Radiation-sensitive composition, interlayer insulating film and method for producing the same, and display device

Abstract

To provide a radiation-sensitive composition having a high radiation sensitivity, excellent storage stability, and a high taper angle, and capable of generating a pattern having excellent size stability after exposure.SOLUTION: This radiation-sensitive composition contains: [A] a polymer component including a first structure unit having an acidic group and a second structure unit having one selected from the group consisting of an oxetane structure and an oxirane structure; and [B] a quinonediazide compound represented by a formula (1). In the formula (1), R1 denotes a hydroxy group or a group obtained by condensating the hydroxy group and a 1, 2-naphtho diazide-sulfonic acid halide. At least one of multiple R1 in the formula is a group obtained by condensating the hydroxy group and the 1, 2-naphtho diazide-sulfonic acid halide. L1 denotes a substituted or unsubstituted alkanediyl group.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Electronic components such as liquid crystal display elements and solid-state imaging elements are provided with an interlayer insulating film that insulates between wiring and a substrate and between wirings. In the manufacturing process of a liquid crystal display element, an interlayer insulating film is formed on a substrate, and a transparent conductive film serving as an electrode and a liquid crystal alignment film are further formed on the interlayer insulating film. As a material for forming the interlayer insulating film, a radiation-sensitive resin composition containing an alkali-soluble resin and a photosensitizer is widely used (see, for example, Patent Document 1). In this technology, generally, a coating film is formed by applying a radiation-sensitive resin composition on a substrate, and then the coating film is exposed through a photomask, and then a development process is performed to form an interlayer insulating film having a desired pattern. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-200698 A Summary of the Invention [Problem to be solved by the invention]

[0004] In order to achieve even higher definition in liquid crystal display elements, it is considered effective to increase the rising angle of the edge portion of the interlayer insulating film, that is, to increase the taper angle. As a means for increasing the taper angle of the interlayer insulating film, it is considered that the molecular weight of the polymer component, which is the main component of the interlayer insulating film, is increased, or the glass transition temperature (Tg) is increased.

[0005] However, when the molecular weight of the polymer component is increased, there is a concern that the sensitivity of the radiation-sensitive resin composition will decrease. In addition, the viscosity of the radiation-sensitive resin composition is likely to increase due to the increase in the molecular weight of the polymer component, and the storage stability may decrease. When the taper angle of the interlayer insulating film is increased by increasing the Tg of the polymer component, the hydrophobicity of the polymer component increases, and there is a concern that the resolution will decrease and a good pattern shape will not be obtained.

[0006] In the manufacturing process of liquid crystal display devices and the like, the time from the end of the exposure process to the start of the development process (Post Exposure Delay (PED) time) can be long. If the reaction of the polymer component (e.g., crosslinking reaction) continues to progress during this PED time even though the exposure process has ended, there is a concern that the pattern shape after development will vary. In order to achieve even higher resolution for liquid crystal display devices and the like, it is required that the reaction of the polymer component does not progress easily after exposure while showing high radiation sensitivity, and that the dimensional stability is excellent.

[0007] The present invention has been made in consideration of the above-mentioned problems, and has as its main object to provide a radiation-sensitive composition which has high radiation sensitivity and excellent storage stability, and is capable of forming a pattern which has a large taper angle and excellent dimensional stability after exposure. [Means for solving the problem]

[0008] According to the present invention, there are provided the following radiation-sensitive composition, interlayer insulating film and method for producing the same, and display element.

[0009] [1] A radiation-sensitive composition comprising: [A] a polymer component (excluding the component [B] below) including a first structural unit having an acidic group, and a second structural unit having at least one structure selected from the group consisting of an oxetane structure and an oxirane structure; and [B] a quinonediazide compound represented by the following formula (1): [ka] (In formula (1), R 1 is a hydroxyl group or a group formed by condensing a hydroxyl group with 1,2-naphthoquinone diazide sulfonic acid halide. 1 At least one of R is a group formed by condensing a hydroxyl group with a 1,2-naphthoquinone diazide sulfonic acid halide. 2 is an alkyl group having 1 to 5 carbon atoms. 1 is a substituted or unsubstituted alkanediyl group. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3, provided that n1+n2≦4. m is an integer of 3 to 12. 1 are the same or different. 2 are the same or different. 1 are the same or different.)

[0010] [2] A method for producing an interlayer insulating film, comprising the steps of: forming a coating film using the radiation-sensitive composition according to [1] above; irradiating at least a portion of the coating film with radiation; developing the irradiated coating film; and heating the developed coating film. [3] An interlayer insulating film formed using the radiation-sensitive composition according to [1] above. [4] A display element having the interlayer insulating film according to [3] above. Effect of the Invention

[0011] The radiation-sensitive composition of the present invention contains the above-mentioned components [A] and [B], and thus can form a pattern having a large taper angle and excellent dimensional stability after exposure. The radiation-sensitive composition of the present invention also has high radiation sensitivity and excellent storage stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "~" means that the numerical range includes the numerical values ​​before and after "~" as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0013] [Radiation sensitive composition] The radiation-sensitive composition of the present disclosure is a polymer composition used for forming, for example, an interlayer insulating film of a display device, and contains the following component [A] and component [B]. [A] [A] A polymer component including a first structural unit having an acidic group and a second structural unit having at least one structure selected from the group consisting of an oxetane structure and an oxirane structure (excluding the component [B] described below). [B] A quinone diazide compound represented by the following formula (1): Note that component [B] is a different compound from component [A], and component [A] does not contain component [B]. [ka] (In formula (1), R 1 is a hydroxyl group or a group formed by condensing a hydroxyl group with 1,2-naphthoquinone diazide sulfonic acid halide. 1 At least one of R is a group formed by condensing a hydroxyl group with a 1,2-naphthoquinone diazide sulfonic acid halide. 2 is an alkyl group having 1 to 5 carbon atoms. 1 is a substituted or unsubstituted alkanediyl group. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3, provided that n1+n2≦4. m is an integer of 3 to 12. 1 are the same or different. 2 are the same or different. 1 are the same or different.)

[0014] Each component contained in the radiation-sensitive composition of the present disclosure and other components that may be blended as necessary will be described below. Note that, unless otherwise specified, each component may be used alone or in combination of two or more.

[0015] Here, in this specification, the term "hydrocarbon group" includes chain-shaped hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain-shaped hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group that do not include a cyclic structure in the main chain and are composed only of a chain structure. However, they may be saturated or unsaturated. The term "alicyclic hydrocarbon group" means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be composed only of an alicyclic hydrocarbon structure, and it also includes those that have a chain structure as a part of it. The term "aromatic hydrocarbon group" means a hydrocarbon group that includes an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and it may include a chain structure or an alicyclic hydrocarbon structure as a part of it. The ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure. The term "cyclic hydrocarbon group" includes alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The term "number of ring members" refers to the number of atoms (carbon atoms, nitrogen atoms, oxygen atoms, etc.) that constitute the ring. When the ring is polycyclic, it means the number of atoms constituting the multiple rings contained in the polycyclic ring.

[0016] <[A] Component> First structural unit The first structural unit is a structural unit having an acidic group. The inclusion of the first structural unit in the component [A] can impart good alkali solubility to the polymer component. In this specification, "alkali soluble" means that the polymer component is soluble in an alkali aqueous solution such as a 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

[0017] The first structural unit is not particularly limited as long as it has an acidic group, but is preferably at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. In this specification, the term "phenolic hydroxyl group" refers to a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0018] The first structural unit is preferably a structural unit derived from an unsaturated monomer having an acidic group (hereinafter also referred to as "first monomer"). Specific examples of the first monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid as monomers constituting structural units having a carboxyl group; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid as monomers constituting structural units having a sulfonic acid group; vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid as monomers constituting structural units having a phenolic hydroxyl group; and 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, 4-hydroxyphenyl(meth)acrylate, and 1,1,1,3,3,3-hexafluoro-2-(4-vinylphenyl)-2-propanol as monomers constituting structural units having a phenolic hydroxyl group. Moreover, maleimide can also be used as the first monomer. In this specification, "(meth)acrylic" is meant to include "acrylic" and "methacrylic".

[0019] In the [A] component, the content of the first structural unit is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total structural units constituting the [A] component, from the viewpoint of making the exposed portion of the coating film made of the radiation-sensitive composition exhibit good developability in an alkaline developer. On the other hand, if the content of the first structural unit is too high, it is considered that the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion becomes small. From this viewpoint, the content of the first structural unit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total structural units constituting the [A] component.

[0020] The component [A] preferably contains, as the first structural unit, at least a structural unit other than a structural unit having a phenolic hydroxyl group, and more preferably contains at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, and a maleimide unit. The component [A] containing, as the first structural unit, a structural unit having such a group (at least one of a carboxy group, a sulfonic acid group, and a maleimide group), is advantageous in that the exposed portion of the coating film made of the radiation-sensitive composition can exhibit good developability in an alkaline developer.

[0021] In the component [A], the content of at least one structural unit selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, and a maleimide unit is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total structural units constituting the component [A], from the viewpoint of making the exposed portion of the coating film made of the radiation-sensitive composition exhibit good developability in an alkaline developer. In addition, from the viewpoint of fully expressing the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion, the content of at least one structural unit selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, and a maleimide unit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total structural units constituting the component [A].

[0022] In addition, when a structural unit having a phenolic hydroxyl group is introduced into the [A] component as the first structural unit, the content ratio of the structural unit having a phenolic hydroxyl group is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, based on all structural units constituting the [A] component, from the viewpoint of improving radiation sensitivity. In addition, from the viewpoint of ensuring the physical properties of the cured film due to the structural unit having a thermal crosslinking group, the content ratio of the structural unit having a phenolic hydroxyl group is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on all structural units constituting the [A] component.

[0023] Second structural unit The second structural unit is a structural unit having at least one selected from the group consisting of an oxetane structure and an oxirane structure. The component [A] contains the second structural unit, which can improve the resolution of the film obtained using the radiation-sensitive composition and the solvent resistance of the cured film. In addition, the cyclic ether group of the second structural unit acts as a crosslinking group, which can form a cured film that is inhibited from deteriorating for a long period of time.

[0024] The second structural unit is preferably a structural unit derived from an unsaturated monomer having at least one structure selected from the group consisting of an oxetane structure and an oxirane structure (hereinafter also referred to as the "second monomer"), and specifically, is preferably a structural unit represented by the following formula (4). [ka] (In formula (4), R 5 is a monovalent group having an oxetane structure or an oxirane structure, R 6 is a hydrogen atom or a methyl group, and X 1 is a single bond or a divalent linking group.

[0025] In the above formula (4), R 5 Examples of the aryl groups include oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl group, 3-ethyloxetanyl group, etc. Among these, R 5 is preferably a monovalent group having an oxirane structure. X 1 Examples of the divalent linking group include a methylene group, an ethylene group, and an alkanediyl group such as a 1,3-propanediyl group.

[0026] Specific examples of the second monomer include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and the like.

[0027] In the [A] component, the content of the second structural unit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total structural units constituting the [A] component. The content of the second structural unit is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, based on the total structural units constituting the [A] component. By setting the content of the second structural unit within the above range, it is preferable that the coating film shows better resolution and the heat resistance and solvent resistance of the obtained cured film can be sufficiently increased.

[0028] In the [A] component, the respective content ratios of the first structural unit and the second structural unit can be set by appropriately combining the numerical ranges of the preferred content ratios of the above-mentioned structural units. Among these, from the viewpoint of making the radiation-sensitive composition have good radiation sensitivity and storage stability, and making the pattern shape of the obtained cured film excellent, it is preferable that the [A] component contains 1% by mass or more and 40% by mass or less of the first structural unit and 10% by mass or more and 60% by mass or less of the second structural unit with respect to all structural units constituting the polymer component. More preferably, it contains 5% by mass or more and 35% by mass or less of the first structural unit and 10% by mass or more and 60% by mass or less of the second structural unit, and even more preferably, it is preferable that it contains 5% by mass or more and 30% by mass or less of the first structural unit and 10% by mass or more and 60% by mass or less of the second structural unit.

[0029] The component [A] may further contain, in addition to the first structural unit and the second structural unit, structural units different from the first and second structural units (hereinafter also referred to as "other structural units"). Examples of the other structural units include a structural unit derived from a (meth)acrylate compound having a heterocyclic structure with 5 or more ring members (hereinafter also referred to as "third structural unit"), a structural unit derived from an aromatic vinyl compound (hereinafter also referred to as "fourth structural unit"), a structural unit derived from an N-substituted maleimide compound (hereinafter also referred to as "fifth structural unit"), a structural unit having a hydroxyl group (excluding phenolic hydroxyl groups) (hereinafter also referred to as "sixth structural unit"), and a structural unit derived from a (meth)acrylic acid alkyl ester compound (hereinafter also referred to as "seventh structural unit").

[0030] Third structural unit The third structural unit is a structural unit derived from a (meth)acrylate compound (hereinafter also referred to as "third monomer") having a heterocyclic structure with 5 or more ring members. The heterocyclic structure with 5 or more ring members possessed by the third monomer is preferably at least one selected from the group consisting of a cyclic ether structure, a cyclic ester structure, a cyclic carbonate structure, a cyclic amide structure, and a cyclic imide structure.

[0031] Specific examples of the heterocyclic structure include cyclic ether structures such as tetrahydrofuran, methyltetrahydrofuran, ethyltetrahydrofuran, tetrahydropyran, methyltetrahydropyran, ethyltetrahydropyran, dioxolane, methyldioxolane, ethyldioxolane, dioxane, methyldioxane, ethyldioxane, morpholine, 1,4,6-trioxaspiro[4.6]undecane, 1,4,6-trioxaspiro[4.4]nonane, 1,4,6-trioxaspiro[4.5]decane, and the like, from which any hydrogen atom has been removed; and cyclic ester structures such as cyclic esters such as tetrahydrofuran, methyltetrahydrofuran, ethyltetrahydrofuran, tetrahydropyran, methyltetrahydropyran, ethyltetrahydropyran, dioxolane, methyldioxolane, ethyldioxane, dioxane, methyldioxane, ethyldioxane, morpholine, 1,4,6-trioxaspiro[4.6]undecane, 1,4,6-trioxaspiro[4.4]nonane, 1,4,6-trioxaspiro[4.5]decane, and the like, from which any hydrogen atom has been removed. Examples of the cyclic carbonate structure include groups obtained by removing any hydrogen atom from a cyclic carbonate ester such as ethylene carbonate or propylene carbonate; examples of the cyclic amide structure include groups obtained by removing any hydrogen atom from a lactam such as γ-lactam, δ-lactam, ε-caprolactam or laurolactam; and examples of the cyclic imide structure include groups obtained by removing any hydrogen atom from an imide ring such as phthalimide or hexahydrophthalimide.

[0032] Specifically, the third structural unit is preferably a structural unit represented by the following formula (5). [ka] (In formula (5), R 7 R is a hydrogen atom or a methyl group. 8is a monovalent group having a heterocyclic structure having 5 or more ring members.

[0033] In the above formula (5), R 8 When R is a monovalent group having a heterocyclic structure having 5 or more ring members, the ring portion of the heterocyclic structure may be directly bonded to the oxygen atom in the above formula (1) or may be bonded via a divalent linking group (for example, an alkanediyl group having 1 to 5 carbon atoms). 8 Among these, R is preferably a monovalent group having a heterocyclic structure having 5 or more ring members. 8 is more preferably a monovalent group having a cyclic ether structure, a cyclic ester structure, a cyclic carbonate structure, a cyclic amide structure, or a cyclic imide structure, and is further preferably a cyclic ether structure.

[0034] R in the above formula (5) 8 When the heterocyclic structure has a cyclic ether structure, the cyclic ether structure preferably has two or more oxygen atoms (-O-) in the ring skeleton, in order to further increase the sensitivity of the radiation-sensitive composition. The cyclic ether structure is more preferably a dioxolane structure, a dioxane structure, or a spiroorthoester structure, even more preferably a dioxolane structure or a dioxane structure, and particularly preferably a dioxolane structure, in order to further increase the sensitivity of the radiation-sensitive composition.

[0035] Specific examples of the third monomer include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2,2-di(meth)acrylate), (meth)acryloyl)methyl, (meth)acrylate (2,2-dimethyl-1,3-dioxolan-4-yl)ethyl, (meth)acryloylmorpholine, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4.6]undecane, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4.4]nonane, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4.5]decane, etc.; Examples of (meth)acrylate compounds having a cyclic ester structure having 5 or more ring members include (γ-butyrolactone-2-yl)(meth)acrylate, (γ-butyrolactone-2-yl)methyl(meth)acrylate, and (δ-valerolactone-2-yl)ethyl(meth)acrylate; Examples of (meth)acrylate compounds having a cyclic carbonate structure having 5 or more ring members include glycerin carbonate (meth)acrylate; Examples of (meth)acrylate compounds having a cyclic amide structure having 5 or more ring members include (γ-lactam-2-yl)(meth)acrylate and (γ-lactam-2-yl)methyl(meth)acrylate; Examples of the (meth)acrylate compound having a cyclic imide structure having 5 or more ring members include N-(meth)acryloyloxyethylhexahydrophthalimide, and the like.

[0036] When the component [A] contains a third structural unit, the content of the third structural unit is preferably 1% by mass or more relative to the total structural units constituting the component [A]. By making the content of the third structural unit 1% by mass or more, it is preferable that the radiation-sensitive composition can be made more sensitive. The content of the third structural unit is more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total structural units constituting the component [A]. In addition, from the viewpoint of improving the pattern shape of the interlayer insulating film after development, the content of the third structural unit is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, relative to the total structural units constituting the component [A].

[0037] Fourth structural unit The aromatic vinyl compound constituting the fourth structural unit is not particularly limited, and examples thereof include styrene-based compounds such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, and diphenylethylene; vinylnaphthalene-based compounds such as vinylnaphthalene and divinylnaphthalene; and heterocyclic vinyl compounds such as vinylpyridine. Of these, the aromatic vinyl compound is preferably a styrene-based compound. In this specification, a structural unit derived from an aromatic vinyl compound having a phenolic hydroxyl group is included in the "first structural unit".

[0038] When the [A] component contains a fourth structural unit, the content of the fourth structural unit is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, based on the total structural units constituting the [A] component. The content of the fourth structural unit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total structural units constituting the [A] component. By making the content of the fourth structural unit 1% by mass or more, the pattern shape of the cured film can be improved. Furthermore, by making the content of the fourth structural unit 30% by mass or less, the glass transition temperature of the polymer component does not become too high, and the deterioration of developability can be suppressed.

[0039] 5th structural unit The N-substituted maleimide compound constituting the fifth structural unit may be a compound in which the hydrogen atom bonded to the nitrogen atom of the maleimide is substituted with a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include a monovalent linear hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Among these, the following is preferred in terms of being able to enhance the effect of improving heat resistance: The N-substituted maleimide compound constituting the fifth structural unit preferably has a monovalent cyclic hydrocarbon group, and more preferably has a monovalent alicyclic hydrocarbon group having a monocycle, a bridged ring, or a spiro ring.

[0040] Specifically, the fifth structural unit is preferably a structural unit represented by the following formula (6). [ka] (In formula (6), R 9 R is a monovalent cyclic hydrocarbon group. 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0041] In the above formula (6), R 9In the formula, the ring structure of the cyclic hydrocarbon group may be directly bonded to the nitrogen atom, or the ring structure may be bonded via a divalent linking group. Examples of the divalent linking group include a methylene group, an ethylene group, and an alkanediyl group such as a 1,3-propanediyl group. Among these, R 9 R is preferably an alicyclic hydrocarbon group in which a ring structure of the cyclic hydrocarbon group is directly bonded to a nitrogen atom, and more preferably an alicyclic hydrocarbon group in which an alicyclic hydrocarbon structure is directly bonded to a nitrogen atom. 10 and R 11 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0042] Specific examples of N-substituted maleimide compounds include compounds having an alicyclic hydrocarbon group such as 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, and N-adamantylmaleimide; and compounds having an aromatic hydrocarbon group such as N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide. Of these, the N-substituted maleimide compound is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, N-(4-methylcyclohexyl)maleimide, N-phenylmaleimide, and N-(4-methylphenyl)maleimide, and more preferably at least one of N-cyclohexylmaleimide and N-phenylmaleimide.

[0043] When the component [A] contains the fifth structural unit, the content of the fifth structural unit is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, based on the total structural units constituting the component [A], from the viewpoint of improving the pattern shape. Also, the content of the fifth structural unit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on the total structural units constituting the component [A], from the viewpoint of suppressing deterioration of developability.

[0044] 6th structural unit The sixth structural unit is preferably a structural unit derived from an unsaturated monomer having a hydroxyl group (excluding phenolic hydroxyl groups) (hereinafter also referred to as "sixth monomer"), and specifically includes a structural unit derived from a monomer having one or more hydroxyl groups bonded to a saturated chain hydrocarbon group. The sixth monomer is not particularly limited, but examples thereof include (meth)acrylic compounds and maleimide compounds.

[0045] Specific examples of the sixth monomer include (meth)acrylic compounds such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and glycerol mono(meth)acrylate; Examples of the maleimide compound include N-(hydroxymethyl)maleimide, N-(2-hydroxyethyl)maleimide, and N-(3-hydroxypropyl)maleimide.

[0046] When the component [A] contains the sixth structural unit, it is preferable in terms of suppressing the decrease in pattern forming ability caused by the variation in pre-bake temperature during film formation, forming a good pattern, and in terms of radiation sensitivity. When the component [A] contains the sixth structural unit, the content ratio of the sixth structural unit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total structural units constituting the component [A], from the viewpoint of suppressing the decrease in pattern forming ability caused by the variation in pre-bake temperature. In addition, the content ratio of the sixth structural unit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, based on the total structural units constituting the component [A], from the viewpoint of suppressing the decrease in developability.

[0047] 7th structural unit Examples of the monomer constituting the seventh structural unit include (meth)acrylic compounds having an alkyl group having 1 to 20 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc. When the component [A] contains the seventh structural unit, the content of the seventh structural unit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on all structural units constituting the component [A].

[0048] In addition to the above, other structural units include structural units derived from unsaturated dicarboxylic acid dialkyl ester compounds such as diethyl itaconate, conjugated diene compounds such as 1,3-butadiene and isoprene, nitrogen-containing vinyl compounds such as (meth)acrylonitrile and (meth)acrylamide, and monomers such as vinyl chloride, vinylidene chloride and vinyl acetate. In the component [A], the content of the other structural units excluding the third to seventh structural units is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total structural units constituting the component [A].

[0049] The [A] component may contain only one type of the first structural unit, or may contain two or more types. The same applies to the second structural unit and other structural units. The content ratio of each structural unit is usually equivalent to the ratio of the monomer used in the production of the polymer component. The [A] component may be composed of one type of polymer, or may be composed of two or more types of polymers, so long as it contains the first structural unit and the second structural unit. That is, the [A] component is a polymer component containing the first structural unit and the second structural unit in the same polymer or different polymers. The [A] component may further contain a polymer that does not have either the first structural unit or the second structural unit as a polymer derived from an unsaturated monomer.

[0050] The component [A] is a component that becomes a base resin in the radiation-sensitive composition. Examples of the form in which the component [A] is contained in the radiation-sensitive composition include [1] a form in which a polymer having a first structural unit and a second structural unit is contained, and [2] a form in which a polymer having a first structural unit and a polymer having a second structural unit are contained. Among these, the above-mentioned [1] is preferred in that the effects of the present disclosure can be obtained while reducing the number of types of components constituting the radiation-sensitive composition.

[0051] The glass transition temperature (Tg) of the polymer constituting the component [A] is preferably 110°C or less, more preferably 105°C or less, and even more preferably 100°C or less, from the viewpoint of improving the shape of the pattern formed using the radiation-sensitive composition and achieving a high taper angle of the cured film. The Tg of the polymer is preferably -20°C or more, more preferably -10°C or more, and even more preferably 0°C or more. In this specification, the Tg of the polymer is a value calculated by a method of proportionally allocating the Tg of the homopolymer corresponding to the structural unit contained in the polymer. The Tg of the homopolymer means the glass transition temperature obtained by DSC measurement (differential scanning calorimetry) at a heating rate of 20°C / min based on JIS K7121-1987.

[0052] In the component [A], the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 or more. Mw of 1,000 or more is preferable in that a cured film having sufficiently high heat resistance and solvent resistance and good developability can be obtained, and that the dimensional stability of the pattern can be improved. Mw is more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 5,000 or more, and particularly preferably 8,000 or more. In addition, from the viewpoint of improving the storage stability and film-forming property of the radiation-sensitive composition, Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, even more preferably 18,000 or less, and particularly preferably 15,000 or less.

[0053] In the component [A], the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.7 or less. When the component [A] is composed of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above range.

[0054] The content of the component [A] is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on the total amount of solids contained in the radiation-sensitive composition. The content of the component [A] is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. By setting the content of the component [A] within the above range, a cured film having sufficiently high heat resistance and solvent resistance, and exhibiting good developability and transparency can be obtained.

[0055] The component [A] can be produced, for example, by using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator, etc., according to a known method such as radical polymerization. Specifically, examples of the polymerization initiator used include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid) dimethyl. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total amount of the monomers used in the reaction. Examples of the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons.

[0056] In the above polymerization reaction, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the type of initiator and monomer and the reaction temperature, but is usually 0.5 to 10 hours. The amount of the organic solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60 mass% relative to the total amount of the reaction solution. The polymer obtained by the polymerization reaction can be isolated using a known isolation method, for example, a method of pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure with an evaporator.

[0057] <[B] component> The quinone diazide compound, which is the component [B], is a cyclic compound represented by the above formula (1) (hereinafter also referred to as "compound (B)"). Compound (B) is a radiation-sensitive acid generator that generates a carboxylic acid upon irradiation with radiation.

[0058] In the above formula (1), R 1is a hydroxyl group or a group formed by condensing a hydroxyl group with a 1,2-naphthoquinone diazide sulfonic acid halide. The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride is particularly preferred.

[0059] R 2 The alkyl group having 1 to 5 carbon atoms may be linear or branched. 2 Specific examples of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. 2 Of these, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0060] L 1 is a substituted or unsubstituted alkanediyl group. 1 By having such a structure, the solubility in a developer is high, and the sensitivity of the radiation-sensitive composition can be increased. 1 In the formula (I), the alkanediyl group may be linear or branched. The number of carbon atoms in the alkanediyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and even further preferably 1 to 3. 1 When is a substituted alkanediyl group, examples of the substituent include a halogen atom and an alkoxy group.

[0061] From the viewpoint of ease of introduction of the 1,2-naphthoquinone diazide sulfonic acid structure, L 1 is preferably a group represented by the following formula (2). [ka] (In formula (2), R 3 and R 4are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. "*" represents a bond.)

[0062] In the above formula (2), R 3 and R 4 When R is an alkyl group having 1 to 3 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 3 and R 4 is preferably a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of increasing the solubility in a developer, R 3 and R 4 It is preferred that one of these groups is a hydrogen atom and the other is a hydrogen atom, a methyl group or an ethyl group.

[0063] m is an integer of 3 to 12. From the viewpoint of excellent solubility in a solvent, transmittance, and heat resistance, m is preferably an integer of 3 to 8, more preferably 3 to 6, and particularly preferably 3 to 5. n1 is an integer of 1 to 3, with 2 or 3 being preferred. n2 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0064] In the above formula (1), L 1 The bonding position of L is not particularly limited. 1 The bonding position of one L 1 The other L 1 With respect to the compound (B), the ortho- or meta-position is preferable, and the meta-position is more preferable. A preferable specific example of the compound (B) is a compound represented by the following formula (1-1). [ka] (In formula (1-1), r is an integer of 1 to 4. 1 , R 2 , L 1 , n1 and n2 are defined as in formula (1) above.

[0065] Compound (B) can be obtained by a condensation reaction between a compound represented by the following formula (3) (hereinafter also referred to as "mother nucleus b") and 1,2-naphthoquinone diazide sulfonic acid halide, thereby introducing a 1,2-naphthoquinone diazide sulfonic acid structure into the phenolic hydroxyl group of the mother nucleus b. [ka] (In formula (3), R 2 , L 1 , n1, n2 and m are defined as in formula (1) above.

[0066] Specific examples of the mother nucleus b include calixresorcinarene derivatives such as C-methylcalix[3]resorcinarene, C-methylcalix[4]resorcinarene, C-methylcalix[6]resorcinarene, C-ethylcalix[3]resorcinarene, C-ethylcalix[4]resorcinarene, C-decylcalix[4]resorcinarene, C-undecylcalix[4]resorcinarene, and C-dodecylcalix[4]resorcinarene. However, the mother nucleus b is not limited to these compounds.

[0067] The condensation reaction of the mother nucleus b with 1,2-naphthoquinone diazide sulfonic acid halide can be carried out according to a known method, for example, a method of reacting at 60 to 90° C. for 12 to 60 hours in the presence of a catalyst such as an acid catalyst, a base catalyst, or a phase transfer catalyst.

[0068] In the condensation reaction to obtain compound (B), the ratio of the mother nucleus b to the 1,2-naphthoquinone diazide sulfonic acid halide is preferably such that the amount of the 1,2-naphthoquinone diazide sulfonic acid halide used is an amount corresponding to 10 to 85 mol %, more preferably an amount corresponding to 15 to 80 mol %, and even more preferably an amount corresponding to 20 to 70 mol %, based on the number of OH groups in the mother nucleus b. By setting the amount of the 1,2-naphthoquinone diazide sulfonic acid halide used within the above range, it is preferable in that the difference in solubility between the exposed and unexposed parts in an alkaline solution can be sufficiently increased while improving the solubility in a solvent, the radiation sensitivity, and the edge shape of the pattern.

[0069] The content of the compound (B) in the radiation-sensitive composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the component [A]. The content of the compound (B) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, relative to 100 parts by mass of the component [A]. When the content of the compound (B) is 2 parts by mass or more, it is preferable that the difference in solubility in an alkaline solution between the irradiated portion and the unirradiated portion can be sufficiently increased, and that a pattern with a high taper angle can be formed. On the other hand, when the content ratio of the compound (B) is 60 parts by mass or less, it is preferable that the decrease in radiation sensitivity can be suppressed, and the amount of unreacted compound (B) can be sufficiently reduced, and the decrease in developability due to the remaining compound (B) can be suppressed.

[0070] <Other ingredients> The radiation-sensitive composition of the present disclosure may further contain components other than the above-mentioned components [A] and [B] (hereinafter also referred to as "other components"). Examples of the other components include the following components [C] and [D]. [C] A compound which is a condensation product of a phenolic compound or an alcoholic compound with a 1,2-naphthoquinone diazide sulfonic acid halide and which is different from compound (B). [D] Solvent.

[0071] <[C] component> The radiation-sensitive composition of the present disclosure may further contain a compound (hereinafter also referred to as "compound (C)") which is a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus c") with 1,2-naphthoquinone diazide sulfonic acid halide and is different from compound (B). Compound (C) is a radiation-sensitive acid generator that generates a carboxylic acid upon irradiation with radiation, just like compound (B). By further containing compound (C) in the radiation-sensitive composition of the present disclosure, it is possible to easily adjust the solubility in a developer, which is preferable in that the radiation sensitivity of the radiation-sensitive composition can be easily adjusted. Note that component [C] is a compound different from components [A] and [B].

[0072] Examples of the mother nucleus c include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other mother nuclei.Specific examples of these include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; tetrahydroxybenzophenones such as 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone; pentahydroxybenzophenones such as 2,3,4,2',6'-pentahydroxybenzophenone; and hexahydroxybenzophenones such as 2,4,6,3',4',5'-hexahydroxybenzophenone. , 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; (polyhydroxyphenyl)alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'- tetramethyl-1,1'-spirobiindene-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.; other mother nuclei include, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 2-[bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl], etc.

[0073] Of these, preferred mother nuclei c are 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol.

[0074] The 1,2-naphthoquinone diazide sulfonic acid halide to be reacted with the mother nucleus c is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specifically, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, etc. can be mentioned. Among these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride can be preferably used.

[0075] In the condensation reaction to obtain the compound (C), the ratio of the mother nucleus c to the 1,2-naphthoquinone diazide sulfonic acid halide is preferably 30 to 85 mol %, more preferably 50 to 70 mol %, relative to the number of OH groups in the mother nucleus c. The condensation reaction can be carried out according to a known method. The 1,2-quinone diazide compound is obtained by the condensation reaction of the mother nucleus c and the 1,2-naphthoquinone diazide sulfonic acid halide.

[0076] When the radiation-sensitive composition of the present disclosure contains compound (C), the content of compound (C) in the radiation-sensitive composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, per 100 parts by mass of component [A]. The content of compound (C) is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, per 100 parts by mass of component [A].

[0077] In the radiation-sensitive composition, the total content of the radiation-sensitive acid generators (i.e., the total amount of compound (B) and compound (C)) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of component [A], from the viewpoint of generating a sufficient amount of acid upon irradiation with radiation, thereby sufficiently increasing the difference in solubility between exposed and unexposed areas in an alkaline solution in the coating film, and achieving good patterning. Also, from the viewpoint of suppressing a decrease in developability due to remaining unreacted acid generators, the total content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of component [A].

[0078] In addition, when the compound (B) and the compound (C) are used in combination in the radiation-sensitive composition of the present disclosure, the ratio of the compound (B) to 100 parts by mass of the total amount of the compound (B) and the compound (C) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more. When the ratio of the compound (B) is within the above range, it is preferable that a pattern having a shape with a larger edge rise angle can be obtained, and that a pattern having a stable shape can be formed even when the exposure time (PED time) is extended. In addition, from the viewpoint of ease of adjusting the radiation sensitivity of the radiation-sensitive composition, the ratio of the compound (B) to 100 parts by mass of the total amount of the compound (B) and the compound (C) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less.

[0079] <[D] component> The radiation-sensitive composition of the present disclosure is a liquid composition in which the component [A], the component [B], and other components blended as necessary are dissolved or dispersed in a solvent, preferably the component [D]. The solvent used is preferably an organic solvent that dissolves each of the components blended in the radiation-sensitive composition and does not react with each of the components.

[0080] Specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, the solvent used in preparing the radiation-sensitive composition of the present disclosure preferably contains at least one selected from the group consisting of ethers and esters, and 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.

[0081] Other components that may be contained in the radiation-sensitive composition of the present disclosure include, in addition to the above, for example, a reaction initiator (a photoradical polymerization initiator, a photocationic polymerization initiator, etc.), a polyfunctional polymerizable compound (a polyfunctional (meth)acrylate, etc.), an adhesion aid (a functional silane coupling agent, etc.), a surfactant (a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, etc.), a polymerization inhibitor, an antioxidant, a chain transfer agent, etc. The blending ratio of these components is appropriately selected according to each component within a range that does not impair the effects of the present disclosure.

[0082] The solid content concentration of the radiation-sensitive composition of the present disclosure (the ratio of the total mass of the components other than the component [D] in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 5 to 60 mass%. A solid content concentration of 5 mass% or more is preferable in that a sufficient thickness of the coating film can be ensured when the radiation-sensitive composition is applied onto a substrate. In addition, a solid content concentration of 60 mass% or less is preferable in that the thickness of the coating film does not become too large, and furthermore, the viscosity of the radiation-sensitive composition can be appropriately increased, and good coatability can be ensured. The solid content concentration in the radiation-sensitive composition is more preferably 10 to 55 mass%, and even more preferably 15 to 50 mass%.

[0083] <Interlayer insulating film and its manufacturing method> The interlayer insulating film of the present disclosure is formed by the radiation-sensitive composition prepared as described above. The radiation-sensitive composition of the present disclosure has high radiation sensitivity and is good in patterning by radiation exposure. In particular, the radiation-sensitive composition of the present disclosure can form an organic film having a larger edge angle (taper angle) of the pattern and a good shape. Therefore, the radiation-sensitive composition of the present disclosure can be preferably used as a material for forming, for example, an interlayer insulating film, a planarizing film, a spacer, a protective film, a colored pattern film for a color filter, a partition wall, etc. In particular, the radiation-sensitive composition of the present disclosure is useful as a polymer composition for forming an interlayer insulating film of a display element, in that the display element can be made highly precise when applied to an organic film constituting the display element.

[0084] In producing an interlayer insulating film, a positive cured film can be formed by irradiation with radiation (ultraviolet rays, far ultraviolet rays, visible light, etc.) using the radiation-sensitive composition of the present disclosure. The interlayer insulating film of the present disclosure can be produced, for example, by a method including the following steps 1 to 4. (Step 1) A step of forming a coating film using the above-mentioned radiation-sensitive composition. (Step 2) A step of exposing at least a part of the coating film to light. (Step 3) Developing the coating. (Step 4) Heating the developed coating. Each step will be described in detail below.

[0085] [Step 1: Film formation step] In this process, the radiation-sensitive composition is applied to a surface on which a film is to be formed (hereinafter also referred to as "film-forming surface"), and the solvent is preferably removed by a heat treatment (pre-bake) to form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, when a planarizing film is formed using the radiation-sensitive composition, the radiation-sensitive composition is applied to a substrate provided with switching elements such as TFTs to form a coating film. As the substrate, for example, a glass substrate or a resin substrate is used.

[0086] Examples of methods for applying the radiation-sensitive composition include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet. Among these, spin coating, slit die coating, and bar coating are preferred. Pre-baking conditions vary depending on the types and content ratios of each component in the radiation-sensitive composition, but are, for example, 60 to 130° C. and 0.5 to 10 minutes. The thickness of the coating film formed (i.e., the film thickness after pre-baking) is preferably 1 to 12 μm.

[0087] [Step 2: Exposure step] In this step, at least a part of the coating film formed in step 1 above is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, an interlayer insulating film having a pattern can be formed. Examples of radiation include ultraviolet rays, far ultraviolet rays, visible light, X-rays, and charged particle beams such as electron beams. Among these, ultraviolet rays are preferred, and examples of such beams include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 is preferred.

[0088] [Process 3: Development process] In this step, the coating film irradiated in step 2 is developed. Specifically, the coating film irradiated in step 2 is developed with a developer to remove the irradiated portion, thereby performing positive development. Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of the alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of JP-A-2016-145913. From the viewpoint of obtaining appropriate developability, the alkali concentration in the aqueous alkali solution is preferably 0.1 to 5.0 mass%. Examples of the development method include a suitable method such as a puddle method, a dipping method, a rocking immersion method, and a shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, it is preferable to perform a rinse treatment by washing with running water on the patterned coating film.

[0089] [Process 4: Heating process] In this step, the coating film developed in step 3 above is heated (post-baked). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120 to 250° C. The heating time is, for example, 5 to 40 minutes when the heat treatment is performed on a hot plate, and 10 to 80 minutes when the heat treatment is performed in an oven. In this manner, a cured film having a desired pattern can be formed on a substrate.

[0090] <Display element> The display element of the present disclosure has a cured film such as an interlayer insulating film formed using the radiation-sensitive composition. Examples of the display element include a liquid crystal display element and an organic electroluminescence (EL) display element. The interlayer insulating film formed using the radiation-sensitive composition can also function as a planarizing film or a protective film.

[0091] The display element of the present disclosure can be effectively applied to various applications, and can be used as various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays. EXAMPLES

[0092] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by weight unless otherwise specified.

[0093] [Weight average molecular weight (Mw) and number average molecular weight (Mn)] The Mw and Mn of the polymer were measured by the following method. Measurement method: Gel permeation chromatography (GPC) method Equipment: Showa Denko GPC-101 GPC column: Shimadzu GLC GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined Mobile phase: Tetrahydrofuran Column temperature: 40℃ ·Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0094] [Glass transition temperature (Tg)] The Tg of the polymer was calculated by a method of proportionally dividing the Tg of the homopolymer corresponding to the structural unit in the polymer. The Tg of the homopolymer is the glass transition temperature determined by DSC measurement (differential scanning calorimetry) at a heating rate of 20° C. / min according to JIS K7121-1987.

[0095] [Monomer] The monomers used in the synthesis of the polymer are as follows: First Monomer M-1: Methacrylic acid M-2: 4-Hydroxyphenyl methacrylate M-3: 1,1,1,2,2,2-hexafluoro-2-(4-vinylphenyl)-2-propanol M-4: Maleimide M-5: p-isopropenylphenol 《Second Monomer》 M-6: Glycidyl methacrylate M-7: 3-methacryloyloxymethyl-3-ethyloxetane M-8: 3,4-epoxycyclohexylmethyl methacrylate Other Monomers M-9: N-cyclohexylmaleimide M-10: N-phenylmaleimide M-11: Methyl methacrylate M-12: Tricyclo[5.2.1.0 2,6 ]Decan-8-yl acrylate M-13: (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate M-14: Tetrahydrofurfuryl acrylate M-15: 2-Hydroxyethyl methacrylate M-16: Acryloylmorpholine M-17: Styrene

[0096] <Polymer synthesis> [Synthesis Example 1] Synthesis of polymer (A-1) In a flask equipped with a cooling tube and a stirrer, 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were charged. Subsequently, monomers were charged in the ratios shown in Table 1, and the atmosphere was replaced with nitrogen. The temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-1). The solid content of this polymer solution was 34.0% by mass, and the Mw of polymer (A-1) was 11,000, the molecular weight distribution (Mw / Mn) was 2.3, and the Tg was 95°C.

[0097] [Synthesis Examples 2 to 5] Synthesis of Polymers (A-2) to (A-5) Polymer solutions containing polymers (A-2) to (A-5) each having the same solid content concentration, molecular weight and molecular weight distribution as polymer (A-1) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts (parts by mass) of each component shown in Table 1 were used.

[0098] [Synthesis Example 6] Synthesis of polymer (A-6) In a flask equipped with a cooling tube and a stirrer, 4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were charged. Subsequently, monomers were charged in the ratios shown in Table 1, and the atmosphere was replaced with nitrogen. The temperature of the solution was then raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-6). The solid content of this polymer solution was 34.0% by mass, and the Mw of polymer (A-6) was 25,000, the molecular weight distribution (Mw / Mn) was 3.1, and the Tg was 95°C.

[0099] [Table 1]

[0100] <Preparation of Radiation-Sensitive Resin Composition> A radiation-sensitive resin composition was prepared using the polymer synthesized above. The polymer, photosensitizer and other components used in the preparation of the radiation-sensitive resin composition are shown below. Polymer A-1 to A-7: Polymers (A-1) to (A-6) listed in Table 1 Photoacid generator B-1: Condensation product of C-methylcalix[4]resorcinarene (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B-2: Condensation product of C-methylcalix[4]resorcinarene (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (4.0 mol) B-3: Condensation product of C-methylcalix[3]resorcinarene (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol) B-4: Condensation product of C-methylcalix[6]resorcinarene (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol) B-5: Condensation product of 4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) B-6: Condensation product of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) Other Ingredients C-1: C-methylcalix[4]resorcinarene

[0101] [Example 1] A polymer solution containing the polymer (A-1) was mixed with 20 parts of a photoacid generator (B-1) in an amount equivalent to 100 parts (solid content) of the polymer (A-1), and diethylene glycol ethyl methyl ether was added thereto so that the final solid content concentration was 30% by mass. The mixture was then filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive resin composition.

[0102] [Examples 2 to 8, Comparative Examples 1 to 4] The radiation-sensitive resin compositions of Examples 2 to 8 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 2 were used.

[0103] <Evaluation> Cured films were formed using the radiation-sensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4, and the following items were evaluated by the methods described below. The evaluation results are shown in Table 2.

[0104] [Radiation sensitivity] Using a spinner, the radiation-sensitive resin composition was applied onto a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, a developing solution consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform a development process at 25°C for 60 seconds, and then the substrate was washed with running ultrapure water for 1 minute. At this time, the minimum exposure dose capable of forming a line-and-space pattern with a width of 10 μm was measured. This measured value was 150 J / m 2 Less than 150J / m 2 More than 200J / m 2 B: Less than 200J / m 2 More than 250J / m 2 Less than 250J / m 2 The above was rated D. Cases A and B can be evaluated as excellent radiation sensitivity, case C as good radiation sensitivity, and case D as poor radiation sensitivity.

[0105] [Evaluation of lithography shape] Using a spinner, the radiation-sensitive resin composition was applied onto a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was irradiated with ultraviolet light equivalent to the radiation sensitivity from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, a development process was carried out at 25°C for 60 seconds using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and then washed with running ultrapure water for 1 minute. Next, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the film to 3000 J / m 2 After irradiating the entire surface of the substrate with light, the substrate was baked for 30 minutes in an oven heated to 230°C to obtain a cured film. The cross-sectional shape of the 10μm-wide line and space pattern was observed using a scanning electron microscope (SEM) to measure the angle of contact between the substrate surface and the cured film. Measurements of 55 degrees or more were rated A, 45 degrees or more but less than 55 degrees B, 30 degrees or more but less than 45 degrees C, and 20 degrees or less D. Cases A and B indicate that the lithographic shape is excellent, case C indicates that the lithographic shape is good in terms of radiation sensitivity, and case D indicates that the lithographic shape is poor.

[0106] [Evaluation of dimensional stability after exposure] Using a spinner, the radiation-sensitive resin composition was applied onto a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was irradiated with ultraviolet light equivalent to the radiation sensitivity from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, using a developer consisting of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, the substrate was immediately developed at 25°C for 60 seconds after the ultraviolet light irradiation, and then washed with running ultrapure water for 1 minute. At this time, the size of the line-and-space pattern with a width of 10 μm was measured. In addition, the same process as above was performed with a time (retentative time) from ultraviolet light irradiation to development set to 30 minutes, and the size of the line-and-space pattern with a width of 10 μm was measured. The difference in the measured values ​​was rated as A when it was less than 2 μm, B when it was 2 μm or more and less than 3 μm, and C when it was 3 μm or more. In the case of A, the post-exposure dimensional stability can be evaluated as excellent, in the case of B, the post-exposure dimensional stability can be evaluated as good, and in the case of C, the post-exposure dimensional stability can be evaluated as poor.

[0107] [Evaluation of storage stability] Using a spinner, the radiation-sensitive resin composition was applied onto a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was irradiated with ultraviolet light equivalent to the radiation sensitivity from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, a developing solution consisting of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used to perform a development process for 60 seconds at 25°C, and then the substrate was washed with running ultrapure water for 1 minute. At this time, the size of the line-and-space pattern with a width of 10 μm was measured. In addition, the radiation-sensitive resin composition was left at 23°C for 7 days after preparation, and the size of the line-and-space pattern was measured in the same process. The difference in the measured values ​​was rated as A when it was less than 2 μm, B when it was 2 μm or more and less than 3 μm, and C when it was 3 μm or more. The storage stability can be evaluated as A being excellent, B being good, and C being poor.

[0108] [Table 2]

[0109] As shown in Table 2, the radiation-sensitive resin compositions of Examples 1 to 8 exhibited good radiation sensitivity, and the obtained cured films were excellent in lithography profile, post-exposure dimensional stability, and storage stability. In addition, when Example 1 and Example 5, which used (B-1) as a photoacid generator, were compared, Example 1, which used the lower molecular weight polymer (A-1), was superior in radiation sensitivity, post-exposure dimensional stability, and storage stability compared to Example 5, which used the higher molecular weight polymer (A-6).

[0110] In contrast, Comparative Example 1, which does not contain compound (B) as a photoacid generator, was inferior to Examples 1 to 8 in terms of lithography profile and post-exposure dimensional stability. Among Comparative Examples 2 and 3, which do not contain compound (B), Comparative Example 2, which contains a high Tg polymer (A-5), had low radiation sensitivity, and Comparative Example 3, which contains a high molecular weight polymer (A-6), had low radiation sensitivity and insufficient post-exposure dimensional stability. Furthermore, Comparative Example 4, which uses unsubstituted calixarene instead of compound (B) and compound (C) as a photoacid generator, had insufficient post-exposure dimensional stability.

Claims

1. [A] a polymer component including a first structural unit having an acidic group and a second structural unit having at least one structure selected from the group consisting of an oxetane structure and an oxirane structure (excluding the component [B] described below); [B] a quinone diazide compound represented by the following formula (1), and [C] a condensation product of a phenolic compound or an alcoholic compound with a 1,2-naphthoquinone diazide sulfonic acid halide, which is different from the compound represented by the following formula (1): A radiation-sensitive composition comprising: 【Chemistry 1】 (In formula (1), R １ is a hydroxyl group or a group formed by condensing a hydroxyl group with 1,2-naphthoquinone diazide sulfonic acid halide. １ At least one of R is a group formed by condensing a hydroxyl group with a 1,2-naphthoquinone diazide sulfonic acid halide. ２ is an alkyl group having 1 to 5 carbon atoms. １ is a substituted or unsubstituted alkanediyl group. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3, provided that n1+n2≦4. m is an integer of 3 to 12. １ are the same or different. ２ are the same or different. １ are the same or different.)

2. Said L １ The radiation-sensitive composition according to claim 1 , wherein: 【Chemistry 2】 (In formula (2), R ３ and R ４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. "*" represents a bond.)

3. 3. The radiation-sensitive composition according to claim 1, wherein m is an integer of 3 to 6.

4. 4. The radiation-sensitive composition according to claim 1, wherein the polymer component has a weight average molecular weight of 2,000 to 30,000.

5. 5. The radiation-sensitive composition according to claim 1, wherein the content of the quinone diazide compound is 5 to 40 parts by mass based on 100 parts by mass of the polymer component.

6. 6. The radiation-sensitive composition according to claim 1, wherein the first structural unit is at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit.

7. The radiation-sensitive composition according to any one of claims 1 to 6, which is used for forming an interlayer insulating film.

8. A step of forming a coating film using a radiation-sensitive composition; exposing at least a portion of the coating to radiation; developing the coating film that has been irradiated with radiation; heating the developed coating; A method for producing an interlayer insulating film, comprising: The radiation-sensitive composition comprises [A] a polymer component including a first structural unit having an acidic group and a second structural unit having at least one structure selected from the group consisting of an oxetane structure and an oxirane structure (excluding the component [B] described below); and [B] a quinone diazide compound represented by the following formula (1): The method for producing an interlayer insulating film comprising the steps of: 【Chemistry 3】 (In formula (1), R 1 is a hydroxyl group or a group formed by condensing a hydroxyl group with 1,2-naphthoquinone diazide sulfonic acid halide. However, at least one of the multiple R 1 in the formula is a group formed by condensing a hydroxyl group with 1,2-naphthoquinone diazide sulfonic acid halide. R 2 is an alkyl group having 1 to 5 carbon atoms. L 1 is a substituted or unsubstituted alkanediyl group. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3, with the proviso that n1+n2≦4. m is an integer of 3 to 12. Multiple R 1 in the formula are the same or different. Multiple R 2 in the formula are the same or different. Multiple L 1 in the formula are the same or different.)

9. An interlayer insulating film formed using the radiation-sensitive composition according to any one of claims 1 to 7.

10. A display element comprising the interlayer insulating film according to claim 9 .

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