CN113219690A - Liquid crystal display element and method for manufacturing the same, radiation-sensitive composition, interlayer insulating film and method for manufacturing the same - Google Patents

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

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Publication number
CN113219690A
CN113219690A CN202110154357.5A CN202110154357A CN113219690A CN 113219690 A CN113219690 A CN 113219690A CN 202110154357 A CN202110154357 A CN 202110154357A CN 113219690 A CN113219690 A CN 113219690A
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structural unit
liquid crystal
group
radiation
mass
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角田裕志
徳本爱香
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • G—PHYSICS
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
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    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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    • G02F1/133514—Colour filters
    • G—PHYSICS
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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    • G02F1/1343—Electrodes
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    • G—PHYSICS
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • G—PHYSICS
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Geometry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a liquid crystal display element capable of sufficiently suppressing generation of bubbles, a method for manufacturing the same, a radiation-sensitive composition, an interlayer insulating film, and a method for manufacturing the same. A method of manufacturing a liquid crystal display element includes: a forming step of forming an interlayer insulating film on a substrate; and an irradiation step of irradiating the object having the interlayer insulating film with light after the interlayer insulating film is formed, wherein the interlayer insulating film is formed using a radiation-sensitive composition containing the component (A), the component (B), and the component (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 with a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less, a second structural unit having an acid group, and a third structural unit having a cyclic ether group with a ring number of 3 or 4. (B) A quinone diazide compound. (C) A solvent.

Description

Liquid crystal display element and method for manufacturing the same, radiation-sensitive composition, interlayer insulating film and method for manufacturing the same
Technical Field
The 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
In a liquid crystal display element, an interlayer insulating film is provided to insulate between wirings and a substrate or between wirings. In a process for manufacturing a liquid crystal display element, an interlayer insulating film is formed on a substrate, and a transparent conductive film or a liquid crystal alignment film as an electrode is further formed on the interlayer insulating film. In forming a transparent conductive film or a liquid crystal alignment film, the interlayer insulating film is exposed to high temperature conditions or is irradiated with radiation such as ultraviolet rays, and therefore, the interlayer insulating film is required to have resistance to heat or light.
As one of the methods for manufacturing a liquid crystal display element, there is a Polymer Stabilized Alignment (PSA) technique. The PSA technology is as follows: the photopolymerizable monomer is mixed into the liquid crystal material in advance, and after the liquid crystal cell is assembled, the liquid crystal cell is irradiated with light in a state where a voltage is applied between a pair of electrodes sandwiching the liquid crystal layer, whereby the photopolymerizable monomer is polymerized to control the molecular orientation of the liquid crystal molecules. According to the above-described technique, there are advantages in that an increase in the viewing angle and a high-speed response can be achieved.
When a liquid crystal display element is manufactured by the PSA technique, there are cases where unreacted components in the interlayer insulating film react with light irradiated to the liquid crystal cell, or where organic materials constituting the interlayer insulating film undergo a photodecomposition reaction, thereby generating low-molecular-weight components. It is considered that the low molecular weight component thus generated is generally adsorbed to a component of the interlayer insulating film or the like and stays in the interlayer insulating film or on the film surface. However, when the liquid crystal display element receives an external force or the like, bubbles due to the low molecular weight component may be generated, and may appear in the pixel region when the liquid crystal display element is used.
Therefore, in the liquid crystal display device, there has been proposed a technique for suppressing foaming of an interlayer insulating film caused by light irradiation in a manufacturing process (for example, see patent document 1). Patent document 1 discloses that an interlayer insulating film is formed so that the transmittance of light having a wavelength of 310nm becomes 70% or more when the film thickness is 2 μm.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2016-200698
Disclosure of Invention
[ problems to be solved by the invention ]
The foaming in the interlayer insulating film due to the low molecular weight component may affect the reliability of the liquid crystal display element. In particular, in recent years, as the use of liquid crystal display elements has been expanded, more sophisticated liquid crystal display elements have been required, and it is desired to reduce the generation of bubbles as much as possible. Such foaming is considered to occur not only by light irradiation by PSA technology but also by light irradiation treatment performed after formation of an interlayer insulating film, such as light irradiation for curing a sealing material or light irradiation for forming a liquid crystal alignment film by a photo-alignment method.
The present invention has been made in view of the above problems, and a main object thereof is to provide a method for manufacturing a liquid crystal display element, which can obtain a liquid crystal display element in which generation of bubbles is sufficiently suppressed, and a radiation-sensitive composition.
[ means for solving problems ]
The present inventors considered that one of the causes of the foaming generated in the liquid crystal display element is: in the polymer having a structural unit derived from a methacrylate ester, which is a material used for forming an interlayer insulating film, the main chain thereof is decomposed. Further, based on the above-mentioned assumption, it has been found that the above-mentioned problems can be solved by making the radiation-sensitive composition used for forming the interlayer insulating film have a specific composition. That is, the present invention provides the following method for manufacturing a liquid crystal display element, radiation-sensitive composition, interlayer insulating film, and liquid crystal display element.
[1] A method of manufacturing a liquid crystal display element includes: a forming step of forming an interlayer insulating film on a substrate; and an irradiation step of irradiating the object having the interlayer insulating film with light after the interlayer insulating film is formed, wherein the interlayer insulating film is formed using a radiation-sensitive composition containing the following component (A), component (B) and component (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 with a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less, a second structural unit having an acid group, and a third structural unit having a cyclic ether group with a ring number of 3 or 4;
(B) a quinone diazide compound;
(C) a solvent.
[2] A radiation-sensitive composition comprising: (A) the composition comprises 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 having a hetero ring structure having a ring element number of 5 or more, at least one 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, a second structural unit having an acid group, and a third structural unit having a cyclic ether group having a ring element number of 3 or 4.
[3] A radiation-sensitive composition comprising: (A) the composition contains a polymer component, (B) a quinone diazide compound, and (C) a solvent, wherein the component (A) contains, relative to all structural units constituting the polymer component, 8 to 50 mass% of a first structural unit, 0.5 to less than 20 mass% of a second structural unit (excluding a structural unit having a phenolic hydroxyl group), and 10 to 60 mass% of a third structural unit, the first structural unit being derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure with a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less, the second structural unit having an acid group, and the third structural unit having a cyclic ether group with a ring number of 3 or 4.
[4] A method of manufacturing an interlayer insulating film, comprising: a step of forming a coating film using the radiation-sensitive composition according to [2] or [3 ]; irradiating at least a part of the coating film with radiation; a step of developing the coating film after irradiation with radiation; and heating the developed coating film.
[5] An interlayer insulating film formed using the radiation-sensitive composition of [2] or [3 ].
[6] A liquid crystal display element having the interlayer insulating film of [5 ].
[ Effect of the invention ]
According to the production method and radiation-sensitive composition of the present invention, a liquid crystal display element in which bubbles generated by irradiating an interlayer insulating film with light are sufficiently suppressed can be obtained by forming the interlayer insulating film using a radiation-sensitive composition containing the component (a), the component (B), and the component (C).
Drawings
Fig. 1 is a diagram showing a schematic configuration of a liquid crystal display element.
[ description of symbols ]
10: liquid crystal display element
11: array substrate
12: liquid crystal layer
13: opposite substrate
14. 28: substrate
15: base coating film
16：TFT
17: interlayer insulating film
18: pixel electrode
19: semiconductor layer
21: gate insulating film
22: grid electrode
23: source electrode
24: drain electrode
25: inorganic insulating film
26a, 26 b: contact hole
27. 33: liquid crystal alignment film
29: black matrix
31: color filter
32: common electrode
Detailed Description
The following describes details of the embodiments. In the present specification, the numerical range of "to" is used to include numerical values before and after "to" as the lower limit and the upper limit. The "structural unit" is a unit mainly constituting the main chain structure, and means that at least 2 or more units are contained in the main chain structure.
[ radiation-sensitive composition ]
The disclosed radiation-sensitive composition is an interlayer insulating film for forming a liquid crystal display element. The radiation-sensitive composition contains 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 with a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less, a second structural unit having an acid group, and a third structural unit having a cyclic ether group with a ring number of 3 or 4.
(B) A quinone diazide compound.
(C) A solvent.
Hereinafter, each component contained in the radiation-sensitive composition of the present disclosure and other components blended as necessary will be described. Further, as long as each component is not particularly mentioned, one kind may be used alone, or two or more kinds may be used in combination.
Here, in the present specification, the term "hydrocarbon group" is intended to include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that do not include a cyclic structure in the main chain but are composed of only a chain structure. Wherein the unsaturated moiety may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group having only an alicyclic hydrocarbon structure as a ring structure and not having an aromatic ring structure. Here, the alicyclic hydrocarbon does not need to be constituted by only the structure of the alicyclic hydrocarbon, and a group having a chain structure in a part thereof is also included. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. In addition, the structure may not necessarily be composed of only an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof. The ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent including a hydrocarbon structure. The term "cyclic hydrocarbon group" is intended to include alicyclic hydrocarbon groups and aromatic hydrocarbon groups.
< component (A) >
First structural unit
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 a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less (hereinafter also referred to as "first monomer"). The "acrylate compound" is a compound having an acryloyloxy group as a group participating in polymerization, and specifically represented by the formula "CH2＝CH-CO-O-R20"(wherein, R is20A monovalent organic group having 1 or more carbon atoms).
Examples of the heterocyclic structure having a ring member number of 5 or more in the first monomer include a group obtained by removing an arbitrary hydrogen atom from a heterocyclic ring having a ring member number of 5 or moreThe heterocyclic ring having 5 or more ring members has-O-, -CO-O-, -CO-S-, -O-CO-O-, -O-CO-S-, -CO-NR-, -and the like among carbon-carbon bonds in a ring skeleton in an aliphatic ring comprising a monocyclic ring, a condensed ring, a bridged ring or a spiro ring1-、-CO-NR1-CO- (wherein, R1Hydrogen atom or C1-10 monovalent hydrocarbon group).
The ring of the heterocyclic structure may be any 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, and 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 still more preferably 10 or less. When the heterocyclic structure is a polycyclic structure, the "number of ring members" refers to the total number of atoms of 2 or more rings constituting the polycyclic structure. The heterocyclic structure may also have a substituent on the ring portion. Examples of the substituent include a monovalent hydrocarbon group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms.
In the above, the hetero ring structure of 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).
[ solution 1]
Figure BDA0002933998740000041
In the formulae (a-1) to (a-6), R10Is an alkyl group having 1 to 5 carbon atoms or 2R's present on the same carbon10Combined with each other to said 2R10A ring structure formed by the bonded carbon atoms; r11An alkyl group having 1 to 5 carbon atoms; r12Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m is 0 to 2N is an integer of 1 to 3; r is an integer of 1-3; "+" indicates a bond)
In the formulae (a-1) to (a-6), R10And R11The alkyl group having 1 to 5 carbon atoms may be straight or branched, and is preferably straight. With respect to R10And R11Among these, the C1-5 alkyl group is preferably C1-3, and more preferably methyl or ethyl.
As 2R's present on the same carbon10Is bonded with the 2R10The ring structure formed by the bonded carbon atoms together can be exemplified by: 1,4, 6-trioxaspiro [4.6]]Undecane, 1,4, 6-trioxaspiro [4.4]]Nonane, 1,4, 6-trioxaspiro [4.5]]Spiro orthoester structure such as decane.
m is preferably 0 or 1. n is preferably 1 or 2, more preferably 1. r is preferably 1 or 2, more preferably 1.
In the formulae (a-5) and (a-6), the bond may also be formed by removing R12Having hydrogen atoms.
Specific examples of the heterocyclic structure include a cyclic ether structure such as: a group obtained by removing an arbitrary hydrogen atom from a cyclic ether 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, or 1,4, 6-trioxaspiro [4.5] decane; examples of the cyclic ester structure include: a group obtained by removing an arbitrary hydrogen atom from a lactone such as γ -butyrolactone, γ -valerolactone, δ -valerolactone or ∈ -caprolactone; examples of the cyclic carbonate structure include: a group obtained by removing an arbitrary hydrogen atom from a cyclic carbonate such as ethylene carbonate or propylene carbonate; examples of the cyclic amide structure include: a group obtained by removing an arbitrary hydrogen atom from a lactam such as γ -lactam, δ -lactam, e-caprolactam, and laurolactam (laurolactam); examples of the cyclic imide structure include: a group obtained by removing an arbitrary hydrogen atom from an imide ring such as phthalimide or hexahydrophthalimide.
Specifically, the first structural unit is preferably a structural unit represented by the following formula (1).
[ solution 2]
Figure BDA0002933998740000051
(in the formula (1), R2A monovalent group having a hetero ring structure with a ring number of 5 or more or an alkyl group having 1 to 3 carbon atoms)
In the formula (1), in R2In the case of a monovalent group having a heterocyclic structure with a ring number of 5 or more, the ring part 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 (for example, an alkanediyl group having 1 to 5 carbon atoms). In order to obtain a radiation-sensitive composition having high radiation sensitivity and further reduce foaming of a liquid crystal display element, R is2Preferably a monovalent group having a heterocyclic structure with a ring number of 5 or more. Of these, especially, R2More preferably a monovalent group having a cyclic ether structure, a cyclic ester structure, a cyclic carbonate structure, a cyclic amide structure, or a cyclic imide structure, and still more preferably a cyclic ether structure.
R in the first structural unit and the formula (1)2When the hetero ring structure is a cyclic ether structure, the number of oxygen atoms (-O-) contained in the ring skeleton is preferably 2 or more 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 spiro orthoester structure, still more preferably a dioxolane structure or a dioxane structure, and particularly preferably a dioxolane structure.
Specific examples of the first monomer include an acrylate compound having a cyclic ether structure with a ring number of 5 or more, for example: tetrahydrofurfuryl acrylate, tetrahydropyranyl acrylate, 5-ethyl-1, 3-dioxan-5-ylmethyl acrylate, 5-methyl-1, 3-dioxan-5-ylmethyl acrylate, 2-methyl-2-ethyl-1, 3-dioxolan-4-yl methyl acrylate, 2-dimethyl-1, 3-dioxolan-4-yl ethyl acrylate, 2-acryloyloxymethyl-1, 4, 6-trioxaspiro [4.6] undecane, sodium acrylate, and mixtures thereof, 2-acryloyloxymethyl-1, 4, 6-trioxaspiro [4.4] nonane, 2-acryloyloxymethyl-1, 4, 6-trioxaspiro [4.5] decane, etc.;
examples of the acrylate compound having a cyclic ester structure having a ring number of 5 or more include: gamma-butyrolactone-2-yl acrylate, gamma-butyrolactone-2-yl methyl acrylate, delta-valerolactone-2-yl ethyl acrylate, and the like;
examples of the acrylate compound having a cyclic carbonate structure having a ring element number of 5 or more include glycerol carbonate acrylate;
examples of the acrylate compound having a cyclic amide structure having a ring element number of 5 or more include: gamma-lactam-2-yl acrylate, gamma-lactam-2-yl methyl acrylate, and the like;
examples of the acrylate compound having a cyclic imide structure having a ring member number of 5 or more include N-acryloyloxyethylhexahydrophthalimide and the like;
examples of the acrylate compound having an alkyl group having 3 or less carbon atoms include: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and the like. Among these, the first monomer is preferably an acrylate compound having a heterocyclic structure with a ring number of 5 or more, from the viewpoint of further improving the radiation sensitivity of the radiation-sensitive composition.
In the component (a), the content ratio of the first structural unit is preferably 5% by mass or more with respect to all the structural units constituting the component (a). When the content ratio of the first structural unit is 5% by mass or more, the sensitivity of the radiation-sensitive composition can be increased, and the foaming of the liquid crystal display element can be suppressed while suppressing the outgas from the cured film. From this viewpoint, the content ratio of the first structural unit is more preferably 8% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 20% by mass or more, and particularly more preferably 25% by mass or more, relative to all the structural units constituting the component (a). In addition, the content ratio of the first structural unit is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less with respect to all the structural units constituting the component (a), from the viewpoint of improving the pattern shape of the interlayer insulating film after development.
A second structural unit
The second structural unit is a structural unit having an acid group. By including the second structural unit in the component (a), the polymer component can be imparted with good alkali solubility.
The second structural unit is not particularly limited as long as it has an acid group, and 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 the present specification, the term "phenolic hydroxyl group" refers to a hydroxyl group directly bonded to an aromatic ring (e.g., benzene ring, naphthalene ring, anthracene ring, etc.).
The second structural unit is preferably a structural unit derived from an unsaturated monomer having an acid group (hereinafter also referred to as "second monomer"). Specific examples of the second monomer include monomers constituting a 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; examples of the monomer constituting the structural unit having a sulfonic acid group include: vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, (meth) acryloyloxyethylsulfonic acid, and the like; examples of the monomer constituting the structural unit having a phenolic hydroxyl group include: 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and the like. In addition, as the second monomer, maleimide may also be used. In the present specification, the term "(meth) acrylic group" means including an "acrylic group" and a "methacrylic group".
In the component (a), the content of the second constitutional unit is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and further more preferably 3% by mass or more, with respect to all the constitutional units constituting the component (a), from the viewpoint of making the exposed portion of the coating film containing the radiation-sensitive composition exhibit good developability with respect to an alkaline developer. On the other hand, if the content ratio of the second constitutional unit is too large, the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion is considered to be small. From this viewpoint, the content ratio of the second constitutional unit is preferably less than 40% by mass, more preferably 35% by mass or less, and still more preferably 30% by mass or less with respect to all the constitutional units constituting the component (a).
(A) The component (b) preferably contains at least a structural unit other than the structural unit having a phenolic hydroxyl group as the second structural unit, and more preferably contains at least one 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 as the second structural unit. The component (a) preferably contains a structural unit having such a group (a carboxyl group, a sulfonic acid group, a maleimide group) as the second structural unit, so that the exposed portion of the coating film containing the radiation-sensitive composition can exhibit good developability with an alkaline developer.
In the component (a), the content of the structural unit other than the structural unit having a phenolic hydroxyl group in the second structural unit is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 3% by mass or more, with respect to all the structural units constituting the component (a), from the viewpoint of making the exposed portion of the coating film containing the radiation-sensitive composition exhibit good developability with respect to an alkaline developer. In addition, the content ratio of the structural unit other than the structural unit having a phenolic hydroxyl group in the second structural unit is preferably less than 20% by mass, more preferably 18% by mass or less, even more preferably 16% by mass or less, and even more preferably 15% by mass or less with respect to all the structural units constituting the component (a), from the viewpoint of sufficiently showing the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion.
In the case where the structural unit having a phenolic hydroxyl group is introduced into the component (a) as the second structural unit, the content ratio of the structural unit having a phenolic hydroxyl group to all the structural units constituting the component (a) is preferably 0.5% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, from the viewpoint of further improving the radiation sensitivity. In addition, from the viewpoint of ensuring the physical properties of the cured film due to the structural unit having a thermally crosslinkable group, the content ratio of the structural unit having a phenolic hydroxyl group is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less with respect to all the structural units constituting the component (a).
A third structural unit
The third structural unit is a structural unit having a cyclic ether group having a ring element number of 3 or 4. By including the third structural unit in the component (a), the resolution of a film obtained using the radiation-sensitive composition and the solvent resistance of a cured film can be improved. In addition, a cured film in which deterioration is suppressed for a long period of time can be formed by the cyclic ether group of the third structural unit functioning as a crosslinkable group. The third structural unit is preferably a structural unit having at least one selected from the group consisting of an oxetane structure and an oxetane structure.
The third structural unit is preferably a structural unit derived from an unsaturated monomer having a cyclic ether group having a ring element number of 3 or 4 (hereinafter also referred to as "third monomer"), and more specifically, is preferably a structural unit represented by the following formula (3).
[ solution 3]
Figure BDA0002933998740000081
(in the formula (3), R3Is a monovalent radical having an oxetane or oxetane structure, R4Is a hydrogen atom or a methyl group, X1Is a single bond or a divalent linking group)
In the formula (3), as R3Examples thereof include: oxopropyl, oxetanyl, 3, 4-epoxycyclohexyl, 3, 4-epoxytricyclo [5.2.1.02,6]Decyl, 3-ethyloxetanyl, and the like. Among these, R is highly reactive3A monovalent group having an oxetane structure is preferable.
As X1Examples of the divalent linking group of (3) include: alkanediyl groups such as methylene, ethylene and 1, 3-propanediyl.
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 ] meth) acrylate2,6]Decyl ester, (3-methyloxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) meth) acrylate, (oxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, and the like.
In component (a), the content of the third structural unit is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, based on all the structural units constituting component (a). The content ratio of the third structural unit is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less, based on all the structural units constituting the component (a). When the content ratio of the third structural unit is in the above range, the coating film exhibits better resolution and the heat resistance and solvent resistance of the obtained cured film can be sufficiently improved, which is preferable.
In component (a), the respective content ratios of the first constitutional unit, the second constitutional unit, and the third constitutional unit can be set by appropriately combining the numerical ranges of the preferable content ratios of the respective constitutional units. Among these, the component (a) preferably contains 5 mass% or more and 60 mass% or less of the first structural unit, 0.5 mass% or more and less than 40 mass% of the second structural unit, and 10 mass% or more and 60 mass% or less of the third structural unit with respect to all the structural units constituting the polymer component, from the viewpoint that the radiation-sensitive composition exhibits good radiation sensitivity and the cured film obtained has excellent pattern shape, outgassing characteristics, and foaming resistance. More preferably, the resin composition may contain 8 mass% or more and 60 mass% or less of the first structural unit, 0.5 mass% or more and less than 35 mass% of the second structural unit, and 10 mass% or more and 60 mass% or less of the third structural unit, and further preferably may contain 10 mass% or more and 50 mass% or less of the first structural unit, 0.5 mass% or more and 30 mass% or less of the second structural unit, and 10 mass% or more and 60 mass% or less of the third structural unit.
In the component (a), the content ratio of each of the first structural unit, the second structural unit (excluding the structural unit having a phenolic hydroxyl group), and the third structural unit is preferably 5 mass% or more and 60 mass% or less of the first structural unit, 0.5 mass% or more and less than 20 mass% of the second structural unit, and 10 mass% or more and 60 mass% or less of the third structural unit with respect to all the structural units constituting the polymer component, from the viewpoint that the radiation-sensitive composition exhibits good radiation sensitivity and the cured film obtained has excellent pattern shape, outgassing characteristics, and foaming resistance. More preferably, the component (a) may contain, with respect to all the structural units constituting the polymer component, 8 mass% or more and 60 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 mass% or more and 60 mass% or less of the third structural unit, and further preferably may contain 10 mass% or more and 50 mass% or less of the first structural unit, 0.5 mass% or more and 18 mass% or less of the second structural unit (excluding the structural unit having a phenolic hydroxyl group), and 10 mass% or more and 60 mass% or less of the third structural unit.
(A) The component (b) may contain a first structural unit, a second structural unit, and a third structural unit, and may further contain a structural unit (hereinafter, also referred to as "other structural unit") different from the first structural unit to the third structural unit. Examples of other structural units include: a structural unit derived from an aromatic vinyl compound (hereinafter also referred to as "fourth structural unit"), a structural unit derived from an N-substituted maleimide compound (hereinafter also referred to as "fifth structural unit"), a structural unit having a hydroxyl group (excluding a phenolic hydroxyl group) (hereinafter also referred to as "sixth structural unit"), and a structural unit derived from a methacrylate ester compound having an alkyl group having 3 or less carbon atoms (hereinafter also referred to as "seventh structural unit"). The component (a) preferably contains at least one of the fourth structural unit and the fifth structural unit, so that the glass transition temperature Tg of the polymer component can be appropriately increased and a cured film having a good pattern shape can be obtained.
A fourth structural unit
The aromatic vinyl compound constituting the fourth structural unit is not particularly limited, and examples thereof include: styrene compounds such as 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-dimethylaminoethylstyrene, N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene and diphenylethylene; vinyl naphthalene compounds such as vinyl naphthalene and divinyl naphthalene; heterocyclic vinyl compounds such as vinylpyridine and the like. Among these, the aromatic vinyl compound is preferably a styrene-based compound. In the present specification, a structural unit derived from an aromatic vinyl compound having a phenolic hydroxyl group is included in the "second structural unit".
In component (a), the content ratio of the fourth structural unit is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more, relative to all the structural units constituting component (a). The content ratio of the fourth structural unit is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on all the structural units constituting the component (a). By setting the content ratio of the fourth structural unit to 1 mass% or more, a cured film having a more favorable pattern shape can be obtained. Further, by setting the content ratio of the fourth structural unit to 30% by mass or less, the glass transition temperature of the polymer component does not become excessively high, and a decrease in developability can be suppressed.
A fifth structural unit
Examples of the N-substituted maleimide compound constituting the fifth structural unit include compounds in which a hydrogen atom bonded to a nitrogen atom of maleimide is substituted with a monovalent hydrocarbon group. As the monovalent hydrocarbon group, there may be mentioned: 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 monocyclic ring, a bridged ring or a spiro ring, in terms of further improving the effect of improving the heat resistance.
Specifically, the fifth structural unit is preferably a structural unit represented by the following formula (5).
[ solution 4]
Figure BDA0002933998740000101
(in the formula (5), R5Is a monovalent cyclic hydrocarbon group; r6And R7Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)
In the formula (5), with respect to R5The cyclic hydrocarbon group may have a ring structure directly bonded to the nitrogen atom, or the ring structure may be bonded to the nitrogen atom via a divalent linking group. Examples of the divalent linking group include: alkanediyl groups such as methylene, ethylene and 1, 3-propanediyl. In these, R5Preferably, the cyclic structure of the cyclic hydrocarbon group is directly bonded to the nitrogen atomMore preferably, the alicyclic hydrocarbon group is one in which the structure of the alicyclic hydrocarbon is directly bonded to a nitrogen atom. R6And R7Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
Specific examples of the N-substituted maleimide compound include compounds having an alicyclic hydrocarbon group such as: n-cyclohexylmaleimide, N-cyclopentylmaleimide, N- (2-methylcyclohexyl) maleimide, N- (4-ethylcyclohexyl) maleimide, N- (2, 6-dimethylcyclohexyl) maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, etc.; examples of the compound having an aromatic hydrocarbon group include: n-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-ethylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide and the like. Of these, the N-substituted maleimide compound is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, N- (4-methylcyclohexyl) maleimide, N-phenylmaleimide and N- (4-methylphenyl) maleimide, and more preferably at least one selected from the group consisting of N-cyclohexylmaleimide and N-phenylmaleimide.
In the component (a), the content ratio of the fifth constitutional unit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more with respect to all the constitutional units constituting the component (a) from the viewpoint of improving the pattern shape. From the viewpoint of suppressing the deterioration of the developability, the content ratio of the fifth structural unit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less with respect to all the structural units constituting the component (a).
Sixth structural Unit
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 "sixth monomer"), and specifically, a structural unit derived from a monomer having 1 or more hydroxyl groups bonded to a saturated chain hydrocarbon group is exemplified. The sixth monomer is not particularly limited, and examples thereof include a (meth) acrylic compound and a maleimide compound.
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, glycerol mono (meth) acrylate, and the like;
examples of the maleimide compound include: n- (hydroxymethyl) maleimide, N- (2-hydroxyethyl) maleimide, N- (3-hydroxypropyl) maleimide and the like.
When the component (a) includes the sixth constitutional unit, the decrease in the pattern forming ability due to the variation in the prebaking temperature at the time of film formation can be suppressed, and a good pattern can be formed, which is preferable in terms of this point and the radiation sensitivity. In the component (a), the content ratio of the sixth constitutional unit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, with respect to all constitutional units constituting the component (a), from the viewpoint of suppressing the decrease in the pattern formability due to the variation in the prebaking temperature. From the viewpoint of suppressing the deterioration of the developability, the content ratio of the sixth structural unit is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less with respect to all the structural units constituting the component (a).
A seventh structural unit
Examples of monomers constituting the seventh constitutional unit include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate. In component (a), the content ratio of the seventh constitutional unit is preferably 55% by mass or less, more preferably 45% by mass or less, further preferably 35% by mass or less, further preferably 25% by mass or less, with respect to all the constitutional units constituting component (a).
Examples of the other constitutional units include, in addition to the above-mentioned constitutional units: alkyl (meth) acrylate 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. The content ratio of the structural units other than the fourth to sixth structural units in component (a) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less with respect to all the structural units constituting component (a).
(A) The component (b) may contain only one kind of the first structural unit, or may contain two or more kinds. The same applies to the second structural unit, the third structural unit and the other structural units. The content ratio of each structural unit is generally equivalent to the ratio of a monomer used for producing the polymer component. (A) The component (b) may contain one kind of polymer or two or more kinds of polymers as long as it contains the first structural unit, the second structural unit and the third structural unit. That is, the component (a) includes a first structural unit, a second structural unit, and a third structural unit in the same polymer or different polymers. The component (a) may further contain a polymer having no first structural unit, no second structural unit, or no third structural unit.
Examples of the form of the component (a) contained in the radiation-sensitive composition include: 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"); 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; 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; examples of the polymer include 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, the above [1] is preferable in terms of reducing the amount of the components constituting the radiation-sensitive composition and obtaining the effect of suppressing foaming. The polymer constituting the component (a) is preferably an alkali-soluble resin. In the present specification, the term "alkali-soluble" means that the compound can be dissolved or swollen in an alkaline aqueous solution such as a 2.38 mass% aqueous tetramethylammonium hydroxide solution.
In the component (a), the weight average molecular weight (Mw) in terms of polystyrene obtained by Gel Permeation Chromatography (GPC) is preferably 2000 or more. When Mw is 2000 or more, a cured film having sufficiently high heat resistance and solvent resistance and exhibiting good developability can be obtained, which is preferable. Mw is more preferably 5000 or more, still more preferably 6000 or more, and particularly preferably 8000 or more. From the viewpoint of improving the film-forming property, Mw is preferably 50000 or less, more preferably 30000 or less, further preferably 20000 or less, further preferably 18000 or less, particularly preferably 15000 or less.
In the 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 further preferably 2.7 or less. When the component (a) contains two or more polymers, the Mw and Mw/Mn of each polymer preferably satisfy the above ranges.
(A) The content ratio of the component (b) is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, based on the total amount of solid components contained in the radiation-sensitive composition. The content of the component (a) is preferably 95% by mass or less, and more preferably 90% by mass or less, based on the total amount of solid components contained in the radiation-sensitive composition. By setting the content ratio of the component (a) in the above range, a cured film having sufficiently high heat resistance and solvent resistance and exhibiting good developability and transparency can be obtained.
The component (a) can be produced by a known method such as radical polymerization in an appropriate solvent in the presence of a polymerization initiator or the like, using an unsaturated monomer capable of introducing each of the above-mentioned structural units. Specifically, examples of the polymerization initiator to be used include: azo compounds such as 2,2' -azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), and dimethyl 2,2' -azobis (isobutyrate). 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. Examples of the polymerization solvent include: alcohols, ethers, ketones, esters, hydrocarbons, and the like.
In the polymerization, the reaction temperature is usually from 30 ℃ to 180 ℃. The reaction time varies depending on the kind of the initiator and the monomer or the reaction temperature, and is usually 0.5 to 10 hours. The amount of the organic solvent used is preferably 0.1 to 60% by mass of the total amount of the monomers used in the reaction, relative to the total amount of the reaction solution. The polymer obtained by the polymerization reaction can be isolated, for example, by the following known isolation methods: a method in which the reaction solution is poured into a large amount of a poor solvent, and the precipitate obtained thereby is dried under reduced pressure; and a method of distilling off the reaction solution under reduced pressure using an evaporator.
< ingredient (B) >
The quinonediazide compound as the component (B) is a radiation-sensitive acid generator that generates carboxylic acid by irradiation with radiation. The quinone diazide compound is preferably a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") and 1, 2-naphthoquinone diazide sulfonyl halide.
Examples of the parent nucleus include: trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkanes, other parent nuclei. Specific examples of these include trihydroxybenzophenone such as: 2,3, 4-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, and the like; 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 '-tetrahydroxy-3' -methoxybenzophenone and the like; examples of the pentahydroxybenzophenones include: 2,3,4,2',6' -pentahydroxybenzophenone and the like; examples of hexahydroxybenzophenones include: 2,4,6,3',4',5 '-hexahydroxybenzophenone, 3,4,5,3',4',5' -hexahydroxybenzophenone, and the like; examples of (polyhydroxyphenyl) alkanes include: bis (2, 4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1, 1-tris (p-hydroxyphenyl) ethane, bis (2,3, 4-trihydroxyphenyl) methane, 2-bis (2,3, 4-trihydroxyphenyl) propane, 1,1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4'- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol, bis (2, 5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl methane, 3,3',3 '-tetramethyl-1, 1' -spirobisindan-5, 6,7,5',6',7' -hexanol, 2, 4-trimethyl-7, 2',4' -trihydroxyflavan, etc.; examples of other parent nuclei include: 2-methyl-2- (2, 4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxytryptane, 2- [ bis { (5-isopropyl-4-hydroxy-2-methyl) phenyl } methyl ], and the like.
Of these, 2,3,4,4 '-tetrahydroxybenzophenone, 1,1, 1-tris (p-hydroxyphenyl) methane, 1,1, 1-tris (p-hydroxyphenyl) ethane and 4,4' - [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol are preferable as the parent nucleus.
As the 1, 2-naphthoquinone diazide sulfonyl halide, 1, 2-naphthoquinone diazide sulfonyl chloride is preferable. Specifically, there may be mentioned: 1, 2-naphthoquinonediazide-4-sulfonyl chloride, 1, 2-naphthoquinonediazide-5-sulfonyl chloride and the like. Of these, as the 1, 2-naphthoquinone diazide sulfonyl halide, 1, 2-naphthoquinone diazide-5-sulfonyl chloride can be preferably used.
In the condensation reaction for obtaining the condensate, the ratio of the 1, 2-naphthoquinone diazide sulfonyl halide to the parent nucleus is set to an amount corresponding to preferably 30 to 85 mol%, more preferably 50 to 70 mol%, of the 1, 2-naphthoquinone diazide sulfonyl halide with respect to the number of OH groups in the parent nucleus. The condensation reaction may be carried out according to a known method. The 1, 2-quinonediazide compound can be obtained by condensation reaction of mother nucleus and 1, 2-naphthoquinonediazide sulfonyl halide.
The content of the component (B) in the radiation-sensitive composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more, per 100 parts by mass of the component (a). The content of the component (B) is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less, per 100 parts by mass of the component (a). When the content ratio of the component (B) is 2 parts by mass or more, an acid can be sufficiently generated by irradiation with radiation, and the difference in solubility in an alkaline solution between the irradiated portion and the non-irradiated portion is sufficiently large. This enables favorable patterning. Further, the amount of acid to be reacted with the component (A) can be increased, and heat resistance and solvent resistance can be sufficiently ensured. On the other hand, if the content ratio of the component (B) is 100 parts by mass or less, the unreacted component (B) can be sufficiently reduced, and the deterioration of the developability due to the remaining component (B) can be suppressed, which is preferable.
< ingredient (C) >
The radiation-sensitive composition of the present disclosure is a liquid composition in which the component (a), the component (B), and optionally other components are preferably dissolved or dispersed in a solvent as the component (C). The solvent used is preferably an organic solvent which dissolves each component formulated in the radiation-sensitive composition and does not react with each component.
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, ethyl 3-ethoxypropionate, etc.; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Among these, the solvent used for 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 acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates.
< other ingredients >
The radiation-sensitive composition of the present disclosure may further contain, in addition to the above-mentioned component (a), component (B), and component (C), other components (hereinafter, also referred to as "other components"). Examples of the other components include: a reaction initiator (photo radical polymerization initiator, photo cation polymerization initiator, etc.), a polyfunctional polymerizable compound (polyfunctional (meth) acrylate, etc.), an adhesion promoter (functional silane coupling agent, etc.), a surfactant (fluorine-based surfactant, silicone-based surfactant, nonionic surfactant, etc.), a polymerization inhibitor, an antioxidant, a chain transfer agent, etc. The blending ratio of these components may be appropriately selected depending on each component within a range not impairing the effect of the present disclosure.
The solid content concentration (the ratio of the total mass of components other than the component (C) in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) of the radiation-sensitive composition of the present disclosure is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 5 to 60 mass%. When the solid content concentration is 5% by mass or more, the film thickness of the coating film can be sufficiently ensured when the radiation-sensitive composition is coated on a substrate, which is preferable. Further, when the solid content concentration is 60 mass% or less, the film thickness of the coating film is not excessively increased, and the viscosity of the radiation-sensitive composition can be appropriately increased, so that good coatability can be secured, which is preferable. The solid content concentration in the radiation-sensitive composition is more preferably 10 to 55% by mass, and still more preferably 15 to 50% by mass.
< interlayer insulating film and method for producing same >
The interlayer insulating film of the present disclosure may be formed of the radiation-sensitive composition prepared as described. According to the radiation-sensitive composition, a film with less outgas generation accompanying heating can be formed, and therefore, when the radiation-sensitive composition is used as a composition for forming an organic film constituting a liquid crystal display element, foaming can be suppressed in the liquid crystal display element. In addition, the radiation-sensitive composition has high radiation sensitivity and is also excellent in patterning by radiation irradiation. Therefore, the radiation-sensitive composition is useful as a polymer composition for forming an interlayer insulating film of a liquid crystal display element.
When the interlayer insulating film is produced, the radiation-sensitive composition is used, whereby a positive type cured film can be formed by irradiation with radiation (ultraviolet rays, far ultraviolet rays, visible rays, and the like). The interlayer insulating film of the present disclosure can be produced by a method including, for example, the following steps 1 to 4.
(step 1) a step of forming a coating film using the radiation-sensitive composition.
(step 2) exposing at least a part of the coating film.
(step 3) a step of developing the coating film.
(step 4) a step of heating the developed coating film.
Hereinafter, each step will be described in detail.
[ Process 1: film formation Process)
In this step, the radiation-sensitive composition is applied to a film-forming surface (hereinafter also referred to as a "film-forming surface"), and preferably a solvent is removed by heat treatment (pre-baking) to form a coating film on the film-forming surface. The material of the film formation surface is not particularly limited. For example, when a planarizing film is formed using a radiation-sensitive composition, the radiation-sensitive composition is applied to a substrate provided with a switching element such as a Thin Film Transistor (TFT) to form a coating film. As the substrate, for example, a glass substrate or a resin substrate can be used.
Examples of the method for applying the radiation-sensitive composition include: spray method, roll coating method, spin coating method, slit die coating method, bar coating method, ink jet method. Among these, it is preferable to perform the coating by a spin coating method, a slit die coating method, or a bar coating method. The prebaking conditions may vary depending on the kind and content ratio of each component of the radiation-sensitive composition, and may be, for example, 0.5 to 10 minutes at 60 to 130 ℃. The film thickness of the formed coating film (i.e., the film thickness after the pre-baking) is preferably 1 to 12 μm.
[ step 2: exposure Process
In this step, at least a part of the coating film formed in the step 1 is irradiated with radiation. At this time, the coating film is irradiated with radiation through a mask having a predetermined pattern, whereby an interlayer insulating film having a pattern can be formed. Examples of the radiation include: charged particle beams such as ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. Of these, ultraviolet rays are preferable, and examples thereof include g rays (wavelength: 436nm) and i rays (wavelength: 365 nm). The exposure amount of the radiation is preferably 0.1J/m2～20,000J/m2。
[ step 3: development Process
In this step, the coating film irradiated with the radiation in the step 2 is developed. Specifically, the following positive type development was performed: the coating film irradiated with the radiation in step 2 is developed with a developing solution, and the irradiated portion of the radiation is removed. As the developer, for example, an aqueous solution of an alkali (alkaline compound) is cited. Examples of the base include: sodium hydroxide, tetramethylammonium hydroxide, and a base as exemplified in paragraph [0127] of Japanese patent laid-open No. 2016-145913. From the viewpoint of obtaining appropriate developability, the alkali concentration in the alkaline aqueous solution is preferably 0.1 to 5.0 mass%. As the developing method, there are listed: a liquid coating method, an immersion method, a shaking immersion method, a spraying method, and the like. The development time also varies depending on the composition of the composition, and is, for example, 30 seconds to 120 seconds. Further, it is preferable that the patterned coating film is subjected to rinsing treatment by running water cleaning after the developing step.
[ step 4: heating procedure
In this step, a treatment (post-baking) of heating the coating film developed in the step 3 is performed. The post-baking can be performed using a heating device such as an oven or a hot plate. The post-baking conditions are, for example, heating temperatures of 120 to 250 ℃. The heating time is, for example, 5 to 40 minutes in the case of heating treatment on a hot plate, or 10 to 80 minutes in the case of heating treatment in an oven. By performing the above process, a cured film having a desired pattern can be formed on the substrate.
< liquid crystal display element >
The liquid crystal display element of the present disclosure has an interlayer insulating film formed using the radiation-sensitive composition. Hereinafter, an embodiment of the liquid crystal display element of the present disclosure will be described with reference to fig. 1.
In fig. 1, a liquid crystal display element 10 is an active matrix type having a plurality of pixels formed in a matrix. In this embodiment, the liquid crystal display element 10 is manufactured using the PSA technique. The liquid crystal display element 10 includes: an array substrate 11, and a counter substrate 13 disposed to face the array substrate 11. A liquid crystal layer 12 is formed by sealing liquid crystal between a pair of substrates including the array substrate 11 and the counter substrate 13.
As shown in fig. 1, the array substrate 11 includes: an insulating substrate 14 such as a glass substrate or a resin substrate, a base coat film 15, a TFT 16, an inorganic insulating film 25, an interlayer insulating film 17, and a pixel electrode 18. The TFT 16 includes a semiconductor layer 19 including polysilicon (p-Si), a gate insulating film 21, a gate electrode 22, a source electrode 23, and a drain electrode 24, and is provided for each pixel. The TFT 16 is formed by a known method such as photolithography using a known material.
The interlayer insulating film 17 is formed on the substrate 14 by photolithography using the radiation-sensitive composition. The interlayer insulating film 17 is formed on the entire surface of the substrate 14 so as to cover the TFTs 16. By forming the interlayer insulating film 17 on the substrate 14 having the TFT 16, surface unevenness caused by the TFT 16 is planarized. In addition, by providing the interlayer insulating film 17, an increase in capacitive coupling between the pixel electrode 18 and the signal line can be suppressed. The thickness of the interlayer insulating film 17 is preferably 1 to 5 μm, and more preferably 2 to 4 μm from the viewpoint of sufficiently having the insulating function and the planarizing function.
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 through 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.
The opposing substrate 13 includes: a transparent and 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 red (R), green (G), and blue (B) colored sub-pixels (sub-pixels), and is formed by a known method such as photolithography. The common electrode 32 is a planar electrode formed of a transparent conductive film such as ITO (indium tin oxide), and is provided over a plurality of pixels. A liquid crystal alignment film 33 is formed on the electrode formation surface of the counter substrate 13.
The array substrate 11 and the counter substrate 13 are disposed with a predetermined gap (cell gap) therebetween so that the alignment film formation surface of the array substrate 11 faces the alignment film formation surface of the counter substrate 13. The peripheral edges of the pair of substrates disposed to face each other are bonded together with a sealing material (not shown). As a material of the sealing material, a material (for example, thermosetting resin or photocurable resin) known as a sealing agent for a liquid crystal device 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. Thereby, the liquid crystal layer 12 is disposed in contact with the liquid crystal alignment film 27 and the liquid crystal alignment film 33.
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"). As a result, in the liquid crystal layer 12, PSA layers (not shown) as polymer layers are formed on the array substrate 11 side and the counter substrate 13 side. The PSA layer is formed by: after the liquid crystal cell is constructed, liquid crystal molecules are aligned in a pre-tilt state, and a photopolymerizable monomer previously mixed into a polymerizable liquid crystal composition is photopolymerized in the above state. In the liquid crystal display element 10, the initial alignment of the liquid crystal molecules in the liquid crystal layer 12 is controlled by the PSA layer.
In the liquid crystal display element 10, a polarizing plate (not shown) is disposed outside each of the array substrate 11 and the counter substrate 13. The array substrate 11 has a terminal area provided at its outer edge. The liquid crystal display element 10 is driven by connecting a driver Integrated Circuit (IC) or the like for driving liquid crystal to the terminal area.
< method for manufacturing liquid crystal display element >
The cured film formed using the radiation-sensitive composition has a high effect of suppressing foaming associated with light irradiation. Therefore, it is preferable to perform various light irradiation steps for manufacturing a liquid crystal display element after forming the cured film, in order to suppress foaming caused by the light irradiation even when the cured film is irradiated with light. Examples of the light irradiation treatment performed after the formation of the cured film include: a light irradiation treatment for hardening the sealing material; a light irradiation treatment for forming a liquid crystal alignment film by a photo-alignment method; and a light irradiation treatment for adjusting the light transmittance in the visible light region of the formed cured film by utilizing the photobleaching (photobleaching) performance of the quinonediazide compound.
Among these, the radiation-sensitive composition is particularly suitable for use in forming an interlayer insulating film of a display device manufactured by PSA technology. In the PSA technology, the amount of light irradiated to polymerize the photopolymerizable monomer in the liquid crystal composition is relatively large, and it can be said that the following is likely to occur due to the light: causing a reaction of an unreacted component in the interlayer insulating film or decomposition of a polymer component in the interlayer insulating film. In this respect, it is preferable that the interlayer insulating film is formed of the radiation-sensitive composition to sufficiently suppress generation of bubbles due to light irradiation.
The liquid crystal display element of the present disclosure can be manufactured by a method including the following steps a and B, for example.
Step A: and forming an interlayer insulating film on a substrate using the radiation-sensitive composition.
And a step B: and irradiating the object having the interlayer insulating film with light after the interlayer insulating film is formed.
When a liquid crystal display element is manufactured by the PSA technique, specifically, it is preferable to manufacture the liquid crystal display element by a method further including the following step X and performing the following step B1 as the step B.
Step X: and a step of configuring a liquid crystal cell by disposing a pair of substrates including a substrate having an interlayer insulating film, facing each other with a layer including a polymerizable liquid crystal composition interposed therebetween.
Step B1: and irradiating the liquid crystal cell with light while applying a voltage to the layer containing the polymerizable liquid crystal composition.
Hereinafter, a method for manufacturing a liquid crystal display device according to the present disclosure will be described by taking a case where a liquid crystal display device is manufactured by PSA technology as an example.
In manufacturing a liquid crystal display element, first, an array substrate and a counter substrate are prepared. Specifically, first, TFTs, wirings, and the like are formed on a transparent substrate such as a glass substrate by a known method such as photolithography. Then, the radiation-sensitive composition is applied to the TFT formation surface of the transparent substrate to form an interlayer insulating film (step a). The interlayer insulating film is formed by a method including, for example, the steps 1 to 4. Thereafter, a pixel electrode is formed on the interlayer insulating film. The pixel electrode is formed by: a conductive film including ITO or the like is formed by a known method such as a sputtering method, and then patterned by a photolithography method. In addition, unlike the array substrate, a color filter, a common electrode, and the like are formed on a transparent substrate such as a glass substrate by a known method such as photolithography, and an opposing substrate is manufactured.
Then, a liquid crystal alignment agent is applied to the substrate on which the electrode is formed, and preferably, the coated surface is heated (pre-baking and post-baking), thereby forming a coating film on the substrate. Thereafter, the coating film is subjected to an orientation treatment as necessary. Examples of the orientation treatment include: rubbing treatment of wiping the coating film in a fixed direction with a roller around which a cloth containing fibers such as nylon, rayon, and cotton is wound; and photo-alignment treatment for applying liquid crystal alignment ability to a coating film formed on a substrate by irradiating the coating film with light using a liquid crystal alignment agent.
Then, an array substrate on which an interlayer insulating film, a pixel electrode, 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 so that alignment film forming surfaces thereof face each other. A liquid crystal cell is constructed by disposing a liquid crystal layer in which a photopolymerizable monomer is mixed between an array substrate and a counter substrate (step X).
The liquid crystal layer is formed by, for example, the following method: a method in which a polymerizable liquid crystal composition is dropped or coated on One of the substrates coated with a sealing material, and then the other substrate is bonded (One Drop Filling (ODF) method); a method of bonding peripheral portions of a pair of substrates disposed to face each other with a sealing material interposed therebetween, filling a polymerizable liquid crystal composition into a cell gap surrounded by the surfaces of the substrates and the sealing material, and sealing the filling hole. As the photopolymerizable monomer, a compound having 2 or more (meth) acryloyl groups can be preferably used in terms of high polymerizability by light, and for example, a polyfunctional (meth) acrylic compound having a mesogen skeleton or the like can be used.
In the next step, the obtained liquid crystal cell is irradiated with light (step B). Light irradiation to the liquid crystal cell is performed in a state where a predetermined voltage for driving the liquid crystal molecules is applied between the electrodes (step B1). The applied voltage may be, for example, a dc voltage of 5V to 50V or an ac voltage. Examples of the light to be irradiated include ultraviolet rays and visible rays including light having a wavelength of 150nm to 800 nm. Of these, ultraviolet rays containing light having a wavelength of 300nm to 400nm are preferable. Regarding the direction of light irradiation, the radiation used is linearly polarized lightOr partially polarized light, the substrate surface may be irradiated from a vertical direction, or the substrate surface may be irradiated from an oblique direction, or a combination of these directions may be irradiated. When non-polarized radiation is irradiated, the irradiation direction is set to be an oblique direction. The dose of light irradiation is preferably 1,000J/m2～200,000J/m2More preferably 1,000J/m2～100,000J/m2. In the case of manufacturing a liquid crystal display element by the PSA method, the liquid crystal cell corresponds to an "object having an interlayer insulating film".
Then, a polarizing plate was 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 plate in which a polarizing film called an "H film" in which iodine is absorbed while polyvinyl alcohol is stretched and oriented, and a polarizing plate including an H film itself, which are sandwiched between cellulose acetate protective films.
The liquid crystal display element of the present disclosure described in detail above can be effectively applied to various uses, for example, as: a clock, a portable game machine, a word processor (word processor), a notebook Personal computer (note type Personal computer), a car navigation system (car navigation system), a camcorder (camrecorder), a Personal Digital Assistant (PDA), a Digital camera (Digital camera), a mobile phone, a smart phone, various monitors, a liquid crystal television, various display devices such as an information display, and the like.
[ examples ]
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "part(s)" and "%" are based on mass unless otherwise specified. In this example, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by the following methods.
[ weight average molecular weight (Mw) and number average molecular weight (Mn) ]
The Mw and Mn of the polymer were measured by the following methods.
The measurement method: gel Permeation Chromatography (GPC) method
An apparatus: GPC-101 of Showa electrician
GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 of Shimadzu GLC corporation were combined
The mobile phase: tetrahydrofuran (THF)
Column temperature: 40 deg.C
Flow rate: 1.0 mL/min
Sample concentration: 1.0% by mass
Sample injection amount: 100 μ L
The detector: differential refractometer
Standard substance: monodisperse polystyrene
[ Single dose ]
The monomers used in the synthesis of the polymer are as follows.
First Individual volume
M-1: tetrahydrofurfuryl acrylate
M-2: acrylic acid 5-ethyl-1, 3-dioxane-5-yl methyl ester
M-3: acrylic acid (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl ester
M-4: acrylic acid methyl ester
M-5: acrylic acid ethyl ester
M-6: acrylic acid (gamma-butyrolactone-2-yl) ester
M-7: acrylic acid (gamma-butyrolactam-2-yl) ester
M-8: n-acryloyloxyethyl hexahydrophthalimide
M-9: glycerol carbonate acrylate
Second Individual Quantum
M-10: methacrylic acid
M-11: maleimide
M-12: para-isopropenylphenol
Third Individual Quantum
M-13: glycidyl methacrylate
M-14: 3, 4-epoxycyclohexylmethyl methacrylate
M-15: 3-methacryloyloxymethyl-3-ethyloxetane
Other Individual subjects
M-16: acrylic acid (2-methoxyethyl) ester
M-17: tetrahydrofurfuryl methacrylate
M-18: methacrylic acid n-butyl ester
M-19: n-cyclohexyl maleimide
M-20: methacrylic acid methyl ester
M-21: styrene (meth) acrylic acid ester
M-22: n- (2-hydroxyethyl) maleimide
M-23: glycerol monomethacrylate
M-24: 2-Hydroxyethyl methacrylate
M-25: 2-hydroxypropyl methacrylate
< Synthesis of Polymer (1) >)
Synthesis example 1 Synthesis of Polymer (A-1)
In a flask equipped with a cooling tube and a stirrer, 13 parts of dimethyl 2,2' -azobis (isobutyrate) and 200 parts of diethylene glycol ethyl methyl ether were charged. Then, 10 parts of tetrahydrofurfuryl acrylate, 8 parts of methacrylic acid, 30 parts of glycidyl methacrylate, and 52 parts of methyl methacrylate were charged, and nitrogen substitution was performed. While the solution in the flask was slowly stirred, the temperature of the solution was raised to 80 ℃ and the temperature was maintained for 5 hours, thereby obtaining a polymer solution containing polymer (a-1). The polymer solution had a solid content concentration of 34.5% by mass, the Mw of the polymer (A-1) was 11,000, and the molecular weight distribution (Mw/Mn) was 2.2.
Synthesis examples 2 to 31 and comparative Synthesis examples 1 to 4 Synthesis of polymers (A-2) to (A-13) and polymers (CA-1) to (CA-4)
Polymer solutions containing polymers (A-2) to (A-31) and polymers (CA-1) to (CA-4) having the same levels of solid content concentration, molecular weight and molecular weight distribution as polymer (A-1) were obtained in the same manner as in Synthesis example 1, except that the components were used in the same types and amounts (parts by mass) as those shown in Table 1.
Figure BDA0002933998740000201
Preparation of < radiation-sensitive resin composition (1) >
Using the synthesized polymer to prepare a radiation-sensitive resin composition. The polymer and acid generator used for the preparation of the radiation-sensitive resin composition are shown below.
Polymers
A-1 to A-31: polymers (A-1) to (A-31) synthesized in Synthesis examples 1 to 31
CA-1 to CA-4: comparative Synthesis examples 1 to 4 Polymer (CA-1) to Polymer (CA-4)
Acid generator
B-1: condensate of 4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol (1.0 mol) and 1, 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)
[ example 1]
To the polymer solution containing the polymer (A-1), 20 parts of an acid generator (B-1) was mixed in an amount corresponding to 100 parts (solid content) of the polymer (A-1), and diethylene glycol ethyl methyl ether was added so that the final solid content concentration became 30 mass%. Then, filtration was carried out using a membrane filter having a pore size of 0.2 μm to prepare a composition (S-1).
Examples 2 to 31 and comparative examples 1 to 4
Radiation-sensitive resin compositions of examples 2 to 31 and comparative examples 1 to 4 were prepared in the same manner as in example 1, except that the components were used in the kinds and blending amounts (parts by mass) shown in table 2.
[ Table 2]
[ Table 2]
Figure BDA0002933998740000221
< evaluation (1) >
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 compositions (CS-1) to (CS-4)), and the following items were evaluated by the methods described below. The evaluation results are shown in table 3.
[ sensitivity to radiation ]
On the glass substrate, Hexamethyldisilazane (HMDS) was coated using a spinner, and heated at 60 ℃ for 1 minute (HMDS treatment). The radiation-sensitive resin compositions prepared as described above were applied to the chromium film-forming glass substrate after the HMDS treatment using a spinner, and prebaked at 90 ℃ for 2 minutes to form a coating film having a thickness of 3.0 μm. Then, the exposure amount was changed by using an exposure machine ("PLA-501F" of Canon corporation: using an ultrahigh pressure mercury lamp), and the coating film was exposed through a mask having a line-to-space (10: 1) pattern of 60 μm. Thereafter, the resultant was developed by a liquid-coating method at 25 ℃ using a 2.38 mass% aqueous tetramethylammonium hydroxide solution. The development time was set to 80 seconds. Then, the chromium film-forming glass substrate after HMDS treatment was patterned by rinsing with ultrapure water for 1 minute with running water and then drying. The whole surface of the coating is subjected to 300J/m2And heating the chromium film-formed glass substrate in a clean oven at 230 ℃ for 30 minutes to obtain an interlayer insulating film. The exposure amount required for complete dissolution of the 6 μm space pattern upon development was investigated. The smaller the exposure amount, the better the radiation sensitivity.
(evaluation criteria)
AA: less than 200J/m2
A: less than 300J/m2
A-：300J/m2Above and below 400J/m2
B：200J/m2Above and below 400J/m2
C：400J/m2Above and below 800J/m2
D：800J/m2The above
[ Pattern shape ]
The cross-sectional shape of the interlayer insulating film pattern distinguishable by the optimum exposure amount was observed with a scanning electron microscope. At the end point where the interlayer insulating film pattern and the substrate are in contact with each other, a tangent is drawn to the interlayer insulating film pattern, and the angle formed by the tangent and the substrate surface is calculated. The higher the angle, the more evaluated is that the pattern shape is maintained well even after heating at 230 ℃.
(evaluation criteria)
AA: over 60 degrees
A: 50 DEG or more and less than 60 DEG
B: 40 DEG or more and less than 50 DEG
C: more than 30 degrees and less than 40 degrees
D: less than 30 °
[ gas escape characteristics ]
After the radiation-sensitive resin composition was coated on a silicon substrate using a spinner, it was prebaked on a hot plate at 90 ℃ for 2 minutes to form a coating film having an average thickness of 3.0 μm. Further, the resultant was calcined in an oven heated to 230 ℃ for 30 minutes to form a cured film. Then, the silicon substrate was cut into a size of 1cm × 5cm, and baked at 230 ℃ for 15 minutes using a P & T-GCMS apparatus including JTD-505 manufactured by japan analytical industry (stock) and GC-QP-2010 manufactured by shimadzu corporation (stock), thereby obtaining a chromatogram (chromatogram). The amount of outgassing was calculated from the following equation (1) using the peak area of C18 in the chromatogram measured using the cured film and the peak area of the chromatogram of the standard sample C18 measured separately using the same apparatus. In the following expression (1), the introduced amount of the standard sample is the introduced amount of the standard sample introduced into the apparatus when obtaining the chromatogram of the standard sample C18.
Amount of outgas (. mu.g) (peak area of chromatogram of cured film/peak area of standard sample) × amount of introduced standard sample (. mu.g) … (1)
As evaluation criteria, the case where the amount of outgas was less than 5. mu.g was referred to as "A", the case where the amount was 5. mu.g or more and less than 10. mu.g was referred to as "B", the case where the amount was 10. mu.g or more and less than 50. mu.g was referred to as "C", and the case where the amount was 50. mu.g or more was referred to as "D".
[ resistance to foaming ]
A liquid crystal display element was produced in the following procedure, and using the produced liquid crystal display element, an impact was applied in a high temperature (80 ℃) state, and the presence or absence of foaming in the pixel was confirmed. The impact on the liquid crystal display element is given by dropping a bullet ball (pachinko ball) 30cm from above the liquid crystal display element. The marble used was a steel marble having a weight of 5.5g and a diameter of 11 mm. By applying the impact, a case where no bubble is generated at all in the pixel of the liquid crystal display element is evaluated as "a", a case where a slight bubble is generated is evaluated as "B", a case where a bubble is generated but the density of the bubble is small is evaluated as "C", and a case where a bubble is generated and the density of the bubble is large is evaluated as "D".
(production of liquid Crystal display element)
An active matrix type Vertical Alignment (VA) mode color liquid crystal display element having the same structure as the liquid crystal display element 10 of fig. 1 was manufactured.
First, a TFT having a semiconductor layer and an electrode layer made of p-Si, a wiring, and an inorganic insulating film made of SiN are disposed on an insulating glass substrate made of alkali-free glass according to a known method, and an array substrate having the TFT is prepared. The TFT is formed by repeating a normal semiconductor layer formation, a known insulating layer formation, etching by photolithography, and the like in accordance with a known method.
Then, the prepared radiation-sensitive resin composition was coated on an array substrate using a slit die coater. Then, the film was prebaked on a hot plate at 90 ℃ for 2 minutes to evaporate the organic solvent, thereby forming a coating film. Subsequently, UV (ultraviolet) light was irradiated through a pattern mask using a UV exposure machine ("PLA-501F" by Canon corporation: using an ultra-high pressure mercury lamp. The irradiation is performed with the exposure amount determined in the evaluation of the radiation sensitivity. Thereafter, a development treatment was performed at 25 ℃ for 80 seconds by a liquid coating method using a tetramethylammonium hydroxide aqueous solution (developer) having a concentration of 2.38 mass%. After the development treatmentThe coating film was washed with ultrapure water for 1 minute with running water and dried. Then, the whole surface of the coating film was subjected to 300J/m2And heating the substrate in a clean oven at 230 ℃ for 30 minutes to obtain an interlayer insulating film. A contact hole is formed in an interlayer insulating film on a substrate by patterning. Then, a film containing ITO is formed on the interlayer insulating film by a sputtering method, and a pixel electrode is formed by patterning by a photolithography method. The formed pixel electrode is connected to the TFT through the contact hole.
Next, a color filter substrate was prepared, and a liquid crystal alignment agent (product name: JALS2095-S2, manufactured by JSR) was applied to the electrode arrangement surfaces of the array substrate and the color filter substrate using a spinner, followed by heating at 80 ℃ for 1 minute and then at 180 ℃ for 1 hour to form an alignment film having a film thickness of 60 nm. As the color filter substrate, a substrate in which color filters of 3 colors (red, green, and blue) and a black matrix are arranged in a lattice shape on a transparent glass substrate, and a planarization film and a common electrode are formed on the color filters is used. As the common electrode, a transparent electrode containing ITO was used.
Next, after applying an ultraviolet-curable sealing material to the outer peripheral edge portion of one of the array substrate and the color filter substrate, a polymerizable liquid crystal composition is dropped inside the sealing material using a dispenser. As the polymerizable liquid crystal composition, a composition prepared by adding a polymerizable component exhibiting photopolymerization to a nematic liquid crystal having negative dielectric anisotropy is used. Thereafter, the array substrate and the color filter substrate are bonded in vacuum, the light source is moved along the coating region of the sealing material, and the sealing material is irradiated with UV light to cure the sealing material. Thereby, a layer of the polymerizable liquid crystal composition is formed between the array substrate and the color filter substrate.
Next, in a state where a voltage for turning on the TFTs of the array substrate is applied to the gate electrodes of the TFTs, an alternating voltage is applied between the source electrodes of the TFTs and the common electrode on the color filter substrate, and the liquid crystals in the layer of the polymerizable liquid crystal composition are aligned in an inclined manner. Then, a layer of the polymerizable liquid crystal composition is irradiated with ultraviolet light from the array substrate side while maintaining the state in which the liquid crystal is aligned in an inclined manner, using an ultrahigh pressure mercury lamp, to form a liquid crystal layer in which the liquid crystal is aligned substantially vertically with a pretilt angle in a predetermined direction. In this manner, a VA-mode color liquid crystal display device was manufactured.
[ Table 3]
[ Table 3]
Figure BDA0002933998740000261
As shown in table 3, the radiation-sensitive resin compositions of examples 1 to 31 exhibited good radiation sensitivity, and the cured films obtained were excellent in pattern shape, outgassing characteristics, and foaming resistance. On the other hand, the radiation sensitivity, pattern shape, outgassing characteristics, and foaming resistance of the radiation-sensitive resin compositions of comparative examples 1 to 4 were inferior to those of examples.
< Synthesis of Polymer (2) >)
Synthesis examples 32 to 42 Synthesis of polymers (A-32) to (A-42)
A polymer solution containing polymers (A-32) to (A-42) having the same levels of solid content concentration, molecular weight, and molecular weight distribution as polymer (A-1) was obtained in the same manner as in Synthesis example 1, except that the components were used in the same types and amounts (parts by mass) as those shown in Table 4. Table 4 also shows the monomer compositions of synthesis example 1, synthesis example 6, synthesis example 11, synthesis example 14, and synthesis example 20, and comparative synthesis example 1.
Figure BDA0002933998740000281
Preparation of < radiation-sensitive resin composition (2) >
The synthesized polymer was used to prepare a radiation-sensitive resin composition having the composition shown in table 5. The polymer and acid generator used for the preparation of the radiation-sensitive resin composition are shown below.
Polymers
A-1, A-6, A-11, A-14, A-20, A-32 to A-42: synthesis examples 1, 6, 11, 14, 20, 32 to 42, Polymer (A-1), Polymer (A-6), Polymer (A-11), Polymer (A-14), Polymer (A-20), Polymer (A-32) to Polymer (A-42)
CA-1: comparative Polymer synthesized in Synthesis example 1 (CA-1)
Acid generator
B-1: condensate of 4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol (1.0 mol) and 1, 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)
[ Table 5]
[ Table 5]
Figure BDA0002933998740000291
< evaluation (2) >
A cured film was formed using the radiation-sensitive resin compositions (composition (S-1), composition (S-6), composition (S-11), composition (S-14), composition (S-20), compositions (S-32) to (S-42), and composition (CS-1)) of example 1, example 6, example 11, example 14, example 20, examples 32 to 42, and comparative example 1, and the radiation sensitivity, pattern shape, outgassing characteristics, and foaming resistance were evaluated in the same manner as in the above evaluation (1). Further, the prebaking temperature dependency was evaluated by the method described below. The evaluation results are shown in table 6.
< Pre-baking temperature dependency >
In the evaluation of the radiation sensitivity, a pattern was formed on a glass substrate under the same conditions except that the prebaking temperature was changed from 90 ℃ to 100 ℃, and the exposure amount required for complete dissolution of a 6 μm space pattern in development was examined. The exposure amount was fixed, the prebaking temperature was set to 90 ℃, the pattern was formed under the same conditions, and the difference between the line width when the prebaking temperature was set to 100 ℃ and the line width when the prebaking temperature was set to 90 ℃ was determined. The smaller the difference in line width, the better the prebaking temperature dependence.
(evaluation criteria)
A: less than 0.5 μm
B: 0.5 μm or more and less than 1.0 μm
C: 1.0 μm or more and less than 2.0 μm
D: 2.0 μm or more
[ Table 6]
[ Table 6]
Figure BDA0002933998740000301
As shown in table 6, the radiation-sensitive resin compositions of examples 1, 6, 11, 14, 20, and 32 to 42 exhibited good radiation sensitivity, and the cured films obtained therefrom were excellent in pattern shape, outgassing property, and foaming resistance. In addition, the radiation-sensitive resin compositions of examples 1, 6, 11, 14, 20, and 32 to 42 exhibited less variation in pattern formability due to the difference in the pre-baking temperature, and were better than those of comparative example 1. In particular, the radiation-sensitive resin compositions of examples 32 to 42, in which the polymer component includes a structural unit having a hydroxyl group (sixth structural unit), are particularly excellent in the evaluation that the pre-baking temperature dependency is a or B.

Claims (18)

1. A method of manufacturing a liquid crystal display element includes: a forming step of forming an interlayer insulating film on a substrate; and
an irradiation step of irradiating an object including the interlayer insulating film with light after the interlayer insulating film is formed, in the method for manufacturing a liquid crystal display element,
the interlayer insulating film is formed using a radiation-sensitive composition containing the following component (A), component (B) and component (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 with a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less, a second structural unit having an acid group, and a third structural unit having a cyclic ether group with a ring number of 3 or 4;
(B) a quinone diazide compound;
(C) a solvent.
2. The method for manufacturing a liquid crystal display element 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 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),
Figure FDA0002933998730000011
in the formulae (a-1) to (a-6), R10Is an alkyl group having 1 to 5 carbon atoms or 2R's present on the same carbon10Combined with each other to said 2R10A ring structure formed by the bonded carbon atoms; r11An alkyl group having 1 to 5 carbon atoms; r12Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m is an integer of 0 to 2, and n is an integer of 1 to 3; r is an integer of 1-3; "" indicates a bond.
4. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the heterocyclic structure is a dioxolane structure.
5. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the component (a) further comprises a structural unit derived from at least one monomer selected from the group consisting of an aromatic vinyl compound and an N-substituted maleimide compound.
6. 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.
7. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the third structural unit is a structural unit having at least one selected from the group consisting of an oxetane structure and an oxetane structure.
8. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the component (a) is contained with respect to all structural units constituting the polymer component
8 to 60 mass% of the first structural unit,
0.5 mass% or more and less than 20 mass% of the second structural unit, wherein 10 mass% or more and 60 mass% or less of the third structural unit is excluded from structural units having a phenolic hydroxyl group.
9. The method for manufacturing a liquid crystal display element according to claim 1 or 2, further comprising: a step of forming a liquid crystal cell by disposing a pair of substrates including the substrate having the interlayer insulating film so as to face each other with a layer containing a polymerizable liquid crystal composition interposed therebetween, and
the irradiation step is a step of irradiating the liquid crystal cell with light in a state where a voltage is applied to a layer containing the polymerizable liquid crystal composition.
10. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the component (B) is a condensate of a phenolic compound or an alcoholic compound and 1, 2-naphthoquinone diazide sulfonyl halide.
11. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the component (C) contains at least one selected from the group consisting of ethers and esters.
12. A radiation-sensitive composition comprising: (A) a polymer component,
(B) Quinone diazide compound, and
(C) a solvent, a solvent and a solvent, wherein the solvent is a solvent,
the component (A) comprises: a first structural unit derived from an acrylate compound having a heterocyclic structure with a ring number of 5 or more, a second structural unit having an acid group, and a third structural unit having a cyclic ether group with a ring number of 3 or 4,
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.
13. The radiation-sensitive composition of claim 12, wherein the heterocyclic structure is a dioxolane structure.
14. A radiation-sensitive composition comprising: (A) a polymer component,
(B) Quinone diazide compound, and
(C) a solvent, a solvent and a solvent, wherein the solvent is a solvent,
the component (A) contains, relative to all structural units constituting the polymer component, 8 to 60 mass% of a first structural unit, 0.5 to less than 20 mass% of a second structural unit, excluding a structural unit having a phenolic hydroxyl group, and 10 to 60 mass% of a third structural unit, the first structural unit being derived from at least one selected from the group consisting of an acrylate compound having a heterocyclic structure with a ring number of 5 or more and an acrylate compound having an alkyl group with a carbon number of 3 or less, the second structural unit having an acid group, and the third structural unit having a cyclic ether group with a ring number of 3 or 4.
15. The radiation-sensitive composition according to any one of claims 12 to 14, which is used for forming an interlayer insulating film.
16. A method of manufacturing an interlayer insulating film, comprising: a step of forming a coating film using the radiation-sensitive composition according to any one of claims 12 to 15;
irradiating at least a part of the coating film with radiation;
a step of developing the coating film after irradiation with radiation; and
and heating the developed coating film.
17. An interlayer insulating film formed using the radiation-sensitive composition according to any one of claims 12 to 15.
18. A liquid crystal display element having the interlayer insulating film according to claim 17.
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