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, biological sensor, and neuromorphic device

Abstract

The purpose of the present invention is to provide: a radiation-sensitive composition which is capable of forming a gate insulating film pattern (cured film) that has elasticity and can exhibit pattern formability, capacitance, and chemical resistance at a sufficient level; a pattern (cured film) formed from the radiation-sensitive composition; a method for producing the same; and a cured film for a gate insulating film. Comprising the cured 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 biological sensor, and a neuromorphic device. The present invention relates to a radiation-sensitive composition for forming a gate insulating film (excluding a composition comprising a cresol novolac and a quinonediazide compound), a radiation-sensitive composition containing: 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 polyamic acid ester (A3); a radiation-sensitive compound (B); and an ionic liquid (C).

Description

TECHNICAL FIELD

[0001] The present application relates to a radiation-sensitive composition for forming a gate insulating film, a pattern and a manufacturing method thereof, a hardened 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 biological sensor, and a neuromorphic device. BACKGROUND

[0002] A field effect transistor such as a thin film transistor (TFT) is widely used as a unit electronic element of a semiconductor memory integrated circuit, a high-frequency signal amplification element, a liquid crystal drive element, and the like. Among them, in various display devices such as a liquid crystal display (LCD), an organic electroluminescence (EL) display device, and the like, it is widely used as a switching element that applies a drive voltage to a display element to drive the display device.

[0003] The thin film transistor generally includes a semiconductor layer, a gate electrode, a source electrode, and a drain electrode, and controls a current flowing through the semiconductor layer by applying a voltage between the source electrode and the drain electrode from the gate electrode via a gate insulating film. In the past, in the formation of the gate insulating film, silicon oxide (SiO2) or silicon nitride (SiN) or the like as an inorganic material has been used.

[0004] In recent years, flexible devices such as flexible displays are being actively developed, and in order to be suitable for such flexible devices, stretchability is required for transistors such as TFTs, and of course, stretchability is required for gate insulating films. However, the gate insulating film formed of the inorganic material sometimes lacks stretchability and breaks.

[0005] Regarding the transistor having stretchability, an organic thin film transistor (OTFT) in which each structural member is composed of an organic material has attracted attention, and in recent years, a large amount of research and development has been conducted. In addition, as an organic material for forming a gate insulating film, for example, an ionic gel is known, which is formed by mixing an ionic liquid in a positive type photoresist containing cresol novolak to which naphthoquinonediazide as a photosensitizer is added (for example, refer to Patent Document 1).

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent Laid-Open No. 2016-80998 SUMMARY

[0009] The problem that the invention aims to solve

[0010] In recent years, there has been a demand for developing transistors that are flexible and have low drive voltages, suitable for flexible devices. This also requires the gate insulating film used in such transistors to be flexible, and consequently, to possess characteristics such as patterning ability, high capacitance, and chemical resistance.

[0011] Therefore, the object of the present invention is to provide a linearly emitting composition capable of forming a gate insulating film with stretchability and sufficient level of patterning ability, capacitance and chemical resistance, a pattern (hardened film) formed by said linearly emitting composition and a method for manufacturing the same, a hardened film for a gate insulating film, a semiconductor element including said hardened film, an organic electrochemical transistor, an organic EL display device, a liquid crystal display device, a light emitting diode (LED) display device, a quantum dot light emitting display device, a wearable device, an electronic skin device, a biosensor, and a neuromorphic device.

[0012] Technical means to solve the problem

[0013] The inventors have made repeated efforts to solve this problem and have found that the objective can be achieved by formulating a polymer (A) with a specific structure, a radiosensitive linear compound (B), and an ionic liquid (C) into a radiosensitive linear composition, thus completing the present invention.

[0014] In one embodiment, the present invention relates to an inductively linearized composition for forming a gate insulating film (excluding compositions comprising cresol varnish and quinone diazide compounds), which contains:

[0015] At least one polymer (A) selected from the group consisting of polymers (A1) containing structural units (I) having acid groups, siloxane polymers (A2), and polyamic acids or polyamic esters (A3).

[0016] Radiosensitive linear compound (B), and

[0017] Ionic liquids (C).

[0018] In another embodiment, the present invention relates to a method for manufacturing a pattern and a pattern obtained by the method, the method comprising:

[0019] The process of forming the gate insulating film by coating a substrate with an inductively linearized composition;

[0020] The process of irradiating at least a portion of the coating with radiation; and

[0021] A process of developing a pattern from a coating film irradiated with said radiation.

[0022] In another embodiment, the present invention relates to a hardened film for a gate insulating film formed using the aforementioned gate insulating film forming radiometric linear composition, and to semiconductor devices, organic electrochemical transistors, organic EL display devices, liquid crystal display devices, micro LED display devices, quantum dot light-emitting display devices, wearable devices, electronic skin devices, biosensors, and neuromorphic devices including the hardened film.

[0023] The effects of the invention

[0024] The radiosensitive linear composition for forming a gate insulating film of the present invention can construct a pattern (hardened film) with excellent patterning properties, capacitance, and chemical resistance. Transistors having the pattern (hardened film) as a gate insulating film can be driven at low voltage and also exhibit stretchability. This is because the radiosensitive linear composition for forming a gate insulating film contains an ionic liquid, and if the pattern (hardened film) obtained from the composition is used as a gate insulating film, an electrical double layer can be formed, thereby reducing the driving voltage of the transistor. Furthermore, compared to gate insulating films containing inorganic materials, the stretchability is also superior. Additionally, by preparing a radiosensitive linear composition containing a specific polymer (A), a radiosensitive linear compound (B), and an ionic liquid (C), excellent patterning properties and chemical resistance are also achieved.

[0025] In the method for manufacturing the pattern of the present invention, since the radiosensitive linear composition capable of forming a pattern (hardened film) with good pattern-forming properties and excellent capacitance and chemical resistance is used, high-quality patterns (hardened films) can be formed efficiently. The patterns (hardened films) of the present invention exhibit excellent pattern-forming properties, capacitance, and chemical resistance due to the use of the radiosensitive linear composition.

[0026] The semiconductor elements, organic electrochemical transistors, organic EL display devices, liquid crystal display devices, micro LED display devices, quantum dot light-emitting display devices, wearable devices, electronic skin devices, biosensors, and neuromorphic devices of the present invention are of high quality due to the inclusion of patterns (hardened films) with excellent patterning properties, capacitance, and chemical resistance. Detailed Implementation

[0027] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0028] The following provides a detailed description of matters related to the implementation method. Furthermore, in this specification, the numerical range indicated by “~” means the values ​​before and after the “~” are considered as lower and upper limits. A “structural unit” refers to a unit that primarily constitutes the main chain structure, and is one of at least two units contained within the main chain structure.

[0029] In this specification, "hydrocarbon group" encompasses chain-like hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain-like hydrocarbon group" refers to a straight-chain hydrocarbon group or branched hydrocarbon group that contains only a chain structure in its main chain and no cyclic structure. It can be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as its ring structure and does not contain an aromatic ring structure. It is not necessary to contain only an alicyclic hydrocarbon structure; it may also include those with a chain structure in a portion of their structure. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure. It is not necessary to contain only an aromatic ring structure; it may also contain a chain structure or an alicyclic hydrocarbon structure in a portion of its structure. Furthermore, the ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may also have substituents containing hydrocarbon structures. "Cyclic hydrocarbon group" encompasses both alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0030] In this specification, "(meth)acryloyl" means including both "acryloyl" and "methacryloyl", "(meth)acrylic acid" means including both "acrylic acid" and "methacrylic acid", and "(meth)acrylate" means including both "acrylate" and "methacrylate".

[0031] Radioactive linear compositions

[0032] The radiosensitive linear composition of this embodiment (hereinafter also simply referred to as the "composition") contains at least one polymer (A) selected from the group consisting of a polymer (A1) comprising a structural unit (I) having an acid group, a siloxane polymer (A2), and a polyamic acid or polyamic ester (A3). The radiosensitive linear composition of the present invention does not contain compositions that simultaneously contain both cresol phenolic varnish and a quinone diazide compound.

[0033] The radioactive linear composition of the present invention is suitable for use in forming gate insulating films because it can form patterns (hardened films) with good patterning properties and excellent capacitance and chemical resistance.

[0034] <Polymer (A)>

[0035] The polymer (A) is selected from at least one of the group consisting of polymers (A1) containing structural units (I) having acid groups, siloxane polymers (A2), and polyamic acids or polyamic esters (A3).

[0036] (Polymer (A1))

[0037] The polymer (A1) is an aggregate of polymers containing structural units (I) having acid groups (hereinafter, the aggregate is also referred to as the "base polymer"). The structural unit (I) need only be contained in at least one polymer constituting the base polymer. The polymer (A1) may also contain structural units other than structural units (I). The structural units contained in the polymer (A1) will be described below.

[0038] [Structural Unit (I)]

[0039] The polymer (A1) can improve its solubility (alkali solubility) in alkaline developing solutions or enhance its curing reactivity by having structural units (I) with acid groups. Furthermore, in this specification, "alkali solubility" means that it can dissolve or swell in alkaline aqueous solutions such as a 2.38% by mass solution of tetramethylammonium hydroxide.

[0040] The structural unit (I) is not particularly limited as long as it has an acid group, but is preferably selected from at least one of the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. In addition, in this specification, the term "phenolic hydroxyl group" refers to a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0041] Structural unit (I) is preferably derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having acid groups are provided below.

[0042] As monosaccharides that constitute structural units with carboxyl groups, examples include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, medoconic acid, and itaconic acid.

[0043] Examples of monosemblables that constitute structural units having sulfonic acid groups include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, and (meth)acryloyloxyethyl sulfonic acid.

[0044] Examples of monomorphs that constitute structural units with phenolic hydroxyl groups include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl methacrylate.

[0045] In addition, maleimide can also be used as a monolith that constitutes structural unit (I).

[0046] Among these, unsaturated monocarboxylic acids and maleimides are preferred, and (meth)acrylic acid and maleimides are more preferred.

[0047] The basic polymer may contain one structural unit (I) or a combination of two or more structural units (I).

[0048] The lower limit of the content ratio (total content ratio in the case of multiple structural units) of structural unit (I) relative to all structural units constituting the base polymer is preferably 1% by mass, more preferably 2% by mass, and even more preferably 5% by mass. Furthermore, the upper limit of the content ratio is preferably 40% by mass, more preferably 35% by mass, even more preferably 30% by mass, and particularly preferably 20% by mass. By setting the content ratio of structural unit (I) within the aforementioned range, good solubility in alkaline developing solutions is imparted, and therefore preferred.

[0049] [Structural Unit (II)]

[0050] The polymer (A1) may contain structural units (II) having one or more groups selected from the group consisting of oxetyl and oxetylpropyl. The inclusion of structural units (II) in the polymer (A1) further improves the resolution or adhesion of the film, and is therefore preferred. Furthermore, by utilizing the epoxy group as a crosslinking group, a pattern (hardened film) with high heat resistance and long-term degradation suppression can be formed. Structural units (II) are preferably derived from unsaturated monomers having epoxy groups, and more specifically, are preferably structural units represented by the following formula (1).

[0051] [Chemistry 1]

[0052]

[0053] (In equation (1), R) 21 It is a monovalent group having an oxetine propyl or oxetine butyl group; R α It can be a hydrogen atom, methyl, hydroxymethyl, cyano, or trifluoromethyl; X 1 (For single-bond or divalent linkages)

[0054] In the above equation (1), R is... 21 Examples include: oxetyl propyl, oxetyl butyl, 3,4-epoxycyclohexyl, 3,4-epoxytricyclic [5.2.1.0] 2,6 Decyl, 3-methyloxetyl, 3-ethyloxetyl, etc.

[0055] As X 1 The divalent linker is preferably a alkyl dimethyl group, such as methylene, ethylene, or 1,3-propanediyl.

[0056] Specific examples of monomers providing structural unit (II) represented by formula (1) include, for example: glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0] 2,6 [Methyl methyl methacrylate, 3-methyloxetane-3-yl methacrylate, 3-ethyloxetane-3-yl methacrylate, methyl methacrylate, 3-ethyloxetane-3-yl methacrylate, etc. Among these, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3-ethyloxetane-3-yl methacrylate are preferred.]

[0057] The base polymer may contain one structural unit (II) or a combination of two or more structural units (II).

[0058] When the polymer (A1) contains structural unit (II), the lower limit of the content ratio (total content ratio in the case of multiple structural units) of structural unit (II) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 15% by mass, and even more preferably 25% by mass. Furthermore, the upper limit of the content ratio is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. By setting the content ratio of structural unit (II) within the aforementioned range, the coating film exhibits better resolution, and the heat resistance and chemical resistance of the obtained pattern (hardened film) can be significantly improved; therefore, this is preferable.

[0059] [Structural Unit (III)]

[0060] In the case that the radiosensitive linear composition of the present invention is a chemically amplified composition (hereinafter referred to as the "third composition"), from the viewpoint that a coating with excellent development adhesion can be formed, it is preferable that the polymer (A1) further comprises a structural unit (III) having one or more groups selected from the group represented by the following formula (2) and acid-dissociable groups.

[0061] [Chemistry 2]

[0062]

[0063] (In equation (2), R) 1 R 2 and R 3 Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl or phenyl group having 1 to 10 carbon atoms; wherein, R1 R 2 and R 3 At least one of them is an alkoxy group having 1 to 6 carbon atoms; "Indicates a bond"

[0064] As R 1 ~R 3 Alkoxy groups with 1 to 6 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc. Among these, R... 1 ~R 3 The alkoxy group is preferably methoxy or ethoxy.

[0065] R 1 ~R 3 The alkyl group having 1 to 10 carbon atoms can be either straight-chain or branched. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among these, methyl, ethyl, or propyl is preferred.

[0066] From the perspective of obtaining a heat-resistant hardened film by forming a cross-linked structure and improving the storage stability of the radiosensitive linear composition, R is preferred. 1 ~R 3 At least one of them is an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all of them are alkoxy groups.

[0067] In the above, R 1 Preferably, it is an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy or ethoxy group. 2 and R 3 Preferably, it is a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a phenyl group; more preferably, it is a hydroxyl group, an alkoxy group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms.

[0068] In structural unit (III), the group represented by formula (2) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. Furthermore, in this specification, "aromatic ring group" refers to a group formed by removing n (n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of such aromatic rings include: benzene rings, naphthalene rings, and anthracene rings. The ring may have substituents such as alkyl groups. Examples of such chain hydrocarbon groups bonded to the group represented by formula (2) include: alkyldiyl groups, alkenediyl groups, etc.

[0069] In this embodiment, the group represented by formula (2) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. That is, structural unit (III) is preferably composed of at least one group selected from the group represented by formula (2-1), formula (2-2), and formula (2-3).

[0070] [Chemistry 3]

[0071]

[0072] (In equations (2-1), (2-2), and (2-3), A) 1 and A 2 Each is independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; n1 is an integer from 0 to 4; n2 is an integer from 0 to 6; wherein, when n1 is 2 or more, multiple A atoms... 1 They are either identical or different bases; when n² is greater than 2, multiple A's are... 2 For mutually identical or different bases; R 31 It is an alkyl diol; R 1 R 2 and R 3 It has the same meaning as the above formula (2); "Indicates a bond"

[0073] As A 1 and A 2 The alkoxy group having 1 to 6 carbon atoms can be suitably represented by R of formula (2). 1 ~R 3 Examples include alkoxy groups having 1 to 6 carbon atoms. Additionally, as A... 1 and A 2 Alkyl groups having 1 to 6 carbon atoms may suitably employ R of formula (2). 1 ~R 3 The alkyl group having 1 to 10 carbon atoms that corresponds to the group having 1 to 6 carbon atoms.

[0074] The group "-SiR" bonded to the aromatic ring 1 R 2 R 3 The position of " relative to A" 1 and A 2 Other bases besides these can be in any position. For example, in the case of equation (2-1), "-SiR" 1 R 2 R 3 The position of “” can be any of the adjacent, intermediate, or opposite positions, with the opposite position being preferred.

[0075] n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0 to 2, more preferably 0.

[0076] In the above equation (2-3), R 31 Preferably, it is linear. From the viewpoint of improving the heat resistance of the obtained hardened film, R 31 Preferably, it has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

[0077] In equations (2-1) to (2-3), the structural unit (III) preferably has at least one from the group consisting of the bases represented by equation (2-1) and the bases represented by equation (2-2). Additionally, in the base "-SiR..." 1 R 2 R 3 "When directly bonded to an aromatic ring, the silanol groups generated in the presence of water can be stabilized. This improves the solubility of the exposure section in alkaline developer and allows for the formation of good patterns, which is preferable in this respect. Among these, structural unit (III) is particularly preferred to be a structural unit having the base represented by the formula (2-1)."

[0078] The structural unit (III) is preferably a structural unit derived from a monolith having polymeric carbon-carbon unsaturated bonds (hereinafter also referred to as "unsaturated monolith"), and more specifically, preferably at least one selected from the group consisting of the structural unit represented by the following formula (2a-1) and the structural unit represented by the following formula (2a-2).

[0079] [Chemistry 4]

[0080]

[0081] (In equations (2a-1) and (2a-2), R) α1 It can be a hydrogen atom, methyl, hydroxymethyl, cyano, or trifluoromethyl; R 32 and R 33 Each is independently a divalent aromatic cyclic group or a chain hydrocarbon group; R 1 R 2 and R 3 (This has the same meaning as equation (2) above)

[0082] In equations (2a-1) and (2a-2), R 32 R 33 The divalent aromatic cyclic group is preferably a substituted or unsubstituted phenylene or a substituted or unsubstituted naphthylene. The divalent chain hydrocarbon group is preferably an alkyldiyl group having 1 to 6 carbon atoms, more preferably an alkyldiyl group having 1 to 4 carbon atoms.

[0083] Regarding the aspects of obtaining patterns (hardened films) with higher heat resistance and hardness, and improving the solubility of the exposure section in alkaline developing solutions, R... 32 R 33 Preferably, it is a divalent aromatic cyclic group, and particularly preferably a substituted or unsubstituted phenylene group.

[0084] As specific examples of the structural unit represented by equation (2a-1), structural units represented by equations (2a-1-1) and (2a-1-2) can be listed below. Furthermore, as specific examples of the structural unit represented by equation (2a-2), structural units represented by equations (2a-2-1) and (2a-2-2) can be listed below.

[0085] [Chemistry 5]

[0086]

[0087] (In equations (2a-1-1), (2a-1-2), (2a-2-1), and (2a-2-2), R) 34 and R 35 Each is independently an alkyl group having 1 to 4 carbon atoms, R 36 n 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 from 1 to 4; A 1 A 2 n1 and n2 have the same meaning as equations (2-1) and (2-2); R α1 (This has the same meaning as equations (2a-1) and (2a-2) mentioned above)

[0088] Specific examples of monomorphs constituting structural unit (III) include: styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloyloxyphenyltrimethoxysilane, (meth)acryloyloxyphenyltriethoxysilane, (meth)acryloyloxyphenylmethoxydimethoxysilane, (meth)acryloyloxyphenylethyldiethoxysilane, etc.; trimethoxy (4 (-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloyloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, etc.

[0089] The term "acid-dissociable group" refers to a group that substitutes for hydrogen atoms in acidic functional groups such as phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups, and is a group that dissociates through the action of an acid. For example, the acid generated from a photoacid generator during exposure causes the acid-dissociable group to dissociate and generate a carboxyl group, etc. This creates a difference in the solubility of the developer between the exposed and unexposed areas of the coating, enabling pattern formation.

[0090] The acid dissociative group is preferably the group represented by formula (3-1) or the group represented by formula (3-2).

[0091] [Chemistry 6]

[0092]

[0093] (In equation (3-1), R) 4 and R 5 Each group is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group formed by substituting at least a portion of the hydrogen atoms in the hydrocarbon group with a hydroxyl group, a halogen atom, or a cyano group; wherein, R is absent. 4 and R 5 The case where both are hydrogen atoms; R 6 A hydrocarbon group having 1 to 30 carbon atoms, a group having an oxygen atom or a sulfur atom at the carbon-carbon inter-carbon or bond side end of the hydrocarbon group, or a group having at least a portion of the hydrogen atoms of these groups substituted by a hydroxyl group, a halogen atom, or a cyano group; R 7 It consists of carbon atoms or silicon atoms;

[0094] In equation (3-2), R 8 ~R 14 Each is 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 They can be the same or different;

[0095] In equations (3-1) and (3-2), " (This indicates the bonding location)

[0096] As R 4 ~R 6 Hydrocarbon groups with 1 to 30 carbon atoms can be listed as follows: chain hydrocarbon groups with 1 to 30 carbon atoms, alicyclic hydrocarbon groups with 3 to 30 carbon atoms, and aromatic hydrocarbon groups with 6 to 30 carbon atoms.

[0097] Examples of chain-like hydrocarbon groups having 1 to 30 carbon atoms include straight-chain or branched saturated hydrocarbon groups having 1 to 30 carbon atoms, and straight-chain or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of straight-chain or branched saturated hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, n-octyl, n-dodecyl, n-tetradecyl, and n-octadecyl. Examples of monovalent straight-chain or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as vinyl, propynyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0098] Examples of alicyclic hydrocarbon groups with 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 cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups. Examples of polycyclic saturated hydrocarbon groups include borneol, norborneol, adamantyl, tricyclic decyl, tetracyclic dodecyl, and other bridged alicyclic hydrocarbon groups. Examples of monocyclic unsaturated hydrocarbon groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and other monocyclic cycloalkenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include norbornel, tricyclic decenyl, tetracyclic dodecenyl, and other polycyclic cycloalkenyl groups. Furthermore, a bridged alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which two non-adjacent carbon atoms constituting the alicyclic ring are bonded together by a linker containing one or more carbon atoms.

[0099] The aromatic hydrocarbon group having 6 to 30 carbon atoms can be a structure formed by a single ring, a condensed ring, or a structure formed by an aromatic ring and an aliphatic hydrocarbon group. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl.

[0100] R as in equation (3-1) 4 ~R 6 Each of the alkyl groups is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0101] As R 8 ~R 14 Hydrocarbon groups with 1 to 12 carbon atoms can be appropriately used, such as the R group. 4 ~R 6 The groups in hydrocarbon groups with 1 to 30 carbon atoms that correspond to the groups with 1 to 12 carbon atoms.

[0102] m is 1 or 2. When m is 2, multiple R... 11 and R 12They can be the same or different.

[0103] As a structural unit having the acid dissociative group, the structural unit represented by the following formulas (3-1-1) and (3-1-2) is preferred.

[0104] [Chemistry 7]

[0105]

[0106] In equations (3-1-1) and (3-1-2), m1 is 0 or 1. α1 R in equations (2a-1) and (2a-2) α1 They have the same meaning. R 4 ~R 14 R in equations (3-1) and (3-2) 4 ~R 14 They have the same meaning.

[0107] L in equations (3-1-1) and (3-1-2) 1 L 2 They are independent single-bond and divalent linkage groups, respectively.

[0108] As the L 1 L 2 Divalent linkages in alkyl groups can be listed as: alkyldiyl, cycloalkyldiyl, alkenyl, and aryldiyl.

[0109] As the alkyl diene, examples of X in formula (1) can be listed. 1 The same as the divalent linkage base.

[0110] Examples of cycloalkyl dimethyl groups include monocyclic cycloalkyl dimethyl groups such as cyclopentanediyl and cyclohexanediyl, and polycyclic cycloalkyl dimethyl groups such as norbornenediyl and adamantanediyl.

[0111] Examples of the alkenyl groups include: ethylenediyl, propylenediyl, butenediyl, etc.

[0112] Examples of the aryl dimethyl group include phenylene, methylphenylene, and naphthylene. Preferably, the aryl dimethyl group has 6 to 15 carbon atoms.

[0113] The base polymer may contain one structural unit (III) or a combination of two or more structural units (III).

[0114] When the polymer (A1) contains structural unit (III), the lower limit of the content ratio of structural unit (III) (or the total content ratio in the case of multiple structural units) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. Furthermore, the upper limit of the content ratio is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. By setting the content ratio of structural unit (III) within the aforementioned range, the coating film exhibits better resolution, which is preferable in this respect.

[0115] [Structural Unit (IV)]

[0116] The polymer (A) may further comprise structural units (IV), namely structural units (IV) derived from at least one monotonous structural unit selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and dialkyl dicarboxylic acid compounds. By incorporating these structural units (IV) into the polymer, the glass transition temperature of the polymer (A1) composition can be adjusted, and the pattern shape of the resulting hardened film after melt flow can be adjusted, which is preferred in this respect.

[0117] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate.

[0118] Examples of (meth)acrylates having an alicyclic structure include: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclohexyl (meth)acrylate [5.2.1.0]. 2,6 ] Decane-8-yl ester, (meth)acrylate tricyclic [5.2.1.0] 2,5 Decane-8-yloxyethyl ester, isobornyl acrylate, etc.

[0119] Examples of (meth)acrylates having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0120] Examples of such aromatic vinyl compounds include: styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc.

[0121] Examples of the N-substituted maleimide compounds include: N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.

[0122] Examples of vinyl compounds having heterocyclic structures include: tetrahydrofurfuryl (meth)acrylate, tetrahydropyran acrylate, 5-ethyl-1,3-dioxane-5-yl methyl acrylate, 5-methyl-1,3-dioxane-5-yl methyl acrylate, (2-methyl-2-ethyl-1,3-dioxane-4-yl)methyl acrylate, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) acrylate, glyceryl carbonate (meth)acrylate, (γ-lactam-2-yl) acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, etc.

[0123] Examples of conjugated diene compounds include 1,3-butadiene and isoprene; examples of nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of unsaturated dialkyl dicarboxylic acid esters include diethyl itaconic acid. In addition, examples of monomers constituting other structural units include vinyl chloride, vinylidene chloride, and vinyl acetate.

[0124] As a monolithic entity providing the structural unit (IV), it is preferably composed of at least one selected from the group consisting of alkyl methacrylates, aromatic vinyl compounds and N-substituted maleimide compounds, more preferably at least one selected from the group consisting of methyl methacrylates and styrene.

[0125] The base polymer may contain one structural unit (IV) or a combination of two or more structural units (IV).

[0126] When the polymer (A1) contains structural units (IV), the lower limit of the content ratio of structural units (IV) (or the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass. Furthermore, the upper limit of the content ratio is preferably 60% by mass, more preferably 50% by mass. By setting the content ratio of structural units (IV) within the aforementioned range, the glass transition temperature of the polymer (A1) can be appropriately increased, which is preferable in this respect.

[0127] (Synthesis method of polymer (A1))

[0128] The polymer (A1) can be manufactured, for example, using an unsaturated monomer capable of incorporating the structural units, in a suitable solvent, in the presence of a polymerization initiator, by known methods such as free radical polymerization.

[0129] Examples of azo compounds that can be used as polymerization initiators include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and dimethyl 2,2'-azobis(isobutyric acid) ester. The preferred proportion of the polymerization initiator used is 0.01 to 30 parts by mass relative to 100 parts by mass of the total monomer used in the reaction.

[0130] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably set to be 0.1% to 60% by mass of the total amount of the monomers used in the reaction relative to the total amount of the reaction solution.

[0131] In polymerization, the reaction temperature is typically 30°C to 180°C. The reaction time varies depending on the type of polymerization initiator and monomer, or the reaction temperature, and is usually 0.5 hours to 10 hours. The polymer obtained through polymerization can be used directly in the reaction solution for the preparation of radiosensitive linear compositions, or it can be used after separation from the reaction solution. Polymer separation can be carried out using known methods such as injecting the reaction solution into a large volume of undesirable solvent and drying the resulting precipitate under reduced pressure, or removing the precipitate by vacuum distillation using an evaporator.

[0132] The weight-average molecular weight (Mw) of the polymer contained in the polymer component, converted from polystyrene by gel permeation chromatography (GPC), is preferably 2,000 or more. If Mw is 2,000 or more, a hardened film with sufficiently high heat resistance or chemical resistance and good developability can be obtained, which is preferable in this respect. 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 achieving good 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.

[0133] Furthermore, the molecular weight distribution (Mw / Mn) represented by the ratio of weight average molecular weight Mw to 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. In addition, when the base polymer comprises two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer respectively satisfy the aforementioned range.

[0134] (Siloxane polymer (A2))

[0135] The siloxane polymer (A2) is not particularly limited as long as it can form a hardened film through hydrolysis and condensation. The siloxane polymer (A2) is preferably a polymer obtained by hydrolyzing a hydrolytic silane compound represented by the following formula (4).

[0136] (R 51 ) r Si(OR 52 ) 4-r (4)

[0137] (In equation (4), R) 51 It is a non-hydrolyzable monovalent group; R 52 It is an alkyl group having 1 to 4 carbon atoms; r is an integer from 0 to 3; wherein, when r is 2 or 3, the multiple R in the formula 51They may be identical or different; when r is 0 to 2, the multiple R in the formula 52 (Same or different)

[0138] As R 51 Examples include: alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, groups having (meth)acryloyl groups, and groups having epoxy groups.

[0139] As R 52 Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. Among these, R... 52 Methyl or ethyl is preferred.

[0140] r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0141] Specific examples of the monomers constituting siloxane polymers,

[0142] Examples of silane compounds having four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzoxysilane, and tetran-propoxysilane.

[0143] Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane.

[0144] Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane.

[0145] Examples of silane compounds having a hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

[0146] Siloxane polymers can be obtained by hydrolyzing or condensing one or more hydrolyzable silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. During the hydrolysis or condensation reaction, the hydrolytic group (-OR) of the hydrolyzable silane compound is... 52The total amount of water used is 1 mole, and the preferred proportion of water is 0.1 mole to 3 moles, more preferably 0.2 moles to 2 moles, and even more preferably 0.5 moles to 1.5 moles. By using this amount of water, the hydrolysis-condensation reaction rate can be optimized.

[0147] Catalysts used in hydrolysis and condensation reactions include, for example, 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 can be set appropriately. It is preferably 0.0001 mol to 0.2 mol relative to 1 mol of hydrolyzable silane compound, and more preferably 0.0005 mol to 0.1 mol.

[0148] Examples of organic solvents used in the hydrolysis and condensation reactions include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, non-water-soluble or poorly water-soluble organic solvents are preferred, such as ethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propionate esters. The proportion of organic solvent used is preferably 10 to 10,000 parts by mass relative to a total of 100 parts by mass of the hydrolyzable silane compound used in the reaction, more preferably 50 to 1,000 parts by mass.

[0149] During the hydrolysis and condensation reactions, it is preferable to set the reaction temperature to below 130°C, more preferably to 40°C to 100°C. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 12 hours. During the reaction, the mixture can be stirred or placed under reflux. Alternatively, after the hydrolysis and condensation reactions, a dehydrating agent can be added to the reaction solution, followed by evaporation, thereby removing water and the generated alcohol from the reaction system.

[0150] For siloxane polymers, the weight-average molecular weight (Mw) of the polystyrene obtained by GPC is preferably 500 or more. If Mw is 500 or more, a pattern (hardened film) exhibiting sufficiently high heat resistance or solvent resistance and good developability can be obtained, which is preferable in this respect. Mw is more preferably 1000 or more. Furthermore, from the viewpoint of good film-forming properties and suppression of reduced radioactive linearity, Mw is preferably 10000 or less, more preferably 5000 or less. Additionally, the molecular weight distribution (Mw / Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0151] (Polyamic acid or polyamic acid ester (A3))

[0152] The polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[0153] Examples of tetracarboxylic dianhydrides include, for example, aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include...

[0154] Examples of aliphatic tetracarboxylic dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydrides.

[0155] Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxylated cyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxylated bicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride.

[0156] Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)phthalic anhydride, ethylene glycol bis(triphenylene)phthalic anhydride ester, 4,4'-carbonyl phthalic anhydride, 4,4'-oxyphthalic anhydride, and propane-1,3-dimethylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ester). In addition, the tetracarboxylic dianhydride described in Japanese Patent Application Publication No. 2010-97188 may also be used. One or more of these tetracarboxylic dianhydrides may be used alone or in combination.

[0157] Among these, the tetracarboxylic dianhydride is preferably an aromatic tetracarboxylic dianhydride, and more preferably a 4,4'-oxydiphthalic anhydride.

[0158] There are no particular limitations on the diamines mentioned above, and examples include: aliphatic diamines, alicyclic diamines, aromatic diamines, and diamino organosiloxanes.

[0159] Examples of aliphatic diamines include: m-phenylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc.

[0160] Examples of alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine).

[0161] Examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]adipic acid, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diphenylbenzene. Aminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylene diisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4,4'-diaminobenzoylaniline, 4,4'-diaminostilbene, and other main-chain diamines represented by the following formula (S-1);

[0162] [Chemistry 8]

[0163]

[0164] (In formula (S-1), X is -O-, -S-, -CO-, -SO2-, -CH2-, -C(CH3)2-, -C(CH3)(C2H5)- or -C(CF3)2-)

[0165] Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-di Cholesterol aminobenzoate, lanostane 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestan, 3,6-bis(4-aminophenoxy)cholestan, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid=5ξ-cholestan-3-yl, and other side-chain diamines represented by the following formula (S-2);

[0166] [Chemistry 9]

[0167]

[0168] (In formula (S-2), X) I and X II Each is independently a single bond, -O-, -COO- or -OCO- (where, " "Indicates with X" I (the bond of the bond); R I It is an alkyldiyl group with 1 to 3 carbon atoms; R II It is a single bond or an alkyl diel with 1 to 3 carbon atoms; R III It is an alkyl, alkoxy, fluoroalkyl, 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; where 1 ≦ a + b + c ≦ 3)

[0169] Examples of diamino organosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. In addition to these, the diamine described in Japanese Patent Application Publication No. 2010-97188 may also be used.

[0170] Among these, the diamine is preferably an aromatic diamine or a diamino organosiloxane, more preferably a compound represented by formula (S-1) or 1,3-bis(3-aminopropyl)-tetramethyldisiloxane.

[0171] The diamine may be used alone or in combination of two or more.

[0172] Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride with a diamine and, as needed, a molecular weight adjuster. The preferred ratio of tetracarboxylic dianhydride to diamine used in the synthesis reaction of polyamic acid is 0.2 to 2 equivalents relative to the amino group of the diamine and the anhydride group of the tetracarboxylic dianhydride. Examples of molecular weight adjusters include: maleic anhydride, phthalic anhydride, itaconic anhydride, and other monoanhydrides; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The preferred ratio of the molecular weight adjuster is 20 parts by mass or less, relative to a total of 100 parts by mass of the tetracarboxylic dianhydride and diamine used.

[0173] The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The preferred reaction temperature is -20°C to 150°C, and the preferred reaction time is 0.1 hours to 24 hours. Examples of organic solvents used in the reaction include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphoric triamine, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount (a) of the organic solvent used is preferably set to be 0.1% to 50% by mass relative to the total amount (a+b) of the tetracarboxylic dianhydride and diamine.

[0174] A reaction solution obtained by dissolving polyamic acid is obtained in the manner described. The reaction solution can be used directly for the preparation of the radiosensitive linear composition, or it can be used for the preparation of the radiosensitive linear composition after separating the polyamic acid contained in the reaction solution.

[0175] The polyamic acid ester can be obtained, for example, by methods such as: [I] reacting the polyamic acid obtained by the synthesis reaction with an esterifying agent; [II] reacting a tetracarboxylic acid diester with a diamine; [III] reacting a tetracarboxylic acid diester dihalide with a diamine. The polyamic acid ester contained in the radiosensitive linear composition of the present invention may have only an amide ester structure, or it may be a partial esterification containing both an amide acid structure and an amide ester structure. The reaction solution obtained by dissolving the polyamic acid ester can be used directly for the preparation of the radiosensitive linear composition, or it can be used for the preparation of the radiosensitive linear composition after separating the polyamic acid ester contained in the reaction solution.

[0176] The content of 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, relative to the total amount of solid components contained in the radiosensitive linear composition (i.e., the total mass of components other than the solvent in the radiosensitive linear composition). Furthermore, the content of polymer (A) is preferably 99% by mass or less, more preferably 95% by mass or less, relative to the total amount of solid components contained in the radiosensitive linear composition. By setting the content of polymer (A) within the aforementioned range, pattern formation properties, chemical resistance, and substrate adhesion can be sufficiently improved.

[0177] <Radiosensitive linear compound (B)>

[0178] The radiosensitive linear composition (B) comprises the polymer (A) and the radiosensitive linear compound (B). By irradiating the radiosensitive linear composition (B) with radiation (visible light, ultraviolet light, far ultraviolet light, etc.), positive or negative patterns can be formed. Examples of radiosensitive linear compounds (B) include photoacid generators, photopolymerization initiators, and photoalkali generators. Preferably, at least one of the group consisting of quinone diazide compound (B-1), photopolymerization initiator (B-2), and photoacid generator (B-3) is used as the radiosensitive linear compound (B).

[0179] Here, when using a photoacid generator or a photoalkali generator as a radiosensitive linear compound, positive or negative patterns can be formed by changing the solubility of the exposed portion in the developer. Alternatively, when the photoacid generator or photoalkali generator functions as a curing catalyst, the solubility of the exposed portion in the developer decreases as curing of the exposed portion is promoted, thereby also forming a negative pattern. On the other hand, when using a photopolymerization initiator as a radiosensitive linear compound, for example, by reacting with a compound having a vinyl or (meth)acryloyl group to promote curing of the exposed portion, the solubility of the exposed portion in the developer decreases, thereby forming a negative pattern.

[0180] Specific examples of the radiosensitive linear composition of the present invention include:

[0181] A radiosensitive linear composition (first composition) comprises the polymer (A), a quinone diazide compound (B-1) as a radiosensitive linear compound (B), and an ionic liquid (C).

[0182] A negative-type radiosensitive linear composition (second composition) comprises the polymer (A), a photopolymerization initiator (B-2) as a radiosensitive linear compound (B), a polymerizable monomer (X1), and a solvent (C);

[0183] A chemically amplified radiosensitive linear composition (third composition) comprises the polymer (A), a photoacid generator (B-3) as a radiosensitive linear compound (B), and an ionic liquid (C).

[0184] The first to third radioactive linear compositions will be described below.

[0185] (First Composition)

[0186] The first composition is a radiosensitive composition comprising a quinone diazide compound (B-1) as a radiosensitive linear compound (B).

[0187] (quinone diazide compound (B-1))

[0188] The quinone diazide compound (B-1) is a compound that produces a carboxylic acid by irradiation with radiation. Examples of quinone diazide compounds (B-1) include condensates of phenolic or alcoholic compounds (hereinafter also referred to as "cores") with o-naphthoquinone diazide compounds. Among these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the core and an o-naphthoquinone diazide compound. Specific examples of cores include the compounds described in paragraphs

[0065] to

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

[0189] Specific examples of quinone diazide compounds (B-1) include compounds containing phenolic hydroxyl groups selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and ester compounds with 1,2-naphthoquinone diazide-4-sulfonyl chloride or 1,2-naphthoquinone diazide-5-sulfonyl chloride. Among these, the preferred condensate of 4,4'-[1-[4-[1-[4-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinone diazide-5-sulfonyl chloride is the quinone diazide-5-sulfonyl chloride.

[0190] These quinone diazide compounds (B-1) can be used alone or in combination of two or more. The lower limit of the content of quinone diazide compound (B-1) relative to 100 parts by mass of polymer (A) in the first composition is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 15 parts by mass. Furthermore, the upper limit of the content of quinone diazide compound (B-1) relative to 100 parts by mass of polymer (A) in the first composition is preferably 50 parts by mass, more preferably 30 parts by mass. If the content of quinone diazide compound (B-1) is set to 5 parts by mass or more, the carboxylic acid is sufficiently generated by irradiating the first composition with radiation, which sufficiently increases the difference in solubility of the irradiated and unirradiated portions in the developer, allowing for good patterning; this is preferable in this respect. In addition, increasing the amount of carboxylic acid participating in the reaction with the polymer components sufficiently ensures heat resistance and chemical resistance; this is preferable in this respect. On the other hand, by setting the content of quinone diazide compound to 50 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, and the decrease in developability caused by the residue of quinone diazide compound can be suppressed, which is preferable in this respect.

[0191] (Second Composition)

[0192] The second composition is a negatively radiosensitive linear composition comprising a photopolymerization initiator (B-2) as a radiosensitive linear compound (B) and comprising a polymerizable monomer (X1).

[0193] (Photopolymerization initiator (B-2))

[0194] As the photopolymerization initiator (B-2), a compound that senses and initiates and promotes the polymerization of the polymerizable monomer (X1) with a wavelength of 300 nm or higher (preferably 300 nm to 450 nm) is preferably used. When using a photopolymerization initiator (B-2) that does not directly sense photochemical rays with a wavelength of 300 nm or higher, it can also sense and initiate and promote the polymerization of the polymerizable monomer (X1) with a wavelength of 300 nm or higher by using it in conjunction with a sensitizer.

[0195] Known compounds can be used as photopolymerization initiators (B-2). Specific examples include: oxime ester compounds, organohalogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organoperoxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboronic acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, acylphosphine (oxide) compounds, etc. In terms of further improving the sensitivity of the third composition, at least one of these is preferably selected from the group consisting of oxime ester compounds, α-aminoketone compounds, and hexaarylbiimidazole compounds, more preferably oxime ester compounds or α-aminoketone compounds. Furthermore, commercially available products can also be used as photopolymerization initiators (B-2), such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF).

[0196] These photopolymerization initiators (B-2) can be used alone or in combination of two or more. The lower limit of the content of photopolymerization initiator (B-2) relative to 100 parts by mass of the polymerizable monomer (X1) contained in the second composition is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 10 parts by mass. Furthermore, the upper limit of the content of photopolymerization initiator (B-2) relative to 100 parts by mass of the polymerizable monomer (X1) is preferably 45 parts by mass, more preferably 35 parts by mass, and even more preferably 25 parts by mass.

[0197] (Polymerized monolith (X1))

[0198] The second composition contains a polymerizable monomer (X1). The polymerizable monomer (X1) contained in the second composition is a compound having one or more polymerizable groups, preferably two or more. Examples of polymerizable groups include: vinyl unsaturated groups, oxetyl, oxetyl, N-alkoxymethylamino, etc. Among these, vinyl unsaturated groups and N-alkoxymethylamino are preferred in terms of high polymerizability, and vinyl-containing groups such as (meth)acryloyl, vinyl, and vinylphenyl are preferred.

[0199] Specifically, as a polymerizable monomer (X1), it 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 in one molecule of polymerizable monomer (X1) is preferably two to ten, more preferably two to eight.

[0200] Specific examples of polymerizable monomers (X1) that are compounds having two or more (meth)acryloyl groups include: polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid; polyfunctional (meth)acrylates modified with caprolactone; polyfunctional (meth)acrylates modified with epoxide; polyfunctional urethane (meth)acrylates obtained by reacting hydroxyl-containing (meth)acrylates with polyfunctional isocyanates; and polyfunctional (meth)acrylates with carboxyl groups obtained by reacting hydroxyl-containing (meth)acrylates with acid anhydrides.

[0201] Compounds having two or more N-alkoxymethyl amino groups include, for example, compounds with melamine, benzoguanamine, or urea structures. Furthermore, the terms melamine or benzoguanamine structures refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as the basic skeleton, and also include melamine, benzoguanamine, or their condensates. Specific examples of compounds having two or more N-alkoxymethyl amino 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)glycourea.

[0202] As a polymerizable monomer (X1), the preferred options are polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylate, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates having carboxyl groups, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanidine. More preferably, polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, and polyfunctional (meth)acrylates having carboxyl groups are obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylate. Even more preferably, polyfunctional (meth)acrylates are obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylate.

[0203] Specific examples of polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds 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, and dipentaerythritol polyacrylate. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol polyacrylate are particularly preferred in terms of increasing the density of intermolecular or intramolecular crosslinking and further improving the curability of the film through low-temperature calcination.

[0204] These polymeric monomers (X1) can be used alone or in combination of two or more. The lower limit of the content of polymeric monomer (X1) relative to 100 parts by weight of polymer (A) contained in the second composition is preferably 20 parts by weight, more preferably 25 parts by weight, and even more preferably 30 parts by weight. Furthermore, the upper limit of the content of polymeric monomer (X1) relative to 100 parts by weight of polymer (A) is preferably 300 parts by weight, more preferably 200 parts by weight, and even more preferably 100 parts by weight. If the content ratio of polymeric monomer (X1) is within the aforementioned range, sufficient curability and sufficient alkaline developability as a curing film can be ensured, and the generation of scale, film residue, etc., on the unexposed substrate or the light-shielding layer can be sufficiently suppressed; therefore, this is preferable.

[0205] (Third Composition)

[0206] The third composition is a chemically amplified radioactive linear composition comprising a photoacid generator (B-3) as a radioactive linear compound (B). The polymer (A) in the third composition is a polymer (A1) comprising a structural unit (III) having one or more groups selected from the group represented by the formula (2) and acid-dissociable groups.

[0207] (Photoacid generator (B-3))

[0208] Photoacid generators (B-3) are any compounds that generate acid in response to radiation (i.e., radiosensitive acid generators), and there are no particular limitations. Examples of photoacid generators (B-3) include: oxime sulfonates, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylic acid ester compounds.

[0209] Specific examples of oxime sulfonate compounds, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylic acid ester compounds include, for example, compounds described in paragraphs

[0078] to

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

[0210] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (5).

[0211] [Chemistry 10]

[0212]

[0213] (In equation (5), R) 40 A monovalent hydrocarbon group, or a monovalent group formed by substituting some or all of the hydrogen atoms of the hydrocarbon group with substituents; "Indicates a bond"

[0214] In equation (5), R is... 40 Monovalent hydrocarbon groups, such as alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 4 to 12 carbon atoms, and aryl groups having 6 to 20 carbon atoms, can be used as substituents, such as alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, side oxygen groups, and halogen atoms.

[0215] If oxime sulfonate compounds are to be exemplified, the following can be listed: (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 the compounds described in International Publication No. 2016 / 124493, etc. Commercially available oxime sulfonate compounds include BASF's Irgacure PAG121.

[0216] If sulfonylimide compounds are to be exemplified, the following can be listed: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphor ... N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, trifluoromethanesulfonic acid-1,8-naphthalenediamide.

[0217] These photoacid generating agents (B-3) can be used alone or in combination of two or more. The lower limit of the content of the photoacid generating agent (B-3) relative to 100 parts by mass of polymer (A) formulated in the third composition is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, and even more preferably 2 parts by mass. Furthermore, the upper limit of the content of the photoacid generating agent (B-3) relative to 100 parts by mass of polymer (A) formulated in the third composition is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass. Setting the content of the photoacid generating agent (B-3) to 1 part by mass or more allows for good patterning and ensures sufficient heat resistance, which is advantageous in this respect. Furthermore, setting the content of the photoacid generating agent (B-3) to 30 parts by mass or less sufficiently reduces the amount of unreacted photoacid generating agent after exposure, suppressing the decrease in developability caused by the residue of the photoacid generating agent, which is advantageous in this respect.

[0218] <Ionic Liquid (C)>

[0219] Ionic liquids contain a pair of anions and cations, and there are no special restrictions as long as they are molten salts that are liquid below 100°C (room temperature molten salts).

[0220] Examples of anions that can be used as ionic liquids include halogen anions, boron anions, phosphorus anions, organic sulfonic acid anions, and sulfonamide anions. Preferably, anions having at least one electron-withdrawing group selected from the group consisting of a halogen group (preferably a fluorine group) and a cyano group are preferred. Specifically, an example is (FSO₂)₂N. - (CF3SO2)2N - (CF3CF2SO2)2N - (CF3SO2)3C - ,Br - AlCl4 - Al2Cl7- NO3 - BF4 - PF6 - CH3COO - CF3COO - CF3CF2CF2COO - CF3SO3 - CF3(CF2)3SO3 - AsF6 - SbF6 - CH3CH2OSO3 - CH3(CH2)7OSO3 - N(CN)2 - C(CN)3 - Cl - I - PF3(C2F5)3 - P3(CF3)3 - BF2(CF)2 - BF3 (CF3) - B(CN)4 - wait.

[0221] The cation of the ionic liquid is preferably a nitrogen-containing cation, a sulfur-containing cation, or a phosphorus-containing cation, and more preferably at least one selected from the group consisting of imidazole-based cations, pyrrolidine-based cations, pyridine-based cations, piperidine-based cations, phosphonium-based cations, sulfonium-based cations, and ammonium-based cations.

[0222] Examples of imidazolium cations include: 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-methyl-3-propylimidazolium cation, 1-methyl-3-butylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-methyl-3-hexylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-pentyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-heptyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-methyl-3-octylimidazolium cation, 1-nonyl-3-methylimidazolium cation, and 1-undecyl-3-methylimidazolium cation. Ions, 1-dodecyl-3-methylimidazolium cation, 1-tridecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1-pentadecanyl-3-methylimidazolium cation, 1-hexadecyl-3-methylimidazolium cation, 1-heptadecyl-3-methylimidazolium cation, 1-octadecyl-3-methylimidazolium cation, 1-undecyl-3-methylimidazolium cation, 1-benzyl-3-methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1,3-bis(dodecyl)imidazolium cation, 1-allyl-3-methylimidazolium cation, 1-allyl-3-ethylimidazolium cation, etc.

[0223] Examples of pyrrolidone cations include: 1-methyl-1-propylpyrrolidone cation, 1-butyl-1-methylpyrrolidone cation, 1-methyl-1-butylpyrrolidone cation, and 1-ethyl-1-methylpyrrolidone cation.

[0224] Examples of pyridinium cations include: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation.

[0225] Examples of piperidinium cations include 1-methyl-1-propylpiperidinium cation, 1-butyl-1-methylpiperidinium cation, and 1-ethyl-1-methylpiperidinium cation.

[0226] Examples of phosphonium-based cations include: tributylmethylphosphonium cation, tributyl-n-octylphosphonium cation, tetraphenylphosphonium cation, tetraethylphosphonium cation, tetra-n-octylphosphonium cation, methyltriphenylphosphonium cation, isopropyltriphenylphosphonium cation, methoxycarbonylmethyl(triphenyl)phosphonium cation, ethyltriphenylphosphonium cation, butyltriphenylphosphonium cation, and (1-naphthylmethyl)triphenylphosphonium cation.

[0227] Examples of sulfonium cations include: trimethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, diphenyl(methyl)sulfonium cation, tri-n-butylsulfonium cation, tri-p-tolylsulfonium cation, triphenylsulfonium cation, and cyclopropyldiphenylsulfonium cation.

[0228] Examples of ammonium cations include: tetraethylammonium cation, tetrabutylammonium cation, methyltrioctylammonium cation, tetradecyltrihexylammonium cation, glycidyltrimethylammonium cation, and trimethylaminoethyl acrylate cation.

[0229] As the ionic liquid (C), all combinations of the anion and the cation can be suitably used, among which, preferably, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, bis(trifluoromethanesulfonyl)azonyl alkylate; 1-methyl-1-propylpyrrolidone-1-onium, bis(trifluoromethanesulfonyl)azonyl alkylate; 1-butyl-1-methylpyrrolidone-1-onium, bis(trifluoromethanesulfonyl)azonyl alkylate; 1-methyl-1-propylpiperidine- 1-Onium, bis(trifluoromethylsulfonyl) alkylate; tributyl(methyl)phosphonium, bis(fluorosulfonyl) alkylate; 1-ethyl-3-methylimidazolium-3-onium, bis(fluorosulfonyl) alkylate; 1-methyl-1-propylpyrrolidone-1-onium, bis(1,1,2,2,2-pentafluoroethylsulfonyl) alkylate; 1-ethyl-3-methylimidazolium-3-onium, bis(1,1,2,2,2-pentafluoroethylsulfonyl) alkylate; 1-butyl-3- Methylimidazolium-3-onium, bis(trifluoromethanesulfonyl) alkylate; 1-butyl-1-methylpridine-1-onium, bis(trifluoromethanesulfonyl) alkylate; 1-methyl-3-prop-2-enylimidazolium-1-onium, bis(trifluoromethanesulfonyl) alkylate; 1-ethyl-3-prop-2-enylimidazolium-3-onium, 1-ethyl-3-methylimidazolium-3-onium; acetate, 1-ethyl-3-methylimidazolium-3-onium; ethyl sulfate, 1-ethyl- 3-Methylimidazol-3-onium; tetrafluoroborate, cyanoiminomethylene alkylate; 1-ethyl-3-methylimidazol-3-onium, 2,2-dicyanoethylimidazolate; 1-ethyl-3-methylimidazol-3-onium, 1-methyl-3-propylimidazol-1-onium; hexafluorophosphate, 1-ethyl-3-methylimidazol-3-onium; chloride, 1-ethyl-3-methylimidazol-3-onium; iodide, 1-ethyl-3-methylimidazolium octyl sulfate, etc.

[0230] The molecular weight of the ionic liquid (C) is not particularly limited, but is preferably 600 or less, more preferably 550 or less. In addition, it is usually 50 or more.

[0231] The ionic conductivity of the ionic liquid (C) is preferably 0.5 mS / cm or higher, more preferably 1.0 mS / cm or higher. Furthermore, the ionic conductivity is preferably 30 mS / cm or lower, more preferably 20 mS / cm or lower. By achieving this range of ionic conductivity, better capacitance can be imparted.

[0232] These ionic liquids (C) can be used alone or in combination of two or more. The lower limit of the content of ionic liquid (C) relative to 100 parts by mass of polymer (A) is preferably 5 parts by mass, more preferably 10 parts by mass, further preferably 50 parts by mass, and particularly preferably 100 parts by mass. Furthermore, the upper limit of the content of ionic liquid (C) relative to 100 parts by mass of polymer (A) is preferably 500 parts by mass, more preferably 400 parts by mass, and further preferably 380 parts by mass. Setting the content of ionic liquid (C) to 5 parts by mass or more provides good capacitance, which is advantageous in this respect. Additionally, setting the content of ionic liquid (C) to 500 parts by mass or less is advantageous in terms of shape stability during patterning or substrate adhesion.

[0233] <Close Contact Agent (D)>

[0234] The radiosensitive linear composition of the present invention may contain a bonding aid (D). The bonding aid is a component that improves the adhesion between the pattern (hardened film) formed using the radiosensitive linear composition and the substrate. Preferably, a functionalized silane coupling agent having a reactive functional group is used as the bonding aid. Examples of reactive functional groups that can be found in a functionalized silane coupling agent include: carboxyl, (meth)acryloyl, epoxy, vinyl, isocyanate, etc.

[0235] Specific examples of functional silane coupling agents include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, etc.

[0236] When the bonding agent (D) is incorporated into the radiosensitive linear composition, the lower limit of its content relative to 100 parts by weight of polymer (A) is preferably 0.01 parts by weight, more preferably 1 part by weight, and even more preferably 3 parts by weight. Furthermore, the upper limit of its content is preferably 30 parts by weight, more preferably 20 parts by weight, and even more preferably 10 parts by weight.

[0237] <Acid Diffusion Control Agent>

[0238] In the radiosensitive linear composition of the present invention, the third composition may contain an acid diffusion control agent. The acid diffusion control agent is a component that controls the diffusion length of acid generated from the photoacid generator (B-3) through exposure. By incorporating the acid diffusion control agent into the third composition, the diffusion length of the acid can be appropriately controlled, resulting in good pattern development. Furthermore, by incorporating the acid diffusion control agent, improved development adhesion and chemical resistance can be achieved, which is preferable in this respect.

[0239] As an acid diffusion control agent, any basic compound used in chemically amplified resists can be selected. Examples of basic compounds include fatty acid amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. Specific examples of basic compounds include compounds described in paragraphs

[0128] to

[0147] of Japanese Patent Application Publication No. 2011-232632. As an acid diffusion control agent, at least one selected from the group consisting of aromatic amines and heterocyclic amines is preferably used.

[0240] Examples of aromatic amines and heterocyclic amines include: 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, N,N-dimethyltoluidine, and other aniline derivatives; imidazoles, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, benzimidazole, 2-phenylbenzimidazole, triphenylimidazolium, and other imidazole derivatives; and pyrroles, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-diphenylimidazolium, etc. Pyrrole derivatives such as methylpyrrole 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-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, nicotine, and other pyridine derivatives, as well as compounds described in Japanese Patent Application Publication No. 2011-232632.

[0241] From the viewpoint of fully obtaining the improved drug resistance effect brought about by the formulation of the acid diffusion control agent when it is incorporated into the radiosensitive linear composition, the lower limit of its content relative to 100 parts by weight of polymer (A) incorporated in the third composition is preferably 0.005 parts by weight, more preferably 0.01 parts by weight. Furthermore, the upper limit of the content of the acid diffusion control agent relative to 100 parts by weight of polymer (A) is preferably 10 parts by weight, more preferably 5 parts by weight.

[0242] <Other Ingredients>

[0243] The radiosensitive linear composition of the present invention may contain components other than those described above (other components). Examples of other components include: curing accelerators, multifunctional polymerizable compounds (multifunctional (meth)acrylates, etc.), surfactants (fluorinated surfactants, silicone surfactants, nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The proportions of these components may be appropriately selected according to each component without impairing the effects of the present disclosure.

[0244] <Solvent (E)>

[0245] The radiosensitive linear composition of the present invention preferably contains a solvent (E). As the solvent (E), it is preferably an organic solvent that dissolves each component formulated in the radiosensitive linear composition and does not react with each component.

[0246] Specific examples of solvents 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 diethylene glycol monomethyl ether, ethylene diethylene glycol ethyl methyl ether, dimethylene 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. Among these, the solvent is preferably at least one selected from the group consisting of ethers and esters, more preferably at least one selected from the group consisting of ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers and propylene glycol monoalkyl ether acetates.

[0247] <Preparation Method of Radiosensitive Linear Composition>

[0248] The radiosensitive linear composition can be prepared, for example, by mixing a polymer (A), a radiosensitive linear compound (B), an ionic liquid (C), and any other components as needed, in a prescribed ratio. The radiosensitive linear composition is preferably filtered after mixing using, for example, a filter with a pore size of approximately 0.05 μm to 0.4 μm. The solids concentration of the radiosensitive linear composition (the proportion of the total mass of components other than the solvent in the total mass of the radiosensitive linear composition) can be appropriately selected considering viscosity or volatility. The solids concentration of the radiosensitive linear 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. If the solids concentration is 5% by mass or more, sufficient film thickness can be ensured when coating the radiosensitive linear composition onto a substrate. Furthermore, if the solids concentration is 60% by mass or less, the film thickness will not become excessive, thereby moderately increasing the viscosity of the radiosensitive linear composition and ensuring good coatability.

[0249] Patterns (hardened films) and their manufacturing methods

[0250] The pattern (hardened film) of the present invention can be formed from the aforementioned radiosensitive linear composition. The radiosensitive linear composition has high radiation sensitivity and good pattern-forming properties. Furthermore, by using the aforementioned radiosensitive linear composition, a pattern (hardened film) that exhibits high adhesion to the substrate after development, has high capacitance, and good chemical resistance can be formed.

[0251] When manufacturing a pattern (hardening film), a positive or negative hardening film can be formed depending on the type of radiosensitive linear compound (B) by using the aforementioned radiosensitive linear composition. The pattern (hardening film) can be manufactured using the aforementioned radiosensitive linear composition, for example by a method comprising the following processes 1 to 4.

[0252] (Process 1) Process for forming a gate insulating film by coating a substrate with an inductively linearized composition.

[0253] (Process 2) The process of irradiating at least a portion of the coating with radiation.

[0254] (Process 3) The process of developing the coating film irradiated with said radiation to form a pattern.

[0255] The following is a detailed explanation of each process.

[0256] [Process 1: Coating Process]

[0257] In this process, the radiosensitive linear composition is coated onto the surface on which the film is formed (hereinafter also referred to as the "film-forming surface"). Preferably, the solvent is removed by heat treatment (pre-baking), thereby forming a coating on the film-forming surface. The material of the film-forming surface is not particularly limited. In this invention, in order to form a gate insulating film, a coating is formed on a substrate containing glass or resin, on which gate electrodes (scan signal lines) are formed.

[0258] Examples of coating methods for the radiosensitive linear composition include spraying, roller coating, spin coating, slot die coating, rod coating, and inkjet coating. Among these, spin coating, slot die coating, or rod coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiosensitive linear composition, and for example, are performed at 60°C to 130°C for 0.5 to 10 minutes. The film thickness formed (i.e., the film thickness after pre-baking) is preferably 0.1 μm to 12 μm. For the radiosensitive linear composition coated on the film-forming surface, vacuum drying (VCD) can also be performed before pre-baking.

[0259] [Process 2: Exposure Process]

[0260] In this process, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, the coating film is irradiated with radiation through a mask having a predetermined pattern, thereby forming a patterned hardened film. 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, such as gamma rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The exposure dose of the radiation is preferably 0.1 J / m². 2 ~20,000 J / m 2 .

[0261] [Process 3: Development Process]

[0262] In this process, the coating film irradiated with radiation in step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 is subjected to positive development, which removes the irradiated portion by developing with a developing solution, or negative development, which removes the unirradiated portion by developing with a developing solution. As a developing solution, an aqueous solution of an alkali (alkaline compound) can be listed as an example. As an alkali, examples include sodium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph

[0127] of Japanese Patent Application Publication No. 2016-145913. The alkali concentration of the alkaline aqueous solution is preferably 0.1% to 5% by mass from the viewpoint of obtaining adequate developability. As a developing method, suitable methods such as liquid coating, immersion, shaking immersion, and spraying can be listed as examples. The developing time also varies depending on the composition of the composition, for example, from 30 seconds to 120 seconds. Furthermore, it is preferable to perform a rinsing treatment based on running water rinsing on the patterned coating film after the developing process.

[0263] [Process 4: Heating Process]

[0264] In this process, the developed coating from step 3 is heated (post-baking). Post-baking can be performed using a heating device such as an oven or a heating plate. Regarding post-baking conditions, the heating temperature is, for example, 120°C to 250°C. For example, when heating is performed on a heating plate, the heating time is 5 minutes to 40 minutes; when heating is performed in an oven, the heating time is 10 minutes to 80 minutes. Performing this process as described above allows a hardened film with the target pattern to be formed on the substrate. Furthermore, in this process, to prevent degradation of the gate electrode, heating can also be performed in an inert gas environment such as nitrogen or argon.

[0265] Semiconductor Components

[0266] The pattern (hardened film) formed using the aforementioned linearly induced emission composition can be used in semiconductor devices. The pattern (hardened film) can suitably serve as a gate insulating film disposed between the semiconductor layer and the gate electrode in a semiconductor device having a semiconductor layer and a gate electrode. Besides using the pattern (hardened film) formed by the linearly induced emission composition of the present invention as a gate insulating film, the semiconductor device can also be manufactured using known methods. Examples of semiconductor devices include transistors such as organic electrochemical transistors (OECT), integrated circuits (ICs), and large-scale integrated circuits (LSIs). Furthermore, the pattern (hardened film) can also be used as an interlayer insulating film, protective film, planarization film, etc., of semiconductor devices.

[0267] Display Devices

[0268] The semiconductor element of the present invention can be suitably used in display devices. That is, the pattern (hardening film) of the present invention can be suitably used in display devices. Examples of such display devices include: liquid crystal display devices, organic EL display devices, light-emitting diode (LED) display devices, quantum dot light-emitting display devices, etc.

[0269] Wearable devices

[0270] The semiconductor element of the present invention is suitable for use in wearable devices such as external devices, surface devices, and internal devices. Specifically, the pattern (hardening film) of the present invention is suitable for use in wearable devices. Furthermore, the pattern (hardening film) of the present invention can be used in flexible wiring, flexible substrates, frames, cover components, cables, sensors, etc., in wearable devices.

[0271] Electronic Skin Devices

[0272] Electronic skin devices are soft and flexible devices that mimic the functions of human skin and can be suitably used in medical implants, robotic sensor skin, and wearable devices.

[0273] Biosensors

[0274] The semiconductor element of this invention is suitable for use in biosensors. That is, the pattern (hardened film) of this invention is suitable for use in biosensors. A biosensor is a sensor that detects the activities of living organisms, particularly animals. 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 vein shape of humans and other animals into electrical or optical signals. Examples of biosensors include non-contact, touch-sensitive, patch, and wearable types.

[0275] Neuromorphic Devices

[0276] The semiconductor element of this invention can be used as a neuromorphic device and is highly suitable as an artificial synapse. That is, the pattern (hardening membrane) of this invention is suitable for use in neuromorphic devices. A neuromorphic device is a component that mimics the human brain (artificially mimicking the relationship between neurons and synapses in the human brain) through a neural network.

[0277] Example

[0278] The present invention will be specifically described below through examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" in the following examples refer to mass.

[0279] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)]

[0280] The Mw and Mn of the polymer were determined by the following method.

[0281] • Determination method: Gel permeation chromatography (GPC)

[0282] • Device: GPC-101 manufactured by Showa Denko Co., Ltd.

[0283] • GPC tubing: Combining GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 manufactured by Shimadzu GLC (stock).

[0284] • Mobile phase: Tetrahydrofuran

[0285] • Column temperature: 40℃

[0286] • Flow rate: 1.0 mL / min

[0287] • Sample concentration: 1.0% by mass

[0288] • Sample injection volume: 100 μL

[0289] • Detector: Differential refractometer

[0290] • Standard reference material: Monodisperse polystyrene

[0291] <Monomers that constitute polymer (A1)>

[0292] The monomers used in the synthesis of polymer (A) are described below.

[0293] (Provide a single volume of structural unit (I))

[0294] MI: Maleimide

[0295] MA: Methacrylic acid

[0296] (Provide a single volume of structural unit (II))

[0297] GMA: Glycidyl methacrylate

[0298] ·OXMA: OXE-30 (manufactured by Osaka Organic Chemicals Co., Ltd.), methyl methacrylate (3-ethyloxetane-3-yl)

[0299] M100: 3,4-epoxycyclohexyl methyl methacrylate

[0300] (Provide a single volume of structural unit (III))

[0301] STMS: Styrene-trimethoxysilane

[0302] (Provide a single volume of structural unit (IV))

[0303] ST: Styrene

[0304] MMA: Methyl methacrylate

[0305] <Monomers that make up polymer (A3)>

[0306] AM-1:

[0307] [Chemistry 11]

[0308]

[0309] <Synthesis of Polymer (A)>

[0310] [Synthesis Example 1] Synthesis of Polymer (A-1)

[0311] Ten parts of 2,2'-azobis(2,4-dimethylpentanonitrile) (ADVN) and 200 parts of propylene glycol monomethyl ether acetate were charged into a flask including a cooling tube and a stirrer. Then, 20 parts of MA, 30 parts of GMA, 20 parts of OXMA, and 30 parts of ST were added. After nitrogen purging, the solution temperature was raised to 70°C while slowly stirring, and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing polymer (A1-1). The solid content concentration of the polymer solution was 34% by mass, the Mw of polymer (A1-1) was 10,500, and the molecular weight distribution (Mw / Mn) was 2.2.

[0312] [Synthesis Examples 2-6] Synthesis of Polymers (A1-2) to (A1-6)

[0313] Using the types and proportions (parts by mass) of each component shown in Table 1, except that polymer solutions containing polymers (A1-2) to (A1-6) having the same solid component concentration as polymer (A1-1) were obtained using the same method as in Synthesis Example 1. Furthermore, in Table 1, "-" indicates that the corresponding component was not used.

[0314] [Table 1]

[0315]

[0316] [Synthesis Example 7] Synthesis of Polymer (A2-1)

[0317] 24 parts of propylene glycol monomethyl ether were added to a flask including a cooling tube and a stirrer, followed by 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloyloxypropyltrimethoxysilane. The mixture was heated until the solution temperature reached 60°C. After reaching 60°C, 0.1 parts of formic acid and 19 parts of water were added, and the solution temperature was raised to 75°C while stirring slowly. This temperature was maintained for 2 hours. After cooling to 45°C, 28 parts by mass of trimethyl orthoformate were added as a dehydrating agent, and the mixture was stirred for 1 hour. The solution temperature was then lowered to 40°C, and evaporation was carried out while maintaining the temperature to remove water and methanol produced during hydrolysis and condensation, thereby obtaining a polymer solution containing polymer (A2-1). The solid content concentration of the polymer solution was 35% by mass, and the weight average molecular weight (Mw) of polymer (A2-1) was 1,800, with a molecular weight distribution (Mw / Mn) of 2.2.

[0318] [Synthesis Example 8] Synthesis of Polymer (A3-1)

[0319] Under a dry nitrogen atmosphere, 80 moles of compound (AM-1), 5 moles of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 100 moles of 4,4'-oxyphthalic anhydride were dissolved in dehydrated N-methyl-2-pyrrolidone (NMP) and reacted at 40°C for 1 hour. A solution of 30 moles of 3-aminophenol as a capping agent was prepared in NMP and added to the solution, and the reaction was carried out at 40°C for 2 hours. Subsequently, 200 moles of N,N-dimethylformamide dimethyl acetal were added relative to the amount of tetracarboxylic acid dianhydride added, and the reaction was carried out at 40°C for 6 hours. After cooling the reaction solution to room temperature, the solution was added to a large volume of distilled water, and the precipitate was recovered by filtration. After washing three times with water, the solution was vacuum dried at 80°C for 20 hours to obtain polymer (A3-1) powder.

[0320] <Preparation of Radiosensitive Linear Compositions>

[0321] The following shows the polymer (A), the radiosensitive linear compound (B), the ionic liquid compound (C), the bonding agent (D), and the polymeric monomer (X1) used in the preparation of the radiosensitive linear composition.

[0322] (Polymer (A))

[0323] A1-1 to A1-6, A2-1, A3-1: Polymers (A1-1), (A1-6), (A2-1), and (A3-1) synthesized in Synthetic Examples 1 to 8.

[0324] (Radiosensitive linear compound (B))

[0325] B-1: A condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (2.0 mol).

[0326] B-2: Irgacure PAG121 (manufactured by BASF)

[0327] B-3: Irgacure OXE-01 (manufactured by BASF)

[0328] (Ionic liquid compounds (C), all of which are manufactured by Kanto Chemical Co., Ltd.)

[0329] C-1: 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[0330] C-2: Bis(trifluoromethylsulfonyl)azanide; 1-methyl-1-propylpyrrolidin-1-ium

[0331] C-3: Bis(trifluoromethylsulfonyl)azanide; 1-butyl-1-methylpyrrolidin-1-ium

[0332] C-4: Bis(trifluoromethylsulfonyl)azanide; 1-methyl-1-propylpiperidin-1-ium

[0333] C-5: Bis(trifluoromethylsulfonyl)azanide; Tributyl(methyl)phosphanium

[0334] C-6: Bis(fluorosulfonyl)azanide; 1-ethyl-3-methylimidazol-3-ium

[0335] C-7: Bis(fluorosulfonyl)azanide; 1-methyl-1-propylpyrrolidin-1-ium

[0336] C-8: Bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide; 1-ethyl-3-methylimidazol-3-ium

[0337] C-9: Bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide; 1-butyl-3-methylimidazol-3-ium

[0338] C-10: 1-Etyl-3-metylimidazoliumoctylsulfate

[0339] C-11: Bis(trifluoromethylsulfonyl)azanide; 1-methyl-3-prop-2-enylimidazol-1-ium

[0340] C-12: Bis(trifluoromethylsulfonyl)azanide; 1-ethyl-3-prop-2-enylimidazol-3-ium

[0341] C-13: 1-Ethyl-3-methylimidazol-3-ium; acetate

[0342] C-14: 1-Ethyl-3-methylimidazol-3-ium; ethyl sulfate

[0343] C-15: 1-Ethyl-3-methylimidazol-3-ium; tetrafluoroborate

[0344] C-16: Cyanoiminomethylene alkylate; 1-ethyl-3-methylimidazol-3-ium

[0345] C-17: 2,2-dicyanoethylideneazanide; 1-ethyl-3-methylimidazol-3-ium

[0346] C-18: 1-Methyl-3-propylimidazol-1-ium; hexafluorophosphate

[0347] C-19: 1-ethyl-3-methylimidazol-3-ium; chloride

[0348] C-20: 1-ethyl-3-methylimidazol-3-ium; iodide

[0349] (Close contact agent (D))

[0350] D-1: 3-Glycidoxypropyltrimethoxysilane

[0351] (Polymerized monolith (X1))

[0352] X-1: Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0353] <Preparation of Radiosensitive Linear Compositions>

[0354] [Example 1]

[0355] A mixture of 20 parts of a radiosensitive linear compound (B-1), 30 parts of an ionic liquid (C-1), and 5 parts of a bonding agent (D-1) was dissolved in propylene glycol monomethyl ether acetate as a solvent, with a solid content concentration of 20% by mass, in an amount equivalent to 100 parts of polymer (A1-1) (solid component). The mixture was then filtered using a 0.2 μm membrane filter to prepare the radiosensitive linear composition.

[0356] [Examples 2-29, Comparative Example 1]

[0357] The radiosensitive linear composition was prepared using the same method as in Example 1, except that the components shown in Table 2 and their proportions (parts by mass) were used. In Table 2, "-" indicates that the corresponding component was not used.

[0358] [Comparative Example 2]

[0359] An ionic gel was prepared by mixing 130 parts of ionic liquid (C-1) with an amount equivalent to 100 parts (solid component) of a positive photoresist (manufactured by MicroChem, S1805: a positive photoresist formed by adding naphthoquinone diazide as a photosensitizer to cresol phenolic varnish). Then, propylene glycol 1-monomethyl ether 2-acetate was added as a solvent to the prepared ionic gel, adjusting the concentration to 20% by mass of the solid component, thereby preparing a radiosensitive linear composition. Furthermore, in Table 2, "S1805" refers to the aforementioned positive photoresist (manufactured by MicroChem, S1805).

[0360] The prepared radiosensitive linear composition was evaluated as follows.

[0361] [Evaluation of Pattern Formation]

[0362] Using a spinner, the radiosensitive linear composition was coated onto a silicon substrate treated with hexamethyl disilazane (HMDS) at 60°C for 60 seconds, followed by pre-baking at 110°C for 2 minutes on a hot plate to form a coating with an average thickness of 1.0 μm. A mask of arbitrary size with a line-to-space pattern of 1:1 width was used to irradiate the coating with a mercury lamp at 100 J / m². 2 The ultraviolet light was then used. Following this, development was performed at 25°C for 60 seconds using a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by rinsing with ultrapure water for 1 minute. The width of the lines and spatial patterns that could be formed was then measured. Values ​​less than 5 μm were rated "A", and values ​​greater than 5 μm were rated "B".

[0363] [Evaluation of capacitor Cp]

[0364] The radiosensitive linear composition was coated onto a glass substrate that had been deposited with indium tin oxide (ITO) to a thickness of 100 nm and calcined at 230°C for 30 min. Then, it was pre-baked at 110°C for 2 min to form a coating film with a thickness of 3.0 μm (formation of the coated substrate). A 5 mm thick layer was then deposited onto this coating film (gate insulating film) using a vapor deposition method. An Al electrode pattern was fabricated to create a sample for dielectric constant measurement. For a substrate with the electrode pattern, the capacitance Cp was measured at a frequency of 10 kHz using an HP16451B electrode and an HP4284A precision inductance-capacitance-resistance (LCR) meter via the capacitance voltage (CV) method. The value was set to 1 × 10⁻⁶. -9 Cases above F are designated as "A", while cases less than 1×10 are designated as "A". -9 F is 3×10 -9 F and above are designated as "B", and those less than 3×10 are designated as "B". -9 F is set to "C". In case A, the capacitance is excellent; in case B, it is rated as good; and in case C, it is rated as poor.

[0365] [Evaluation of chemical resistance]

[0366] The coated substrate prepared in the [Evaluation of Capacitance Cp] section was immersed in Microstrip 2001 (registered trademark) heated to 65°C for 6 minutes. After immersion, the coating was rinsed with ultrapure water for 5 seconds and then dried. The coating thickness before and after treatment was measured using a stylus-type film thickness gauge. The swelling percentage (%) of Microstrip 2001 was calculated according to the following formula, and the chemical resistance was evaluated according to the following criteria.

[0367]

[0368] (Evaluation Criteria)

[0369] A: More than 0%

[0370] B: Less than 0%

[0371] The evaluation criteria are as follows: "A (above 0%)" indicates that the product is insoluble in Microstrip (registered trademark) 2001 and therefore has drug resistance; "B (below 0%)" indicates that the product is soluble in Microstrip (registered trademark) 2001 and therefore does not have drug resistance.

[0372] [Table 2]

[0373]

[0374] As shown in Table 2, the radiosensitive linear compositions of Examples 1 to 29 exhibited good patterning properties, and the hardened films obtained from these compositions showed good capacitance and chemical resistance. In contrast, Comparative Example 1 showed poor capacitance, and Comparative Example 2 showed poor patterning properties and chemical resistance.

Claims

1. An inductively linearized composition for forming a gate insulating film ( wherein, (Except for compositions containing cresol phenolic varnish and quinone diazide compounds), containing: At least one polymer (A) selected from the group consisting of polymers (A1) containing structural units (I) having acid groups, siloxane polymers (A2), and polyamic acids or polyamic esters (A3). Radiosensitive linear compound (B), and Ionic liquids (C).

2. The inductively linearized composition for forming a gate insulating film according to claim 1, wherein, The radiosensitive linear compound (B) comprises a quinone diazide compound (B-1).

3. The inductively linearized composition for forming a gate insulating film according to claim 1, wherein, The radiosensitive linear compound (B) contains a photopolymerization initiator (B-2). The inductively linearized composition for forming the gate insulating film comprises a polymeric monomer (X).

4. The inductively linearized composition for forming a gate insulating film according to claim 1, wherein, The polymer (A1) further comprises a structural unit (III) having one or more groups selected from the group represented by the following formula (2) and acid-dissociable groups. The radiosensitive linear compound (B) contains a photoacid generator (B-3); [Chemistry 1] (In equation (2), R) 1 R 2 and R 3 Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl or phenyl group having 1 to 10 carbon atoms; wherein, R 1 R 2 and R 3 At least one of them is an alkoxy group having 1 to 6 carbon atoms; "Indicates a bond".

5. A method for manufacturing a pattern, comprising: The process of forming a gate insulating film by coating a substrate with an inductively linearized composition as described in any one of claims 1 to 4; The process of irradiating at least a portion of the coating with radiation; as well as A process of developing a pattern from a coating film irradiated with said radiation.

6. The method for manufacturing a pattern according to claim 5, further comprising a process of heating the pattern after the process of forming the pattern.

7. A pattern obtained by the pattern manufacturing method as described in claim 5 or 6.

8. A hardened film for a gate insulating film, obtained from a radioactive composition for forming a gate insulating film as described in any one of claims 1 to 4.

9. A semiconductor device comprising the hardened film as claimed in claim 8.

10. An organic electrochemical transistor comprising the hardened film as claimed in claim 8.

11. An organic electroluminescent display device, comprising the hardened film as described in claim 8.

12. A liquid crystal display device, comprising the hardened film as described in claim 8.

13. A micro-light-emitting diode display device, comprising the hardened film as described in claim 8.

14. A quantum dot light-emitting display device, comprising the hardened film as described in claim 8.

15. A wearable device comprising the hardened film as claimed in claim 8.

16. An electronic skin device comprising the hardening membrane as claimed in claim 8.

17. A biosensor comprising the hardened membrane as described in claim 8.

18. A neuromorphic device comprising the sclerotherapy membrane as claimed in claim 8.

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