Radiation-sensitive composition for forming gate insulating film, pattern, method for producing pattern, cured film for gate insulating film, semiconductor element, organic electrochemical transistor, organic el display device, liquid crystal display device, micro-led display device, quantum dot light-emitting display device, wearable device, electronic skin device, biological sensor, and neuromorphic device

Abstract

The purpose of the present invention is to provide: a radiation-sensitive composition that makes it possible to form a gate insulating film which has elasticity and exhibits sufficient pattern formability and electrical capacitance, and furthermore in which bleed-out is suppressed; a pattern (cured film) formed from the radiation-sensitive composition and a method for producing said pattern; a cured film for a gate insulating film; a semiconductor element provided with said cured film; an organic electrochemical transistor; an organic EL display device; a liquid crystal display device; a micro LED display device; a quantum dot light-emitting display device; a wearable device; an electronic skin device; a biological sensor; and a neuromorphic device. The present invention relates to a radiation-sensitive composition for forming a gate insulating film, the composition containing a polymer (A) having a specific structure, a radiation-sensitive compound (B), and a large-amount ionic liquid (C) having a glass transition temperature of 0°C or lower.

Description

Radiation-sensitive composition for forming gate insulating film, pattern and method for producing same, cured film for gate insulating film, semiconductor element, organic electrochemical transistor, organic EL display device, liquid crystal display device, micro LED display device, quantum dot light-emitting display device, wearable device, electronic skin device, biosensor, and neuromorphic device

[0001] The present invention relates to a radiation-sensitive composition for forming a gate insulating film, a pattern and a method for producing the same, a cured film for a gate insulating film, a semiconductor element, an organic electrochemical transistor, an organic EL display device, a liquid crystal display device, a micro LED display device, a quantum dot light-emitting display device, a wearable device, an electronic skin device, a biosensor, and a neuromorphic device.

[0002] Field-effect transistors such as thin film transistors (TFTs) are widely used as unit electron elements in semiconductor memory integrated circuits, high-frequency signal amplifier elements, liquid crystal driving elements, etc. In particular, they are frequently used as switching elements in various display devices such as liquid crystal displays (LCDs) and organic electroluminescence (EL) display devices, which apply a driving voltage to a display element to drive the display device.

[0003] The thin film transistor generally comprises a semiconductor layer, a gate electrode, a source electrode, and a drain electrode, and a voltage is applied between the source electrode and the drain electrode from the gate electrode via a gate insulating film to control the current flowing through the semiconductor layer. Conventionally, the gate insulating film has been formed using an inorganic material, such as silicon oxide (SiO ２ ) and silicon nitride (SiN), etc. have been used.

[0004] In recent years, the development of flexible devices such as flexible displays has been actively carried out, and transistors such as TFTs are required to have elasticity so that they can be adapted to such flexible devices, and naturally, elasticity is also required for gate insulating films. However, gate insulating films formed from the above-mentioned inorganic materials have poor elasticity and may break.

[0005] Organic thin film transistors (OTFTs), whose constituent elements are made of organic materials, have attracted attention as flexible transistors, and have been the subject of much research and development in recent years. Furthermore, an ion gel, in which an ionic liquid is mixed with a positive photoresist made of cresol novolac to which naphthoquinone diazide is added as a photosensitizer, is known as an organic material for forming a gate insulating film (see, for example, Patent Document 1).

[0006] JP 2016-80998 A

[0007] In recent years, there has been a demand for the development of transistors that are stretchable enough to be compatible with flexible devices and have low driving voltages. The gate insulating films used in such transistors are also required to be stretchable, easy to pattern, and have high capacitance.

[0008] Furthermore, when a low-molecular-weight ionic liquid is added to a photosensitive composition, the low-molecular-weight ionic liquid may bleed out onto the surface of the cured film, or may become cloudy upon development, making patterning difficult.

[0009] Therefore, an object of the present invention is to provide a radiation-sensitive composition capable of forming a gate insulating film that has stretchability, exhibits sufficient pattern formability and electrical capacitance, and is further capable of suppressing bleed-out; a pattern (cured film) formed from the radiation-sensitive composition and a method for producing the same; a cured film for a gate insulating film; a semiconductor element, an organic electrochemical transistor, an organic EL display device, a liquid crystal display device, a micro LED display device, a quantum dot light-emitting display device, a wearable device, an electronic skin device, a biosensor, and a neuromorphic device that include the cured film.

[0010] As a result of extensive investigations aimed at solving the above problem, the present inventors have found that the above object can be achieved by blending a polymer (A) having a specific structure, a radiation-sensitive compound (B), and a polymerized ionic liquid (C) having a glass transition temperature of 5°C or less into a radiation-sensitive composition, and have thus completed the present invention.

[0011] In one embodiment, the present invention relates to a radiation-sensitive composition for forming a gate insulating film, comprising: at least one polymer (A) selected from the group consisting of a polymer (A1) containing a structural unit (I) having an acid group, a siloxane polymer (A2), and a polyamic acid or a polyamic acid ester (A3); a radiation-sensitive compound (B); and a polymerized ionic liquid (C) having a glass transition temperature of 5°C or lower.

[0012] In another embodiment, the present invention relates to a method for producing a pattern, the method including the steps of: applying the radiation-sensitive composition for forming a gate insulating film onto a substrate to form a coating film; irradiating at least a part of the coating film with radiation; and developing the radiation-irradiated coating film to form a pattern. The present invention also relates to a pattern obtained by the method for producing a pattern.

[0013] In another embodiment, the present invention relates to a cured film for a gate insulating film formed using the radiation-sensitive composition for forming a gate insulating film, and to a semiconductor element, an organic electrochemical transistor, an organic EL display device, a liquid crystal display device, a micro LED display device, a quantum dot light-emitting display device, a wearable device, an electronic skin device, a biosensor, or a neuromorphic device, each of which includes the cured film.

[0014] The radiation-sensitive composition for forming a gate insulating film of the present invention can construct a pattern (cured film) that is excellent in pattern formability and capacitance and suppresses bleed-out, and a transistor having the pattern (cured film) as a gate insulating film can be driven at a low voltage and also has elasticity. This is because the radiation-sensitive composition for forming a gate insulating film contains a polymerized ionic liquid (C), and when a pattern (cured film) obtained from the composition is used as a gate insulating film, an electric double layer is formed, thereby reducing the driving voltage of the transistor. Furthermore, the radiation-sensitive composition for forming a gate insulating film has superior elasticity compared to gate insulating films made of inorganic materials. Furthermore, because the polymerized ionic liquid (C) has a large molecular weight, a pattern (cured film) can be formed that suppresses bleed-out.

[0015] The pattern manufacturing method of the present invention uses the radiation-sensitive composition described above, which has good pattern formability and is capable of forming a pattern (cured film) with excellent pattern formability and capacitance and with suppressed bleed-out, and therefore can efficiently form a high-quality pattern (cured film). The pattern (cured film) of the present invention uses the radiation-sensitive composition, so it has excellent pattern formability and capacitance and with suppressed bleed-out.

[0016] The semiconductor elements, organic electrochemical transistors, organic EL displays, liquid crystal displays, micro LED displays, quantum dot luminescent displays, wearable devices, electronic skin devices, biosensors, and neuromorphic devices of the present invention are of high quality because they are provided with patterns (cured films) that have excellent pattern formability, electrical capacitance, and chemical resistance.

[0017] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0018] Matters related to the embodiments will be explained in detail below. In this specification, a numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0019] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure. However, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and it also includes groups that have a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not necessarily have to be composed solely of an aromatic ring structure, and it may also contain a chain structure or an alicyclic hydrocarbon structure as part of it. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure. The term "cyclic hydrocarbon group" refers to both alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0020] In this specification, "(meth)acryloyl" means to include "acryloyl" and "methacryloyl", "(meth)acrylic" means to include "acrylic" and "methacrylic", and "(meth)acrylate" means to include "acrylate" and "methacrylate".

[0021] <Radiation-Sensitive Composition> The radiation-sensitive composition according to this embodiment (hereinafter also simply referred to as "composition") includes at least one polymer (A) selected from the group consisting of a polymer (A1) including a structural unit (I) having an acid group, a siloxane polymer (A2), and a polyamic acid or a polyamic acid ester (A3).

[0022] The radiation-sensitive composition of the present invention has good pattern-forming properties, is capable of forming a pattern (cured film) that has excellent electric capacity and is suppressed from bleeding out, and therefore can be suitably used for forming a gate insulating film.

[0023] <Polymer (A)> The polymer (A) is at least one selected from the group consisting of a polymer (A1) containing a structural unit (I) having an acid group, a siloxane polymer (A2), and a polyamic acid or polyamic acid ester (A3).

[0024] (Polymer (A1)) The polymer (A1) is an assembly of polymers containing a structural unit (I) having an acid group (hereinafter, this assembly will also be referred to as a "base polymer"). The structural unit (I) may be contained in at least one polymer constituting the base polymer. The polymer (A1) may contain a structural unit other than the structural unit (I). Each structural unit contained in the polymer (A1) will be described below.

[0025] [Structural Unit (I)] The structural unit (I) having an acid group in the polymer (A1) can increase the solubility (alkali solubility) of the polymer (A1) in an alkaline developer and can increase the curing reactivity of the polymer (A1). In this specification, "alkali soluble" means that the polymer (A1) can be dissolved or swelled in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0026] The structural unit (I) is not particularly limited as long as it has an acid group, but is preferably at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. In this specification, the term "phenolic hydroxyl group" refers to a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0027] The structural unit (I) is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of the unsaturated monomer having an acid group include: monomers constituting structural units having a carboxy group, such as unsaturated monocarboxylic acids (e.g., (meth)acrylic acid, crotonic acid, 4-vinylbenzoic acid, etc.); unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc.); monomers constituting structural units having a sulfonic acid group, such as vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc.; and monomers constituting structural units having a phenolic hydroxyl group, such as 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc.

[0028] Furthermore, maleimide can also be used as a monomer constituting the structural unit (I).

[0029] Among these, unsaturated monocarboxylic acids and maleimides are preferred, and (meth)acrylic acid and maleimides are more preferred.

[0030] The base polymer may contain one type of structural unit (I) or a combination of two or more types.

[0031] The lower limit of the content of the structural unit (I) (the total content when multiple types are contained) relative to all structural units constituting the base polymer is preferably 1% by mass, more preferably 2% by mass, and even more preferably 5% by mass. The upper limit of the content is preferably 40% by mass, more preferably 35% by mass, even more preferably 30% by mass, and particularly preferably 20% by mass. By keeping the content of the structural unit (I) within the above range, good solubility in an alkaline developer can be imparted, which is preferable.

[0032] [Structural Unit (II)] The polymer (A1) may contain a structural unit (II) having one or more groups selected from the group consisting of an oxetanyl group and an oxiranyl group. The polymer (A1) preferably contains the structural unit (II), since this can further improve the film resolution and adhesion. Furthermore, the epoxy group acts as a crosslinkable group, allowing the formation of a pattern (cured film) that is highly heat-resistant and inhibits deterioration over a long period of time. The structural unit (II) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, and more specifically, is preferably a structural unit represented by the following formula (a1): (In formula (a1), R ２１ is a monovalent group having an oxiranyl group or an oxetanyl group. α is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. １ is a single bond or a divalent linking group.

[0033] In the above formula (a1), R ２１ Examples thereof include an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxytricyclo[5.2.1.0 ２,６ ]decyl group, 3-methyloxetanyl group, 3-ethyloxetanyl group, and the like.

[0034] X １ The divalent linking group is preferably a methylene group, an ethylene group, or an alkanediyl group such as a 1,3-propanediyl group.

[0035] Specific examples of the monomer that provides the structural unit (II) represented by the above formula (a1) include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ２，６]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, etc. Among these, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate are preferred.

[0036] The base polymer may contain one type of structural unit (II) or a combination of two or more types.

[0037] When polymer (A1) contains structural unit (II), the lower limit of the content of structural unit (II) (the total content when multiple types are contained) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 15% by mass, and even more preferably 25% by mass. The upper limit of the content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. By setting the content of structural unit (II) within the above range, the coating film exhibits better resolution and the heat resistance of the resulting pattern (cured film) can be sufficiently increased, which is preferable.

[0038] [Structural Unit (III)] When the radiation-sensitive composition of the present invention is a chemically amplified composition (the “third composition” described later), it is preferable that the polymer (A1) further contains a structural unit (III) having one or more groups selected from the group consisting of a group represented by the following formula (a2) and an acid-dissociable group, from the viewpoint of being able to form a coating film having excellent development adhesion: (In formula (a2), R １ , R ２ and R ３ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. １ , R ２ and R ３ At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" indicates a bond.)

[0039] R １ ~R ３ Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a tert-butoxy group. １ ~R ３ The alkoxy group is preferably a methoxy group or an ethoxy group.

[0040] R １ ~R ３ The alkyl group having 1 to 10 carbon atoms may be either linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group, an ethyl group, or a propyl group is preferred.

[0041] From the viewpoint of obtaining a cured film having excellent heat resistance by forming a crosslinked structure and from the viewpoint of improving the storage stability of the radiation-sensitive composition, R １ ~R ３ At least one of the groups is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably two or more of the groups are alkoxy groups, and particularly preferably all of the groups are alkoxy groups.

[0042] Among the above, R １ 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. ２ and R ３ is preferably a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and more preferably a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0043] In the structural unit (III), the group represented by the above formula (a2) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. In this specification, the term "aromatic ring group" refers to a group obtained by removing n hydrogen atoms (n is an integer) from the ring portion of an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. The ring may have a substituent such as an alkyl group. Examples of the chain hydrocarbon group to which the group represented by the above formula (a2) is bonded include an alkanediyl group and an alkenediyl group.

[0044] The group represented by the formula (a2) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain, among the above. That is, the structural unit (III) preferably has at least one selected from the group consisting of a group represented by the following formula (i), a group represented by the following formula (ii), and a group represented by the following formula (iii): (In formula (i), formula (ii), and formula (iii), A １ and A ２ are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. However, when n1 is 2 or more, multiple A １ are the same or different groups. When n2 is 2 or more, a plurality of A ２ are the same or different groups. ３１ is an alkanediyl group. １ , R ２ and R ３ has the same meaning as in formula (a2). "*" represents a bond.

[0045] A １ and A ２ The alkoxy group having 1 to 6 carbon atoms includes R １ ~R ３ The alkoxy groups having 1 to 6 carbon atoms listed above can be suitably used. １ and A ２ The alkyl group having 1 to 6 carbon atoms is R １ ~R３ Among the alkyl groups having 1 to 10 carbon atoms, groups having 1 to 6 carbon atoms can be suitably used.

[0046] The group "-SiR" bonded to the aromatic ring １ R ２ R ３ " is located at A １ and A ２ For example, in the case of formula (i) above, the group "-SiR １ R ２ R ３ The position of " may be any of the ortho, meta, and para positions, and is preferably the para position.

[0047] n1 is preferably 0 or 1, and more preferably 0. n2 is preferably 0 to 2, and more preferably 0.

[0048] In the above formula (iii), R ３１ From the viewpoint of increasing the heat resistance of the resulting cured film, R ３１ is preferably a group having 1 to 6 carbon atoms, and more preferably a group having 1 to 4 carbon atoms.

[0049] The structural unit (III) preferably has at least one selected from the group consisting of the group represented by the formula (i) and the group represented by the formula (ii) among the formulas (i) to (iii). １ R ２ R ３ " is directly bonded, it is possible to stabilize the silanol groups generated in the presence of water. This is preferable in that the solubility of the exposed area in an alkaline developer can be increased, and a good pattern can be formed. Among these, it is particularly preferable that the structural unit (III) is a structural unit having a group represented by the above formula (i).

[0050] The structural unit (III) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as an "unsaturated monomer"), and specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (2a-1) and structural units represented by the following formula (2a-2): (In formula (2a-1) and formula (2a-2), R α１ is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. ３２ and R ３３ R are each independently a divalent aromatic ring group or a chain hydrocarbon group. １ , R ２ and R ３ has the same meaning as the above formula (a2).

[0051] In the above formula (2a-1) and formula (2a-2), R ３２ , R ３３ The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalene 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.

[0052] R is advantageous in that it can produce a pattern (cured film) with higher heat resistance and hardness, and can increase the solubility of the exposed area in an alkaline developer. ３２ , R ３３ Among the above, is preferably a divalent aromatic ring group, and particularly preferably a substituted or unsubstituted phenylene group.

[0053] Specific examples of the structural unit represented by formula (2a-1) include structural units represented by formulas (2a-1-1) and (2a-1-2) below. Specific examples of the structural unit represented by formula (2a-2) include structural units represented by formulas (2a-2-1) and (2a-2-2) below. (In formula (2a-1-1), formula (2a-1-2), formula (2a-2-1), and formula (2a-2-2), R ３４ and R ３５ are each independently an alkyl group having 1 to 4 carbon atoms. ３６ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. n3 is an integer of 1 to 4. A １ , A ２, n1 and n2 have the same meanings as in formula (i) and formula (ii). α１ has the same meaning as the above formula (2a-1) and formula (2a-2).

[0054] Specific examples of the monomer constituting the structural unit (III) include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, and the like; trimethoxy(4-vinylnaphthalene)silane; (meth)acryloxypropyl)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.

[0055] The "acid-dissociable group" refers to a group in which a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group is substituted, and refers to a group that dissociates under the action of an acid. For example, an acid generated from a photoacid generator upon exposure dissociates the acid-dissociable group to generate a carboxyl group or the like. This results in a difference in solubility in a developer between the exposed and unexposed areas of the coating film, making it possible to form a pattern.

[0056] The acid-dissociable group is preferably a group represented by the following formula (3a-1) or a group represented by the following formula (3a-2). (In formula (3a-1), R ４ and R ５are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least a portion of the hydrogen atoms of the hydrocarbon group has been substituted with a hydroxy group, a halogen atom, or a cyano group. ４ and R ５ There is no case where both R are hydrogen atoms. ６ R is a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom or a sulfur atom between carbon atoms or at the bond-side terminal of this hydrocarbon group, or a group in which at least a portion of the hydrogen atoms of these groups have been substituted with a hydroxy group, a halogen atom or a cyano group. ７ is a carbon atom or a silicon atom. ８ ~R １４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. m is 1 or 2. When m is 2, multiple R １１ and R １２ may be the same or different. In formula (3a-1) and formula (3a-2), "*" indicates a bonding site.

[0057] R ４ ~R ６ Examples of the hydrocarbon group having 1 to 30 carbon atoms include a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0058] Examples of the linear hydrocarbon group having 1 to 30 carbon atoms include linear or branched saturated hydrocarbon groups having 1 to 30 carbon atoms, and linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of the linear or branched saturated hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, n-octyl, n-dodecyl, n-tetradecyl, and n-octadecyl. Examples of the monovalent linear or branched unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0059] Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups, and monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as bornyl, norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norbornenyl, tricyclodecenyl, and tetracyclododecenyl. The bridged alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms that constitute the alicyclic ring are linked by a linking group containing one or more carbon atoms.

[0060] The aromatic hydrocarbon group having 6 to 30 carbon atoms may have a structure in which monocyclic rings are linked, a condensed ring, or a structure in which an aromatic ring is linked to an aliphatic hydrocarbon group. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthryl; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl.

[0061] R in the above formula (3-1) ４ ~R ６ are each independently preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0062] R ８ ~R １４ The hydrocarbon group having 1 to 12 carbon atoms is the same as the above R ４ ~R ６ Among the hydrocarbon groups having 1 to 30 carbon atoms, groups having 1 to 12 carbon atoms can be suitably used.

[0063] m is 1 or 2. When m is 2, a plurality of R １１ and R １２ may be the same or different.

[0064] As the structural unit having the acid-dissociable group, for example, structural units represented by the following formulae (3a-1-1) and (3a-1-2) are preferred.

[0065] In the above formulas (3a-1-1) and (3a-1-2), m1 is 0 or 1. α１ is R in the above formula (2a-1) and formula (2a-2). α１ It is synonymous with R ４ ~R １４ is R in the above formulas (3a-1) and (3a-2). ４ ~R １４ is synonymous with.

[0066] L in the above formulas (3a-1-1) and (3a-1-2) １ , L ２ are each independently a single bond or a divalent linking group.

[0067] The above L １ , L ２ Examples of the divalent linking group in include an alkanediyl group, a cycloalkanediyl group, an alkenediyl group, and an arenediyl group.

[0068] The alkanediyl group is represented by X in formula (a1). １ Examples of the divalent linking group include the same as those of the divalent linking group.

[0069] Examples of the cycloalkanediyl group include monocyclic cycloalkanediyl groups such as a cyclopentanediyl group and a cyclohexanediyl group; and polycyclic cycloalkanediyl groups such as a norbornanediyl group and an adamantanediyl group.

[0070] Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, and a butenediyl group.

[0071] Examples of the arenediyl group include a phenylene group, a tolylene group, a naphthylene group, etc. The arenediyl group is preferably an arenediyl group having 6 to 15 carbon atoms.

[0072] The base polymer may contain one type of structural unit (III) or a combination of two or more types.

[0073] When polymer (A1) contains structural unit (III), the lower limit of the content of structural unit (III) (total content when multiple types are contained) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass, based on all structural units constituting the base polymer. The upper limit of the content is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. By keeping the content of structural unit (III) within the above range, the coating film exhibits better resolution, which is preferable.

[0074] [Structural Unit (IV)] The polymer (A) may further contain a structural unit (IV) derived from at least one monomer selected from the group consisting of a (meth)acrylic acid alkyl ester, a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, a vinyl compound having a heterocyclic structure, a conjugated diene compound, a nitrogen-containing vinyl compound, and an unsaturated dicarboxylic acid dialkyl ester compound. Introducing such a structural unit (IV) into the polymer is preferred in that it can adjust the glass transition temperature of the polymer (A1) component and improve the pattern shapeability of the resulting cured film.

[0075] Examples of the (meth)acrylic acid alkyl ester 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.

[0076] Examples of the (meth)acrylic acid ester having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and the like. ２，６ ] decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 ２，５ ] decan-8-yloxyethyl, isobornyl (meth)acrylate, and the like.

[0077] Examples of the (meth)acrylic acid ester having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0078] Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, and vinylpyridine.

[0079] Examples of the N-substituted maleimide compound include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide.

[0080] Examples of vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) (meth)acrylate, glycerin carbonate (meth)acrylate, (γ-lactam-2-yl) (meth)acrylate, and N-(meth)acryloxyethylhexahydrophthalimide.

[0081] Examples of the conjugated diene compound include 1,3-butadiene, isoprene, etc., examples of the nitrogen-containing vinyl compound include (meth)acrylonitrile, (meth)acrylamide, etc., and examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconate, etc. Furthermore, examples of the monomers constituting the other structural units include, in addition to the above, monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, etc.

[0082] The monomer that provides the structural unit (IV) preferably includes at least one selected from the group consisting of alkyl (meth)acrylates, aromatic vinyl compounds, and N-substituted maleimide compounds, and more preferably includes at least one selected from the group consisting of methyl (meth)acrylate and styrene.

[0083] The base polymer may contain one or more types of structural unit (IV).

[0084] When polymer (A1) contains structural unit (IV), the lower limit of the content of structural unit (IV) (the total content when multiple types are contained) is preferably 1 mass%, more preferably 3 mass%, and even more preferably 5 mass%, based on all structural units constituting the base polymer. The upper limit of this content is preferably 60 mass%, more preferably 50 mass%. By setting the content of structural unit (IV) within this range, the glass transition temperature of polymer (A1) can be suitably increased, which is preferable.

[0085] (Method for synthesizing polymer (A1)) The polymer (A1) can be produced, for example, by using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator according to a known method such as radical polymerization.

[0086] Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyrate) dimethyl. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total amount of the monomers used in the reaction.

[0087] Examples of the polymerization solvent include alcohols, ethers, ketones, esters, hydrocarbons, etc. The amount of the polymerization solvent used is preferably an amount such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass relative to the total amount of the reaction solution.

[0088] In the polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the types 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 for preparing the radiation-sensitive composition as it is dissolved in the reaction solution, or may be used for preparing the radiation-sensitive composition after being isolated from the reaction solution. The polymer can be isolated by known isolation methods, such as a method of pouring the reaction solution into a large amount of a poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator.

[0089] The weight average molecular weight (Mw) of the polymer contained in the polymer component, as measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 2,000 or more. Mw of 2,000 or more is preferable in that it is possible to obtain a cured film having sufficiently high heat resistance and chemical resistance and exhibiting 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, 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.

[0090] The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. When the base polymer is composed of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above ranges.

[0091] (Siloxane Polymer (A2)) The siloxane polymer (A2) is not particularly limited as long as it can form a cured film by hydrolysis and condensation. The siloxane polymer (A2) is preferably a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (4a): (R ５１ ) ｒ Si(OR ５２ ) ４－ｒ (4a) (In formula (4a), R ５１ is a non-hydrolyzable monovalent group. ５２ is an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. r is an integer from 0 to 3. However, when r is 2 or 3, multiple R ５１ When r is 0 to 2, multiple R ５２ are the same or different.)

[0092] R ５１Examples of the alkyl group include 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.

[0093] R ５２ Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. ５２ is preferably a methyl group or an ethyl group.

[0094] r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0095] Specific examples of the monomer constituting the siloxane polymer include silane compounds having four hydrolyzable groups, such as 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, and 3-(meth)acryloxypropyltriethoxysilane; examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane; and examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

[0096] The siloxane polymer 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 an organic solvent. The amount of water used in the hydrolysis and condensation reaction depends on the amount of hydrolyzable groups (-OR ５２ The amount of water is preferably 0.1 to 3 mol, more preferably 0.2 to 2 mol, and even more preferably 0.5 to 1.5 mol, relative to 1 mol of the total amount of the components (a) and (b). By using such an amount of water, the reaction rate of the hydrolysis and condensation can be optimized.

[0097] Examples of catalysts used in the hydrolysis and condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, etc. 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 mol, more preferably 0.0005 to 0.1 mol, per mol of the hydrolyzable silane compound.

[0098] Examples of organic solvents used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use water-insoluble or slightly water-soluble organic solvents, such as ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid ester compounds. The proportion of the 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 of the hydrolyzable silane compounds used in the reaction.

[0099] During the hydrolysis and condensation reaction, the reaction temperature is preferably 130°C or lower, more preferably 40 to 100°C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. During the reaction, the mixed solution may be stirred or may be placed under reflux. After the hydrolysis and condensation reaction, a dehydrating agent may be added to the reaction solution, followed by evaporation to remove water and the produced alcohol from the reaction system.

[0100] The siloxane polymer preferably has a weight average molecular weight (Mw) of 500 or more in terms of polystyrene measured by GPC. An Mw of 500 or more is preferred in that it has sufficiently high heat resistance and solvent resistance and can provide a pattern (cured film) that exhibits good developability. Mw is more preferably 1,000 or more. Furthermore, from the viewpoint of improving film-forming properties and suppressing a decrease in radiation sensitivity, Mw is preferably 10,000 or less, more preferably 5,000 or less. Furthermore, the molecular weight distribution (Mw / Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0101] (Polyamic Acid or Polyamic Acid Ester (A3)) The polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[0102] Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, etc. Specific examples of these include: aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride; Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, and propane-1,3-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate). Alternatively, the tetracarboxylic dianhydrides described in JP-A-2010-97188 can be used. The above tetracarboxylic dianhydrides can be used alone or in combination of two or more.

[0103] Among these, the tetracarboxylic dianhydride preferably includes an aromatic tetracarboxylic dianhydride, and more preferably includes 4,4'-oxydiphthalic anhydride.

[0104] The diamine is not particularly limited, and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.

[0105] Examples of the aliphatic diamine include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine.

[0106] Examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine).

[0107] Examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. nyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4,4'-diaminostilbenzene, 1,4-bis(4-aminophenyl)-piperazine, and compounds represented by the following formula (S-1): (In formula (S-1), X is —O—, —S—, —CO—, —SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CH ３ ) (C ２H ５ ) - or -C(CF ３ ) ２ Main chain diamines such as dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diamino Cholestanyl aminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, the following formula (S-2): (In formula (S-2), X Ｉ and X ＩＩ are each independently a single bond, —O—, *-COO— or *-OCO— (wherein “*” represents X Ｉ It shows the bond with . Ｉ is an alkanediyl group having 1 to 3 carbon atoms. ＩＩ is a single bond or an alkanediyl group having 1 to 3 carbon atoms. ＩＩＩ is an alkyl group, alkoxy group, fluoroalkyl group, or fluoroalkoxy group having 1 to 20 carbon atoms. a is 0 or 1. b is an integer from 0 to 3. c is an integer from 0 to 2. d is 0 or 1, provided that 1≦a+b+c≦3. Side chain diamines such as compounds represented by the following formula: An example of a diaminoorganosiloxane is 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. In addition to these, diamines described in JP 2010-97188 A can be used.

[0108] Among these, the diamine preferably includes an aromatic diamine or a diaminoorganosiloxane, and more preferably includes a compound represented by formula (S-1) above or 1,3-bis(3-aminopropyl)-tetramethyldisiloxane.

[0109] The above diamines can be used alone or in combination of two or more.

[0110] Polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine, optionally with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is preferably such that 0.2 to 2 equivalents of the acid anhydride groups of the tetracarboxylic dianhydride are used per equivalent of the amino groups of the diamine. Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The molecular weight modifier is preferably used in an amount of 20 parts by mass or less per 100 parts by mass of the total of the tetracarboxylic dianhydride and diamine used.

[0111] The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably −20°C to 150°C, and the reaction time is preferably 0.1 to 24 hours. Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents include one or more solvents selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenols, or mixtures of one or more of these solvents with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of organic solvent (a) used is preferably an amount such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by mass relative to the total amount (a + b) of the reaction solution.

[0112] In this manner, a reaction solution containing a dissolved polyamic acid is obtained. This reaction solution may be used as is for preparing a radiation-sensitive composition, or the polyamic acid contained in the reaction solution may be isolated and then used for preparing a radiation-sensitive composition.

[0113] The polyamic acid ester can be obtained, for example, by [I] a method of reacting the polyamic acid obtained by the synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine. The polyamic acid ester contained in the radiation-sensitive composition of the present invention may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution in which the polyamic acid ester is dissolved may be used directly for preparing the radiation-sensitive composition, or the polyamic acid ester contained in the reaction solution may be isolated and then used for preparing the radiation-sensitive composition.

[0114] The content of the polymer (A) is preferably 20% 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 (i.e., the total mass of components other than the solvent in the radiation-sensitive composition). The content of the polymer (A) is preferably 99% by mass or less, more preferably 95% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. By setting the content of the polymer (A) within the above range, it is possible to sufficiently improve pattern formability and substrate adhesion.

[0115] <Radiation-Sensitive Compound (B)> The radiation-sensitive composition (B) contains the radiation-sensitive compound (B) in addition to the polymer (A). A positive or negative pattern can be formed by irradiating the radiation-sensitive composition (B) with radiation (visible light, ultraviolet light, far ultraviolet light, etc.). Examples of the radiation-sensitive compound (B) include a photoacid generator, a photopolymerization initiator, and a photobase generator. Of these, at least one selected from the group consisting of a quinone diazide compound (B-1), a photopolymerization initiator (B-2), and a photoacid generator (B-3) can be preferably used as the radiation-sensitive compound (B).

[0116] Here, when a photoacid generator or a photobase generator is used as the radiation-sensitive compound, the solubility of the exposed portion in a developer changes, thereby forming a positive or negative pattern. Furthermore, when the photoacid generator or the photobase generator functions as a curing catalyst and promotes curing of the exposed portion, the solubility of the exposed portion in a developer decreases, thereby forming a negative pattern. On the other hand, when a photopolymerization initiator is used as the radiation-sensitive compound, for example, the reaction with a compound having a vinyl group or a (meth)acryloyl group promotes curing of the exposed portion, thereby reducing the solubility of the exposed portion in a developer, thereby forming a negative pattern.

[0117] Specific embodiments of the radiation-sensitive composition of the present invention include: a radiation-sensitive composition (first composition) containing the polymer (A), a quinone diazide compound (B-1) as the radiation-sensitive compound (B), and a polymerized ionic liquid (C); a negative-tone radiation-sensitive composition (second composition) containing the polymer (A), a photopolymerization initiator (B-2) as the radiation-sensitive compound (B), a polymerizable monomer (X1), and a solvent (C); and a chemically amplified radiation-sensitive composition (third composition) containing the polymer (A), a photoacid generator (B-3) as the radiation-sensitive compound (B), and a polymerized ionic liquid (C). The first to third radiation-sensitive compositions will be described below.

[0118] (First Composition) The first composition is a radiation-sensitive composition containing a quinone diazide compound (B-1) as the radiation-sensitive compound (B).

[0119] (Quinone diazide compound (B-1)) The quinone diazide compound (B-1) is a compound that generates a carboxylic acid upon irradiation with radiation. Examples of the quinone diazide compound (B-1) include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") with an orthonaphthoquinone diazide compound. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the mother nucleus with an orthonaphthoquinone diazide compound. Specific examples of the mother nucleus include the compounds described in paragraphs

[0065] to

[0070] of JP 2014-186300 A.

[0120] Specific examples of the quinone diazide compound (B-1) 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, 1,4-bis[1-(4-hydroxyphenyl)-1- and ester compounds of a phenolic hydroxyl group-containing compound selected from 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Among these, the quinonediazide compound (B-1) is preferably a condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

[0121] These quinone diazide compounds (B-1) may be used alone or in combination of two or more. The lower limit of the content of the quinone diazide compound (B-1) is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 15 parts by mass, relative to 100 parts by mass of the polymer (A) blended in the first composition. The upper limit of the content of the quinone diazide compound (B-1) is preferably 50 parts by mass, more preferably 30 parts by mass, relative to 100 parts by mass of the polymer (A) blended in the first composition. A content of the quinone diazide compound (B-1) of 5 parts by mass or more is preferred because carboxylic acid is sufficiently generated by irradiation of the first composition, the difference in solubility between the irradiated and unirradiated portions in the developer can be sufficiently increased, and good patterning can be achieved. This is also preferred because the amount of carboxylic acid involved in the reaction with the polymer component can be increased, thereby ensuring sufficient heat resistance and chemical resistance. On the other hand, by setting the content of the quinone diazide compound to 50 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, and a decrease in developability due to the remaining quinone diazide compound can be suppressed, which is preferable.

[0122] (Second Composition) The second composition is a negative radiation-sensitive composition that contains a photopolymerization initiator (B-2) as the radiation-sensitive compound (B) and also contains a polymerizable monomer (X1).

[0123] (Photopolymerization initiator (B-2)) As the photopolymerization initiator (B-2), a compound that is sensitive to actinic rays with a wavelength of 300 nm or more (preferably 300 to 450 nm) and initiates and promotes polymerization of the polymerizable monomer (X1) can be preferably used. When a photopolymerization initiator (B-2) that is not directly sensitive to actinic rays with a wavelength of 300 nm or more is used, it may be used in combination with a sensitizer so that it is sensitive to actinic rays with a wavelength of 300 nm or more and initiates and promotes polymerization of the polymerizable monomer (X1).

[0124] Known compounds can be used as the photopolymerization initiator (B-2). Specific examples include oxime ester compounds, organic halogenated compounds, oxidiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, at least one selected from the group consisting of oxime ester compounds, α-aminoketone compounds, and hexaarylbiimidazole compounds is preferred, with oxime ester compounds or α-aminoketone compounds being more preferred, in terms of being able to further increase the sensitivity of the second composition. Furthermore, commercially available products may also be used as the photopolymerization initiator (B-2), such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF).

[0125] These photopolymerization initiators (B-2) may be used alone or in combination of two or more. The lower limit of the content of the photopolymerization initiator (B-2) is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 10 parts by mass, relative to 100 parts by mass of the polymerizable monomer (X1) contained in the second composition. The upper limit of the content of the photopolymerization initiator (B-2) is preferably 45 parts by mass, more preferably 35 parts by mass, and even more preferably 25 parts by mass, relative to 100 parts by mass of the polymerizable monomer (X1).

[0126] (Polymerizable Monomer (X1)) The second composition contains a polymerizable monomer (X1). The polymerizable monomer (X1) contained in the second composition is a compound having one or more, preferably two or more, polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Of these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred because of their high polymerizability, and vinyl group-containing groups such as a (meth)acryloyl group, a vinyl group, and a vinylphenyl group are preferred.

[0127] Specifically, the polymerizable monomer (X1) is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and particularly preferably a compound having two or more (meth)acryloyl groups. The number of polymerizable groups per molecule of the polymerizable monomer (X1) is preferably 2 to 10, more preferably 2 to 8.

[0128] Specific examples of the polymerizable monomer (X1) include compounds having two or more (meth)acryloyl groups, such as polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

[0129] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The terms "melamine structure" and "benzoguanamine structure" refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are concepts that include melamine, benzoguanamine, and condensates thereof. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)glycoluril.

[0130] As the polymerizable monomer (X1), preferred are polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates having a carboxy group, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanamine; more preferred are polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, polyfunctional urethane (meth)acrylates, and polyfunctional (meth)acrylates having a carboxy group; and even more preferred are polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid.

[0131] Specific examples of polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol polyacrylate, etc. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol polyacrylate are particularly preferred, since they increase the intermolecular or intramolecular crosslinking density and can further improve the curability of the film even by low-temperature baking.

[0132] These polymerizable monomers (X1) may be used alone or in combination of two or more. The lower limit of the content of the polymerizable monomer (X1) is preferably 20 parts by mass, more preferably 25 parts by mass, and even more preferably 30 parts by mass, relative to 100 parts by mass of the polymer (A) contained in the second composition. The upper limit of the content of the polymerizable monomer (X1) is preferably 300 parts by mass, more preferably 200 parts by mass, and even more preferably 100 parts by mass, relative to 100 parts by mass of the polymer (A). When the content ratio of the polymerizable monomer (X1) is within the above range, it is preferable in that sufficient curability and sufficient alkali developability of the cured film can be ensured, and the occurrence of background smear, film residue, etc. on the substrate or light-shielding layer in unexposed areas can be sufficiently suppressed.

[0133] (Third Composition) The third composition is a chemically amplified radiation-sensitive composition containing a photoacid generator (B-3) as the radiation-sensitive compound (B). The polymer (A) in the third composition is a polymer (A1) containing a structural unit (III) having one or more groups selected from the group consisting of a group represented by formula (a2) and an acid-dissociable group.

[0134] (Photoacid Generator (B-3)) The photoacid generator (B-3) is not particularly limited as long as it is a compound that generates an acid in response to radiation (i.e., a radiation-sensitive acid generator). Examples of the photoacid generator (B-3) include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylate ester compounds.

[0135] Specific examples of the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate ester compound, and carboxylate ester compound include the compounds described in paragraphs

[0078] to

[0106] of JP 2014-157252 A and the compounds described in WO 2016 / 124493. From the viewpoint of radiation sensitivity, at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds can be preferably used as the photoacid generator.

[0136] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (t1): (In formula (t1), R ４０ represents a monovalent hydrocarbon group or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group have been substituted with substituents. "*" represents a bond.)

[0137] In the above formula (t1), R ４０ Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an oxo group, and a halogen atom.

[0138] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in WO 2016 / 124493. Commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

[0139] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0140] These photoacid generators (B-3) may be used alone or in combination of two or more. The lower limit of the content of the photoacid generator (B-3) is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, and even more preferably 2 parts by mass, relative to 100 parts by mass of the polymer (A) blended in the third composition. The upper limit of the content of the photoacid generator (B-3) is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass, relative to 100 parts by mass of the polymer (A) blended in the third composition. A content of the photoacid generator (B-3) of 1 part by mass or more is preferable in that good patterning can be achieved and sufficient heat resistance can be ensured. A content of the photoacid generator (B-3) of 30 parts by mass or less is preferable in that the amount of unreacted photoacid generator after exposure can be sufficiently reduced, and a decrease in developability due to residual photoacid generator can be suppressed.

[0141] <Polymerized ionic liquid (C)> The polymerized ionic liquid (C) is a polymer containing an anionic moiety and a cationic moiety constituting the ionic liquid, and is preferably a polymer having the anionic moiety and the cationic moiety constituting the ionic liquid as a side chain moiety. "Having as a side chain moiety" means that the anionic moiety or the cationic moiety is bonded (covalently bonded) to the main chain as a side chain structure of the polymer. In the case of a polymer that is bonded three-dimensionally and the main chain cannot be clearly identified, such as polysiloxane, a group bonded to Si other than the Si-O bond is used as the side chain moiety. When the anionic moiety is bonded to the main chain as a side chain structure of the polymer, the cationic moiety forms an ionic bond with the anionic moiety as a counter ion of the anionic moiety to form a salt. On the other hand, when the cationic moiety is bonded to the main chain as a side chain structure of the polymer, the anionic moiety forms an ionic bond with the cationic moiety as a counter ion of the cationic moiety to form a salt.

[0142] The polymerized ionic liquid (C) may also be referred to as "Poly (ionic liquid) Block Copolymers" (ACS Appl. Polym. Mater. 2023, 5, 2639-2653), "Polymerized Ionic Liquids" (J. Phys. Chem. B 2017, 121, 11511-11519), or "polymeric ionic liquids" (Polymer 55 (2014) 3385-3396).

[0143] The glass transition temperature of the polymerized ionic liquid (C) is 5°C or lower, preferably 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower. The lower limit of the glass transition temperature is not particularly limited, and the lower the better, but it is usually about -100°C. By having the glass transition temperature in the above range, ionic conductivity is ensured even though the polymer is a polymer.

[0144] The lower limit of the weight average molecular weight (Mw) of the polymerized ionic liquid (C) is preferably 1,000, more preferably 5,000, even more preferably 10,000, and particularly preferably 50,000. The upper limit of the weight average molecular weight (Mw) is not particularly limited, but is preferably 1,000,000, and more preferably 500,000. The weight average molecular weight (Mw) is a polystyrene-equivalent value measured by gel permeation chromatography (hereinafter abbreviated as GPC).

[0145] The polymer having the anion moiety and cation moiety constituting the ionic liquid as side chain moieties of the polymer is preferably an acrylic polymer or a polysiloxane polymer, and more preferably an acrylic polymer.

[0146] As the polymerized ionic liquid (C), a polymer in which an anionic moiety is bonded to the main chain as a side chain structure of the polymer and a cationic moiety is ionic bonded to the anionic moiety bonded to the main chain as a counter ion to form a salt is preferably one containing one or more partial structures (C1) selected from the group consisting of the following formulae (C1-1) and (C1-2): (In formulas (C1-1) and (C1-2), Rc １１ is a halogen atom or a substituted or unsubstituted chain hydrocarbon group. ｍ＋ is a proton or an onium cation. m is an integer of 1 to 3. * is a bond to another structure in the polymerized ionic liquid (C).

[0147] The above R ｃ１１ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferred.

[0148] The above R ｃ１１ The chain hydrocarbon group represented by R ４ ~R ６ Preferably, a chain hydrocarbon group having 1 to 30 carbon atoms as shown in the formula (I) can be used. Also included are groups in which some or all of the hydrogen atoms in the chain hydrocarbon group have been substituted with a substituent. Examples of the substituent include the substituent (T) described below.

[0149] Among these, R ｃ１１ As the alkyl group, a halogen atom or a halogenated chain hydrocarbon group in which some or all of the hydrogen atoms in the chain hydrocarbon group have been substituted with halogen atoms is preferred, a halogen atom or a monovalent halogenated chain hydrocarbon group having 1 to 10 carbon atoms is more preferred, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is still more preferred, and a fluorine atom or a trifluoromethyl group is particularly preferred.

[0150] Above X ｍ＋ Examples of the onium cation represented by the formula (I) include an ammonium cation, a phosphonium cation, a sulfonium cation, an imidazolium cation, a pyrrolidinium cation, and a diazonium cation.

[0151] The ammonium cation is preferably an organic ammonium cation, such as tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristearylmonomethylammonium, cetyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, triamylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, benzyldimethyloctylammonium, dialkyl (alkyl is C14 to C18)dimethylammonium, etc. Of these, tetramethylammonium and tetraethylammonium are preferred.

[0152] The phosphonium cation is preferably an organic phosphonium cation, and examples thereof include tetraalkylphosphoniums such as methyltrioctylphosphonium, methyltripropylphosphonium, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, and dihexyldioctylphosphonium; aryltrialkylphosphoniums such as benzyltributylphosphonium; dialkyldiarylphosphoniums such as dibutyldiphenylphosphonium; alkyltriphenylphosphoniums such as butyltriphenylphosphonium; and tetraarylphosphoniums such as benzyltriphenylphosphonium. Among these, methyltripropylphosphonium is preferred.

[0153] Examples of the imidazolium cation include N-methylimidazolium cation, N-ethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-propene-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1,2,3-trimethylimidazolium cation, and 1,2,3,4-tetramethylimidazolium cation. ammonium cation, 1-allyl-3-methylimidazolium cation, N-propylpyridinium cation, N-butylpyridinium cation, 1,4-dimethylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-butyl-2,4-dimethylpyridinium cation, trimethylammonium cation, ethyldimethylammonium cation, diethylmethylammonium cation, triethylammonium cation, tetramethylammonium cation, triethylmethylammonium cation, tetraethylammonium cation, etc. Among these, dialkylimidazolium cations such as 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, and 1-hexyl-3-methylimidazolium cation, and 1-propene-3-methylimidazolium cation are preferred.

[0154] Examples of the pyrrolidinium cation include N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N,N-diethylpyrrolidinium, N-propyl-N-methylpyrrolidinium, N-butyl-N-methylpyrrolidinium, N-pentyl-N-methylpyrrolidinium, and N-hexyl-N-methylpyrrolidinium.

[0155] Examples of the sulfonium cation include those described in paragraph

[0063] of JP-A No. 2009-073871. Examples of the diazonium cation include those described in paragraph

[0374] of JP-A No. 2002-332271.

[0156] The polymerized ionic liquid (C1) having the partial structure (C1) is preferably, for example, a polymer having a structural unit (X) represented by the following formula (1) or formula (2). (In formulas (1) and (2), R ｃ１ is a hydrogen atom, a methyl group, or a trifluoromethyl group. ｃ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, or is bonded to a silicon atom of a different structural unit to form a siloxane bond. ｃ１１ , L ｃ１２ is a single bond or a divalent linking group. ｃ１２ , R ｃ１３ , R ｃ１４ is a single bond or a divalent organic group having 1 to 20 carbon atoms. D is a partial structure (C1) represented by the above formula (C1-1) or formula (C1-2).

[0157] The above R ｃ１２ , R ｃ１３ , R ｃ１４ As the divalent organic group having 1 to 20 carbon atoms, a group in which one hydrogen atom has been removed from a monovalent organic group having 1 to 20 carbon atoms can be suitably used.

[0158] Examples of the monovalent organic group having 1 to 20 carbon atoms include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group (α) having a divalent heteroatom-containing group between carbon atoms of the hydrocarbon group or at the end of the hydrocarbon group, a group (β) in which some or all of the hydrogen atoms in the hydrocarbon group or the group (α) have been substituted with a monovalent heteroatom-containing group, and combinations thereof.

[0159] The monovalent hydrocarbon group having 1 to 20 carbon atoms includes R ４ ~R ６Among hydrocarbon groups having 1 to 30 carbon atoms represented by the following formula, those having the corresponding number of carbon atoms can be suitably used.

[0160] Examples of heteroatoms constituting the monovalent heteroatom-containing group and divalent heteroatom-containing group 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.

[0161] Examples of the monovalent heteroatom-containing group include a hydroxy group, a carboxy group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.

[0162] Examples of the divalent heteroatom-containing group include -CO-, -C(=O)O-, -CS-, -NR'-, -O-, -S-, -SO-, and -SO ２ -, or a group formed by combining these groups. R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0163] Among these, the above R ｃ１２ , R ｃ１３ , R ｃ１４ As the alkyl group, alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, and hexanediyl group, and arenediyl groups such as benzenediyl group, toluenediyl group, xylenediyl group, and naphthalenediyl group are preferred, and alkanediyl groups are more preferred.

[0164] The above R ｃ１ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0165] The above R ｃ２ As the alkyl group having 1 to 10 carbon atoms, R １ ~R ３ In the above formula, alkyl having 1 to 10 carbon atoms can be preferably used.

[0166] The above R ｃ２As the fluorinated alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms can be suitably used.

[0167] The above R ｃ２ can bond with silicon atoms of different structural units to form siloxane bonds. By bonding with silicon atoms of different structural units to form siloxane bonds, three-dimensional bonds are formed. In this case, R ｃ２ is *-O-(Si(R ｔ１ ) (R ｔ２ )-O) ｔ -**. In the formula, R ｔ１ , R ｔ２ are each a hydrogen atom or an organic group having 1 to 20 carbon atoms, * represents a bond to Si in formula (2), and ** represents a bond to a silicon atom in a different structural unit. t is an integer of 0 to 10. As a divalent organic group having 1 to 20 carbon atoms, R ｃ１２ , R ｃ１３ , R ｃ１４ A divalent organic group having 1 to 20 carbon atoms in the above formula can be suitably used.

[0168] The above L ｃ１１ , L ｃ１２ Examples of the divalent linking group represented by the formula: ２ Among these, L ｃ１ is preferably a single bond or —COO—, and more preferably —COO—. ｃ１２ is preferably a single bond or —S—.

[0169] The above D is a partial structure (C1) represented by the above formula (C1-1) or formula (C1-2), and the partial structure (C1) represented by the above formula (C1-1) is preferred.

[0170] The structural unit represented by the above formula (1) is preferably, for example, a structural unit represented by the following formulas (1-1) and (1-2), and the structural unit represented by the above formula (2) is preferably, for example, a structural unit represented by the following formulas (2-1) and (2-2). (In formulas (1-1), (1-2), (2-1), (2-2), R ｃ１２１ , R ｃ１２３ , R ｃ１３１ , R ｃ１４１ , R ｃ１４２ are each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms. ｃ１２２ , R ｃ１４３ are each independently a divalent chain hydrocarbon group having 1 to 5 carbon atoms. m11 and m12 are each independently an integer of 1 to 10. R ｃ１ , R ｃ２ , L ｃ１１ , L ｃ１２ , D has the same meaning as in the above formulas (1) and (2).

[0171] The above R ｃ１２１ , R ｃ１２３ , R ｃ１３１ , R ｃ１４１ , R ｃ１４２ As the divalent hydrocarbon group having 1 to 10 carbon atoms represented by the formula (3a-1), R ４ ~R ６ Among hydrocarbon groups having 1 to 30 carbon atoms and represented by the formula (I), groups in which one hydrogen atom has been removed from a group having the corresponding carbon number can be suitably used. The hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; a carboxy group; a cyano group; a nitro group; an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, an acyloxy group, or a group in which a hydrogen atom of any of these groups has been substituted with a halogen atom; and a substituent (T) such as an oxo group (═O).

[0172] Among these, R ｃ１２１ , R ｃ１２３ , R ｃ１３１ , R ｃ１４１ , R ｃ１４２ As the alkyl group, an alkanediyl group having 1 to 5 carbon atoms is preferred.

[0173] The above R ｃ１２２ , R ｃ１４３ As the divalent chain hydrocarbon group having 1 to 5 carbon atoms represented by the formula (3a-1), R ４ ~R ６Among the chain hydrocarbon groups having 1 to 30 carbon atoms in the above, groups in which one hydrogen atom has been removed from the corresponding carbon number can be suitably used. ｃ１２２ , R ｃ１４３ As the alkyl group, an ethanediyl group or a propanediyl group is preferred, and an ethanediyl group is more preferred.

[0174] The above m11 and m12 are integers of 1 to 10, and preferably integers of 1 to 5.

[0175] The structural unit (X) preferably has a polyalkylene oxide chain, and more preferably has a polyethylene oxide chain.

[0176] Examples of the anion moiety of the structural unit (X) include the following structures. (In the formula, R ｃ１ has the same meaning as formula (1). p1 is an integer of 1 to 5. p is an integer of 1 to 5.

[0177] (In the formula, R ｃ２ has the same meaning as formula (2). q1 is an integer of 1 to 10. r is an integer of 1 to 5.

[0178] As the monomer that provides the structural unit (X), all combinations of the above anions and the above cations can be suitably used. Among these, 1-butyl-3-methylimidazolium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide and the like are preferred.

[0179] The lower limit of the content of the structural unit (X) (the total content when multiple types are contained) is preferably 2% by mass, more preferably 6% by mass, and even more preferably 10% by mass, based on all structural units constituting the polymerized ionic liquid (C). The upper limit of the content is preferably 100% by mass, more preferably 90% by mass, and even more preferably 80% by mass. By setting the content of the structural unit (X) within the above range, the effects of the ionic liquid can be efficiently exhibited.

[0180] The polymer in which the polymerized ionic liquid (C) has a cationic moiety bonded to the main chain as a side chain structure of the polymer and an anionic moiety bonded to the main chain as a counter ion to form a salt by ionic bonding with the cationic moiety is preferably, for example, a polymer having one or more partial structures (C2) selected from the group consisting of the following formulae (C2-1), (C2-2), (C2-3), (C2-4), and (C2-5): (In formulas (C2-1) to (C2-5), R ｃ２２ , R ｃ２３ , R ｃ２４ , R ｃ２５ , R ｃ２６ , R ｃ２８ , R ｃ３０ , R ｃ３１ , R ｃ３２ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group containing —O—, —CO— or —COO— between carbon atoms in the hydrocarbon group having 1 to 20 carbon atoms. ｃ２１ , R ｃ２７ , R ｃ２９ are each independently a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group containing —O—, —CO— or —COO— between carbon atoms in the hydrocarbon group having 1 to 20 carbon atoms. s1 is 0 or 1. Y － is an anion. * is a bond to another structure in the polymerized ionic liquid (C).

[0181] R ｃ２２ , R ｃ２３ , R ｃ２４ , R ｃ２５ , R ｃ２６ , R ｃ２８ , R ｃ３０ , R ｃ３１ , R ｃ３２ , R ｃ２１ , R ｃ２７ , R ｃ２９ The hydrocarbon group in the formula (3a-1) is R ４ ~R ６Among the hydrocarbon groups having 1 to 30 carbon atoms in the above, those having the corresponding carbon number can be suitably employed. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent (T). Groups containing -O-, -CO-, or -COO- between carbon atoms in the hydrocarbon group having 1 to 20 carbon atoms can also be suitably employed, and examples thereof include groups having a polyalkylene oxide chain. Among these, R ｃ２２ , R ｃ２３ , R ｃ２４ , R ｃ２５ , R ｃ２６ , R ｃ２８ , R ｃ３０ , R ｃ３１ , R ｃ３２ , R ｃ２１ , R ｃ２７ , R ｃ２９ As the alkyl group, a chain hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0182] Above Y － Examples of the anion represented by the formula (FSO) include a halogen anion, a boron anion, a phosphorus anion, an organic sulfonate anion, and a sulfonylimide anion. However, an anion having at least one electron-withdrawing group selected from the group consisting of a halo group (preferably a fluoro group) and a cyano group is preferred. Specifically, for example, (FSO ２ ) ２ N － , (CF ３ SO ２ ) ２ N － , (CF ３ CF ２ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － ,Br － , AlCl ４ － , Al ２ Cl ７ － , NO ３ － , B.F. ４ － , P.F.６ － , C.H. ３ COO － , C.F. ３ COO － , C.F. ３ CF ２ CF ２ COO － , C.F. ３ SO ３ － , C.F. ３ (CF ２ ) ３ SO ３ － , AsF ６ － , SbF ６ － , C.H. ３ CH ２ OSO ３ － , C.H. ３ (CH ２ ) ７ OSO ３ － , N (CN) ２ － , C(CN) ３ － , Cl － , I － , P.F. ３ (C ２ F ５ ) ３ － , P ３ (CF ３ ) ３ － , B.F. ２ (CF) ２ － , B.F. ３ (CF ３ ) － , B(CN) ４ － Among these, (FSO ２ ) ２ N － , (CF ３ SO ２ ) ２ N － , B.F. ４ － , P.F. ６ － is preferred.

[0183] The polymerized ionic liquid (C2) having the partial structure (C2) is preferably a polymer having a structural unit (XI) represented by the following formula (3) or (4). (In formulas (3) and (4), R ｃ１ is a hydrogen atom, a methyl group, or a trifluoromethyl group. ｃ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms. ｃ２１ , L ｃ２２ is a single bond or a divalent linking group. ｃ３３ , R ｃ３４ , R ｃ３５ represents a single bond or a divalent organic group having 1 to 20 carbon atoms. A represents a partial structure (C2) represented by the above formula (C2-1), formula (C2-2), formula (C2-3), formula (C2-4), or formula (C2-5).

[0184] The above R ｃ１ , R ｃ２ is R in the above formulas (1) and (2). ｃ１ , R ｃ２ is synonymous with.

[0185] L ｃ２１ , L ｃ２２ The divalent linking group in the formula (1) is ｃ１１ Among these, divalent linking groups represented by the formula: ｃ２１ is preferably a single bond or —COO—, and more preferably —COO—. ｃ２２ is preferably a single bond or —S—.

[0186] The above R ｃ３３ , R ｃ３４ , R ｃ３５ In the formula (1) and (2), the divalent organic group having 1 to 20 carbon atoms is R ｃ１２ , R ｃ１３ , R ｃ１４ Among these, divalent organic groups having 1 to 20 carbon atoms in the above R ｃ３３ , R ｃ３４ , R ｃ３５As the alkyl group, alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, and hexanediyl group, and arenediyl groups such as benzenediyl group, toluenediyl group, xylenediyl group, and naphthalenediyl group are preferred, and alkanediyl groups are more preferred.

[0187] A is a partial structure (C2) represented by the above formula (C2-1), formula (C2-2), formula (C2-3), formula (C2-4), or formula (C2-5), and among these, the partial structure represented by formula (C2-1) is preferred.

[0188] The structural unit represented by the above formula (3) is preferably, for example, a structural unit represented by the following formulas (3-1) and (3-2), and the structural unit represented by the above formula (4) is preferably, for example, a structural unit represented by the following formulas (4-1) and (4-2). (In formulas (3-1), (3-2), (4-1), (4-2), R ｃ３３１ , R ｃ３３３ , R ｃ３４１ , R ｃ３５１ , R ｃ３５２ are each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms. ｃ３３２ , R ｃ３５３ are each independently a divalent chain hydrocarbon group having 1 to 5 carbon atoms. m21 and m22 are each independently an integer of 1 to 10. R ｃ１ , R ｃ２ , L ｃ２１ , L ｃ２２ , A has the same meaning as in the above formulas (3) and (4).

[0189] The above R ｃ３３１ , R ｃ３３３ , R ｃ３４１ , R ｃ３５１ , R ｃ３５２ As the divalent hydrocarbon group having 1 to 10 carbon atoms represented by the formula (3a-1), R ４ ~R ６ Among hydrocarbon groups having 1 to 30 carbon atoms represented by the following formula, groups in which one hydrogen atom has been removed from a hydrocarbon group having the corresponding number of carbon atoms can be suitably used. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent (T) described above.

[0190] Among these, R ｃ３３１ , R ｃ３３３ , R ｃ３４１ , R ｃ３５１ , R ｃ３５２ As the alkyl group, an alkanediyl group having 1 to 5 carbon atoms is preferred.

[0191] The above R ｃ３３２ , R ｃ３５３ As the divalent chain hydrocarbon group having 1 to 5 carbon atoms represented by the formula (3a-1), R ４ ~R ６ Among the chain hydrocarbon groups having 1 to 30 carbon atoms in the above, groups in which one hydrogen atom has been removed from the corresponding carbon number can be suitably used. ｃ３３２ , R ｃ３５３ As the alkyl group, an ethanediyl group or a propanediyl group is preferred, and an ethanediyl group is more preferred.

[0192] The above m21 and m22 are integers of 1 to 10, and integers of 1 to 5 are preferred.

[0193] The structural unit (XI) preferably has a polyalkylene oxide chain, and more preferably has a polyethylene oxide chain.

[0194] Examples of the cation moiety of the structural unit (XI) include the following structures. (In the formula, R ｃ１ has the same meaning as formula (3). p is an integer of 1 to 5. p1 is an integer of 1 to 5.

[0195] (In the formula, R ｃ２ has the same meaning as formula (4). q1 is an integer from 1 to 10. r is an integer from 1 to 5.

[0196] As the monomer that provides the structural unit (XI), all combinations of the above anions and the above cations can be suitably used. Among these, 1-[2-(2-(methacryloyloxy)ethoxy)ethoxy]ethyl]-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and the like are preferred.

[0197] The lower limit of the content of the structural unit (XI) (the total content when multiple types are contained) is preferably 2% by mass, more preferably 6% by mass, and even more preferably 10% by mass, based on all structural units constituting the polymerized ionic liquid (C). The upper limit of the content is preferably 100% by mass, more preferably 90% by mass, and even more preferably 80% by mass. By setting the content of the structural unit (XI) within the above range, the effects of the ionic liquid can be efficiently exhibited.

[0198] <Other Structural Units> The polymerized ionic liquid (C) may contain structural units other than the structural unit (X) and the structural unit (XI). Examples of the other structural units include a structural unit (XII) derived from an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter also referred to as an unsaturated monomer (d1)), and a structural unit (XIII) derived from an ethylenically unsaturated monomer having no carboxy groups (hereinafter also referred to as an unsaturated monomer (d2)).

[0199] Examples of the unsaturated monomer (d1) include (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, etc. The unsaturated monomer (d1) can be used alone or in combination of two or more.

[0200] Examples of the unsaturated monomer (d2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene; Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-phenylethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0] ２，６ ] (meth)acrylic acid esters such as decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of para-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane; cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ２，６ ] vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane; and macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

[0201] The unsaturated monomers (d2) may be used alone or in combination of two or more.

[0202] The unsaturated monomer (d2) is preferably a (meth)acrylic acid ester, and more preferably polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth)acrylate or 2-phenylethyl (meth)acrylate.

[0203] When the polymerized ionic liquid (C) contains the above-mentioned other structural unit (XII) or (XIII), the lower limit of the content of the structural unit (XII) or (XIII) (when multiple types are contained, the total content) is preferably 0% by mass, more preferably 10% by mass, and even more preferably 20% by mass, based on all structural units constituting the polymerized ionic liquid (C). The upper limit of the content is preferably 98% by mass, more preferably 94% by mass, and even more preferably 90% by mass. By setting the content of the structural unit (XII) or (XIII) within the above range, the effect of the ionic liquid can be efficiently exhibited.

[0204] The polymerized ionic liquid (C) can be polymerized by the same method as that for the polymer (A).

[0205] The polymerized ionic liquid (C) may be used alone or in combination of two or more. The lower limit of the content of the polymerized ionic liquid (C) is preferably 80 parts by mass, more preferably 100 parts by mass, even more preferably 150 parts by mass, even more preferably 200 parts by mass, and particularly preferably 250 parts by mass, relative to 100 parts by mass of the polymer (A). The upper limit of the content of the polymerized ionic liquid (C) is preferably 600 parts by mass, more preferably 500 parts by mass, and even more preferably 450 parts by mass, relative to 100 parts by mass of the polymer (A). When the content of the polymerized ionic liquid (C) is 80 parts by mass or more, it is preferable in that good electrical capacity can be imparted. Furthermore, by making the content of the polymerized ionic liquid (C) 600 parts by mass or less, it is preferable in terms of shape stability and substrate adhesion during patterning.

[0206] <Adhesion Aid (D)> The radiation-sensitive composition of the present invention may contain an adhesion aid (D). The adhesion aid is a component that improves the adhesion between a pattern (cured film) formed using the radiation-sensitive composition and a substrate. As the adhesion aid, a functional silane coupling agent having a reactive functional group can be preferably used. Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0207] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0208] When the adhesion aid (D) is blended in the radiation-sensitive composition, the lower limit of the content thereof is preferably 0.01 parts by mass, more preferably 1 part by mass, and even more preferably 3 parts by mass, relative to 100 parts by mass of the polymer (A), and the upper limit of the content thereof is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass.

[0209] <Acid Diffusion Controller> Of the radiation-sensitive compositions of the present invention, the third composition may contain an acid diffusion controller. The acid diffusion controller is a component that controls the diffusion length of the acid generated from the photoacid generator (B-3) upon exposure. By incorporating an acid diffusion controller into the third composition, the acid diffusion length can be appropriately controlled, thereby improving pattern developability. In addition, by incorporating an acid diffusion controller, chemical resistance can be enhanced while improving development adhesion, which is preferable.

[0210] The acid diffusion controller can be arbitrarily selected from basic compounds used in chemically amplified resists. Examples of basic compounds include fatty acid amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylates. Specific examples of basic compounds include the compounds described in paragraphs

[0128] to

[0147] of JP-A-2011-232632. The acid diffusion controller can preferably be at least one selected from the group consisting of aromatic amines and heterocyclic amines.

[0211] Examples of aromatic amines and heterocyclic amines include aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine; imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and triphenylimidazole; pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, and 2H-pyrrole derivatives such as 2H-pyrrole, ... pyrrole derivatives such as 5-dimethylpyrrole and N-methylpyrrole; pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, and nicotine, as well as compounds described in JP-A-2011-232632.

[0212] When an acid diffusion controller is incorporated into the radiation-sensitive composition, the lower limit of the content thereof is preferably 0.005 parts by mass, more preferably 0.01 parts by mass, relative to 100 parts by mass of the polymer (A) incorporated into the third composition, from the viewpoint of fully obtaining the effect of improving chemical resistance due to the incorporation of the acid diffusion controller, and the upper limit of the content of the acid diffusion controller is preferably 10 parts by mass, more preferably 5 parts by mass, relative to 100 parts by mass of the polymer (A).

[0213] <Other Components> The radiation-sensitive composition of the present invention may contain components other than those described above (other components). Examples of other components include a curing accelerator, a polyfunctional polymerizable compound (such as a polyfunctional (meth)acrylate), a surfactant (such as a fluorine-based surfactant, a silicone-based surfactant, or a nonionic surfactant), a polymerization inhibitor, an antioxidant, and a chain transfer agent. The blending ratio of these components is appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.

[0214] <Solvent (E)> The radiation-sensitive composition of the present invention preferably contains a solvent (E). The solvent (E) is preferably an organic solvent that dissolves each component blended in the radiation-sensitive composition but does not react with each component.

[0215] Specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, octanol, and 1-methoxy-2-propanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, the solvent preferably contains at least one selected from the group consisting of ethers and esters, and more preferably contains at least one selected from the group consisting of ethylene glycol alkyl ether acetate, diethylene glycols, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate.

[0216] <Method for Preparing Radiation-Sensitive Composition> The radiation-sensitive composition can be prepared, for example, by mixing the polymer (A), the radiation-sensitive compound (B), and the polymerized ionic liquid (C), and, if necessary, other optional components, in a predetermined ratio. After mixing, the radiation-sensitive composition is preferably filtered, for example, through a filter having a pore size of approximately 0.05 μm to 0.4 μm. The solids concentration of the radiation-sensitive composition (the proportion of the total mass of the components other than the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected taking into consideration viscosity, volatility, and the like. The solids concentration of the radiation-sensitive composition is preferably in the range of 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 12 to 50% by mass. A solids concentration of 5% by mass or more ensures a sufficient coating thickness when the radiation-sensitive composition is applied to a substrate. Furthermore, when the solid content is 60% by mass or less, the thickness of the coating film does not become too large, and furthermore, the viscosity of the radiation-sensitive composition can be increased appropriately, ensuring good coatability.

[0217] <<Pattern (Cured Film) and Manufacturing Method Thereof>> The pattern (cured film) of the present invention is formed from the radiation-sensitive composition. The radiation-sensitive composition has high radiation sensitivity and good pattern-forming properties. Furthermore, by using the radiation-sensitive composition, it is possible to form a pattern (cured film) that exhibits high adhesion to a substrate even after development, has high capacitance, and has good chemical resistance.

[0218] When producing a pattern (cured film), the radiation-sensitive composition can be used to form a positive- or negative-tone cured film depending on the type of radiation-sensitive compound (B). The pattern (cured film) can be produced using the radiation-sensitive composition, for example, by a method including the following steps 1 to 4: (Step 1) applying the radiation-sensitive composition for forming a gate insulating film onto a substrate to form a coating film; (Step 2) irradiating at least a portion of the coating film with radiation; and (Step 3) developing the irradiated coating film to form a pattern. Each step will be described in detail below.

[0219] [Step 1: Coating Step] In this step, the radiation-sensitive composition is coated on a surface on which a film is to be formed (hereinafter also referred to as "film-forming surface"), and the solvent is removed, preferably by heat treatment (pre-baking), to form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. In the present invention, to form a gate insulating film, a coating film is formed on a substrate made of glass, resin, or the like, on which a gate electrode (scanning signal line) has been formed.

[0220] 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, and bar coating are preferred. Pre-baking conditions vary depending on the types and content ratios of each component in the radiation-sensitive composition, but are, for example, 60 to 130°C and 0.5 to 10 minutes. The thickness of the coating film formed (i.e., the film thickness after pre-baking) is preferably 0.1 to 12 μm. The radiation-sensitive composition applied to the surface to be coated may be subjected to reduced pressure drying (VCD) before pre-baking.

[0221] [Step 2: Exposure Step] In this step, at least a portion of the coating film formed in step 1 above is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film having a pattern can be formed. The pattern of the mask corresponds to the pattern of the gate insulating film. Examples of radiation include ultraviolet light, far ultraviolet light, visible light, X-rays, and charged particle beams such as electron beams. Among these, ultraviolet light is preferred, and examples include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m ２ is preferred.

[0222] [Step 3: Development Step] In this step, the coating film irradiated in step 2 above is developed. Specifically, the coating film irradiated in step 2 is developed using a developer to remove the irradiated portions (positive development), or to remove the unirradiated portions (negative development). Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of JP 2016-145913 A. The alkali concentration in the aqueous alkali solution is preferably 0.1 to 5% by mass in order to obtain adequate developability. Examples of the development method include a puddle method, a dipping method, a swing immersion method, and a 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, the patterned coating film is preferably rinsed with running water.

[0223] [Step 4: Heating Step] In this step, the coating film developed in step 3 above is heated (post-baked). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when the heating treatment is performed on a hot plate, and 10 to 80 minutes when the heating treatment is performed in an oven. In this manner, a cured film with the desired pattern can be formed on the substrate. Furthermore, to prevent deterioration of the gate electrode in this step, heating may be performed in an inert gas atmosphere such as nitrogen or argon.

[0224] <Semiconductor Device> A pattern (cured film) formed using the radiation-sensitive composition can be used in a semiconductor device. The pattern (cured film) can be suitably used as a gate insulating film disposed between a semiconductor layer and a gate electrode of a semiconductor device having the semiconductor layer and the gate electrode. The semiconductor device can be manufactured using a known method, except that a pattern (cured film) formed from the radiation-sensitive composition of the present invention is used as the gate insulating film. Examples of semiconductor devices include transistors such as organic electrochemical transistors (OECTs), and integrated circuits such as ICs and LSIs. The pattern (cured film) can also be used as an interlayer insulating film, protective film, planarizing film, etc. of a semiconductor device.

[0225] <Display Device> The semiconductor element of the present invention can be suitably used in a display device. That is, the pattern (cured film) of the present invention can be suitably used in a display device. Examples of such a display device include a liquid crystal display device, an organic EL display device, a micro LED (Light Emitting Diode) display device, and a quantum dot light-emitting display device.

[0226] <Wearable Devices> The semiconductor element of the present invention can be suitably used in wearable devices such as extracorporeal devices, surface-of-body devices, and intracorporeal devices. That is, the pattern (cured film) of the present invention can be suitably used in wearable devices. More specifically, the pattern (cured film) of the present invention can be used in stretchable wiring, stretchable substrates, housings, cover members, cables, sensors, and the like in wearable devices.

[0227] <<Electronic Skin Device>> An electronic skin device is a flexible and stretchable device that mimics the functions of human skin, and can be suitably used for medical implants, robotic sensor skin, and the above-mentioned wearable devices.

[0228] <Biosensor> The semiconductor element of the present invention can be suitably used in a biosensor. That is, the pattern (cured film) of the present invention can be suitably used in a biosensor. A biosensor is a sensor that detects the living activity of a living organism, particularly an animal. More specifically, examples include sensors that convert information such as body temperature, electrocardiogram, electromyogram, blood pressure, heart rate, cardiac output, blood glucose level, blood oxygen concentration, respiratory rate, and venous pattern of an animal such as a human into an electrical signal or an optical signal. Examples of the form of the biosensor include non-contact type, touch type, patch type, and wearable type.

[0229] <<Neuromorphic Device>> The semiconductor element of the present invention can be used as a neuromorphic device and is highly suitable as an artificial synapse. That is, the pattern (cured film) of the present invention can be suitably used in a neuromorphic device. A neuromorphic device is an element that mimics the human brain using a neural network (artificially mimics the relationship between neurons and synapses in the human brain).

[0230] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" are by mass unless otherwise specified.

[0231] [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 Apparatus: GPC-101 manufactured by Showa Denko K.K. GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC Corporation combined together Mobile phase: tetrahydrofuran Column temperature: 40°C Flow rate: 1.0 mL / min Sample concentration: 1.0 mass% Sample injection amount: 100 μL Detector: differential refractometer Standard material: monodisperse polystyrene

[0232] [Glass Transition Temperature (Tg)] The glass transition temperature (Tg) was measured by the following method. Measurement method: Differential scanning calorimetry (DSC) method Apparatus: TAQ2000 manufactured by TA Instruments Sample pan: Made of aluminum Measurement method: After setting the sample, it was equilibrated at 383 K for 30 minutes, then cooled to 183 K, and heated to 453 K. The heating and cooling cycle was then repeated three times at a rate of 10 K / min. The glass transition temperature (Tg) was determined as the midpoint of the specific heat step during cooling.

[0233] <Monomers Constituting Polymer (A)> The monomers used in the synthesis of Polymer (A) are as follows: (Monomer providing structural unit (I)) MI: Maleimide MA: Methacrylic acid (Monomer providing structural unit (II)) GMA: Glycidyl methacrylate OXMA: OXE-30 (Osaka Organic Chemical Industry Ltd.), (3-ethyloxetan-3-yl)methyl methacrylate M100: 3,4-epoxycyclohexylmethyl methacrylate (Monomer providing structural unit (III)) STMS: Styryltrimethoxysilane (Monomer providing structural unit (IV)) ST: Styrene MMA: Methyl methacrylate AM-1:

[0234] <Synthesis of Monomers Constituting Polymerized Ionic Liquid (C)> [Synthesis Example C1] Synthesis of ILMC: 1-[2-(2-(methacryloyloxy)ethoxy)ethoxy]ethyl]-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 23.7 g of 2-[2-(chloroethoxy)-ethoxy]ethanol (Tokyo Chemical Industry Co., Ltd.) was added dropwise to 60 mL of anhydrous methanol, and the resulting solution was then added dropwise to a solution of 10.0 g of N-methylimidazole (Tokyo Chemical Industry Co., Ltd.) in 25 mL of methanol at 0 to 1°C. The reaction mixture was stirred at 0 to 1°C for 1 hour, then at 20°C for 12 hours, at 40°C for 24 hours, and finally at 55°C for 30 hours. The solvent was removed under reduced pressure at 50°C, and the remaining viscous liquid was extracted with anhydrous acetonitrile (3 times x 50 mL) with vigorous stirring. The product was dried at 50°C / 1 mmHg for 6 hours. A slightly yellow, viscous liquid, 1-[2-(2-(2-hydroxyethoxy)ethoxy)ethyl]-3-methylimidazolium chloride, was obtained. Next, 6.25 g of distilled methacryloyl chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 mL of anhydrous acetonitrile, placed in a round-bottom flask, and cooled to 0 to 1°C in an ice bath. A solution of 10.0 g of 1-[2-(2-(2-hydroxyethoxy)ethoxy)ethyl]-3-methylimidazolium chloride dissolved in 20 mL of acetonitrile was slowly added dropwise to the cooled methacryloyl chloride solution, and the mixture was stirred at 0 to 1°C for 1.5 hours with gentle agitation. The ice bath was then removed, and the reaction mixture was reacted at 20°C for 5 hours and finally at 40°C for 12 hours. The resulting solution was washed with diethyl ether (5 times 15 mL) to remove excess methacryloyl chloride. After evaporation of the residual ether, the reaction mixture was dissolved in dichloromethane and precipitated in ethyl acetate. A catalytic amount of 4-methoxyphenol was then added to the product, which was then dried at 25°C / 14 mmHg for 2 hours and then further dried at 25°C / 1-2 mmHg for 2 hours to give 1-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-3-methylimidazolium chloride.9.04 g of lithium bis(trifluoromethylsulfonyl)imide (Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 mL of distilled water and added dropwise to a solution of 9.09 g of 1-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-3-methylimidazolium chloride in 15 mL of water. The mixture was stirred at 25°C for 2 hours to obtain an oily precipitate. The upper aqueous layer was removed, and the oily precipitate was redissolved in 90 mL of dichloromethane. The dichloromethane solution was washed with water three times (30 mL), and then with anhydrous MgSO. ４ The magnesium sulfate was filtered off, and the dichloromethane was removed under reduced pressure at -30°C, followed by further drying at 30°C / 1 mmHg for 2 hours. The final product was obtained as a slightly brown, transparent liquid (yield: 60%).

[0235] Synthesis Example C2: Synthesis of ILMA: 1-butyl-3-methylimidazolium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide. 15.0 g of potassium 3-(methacryloyloxy)propane-1-sulfonate (1) (Tokyo Chemical Industry Co., Ltd.) was suspended in 25 mL of anhydrous tetrahydrofuran under atmospheric protection. 1.7 mL of N,N-dimethylformamide was added as a catalyst using a syringe. The reaction flask was cooled to 0-1°C, and 39.9 g of excess thionyl sulfate (Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring. The reaction proceeded for 1 hour at 0-1°C and then for 12 hours at room temperature. The resulting suspension was carefully poured into 200 mL of ice water. The upper aqueous layer was removed, and the lower organic oily layer was diluted with 80 mL of dichloromethane. The dichloromethane solution was washed with 6 x 25 mL of water and then dried over anhydrous magnesium sulfate. ４The mixture was filtered, and the dichloromethane was evaporated under reduced pressure at below 30°C. The final yellow, transparent liquid was dried at 25°C / 12 mmHg for 2 hours and then at 25°C / 1-2 mmHg for 8 hours to obtain chlorosulfonylpropyl methacrylate. 7.3 g of trifluoromethanesulfonamide (Tokyo Chemical Industry Co., Ltd.) was placed in a flask, and 10.9 g of distilled anhydrous triethylamine (Tokyo Chemical Industry Co., Ltd.) was added with stirring. The reaction mixture was further diluted with 40 mL of anhydrous tetrahydrofuran, and the resulting colorless solution was cooled to 0°C in an ice bath. 11.1 g of chlorosulfonylpropyl methacrylate was added dropwise to the cooled tetrahydrofuran solution of trifluoromethanesulfonimide and triethylamine in anhydrous tetrahydrofuran. The reaction proceeded at 0°C for 1 hour and then at room temperature for another 1 hour. The resulting precipitate was removed by filtration, and the filtrate was lightly evaporated at room temperature. The remaining yellow, transparent liquid was redissolved in 90 mL of dichloromethane. The dichloromethane solution was washed with water (4 x 35 mL) and dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered, 4-methoxyphenol was added as a catalyst, and the dichloromethane was evaporated under reduced pressure at below 30°C. The remaining yellow, transparent liquid was finally dried over phosphorus pentoxide in a special flask at 35°C / 12 mmHg for 1 hour and then at 35°C / 1-2 mmHg for 3 hours to obtain triethylammonium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide. 30.0 g of triethylammonium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide was dissolved in 45 mL of anhydrous THF and stirred at room temperature under an inert gas atmosphere. 1.3 g of lithium hydride (Sigma-Aldrich) was added in one portion, and the resulting suspension was stirred at 30°C overnight. The unreacted lithium hydride was then removed by filtration, and the solution was concentrated under reduced pressure to give a yellow viscous liquid. The product was washed with hexane (3 x 40 mL), dried at 25 °C / 15 mmHg, and finally crystallized in anhydrous DCM to give a white crystalline powder.The powder was filtered under an inert gas atmosphere and dried overnight at 25°C / 1 mmHg to obtain lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide. 32.50 g of lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide was added dropwise to 150 ml of Milli-Q water and, with stirring at room temperature, added to 60 mL of an aqueous solution containing 21.10 g of 1-butyl-3-methylimidazolium bromide (Tokyo Chemical Industry Co., Ltd.). The resulting emulsion was stirred at room temperature for 2 hours. The organic solvent was extracted from the reaction mixture with dichloromethane. The mixture was washed with water (4 times x 30 mL) and dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate solution was filtered, a catalytic amount of 4-methoxyphenol was added, and the dichloromethane was removed under reduced pressure at room temperature. The mixture was then dried at 25°C / 0.08 mmHg for 8 hours. The final product was a pale yellow transparent liquid (yield: 30%).

[0236] Synthesis of Polymer (A) Synthesis Example 1 Synthesis of Polymer (A-1) 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN) and 200 parts of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, 20 parts of MA, 30 parts of GMA, 20 parts of OXMA, and 30 parts of ST were charged, and the atmosphere was purged with nitrogen. With gentle stirring, the temperature of the solution was raised to 70°C and maintained at this temperature for 5 hours, yielding a polymer solution containing Polymer (A-1). The solids concentration of this polymer solution was 34% by mass, and the Mw of Polymer (A-1) was 10,500, with a molecular weight distribution (Mw / Mn) of 2.2.

[0237] Synthesis Examples 2 to 6: Synthesis of Polymers (A-2) to (A-6) Polymer solutions containing polymers (A-2) to (A-6) having solids concentrations equivalent to that of polymer (A-1) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts (parts by mass) of each component were used as shown in Table 1. In Table 1, "-" indicates that the corresponding component was not used.

[0238]

[0239] Synthesis Example 7 Synthesis of Polymer (A-7) 24 parts of propylene glycol monomethyl ether was charged into a flask equipped with a condenser and a stirrer, followed by 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloyloxypropyltrimethoxysilane, and the solution was heated until the temperature reached 60°C. After the solution temperature reached 60°C, 0.1 parts of formic acid and 19 parts of water were charged, and the solution temperature was raised to 75°C with gentle stirring, and this temperature was maintained for 2 hours. After cooling to 45°C, 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Furthermore, the solution temperature was raised to 40°C, and evaporation was performed while maintaining the temperature to remove water and methanol generated by hydrolysis condensation, thereby obtaining a polymer solution containing polymer (A-7). The solids concentration of this polymer solution was 35% by mass, and the weight average molecular weight (Mw) of the polymer (A-7) was 1,800, and the molecular weight distribution (Mw / Mn) was 2.2.

[0240] Synthesis Example 8 Synthesis of Polymer (A-8) Under a dry nitrogen stream, 80 parts by mole of compound (AM-1), 5 parts by mole of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 100 parts by mole of 4,4'-oxydiphthalic anhydride were dissolved in dehydrated N-methyl-2-pyrrolidone (NMP) and reacted at 40°C for 1 hour. 30 parts by mole of 3-aminophenol was added as an end-capping agent in NMP solution, and the reaction was carried out at 40°C for 2 hours. Next, 200 parts by mole of N,N-dimethylformamide dimethyl acetal was added relative to the tetracarboxylic dianhydride added, and the reaction was carried out at 40°C for 6 hours. After the reaction solution was cooled to room temperature, it was poured into a large amount of distilled water, and the resulting precipitate was collected by filtration, washed three times with water, and then vacuum-dried at 80°C for 20 hours to obtain a powder of polymer (A-8).

[0241] Synthesis of Polymerized Ionic Liquid (C) Synthesis Example 9 Synthesis of Polymerized Ionic Liquid (C-1) 1.02 g of poly(ethylene glycol) methyl ether methacrylate (Mn = 500 g / mol) (Sigma-Aldrich) and 0.23 g of ILMA were dissolved in 3.00 g of anhydrous N,N-dimethylformamide (Tokyo Chemical Industry Co., Ltd.), to which 0.87 mg of 2,2-azobis(isobutyronitrile) (Tokyo Chemical Industry Co., Ltd.) and 7.40 mg of 4-cyano-4-phenylcarbonothionylthio)pentanoic acid (Sigma-Aldrich) were added, followed by stirring until the solution became clear. The solution was purged with argon in a three-neck flask equipped with a stir bar and heated at 60°C for 15 hours. The resulting viscous solution was cooled to room temperature (RT), diluted with N,N-dimethylformamide, and precipitated in an excess of diethyl ether. The copolymer was redissolved in ultrapure water and dialyzed against water for two days. 40 mg of 4-methoxyphenol was added to the resulting aqueous solution, and the mixture was dried for 12 hours at 50°C / 0.08 mmHg in an oven filled with diphosphorus pentoxide to obtain a pink viscous liquid. 0.50 g of the pink viscous liquid, 0.46 g of 2-phenylethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), and 0.40 mg of 2,2'-azobis(isobutyronitrile) were dissolved in 2.87 g of anhydrous N,N-dimethylformamide. The atmosphere was replaced with argon in a three-neck flask equipped with a stirring bar, and the mixture was heated at 60°C for 15 hours. The reaction was then stopped by rapid cooling with liquid nitrogen. The resulting viscous solution was diluted with dichloromethane, precipitated in excess diethyl ether, and dried at 25°C / 0.1 mbar for 24 hours, then at 50°C / 0.1 mbar in an oven filled with diphosphorus pentoxide for 24 hours to obtain a white solid wax (C-1) (yield: 40%, weight-average molecular weight: 100,000, glass transition temperature: -51°C). The ratio of poly(ethylene glycol) methyl ether methacrylate, ILMA, and 2-phenylethyl methacrylate used in the polymerized ionic liquid (C-1) was 42:10:48 (mass ratio).

[0242] Synthesis Example 10: Synthesis of Polymerized Ionic Liquid (C-2) 1.02 g of poly(ethylene glycol) methyl ether methacrylate (Mn = 500 g / mol) and 0.23 g of ILMC were dissolved in 3.00 g of anhydrous N,N-dimethylformamide. To this solution, 0.87 mg of 2,2'-azobis(isobutyronitrile) and 7.40 mg of 4-cyano-4-(phenylcarbonothionylthio)pentanoic acid were added and stirred until the solution became clear. The solution was placed in a three-necked flask equipped with a stir bar, purged with argon, and heated at 60°C for 15 hours. The resulting viscous solution was cooled to room temperature, diluted with N,N-dimethylformamide, and precipitated in an excess of diethyl ether. The copolymer was redissolved in ultrapure water and dialyzed against water for two days. 40 mg of 4-methoxyphenol was added to the resulting aqueous solution, and the mixture was dried in an oven filled with diphosphorus pentoxide at 50°C / 0.1 mbar for 12 hours to obtain a pink viscous liquid. 0.50 g of the pink viscous liquid, 0.46 g of 2-phenylethyl methacrylate, and 0.40 mg of 2,2'-azobis(isobutyronitrile) were dissolved in 2.87 g of anhydrous N,N-dimethylformamide, and the atmosphere was replaced with argon in a three-neck flask equipped with a stirring bar. The mixture was then heated at 60°C for 15 hours. The reaction was then stopped by rapid cooling with liquid nitrogen. The resulting viscous solution was diluted with dichloromethane, precipitated in excess diethyl ether, and dried at 25°C / 0.1 mbar for 24 hours, then at 50°C / 0.1 mbar in an oven filled with diphosphorus pentoxide for 24 hours to obtain a pink solid waxy product (C-2) (yield: 40%, weight-average molecular weight: 100,000, glass transition temperature: -53°C). The ratio of poly(ethylene glycol) methyl ether methacrylate, ILMC, and 2-phenylethyl methacrylate used in the polymerized ionic liquid (C-2) was 42:10:48 (mass ratio).

[0243] Synthesis Example 11: Synthesis of Polymerized Ionic Liquid (C-3) 1.02 g of poly(ethylene glycol) methyl ether methacrylate (Mn = 500 g / mol), 0.23 g of ILMC, and 1.2 g of 2-phenylethyl methacrylate were dissolved in 8.00 g of anhydrous N,N-dimethylformamide. To this was added 8.05 mg of 2,2'-azobis(isobutyronitrile), and the mixture was stirred until the solution became clear. The solution was placed in a three-neck flask equipped with a stir bar, purged with argon, and then heated at 60°C for 15 hours. The resulting viscous solution was cooled to room temperature, diluted with N,N-dimethylformamide, and precipitated in an excess amount of diethyl ether. The copolymer was redissolved in ultrapure water and dialyzed against water for two days. To the resulting aqueous solution, 40 mg of 4-methoxyphenol was added, and the mixture was dried in an oven filled with diphosphorus pentoxide at 50°C / 0.1 mbar for 12 hours to obtain a pink viscous liquid (C-3) (yield: 60%, weight-average molecular weight: 100,000, glass transition temperature: -45°C). The ratio of poly(ethylene glycol) methyl ether methacrylate, ILMC, and 2-phenylethyl methacrylate used in the polymerized ionic liquid (C-3) was 42:10:48 (mass ratio).

[0244] Synthesis Example 12: Synthesis of Polymerized Ionic Liquid (C-4) 0.23 g of ILMC and 1.2 g of 2-phenylethyl methacrylate were dissolved in 8.00 g of anhydrous N,N-dimethylformamide. 7.75 mg of 2,2'-azobis(isobutyronitrile) was added and stirred until the solution became clear. The solution was placed in a three-necked flask equipped with a stir bar, purged with argon, and heated at 60°C for 15 hours. The resulting viscous solution was cooled to room temperature, diluted with N,N-dimethylformamide, and precipitated in an excess amount of diethyl ether. The copolymer was redissolved in ultrapure water and dialyzed against water for two days. 40 mg of 4-methoxyphenol was added to the resulting aqueous solution, and the mixture was dried in an oven filled with diphosphorus pentoxide at 50°C / 0.1 mbar for 12 hours to obtain a pink viscous liquid (C-4) (yield: 60%, weight-average molecular weight: 100,000, glass transition temperature: 5°C). The ratio of ILMC to 2-phenylethyl methacrylate used in the polymerized ionic liquid (C-4) was 16:84 (mass ratio).

[0245] Synthesis Example 13 Synthesis of Polymerized Ionic Liquid (C-5) 2.0 g of poly(methylhydrosiloxane) (Sigma-Aldrich) and 5.0 g of 5-bromo-1-pentene (Tokyo Chemical Industry Co., Ltd.) were placed in a three-necked flask equipped with a stirrer. The reaction vessel was purged with argon for 20 minutes, and 30 μL of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (Sigma-Aldrich) was added. The reaction mixture was stirred at 60°C for 15 hours. After completion of the reaction, the solvent was removed and the resulting mixture was precipitated in excess methanol to obtain polymethylhydrosiloxane-graft-5-bromo-1-pentene as a brown oil. A two-necked round-bottom flask equipped with a stirrer was charged with a solution of 2.4 g of polymethylhydrosiloxane graft-5-bromo-1-pentene in 30 mL of dichloromethane and 1.03 g of 1-methylimidazole (Tokyo Chemical Industry Co., Ltd.). The reaction was stirred at 70°C for 72 hours. After completion of the reaction, the solvent was removed under reduced pressure, the mixture was washed three times with dichloromethane, and vacuum dried at 40°C to obtain polymethylhydrosiloxane graft-5-imidazolium-1-pentene bromide. A round-bottom flask equipped with a stirrer was charged with 1.0 g of polymethylhydrosiloxane graft-5-imidazolium-1-pentene bromide, with 20 mL of ultrapure water to prepare a solution, to which 1.3 g of lithium bis(trifluoromethanesulfonyl)imide (Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at room temperature for 7 days. The precipitate was further washed three times with ultrapure water and dried in vacuum at 40° C. to obtain (C-5) in the form of a viscous liquid (weight average molecular weight: 3,000, Tg: −40° C.).

[0246] Synthesis Example 14 Synthesis of Polymer (CC-1) 0.23 g of ILMC and 3.9 g of phenyl methacrylate (Tokyo Chemical Industry Co., Ltd.) were dissolved in 8.00 g of anhydrous N,N-dimethylformamide, and 7.75 mg of 2,2'-azobis(isobutyronitrile) was added. Stirring was continued until the solution became clear. The solution was placed in a three-necked flask equipped with a stirring bar, purged with argon, and heated at 60°C for 15 hours. The resulting viscous solution was cooled to room temperature, diluted with N,N-dimethylformamide, and precipitated in an excess amount of ethyl ether. The copolymer was redissolved in ultrapure water and dialyzed against water for two days. To the resulting aqueous solution, 40 mg of 4-methoxyphenol was added, and the mixture was dried in an oven filled with diphosphorus pentoxide at 50°C / 0.1 mbar for 12 hours to obtain a pink viscous liquid (CC-1) (yield: 60%, weight-average molecular weight: 100,000, glass transition temperature: 45°C).

[0247] <Preparation of Radiation-Sensitive Composition> The polymer (A), radiation-sensitive compound (B), polymerized ionic liquid (C), adhesion aid (D), and polymerizable monomer (X1) used in the preparation of the radiation-sensitive composition are shown below. (Polymer (A)) A1 to A8: Polymers (A-1) to (A-8) synthesized in Synthesis Examples 1 to 8. (Radiation-sensitive compound (B)) B-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol). B-2: Irgacure PAG121 (manufactured by BASF). B-3: Irgacure OXE-01 (manufactured by BASF). (Polymerized ionic liquid (C)) C-1 to C-5: Polymerized ionic liquids (C-1) to (C-5) synthesized in Synthesis Examples 9 to 13. CC-1: Polymer (CC-1) synthesized in Synthesis Example 14. (Adhesion aid (D)) D-1: 3-glycidoxypropyltrimethoxysilane (Polymerizable monomer (X1)) X-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0248] <Preparation of Radiation-Sensitive Composition> [Example 1] 20 parts of radiation-sensitive compound (B-1), 100 parts of polymerized ionic liquid (C-1), and 5 parts of adhesion aid (D-1) were mixed in an amount equivalent to 100 parts (solid content) of polymer (A-1), and propylene glycol monomethyl ether acetate was added as a solvent to dissolve the mixture to a solid content concentration of 20 mass %. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0249] [Examples 2 to 14, Comparative Example 1] Radiation-sensitive compositions were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component were used as shown in Table 2. In Table 2, "-" indicates that the corresponding component was not used.

[0250] The radiation-sensitive compositions prepared above were subjected to the following evaluations.

[0251] [Evaluation of Pattern Formability] Using a spinner, the radiation-sensitive composition was applied to a silicon substrate that had been treated with HMDS (hexamethyldisilazane) at 60°C for 60 seconds, and then prebaked on a hot plate at 110°C for 2 minutes to form a coating film with an average thickness of 1.0 µm. This coating film was irradiated with 100 J / m² of light from a mercury lamp through a mask having a line and space pattern of arbitrary size with a line and space width of 1:1. ２ The sample was irradiated with ultraviolet light of 1000 kJ / cm. Then, a development process was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C for 60 seconds, followed by rinsing with running ultrapure water for 1 minute. At this time, the width at which a line and space pattern could be formed was measured. A measurement value of less than 5 μm was evaluated as "A," a measurement value of 5 μm or more was evaluated as "B," and a measurement value of impossible to form was evaluated as "C."

[0252] [Evaluation of Capacitance Cp] The radiation-sensitive composition was applied to a glass substrate on which ITO had been vapor-deposited to a thickness of 100 nm and pre-baked at 230°C for 30 minutes, and then pre-baked at 110°C for 2 minutes to form a coating film with a thickness of 3.0 μm (formation of substrate with coating film). A 5 mmφ Al electrode pattern was formed on this coating film (gate insulating film) by vapor deposition to prepare a sample for dielectric constant measurement. For the substrate with this electrode pattern, capacitance Cp was measured by the CV method at a frequency of 10 kHz using a Yokogawa-Hewlett-Packard HP16451B electrode and HP4284A precision LCR meter. This value was 1×10 －９ If it is F or above, it is "A", 1 x 10 －９ Less than F 3 x 10 －１０ F or above is "B", 3 x 10 －１０ A rating of less than F was rated as "C." A was rated as extremely good capacitance, B was rated as good, and C was rated as poor.

[0253] [Evaluation of Bleed-Out] Using a spinner, a radiation-sensitive composition was applied to a silicon substrate that had been treated with HMDS (hexamethyldisilazane) at 60° C. for 60 seconds, and then the substrate was pre-baked on a hot plate at 110° C. for 2 minutes, after which it was visually inspected for the occurrence of liquid bleeding. If no bleeding occurred, the evaluation was "absent," and if bleeding occurred, the evaluation was "present."

[0254]

[0255] As shown in Table 2, the radiation-sensitive compositions of Examples 1 to 14 exhibited good pattern formability, and the cured films obtained from these compositions had good pattern formability and capacitance, and no bleed-out was observed. In Comparative Example 1, on the other hand, the capacitance was poor.

Claims

at least one polymer (A) selected from the group consisting of a polymer (A1) containing a structural unit (I) having an acid group, a siloxane polymer (A2), and a polyamic acid or a polyamic acid ester (A3); a radiation-sensitive compound (B); a polymerized ionic liquid (C) having a glass transition temperature of 5°C or less; A radiation-sensitive composition for forming a gate insulating film, comprising: 　 The polymerized ionic liquid (C) is a polymer having an anion moiety and a cation moiety, 2. The radiation-sensitive composition for forming a gate insulating film according to claim 1, wherein the polymer is an acrylic polymer or a polysiloxane polymer.

2. The radiation-sensitive composition for forming a gate insulating film according to claim 1, wherein the polymerized ionic liquid (C) includes one or more partial structures (C1) selected from the group consisting of the following formulae (C1-1) and (C1-2): (In formulas (C1-1) and (C1-2), Rc １１ is a halogen atom or a substituted or unsubstituted chain hydrocarbon group. X ｍ＋ is a proton or an onium cation. 　 m is an integer of 1 to 3. * indicates a bond to another structure in the polymerized ionic liquid (C).

4. The radiation-sensitive composition for forming a gate insulating film according to claim 3, wherein the polymerized ionic liquid (C) is a polymer having a structural unit (X) represented by the following formula (1) or (2): (In formulas (1) and (2), R ｃ１ is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ｃ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, or is bonded to a silicon atom of a different structural unit to form a siloxane bond. L ｃ１１ , L ｃ１２ is a single bond or a divalent linking group. R ｃ１２ , R ｃ１３ , R ｃ１４ is a single bond or a divalent organic group having 1 to 20 carbon atoms. D is a partial structure (C1) represented by the above formula (C1-1) or formula (C1-2).

2. The radiation-sensitive composition for forming a gate insulating film according to claim 1, wherein the polymerized ionic liquid (C) comprises one or more partial structures (C2) selected from the group consisting of the following formulae (C2-1), (C2-2), (C2-3), (C2-4), and (C2-5): (In formulas (C2-1) to (C2-5), R ｃ２２ , R ｃ２３ , R ｃ２４ , R ｃ２５ , R ｃ２６ , R ｃ２８ , R ｃ３０ , R ｃ３１ , R ｃ３２ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group containing —O—, —CO— or —COO— between carbon atoms in the hydrocarbon group having 1 to 20 carbon atoms. R ｃ２１ , R ｃ２７ , R ｃ２９ are each independently a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group containing —O—, —CO— or —COO— between carbon atoms in the hydrocarbon group having 1 to 20 carbon atoms. s1 is 0 or 1. Y － is an anion. * indicates a bond to another structure in the polymerized ionic liquid (C).

6. The radiation-sensitive composition for forming a gate insulating film according to claim 5, wherein the polymerized ionic liquid (C) is a polymer having a structural unit (XI) represented by the following formula (3) or (4): (In formulas (3) and (4), R ｃ１ is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ｃ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms. L ｃ２１ , L ｃ２２ is a single bond or a divalent linking group. R ｃ３３ , R ｃ３４ , R ｃ３５ is a single bond or a divalent organic group having 1 to 20 carbon atoms. A is a partial structure (C2) represented by the above formula (C2-1), formula (C2-2), formula (C2-3), formula (C2-4), or formula (C2-5).

2. The radiation-sensitive composition for forming a gate insulating film according to claim 1, wherein the polymerized ionic liquid (C) has a polyalkylene oxide chain.

2. The radiation-sensitive composition for forming a gate insulating film according to claim 1, wherein the radiation-sensitive compound (B) includes a quinone diazide compound (B-1). 　 the radiation-sensitive compound (B) contains a photopolymerization initiator (B-2), The radiation-sensitive composition for forming a gate insulating film according to claim 1 , which comprises a polymerizable monomer (X). 　 The polymer (A1) further comprises a structural unit (III) having one or more groups selected from the group consisting of a group represented by the following formula (a2) and an acid-dissociable group:

2. The radiation-sensitive composition for forming a gate insulating film according to claim 1, wherein the radiation-sensitive compound (B) includes a photoacid generator (B-3). (In formula (a2), R １ , R ２ and R ３ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. １ , R ２ and R ３ At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" indicates a bond.) 　 a step of applying the radiation-sensitive composition for forming a gate insulating film according to any one of claims 1 to 10 onto a substrate to form a coating film; irradiating at least a portion of the coating film with radiation; developing the radiation-irradiated coating film to form a pattern; A method for manufacturing a pattern, comprising: 　 The method for manufacturing a pattern according to claim 11, further comprising the step of heating the pattern after the step of forming the pattern. 　 A pattern obtained by the method for producing a pattern according to claim 11. 　 A cured film for a gate insulating film obtained from the radiation-sensitive composition for forming a gate insulating film according to any one of claims 1 to 10. 　 A semiconductor device comprising the cured film according to claim 14. 　 An organic electrochemical transistor comprising the cured film according to claim 14. 　 An organic electroluminescence display device comprising the cured film according to claim 14. 　 A liquid crystal display device comprising the cured film according to claim 14. 　 A micro LED display device comprising the cured film according to claim 14. 　 A quantum dot light-emitting display device comprising the cured film according to claim 14. 　 A wearable device comprising the cured film according to claim 14. 　 An electronic skin device comprising the cured film of claim 14. 　 A biosensor comprising the cured film according to claim 14. 　 A neuromorphic device comprising the cured membrane of claim 14.

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