the side chains of polymer (C) interact with the quinone diazide compound (B). As a result, the solubility in the exposed area is improved compared to quinone diazide compound (B) alone, and the solubility in the unexposed area is further reduced. It is presumed that the difference in dissolution rates between the exposed and unexposed areas increases, resulting in a composition with excellent radiation sensitivity. In addition, by using polymer (C), the amount of quinone diazide compound (B) used can be reduced, improving transparency. Furthermore, the combination of alkali-soluble polymer (A) and polymer (C) having a specific structure provides excellent dry etching resistance. [Modes for carrying out the invention]

[0014] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0015] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the values ​​indicated before and after "~" as the lower and upper limits, respectively. "Structural unit" refers to a unit that mainly constitutes the main chain structure and is included in the main chain structure in pairs or more.

[0016] 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 an alicyclic hydrocarbon group or an aromatic hydrocarbon group may have substituents consisting of hydrocarbon structures.

[0017] In this specification, "(meth)acryloyl" encompasses "acryloyl" and "methacryloyl," and "(meth)acrylic" encompasses "acrylic" and "methacrylic." "(meth)acrylate" encompasses "acrylate" and "methacrylate."

[0018] In this specification, "organic group" means a group having at least one carbon atom (excluding groups that constitute a functional or characteristic group on their own, such as -CN, -COOH, -CO-, -COO-, -O-CO-O-, etc.).

[0019] ≪Radiation-sensitive composition≫ The radiation-sensitive composition according to this embodiment (hereinafter also referred to as "this composition") is Alkali-soluble polymer (A) (excluding polymer (C) below) and Quinone diazide compound (B) and, A polymer (C) containing a structural unit (V) represented by the following formula (1), and a structural unit (VI) derived from at least one compound selected from the group consisting of maleimide, N-substituted maleimide, and maleic anhydride, wherein the total content of structural unit (V) and structural unit (VI) is 55% by mass or more relative to the total structural units constituting polymer (C), It contains solvent (S). [ka] (In formula (1), R A This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ar has an aromatic ring structure. R 1 R is a halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, or a monovalent organic group having 1 to 20 carbon atoms. 1 If multiple R 1 They are either the same or different. n1 is an integer between 0 and 10.

[0020] The following describes each component contained in this composition, as well as any other components that may be added as needed.

[0021] <Alkali-soluble polymer (A)> The alkali-soluble polymer (A) is an aggregate of polymerization chains, excluding polymer (C) described below (hereinafter, this aggregate is also referred to as "base polymer (A)"). The alkali-soluble polymer (A) is preferably at least one selected from the group consisting of polymers (A1) containing an acidic structural unit (I), polyimide polymers (A2), and siloxane polymers (A3), with polymers (A1) containing an acidic structural unit (I) being preferred. Hereinafter, "alkali-soluble" means that it is soluble or swellable in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C.

[0022] <Polymer (A1)> The polymer (A1) described above is preferably a (meth)acrylic polymer containing structural unit (I) having an acidic group. Polymer (A1) may also contain structural units other than structural unit (I). The following describes each structural unit included in polymer (A1).

[0023] [Structural Unit (I)] By including a structural unit (I) having an acidic group in the polymer (A1), the solubility (alkali solubility) of the polymer (A1) in an alkaline developer can be increased, and the curing reactivity can be enhanced.

[0024] The acidic group is preferably at least one selected from the group consisting of carboxyl groups, maleimide groups, sulfo groups, fluorine-containing alcoholic hydroxyl groups (groups containing a structure in which at least one fluorine atom or fluoroalkyl group is bonded to the carbon atom to which the hydroxyl group is bonded), phosphoric acid groups, phosphonic acid groups, phenolic hydroxyl groups, and phosphinic acid groups. Among these, at least one selected from carboxyl groups, phenolic hydroxyl groups, and fluorine-containing alcoholic hydroxyl groups is more preferred as the acidic group. These acidic groups are preferred because they have high curing reactivity and can produce a cured film with excellent heat resistance. In this specification, "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, naphthalene ring, anthracene ring, etc.).

[0025] Structural unit (I) is preferably a structural unit derived from an unsaturated monomer having an acidic group. Specific examples of unsaturated monomers having an acidic group include: Monomers that provide structural units containing a carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic 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 that give structural units containing a sulfo group include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc. As monomers that provide structural units having phenolic hydroxyl groups, 4-hydroxystyrene, 2-isopropenylphenol, 3-isopropenylphenol, 4-isopropenylphenol, hydroxyphenyl (meth) acrylate, etc.; As monomers that provide structural units having maleimide groups, maleimide etc. can be respectively cited.

[0026] Further, specific examples of the structural unit having a fluorine-containing alcoholic hydroxyl group include, for example, structural units represented by each of the following formulas (5-1) to (5-8). [Chemical formula] (In formulas (5-1) to (5-8), R A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group.)

[0027] Among the above, as the structural unit (I), a structural unit derived from (meth) acrylic acid, 2-isopropenylphenol, or hydroxyphenyl (meth) acrylate, and the structural unit represented by the above formula (5-7) are preferable.

[0028] The base polymer (A) may contain one or a combination of two or more of the structural units (I).

[0029] When the polymer (A) contains the structural unit (I), the lower limit value of the content ratio of the structural unit (I) (when a plurality of types are included, the total content ratio) is preferably 1% by mass, more preferably 5% by mass, still more preferably 10% by mass, and particularly preferably 20% by mass with respect to all the structural units constituting the base polymer (A). Further, the upper limit value of the above content ratio is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass. Setting the content ratio of the structural unit (I) within the above range is preferable because it can impart good solubility in an alkali developer.

[0030] [Structural unit (II)] Polymer (A) preferably contains structural units (II) having crosslinkable groups, as this can further enhance radiation sensitivity and adhesion of the cured film. The crosslinkable group is not particularly limited as long as it undergoes a curing reaction by heat treatment, but at least one selected from the group consisting of cyclic ether groups such as oxyranyl groups and oxetanyl groups, and ethylenically unsaturated groups is preferred, with cyclic ether groups being more preferred, due to its high thermosetting properties.

[0031] (Structural unit having a cyclic ether group (II-1)) Examples of cyclic ether groups include oxetanyl groups and oxyranyl groups. Structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an oxetanyl group and an oxyranyl group. Specifically, for example, a structural unit represented by the following formula (a1) or formula (a2) is preferred.

[0032] [ka] (In formulas (a1) and (a2), R 21 This is a monovalent group having an oxyranyl group or an oxetanyl group. R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 1 (This is a single bond or a divalent linking group.)

[0033] In the above equations (a1) and (a2), R 21 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups, 3-methyloxetanyl groups, and 3-ethyloxetanyl groups.

[0034] X 1Examples of divalent linking groups include alkanediyl groups such as methanediyl, ethanediyl, and 1,3-propanediyl groups, as well as groups containing -O- between the carbon-carbon bonds of the alkanediyl group.

[0035] Specific examples of monomers that give structural unit (II) represented by the above formulas (a1) and (a2) include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, etc.

[0036] Among these, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (3-ethyloxetan-3-yl)(meth)acrylate are preferred.

[0037] The base polymer (A) may contain one or more structural units (II) in combination.

[0038] When polymer (A) contains structural unit (II), the lower limit of the content of structural unit (II) (total content if multiple types are included) is preferably 1% by mass, more preferably 5% by mass, even more preferably 10% by mass, and particularly preferably 20% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. Setting the content of structural unit (II) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured film to have sufficiently high heat resistance and chemical resistance.

[0039] [Structural Unit (III)] The polymer (A) may further contain structural units (III) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic rings, heterocyclic vinyl compounds, conjugated dienes, nitrogen-containing vinyl compounds, and unsaturated dialkyl dicarboxylate compounds. Introducing these structural units (III) into the polymer is preferable because it allows for adjusting the glass transition temperature of the polymer (A) components and improving the pattern shape of the resulting cured film.

[0040] 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.

[0041] Examples of (meth)acrylic acid esters having the above alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and tricyclo(meth)acrylate. 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.02,5 Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate.

[0042] Examples of (meth)acrylic acid esters having the above aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0043] Examples of vinyl compounds having the above heterocyclic structure include tetrahydrofuranylmethyl (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, (meth)acrylate (γ-butyrolactone-2-yl), (meth)acrylate glycerin carbonate, (meth)acrylate (γ-lactam-2-yl), and N-(meth)acryloxyethylhexahydrophthalimide.

[0044] 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.

[0045] The monomer that gives the above structural unit (III) preferably includes at least one selected from the group consisting of alkyl (meth)acrylates and vinyl compounds having a heterocyclic structure, with methyl (meth)acrylate and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate being more preferred.

[0046] The base polymer (A) may contain one or more structural units (III) in combination.

[0047] When polymer (A) contains structural unit (III), the lower limit of the content of structural unit (III) (or the total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer (A). The upper limit of the above content is preferably 90% by mass, and more preferably 80% by mass. Setting the content of structural unit (III) within the above range is preferable because it allows the glass transition temperature of polymer (A) to be raised to a moderate level.

[0048] (Structural Unit (IV)) The polymer (A) described above may further have structural unit (IV) containing an amide bond. The inclusion of structural unit (IV) in polymer (A) is preferable because it allows the resulting interlayer insulating film to have excellent adhesion to ITO and copper.

[0049] The structural unit (IV) is preferably the structural unit represented by the following formula (7). [ka] (In formula (7), R 71 This is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. R 72 (A hydrocarbon group has 1 to 5 carbon atoms.)

[0050] R in equation (7) above 72 Examples of hydrocarbon groups having 1 to 5 carbon atoms represented by R include alkyl groups such as methyl, ethyl, and propyl groups; alkenyl groups such as ethenyl and propenyl groups; alkynyl groups such as ethynyl and propynyl groups; and cycloalkyl groups such as cyclopentyl groups. Among these, R 72 Methyl groups, ethyl groups, and ethenyl groups (vinyl groups) are more preferred, with methyl groups being even more preferred.

[0051] R in equation (7) above 71 As a hydrocarbon group having 1 to 3 carbon atoms, R 72 Among the examples of hydrocarbon groups with 1 to 5 carbon atoms represented by , those with 1 to 3 carbon atoms can be cited. 71 Hydrogen atoms and methyl groups are preferred as these elements.

[0052] Examples of unsaturated monomers that give the above structural unit (IV) include N-vinylacetamide, N-vinylpropionamide, and N-vinylbutylamide. Among these, N-vinylacetamide is preferred.

[0053] The base polymer (A) may contain one or more structural units (IV) in combination.

[0054] When polymer (A) contains structural unit (IV), the lower limit of the content of structural unit (IV) (or the total content if multiple types are included) is preferably 0.1% by mass, more preferably 0.5% by mass, and even more preferably 1% by mass, relative to the total structural units constituting the base polymer (A). The upper limit of the above content is preferably 20% by mass, and more preferably 10% by mass. It is preferable to set the content of structural unit (IV) within the above range because the resulting interlayer insulating film can have excellent adhesion to ITO and copper.

[0055] [Structural Units (VII)] The polymer (A) described above may further contain structural unit (VII) having a group represented by the following formula (a3). Including structural unit (VII) is preferable from the viewpoint of forming a coating film with excellent developability. [ka] (In formula (a3), R A1 , R A2 and R A3Each 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.

[0056] 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.

[0057] 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.

[0058] From the viewpoint of obtaining a heat-resistant cured film by forming a cross-linked structure, and from the viewpoint of improving the storage stability of the radiation-sensitive composition, R A1 ~R A3 Preferably, at least one of these groups 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.

[0059] Among the above, R A1 It 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 A3The 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.

[0060] In structural unit (VII), the group represented by formula (a3) ​​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 (a3) ​​is bonded include alkanediyl groups and alkenediyl groups.

[0061] The group represented by formula (a3) ​​above is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. That is, structural unit (VII) preferably has at least one selected from the group consisting of the group represented by formula (i), the group represented by formula (ii), and the group represented by formula (iii). [ka] (In equations (i), (ii), and (iii), 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. n1 is an integer between 0 and 4. n2 is an integer from 0 to 6. However, if n1 is 2 or greater, multiple A 1 These are either the same group or different groups. If n2 is 2 or more, there are multiple A 2 These are either identical or different groups. R 31 This is an alkanediyl group. R A1 , R A2 and R A3This is equivalent to equation (a3) ​​above. The asterisk (*) indicates a bonding operation.

[0062] A 1 and A 2 As an alkoxy group having 1 to 6 carbon atoms, R in the above formula (a3) ​​is A1 ~R A3 The alkoxy groups with 1 to 6 carbon atoms listed above can be preferably used. Also, A 1 and A 2 As an alkyl group having 1 to 6 carbon atoms, R in the above formula (a3) ​​is A1 ~R A3 Among the alkyl groups having 1 to 10 carbon atoms, groups corresponding to 1 to 6 carbon atoms can be suitably adopted.

[0063] Group that bonds to aromatic rings "-SiR" A1 R A2 R A3 The position of " is A 1 and A 2 It may be in any position with respect to the other groups except for . For example, in the case of formula (i) above, the group "-SiR A1 R A2 R A3 The position of " can be the ortho, meta, or para position, and is preferably the para position.

[0064] n1 is preferably 0 or 1, and more preferably 0. n2 is preferably 0 to 2, and more preferably 0.

[0065] In the above equation (iii), R 31 It is preferable that it is linear. From the viewpoint of increasing the heat resistance of the resulting cured film, R 31 The carbon atoms preferably have 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0066] The structural unit (III) preferably has at least one selected from the group consisting of the group represented by formula (i) and the group represented by formula (ii) among the above formulas (i) to (iii). In addition, the aromatic ring may have the group "-SiR A1 R A2 R A3When the group is directly bonded, it becomes possible to stabilize the silanol group that is generated in the presence of water. This is preferable because it allows for higher solubility of the exposed area in the alkaline developer and enables the formation of a good pattern. Among these, structural unit (VII) is particularly preferably a structural unit having the group represented by formula (i) above.

[0067] Structural unit (VII) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "unsaturated monomer"), and more specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (a3-1) and structural units represented by the following formula (a3-2). [ka] (In equations (a3-1) and (a3-2), R α1 This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R 32 and R 33 Each of these is independently a divalent aromatic ring group or a chain-like hydrocarbon group. R A1 , R A2 and R A3 This is equivalent to the above formula (a3).

[0068] In the above equations (a3-1) and (a3-2), R 32 , R 33 The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalylene 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.

[0069] In terms of obtaining a pattern (cured film) with higher heat resistance and hardness, and increasing the solubility of the exposed area in alkaline developer, R 32 , R 33Among 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.

[0070] Specific examples of structural units represented by the above formula (a3-1) include the structural units represented by the following formulas (a3-1-1) and (a3-1-2). Furthermore, specific examples of structural units represented by the above formula (a3-2) include the structural units represented by the following formulas (a3-2-1) and (a3-2-2). [ka] (In equations (a3-1-1), (a3-1-2), (a3-2-1), and (a3-2-2), R 34 and R 35 Each of these is an alkyl group having 1 to 4 carbon atoms. R 36 These are alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, or hydroxyl groups. n3 is an integer between 1 and 4. A 1 , A 2 n1 and n2 are equivalent to equations (i) and (ii) above. R α1 This is equivalent to equations (a3-1) and (a3-2) above.

[0071] Specific examples of monomers constituting structural unit (VII) include, for example, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinylnaph Examples include (thyl)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.

[0072] When polymer (A) contains structural unit (VII), the lower limit of the content of structural unit (VII) (or the total content if multiple types are included) is preferably 10% by mass, more preferably 20% by mass, and even more preferably 30% by mass, relative to the total structural units constituting the base polymer (A). The upper limit of the above content is preferably 80% by mass, and more preferably 70% by mass.

[0073] The base polymer (A) may contain structural units (V) and (VI), as described later, in addition to the structural units (I) to (IV) and (VII) described above.

[0074] When polymer (A) contains structural units (V), the upper limit of the content of structural units (V) (or the total content if multiple types are included) is preferably 35% by mass, more preferably 30% by mass, and even more preferably 25% by mass, relative to the total structural units constituting the base polymer (A). The lower limit is not particularly limited and may not include structural units at all, but may be around 1% by mass.

[0075] When polymer (A) contains structural unit (VI), the upper limit of the content of structural unit (VI) (or the total content if multiple types are included) is preferably 30% by mass, more preferably 25% by mass, even more preferably 20% by mass, and particularly preferably 15% by mass, relative to the total structural units constituting the base polymer (A). The lower limit is not particularly limited and may not be included at all, but may be around 1% by mass.

[0076] The upper limit of the total content of structural units (V) and (VI) in polymer (A) (or the total content if multiple types are included) is preferably less than 55% by mass, more preferably 53% by mass, even more preferably 50% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer (A). The lower limit of the above content is not particularly limited and may not include any structural units, but may be around 1% by mass.

[0077] (Method for synthesizing polymer (A1)) Polymer (A1) can be produced, for example, by using an unsaturated monomer into which each of the above-mentioned structural units can be introduced, in a suitable solvent in the presence of a polymerization initiator, according to known methods such as radical polymerization.

[0078] 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. The amount of polymerization initiator used is preferably 0.01 to 30 parts by mass per 100 parts by mass of the total amount of monomers used in the reaction.

[0079] 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 amount of the reaction solution.

[0080] In polymerization, the reaction temperature is typically 30 to 180°C. The reaction time varies depending on the type of polymerization initiator and monomer and the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction may be used in the preparation of the radiation-sensitive 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 radiation-sensitive 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.

[0081] The weight-average molecular weight (Mw) of the polymer (A) in terms of polystyrene, determined by gel permeation chromatography (GPC), is preferably 2,000 or more. An Mw of 2,000 or more is preferable because it allows for the production of a cured film with sufficiently high heat resistance and chemical resistance, as well as good developability. The Mw of the polymer is more preferably 5,000 or more, even more preferably 6,000 or more, and particularly preferably 7,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less.

[0082] Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is preferably 4.0 or less, and more preferably 3.0 or less. 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.

[0083] The content of polymer (A) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on the total amount of solids contained in the radiation-sensitive composition. Furthermore, the content of polymer (A) is preferably 95% by mass or less, and more preferably 90% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. Setting the content of polymer (A) within the above range is preferable because it allows for the production of a cured film that exhibits sufficiently high chemical resistance, as well as good developability and transparency.

[0084] (Polyimide polymer (A2)) The polyimide polymer (A2) is a polycondensate of a tetracarboxylic dianhydride and a diamine compound, and has an imide ring structure.

[0085] The imidization rate of the polyimide polymer (A2) is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. When the imidization rate is within the above range, the solubility of the polyimide polymer (A2) in the alkaline developer does not become too high, and a radiation-sensitive composition exhibiting good resolution can be obtained. From the viewpoint of ease of synthesis, the imidization rate is preferably 99% or less, and more preferably 95% or less. The imidization rate is expressed as a percentage of the ratio of the number of imid ring structures to the total number of amic acid structures and imid ring structures of the polyimide.

[0086] Polyimide polymers (A2) can be obtained by synthesizing polyamic acid by reacting a tetracarboxylic dianhydride with a diamine compound, and then imidizing the polyamic acid by dehydration and cyclization.

[0087] (Tetracarboxylic acid dianhydride) Examples of tetracarboxylic dianhydrides that constitute the polyimide polymer (A2) include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides.

[0088] Herein, in this specification, "aliphatic tetracarboxylic dianhydride" means a tetracarboxylic dianhydride in which the two acid anhydride groups (-CO-O-CO-) of the tetracarboxylic dianhydride are bonded to a linear or cyclic aliphatic group. That is, an aliphatic tetracarboxylic dianhydride may be a linear tetracarboxylic dianhydride in which the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to a linear structure, or it may be an alicyclic tetracarboxylic dianhydride in which the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to the same or different aliphatic rings, or one of the two acid anhydride groups is bonded to an aliphatic ring and the other is bonded to a linear structure. In addition, an aliphatic tetracarboxylic dianhydride may have an aromatic ring structure insofar as the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to a linear or cyclic aliphatic group. "Aromatic tetracarboxylic dianhydride" means a tetracarboxylic dianhydride in which one or more of the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to an aromatic ring. In aromatic tetracarboxylic dianhydrides, when two acid anhydride groups are both bonded to an aromatic ring, the two acid anhydride groups may be bonded to the same aromatic ring or to different aromatic rings.

[0089] Specific examples of tetracarboxylic dianhydrides constituting polyimide polymers (A2) include, as chain-like tetracarboxylic dianhydrides, 1,2,3,4-butanetetracarboxylic dianhydride and ethylenediaminetetraacetic acid dianhydride. Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, and 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3 Examples include -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 acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, and 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride. Examples of aromatic tetracarboxylic acid dianhydrides include pyromellitic acid dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-carbonyldiphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride. Among these, alicyclic tetracarboxylic dianhydrides are preferred, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is more preferred.

[0090] For the polyimide polymer (A2), the content of structural units derived from aliphatic tetracarboxylic dianhydride is 60 mol% or more relative to the total amount of structural units derived from tetracarboxylic dianhydride in the polyimide polymer (A2). If the content of structural units derived from aliphatic tetracarboxylic dianhydride is less than 60 mol%, the solubility of the polyimide polymer (A2) in the solvent is insufficient, and the coatability of the composition and the surface flatness of the cured film obtained from the composition tend to be poor. In addition, the solubility of tetracarboxylic dianhydride in the polymerization solvent is insufficient, resulting in a low monomer concentration in the polymerization solvent, which tends to lead to poor productivity of the polyimide polymer (A2). From this viewpoint, the content of structural units derived from aliphatic tetracarboxylic dianhydride is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, relative to the total amount of structural units derived from tetracarboxylic dianhydride in the polyimide polymer (A2).

[0091] (Diamine compounds) Examples of diamine compounds that constitute polyimide polymers (A2) include aliphatic diamines and aromatic diamines.

[0092] Hereinafter, in this specification, "aliphatic diamine" means a diamine compound in which two primary amino groups (-NH2) of the diamine compound are bonded to a linear or cyclic aliphatic group. That is, an aliphatic diamine may be a linear diamine in which two primary amino groups of the diamine compound are bonded to a linear structure, or it may be an alicyclic diamine in which two primary amino groups of the diamine compound are bonded to the same or different aliphatic rings, or one of the two primary amino groups is bonded to an aliphatic ring and the other is bonded to a linear structure. In addition, an aliphatic diamine may have an aromatic ring structure as long as the two primary amino groups of the diamine compound are bonded to a linear or cyclic aliphatic group. "Aromatic diamine" means a diamine compound in which one or more of the two primary amino groups of the diamine compound are bonded to an aromatic ring. In an aromatic diamine, when two primary amino groups are both bonded to an aromatic ring, the two primary amino groups may be bonded to the same aromatic ring or to different aromatic rings.

[0093] [Specific Diamines] The diamine constituting the polyimide polymer (A2) preferably has at least one functional group selected from the group consisting of a phenolic hydroxyl group, a carboxyl group, a thiophenol group, and a sulfo group (-SO3H) (hereinafter also referred to as "functional group (F1)"). The number of functional groups (F1) that the specific diamine has is not particularly limited. The number of functional groups (F1) that the specific diamine has is preferably 1 to 6, and more preferably 2 to 4. Among the above, the functional group (F1) is preferably a phenolic hydroxyl group in terms of solubility in alkaline developer and transparency of the cured film.

[0094] The molecular weight of the specific diamine is not particularly limited. In terms of high solubility in the polymerization solvent and the ability to achieve a high monomer concentration in the polymerization solvent, the molecular weight of the specific diamine is preferably 300 or higher, more preferably 350 or higher, even more preferably 450 or higher, and particularly preferably 500 or higher. Furthermore, from the viewpoint of improving the coatability of the composition and the surface flatness of the cured film obtained from this composition, the molecular weight of the specific diamine is preferably 850 or lower, and more preferably 750 or lower.

[0095] In terms of high solubility in polymerization solvents and, consequently, the ability to increase the polyimide concentration in the reaction solution obtained by polymerization, it is preferable that the specific diamine has at least one substructure selected from the group consisting of a fluorene ring structure, an indene ring structure, an indan ring structure, a lactone ring structure, a steroid structure, and an alkyl halide structure. Among these, diamines having a fluorene ring structure are preferred due to their high solubility in polymerization solvents.

[0096] From the viewpoint of ensuring solubility in the polymerization solvent while improving the surface flatness of the cured film obtained with this composition, the specific diamine is preferably an aromatic diamine. Specific examples of the specific diamine include compounds represented by the following formulas (A2-1) to (A2-7). [ka]

[0097] [Other diamines] The diamine compound constituting the polyimide polymer (A2) may consist solely of a specific diamine, or it may be a combination of a specific diamine and a diamine without a functional group (F1) (hereinafter also referred to as "other diamines"). Examples of other diamines include aliphatic diamines, aromatic diamines, and diaminoorganosiloxanes. Examples of aliphatic diamines include linear diamines and alicyclic diamines.

[0098] Other specific examples of diamines include, as chain-like diamines, metaxylylenediamine and hexamethylenediamine. Examples of alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine). Examples of aromatic diamines include 1,1-bis(4-aminophenyl)cyclopentane, 1,1-bis(4-aminophenyl)cyclohexane, 1,1-bis(4-aminophenyl)cycloheptane, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, and 1,3 -Bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy)hexane, 6,6'-(pentamethylenedioxy)bis(3-aminopyridine), N,N'-di(5-amino-2-pyridyl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, bis[2-(4-aminophenyl)ethyl]hexanediic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenethylurea, 2,2-bis[4-(4- [aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(phenylenediisopropylidene)bisaniline, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 3,6-diamino Cryzine, N4,N4'-bis(4-aminophenyl)-N4,N4'-dimethylbenzidine, N,N'-bis(5-aminopyridine-2-yl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,Examples include 4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholestanil 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanostanil 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-diaminobenzoate=5ξ-cholestane-3-yl, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, etc. Examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and 1,3-bis(4-anilino)tetramethyldisiloxane.

[0099] For the polyimide polymer (A2), the content of structural units derived from a specific diamine is preferably 30 mol% or more relative to the total amount of structural units derived from the diamine compound in the polyimide polymer (A2). If the content of structural units derived from a specific diamine is less than 30 mol%, the solubility of the polyimide polymer (A2) in the alkaline developer is insufficient, and the resolution tends to be poor. Furthermore, from the viewpoint of suppressing excessive solubility in the developer of unexposed areas and maintaining good resolution of this composition, the content of structural units derived from a specific diamine is preferably 99 mol% or less, and more preferably 95 mol% or less, relative to the total amount of structural units derived from the diamine compound in the polyimide polymer (A2).

[0100] Polyimide polymers (A2) can be obtained by dehydrating and cyclizing polyamic acid to imidize it. The method for synthesizing polyamic acid is not particularly limited, but for example, the method described in Japanese Patent Application Publication No. 2023-177343 can be suitably employed.

[0101] The weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyimide-based polymer (A2) is preferably 1,000 or more and 500,000 or less, more preferably 2,000 or more and 300,000 or less. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number-average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 5 or less, more preferably 4 or less.

[0102] (Siloxane polymer (A3)) The above siloxane polymer (A3) is not particularly limited as long as it has a structural unit (α) and a structural unit (β) and can form a cured film by hydrolysis and condensation. The siloxane polymer (A3) is preferably a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (9). [Chemical formula] (In formula (9), R 91 is a non-hydrolyzable monovalent group. R 92 is an alkyl group having 1 to 4 carbon atoms. r is an integer from 0 to 3. However, when r is 2 or 3, a plurality of R 91 in the formula are the same group or different groups from each other. When r is from 0 to 2, a plurality of R 92 in the formula are the same group or different groups from each other.)

[0103] R 91 Examples of R

[0104] R 92 include, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a group having a (meth)acryloyl group, and a group having an epoxy group.

[0104] R 92 include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a tert-butyl group, etc. Among these, in terms of high hydrolyzability, R92 A methyl group or an ethyl group is preferred.

[0105] r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0106] Specific examples of monomers that make up siloxane polymers include: Examples of silane compounds having four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetra-n-propoxysilane; Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, etc. Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane; Examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane, respectively.

[0107] Of the above monomers, silane compounds having an acidic group can be used as the monomer that gives structural unit (α). Also, silane compounds having a cyclic ether group (preferably an epoxy group) can be used as the monomer that gives structural unit (β).

[0108] Siloxane polymers can be obtained by hydrolyzing and condensing one or more of the above hydrolyzable silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis and condensation reaction, the proportion of water used depends on the hydrolyzable group (-OR) of the hydrolyzable silane compound. 92 The amount of water is preferably 0.1 to 3 moles, more preferably 0.2 to 2 moles, and even more preferably 0.5 to 1.5 moles, per 1 mole of the total amount of ). By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

[0109] Examples of catalysts used in the hydrolysis-condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and is set appropriately, but is preferably 0.0001 to 0.2 moles, and more preferably 0.0005 to 0.1 moles, per mole of hydrolyzable silane compound. Examples of organic solvents used include hydrocarbons, ketones, esters, ethers, and alcohols. The proportion of organic solvent used is preferably 10 to 10,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the total hydrolyzable silane compound used in the reaction.

[0110] During the hydrolysis-condensation reaction, the reaction temperature is preferably 130°C or lower, and more preferably 40-100°C. The reaction time is preferably 0.5-24 hours, and more preferably 1-12 hours. During the reaction, the mixture may be stirred or kept under reflux. After the hydrolysis-condensation reaction, a dehydrating agent may be added to the reaction solution, and then water and the resulting alcohol may be removed from the reaction system by evaporation.

[0111] The lower limit of the polymer (A) content is preferably 40% by mass, more preferably 50% by mass, and even more preferably 60% by mass, based on the total amount of solids contained in the radiation-sensitive composition.

[0112] <Copolymer (C)> The copolymer (C) contains a structural unit (V) represented by the following formula (1) and a structural unit (VI) derived from at least one compound selected from the group consisting of maleimide, N-substituted maleimide, and maleic anhydride. The structural units (V) and (VI) may be contained in the same polymer chain, or the structural unit (V) may be contained in one polymer chain and the structural unit (VI) may be contained in another polymer chain, as long as the polymer (C) as a whole contains the structural unit (V) and the structural unit (VI). From the viewpoint of sensitivity, it is preferable to contain a polymer chain having both the structural units (V) and (VI). Further, the copolymer (C) contains 55% by mass or more in total of the structural units (V) and (VI) with respect to all the structural units constituting the copolymer.

[0113] [Structural unit (V)] The structural unit (V) is represented by the following formula (1). [Chemical formula] (In formula (1), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ar is an aromatic ring structure. R 1 is a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a monovalent organic group having 1 to 20 carbon atoms. When there are a plurality of Rs 1 , the plurality of Rs 1 are each the same or different. n1 is an integer of 0 to 10.)

[0114] The aromatic ring structure represented by Ar above is not particularly limited as long as it is an aromatic ring structure. Examples of aromatic ring structures include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, anthracene rings, phenalene rings, phenanthrene rings, pyrene rings, fluorene rings, perylene rings, and coronene rings; heteroaromatic rings such as furan rings, pyrrole rings, thiophene rings, phosphole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, carbazole rings, and dibenzofuran rings; or combinations thereof. Among these, benzene rings and naphthalene rings are preferred as aromatic rings, with benzene rings being more preferred.

[0115] The above R 1 Examples of monovalent organic groups having 1 to 20 carbon atoms represented by this formula 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 this 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] Examples of the above-mentioned monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthyl groups; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl groups.

[0120] Examples of heteroatoms that constitute the monovalent heteroatom-containing groups and divalent heteroatom-containing groups mentioned above include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, and halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0121] 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.

[0122] Examples of the above-mentioned divalent heteroatom-containing groups include -CO-, -C(=O)O-, -CS-, -NH-, -O-, -S-, -SO-, -SO2-, or combinations thereof.

[0123] Among these, the above R 1 Preferably, it is at least one selected from the group consisting of a carboxyl group, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a group represented by the following formula (a). Also, R 1 Preferably, it does not contain silicon atoms. [ka] (In formula (a), m is an integer between 1 and 3. The asterisk (*) represents a bond with a carbon atom in the aromatic ring.

[0124] m is an integer between 1 and 3, preferably 1 or 2, and more preferably 1.

[0125] n1 is an integer between 0 and 10, preferably between 0 and 3, and more preferably 0 or 1.

[0126] The above structural unit (V) is preferably represented by the following formula (1-1). [ka] (In formula (1-1), R A This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 1 R is a halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, or monovalent organic group with 1 to 20 carbon atoms. 1 If multiple R 1 They are either the same or different. p is either 0 or 1. n3 is an integer between 0 and 7, where n3 ≤ 2p + 5.

[0127] R A , R 1 This is equivalent to equation (1).

[0128] p is either 0 or 1, and 0 is preferred.

[0129] n3 is an integer between 0 and 7, preferably between 0 and 3, and more preferably 0 or 1.

[0130] Examples of monomers that give the above structural unit (V) 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, 2-isopropenylphenol, 3-isopropenylphenol, 4-isopropenylphenol, 4-vinylbenzoic acid, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 4-hydroxystyrene, vinylnaphthalene, divinylnaphthalene, vinylpyridine, and the like. Of these, styrene compounds are preferred as the structural unit (V). Note that some of the monomers may be monomers that give structural unit (I) (e.g., 4-isopropenylphenol) or monomers that give structural unit (II) (e.g., 4-vinylbenzylglycidyl ether), but in polymer (C), these are included as structural unit (V).

[0131] The lower limit of the content of structural units (V) (total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, even more preferably 15% by mass, and particularly preferably 20% by mass, relative to the total structural units constituting the base polymer (C). The upper limit of the above content is preferably 60% by mass, more preferably 55% by mass, and even more preferably 50% by mass. It is preferable to set the content of structural units (V) within the above range because it is possible to achieve better radiation sensitivity, transmittance, and dry etching resistance.

[0132] (Structural Unit (VI)) Structural unit (VI) is a structural unit derived from at least one compound selected from the group consisting of maleimides, N-substituted maleimides, and maleic anhydride.

[0133] It is preferable that the above structural unit (VI) is a structural unit represented by the following formula (2). [ka] (In formula (2), R 2 (This refers to a hydrogen atom, a substituted or unsubstituted hydrocarbon group.)

[0134] As a hydrocarbon group, R in formula (1) above 1 A monovalent hydrocarbon group having 1 to 20 carbon atoms can be suitably used in this. Among these, the above R 2 Preferably, it is at least one selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alicyclic hydrocarbon group, and a substituted or unsubstituted aromatic hydrocarbon group.

[0135] As for the N-substituted maleimides that give the above structural unit (VI), Examples of compounds having a chain-like hydrocarbon group include N-methylmaleimide, N-propylmaleimide, N-butylmaleimide, etc. Examples of compounds having alicyclic hydrocarbon groups 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, etc. Examples of compounds having aromatic hydrocarbon groups include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-(4-carboxyphenyl)maleimide, N-(4-hydroxyphenyl)maleimide, etc. Each of these can be listed.

[0136] Among the above, maleimide, maleic anhydride, N-methylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-(4-carboxyphenyl)maleimide, N-(4-hydroxyphenyl)maleimide, or N-(4-hydroxyphenyl)maleimide are preferred.

[0137] The lower limit of the content of structural unit (VI) (total content if multiple types are included) is preferably 15% by mass, more preferably 20% by mass, even more preferably 25% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer (C). The upper limit of the above content is preferably 80% by mass, more preferably 75% by mass, and even more preferably 70% by mass. It is preferable to set the content of structural unit (VI) within the above range because it is possible to achieve better radiation sensitivity, transmittance, and dry etching resistance.

[0138] The lower limit of the total content of structural units (V) and (VI) in polymer (C) (or the total content if multiple types are included) is 55% by mass, preferably 60% by mass, and more preferably 80% by mass, relative to the total structural units constituting the base polymer (C). The upper limit of the above content is preferably 95% by mass, and more preferably 90% by mass. It is preferable to set the total content of structural units (V) and (VI) within the above range because it allows for the expression of better radiation sensitivity, transmittance, and dry etching resistance.

[0139] (Other monomers) The polymer (C) described above may contain structural units other than structural units (V) and structural unit (VI), and more preferably further contains at least one structural unit selected from the group consisting of structural units (I), structural unit (III), and structural unit (II), and more preferably further contains at least one structural unit selected from the group consisting of structural units having an acidic group, structural units derived from alkyl (meth)acrylate, and structural units having a cyclic ether group.

[0140] When polymer (C) contains structural unit (I), the lower limit of the content of structural unit (I) (or the total content if multiple types are included) is preferably 0.5% by mass, more preferably 1% by mass, and even more preferably 3% by mass, relative to all structural units constituting the base polymer (C). The upper limit of the above content is preferably 15% by mass, and more preferably 10% by mass. It is preferable to set the content of structural unit (I) within the above range because it can impart good solubility to alkaline developing solution. If structural unit (V) and structural unit (VI) in polymer (C) have acidic groups, structural unit (V) and structural unit (VI) may overlap with structural unit (I), and if structural unit (V) and structural unit (VI) have cyclic ether groups, structural unit (V) and structural unit (VI) may overlap with structural unit (II). For example, 4-isopropenylphenol can be classified as either structural unit (V) or structural unit (I), but the content of 4-isopropenylphenol may be counted as either structural unit (V) or structural unit (I).

[0141] When polymer (C) contains structural unit (III), the lower limit of the content of structural unit (III) (or the total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer (C). The upper limit of the above content is preferably 90% by mass, and more preferably 80% by mass. Setting the content of structural unit (III) within the above range is preferable because it allows the glass transition temperature of polymer (C) to be raised to an appropriate level.

[0142] When polymer (C) contains structural units (II), the lower limit of the content of structural units (II) (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 (C). The upper limit of the above content is preferably 25% by mass, more preferably 20% by mass, and even more preferably 15% by mass. Setting the content of structural units (II) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured film to have sufficiently high heat resistance and chemical resistance.

[0143] The lower limit of the polymer (C) content is preferably 5 parts by mass, more preferably 8 parts by mass, and even more preferably 10 parts by mass, per 100 parts by mass of polymer (A). The upper limit of the polymer (C) content is preferably 60 parts by mass, more preferably 50 parts by mass, and even more preferably 40 parts by mass, per 100 parts by mass of polymer (A). Setting the polymer (C) content within the above range is advantageous because it allows for the acquisition of a cured film with excellent permeability.

[0144] (Method for synthesizing polymer (C)) As a method for synthesizing polymer (C), the synthesis method for polymer (A1) described above can be suitably employed.

[0145] <Quinone diazide compound (B)> This composition contains a quinone diazide compound (B) along with polymers (A) and (C) mentioned above. A positive pattern can be formed by irradiating this composition with radiation (visible light, ultraviolet light, far ultraviolet light, etc.).

[0146] Quinone diazide compounds are compounds that generate carboxylic acids upon irradiation with radiation. Examples of quinone diazide compounds include condensates of phenolic compounds or alcoholic compounds (hereinafter also referred to as "parent compounds") and orthonaphthoquinone diazide compounds. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the parent compound and an orthonaphthoquinone diazide compound. Specific examples of parent compounds include, for example, the compounds described in paragraphs

[0065] to

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

[0147] Specific examples of quinone diazide compounds 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-methyl Examples include ester compounds of a phenolic hydroxyl group-containing compound selected from ethyl]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 with 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, preferred quinone diazide compounds (C) are a condensate of 1,1,1-tri(p-hydroxyphenyl)ethane and 1,2-naphthoquinone diazide-5-sulfonic acid chloride, and a condensate of 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

[0148] These quinone diazide compounds (B) may be used alone or in combination of two or more.

[0149] The lower limit of the content of the above-mentioned quinone diazide compound (B) 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 total of polymers (A) and polymers (C) blended in this composition. The upper limit of the content of the quinone diazide compound (B) is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 16 parts by mass, per 100 parts by mass of the total of polymers (A) and polymers (C) blended in this composition. It is preferable to have a quinone diazide compound (B) content of 1 part by mass or more because sufficient carboxylic acid is generated by irradiation of this composition with radiation, the difference in solubility between the irradiated and unirradiated portions in the developer can be sufficiently large, and good patterning can be achieved. It is also preferable because the amount of carboxylic acid involved in the reaction with the polymer components can be increased, and sufficient heat resistance and chemical resistance can be ensured. Furthermore, even with an amount of quinone diazide compound (B) added of 20 parts by mass or less, or even 16 parts by mass or less, sufficient radiation sensitivity can be obtained, demonstrating that both radiation sensitivity and transparency can be achieved.

[0150] <Solvent (S)> The radiation-sensitive composition of this disclosure is a liquid composition in which a polymer (A), a polymer (C), a quinone diazide compound (B), and other components, which may be added as needed, are dissolved or dispersed in a solvent (S). The solvent used is preferably an organic solvent that dissolves each component of the radiation-sensitive composition and does not react with each component.

[0151] The solvent (S) is not particularly limited and can include, for example, alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. The solvent (S) may be used alone or in combination of two or more types.

[0152] Examples of alcohol-based solvents include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, alkyl alcohols such as diacetone alcohol, and aromatic alcohols such as benzyl alcohol.

[0153] Examples of ether-based solvents include ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0154] Examples of ester solvents include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyhydric alcohol carboxylate solvents such as propylene glycol diacetate; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; and lactone solvents such as γ-butyrolactone and valerolactone.

[0155] Examples of ketone-based solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0156] Among these, ether-based solvents and ester-based solvents are preferred, ester-based solvents are more preferred, and polyhydric alcohol partial ether carboxylate-based solvents are even more preferred. Furthermore, among ether-based solvents and ester-based solvents, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred.

[0157] The solvent (S) content in this composition is not particularly limited, but it is preferable that the composition be prepared so that the solid content (components other than solvent (S)) concentration is within the following ranges. The lower limit of the solid content concentration in this composition is preferably 5% by mass, more preferably 8% by mass, and even more preferably 15% by mass. On the other hand, the upper limit of the solid content concentration is preferably 60% by mass, and more preferably 40% by mass. A solid content concentration of 5% by mass or more in the radiation-sensitive composition is preferable because it ensures sufficient film thickness when the radiation-sensitive composition is applied to a substrate. Furthermore, a solid content concentration of 60% by mass or less is preferable because it prevents the film thickness from becoming excessively large, and allows for a moderately high viscosity of the radiation-sensitive composition, ensuring good coatability.

[0158] <Other ingredients> The radiation-sensitive composition of this disclosure may further contain, in addition to the polymer (A), polymer (C), quinone diazide compound (B), and solvent (S) described above, other components (hereinafter also referred to as "other components"). Examples of other components include reaction initiators (photoradical polymerization initiators, photocationic polymerization initiators, etc.), polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), adhesion aids (functional silane coupling agents, etc.), surfactants (fluorinated surfactants, silicone surfactants, nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The blending ratio of these components is appropriately selected according to each component, within a range that does not impair the effects of this disclosure.

[0159] The radiation-sensitive composition of this disclosure, comprising polymer (A), polymer (C), and quinone diazide compound (B), can exhibit excellent radiation sensitivity, transmittance, and dry etching resistance. Such a radiation-sensitive composition of this disclosure is useful as a radiation-sensitive composition for display elements such as liquid crystal display elements and organic EL display elements.

[0160] <Method for preparing a radiation-sensitive composition> The radiation-sensitive composition of the present invention can be prepared by mixing each component in a predetermined ratio and dissolving it in a solvent (S). The prepared composition is preferably filtered using, for example, a filter with a pore size of about 0.2 μm.

[0161] Interlayer insulating film The interlayer insulating film of the present invention can be formed by curing the radiation-sensitive composition prepared as described above.

[0162] This interlayer insulating film has excellent dry etching resistance, and it is preferable that the film surface Ra after RIE dry etching under conditions where the sccm ratio of CF4 to O2 is 1:5 is less than 10, and more preferably less than 7.

[0163] The thickness of the interlayer insulating film of the present invention is not particularly limited and can be set as appropriate depending on the purpose of use.

[0164] ≪Semiconductor Devices≫ The semiconductor device of this disclosure comprises an interlayer insulating film formed using the above-mentioned radiation-sensitive composition. The interlayer insulating film insulates the connections between wirings in the semiconductor device. The semiconductor device of this disclosure can be manufactured using known methods.

[0165] ≪Method for manufacturing interlayer insulating films≫ The method for manufacturing the interlayer insulating film according to this embodiment is as follows: (Step 1) A step of forming a coating film using a radiation-sensitive composition, (Step 2) A step of irradiating at least a portion of the above coating film with radiation, (Step 3) A step of developing the above coating film after irradiation with radiation, (Step 4) The process includes heating the developed coating film.

[0166] The following provides a detailed explanation of each step.

[0167] <Process 1: Paint film formation process> In this process, a radiation-sensitive composition is applied to the surface on which the film is to be formed (hereinafter also referred to as the "film-forming surface"), and preferably a heat treatment (pre-bake) is performed to remove the solvent and form a coating on the film-forming surface. The material of the film-forming surface is not particularly limited. Specifically, a radiation-sensitive composition is applied to a substrate on which switching elements such as TFTs are provided, and a coating is formed. Examples of substrates used include glass substrates, silicon substrates, and resin substrates. The surface of the substrate on which the coating is formed may have a thin metal film formed thereon depending on the application, and various surface treatments such as HMDS (hexamethyldisilazane) treatment may be applied.

[0168] Examples of methods for applying the radiation-sensitive composition include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, spin coating, slit die coating, or bar coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiation-sensitive composition, but are typically 60 to 130°C for 0.5 to 10 minutes. The thickness of the resulting coating film (i.e., the film thickness after pre-baking) is preferably 0.1 to 12 μm. Vacuum-cured drying (VCD) may be performed on the radiation-sensitive composition applied to the film-forming surface before pre-baking.

[0169] <Step 2: Exposure Process> In this step, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film with a pattern can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, for example, g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m². 2 It is preferable.

[0170] <Process 3: Development process> In this step, the coating film irradiated with radiation in step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 is developed with a developer to remove the irradiated portion, performing positive-type development. Examples of the developer include aqueous solutions of alkali (basic compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and alkalis exemplified in paragraph

[0127] of Japanese Patent Publication No. 2016-145913. From the viewpoint of obtaining appropriate developability, the alkali concentration in the aqueous alkali solution is preferably 0.1 to 5.0% by mass. Appropriate development methods include the liquid-filling method, dipping method, agitation immersion method, and shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, it is preferable to rinse the patterned coating film with running water.

[0171] <Step 4: Heating step> In this step, the coating developed in step 3 above is subjected to a heating process (post-bake). Post-bake can be performed using a heating device such as an oven or a hot plate. Regarding the post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when performing the heating process on a hot plate, and 10 to 80 minutes when performing the heating process 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.

[0172] Furthermore, a post-exposure step may be included between steps 3 and 4 described above. By irradiating the developed coating with radiation, a cured film with excellent melt flow resistance and transparency during the heating process can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, for example, g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2It is preferable.

[0173] The process may include a step of dry etching the cured film after step 4. Dry etching can be performed, for example, using a known dry etching apparatus. The etching gas used for dry etching can be appropriately selected depending on the mask pattern, the elemental composition of the film to be etched, etc. Examples include fluorine-based gases such as CHF3, CF4, C2F6, C3F8, SF6; chlorine-based gases such as Cl2, BCl3; oxygen-based gases such as O2, O3, H2O; reducing gases such as H2, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H4, C3H6, C3H8, HF, HI, HBr, HCl, NO, NH3, BCl3; and inert gases such as He, N2, Ar. These gases can also be used in mixtures. [Examples]

[0174] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" refer to mass unless otherwise specified. In these examples, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by the following method.

[0175] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The Mw and Mn of the polymer were measured by the following method. • Measurement method: Gel permeation chromatography (GPC) method • Equipment: Showa Denko Corporation's GPC-101 • GPC columns: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC Co., Ltd. • Mobile phase: tetrahydrofuran Column temperature: 40°C ·Flow rate: 1.0mL / min • Sample concentration: 1.0% by mass • Sample injection volume: 100 μL • Detector: Differential refractometer • Standard material: Monodisperse polystyrene

[0176] [monomer] The monomers used in the synthesis of the polymer are as follows:

[0177] (Structural unit (V)) M-1: Styrene M-2: α-methylstyrene M-3:4-methylstyrene M-4: 4-Isopropenylphenol (also serves as structural unit (I)) M-5: 4-Vinylbenzoic acid (also serves as structural unit (I)) M-6: 4-Vinylbenzylglycidyl ether (also serves as structural unit (II)) (Structural Unit (VI)) M-9:N-Cyclohexylmaleimide M-10: N-phenylmaleimide M-11: Maleimide (also serves as structural unit (I)) M-12: N-Propylmaleimide M-13: N-benzylmaleimide M-14: N-(4-carboxyphenyl)maleimide (also serves as structural unit (I)) (Structural Unit (I)) M-17: Methacrylic acid M-19:4-Hydroxyphenyl methacrylate (Structural Unit (II)) M-20: Glycidyl methacrylate M-21:3,4-Epoxycyclohexylmethyl methacrylate M-22: Methyl 3-ethyloxetane-3-yl methacrylate (Structural Unit (III)) M-23: Methyl acrylate (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate M-24: Methyl methacrylate (Structural Unit (IV)) M-25: N-vinylacetamide (Structural Unit (VII)) M-26: Triethoxysilylpropyl methacrylate [Chemical formula]

[0178] [Synthesis of Polymer (A-1)] 14 parts of dimethyl 2,2'-azobis(isobutyrate) and 200 parts of diethylene glycol methyl ethyl ether were charged into a flask equipped with a cooling pipe and a stirrer. Subsequently, 13 parts of methacrylic acid, 12 parts of 4-isopropenylphenol, 35 parts of glycidyl methacrylate, 5 parts of 3,4-epoxycyclohexylmethyl methacrylate, 9 parts of N-cyclohexylmaleimide, 10 parts of N-phenylmaleimide, 15 parts of acrylic acid (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl, and 1 part of methyl methacrylate were charged. After nitrogen substitution, while gently stirring, the temperature of the solution was raised to 80 °C and maintained at this temperature for 5 hours to obtain a polymer solution containing Polymer (A-1). The solid content concentration of this polymer solution was 35.0% by mass, the weight average molecular weight (Mw) of Polymer (A-1) was 9,700, and the molecular weight distribution (Mw / Mn) was 2.9. The ratio of each structural unit of Polymer (A-1) was equivalent to the charging ratio of the corresponding monomer. Table 1 shows the components of the monomers used in the synthesis. In Table 1, "-" indicates that the corresponding component was not used. The same applies to the following tables.

[0179] [Synthesis of Polymers (A-2) to Polymers (A-5)] A polymer solution containing Polymers (A-2) to Polymers (A-5) having a solid content concentration, weight average molecular weight, and molecular weight distribution equivalent to those of Polymer (A-1) was obtained by the same method as Polymer (A-1), except that the components of the types and amounts (parts by mass) shown in Table 1 were used.

Table 1

[0180] [Synthesis of Siloxane Polymer (A-6)] In a 2 L three-necked flask equipped with a thermometer, condenser, and stirrer, 30 parts by mass of tetramethoxysilane, 30 parts by mass of propyltrimethoxysilane, and 40 parts by mass of phenyltrimethoxysilane were placed and slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by mass of 5% aqueous acetic acid solution were added dropwise, and the temperature was increased by 5°C per minute to 60°C. The temperature was maintained for 12 hours to carry out condensation polymerization, and the reaction was terminated by cooling to room temperature. Subsequently, the catalyst and unreacted monomers were removed by washing with water and extraction. 30 parts by mass of propylene glycol methyl ether acetate (PGMEA) was added and distilled under reduced pressure to produce a siloxane polymer (A-6) with a solid content of 40%. The weight-average molecular weight of the siloxane polymer was 6,500 (g / mol). In this case, the weight-average molecular weight was the polystyrene-equivalent weight-average molecular weight measured using GPC, and the weight-average molecular weight was measured using the standard analytical method of a gel permeation chromatography (GPC) system using the Waters e2695 Alliance Separation Module.

[0181] [Synthesis of polyimide polymer (A-7)] 100 moles of (AN-1) as a tetracarboxylic dianhydride, 72 moles of (DA-1) and 28 moles of (DA-2) as diamines, and 10 moles of (MA-1) as a monoamine were dissolved in γ-butyrolactone (GBL) and reacted at 40°C for 2 hours to obtain a solution containing 30% by mass of polyamic acid. Next, GBL was added to the obtained polyamic acid solution, and pyridine and acetic anhydride were added in amounts of 2.50 moles each relative to the carboxyl groups of the polyamic acid, and a dehydration and cyclization reaction was carried out at 120°C for 4 hours. After the dehydration and cyclization reaction, the solvent in the system was replaced with fresh GBL, and the solution was further concentrated to obtain a solution containing 25% by mass of polyimide with an imidization rate of 89% (referred to as "polymer (PI-1)"). A small amount of this solution was taken, and GBL was added to make a 10% by mass solution. The viscosity of the solution measured was 30 mPa·s. Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained polymer (A-7) were 9400 and 2900, respectively. The imidation rate of the obtained polymer was 90%. The imidation rate was measured by the following method.

[0182] <Imidification rate of polyimides> A polyimide solution was added to pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature. Then it was dissolved in deuterated dimethyl sulfoxide, with tetramethylsilane as the reference substance, at room temperature. 1 1H-NMR measurements were performed. 1 The imidization rate (%) was determined from the 1H-NMR spectrum using the following formula. Imidization rate (%) = (1 - (β) 1 / ( β 2 ×α)))×100 (1) (In the formula, β 1 This represents the peak area originating from the proton of the NH group, appearing around a chemical shift of 10 ppm, and β 2 α represents the peak area derived from other protons, and α is the ratio of other protons to one proton of the NH group in the polymer precursor (polyamic acid).

[0183] [Synthesis of polymer (C-1)] Fourteen parts of 2,2'-azobis(isobutyrate)dimethyl and 200 parts of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer. Subsequently, 33 parts of styrene, 57 parts of N-cyclohexylmaleimide, and 10 parts of glycidyl methacrylate were charged. After purging with nitrogen, the solution temperature was raised to 90°C while gently stirring, and this temperature was maintained for 4 hours to obtain a polymer solution containing polymer (C-1). The solid content concentration of this polymer solution was 36.0% by mass, the Mw of polymer (C-1) was 7,800, and the molecular weight distribution (Mw / Mn) was 2.5. The proportion of each structural unit of the polymer was equivalent to the charging ratio of the corresponding monomers.

[0184] [Polymer (C-2)~(C-16)] Polymer solutions containing polymers (C-2) to (C-16) having the same solid content concentration, molecular weight, and molecular weight distribution as polymer (C-1) were obtained using the same method as for polymer (C-1), except that the components used were of the types and amounts (parts by mass) shown in Table 2. [Table 2]

[0185] <Preparation of radiation-sensitive composition> A radiation-sensitive composition was prepared using the polymer synthesized above. The polymer and radiation-sensitive compound used in the preparation of the radiation-sensitive composition are shown below.

[0186] (polymer) A-1 to A-7: The polymers synthesized above (A-1) to (A-7) C-1~C-16: The polymers synthesized above (C-1)~(C-16)

[0187] (Radiation sensitive compound) B-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)

[0188] [Example 1] To a polymer solution containing 90 parts by mass (solid content) of (A-1) as polymer (A), 10 parts by mass (solid content) of (C-1) as polymer (C), and 14 parts by mass of radiation-sensitive compound (B-1) were mixed, and propylene glycol monomethyl ether acetate was added at a ratio (mass ratio) of 40% by mass in the total solvent, propylene glycol monomethyl ether was added at 45% by mass in the total solvent, and diethylene glycol methyl ethyl ether was added at 15% by mass in the total solvent so that the final solid content concentration became 20% by mass. Then, it was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0189] [Examples 2 to 20, Comparative Examples 1 to 10] Radiation-sensitive compositions of Examples 2 to 20 and Comparative Examples 1 to 10 were prepared in the same manner as in Example 1, except that the components of the types and blending amounts (parts by mass) shown in Table 3 were used.

[0190] [Evaluation] Interlayer insulating films were formed using the radiation-sensitive compositions (S-1) to (S-20), (CS-1) to (CS-10) of Examples 1 to 20 and Comparative Examples 1 to 10, and the following items were evaluated by the method described below. The evaluation results are shown in Table 3.

[0191] [Radiation Sensitivity] Hexamethyldisilazane (HMDS) was applied to a 6-inch glass wafer using a spinner and heated at 60°C for 1 minute (HMDS treatment). Each of the radiation-sensitive compositions prepared as described above was then applied to the HMDS-treated wafer using a spinner. The spin rate was adjusted to achieve a post-baking film thickness of 3.0 μm. Subsequently, a 4.8 μm thick coating film was formed by drying at 30 Pa for 1 second in a small vacuum drying apparatus, followed by pre-baking at 93°C for 3 minutes. Next, the coating film was exposed using an exposure machine (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp) with varying exposure levels through a mask having a 10 μm × 10 μm rectangular exposure area. Finally, development was performed using a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23°C using the liquid-fill method. The development time was 85 seconds. Next, the wafer was rinsed with ultrapure water for 1 minute, and then dried to form a pattern on the HMDS-treated wafer. 300 mJ / cm² was applied to the entire surface of the coating. 2 The wafer was exposed to light, and then post-baked in a clean oven at 230°C for 30 minutes to obtain a cured film. The amount of exposure required to form a 10 μm × 10 μm pattern during development was investigated. A smaller exposure amount indicates better radiation sensitivity. (Evaluation Criteria) A: 85 mJ / cm 2 less than B: 85mJ / cm 2 More than 100mJ / cm 2 less than C: 100mJ / cm 2 More than 120mJ / cm 2 less than D: 120 mJ / cm 2 That's all.

[0192] [Transmittance] Each of the prepared radiation-sensitive compositions was applied to a 6-inch glass wafer using a spinner. The spin rate was adjusted so that the film thickness after post-baking was 3.0 μm. Subsequently, a 4.8 μm thick coating film was formed by drying at 30 Pa for 1 second in a small vacuum drying apparatus, followed by pre-baking at 93°C for 3 minutes. Then, it was developed by the liquid-build method with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23°C for 85 seconds. Next, a pattern was formed on the HMDS-treated wafer by running water rinsing with ultrapure water for 1 minute and then drying. 300 mJ / cm² was applied to the entire coating film. 2 The wafer was exposed to light, and then post-baked in a clean oven at 230°C for 30 minutes to obtain a cured film. The transmittance of the obtained cured film at a wavelength of 400 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (JASCO Corporation's "V-760"). (Evaluation Criteria) A: Over 96% B: 93% or more, less than 96% C: 90% or more, less than 93% D: Less than 90%

[0193] [Dry etching resistance] A radiation-sensitive composition was applied to a silicon substrate that had been HMDS-treated at 60°C for 60 seconds using a spinner. The composition was then pre-baked on a hot plate at 93°C for 3 minutes to form a coating with an average thickness of 5.0 μm. This coating was then developed at 23°C using a 0.5% by mass aqueous solution of tetramethylammonium hydroxide by the liquid-filling method for 85 seconds. Afterward, the coating was exposed to UV light for a total exposure of 300 mJ, and then heated at 230°C for 30 minutes to obtain a cured film. The resulting cured film was then RIE dry-etched for 200 seconds at a power output of 250 W and a gas ratio of CF4:O2 = 1:5 (measured by sccm). The roughness (Ra) of the film was measured using an atomic force microscope. A smaller Ra value indicates higher dry etching resistance. (Evaluation Criteria) A: Less than 10nm B: 10nm to less than 20nm C:20nm or more

[0194] [Table 3]

[0195] As shown in Table 3, the radiation-sensitive compositions of Examples 1 to 20 exhibited good radiation sensitivity and excellent transmittance and dry etching resistance of the resulting interlayer insulating film. On the other hand, the radiation-sensitive compositions of Comparative Examples 1 to 10 were inferior to the examples in at least one of the following: radiation sensitivity, transmittance, and dry etching resistance.

Claims

1. Alkali-soluble polymer (A) (excluding polymer (C) below) and Quinone diazide compound (B) and A polymer (C) containing a structural unit (V) represented by the following formula (1), and a structural unit (VI) derived from at least one compound selected from the group consisting of maleimide, N-substituted maleimide, and maleic anhydride, wherein the total content of structural unit (V) and structural unit (VI) is 55% by mass or more relative to the total structural units constituting polymer (C), A radiation-sensitive composition containing a solvent (S). 【Chemistry 1】 (In formula (1), R Ａ This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ar has an aromatic ring structure. R １ R is a halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, or a monovalent organic group having 1 to 20 carbon atoms. １ If multiple R １ They are either the same or different. n1 is an integer between 0 and 10.

2. The radiation-sensitive composition according to claim 1, comprising 15% by mass or more of the structural unit (V) and 25% by mass or more of the structural unit (VI) with respect to all structural units constituting the polymer (C).

3. The radiation-sensitive composition according to claim 1, wherein the alkali-soluble polymer (A) is a polymer, siloxane polymer, or polyimide polymer containing structural units having an acidic group and structural units having a cyclic ether group.

4. The radiation-sensitive composition according to claim 1, wherein the above structural unit (V) is represented by the following formula (1-1). 【Chemistry 2】 (In formula (1-1), R Ａ This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R １ R is a halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, or a monovalent organic group having 1 to 20 carbon atoms. １ If multiple R １ They are either the same or different. p is either 0 or 1. n3 is an integer between 0 and 7, where n3 ≤ 2p + 5.

5. The radiation-sensitive composition according to claim 1, wherein the above structural unit (VI) is represented by the following formula (2). 【Transformation 3】 (In formula (2), R ２ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group.)

6. The above R １ The radiation-sensitive composition according to claim 4, wherein the group is at least one selected from the group consisting of a carboxyl group, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a group represented by the following formula (a). 【Chemistry 4】 (In formula (a), m is an integer between 1 and 3. The asterisk (*) represents a bond with a carbon atom in the aromatic ring.

7. The above R ２ The radiation-sensitive composition according to claim 5, wherein is at least one selected from the group consisting of substituted or unsubstituted alicyclic hydrocarbon groups and substituted or unsubstituted aromatic hydrocarbon groups.

8. The radiation-sensitive composition according to claim 1, wherein the polymer (C) contains a polymer chain having both structural unit (V) and structural unit (VI).

9. The radiation-sensitive composition according to claim 1, wherein the polymer (C) further comprises at least one structural unit selected from the group consisting of a structural unit having an acidic group, a structural unit derived from an alkyl (meth)acrylate, and a structural unit having a cyclic ether group.

10. The radiation-sensitive composition according to claim 1, wherein the content of polymer (C) is 5 parts by mass or more and 40 parts by mass or less per 100 parts by mass of polymer (A).

11. The radiation-sensitive composition according to claim 9, wherein the above-mentioned acidic group is at least one selected from the group consisting of a carboxyl group, a maleimide group, a sulfo group, a fluorine-containing alcoholic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phenolic hydroxyl group, and a phosphinic acid group.

12. A radiation-sensitive composition according to claim 1, for use in forming an interlayer insulating film.

13. A step of forming a coating film using the radiation-sensitive composition described in any one of claims 1 to 12, A step of irradiating at least a portion of the coating film with radiation, A step of developing the coating film that has been irradiated with radiation, A method for manufacturing an interlayer insulating film, comprising the step of heating the developed coating film.

14. A method for producing an interlayer insulating film according to claim 13, further comprising a step of dry etching after the above heating step.

15. A method for manufacturing an interlayer insulating film according to claim 13, comprising the step of irradiating the developed coating film with radiation.

16. An interlayer insulating film formed using the radiation-sensitive composition according to any one of claims 1 to 12.

17. A display element having an interlayer insulating film according to claim 16.

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