Liquid crystal display element and method for producing the same, radiation-sensitive composition, interlayer insulating film and method for producing the same

Abstract

The present invention provides a liquid crystal display element and a method for manufacturing the same, a radiation-sensitive composition, an interlayer insulating film, and a method for manufacturing the same, which can fully suppress the generation of bubbles. A method for manufacturing a liquid crystal display element comprises: a formation step of forming an interlayer insulating film on a substrate; and an irradiation step of irradiating an object having the interlayer insulating film with light after the interlayer insulating film is formed. In the manufacturing method, the interlayer insulating film is formed using a radiation-sensitive composition containing components (A), (B), and (C). (A) A polymer component comprising: a first structural unit derived from at least one member selected from the group consisting of an acrylate compound having a heterocyclic structure with 5 or more ring members and an acrylate compound having an alkyl group with 3 or less carbon atoms; a second structural unit having an acid group; and a third structural unit having a cyclic ether group with 3 or 4 ring members. (B) A quinonediazide compound. (C) A solvent.

Description

Technical Field

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

[0002] Liquid crystal display elements are provided with an interlayer insulating film to insulate wiring from the substrate or between wirings. During the manufacturing process of a liquid crystal display element, the interlayer insulating film is formed on the substrate, and then a transparent conductive film or liquid crystal alignment film, which serves as an electrode, is formed on the interlayer insulating film. During the formation of the transparent conductive film or liquid crystal alignment film, the interlayer insulating film is exposed to high temperatures or irradiated with radiation such as ultraviolet rays. Therefore, the interlayer insulating film is required to be resistant to heat and light.

[0003] One of the manufacturing methods for liquid crystal display elements is polymer-sustained alignment (PSA) technology. PSA technology involves pre-mixing a photopolymerizable monomer into a liquid crystal material. After assembling a liquid crystal cell, the cell is irradiated with light while a voltage is applied between a pair of electrodes sandwiching the liquid crystal layer. This polymerizes the photopolymerizable monomer and controls the molecular orientation of the liquid crystal molecules. This technology offers advantages such as increased viewing angle and faster response times.

[0004] When manufacturing liquid crystal display devices using PSA technology, light irradiating the liquid crystal cell may cause unreacted components in the interlayer insulating film to react, or the organic materials constituting the interlayer insulating film to undergo photodecomposition reactions, resulting in the generation of low-molecular-weight components. It is believed that these low-molecular-weight components are generally adsorbed by components of the interlayer insulating film and remain within or on the surface of the interlayer insulating film. However, these low-molecular-weight components can sometimes generate bubbles due to external forces on the liquid crystal display device, and these bubbles may appear in the pixel area during use of the liquid crystal display device.

[0005] Therefore, in the past, a technology for suppressing the foaming of the interlayer insulating film caused by light irradiation during the manufacturing process of liquid crystal display elements has been proposed (for example, see Patent Document 1). Patent Document 1 discloses forming an interlayer insulating film so that the transmittance of light with a wavelength of 310 nm is 70% or more when the film thickness is 2 μm.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-200698 Summary of the Invention

[0009] [Problems to be solved by the invention]

[0010] Foaming caused by low-molecular-weight components in the interlayer insulating film may affect the reliability of liquid crystal display devices. In particular, with the recent expansion of the use of liquid crystal display devices, there is a demand for more sophisticated liquid crystal display devices, and it is desired to minimize the generation of bubbles. Furthermore, this foaming is believed to occur not only due to light irradiation based on PSA technology, but also due to light irradiation treatments performed after the formation of the interlayer insulating film, such as light irradiation used to cure the sealing material or light irradiation used to form a liquid crystal alignment film using a photo-alignment method.

[0011] The present invention has been made in view of the above-mentioned problems, and a main object of the present invention is to provide a method for producing a liquid crystal display element and a radiation-sensitive composition capable of obtaining a liquid crystal display element in which the generation of bubbles is sufficiently suppressed.

[0012] [Technical means to solve the problem]

[0013] The present inventors believe that one of the causes of foaming in liquid crystal display devices is the decomposition of the main chain of a polymer containing structural units derived from methacrylate, a material used to form an interlayer insulating film. Based on this hypothesis, they discovered that the aforementioned problem can be solved by specifying the composition of the radiation-sensitive composition used to form the interlayer insulating film. Specifically, the present invention provides the following methods for manufacturing liquid crystal display devices, radiation-sensitive compositions, interlayer insulating films, and liquid crystal display devices.

[0014] [1] A method for manufacturing a liquid crystal display element, comprising: a forming step of forming an interlayer insulating film on a substrate; and an irradiation step of irradiating light onto an object having the interlayer insulating film after the interlayer insulating film is formed, wherein the interlayer insulating film is formed using a radiation-sensitive composition containing the following components (A), (B), and (C).

[0015] (A) a polymer component comprising: a first structural unit derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure having 5 or more ring members and an acrylate compound having an alkyl group having 3 or less carbon atoms; a second structural unit having an acid group; and a third structural unit having a cyclic ether group having 3 or 4 ring members;

[0016] (B) quinone diazide compounds;

[0017] (C) Solvent.

[0018] [2] A radiation-sensitive composition comprising: (A) a polymer component, (B) a quinonediazide compound, and (C) a solvent, wherein the component (A) comprises a first structural unit derived from an acrylate compound, a second structural unit having an acid group, and a third structural unit having a cyclic ether group having 3 or 4 ring members, wherein the acrylate compound has at least one heterocyclic structure selected from the group consisting of a cyclic ether structure (excluding a tetrahydrofurfuryl structure), a cyclic ester structure, a cyclic carbonate structure, a cyclic amide structure, and a cyclic imide structure as a heterocyclic structure having 5 or more ring members.

[0019] [3] A radiation-sensitive composition comprising: (A) a polymer component, (B) a quinonediazide compound, and (C) a solvent, wherein the component (A) comprises, relative to all structural units constituting the polymer component, 8% by mass or more and 50% by mass or less of a first structural unit, 0.5% by mass or more and less than 20% by mass of a second structural unit (excluding structural units having a phenolic hydroxyl group), and 10% by mass or more and 60% by mass or less of a third structural unit, wherein the first structural unit is derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure having 5 or more ring members and an acrylate compound having an alkyl group having 3 or less carbon atoms, the second structural unit has an acid group, and the third structural unit has a cyclic ether group having 3 or 4 ring members.

[0020] [4] A method for manufacturing an interlayer insulating film, comprising: forming a coating film using the radiation-sensitive composition of [2] or [3]; irradiating at least a portion of the coating film with radiation; developing the coating film after irradiation with radiation; and heating the developed coating film.

[0021] [5] An interlayer insulating film formed using the radiation-sensitive composition according to [2] or [3].

[0022] [6] A liquid crystal display element comprising the interlayer insulating film according to [5].

[0023] [Effects of the Invention]

[0024] According to the production method and radiation-sensitive composition of the present invention, by forming an interlayer insulating film using a radiation-sensitive composition containing the components (A), (B), and (C), a liquid crystal display element can be obtained in which bubbles generated by irradiating the interlayer insulating film with light are sufficiently suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A diagram schematically showing the structure of a liquid crystal display element.

[0026] [Explanation of Symbols]

[0027] 10: Liquid crystal display element

[0028] 11: Array substrate

[0029] 12: Liquid crystal layer

[0030] 13: Opposing substrates

[0031] 14, 28: Substrate

[0032] 15: Base coating

[0033] 16: TFT

[0034] 17: Interlayer insulation film

[0035] 18: Pixel electrode

[0036] 19: Semiconductor layer

[0037] 21: Gate insulating film

[0038] 22: Gate electrode

[0039] 23: Source electrode

[0040] 24: Drain electrode

[0041] 25: Inorganic insulating film

[0042] 26a, 26b: contact holes

[0043] 27, 33: Liquid crystal alignment film

[0044] 29: Black Matrix

[0045] 31: Color filter

[0046] 32: Common electrode DETAILED DESCRIPTION

[0047] The following details the details of the embodiments. Furthermore, in this specification, numerical ranges indicated by "to" include the numerical values ​​before and after "to" as the lower and upper limits. "Constructural unit" refers to a unit that primarily constitutes the main chain structure and refers to a unit that contains at least two or more units in the main chain structure.

[0048] [Radiosensitive composition]

[0049] The radiation-sensitive composition disclosed herein is used for forming an interlayer insulating film of a liquid crystal display device. The radiation-sensitive composition contains the following components (A), (B), and (C).

[0050] (A) A polymer component comprising: a first structural unit derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure having 5 or more ring members and an acrylate compound having an alkyl group having 3 or less carbon members; a second structural unit having an acid group; and a third structural unit having a cyclic ether group having 3 or 4 ring members.

[0051] (B) Quinonediazide compounds.

[0052] (C) Solvent.

[0053] Hereinafter, each component contained in the radiation-sensitive composition of the present disclosure and other components blended as needed will be described. In addition, unless otherwise specified, each component may be used alone or in combination of two or more.

[0054] Here, in this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The so-called "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that does not contain a cyclic structure in the main chain but is composed only of a chain structure. Among them, it may be saturated or unsaturated. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. Among them, it is not necessary to be composed only of an alicyclic hydrocarbon structure, and also includes a group that has a chain structure in part. The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed only of an aromatic ring structure, and also may contain a chain structure or an alicyclic hydrocarbon structure in part. Furthermore, the ring structure possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group may also have a substituent containing a hydrocarbon structure. The term "cyclic hydrocarbon group" includes the meaning of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0055] <(A)Component>

[0056] First structural unit

[0057] The first structural unit is a structural unit derived from at least one monomer selected from the group consisting of an acrylate compound having a heterocyclic structure with 5 or more ring members and an acrylate compound having an alkyl group with 3 or less carbon atoms (hereinafter also referred to as the "first monomer"). In addition, the "acrylate compound" refers to a compound having an acryloyloxy group as a group participating in polymerization, specifically, a compound represented by the formula "CH2=CH-CO-OR 20 ”(Among them, R 20 is a monovalent organic group having 1 or more carbon atoms).

[0058] Examples of the heterocyclic structure having 5 or more ring members possessed by the first monomer include a group formed by removing any hydrogen atom from a heterocyclic ring having 5 or more ring members, wherein the heterocyclic ring having 5 or more ring members has -O-, -CO-, -CO-O-, -CO-S-, -O-CO-O-, -O-CO-S-, -CO-NR- 1 -、-CO-NR 1 -CO-(where R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms).

[0059] The ring possessed by the heterocyclic structure may be any one of a monocyclic ring, a condensed ring, a bridged ring and a spiro ring, preferably a monocyclic ring, a condensed ring or a spiro ring, more preferably a monocyclic ring or a condensed ring. The number of ring members of the heterocyclic structure is preferably 15 or less, more preferably 12 or less, and further preferably 10 or less. Furthermore, in the case where the heterocyclic structure is a polycyclic structure, the so-called "number of ring members" refers to the total number of atoms of the two or more rings constituting the polycyclic structure. The heterocyclic structure may also have a substituent in the ring portion. As the substituent, for example, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, etc. can be listed.

[0060] In the above, the heterocyclic structure possessed by the first structural unit 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. More specifically, the heterocyclic structure is preferably at least one selected from the group consisting of a structure represented by the following formula (a-1), a structure represented by the following formula (a-2), a structure represented by the following formula (a-3), a structure represented by the following formula (a-4), a structure represented by the following formula (a-5), and a structure represented by the following formula (a-6).

[0061] [Chemistry 1]

[0062]

[0063] (In formula (a-1) to formula (a-6), R 10 is an alkyl group having 1 to 5 carbon atoms, or represents two R groups on the same carbon atom. 10 Combined with the two R 10 The carbon atoms to which they are bonded together form a ring structure; R 11 is an alkyl group with 1 to 5 carbon atoms; R 12 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m is an integer of 0 to 2, n is an integer of 1 to 3; r is an integer of 1 to 3; "*" indicates a bond)

[0064] In the above formulas (a-1) to (a-6), R10 and R 11 The alkyl group having 1 to 5 carbon atoms may be linear or branched, but is preferably linear. 10 and R 11 The alkyl group having 1 to 5 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

[0065] As two R 10 Bonded to the two R 10 Examples of the ring structure formed by the bonded carbon atoms include spiroorthoester structures such as 1,4,6-trioxaspiro[4.6]undecane, 1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0066] m is preferably 0 or 1. n is preferably 1 or 2, more preferably 1. r is preferably 1 or 2, more preferably 1.

[0067] In formula (a-5) and formula (a-6), the bonding bond can also be formed by removing R 12 It is formed by the hydrogen atoms it possesses.

[0068] Specific examples of the heterocyclic structure include cyclic ether structures such as tetrahydrofuran, methyltetrahydrofuran, ethyltetrahydrofuran, tetrahydropyran, methyltetrahydropyran, ethyltetrahydropyran, dioxolane, methyldioxolane, ethyldioxolane, dioxane, methyldioxane, ethyldioxane, 1,4,6-trioxaspiro[4.6]undecane, 1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane. Examples of the cyclic ester structure include groups obtained by removing arbitrary hydrogen atoms from cyclic ethers such as γ-butyrolactone, γ- -valerolactone, δ-valerolactone, ε-caprolactone and other lactones by removing any hydrogen atom; cyclic carbonate structures include, for example, groups formed by removing any hydrogen atom from cyclic carbonates such as ethylene carbonate and propylene carbonate; cyclic amide structures include, for example, groups formed by removing any hydrogen atom from lactams such as γ-lactam, δ-lactam, ε-caprolactam and laurolactam; cyclic imide structures include, for example, groups formed by removing any hydrogen atom from imide rings such as phthalimide and hexahydrophthalimide.

[0069] Specifically, the first structural unit is preferably a structural unit represented by the following formula (1).

[0070] [Chemistry 2]

[0071]

[0072] (In formula (1), R 2is a monovalent group having a heterocyclic structure with 5 or more ring members or an alkyl group with 1 to 3 carbon atoms)

[0073] In the formula (1), R 2 In the case of a monovalent group having a heterocyclic structure with 5 or more ring members, the ring portion of the heterocyclic structure may be directly bonded to the oxygen atom in the formula (1), or may be bonded to the oxygen atom in the formula (1) via a divalent linking group (e.g., an alkanediyl group having 1 to 5 carbon atoms). In terms of obtaining a radiation-sensitive composition with high radiation sensitivity and further reducing foaming of a liquid crystal display element, R 2 Preferably, it is a monovalent group having a heterocyclic structure with 5 or more ring members. Among these, in particular, R 2 More preferably, it is 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 still more preferably a cyclic ether structure.

[0074] In the first structural unit and in the formula (1) 2 When the heterocyclic structure is a cyclic ether structure, the cyclic ether structure preferably contains two or more oxygen atoms (—O—) in the ring skeleton, in order to further improve the sensitivity of the radiation-sensitive composition. In order to further improve the sensitivity of the radiation-sensitive composition, the cyclic ether structure is more preferably a dioxolane structure, a dioxane structure, or a spiroorthoester structure, more preferably a dioxolane structure or a dioxane structure, and particularly preferably a dioxolane structure.

[0075] Specific examples of the first monomer include acrylate compounds having a cyclic ether structure with 5 or more ring members: tetrahydrofurfuryl acrylate, tetrahydropyranyl acrylate, 5-ethyl-1,3-dioxane-5-ylmethyl acrylate, 1,3-dioxane-5-ylmethyl acrylate, 5-methyl-1,3-dioxane-5-ylmethyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, Ester, methyl acrylate, ethyl acrylate, 2-acryloyloxymethyl-1,4,6-trioxaspiro[4.6]undecane, 2-acryloyloxymethyl-1,4,6-trioxaspiro[4.4]nonane, 2-acryloyloxymethyl-1,4,6-trioxaspiro[4.5]decane, etc.;

[0076] Examples of the acrylate compound having a cyclic ester structure having 5 or more ring members include (γ-butyrolactone-2-yl) acrylate, (γ-butyrolactone-2-yl) methyl acrylate, and (δ-valerolacton-2-yl) ethyl acrylate.

[0077] Examples of the acrylate compound having a cyclic carbonate structure having 5 or more ring members include glycerol carbonate acrylate and the like;

[0078] Examples of the acrylate compound having a cyclic amide structure having 5 or more ring members include (γ-lactam-2-yl) acrylate and (γ-lactam-2-yl)methyl acrylate.

[0079] Examples of the acrylate compound having a cyclic imide structure having 5 or more ring members include N-acryloyloxyethylhexahydrophthalimide;

[0080] Examples of acrylate compounds having an alkyl group with 3 or less carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate. Among these, the first monomer is preferably an acrylate compound having a heterocyclic structure with 5 or more ring members, as it can further improve the radiation sensitivity of the radiation-sensitive composition.

[0081] In component (A), the content ratio of the first structural unit is preferably 5% by mass or more relative to all the structural units constituting component (A). By setting the content ratio of the first structural unit to 5% by mass or more, it is possible to suppress outgassing from the cured film while highly sensitizing the radiation-sensitive composition, and to suppress foaming of the liquid crystal display element, which is suitable in this respect. From this viewpoint, the content ratio of the first structural unit is more preferably 8% by mass or more relative to all the structural units constituting component (A), further preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and particularly more preferably 25% by mass or more. In addition, from the viewpoint of making the pattern shape of the interlayer insulating film after development good, the content ratio of the first structural unit is preferably 60% by mass or less relative to all the structural units constituting component (A), more preferably 55% by mass or less, further preferably 50% by mass or less, and further more preferably 45% by mass or less.

[0082] Second structural unit

[0083] The second structural unit is a structural unit having an acid group. By including the second structural unit in the component (A), good alkali solubility can be imparted to the polymer component.

[0084] The second structural unit is not particularly limited as long as it has an acid group, but is preferably at least one selected from the group consisting of a structural unit having a carboxyl group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. In this specification, the term "phenolic hydroxyl group" refers to a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0085] The second structural unit is preferably a structural unit derived from an unsaturated monomer having an acid group (hereinafter also referred to as the "second monomer"). Specific examples of the second monomer include monomers constituting the structural unit having a carboxyl group, such as unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and 4-vinylbenzoic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; monomers constituting the structural unit having a sulfonic acid group include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid; and monomers constituting the structural unit having a phenolic hydroxyl group include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol. Maleimide can also be used as the second monomer. Furthermore, in this specification, "(meth)acrylic group" refers to "acrylic group" and "methacrylic group."

[0086] In component (A), from the perspective of ensuring that the exposed portion of the coating film containing the radiation-sensitive composition exhibits good developability in an alkaline developer, the content of the second structural unit relative to the total structural units constituting component (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and further preferably 3% by mass or more. On the other hand, it is believed that if the content of the second structural unit is too high, the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion will decrease. From this perspective, the content of the second structural unit relative to the total structural units constituting component (A) is preferably less than 40% by mass, more preferably 35% by mass or less, and further preferably 30% by mass or less.

[0087] Component (A) preferably contains as a second structural unit at least a structural unit other than a structural unit having a phenolic hydroxyl group, and more preferably contains as a second structural unit at least one member selected from the group consisting of a structural unit having a carboxyl group, a structural unit having a sulfonic acid group, and a maleimide unit. Component (A) containing a structural unit having these groups (carboxyl group, sulfonic acid group, maleimide group) as a second structural unit is preferred in that the exposed portion of the coating film comprising the radiation-sensitive composition exhibits good developability in an alkaline developer.

[0088] In component (A), from the perspective of ensuring that the exposed portion of the coating film comprising the radiation-sensitive composition exhibits good developability in an alkaline developer, the content ratio of the structural units other than the structural units having a phenolic hydroxyl group in the second structural units is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and still more preferably 3% by mass or more, relative to the total structural units constituting component (A). Furthermore, from the perspective of sufficiently expressing the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion, the content ratio of the structural units other than the structural units having a phenolic hydroxyl group in the second structural units is preferably less than 20% by mass, more preferably 18% by mass or less, still more preferably 16% by mass or less, and still more preferably 15% by mass or less, relative to the total structural units constituting component (A).

[0089] When a structural unit having a phenolic hydroxyl group is introduced into component (A) as a second structural unit, the content of the structural unit having a phenolic hydroxyl group is preferably 0.5% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more relative to all the structural units constituting component (A) from the perspective of achieving better radiation sensitivity. Furthermore, from the perspective of ensuring the physical properties of the cured film attributed to the structural unit having a thermally crosslinkable group, the content 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 relative to all the structural units constituting component (A).

[0090] The third structural unit

[0091] The third structural unit is a structural unit having a cyclic ether group with 3 or 4 ring members. The inclusion of the third structural unit in component (A) improves the resolution of the film obtained using the radiation-sensitive composition and the solvent resistance of the cured film. Furthermore, the cyclic ether group in the third structural unit functions as a crosslinking group, allowing the formation of a cured film with suppressed degradation over a long period of time. The third structural unit preferably comprises at least one structural unit selected from the group consisting of an oxetane structure and an oxirane structure.

[0092] The third structural unit is preferably a structural unit derived from an unsaturated monomer having a cyclic ether group having 3 or 4 ring members (hereinafter also referred to as "third monomer"), and specifically, a structural unit represented by the following formula (3) is preferred.

[0093] [Chemistry 3]

[0094]

[0095] (In formula (3), R 3is a monovalent group having an oxetane structure or an oxirane structure, R 4 is a hydrogen atom or a methyl group, X 1 is a single bond or a divalent linking group)

[0096] In the formula (3), R 3 , and examples thereof include: oxacyclopropyl, oxetanyl, 3,4-epoxycyclohexyl, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl, 3-ethyloxetanyl, etc. Among these, R 3 A monovalent group having an oxirane structure is preferred.

[0097] As X 1 Examples of the divalent linking group include methylene, ethylene, and alkanediyl groups such as 1,3-propanediyl.

[0098] Specific examples of the third 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)methyl (meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, etc.

[0099] In component (A), the content ratio of the third structural unit is preferably 10% by mass or more relative to all the structural units constituting component (A), more preferably 15% by mass or more, and further preferably 20% by mass or more. In addition, the content ratio of the third structural unit is preferably 60% by mass or less relative to all the structural units constituting component (A), more preferably 55% by mass or less, and further preferably 50% by mass or less. By setting the content ratio of the third structural unit to the above range, the coating film shows better resolution, and the heat resistance and solvent resistance of the obtained cured film can be fully improved, which is preferred in this respect.

[0100] In the (A) component, the content ratio of each of the first structural unit, the second structural unit, and the third structural unit can be set by appropriately combining the numerical ranges of the preferred content ratios of the structural units. Among these, from the viewpoint of exhibiting good radiation sensitivity to the radiation-sensitive composition and making the obtained cured film have excellent pattern shape, outgassing characteristics, and foaming resistance, the (A) component preferably contains 5% by mass or more and 60% by mass of the first structural unit, 0.5% by mass or more and less than 40% by mass of the second structural unit, and 10% by mass or more and 60% by mass or less of the third structural unit relative to all the structural units constituting the polymer component. More preferably, it can contain 8% by mass or more and 60% by mass of the first structural unit, 0.5% by mass or more and less than 35% by mass of the second structural unit, and 10% by mass or more and 60% by mass or less of the third structural unit, and further preferably, it can contain 10% by mass or more and 50% by mass of the first structural unit, 0.5% by mass or more and 30% by mass of the second structural unit, and 10% by mass or more and 60% by mass or less of the third structural unit.

[0101] Furthermore, in component (A), the proportions of the first structural unit, the second structural unit (excluding the structural unit having a phenolic hydroxyl group), and the third structural unit are such that, relative to all the structural units constituting the polymer component, the first structural unit accounts for 5% by mass or more and 60% by mass or less, the second structural unit accounts for 0.5% by mass or more and less than 20% by mass, and the third structural unit accounts for 10% by mass or more and 60% by mass or less, from the viewpoint of ensuring that the radiation-sensitive composition exhibits good radiation sensitivity and that the obtained cured film has excellent pattern shape, outgassing properties, and foaming resistance. More preferably, the component (A) may contain 8% by mass or more and 60% by mass or less of the first structural unit, 0.5% by mass or more and less than 20% by mass of the second structural unit (excluding the structural unit having a phenolic hydroxyl group), and 10% by mass or more and 60% by mass or less of the third structural unit relative to all the structural units constituting the polymer component. Even more preferably, the component (A) may contain 10% by mass or more and 50% by mass of the first structural unit, 0.5% by mass or more and 18% by mass of the second structural unit (excluding the structural unit having a phenolic hydroxyl group), and 10% by mass or more and 60% by mass or less of the third structural unit.

[0102] Component (A) may also contain, in addition to the first, second, and third structural units, a structural unit different from these first to third structural units (hereinafter also referred to as "other structural units"). Examples of other structural units include a structural unit derived from an aromatic vinyl compound (hereinafter also referred to as the "fourth structural unit"), a structural unit derived from an N-substituted maleimide compound (hereinafter also referred to as the "fifth structural unit"), a structural unit having a hydroxyl group (excluding a phenolic hydroxyl group) (hereinafter also referred to as the "sixth structural unit"), and a structural unit derived from a methacrylate compound having an alkyl group with 3 or fewer carbon atoms (hereinafter also referred to as the "seventh structural unit"). Component (A) containing at least one of the fourth and fifth structural units is preferred because it can appropriately increase the glass transition temperature Tg of the polymer component and can produce a cured film having a good pattern shape.

[0103] ·The fourth structural unit

[0104] As the aromatic vinyl compound constituting the fourth structural unit, there is no particular limitation, and examples thereof 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, styrene compounds such as diphenylethylene; vinylnaphthalene compounds such as vinylnaphthalene and divinylnaphthalene; heterocyclic vinyl compounds such as vinylpyridine, etc. Among these, the aromatic vinyl compound is preferably a styrene compound. Furthermore, in this specification, the structural unit derived from the aromatic vinyl compound having a phenolic hydroxyl group is included in the "second structural unit".

[0105] In component (A), the content ratio of the fourth structural unit is preferably 1% by mass or more relative to all the structural units constituting component (A), more preferably 2% by mass or more, and further preferably 5% by mass or more. In addition, the content ratio of the fourth structural unit is preferably 30% by mass or less relative to all the structural units constituting component (A), more preferably 25% by mass or less, and further preferably 20% by mass or less. By setting the content ratio of the fourth structural unit to 1% by mass or more, a cured film with a better pattern shape can be obtained. In addition, by setting the content ratio of the fourth structural unit to 30% by mass or less, the glass transition temperature of the polymer component will not be too high, and the decline in developability can be suppressed.

[0106] ·Fifth structural unit

[0107] Examples of the N-substituted maleimide compound constituting the fifth structural unit include compounds 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 chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Among these, 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 containing a single ring, a bridged ring, or a spiro ring, in order to further enhance the effect of improving heat resistance.

[0108] Specifically, the fifth structural unit is preferably a structural unit represented by the following formula (5).

[0109] [Chemistry 4]

[0110]

[0111] (In formula (5), R 5 is a monovalent cyclic hydrocarbon group; R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)

[0112] In the formula (5), regarding R 5 The ring structure of the cyclic hydrocarbon group may be directly bonded to the nitrogen atom, or the ring structure may be bonded to the nitrogen atom via a divalent linking group. Examples of divalent linking groups include methylene, ethylene, 1,3-propanediyl and other alkanediyl groups. 5 Preferably, the ring structure of the cyclic hydrocarbon group is directly bonded to the nitrogen atom, and more preferably, the alicyclic hydrocarbon group is directly bonded to the nitrogen atom. 6 and R 7 It is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0113] 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, and N-norbornylmaleimide. , N-tricyclodecylmaleimide, N-adamantylmaleimide, etc.; examples of compounds having an aromatic hydrocarbon group include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. As for the N-substituted maleimide compound, among these, at least one selected from the group consisting of N-cyclohexylmaleimide, N-(4-methylcyclohexyl)maleimide, N-phenylmaleimide, and N-(4-methylphenyl)maleimide is preferred, and at least one of N-cyclohexylmaleimide and N-phenylmaleimide is more preferred.

[0114] In component (A), from the perspective of achieving a good pattern shape, the content ratio of the fifth structural unit relative to all the structural units constituting component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more. Furthermore, from the perspective of suppressing a decrease in developability, the content ratio of the fifth structural unit relative to all the structural units constituting component (A) is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

[0115] ·Sixth structural unit

[0116] The sixth structural unit is preferably a structural unit derived from an unsaturated monomer having a hydroxyl group (excluding a phenolic hydroxyl group) (hereinafter also referred to as the "sixth monomer"). Specifically, examples include structural units derived from monomers having one or more hydroxyl groups bonded to a saturated chain hydrocarbon group. The sixth monomer is not particularly limited, and examples thereof include (meth)acrylic acid compounds and maleimide compounds.

[0117] Specific examples of the sixth monomer include (meth)acrylic acid 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.

[0118] Examples of the maleimide compound include N-(hydroxymethyl)maleimide, N-(2-hydroxyethyl)maleimide, and N-(3-hydroxypropyl)maleimide.

[0119] When the (A) component includes the sixth structural unit, the decrease in pattern forming ability caused by the deviation of the pre-bake temperature during film formation can be suppressed, and a good pattern can be formed, which is suitable in terms of this aspect and the aspect of radiation sensitivity. In the (A) component, from the perspective of suppressing the decrease in pattern forming ability caused by the deviation of the pre-bake temperature, the content ratio of the sixth structural unit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more relative to all the structural units constituting the (A) component. In addition, from the perspective of suppressing the decrease in developability, the content ratio of the sixth structural unit is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less relative to all the structural units constituting the (A) component.

[0120] ·Seventh structural unit

[0121] Examples of monomers constituting the seventh structural unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate. The content of the seventh structural unit in component (A) is preferably 55% by mass or less, more preferably 45% by mass or less, further preferably 35% by mass or less, and further more preferably 25% by mass or less, relative to all the structural units constituting component (A).

[0122] Examples of other structural units, in addition to the aforementioned structural units, include: (meth)acrylate alkyl ester compounds having an alkyl group having 4 or more carbon atoms, such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate; 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 structural units derived from monomers, such as vinyl chloride, vinylidene chloride, and vinyl acetate. In component (A), the content of structural units other than the fourth to sixth 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, relative to all structural units constituting component (A).

[0123] The (A) component may contain only one first structural unit, or may contain two or more. The same applies to the second structural unit, the third structural unit and other structural units. Furthermore, the proportion of each structural unit is generally equivalent to the proportion of the monomers used in the manufacture of the polymer component. As long as the (A) component contains the first structural unit, the second structural unit and the third structural unit, it may contain one polymer or two or more polymers. That is, the (A) component contains the first structural unit, the second structural unit and the third structural unit in the same polymer or different polymers. Furthermore, the (A) component may also contain a polymer that does not have any structural unit of the first structural unit, the second structural unit and the third structural unit.

[0124] Examples of the form in which component (A) is contained in the radiation-sensitive composition include: [1] a form containing a polymer having a first structural unit, a second structural unit, and a third structural unit (hereinafter also referred to as "polymer P"); [2] a form containing a polymer having a first structural unit, a polymer having a second structural unit, and a polymer having a third structural unit; [3] a form containing a polymer having a first structural unit and a third structural unit, and a polymer having a second structural unit and a third structural unit; [4] a form containing a polymer having a first structural unit and a second structural unit, and a polymer having a second structural unit and a third structural unit. Of these, [1] is preferred from the perspective of reducing the number of components constituting the radiation-sensitive composition while achieving an effect of suppressing foaming. The polymer constituting component (A) is preferably an alkali-soluble resin. In this specification, "alkali-soluble" means soluble or swellable in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0125] In component (A), the weight average molecular weight (Mw) of polystyrene conversion obtained by gel permeation chromatography (GPC) is preferably 2000 or more. If Mw is 2000 or more, a cured film having sufficiently high heat resistance or solvent resistance and showing good developability can be obtained, which is preferred in this respect. Mw is more preferably 5000 or more, further preferably 6000 or more, and particularly preferably 8000 or more. In addition, from the viewpoint of making film-forming properties good, Mw is preferably 50000 or less, more preferably 30000 or less, further preferably 20000 or less, further more preferably 18000 or less, and particularly preferably 15000 or less.

[0126] In component (A), the molecular weight distribution (Mw / Mn), represented by 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. Furthermore, when component (A) comprises two or more polymers, it is preferred that the Mw and Mw / Mn of each polymer satisfy the aforementioned ranges.

[0127] The content of 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, relative to the total amount of solids contained in the radiation-sensitive composition. Furthermore, the content of component (A) is preferably 95% by mass or less, more preferably 90% by mass or less, relative to the total amount of solids contained in the radiation-sensitive composition. By setting the content of component (A) within this range, a cured film having sufficiently high heat resistance and solvent resistance, and exhibiting good developability and transparency can be obtained.

[0128] Furthermore, the (A) component can be produced, for example, using an unsaturated monomer capable of introducing each of the structural units, and in a suitable solvent, in the presence of a polymerization initiator, etc., according to a known method such as free radical polymerization. Specifically, as the polymerization initiator used, there can be listed azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl ester. 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 monomers used in the reaction. As the polymerization solvent, there can be listed, for example, alcohols, ethers, ketones, esters, hydrocarbons, etc.

[0129] In the polymerization reaction, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the type of initiator and monomer or the reaction temperature, and is usually 0.5 hours to 10 hours. Regarding the amount of organic solvent used, it is preferably an amount in which the total amount of the monomers used in the reaction is 0.1% by mass to 60% by mass relative to the total amount of the reaction solution. The polymer obtained by the polymerization reaction can be separated using, for example, the following well-known separation methods: a method in which the reaction solution is injected into a large amount of a poor solvent and the precipitate obtained is dried under reduced pressure; a method in which the reaction solution is distilled off under reduced pressure using an evaporator, etc.

[0130] <(B) Ingredient>

[0131] The quinonediazide compound as component (B) is a radiation-sensitive acid generator that generates carboxylic acid upon irradiation with radiation. The quinonediazide compound is preferably a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother nucleus") and a 1,2-naphthoquinonediazidesulfonyl halide.

[0132] Examples of the parent nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkanes, and other parent nuclei. Specific examples of these include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; examples of tetrahydroxybenzophenones include 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone. -3'-methoxybenzophenone, etc.; Pentahydroxybenzophenones include, for example, 2,3,4,2',6'-pentahydroxybenzophenone, etc.; Hexahydroxybenzophenones include, for example, 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; (polyhydroxyphenyl)alkanes include, for example, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane 1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-1-[4-hydroxyphenyl]-1-[4-hydroxyphenyl]-1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]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'-trihydroxyflavane, etc.; other parent nuclei include, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychromane, 2-[bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl], etc.

[0133] Among these, preferred mother nuclei are 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol.

[0134] As the 1,2-naphthoquinonediazidesulfonyl halide, 1,2-naphthoquinonediazidesulfonyl chloride is preferred. Specific examples include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferably used as the 1,2-naphthoquinonediazidesulfonyl halide.

[0135] In the condensation reaction to obtain the condensate, the ratio of the parent core to the 1,2-naphthoquinonediazidesulfonyl halide is preferably 30 to 85 mol%, more preferably 50 to 70 mol%, relative to the number of OH groups in the parent core. The condensation reaction can be carried out according to known methods. The condensation reaction of the parent core with the 1,2-naphthoquinonediazidesulfonyl halide yields a 1,2-quinonediazide compound.

[0136] The content of the (B) component in the radiation-sensitive composition is preferably 2 parts by mass or more relative to 100 parts by mass of the (A) component, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more. In addition, the content of the (B) component is preferably 100 parts by mass or less relative to 100 parts by mass of the (A) component, more preferably 60 parts by mass or less, and further preferably 40 parts by mass or less. If the content of the (B) component is 2 parts by mass or more, acid can be sufficiently generated by irradiation with radiation, making the difference in solubility of the irradiated portion and the unirradiated portion in the alkaline solution sufficiently large. Thus, good patterning can be performed. In addition, the amount of acid participating in the reaction with the (A) component can be increased, and heat resistance and solvent resistance can be fully ensured. On the other hand, if the content of the (B) component is 100 parts by mass or less, the unreacted (B) component can be sufficiently reduced, and the decline in developability caused by the residual (B) component can be suppressed, which is suitable in this respect.

[0137] <(C) Ingredient>

[0138] The radiation-sensitive composition disclosed herein is a liquid composition obtained by dissolving or dispersing component (A), component (B), and optionally other components in a solvent (C). The solvent used is preferably an organic solvent that dissolves the components formulated in the radiation-sensitive composition and does not react with the components.

[0139] 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. Among these, the solvent used in the preparation of 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 acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate.

[0140] <Other ingredients>

[0141] The radiation-sensitive composition of the present disclosure may further contain components other than the above-mentioned components (A), (B), and (C) (hereinafter also referred to as "other components"). Examples of other components include reaction initiators (photoradical polymerization initiators, photocationic polymerization initiators, etc.), polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), adhesion aids (functional silane coupling agents, etc.), surfactants (fluorochemical surfactants, silicone surfactants, nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The proportion of these components can be appropriately selected according to the respective components within the range that does not impair the effects of the present disclosure.

[0142] Regarding the radiation-sensitive composition disclosed herein, its solid content concentration (the ratio of the total mass of the components other than the (C) component in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected in consideration of viscosity or volatility, and is preferably in the range of 5% to 60% by mass. If the solid content concentration is 5% by mass or more, the film thickness of the coating can be sufficiently ensured when the radiation-sensitive composition is applied to the substrate, which is preferred in this respect. In addition, if the solid content concentration is 60% by mass or less, the film thickness of the coating will not become too large, and the viscosity of the radiation-sensitive composition can be appropriately increased, which can ensure good coating properties, which is preferred in this respect. The solid content concentration in the radiation-sensitive composition is more preferably 10% to 55% by mass, and further preferably 15% to 50% by mass.

[0143] <Interlayer insulating film and method for manufacturing the same>

[0144] The interlayer insulating film disclosed herein can be formed from a radiation-sensitive composition prepared as described above. This radiation-sensitive composition can form a film that generates minimal outgassing associated with heating. Therefore, when used as a composition for forming an organic film constituting a liquid crystal display element, foaming can be suppressed within the liquid crystal display element. Furthermore, the radiation-sensitive composition has high radiation sensitivity and is well patterned by radiation irradiation. Therefore, the radiation-sensitive composition is useful as a polymer composition for forming interlayer insulating films in liquid crystal displays.

[0145] When producing an interlayer insulating film, the radiation-sensitive composition can be used to form a positive cured film by irradiating with radiation (ultraviolet rays, extreme ultraviolet rays, visible rays, etc.). The interlayer insulating film of the present disclosure can be produced, for example, by a method including the following steps 1 to 4.

[0146] (Step 1) A step of forming a coating film using the radiation-sensitive composition.

[0147] (Step 2) A step of exposing at least a portion of the coating film to light.

[0148] (Step 3) A step of developing the coating film.

[0149] (Step 4) A step of heating the developed coating film.

[0150] Hereinafter, each step will be described in detail.

[0151] [Step 1: Film Formation Step]

[0152] In this step, the radiation-sensitive composition is applied to the surface on which the film is to be formed (hereinafter also referred to as the "film-forming surface") and preferably subjected to a heat treatment (pre-baking) to remove the solvent, thereby forming a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, when using the radiation-sensitive composition to form a planarizing film, the radiation-sensitive composition is applied to a substrate on which a switching element such as a thin film transistor (TFT) is provided to form a coating film. Examples of the substrate include a glass substrate and a resin substrate.

[0153] Examples of methods for applying the radiation-sensitive composition include spraying, roller coating, spin coating, slot die coating, rod coating, and inkjet coating. Of these, spin coating, slot die coating, or rod coating is preferred. Prebaking conditions vary depending on the type and proportion of the components of the radiation-sensitive composition, but are, for example, performed at 60°C to 130°C for 0.5 to 10 minutes. The thickness of the resulting coating (i.e., the thickness after prebaking) is preferably 1 μm to 12 μm.

[0154] [Process 2: Exposure process]

[0155] In this process, at least a portion of the coating formed in the process 1 is irradiated with radiation. At this time, by irradiating the coating with a mask having a predetermined pattern, an interlayer insulating film having a pattern can be formed. Examples of radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. Among these, ultraviolet rays are preferred, for example, g-rays (wavelength 436nm) and i-rays (wavelength 365nm) can be listed. The exposure amount of radiation is preferably 0.1J / m 2 ~20,000J / m 2 .

[0156] [Process 3: Development process]

[0157] In this process, the coating film irradiated with radiation in the process 2 is developed. Specifically, the following positive development is performed: the coating film irradiated with radiation in the process 2 is developed using a developer, thereby removing the irradiated portion of the radiation. As a developer, for example, an aqueous solution of an alkali (alkaline compound) can be cited. As an alkali, for example, sodium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph

[0127] of Japanese Patent Laid-Open No. 2016-145913 can be cited. From the perspective of obtaining appropriate developability, the alkali concentration in the alkaline aqueous solution is preferably 0.1% by mass to 5.0% by mass. As a developing method, suitable methods such as a coating method, an immersion method, a shaking immersion method, and a spray method can be cited. The developing time also varies depending on the composition of the composition, for example, it is 30 seconds to 120 seconds. Furthermore, it is preferred that the patterned coating film be subjected to a rinse treatment by washing with running water after the developing process.

[0158] [Step 4: Heating step]

[0159] In this process, the coating film developed in the process 3 is heated (post-baking). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding the post-baking conditions, the heating temperature is, for example, 120°C to 250°C. In addition, regarding the heating time, for example, when the heating treatment is performed on a hot plate, it is 5 minutes to 40 minutes, and when the heating treatment is performed in an oven, it is 10 minutes to 80 minutes. As described above, a cured film having a target pattern can be formed on the substrate.

[0160] Liquid crystal display devices

[0161] The liquid crystal display element of the present disclosure has an interlayer insulating film formed using the radiation-sensitive composition. Figure 1 , an embodiment of the liquid crystal display element disclosed in the present invention is described.

[0162] exist Figure 1 In the embodiment, the liquid crystal display element 10 is an active matrix type having a plurality of pixels arranged in a matrix. In this embodiment, the liquid crystal display element 10 is manufactured using PSA technology. The liquid crystal display element 10 includes an array substrate 11 and a counter substrate 13 disposed opposite to the array substrate 11. A liquid crystal layer 12 is formed between the pair of substrates formed by sealing liquid crystals.

[0163] like Figure 1 As shown, array substrate 11 includes an insulating substrate 14 such as a glass substrate or a resin substrate, a base coating film 15, TFTs 16, an inorganic insulating film 25, an interlayer insulating film 17, and pixel electrodes 18. TFTs 16 are composed of a semiconductor layer 19 made of polycrystalline silicon (p-Si), a gate insulating film 21, a gate electrode 22, a source electrode 23, and a drain electrode 24, and are provided for each pixel. TFTs 16 are formed using known materials and known methods such as photolithography.

[0164] The interlayer insulating film 17 is formed on the substrate 14 using the radiation-sensitive composition described above by photolithography. The interlayer insulating film 17 is formed on the entire surface of the substrate 14 so as to cover the TFTs 16. Forming the interlayer insulating film 17 on the substrate 14 having the TFTs 16 flattens the surface irregularities caused by the TFTs 16. Furthermore, the provision of the interlayer insulating film 17 can suppress increases in capacitive coupling between the pixel electrodes 18 and the signal lines. To ensure sufficient insulation and planarization functions, the thickness of the interlayer insulating film 17 is preferably 1 μm to 5 μm, and more preferably 2 μm to 4 μm.

[0165] The pixel electrode 18 is formed of a conductive material (e.g., indium tin oxide (ITO)) on the interlayer insulating film 17. The pixel electrode 18 is electrically connected to the TFT 16 via a contact hole 26a formed in the interlayer insulating film 17 and a contact hole 26b formed in the inorganic insulating film 25. In the array substrate 11, a liquid crystal alignment film 27 is formed on the pixel electrode 18.

[0166] The counter substrate 13 includes a transparent, insulating substrate 28, a black matrix 29, a color filter 31, an overcoat layer (not shown), and a common electrode 32. The color filter 31 includes subpixels colored in red (R), green (G), and blue (B) and is formed using known methods such as photolithography. The common electrode 32 is a planar electrode formed from a transparent conductive film such as ITO (indium tin oxide) and is provided across multiple pixels. A liquid crystal alignment film 33 is formed on the electrode-forming surface of the counter substrate 13.

[0167] The array substrate 11 and the counter substrate 13 are arranged so that the alignment film forming surface of the array substrate 11 faces the alignment film forming surface of the counter substrate 13, separated by a predetermined gap (cell gap). The peripheral edges of the pair of substrates arranged opposite to each other are bonded together using a sealing material (not shown). As the material of the sealing material, a material known as a sealant for liquid crystal devices (for example, a thermosetting resin or a light-curing resin) can be used. The space surrounded by the array substrate 11, the counter substrate 13, and the sealing material is filled with a liquid crystal composition. As a result, the liquid crystal layer 12 is arranged in contact with the liquid crystal alignment film 27 and the liquid crystal alignment film 33.

[0168] The liquid crystal layer 12 has negative dielectric anisotropy. The liquid crystal layer 12 is formed using a liquid crystal composition containing a photopolymerizable monomer (also referred to as a "polymerizable liquid crystal composition"). Thus, in the liquid crystal layer 12, a PSA layer (not shown) is formed as a polymer layer on the array substrate 11 side and the facing substrate 13 side. The PSA layer is formed by pre-tilting the liquid crystal molecules after the construction of the liquid crystal unit, and photopolymerizing the photopolymerizable monomers pre-mixed into the polymerizable liquid crystal composition in the said state. In the liquid crystal display element 10, the initial orientation of the liquid crystal molecules in the liquid crystal layer 12 is controlled by the PSA layer.

[0169] In the liquid crystal display element 10, polarizing plates (not shown) are disposed on the outer sides of each of the array substrate 11 and the counter substrate 13. A terminal region is provided on the outer edge of the array substrate 11. The liquid crystal display element 10 is driven by connecting a driver integrated circuit (IC) or the like for driving the liquid crystal to the terminal region.

[0170] <Method for Manufacturing Liquid Crystal Display Element>

[0171] The cured film formed using the radiation-sensitive composition is highly effective in suppressing foaming associated with light irradiation. Therefore, after forming the cured film, various light irradiation steps for manufacturing liquid crystal display devices can be performed, and even when the cured film is irradiated with light, foaming associated with the light irradiation can be suppressed, which is suitable in this respect. Examples of light irradiation treatments performed after the formation of the cured film include: light irradiation treatment for curing the sealing material; light irradiation treatment for forming a liquid crystal alignment film using a photo-alignment method; and light irradiation treatment for adjusting the transmittance of the formed cured film in the visible light range by utilizing the photobleaching properties of quinonediazide compounds.

[0172] The radiation-sensitive composition is particularly suitable for forming interlayer insulating films in display devices manufactured using PSA technology. In PSA technology, the amount of light used to polymerize the photopolymerizable monomers in the liquid crystal composition is relatively high, and this light can easily cause reactions of unreacted components in the interlayer insulating film or decomposition of polymer components in the interlayer insulating film. In this regard, forming an interlayer insulating film using the radiation-sensitive composition is particularly suitable in that the generation of bubbles caused by light irradiation can be effectively suppressed.

[0173] The liquid crystal display element of the present disclosure can be produced, for example, by a method including the following steps A and B.

[0174] Step A: a step of forming an interlayer insulating film on a substrate using the radiation-sensitive composition.

[0175] Step B: After forming the interlayer insulating film, a step of irradiating light onto the object having the interlayer insulating film.

[0176] When a liquid crystal display element is manufactured using the PSA technology, specifically, it is preferable to manufacture the liquid crystal display element using a method that further includes the following step X and performs the following step B1 as the step B.

[0177] Step X: A step of arranging a pair of substrates each including a substrate having an interlayer insulating film to face each other with a layer containing a polymerizable liquid crystal composition interposed therebetween to construct a liquid crystal cell.

[0178] Step B1: A step of irradiating the liquid crystal cell with light while a voltage is applied to the layer containing the polymerizable liquid crystal composition.

[0179] Hereinafter, the method for manufacturing a liquid crystal display element of the present disclosure will be described by taking a case where a liquid crystal display element is manufactured using the PSA technology as an example.

[0180] When manufacturing a liquid crystal display element, first, an array substrate and a counter substrate are prepared. Specifically, first, TFTs and wirings are formed on a transparent substrate such as a glass substrate using a known method such as photolithography. Then, the radiation-sensitive composition is applied to the TFT formation surface in the transparent substrate to form an interlayer insulating film (process A). The interlayer insulating film is formed, for example, by a method including processes 1 to 4. Thereafter, pixel electrodes are formed on the interlayer insulating film. The pixel electrodes are formed by forming a conductive film including ITO or the like using a known method such as sputtering, and then patterning it using photolithography. In addition, unlike the array substrate, a color filter and a common electrode are formed on a transparent substrate such as a glass substrate using a known method such as photolithography to produce a counter substrate.

[0181] Then, a liquid crystal alignment agent is applied to the substrate on which the electrodes are formed, and the coated surface is preferably heated (pre-baking and post-baking) to form a coating film on the substrate. Thereafter, the coating film is subjected to an orientation treatment as needed. Examples of the orientation treatment include: a friction treatment in which a roller wound with a cloth containing fibers such as nylon, rayon, and cotton is used to wipe the coating film in a fixed direction; and a photo-orientation treatment in which the coating film formed on the substrate using the liquid crystal alignment agent is irradiated with light to impart liquid crystal orientation capability to the coating film.

[0182] Next, an array substrate, on which an interlayer insulating film, pixel electrodes, and a liquid crystal alignment film are sequentially formed, and a counter substrate, on which a color filter, a common electrode, and a liquid crystal alignment film are sequentially formed, are arranged with their alignment film-formed surfaces facing each other. A liquid crystal layer mixed with a photopolymerizable monomer is disposed between the array substrate and the counter substrate, thereby constructing a liquid crystal cell (step X).

[0183] The liquid crystal layer is formed, for example, by the following methods: [1] a method in which a polymerizable liquid crystal composition is dripped or applied onto one substrate coated with a sealing material, followed by laminating the other substrate thereto (one drop filling (ODF) method); [2] a method in which the peripheral portions of a pair of opposing substrates are laminated together with a sealing material with a cell gap therebetween, the polymerizable liquid crystal composition is injected into the cell gap surrounded by the substrate surfaces and the sealing material, and the injection hole is then sealed. As a photopolymerizable monomer, a compound having two or more (meth)acryloyl groups is preferably used due to its high photopolymerizability, such as a multifunctional (meth)acrylic compound having a mesogen skeleton.

[0184] In the next step, the obtained liquid crystal unit is subjected to light irradiation (step B). The light irradiation of the liquid crystal unit is carried out in a state where a prescribed voltage for driving the liquid crystal molecules is applied between the electrodes (step B1). The applied voltage can be set to a DC voltage or an AC voltage of 5V to 50V, for example. As the light to be irradiated, for example, ultraviolet rays and visible light containing wavelengths of 150nm to 800nm ​​can be used. Among these, ultraviolet rays containing wavelengths of 300nm to 400nm are preferred. Regarding the irradiation direction of light, when the radiation used is linearly polarized or partially polarized, the substrate surface can be irradiated from a vertical direction, or from an inclined direction, or these directions can be combined for irradiation. When irradiating non-polarized radiation, the irradiation direction is set to an inclined direction. As the irradiation amount of light, 1,000J / m 2 ~200,000J / m 2 , more preferably 1,000 J / m 2 ~100,000J / m2 When a liquid crystal display element is manufactured by a PSA method, the liquid crystal cell corresponds to an "object having an interlayer insulating film."

[0185] A polarizing plate is then attached to the outer surface of the liquid crystal cell to obtain a liquid crystal display element. Examples of the polarizing plate include a polarizing film called an "H film" sandwiched between cellulose acetate protective films. The "H film" is formed by stretching and aligning polyvinyl alcohol while allowing it to absorb iodine, or a polarizing plate containing the H film itself.

[0186] The liquid crystal display element of the present disclosure described in detail above can be effectively applied to various applications, for example, it can be used as various display devices such as clocks, portable game consoles, word processors, note-type personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), digital cameras, mobile phones, smartphones, various monitors, LCD televisions, information displays, etc.

[0187] [Example]

[0188] The present invention is described in detail below using examples, but the present invention is not limited to these examples. Furthermore, "parts" and "%" in the examples and comparative examples are by weight unless otherwise specified. In these examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers were measured using the following methods.

[0189] [Weight average molecular weight (Mw) and number average molecular weight (Mn)]

[0190] The Mw and Mn of the polymer were measured by the following method.

[0191] ·Determination method: Gel permeation chromatography (GPC)

[0192] Device: Showa Denko GPC-101

[0193] GPC column: Combination of Shimadzu GLC's GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

[0194] Mobile phase: tetrahydrofuran

[0195] Column temperature: 40°C

[0196] Flow rate: 1.0 mL / min

[0197] Sample concentration: 1.0 mass%

[0198] Sample injection volume: 100μL

[0199] Detector: Differential refractometer

[0200] Standard material: monodisperse polystyrene

[0201] [Single body]

[0202] The monomers used in the synthesis of the polymer are as follows.

[0203] The First Single Entity

[0204] M-1: Tetrahydrofurfuryl acrylate

[0205] M-2: 5-ethyl-1,3-dioxane-5-ylmethyl acrylate

[0206] M-3: Methyl acrylate (2-methyl-2-ethyl-1,3-dioxolan-4-yl)

[0207] M-4: Methyl acrylate

[0208] M-5: Ethyl acrylate

[0209] M-6: γ-Butyrolactone-2-yl acrylate

[0210] M-7: γ-butyrolactam-2-yl acrylate

[0211] M-8: N-acryloyloxyethyl hexahydrophthalimide

[0212] M-9: Glyceryl Carbonate Acrylate

[0213] The Second Single Entity

[0214] M-10: Methacrylic acid

[0215] M-11: Maleimide

[0216] M-12: p-Isopropenylphenol

[0217] The Third Monolith

[0218] M-13: Glycidyl methacrylate

[0219] M-14: 3,4-epoxycyclohexylmethyl methacrylate

[0220] M-15: 3-methacryloyloxymethyl-3-ethyloxetane

[0221] Other Single Bodies

[0222] M-16: 2-methoxyethyl acrylate

[0223] M-17: Tetrahydrofurfuryl methacrylate

[0224] M-18: n-Butyl methacrylate

[0225] M-19: N-cyclohexylmaleimide

[0226] M-20: Methyl methacrylate

[0227] M-21: Styrene

[0228] M-22: N-(2-hydroxyethyl)maleimide

[0229] M-23: Glycerol monomethacrylate

[0230] M-24: 2-Hydroxyethyl Methacrylate

[0231] M-25: 2-Hydroxypropyl Methacrylate

[0232] <Polymer Synthesis (1)>

[0233] [Synthesis Example 1] Synthesis of polymer (A-1)

[0234] A flask equipped with a cooling tube and a stirrer was charged with 13 parts of dimethyl 2,2'-azobis(isobutyrate) and 200 parts of diethylene glycol ethyl methyl ether. Subsequently, 10 parts of tetrahydrofurfuryl acrylate, 8 parts of methacrylic acid, 30 parts of glycidyl methacrylate, and 52 parts of methyl methacrylate were added, and the atmosphere was purged with nitrogen. While slowly stirring the solution in the flask, the temperature of the solution was raised to 80°C and maintained at that temperature for 5 hours to obtain a polymer solution containing polymer (A-1). The polymer solution had a solids concentration of 34.5% by mass, an Mw of polymer (A-1) of 11,000, and a molecular weight distribution (Mw / Mn) of 2.2.

[0235] [Synthesis Examples 2 to 31, Comparative Synthesis Examples 1 to 4] Synthesis of Polymers (A-2) to (A-13), and Polymers (CA-1) to (CA-4)

[0236] Except for using the types and blending amounts (parts by mass) of the components shown in Table 1, the same method as in Synthesis Example 1 was used to obtain polymer solutions containing polymers (A-2) to (A-31) and polymers (CA-1) to (CA-4) having solid content concentrations, molecular weights, and molecular weight distributions comparable to those of polymer (A-1).

[0237]

[0238] <Preparation of radiation-sensitive resin composition (1)>

[0239] The polymer synthesized above was used to prepare a radiation-sensitive resin composition. The polymer and acid generator used in the preparation of the radiation-sensitive resin composition are shown below.

[0240] "polymer"

[0241] A-1 to A-31: Polymers (A-1) to (A-31) synthesized in Synthesis Examples 1 to 31

[0242] CA-1 to CA-4: polymers (CA-1) to (CA-4) synthesized in Comparative Synthesis Examples 1 to 4

[0243] Acid Producers

[0244] B-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

[0245] [Example 1]

[0246] To a polymer solution containing polymer (A-1), 20 parts of the acid generator (B-1) were mixed in an amount equivalent to 100 parts (solid content) of polymer (A-1), and diethylene glycol ethyl methyl ether was added so that the final solid content concentration became 30% by mass. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare composition (S-1).

[0247] [Example 2 to Example 31, Comparative Examples 1 to 4]

[0248] Radiation-sensitive resin compositions of Examples 2 to 31 and Comparative Examples 1 to 4 were prepared by the same method as in Example 1, except that the types and blending amounts (parts by mass) of the components shown in Table 2 were used.

[0249] [Table 2]

[0250] [Table 2]

[0251]

[0252] <Evaluation(1)>

[0253] Cured films were formed using the radiation-sensitive resin compositions of Examples 1 to 31 and Comparative Examples 1 to 4 (compositions (S-1) to (S-31), and (CS-1) to (CS-4)). The following parameters were evaluated using the methods described below. The evaluation results are shown in Table 3.

[0254] [Radiation sensitivity]

[0255] On a glass substrate, hexamethyl disilazane (HMDS) was applied using a spinner and heated at 60°C for 1 minute (HMDS treatment). On the chromium film-forming glass substrate after the HMDS treatment, each radiation-sensitive resin composition prepared as described was applied using a spinner and pre-baked at 90°C for 2 minutes to form a coating with a film thickness of 3.0 μm. Subsequently, an exposure machine (Canon's "PLA-501F": using an ultra-high pressure mercury lamp) was used to change the exposure amount, and the coating was exposed through a mask having a line and space pattern of 60 μm (10 to 1). Thereafter, development was performed using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 25°C using a liquid coating method. The development time was set to 80 seconds. Subsequently, the film was rinsed with ultrapure water for 1 minute and then dried to form a pattern on the chromium film-forming glass substrate after the HMDS treatment. 300J / m 2 The chromium-film-forming glass substrate was exposed to light for 30 minutes and heated in a clean oven at 230°C to form an interlayer insulating film. The exposure dose required to completely dissolve the 6μm space pattern during development was examined. Lower exposure doses indicate better radiation sensitivity.

[0256] (Evaluation Criteria)

[0257] AA: less than 200 J / m 2

[0258] A: less than 300J / m 2

[0259] A-: 300J / m 2 Above and less than 400J / m 2

[0260] B: 200J / m 2 Above and less than 400J / m 2

[0261] C: 400J / m2 Above and less than 800J / m 2

[0262] D: 800J / m 2 above

[0263] [Pattern shape]

[0264] The cross-sectional shape of the interlayer insulating film pattern, which can be resolved at the optimal exposure, was observed using a scanning electron microscope. A tangent line was drawn into the interlayer insulating film pattern at the point where the interlayer insulating film pattern contacts the substrate, and the angle between the tangent line and the substrate surface was calculated. The higher the angle, the better the pattern shape was evaluated, even after heating at 230°C.

[0265] (Evaluation Criteria)

[0266] AA: above 60°

[0267] A: 50° or more and less than 60°

[0268] B: 40° or more and less than 50°

[0269] C: 30° or more and less than 40°

[0270] D: less than 30°

[0271] [Outgassing characteristics]

[0272] After applying the radiation-sensitive resin composition to a silicon substrate using a spinner, the composition was pre-baked on a hot plate at 90°C for 2 minutes to form a coating film with an average film thickness of 3.0 μm. Furthermore, the composition was calcined for 30 minutes in an oven heated to 230°C to form a cured film. Subsequently, the silicon substrate was cut into pieces of 1 cm × 5 cm in size and baked at 230°C for 15 minutes using a P&T-GCMS device comprising a JTD-505 manufactured by Japan Analytical Technology Co., Ltd. and a GC-QP-2010 manufactured by Shimadzu Corporation (stock) to obtain a chromatogram. The outgassing amount was calculated using the following formula (1) using the peak area of ​​C18 of the chromatogram measured using the cured film and the peak area of ​​the chromatogram of the standard sample C18 measured using the same device. Furthermore, in the following formula (1), the so-called introduction amount of the standard sample is the introduction amount of the standard sample introduced into the device when the chromatogram of the standard sample C18 is obtained.

[0273] Outgassing amount (μg) = (peak area of ​​the chromatogram of the cured film / peak area of ​​the standard sample) × amount of the standard sample introduced (μg) (1)

[0274] The evaluation criteria are "A" for outgassing less than 5 μg, "B" for 5 μg or more and less than 10 μg, "C" for 10 μg or more and less than 50 μg, and "D" for 50 μg or more.

[0275] [Foaming resistance]

[0276] The liquid crystal display element was manufactured in the following order, and the manufactured liquid crystal display element was used to apply an impact under a high temperature (80°C) state to confirm the presence or absence of bubbles in the pixel. The impact on the liquid crystal display element was given by dropping a pachinko ball from 30 cm above the liquid crystal display element. The pachinko ball used was a spherical body made of steel with a weight of 5.5 g and a diameter of 11 mm. By applying the impact, the situation where no bubbles were generated at all in the pixels of the liquid crystal display element was evaluated as "A", the situation where bubbles were slightly generated was set to "B", the situation where bubbles were generated but the density of the bubbles was small was evaluated as "C", and the situation where bubbles were generated and the density of the bubbles was large was evaluated as "D".

[0277] (Manufacturing of Liquid Crystal Display Elements)

[0278] Manufacturing and Figure 1 The liquid crystal display element 10 has the same structure as an active matrix type vertical alignment (VA) mode color liquid crystal display element.

[0279] First, a TFT having a semiconductor layer and an electrode layer made of p-Si, wiring, and an inorganic insulating film made of SiN are arranged on an insulating glass substrate made of alkali-free glass according to a known method to prepare an array substrate having TFTs. Furthermore, the TFTs are formed according to a known method by repeating conventional semiconductor layer formation, known insulating layer formation, and etching using photolithography.

[0280] Then, a slit die coater is used to coat the prepared radiation-sensitive resin composition on the array substrate. Then, pre-bake at 90°C for 2 minutes on a hot plate to evaporate the organic solvent to form a coating. Then, a UV (ultraviolet) exposure machine (Canon's "PLA-501F": using an ultra-high pressure mercury lamp) is used to irradiate UV light through the pattern mask. The irradiation is carried out at an exposure amount determined in the evaluation of the radiation sensitivity. Thereafter, a 2.38% by mass concentration of tetramethylammonium hydroxide aqueous solution (developer) is used to perform a development treatment for 80 seconds at 25°C using a liquid coating method. After the development treatment, the coating is rinsed with running water using ultrapure water for 1 minute to dry it. Then, the entire surface of the coating is subjected to 300J / m 2The substrate is exposed to light and heated in a clean oven at 230°C for 30 minutes to form an interlayer insulating film. Contact holes are formed in the interlayer insulating film on the substrate by patterning. Subsequently, a film comprising ITO is formed on the interlayer insulating film by sputtering, and pixel electrodes are formed by patterning using photolithography. The formed pixel electrodes are connected to the TFTs via the contact holes.

[0281] Next, a color filter substrate was prepared, and a liquid crystal alignment agent (trade name JALS2095-S2, manufactured by JSR (stock)) was applied to the electrode configuration surfaces of the array substrate and the color filter substrate using a spinner, heated at 80°C for 1 minute, and then heated at 180°C for 1 hour to form an alignment film with a thickness of 60 nm. As a color filter substrate, a substrate in which three colors (red, green, and blue) of color filters and a black matrix are arranged in a grid pattern on a transparent glass substrate, and a flattening film and a common electrode are formed on the color filter. As a common electrode, a transparent electrode comprising ITO is used.

[0282] Secondly, after applying an ultraviolet curable sealing material to the outer peripheral edge of one of the array substrate and the color filter substrate, a dispenser is used to drip a polymerizable liquid crystal composition on the inside of the sealing material. As the polymerizable liquid crystal composition, a composition prepared by adding a polymerizable component showing photopolymerization to a nematic liquid crystal having negative dielectric anisotropy is used. Thereafter, the array substrate and the color filter substrate are bonded in a vacuum, the light source is moved along the coating area of ​​the sealing material, and UV light is irradiated on the sealing material at the same time, thereby hardening the sealing material. Thus, a layer of polymerizable liquid crystal composition is formed between the array substrate and the color filter substrate.

[0283] Next, while the voltage for turning on the TFTs of the array substrate is applied to the gate electrodes of the TFTs, an AC voltage is applied between the source electrodes of the TFTs and the common electrode on the color filter substrate to tilt the liquid crystals of the polymerizable liquid crystal composition layer. Subsequently, while maintaining the tilted orientation of the liquid crystals, an ultrahigh-pressure mercury lamp is used to irradiate the layer of polymerizable liquid crystal composition with ultraviolet light from the array substrate side, thereby forming a liquid crystal layer in which the liquid crystals are pre-tilted in a predetermined direction and are approximately vertically oriented. As described above, a VA-mode color liquid crystal display element is manufactured.

[0284] [Table 3]

[0285] [Table 3]

[0286]

[0287] As shown in Table 3, the radiation-sensitive resin compositions of Examples 1 to 31 exhibited good radiation sensitivity, and the resulting cured films exhibited excellent pattern shape, outgassing properties, and foaming resistance. On the other hand, the radiation-sensitive resin compositions of Comparative Examples 1 to 4 exhibited inferior radiation sensitivity, pattern shape, outgassing properties, and foaming resistance compared to the Examples.

[0288] <Polymer Synthesis (2)>

[0289] [Synthesis Example 32 to Synthesis Example 42] Synthesis of Polymers (A-32) to (A-42)

[0290] Except for using the types and blending amounts (parts by mass) of the components shown in Table 4, polymer solutions containing polymers (A-32) to (A-42) having solid content concentrations, molecular weights, and molecular weight distributions comparable to those of polymer (A-1) were obtained by the same method as in Synthesis Example 1. Table 4 also shows the monomer compositions of Synthesis Examples 1, 6, 11, 14, and 20, as well as Comparative Synthesis Example 1.

[0291]

[0292] <Preparation of radiation-sensitive resin composition (2)>

[0293] The polymer thus synthesized was used to prepare a radiation-sensitive resin composition having the composition shown in Table 5. The polymer and acid generator used in the preparation of the radiation-sensitive resin composition are shown below.

[0294] "polymer"

[0295] A-1, A-6, A-11, A-14, A-20, A-32 to A-42: polymers (A-1), (A-6), (A-11), (A-14), (A-20), (A-32) to (A-42) synthesized in Synthesis Example 1, Synthesis Example 6, Synthesis Example 11, Synthesis Example 14, Synthesis Example 20, and Synthesis Examples 32 to 42

[0296] CA-1: polymer synthesized in Comparative Synthesis Example 1 (CA-1)

[0297] Acid Producers

[0298] B-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

[0299] [Table 5]

[0300] [Table 5]

[0301]

[0302] <Evaluation (2)>

[0303] Cured films were formed using the radiation-sensitive resin compositions of Example 1, Example 6, Example 11, Example 14, Example 20, Examples 32 to 42, and Comparative Example 1 (Composition (S-1), Composition (S-6), Composition (S-11), Composition (S-14), Composition (S-20), Composition (S-32) to Composition (S-42), and Composition (CS-1)). The radiation sensitivity, pattern shape, outgassing characteristics, and foaming resistance were evaluated in the same manner as in Evaluation (1). Furthermore, the pre-bake temperature dependency was evaluated using the method described below. The evaluation results are shown in Table 6.

[0304] <Pre-bake temperature dependence>

[0305] In the radiation sensitivity evaluation, a pattern was formed on a glass substrate under the same conditions, except that the prebake temperature was changed from 90°C to 100°C. The exposure dose required to completely dissolve a 6μm spatial pattern during development was examined. The pattern was formed under the same conditions, maintaining the exposure dose constant and the prebake temperature at 90°C. The difference in line width between the prebake temperatures of 100°C and 90°C was determined. The smaller the difference in line width, the less dependent on the prebake temperature, and the better the result.

[0306] (Evaluation Criteria)

[0307] A: less than 0.5μm

[0308] B: 0.5 μm or more and less than 1.0 μm

[0309] C: 1.0 μm or more and less than 2.0 μm

[0310] D: 2.0 μm or more

[0311] [Table 6]

[0312] [Table 6]

[0313]

[0314] As shown in Table 6, the radiation-sensitive resin compositions of Examples 1, 6, 11, 14, 20, and 32-42 exhibited good radiation sensitivity, and the resulting cured films exhibited excellent pattern shape, outgassing properties, and foaming resistance. Furthermore, the radiation-sensitive resin compositions of Examples 1, 6, 11, 14, 20, and 32-42 exhibited improved pattern forming ability with less variation due to prebake temperature differences compared to Comparative Example 1. In particular, the radiation-sensitive resin compositions of Examples 32-42, whose polymer components contained a structural unit having a hydroxyl group (the sixth structural unit), exhibited excellent prebake temperature dependence, rated A or B.

Claims

1. A method for manufacturing a liquid crystal display element, comprising: forming an interlayer insulating film on the substrate; as well as an irradiation step of irradiating light to an object including the interlayer insulating film after the interlayer insulating film is formed, wherein in the method for manufacturing the liquid crystal display element, The interlayer insulating film is formed using a radiation-sensitive composition containing the following components (A), (B), and (C). (A) a polymer component comprising, relative to all structural units constituting the polymer component, 5% by mass or more and 55% by mass of a first structural unit, 0.5% by mass or more and less than 40% by mass of a second structural unit, 10% by mass or more and 60% by mass or less of a third structural unit, and 1% by mass or more and 40% by mass or less of a fifth structural unit, wherein the first structural unit is derived from at least one member selected from the group consisting of an acrylate compound having a heterocyclic structure with 5 or more ring members and an acrylate compound having an alkyl group with 3 or less carbon atoms, the second structural unit has an acid group, the third structural unit has a cyclic ether group with 3 or 4 ring members, and the fifth structural unit is derived from an N-substituted maleimide compound; (B) quinone diazide compounds; (C) Solvent. 2 . The method for manufacturing a liquid crystal display device according to claim 1 , wherein the heterocyclic structure is 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.

3. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the second structural unit is at least one selected from the group consisting of a structural unit having a carboxyl group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit.

4. A method for manufacturing a liquid crystal display element, comprising: forming an interlayer insulating film on the substrate; as well as an irradiation step of irradiating light to an object including the interlayer insulating film after the interlayer insulating film is formed, wherein in the method for manufacturing the liquid crystal display element, The interlayer insulating film is formed using a radiation-sensitive composition containing the following components (A), (B), and (C). (A) a polymer component comprising: a first structural unit derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure having 5 or more ring members and an acrylate compound having an alkyl group having 3 or less carbon atoms; a second structural unit having a maleimide unit as an acid group; and a third structural unit having a cyclic ether group having 3 or 4 ring members; (B) quinone diazide compounds; (C) Solvent.

5. The method for manufacturing a liquid crystal display element according to any one of claims 1, 2, and 4, wherein the heterocyclic structure is at least one selected from the group consisting of a structure represented by the following formula (a-1), a structure represented by the following formula (a-2), a structure represented by the following formula (a-3), a structure represented by the following formula (a-4), a structure represented by the following formula (a-5), and a structure represented by the following formula (a-6), In formulas (a-1) to (a-6), R 10 is an alkyl group having 1 to 5 carbon atoms, or represents two R groups on the same carbon atom. 10 Combined with the two R 10 The carbon atoms to which they are bonded together form a ring structure; R 11 is an alkyl group with 1 to 5 carbon atoms; R 12 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m is an integer of 0 to 2, n is an integer of 1 to 3; r is an integer of 1 to 3; and "*" represents a bond. 6 . The method for manufacturing a liquid crystal display element according to claim 1 , wherein the heterocyclic structure is a dioxolane structure. 7 . The method for producing a liquid crystal display element according to claim 1 , wherein the component (A) further comprises a structural unit derived from an aromatic vinyl compound. 8 . The method for manufacturing a liquid crystal display device according to claim 1 , wherein the third structural unit is a structural unit having at least one selected from the group consisting of an oxetane structure and an oxirane structure.

9. The method for producing a liquid crystal display element according to claim 4, wherein the component (A) contains 8% by mass or more and 60% by mass or less of the first structural unit, 0.5 mass % or more and less than 20 mass % of the second structural unit, excluding the structural unit having a phenolic hydroxyl group, 10% by mass or more and 60% by mass or less of the third structural unit.

10. The method for manufacturing a liquid crystal display element according to any one of claims 1, 2, and 4, further comprising: A step of arranging a pair of substrates including a substrate having the interlayer insulating film to face each other with a layer containing a polymerizable liquid crystal composition interposed therebetween to construct a liquid crystal cell, and The irradiation step is a step of irradiating the liquid crystal cell with light while a voltage is applied to the layer containing the polymerizable liquid crystal composition. 11 . The method for producing a liquid crystal display element according to claim 1 , wherein the component (B) is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazidesulfonyl halide. 12 . The method for manufacturing a liquid crystal display device according to claim 1 , wherein the component (C) comprises at least one selected from the group consisting of ethers and esters.

13. A radiation-sensitive composition comprising: (A) a polymer component, (B) quinone diazide compounds, and (C) solvent, The component (A) comprises: a first structural unit derived from an acrylate compound having a heterocyclic structure with 5 or more ring members, a second structural unit having an acid group, a third structural unit having a cyclic ether group with 3 or 4 ring members, and a fifth structural unit derived from an N-substituted maleimide compound. The heterocyclic structure is 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, wherein the cyclic ether structure does not include a tetrahydrofurfuryl structure. The radiation-sensitive composition according to claim 13 , wherein the heterocyclic structure is a dioxolane structure.

15. A radiation-sensitive composition comprising: (A) a polymer component, (B) quinone diazide compounds, and (C) solvent, The component (A) comprises: a first structural unit derived from an acrylate compound having a heterocyclic structure with 5 or more ring members, a second structural unit having a maleimide unit as an acid group, and a third structural unit having a cyclic ether group with 3 or 4 ring members. The heterocyclic structure is 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, wherein the cyclic ether structure does not include a tetrahydrofurfuryl structure.

16. A radiation-sensitive composition comprising: (A) a polymer component, (B) quinone diazide compounds, and (C) solvent, The component (A) includes, relative to all structural units constituting the polymer component, 8% by mass or more and 55% by mass or less of a first structural unit, 0.5% by mass or more and less than 20% by mass of a second structural unit, excluding the structural unit having a phenolic hydroxyl group, 10% by mass or more and 60% by mass or less of a third structural unit, and 1% by mass or more and 40% by mass or less of a fifth structural unit, wherein the first structural unit is derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure having 5 or more ring members and an acrylate compound having an alkyl group having 3 or less carbon atoms, the second structural unit has an acid group, the third structural unit has a cyclic ether group having 3 or 4 ring members, and the fifth structural unit is derived from an N-substituted maleimide compound.

17. A radiation-sensitive composition comprising: (A) a polymer component, (B) quinone diazide compounds, and (C) solvent, The component (A) includes, relative to all structural units constituting the polymer component, 8% by mass or more and 60% by mass of first structural units, 0.5% by mass or more and less than 20% by mass of second structural units, excluding structural units having a phenolic hydroxyl group, and 10% by mass or more and 60% by mass or less of third structural units, wherein the first structural unit is derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure having 5 or more ring members and an acrylate compound having an alkyl group having 3 or less carbon members, the second structural unit has a maleimide unit as an acid group, and the third structural unit has a cyclic ether group having 3 or 4 ring members. 18 . The radiation-sensitive composition according to claim 13 , which is used for forming an interlayer insulating film.

19. A method for manufacturing an interlayer insulating film, comprising: A step of forming a coating film using the radiation-sensitive composition according to any one of claims 13 to 18; a step of irradiating at least a portion of the coating film with radiation; a step of developing the coating film after irradiation with radiation; and a step of heating the developed coating film. 20 . An interlayer insulating film formed using the radiation-sensitive composition according to claim 13 .

21. A liquid crystal display element comprising the interlayer insulating film according to claim 20.

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