JP2016014849A - Radiation-sensitive resin composition, insulating film, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition to be used for forming an insulating film with controllable dielectric characteristics, and an insulating film and liquid crystal display element using the composition.SOLUTION: The radiation-sensitive resin composition comprises [A] a polymer, [B] a photosensitive agent, and [C] a compound comprising titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium and lead, in which the [C] compound has a particle diameter of 0.01 μm to 0.1 μm and a c/a axial ratio of 1.0025 to 1.010. An array substrate 1 is manufactured by using a substrate 4 on which an active element 8 and an organic insulating film 12 are fabricated, and by forming a common electrode 14 on the organic insulating film 12, forming an insulating film 33 by using the radiation-sensitive resin composition, and then arranging a pixel electrode 9 thereon. A liquid crystal display element is constituted by using the array substrate 1.

Description

  The present invention relates to a radiation-sensitive resin composition, an insulating film, and a display element.

  In recent years, a display element using liquid crystal, that is, a liquid crystal display element has been actively developed because of advantages such as reduction in thickness and weight as compared with a conventional CRT display device.

  The liquid crystal display element has a structure in which liquid crystal is sandwiched between a pair of substrates. An alignment film can be provided on the surface of these substrates for the purpose of controlling the alignment of the liquid crystal. In addition, the pair of substrates is sandwiched between, for example, a pair of deflecting plates. When an electric field is applied between the substrates, the orientation of the liquid crystal changes, and light is partially transmitted or shielded. A liquid crystal display element can display an image using such characteristics and provide a thin and lightweight display element.

  With the development of an active matrix system in which an active element for switching is arranged for each pixel, a liquid crystal display element can realize a good image quality with excellent contrast ratio and response performance. Furthermore, the liquid crystal display element has also overcome problems such as high definition, colorization, and widening of the viewing angle, and has recently been used as a display element for portable electronic devices such as smartphones and large and thin display elements for televisions. Has reached.

  In liquid crystal display elements, various liquid crystal modes having different initial alignment states and different alignment changing operations are known. For example, TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Planes Switching), FFS (Fringe Field Switching), VA (Vertical Alignment), OCB (Optic) Yes.

  Among the liquid crystal modes, the IPS mode and the FFS mode, which is an example of the IPS mode, are liquid crystal modes that have attracted particular attention in recent years because they have a wide viewing angle, a fast response speed, and a high contrast ratio. In the present invention, the IPS mode refers to a liquid crystal mode in which the liquid crystal performs a switching (alignment change) operation in the plane of the substrate sandwiching it. Therefore, unless otherwise distinguished, the concept includes a IPS mode in a narrow sense called a so-called lateral electric field method and an FFS mode in which liquid crystal is switched in the plane of the substrate using an oblique electric field (fringe electric field).

  In a liquid crystal display element of an IPS mode including the FFS mode (hereinafter sometimes simply referred to as “IPS mode”), the liquid crystal sandwiched between a pair of substrates is substantially parallel to the substrate. The initial orientation state is controlled. By applying a voltage between the pixel electrode and the common electrode arranged on one of these substrates, an electric field mainly composed of components parallel to the substrate plane (so-called lateral electric field or oblique electric field (fringe electric field)). And the alignment state of the liquid crystal having dielectric anisotropy changes. Therefore, in the IPS mode, the change in the orientation of the liquid crystal due to voltage application is mainly the rotation of the liquid crystal molecules in a plane parallel to the substrate plane, as the name suggests.

  For this reason, the IPS mode is different from the liquid crystal mode in which the liquid crystal aligned in parallel such as the TN mode operates by applying voltage, and the change in the tilt angle of the liquid crystal relative to the substrate holding the liquid crystal is small. For this reason, in the IPS mode liquid crystal display element, the change in the effective value of retardation accompanying voltage application is reduced, and a high-quality image display with a wide viewing angle is possible.

  In the IPS mode liquid crystal display element as described above, an inorganic insulating film made of an inorganic material is laminated on a transparent solid electrode (for example, a common electrode), and a comb-shaped electrode (for example, a pixel electrode) is formed thereon. ) Are being developed (see, for example, Patent Document 1 or Patent Document 2). According to this structure, the aperture ratio of the pixel is improved and an image display with high luminance is realized.

JP 2011-48394 A JP 2011-59314 A

  With regard to IPS mode liquid crystal display elements, in recent years, there has been a demand for higher image quality, particularly higher definition, in order to cope with higher resolution and higher image quality of display elements of portable electronic devices such as televisions and smartphones. Yes.

  In an IPS mode liquid crystal display element, an active element for switching such as a thin film transistor (TFT) is disposed on one of a pair of substrates sandwiching liquid crystal. A pixel electrode, a common electrode, wirings connected to the pixel electrode, and the like are also arranged to constitute an array substrate. For this reason, in the IPS mode liquid crystal display element, the number of constituent members disposed on the array substrate increases, and the electrode structure and wiring layout structure on the array substrate are more complicated than those of other liquid crystal modes such as the TN mode. It will be something. For this reason, there is a concern that the area of the pixel electrode in the pixel is reduced and the aperture ratio of the pixel is lowered to lower the luminance of the display in order to further increase the definition.

  In Patent Document 2, a pixel electrode having a portion formed in a comb-like shape on a solid common electrode through an interlayer insulating film made of an inorganic material (hereinafter also referred to as “inorganic interlayer insulating film”). An array substrate on which (hereinafter also referred to as “comb-like pixel electrodes”) is disposed is disclosed. Patent Document 2 discloses a technique in which an insulating film made of an organic material (hereinafter, simply referred to as “organic insulating film”) is provided between a solid common electrode and an underlying wiring. Has been. By providing this organic insulating film, an increase in the aperture ratio can be expected while suppressing an increase in coupling capacitance between the pixel electrode and the wiring.

  In that case, in the conventional IPS mode liquid crystal display element described in Patent Document 2, a dense common electrode and a comb-like pixel electrode are provided to ensure insulation between them. An inorganic interlayer insulating film made of SiN (silicon nitride) is provided. The inorganic interlayer insulating film made of SiN is usually formed by CVD (Chemical Vapor Deposition).

  Therefore, in the conventional IPS mode liquid crystal display element, it is necessary to provide a CVD process when forming the inorganic interlayer insulating film between the common electrode and the comb-like pixel electrode, and the manufacturing apparatus is large-scale. It was. In order to improve productivity, if an attempt is made to use a large substrate, an increasingly large manufacturing apparatus is required. For this reason, in the conventional IPS mode liquid crystal display element, the formation of the inorganic interlayer insulating film is one of the restrictions for improving the productivity, and also increases the cost.

  Therefore, in the IPS mode liquid crystal display element, a technique for easily forming an interlayer insulating film disposed between the common electrode and the comb-like pixel electrode is required. That is, there is a need for an insulating film that can be easily formed on a large substrate without requiring a large-scale manufacturing apparatus for CVD or the like. The insulating film preferably has excellent patternability, light transmission characteristics, and insulating properties, and preferably has the same dielectric characteristics and refractive index characteristics as those of conventional interlayer insulating films. In particular, it is preferable to provide similar dielectric characteristics so that it can be easily combined with an inorganic interlayer insulating film made of SiN in combination with a conventional TFT.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a radiation sensitive resin composition used for forming an insulating film capable of controlling dielectric characteristics.

  Another object of the present invention is to provide an insulating film that can be easily formed and whose dielectric characteristics can be controlled.

  Another object of the present invention is to provide a display element including an insulating film that can be easily formed and whose dielectric characteristics can be controlled.

The first aspect of the present invention is:
[A] polymer,
[B] a photosensitive agent, and [C] a radiation-sensitive resin composition comprising a compound containing titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium, and lead. Because
[C] The compound has a particle diameter of 0.01 μm or more and 0.1 μm or less, that is, a range of 0.01 μm to 0.1 μm, and a c / a axial ratio of 1.0025 to 1.010. The present invention relates to a radiation sensitive resin composition.

  1st aspect of this invention WHEREIN: It is preferable that a [A] polymer is a polymer containing the structural unit which has a carboxyl group.

  In the first aspect of the present invention, it is preferable that [B] the photosensitizer contains at least one selected from a photoradical polymerization initiator and a photoacid generator.

  In the first embodiment of the present invention, the [C] compound is preferably barium titanate.

  In the first embodiment of the present invention, it further comprises [D] a polymer having at least one of a urethane bond and an amide bond, and a (meth) acrylate compound having at least one of a urethane bond and an amide bond. It is preferable to include at least one selected from the group.

  In the first aspect of the present invention, it is preferably used for forming an insulating film of a display element.

  A second aspect of the present invention relates to an insulating film formed using the radiation-sensitive resin composition of the first aspect of the present invention.

  A third aspect of the present invention relates to a display element including an insulating film formed from the radiation-sensitive resin composition of the first aspect of the present invention.

  According to the first aspect of the present invention, it is possible to obtain a radiation-sensitive resin composition capable of easily forming an insulating film capable of controlling dielectric characteristics.

  According to the second aspect of the present invention, it is possible to obtain an insulating film which can be easily formed and whose dielectric characteristics can be controlled.

  According to the third aspect of the present invention, a display element including an insulating film that can be easily formed and whose dielectric characteristics can be controlled is obtained.

It is a top view which shows typically the principal part structure of the pixel part of the array substrate of embodiment of this invention. It is a figure which shows typically the cross-sectional structure along the A-A 'line | wire of FIG. It is typical sectional drawing of the liquid crystal display element of embodiment of this invention.

  The conventional liquid crystal display element described in Patent Document 2 and the like described above is an FFS mode liquid crystal display element in the IPS mode, and includes a solid common electrode and a comb-like pixel electrode provided on the upper layer. Have Between them, an inorganic interlayer insulating film made of SiN is provided. Since the formation of the inorganic interlayer insulating film made of SiN is performed by a film forming method such as CVD, a large-scale manufacturing apparatus is required.

  In order to replace the inorganic interlayer insulating film made of SiN and realize an interlayer insulating film that can be formed by a simple method, it is preferable to apply a coating type insulating film made of an organic material. If this coating type organic insulating film can be used to replace a conventional inorganic interlayer insulating film, a simple interlayer insulating film can be formed in an IPS mode liquid crystal display element including an FFS mode. Furthermore, it becomes easy to apply a large substrate, and the productivity of an array substrate for forming a liquid crystal display element and a liquid crystal display element using the same can be improved.

  Therefore, although an alternative to an inorganic interlayer insulating film by a coating type insulating film made of an organic material is studied, in order to realize this, the insulating film is required to have patterning properties, light transmittance, and insulating properties. Therefore, it is preferable that the insulating film can be formed using a liquid resin composition that can be patterned and using a coating method or the like.

  Furthermore, the insulating film made of an organic material that can replace the inorganic interlayer insulating film preferably has the same dielectric characteristics and refractive index characteristics as the conventional interlayer insulating film. In particular, it is preferable that the insulating film can be used in the same manner as an inorganic interlayer insulating film made of SiN in combination with a TFT which is a conventionally used active element for switching. Therefore, the insulating film is preferably controllable so that the capacitance C is equal to or higher than that of the inorganic interlayer insulating film made of SiN.

At this time, the electrostatic capacity C of a member such as an interlayer insulating film, which is considered in combination with the TFT, can be expressed by C = ε × (S / d). Here, ε is a dielectric constant of a member constituting the interlayer insulating film or the like. S is the area of the member, and in the case of an interlayer insulating film, it can be the electrode area. d is the thickness of the member, and in the case of an interlayer insulating film, it is the film thickness. Ε is expressed by ε = ε ₀ × k. At this time, ε ₀ is a dielectric constant in a vacuum and is a constant. k is a relative dielectric constant of the member, and is a value specific to the member.

  The relative dielectric constant k of SiN is 6-7, and has a larger value than the relative dielectric constant of a resin such as an ethylene resin or an acrylic resin of 2-4, that is, 2-4. Therefore, when an insulating film is to be formed using a resin composition, it is necessary to control to increase the relative dielectric constant of the constituent components so that the capacitance is equal to or higher than that of the inorganic interlayer insulating film made of SiN. . At the same time, it is required to maintain insulating properties and realize good patterning properties.

  Therefore, the present inventor can apply a technique for increasing the relative dielectric constant of the constituent components to control the dielectric constant to a desired value, for example, an organic material that can be controlled to be similar to an interlayer insulating film made of SiN. An insulating film made of material was developed.

  In addition, the insulating film of the present invention can have a higher refractive index than an organic film using a conventional organic material, and can have a refractive index similar to that of a conventional inorganic interlayer insulating film made of SiN. . Since the interlayer insulating film used for forming the array substrate of the present invention has such a refractive index characteristic, in the liquid crystal display element of the present invention using the interlayer insulating film, the electrodes are conspicuous on the screen. Can be reduced.

  The insulating film of the present invention can be easily formed by coating using a radiation-sensitive resin composition, and can be patterned as desired for the configuration of the liquid crystal display element.

  As a result, the insulating film of the present invention can replace the conventional inorganic interlayer insulating film made of SiN, and the active element, the common electrode, the pixel electrode, and the book disposed between the common electrode and the pixel electrode. An array substrate having the insulating film of the invention can be provided. Then, the display element of the present invention using the array substrate can be provided.

Hereinafter, the radiation-sensitive resin composition of the present invention that forms an insulating film of the present invention that can replace the conventional inorganic interlayer insulating film, a liquid crystal display element that is an example of a display element including the insulating film of the present invention, and The formation of the insulating film of the present invention will be described.
In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the embodiment of the present invention used for the production of the insulating film of the embodiment of the present invention is a resin composition having radiation sensitivity. The radiation-sensitive resin composition of the present embodiment can have either a positive-type radiation sensitivity or a negative-type radiation sensitivity.

  The radiation-sensitive resin composition of the present embodiment includes a [A] polymer that is the [A] component, a [B] photosensitive agent that is the [B] component, and a [C] titanium oxide that is the [C] component. And a compound containing at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium and lead (hereinafter sometimes simply referred to as [C] compound) as an essential component. To do.

  And when the radiation sensitive resin composition of this embodiment is a positive type radiation sensitive resin composition, [B] a photosensitive agent is a photo-acid generator or contains a photo-acid generator. Is preferred. Moreover, when the radiation sensitive resin composition of this embodiment is a negative radiation sensitive resin composition, [B] a photosensitizer is a radical photopolymerization initiator or contains radical photopolymerization initiator It is preferable to do.

  Furthermore, the radiation-sensitive resin composition of the present embodiment includes a [D] urethane bond and an amide bond, which are [D] components, in order to control the dielectric properties of the insulating film of the embodiment of the present invention obtained. It includes at least one selected from the group consisting of a polymer having at least one and a (meth) acrylate compound having at least one of a urethane bond and an amide bond (hereinafter sometimes simply referred to as [D] compound). It is preferable.

  Moreover, unless the radiation sensitive resin composition of this embodiment impairs the effect of this invention, you may contain another arbitrary component.

  Hereinafter, each component contained in the radiation sensitive resin composition of this embodiment is demonstrated in detail.

<[A] polymer>
In the radiation sensitive resin composition of the present embodiment, the [A] polymer as the component [A] is an insulating film of the embodiment of the present invention formed using the radiation sensitive resin composition of the present embodiment. It is a component used as a base material.

  And it is preferable that the [A] polymer is alkali-soluble resin so that the radiation sensitive resin composition of this embodiment may be provided with the desired patterning property. In that case, the [A] polymer is not particularly limited as long as it is a polymer having alkali developability. However, the polymer corresponding to the above-mentioned [D] compound is excluded.

  As a preferable [A] polymer, the polymer containing the structural unit which has a carboxyl group can be mentioned.

  And [A] polymer is polymerization of unsaturated double bonds or epoxy groups so that the insulating film of the embodiment of the present invention can be formed as a cured film using the radiation sensitive resin composition of the present embodiment. Those containing a structural unit having a sex group are more desirable. Therefore, as the [A] polymer, a polymer containing a structural unit having a carboxyl group and further containing a structural unit having a polymerizable group is more preferable.

  In this case, in the [A] polymer, the preferred structural unit having a polymerizable group is at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. (Hereinafter, the specific structural unit may be referred to.) [A] When the polymer contains the specific structural unit, a cured film having excellent surface curability and deep part curability, that is, the insulating film of the embodiment of the present invention can be formed.

  The structural unit having the (meth) acryloyloxy group is, for example, a method of reacting an epoxy group in a copolymer with (meth) acrylic acid, a (meth) acryl having an epoxy group in a carboxyl group in the copolymer By a method of reacting an acid ester, a method of reacting a (meth) acrylic acid ester having an isocyanate group with a hydroxyl group in the copolymer, a method of reacting (meth) acrylic acid at an acid anhydride site in the copolymer, etc. Can be formed. Among these, a method of reacting a carboxyl group in the copolymer with a (meth) acrylic ester having an epoxy group is preferable.

  The [A] polymer containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group is at least selected from the group consisting of (A1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. One type (hereinafter also referred to as “(A1) compound”) and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”) can be copolymerized and synthesized. . In this case, the [A] polymer includes a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound. It becomes a copolymer containing.

  [A] The polymer is obtained by, for example, copolymerizing a compound (A1) that provides a carboxyl group-containing structural unit and a compound (A2) that provides an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. When the radiation-sensitive resin composition of this embodiment is a positive type, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) is further included. In addition, it can be a copolymer. Further, in the production of the [A] polymer, the compound (A4) (derived from the compounds (A1), (A2) and (A3)) together with the compound (A1), the compound (A2) and the compound (A3). An unsaturated compound that gives a structural unit other than the structural unit) may be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) Compound]
Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

  Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like. It is done.

  Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.

  These (A1) compounds may be used alone or in combination of two or more.

  The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-25 mass% are more preferable. (A1) By making the usage-amount of a compound into 5 mass%-30 mass%, while optimizing the solubility with respect to the aqueous alkali solution of [A] alkali-soluble resin, the insulating film excellent in radiation sensitivity is obtained.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. Epoxy heptyl, methacrylic acid 6,7-epoxy heptyl, α-ethylacrylic acid-6,7-epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and the like are preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the insulating film and the like.

As an unsaturated compound having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

  Of these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (A2) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-50 mass% are more preferable. (A2) By making the usage-amount of a compound into 5 mass%-60 mass%, the cured film which has the outstanding sclerosis | hardenability etc., ie, the insulating film of this Embodiment, can be formed.

[(A3) Compound]
Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

  Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.

  Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

  As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable.

  These (A3) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass based on the sum of the compound (A1), the compound (A2) and the compound (A3) (optional (A4) compound if necessary). 5 mass%-25 mass% are more preferable.

[(A4) Compound]
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. Examples of (A4) compounds include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

  Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate]. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.

  These (A4) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A4) used is preferably 10% by mass to 80% by mass based on the total of the compound (A1), the compound (A2) and the compound (A4) (and any (A3) compound).

<[A] Polymer Synthesis Method 1 Containing Structural Unit Having Carboxyl Group and Structural Unit Having Epoxy Group as Polymerizable Group>
[A] The polymer can be produced, for example, by copolymerizing the compound (A1) and the compound (A2) (arbitrary (A3) compound and (A4) compound) in the presence of a polymerization initiator in a solvent. . According to this synthesis method, a copolymer containing at least an epoxy group-containing structural unit can be synthesized.

  [A] Solvents used in the polymerization reaction for producing the polymer include, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol mono Examples include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.

  [A] As the polymerization initiator used in the polymerization reaction for producing the polymer, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile).

  [A] In the polymerization reaction for producing the polymer, a molecular weight modifier can be used for the purpose of adjusting the molecular weight.

  Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

[A] As for the weight average molecular weight (Mw) of a polymer, 1000-30000 are preferable and 5000-20000 are more preferable. [A] By making Mw of a polymer into the said range, the sensitivity with respect to the radiation and developability of the radiation sensitive resin composition of this embodiment can be improved. The polymer Mw and number average molecular weight (Mn) in this specification were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Polymer Synthesis Method 2 Containing Structural Unit Having Carboxyl Group and Structural Unit Having (Meth) acrylic Group as Polymerizable Group>
[A] The polymer may be, for example, a copolymer that can be synthesized by using one or more of the above-described (A1) compounds (hereinafter sometimes referred to as “specific copolymer”) and the above-mentioned (A2) compound. And can be synthesized. According to such a synthesis method, a copolymer containing at least a structural unit having a (meth) acryloyloxy group can be synthesized.

  [A] The structural unit having a (meth) acryloyloxy group contained in the polymer is obtained by reacting a carboxyl group in the copolymer with a (meth) acrylic acid ester having an epoxy group, and (meth) after the reaction. The structural unit having an acrylic group is represented by the following formula (1). This structural unit is obtained by reacting the carboxyl group in the specific copolymer derived from the compound (A1) with the epoxy group of the compound (A2) to form an ester bond.

In the above formula (1), R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group. c is an integer of 1-6. R ¹² is a divalent group represented by the following formula (2-1) or the following formula (2-2).

In the above formula (2-1), R ¹³ is a hydrogen atom or a methyl group. In the above formula (2-1) and the above formula (2-2), * represents a site bonded to an oxygen atom.

For the structural unit represented by the above formula (1), for example, when a compound having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate as the compound (A2), the above formula R ^{12 in} (1) is the above formula (2-1). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted as the compound (A2), R ¹² in the above formula (1) becomes the above formula (2-2).

In the synthesis of the specific copolymer, a compound other than the (A1) compound, for example, the above-described (A3) compound, (A4) compound, or the like may be used as a copolymerization component. These compounds include methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, tricyclomethacrylate [5.2.1.0 ^2,6 from the viewpoint of copolymerization reactivity. Decan-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, and 1,3-butadiene are preferred.

  Examples of the copolymerization method of the specific copolymer include a method of polymerizing the compound (A1) and, if necessary, the compound (A3) using a radical polymerization initiator in a solvent.

  Examples of the radical polymerization initiator include the same ones as exemplified in the above-mentioned item [A] polymer. The usage-amount of a radical polymerization initiator is 0.1 mass%-50 mass% with respect to 100 mass% of polymerizable unsaturated compounds, Preferably it is 0.1 mass%-20 mass%.

  The specific copolymer may be used for the production of the [A] polymer as it is in the polymerization reaction solution, or may be used for the production of the [A] polymer after the copolymer is once separated from the solution.

  The molecular weight distribution (Mw / Mn) of the specific copolymer is preferably 5.0 or less, and more preferably 3.0 or less. By making molecular weight distribution (Mw / Mn) 5.0 or less, the shape of the pattern obtained can be kept favorable. The insulating film containing the specific copolymer having the molecular weight distribution (Mw / Mn) in the specific range has a high developability. That is, a predetermined pattern can be easily formed without causing a development residue in the development process.

  The content of the structural unit derived from the (A1) compound of the specific copolymer is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, and particularly preferably 8% by mass to 40% by mass. .

  The content rate of the structural unit derived from compounds, such as (A3) compound other than (A1) compound of a specific copolymer, and (A4) compound, is 10 mass%-90 mass%, 20 mass%-80 mass%. .

  In the reaction of the specific copolymer with the compound (A2), an unsaturated compound having an epoxy group is preferably added to the copolymer solution containing a polymerization inhibitor in the presence of a suitable catalyst as necessary. And stirring for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 hours to 12 hours.

  The proportion of the compound (A2) used is preferably 5% by mass to 99% by mass and more preferably 10% by mass to 97% by mass with respect to the carboxyl group derived from the compound (A1) in the copolymer. (A2) By making the usage-amount of a compound into the said range, the reactivity with a copolymer, the sclerosis | hardenability of an insulating film, etc. improve more. (A2) A compound can be used individually or in mixture of 2 or more types.

<[B] Photosensitive agent>
[B] Photosensitizer contained in the radiation-sensitive resin composition of the embodiment of the present invention includes a compound capable of initiating polymerization by generating radicals in response to radiation (that is, [B-1] initiation of photoradical polymerization. Agent) or a compound that generates an acid in response to radiation (that is, [B-2] photoacid generator). The radiation sensitive resin composition of this embodiment can have radiation sensitivity by containing [B] a photosensitizer, for example, has positive radiation sensitivity or negative radiation sensitivity. Can do.

  Examples of the [B-1] photoradical polymerization initiator of the radiation-sensitive resin composition of the present embodiment include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds may be used alone or in combination of two or more.

  Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -octane-1-one oxime- O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  As the acetophenone compound, an α-aminoketone compound is preferable, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are preferred.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, of which 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Biimidazole is more preferred.

  [B-1] The radical photopolymerization initiator can be used alone or in admixture of two or more as described above. [B-1] The content ratio of the radical photopolymerization initiator is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the component [A]. [B-1] By setting the use ratio of the photo radical polymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition has a high solvent resistance, a high hardness and a low exposure amount. A cured film having high adhesion can be formed. As a result, the insulating film according to the embodiment of the present invention having excellent characteristics can be provided.

  Next, as [B-2] photoacid generator which is [B] photosensitizer of the radiation sensitive resin composition of this embodiment, for example, an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, Examples include diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinonediazide compounds. These [B-2] photoacid generators may be used alone or in combination of two or more.

  As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (3) is preferable.

In the above formula (3), R ^a is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

The alkyl group represented by R ^a in the above formula (3) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- Examples thereof include alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptylfluoropropyl group, and the like.

As an alicyclic hydrocarbon group represented by said Ra, ^a C4-C12 alicyclic hydrocarbon group is preferable. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ^a is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-yl). Ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2- Examples include ylidene)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like, which are commercially available.

  Examples of the onium salt described above include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and benzylsulfonium salt.

As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Phosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferred.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl Reimido, 4-methylphenyl-sulfonyloxy) diphenyl maleimide, and the like.

  Preferable examples of the sulfonic acid ester compound include haloalkylsulfonic acid esters, and more preferable examples include N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester.

  Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide or 1,2-naphthoquinonediazidesulfonic acid amide. Can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei other than the mother nucleus.

As a specific example of the above mother nucleus, for example,
As trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc .;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
As pentahydroxybenzophenone, 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
As hexahydroxybenzophenone, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone, etc .;
As (polyhydroxyphenyl) alkane, 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, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4- Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4 -Hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6 , 7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
Can be mentioned.

  Examples of the other mother nucleus include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1 -(4-Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl } -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these, as the mother nucleus, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [ 1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  The 1,2-naphthoquinone diazide sulfonic acid halide described above is preferably 1,2-naphthoquinone diazide sulfonic acid chloride, and 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5- Sulfonic acid chloride is more preferable, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferable.

  As the 1,2-naphthoquinone diazide sulfonic acid amide described above, 2,3,4-triaminobenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide is preferable.

  In the condensation reaction of the above-described phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinone diazide sulfonic acid halide corresponding to a range of from% to 85% by mole, more preferably from 50% to 70% by mole, can be used. In addition, the said condensation reaction can be implemented by a well-known method.

  As the above [B-2] photoacid generator, an oxime sulfonate compound, an onium salt, a sulfonimide compound, and a quinonediazide compound are preferable, and an oxime sulfonate compound and a quinonediazide compound are more preferable. [B-2] By using the above-described compound as the photoacid generator, the radiation-sensitive resin composition of the present embodiment containing the compound can improve sensitivity and solubility.

  [B-2] The content of the photoacid generator is preferably 0.1 part by mass to 50 parts by mass and more preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the component [A]. [B-2] By setting the content of the photoacid generator within the above range, the sensitivity of the radiation-sensitive resin composition of the present embodiment can be optimized, and a cured film having a high surface hardness can be formed. In addition, an insulating film according to an embodiment of the present invention can be provided.

<[C] Compound containing titanium oxide and metal element>
[C] component of the radiation sensitive resin composition of embodiment of this invention contains a titanium oxide and at least 1 sort (s) of metal element chosen from the group which consists of barium, strontium, calcium, magnesium, zirconium, and lead. Compound (hereinafter sometimes referred to simply as [C] compound). In the radiation sensitive resin composition of the embodiment of the present invention, the component [C] is a component that enables control to improve the dielectric constant and refractive index of the insulating film of the embodiment of the present invention to be formed.

  Examples of the above-mentioned [C] compound include barium titanate, strontium titanate, calcium titanate, magnesium titanate, zirconium titanate and lead titanate.

  These [C] compounds may be used individually by 1 type, or can also be used in combination of 2 or more type.

  [C] The shape of the compound is not particularly limited, and may be spherical or amorphous, and may be hollow particles, porous particles, core-shell type particles, or the like.

  Moreover, the particle diameter of a [C] compound can be calculated | required with the dynamic light-scattering method, and it is preferable that it is the range of 0.01 micrometer-0.1 micrometer. When the particle diameter of the compound [C] is in the above range, the desired patterning performance can be realized in the radiation-sensitive resin composition of the present embodiment. Further, if the particle size of the [C] compound is less than 0.01 μm, the particles are likely to aggregate and storage stability may be lowered. If it exceeds 0.1 μm, the haze of the insulating film as a cured film increases. There is a fear.

  In the [C] compound, the c / a axis ratio, which is the ratio of the c-axis length to the a-axis length of the crystal lattice, is preferably 1.0025 to 1.010. When the c / a axial ratio is in the range of 1.0025 to 1.010, both the particle diameter in the above range and excellent dielectric constant characteristics (high relative dielectric constant) can be realized.

And as a more preferable [C] compound of the radiation sensitive resin composition of embodiment of this invention, a barium titanate and strontium titanate can be mentioned from a viewpoint of high dielectric constant, Especially preferable [C] An example of the compound is barium titanate (BaTiO ₃ ).

  When a particularly preferable barium titanate is selected as the [C] compound of the radiation-sensitive resin composition of the embodiment of the present invention, as described above, the shape is not particularly limited, and may be spherical or amorphous. Of course, it may be hollow particles, porous particles, core-shell type particles or the like.

  Further, the particle diameter of barium titanate particularly preferable as the [C] compound can be determined by the dynamic light scattering method as described above, and is preferably in the range of 0.01 μm to 0.1 μm. When the particle diameter of the compound [C] is in the above range, the desired patterning performance can be realized in the radiation-sensitive resin composition of the present embodiment. In addition, if the particle size of the barium titanate, which is the [C] compound, is less than 0.01 μm, the particles are likely to aggregate and storage stability may be reduced. If it exceeds 0.1 μm, the insulating film is a cured film There is a risk that the haze of the product becomes high.

  And in barium titanate especially preferable as a [C] compound, it is desirable that c / a axial ratio is 1.0025-1.010. When the c / a axial ratio is in the range of 1.0025 to 1.010, both the particle diameter in the above range and excellent dielectric constant characteristics (high relative dielectric constant) can be realized.

  [C] The compound is desirably dispersed in a dispersion medium together with a dispersant and used as a particle dispersion in the radiation-sensitive resin composition of the present embodiment. Thus, by containing a dispersing agent, in the radiation sensitive resin composition of this embodiment, a [C] compound can be disperse | distributed uniformly, applicability | paintability can be improved, and the adhesiveness of the insulating film obtained is improved. In addition, the dielectric constant and refractive index can be increased uniformly without bias.

  Examples of the dispersant include nonionic dispersants, cationic dispersants, anionic dispersants, and the like, but nonionic dispersants are preferable from the viewpoint of improving positive radiation sensitivity and patterning properties. Examples of such nonionic dispersants include polyoxyethylene alkyl phosphate esters, amide amine salts of high molecular weight polycarboxylic acids, ethylenediamine PO-EO condensates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, alkyl glucosides, polyoxyethylenes. Mention may be made of oxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or fatty acid alkanolamides.

  The dispersion medium is not particularly limited as long as the [C] compound can be uniformly dispersed. A dispersion medium can function a dispersing agent effectively, and can disperse | distribute a [C] compound uniformly.

  Examples of the dispersion medium 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, and propylene glycol monoethyl ether acetate; ethylene Ethers such as glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether; esters such as propylene glycol monomethyl ether acetate and methyl-3-methoxypropionate; dimethylformamide, N, N-dimethyl Amides such as acetoacetamide and N-methylpyrrolidone; acetone, methyl ethyl ketone Methyl isobutyl ketone and cyclohexanone; benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene. Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, methanol, isopropyl alcohol, and propylene glycol monomethyl ether are preferable. Methyl ethyl ketone, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, methyl-3- Methoxypropionate is more preferred. The dispersion medium can be used alone or in combination of two or more.

  Content of the [C] compound in the dispersion liquid mentioned above becomes like this. Preferably they are 5 mass%-50 mass%, More preferably, they are 10 mass%-40 mass%.

  In the radiation sensitive resin composition of the embodiment of the present invention, the amount of the [C] compound is not particularly limited, but is 0.1 parts by mass to 1500 parts by mass with respect to 100 parts by mass of the [A] component. Preferably, 1 part by mass to 1000 parts by mass is more preferable. When the compounding amount of the [C] compound is less than 0.1 parts by mass, the effect of improving the dielectric constant of the obtained cured film cannot be obtained sufficiently. On the other hand, when the compounding amount of the [C] compound exceeds 1500 parts by mass, the applicability of the radiation-sensitive resin composition of the present embodiment is lowered, and the desired patterning performance may not be obtained. Furthermore, the haze of the cured film obtained may increase.

<[D] Polymer having at least one of urethane bond and amide bond and (meth) acrylate compound>
The radiation-sensitive resin composition of the embodiment of the present invention contains [A] a polymer, [B] a photosensitizer and a [C] compound as essential components, and [D] of urethane bonds and amide bonds. At least one selected from the group consisting of a polymer having at least one and a (meth) acrylate compound having at least one of a urethane bond and an amide bond (hereinafter sometimes simply referred to as [D] compound. ) Can be included. In addition, the polymer which has at least one of the urethane bond and amide bond which are [D] compounds is polymers other than the above-mentioned [A] polymer.

  In the radiation sensitive resin composition of the present embodiment, the [D] compound is a component for improving the relative dielectric constant of the insulating film of the obtained embodiment of the present invention. By containing the compound [D], it is possible to improve the relative dielectric constant of the obtained insulating film of the embodiment of the present invention. As a result, in the radiation-sensitive resin composition of the present embodiment, it is possible to adjust components in the direction of decreasing the content of the [C] compound, and patterning performance and insulating properties can be further improved.

  Since the compound [D] is used as a component of the insulating film of the embodiment of the present invention formed as a cured film, light such as an unsaturated double bond or the like, such as the (meth) acrylate compound described above Those having a thermal crosslinking site are more desirable.

  As the (meth) acrylate compound having a urethane bond, commercially available urethane (meth) acrylate can be used.

  For example, commercially available products include AH-600 (phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer), AT-600 (phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer), UA-306H (pentaerythritol) manufactured by Kyoeisha Chemical Co., Ltd. Triacrylate hexamethylene diisocyanate urethane prepolymer), UA-306T (pentaerythritol triacrylate toluene diisocyanate urethane prepolymer), UA-306I (pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer), and UA-510H (dipentaerythritol penta). Acrylate hexamethylene diisocyanate urethane prepolymer ); Shin-Nakamura Chemical Co., Ltd. U-4HA, U-6HA, U-6LPA, U-53H, A-9300, A-9300CL1, and UA-122P, Daicel-Cytec Ebecryl (registered trademark) 284, Ebecryl 285, Ebecryl294 / 25HD, Ebecryl4820, Ebecryl4858, Ebecryl8402, Ebecryl8405, Ebecryl9270, Ebecryl8311, Ebecryl8701, Ebecryl230, Ebecryl244, Ebecryll245, Ebecryl264, Ebecryl265, Ebecryl270, Ebecryl280 / 15IB, Ebecryl1259, Ebecryl5129, Ebecryl8210, Ebecryl830 , Ebecryl8307, Ebecryl8411, Ebecryl8804, Ebecryl8807, Ebecryl9227EA, Ebecryl9250, KRM (registered trademark) 8200, KRM7735, KRM8296, KRM8452, Ebecryl204, Ebecryl205, Ebecryl210, Ebecryl215, Ebecryl220, and Ebecryl6202; Nippon Synthetic Chemical Industry Co., Ltd. UV-1700B, UV -6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-7650B, etc .; Daiichi Kogyo Seiyaku R-1214, R-1220 , R-1301, R-1304, R-1306X, -1308, R-1602, and R-1150D; and Negami Industrial Co., Ltd. UN-333, UN-1255, UN-2600, UN-2700, UN-5500, UN-6060PTM, UN-6060P, UN-6200, UN-6300, UN-6301, UN-7600, UN-7700, UN-9000PEP, UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN- 905, UN-952, UN-9600, UN-906, and the like.

  These (meth) acrylate compounds can be used alone or in combination of two or more.

  In addition, the polyurethane resin which is an example of a polymer having a urethane bond is not particularly limited, but for example, a polyurethane resin obtained by reacting an isocyanate group with a polyol to extend a chain is preferable. Examples of the polyol include polyester polyol, polyether polyol, and acrylic polyol. Examples of commercially available polyurethane resins include the Juliano series (Arakawa Chemical Co., Ltd.), the Olester series (Mitsui Chemicals Co., Ltd.), the Arotane series (Nihon Shokubai Co., Ltd.)

  These polyurethane resin products may be used alone or in combination of two or more.

  Examples of the (meth) acrylate compound having an amide bond include (meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- Butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-di Chill (meth) acrylamide.

  These (meth) acrylate compounds can be used alone or in combination of two or more.

  Examples of the polymer having an amide bond include a polymer formed by using the above-mentioned (meth) acrylate compound having an amide bond as a constituent component or an additive in a raw material composition.

  As for content of the [D] compound in the radiation sensitive resin composition of this embodiment, 1 mass%-20 mass% are preferable with respect to the whole radiation sensitive resin composition. Moreover, when the radiation sensitive resin composition of this embodiment contains an organic solvent, content of the [D] compound in a radiation sensitive resin composition is 5 mass% with respect to the sum total of the component except an organic solvent. It is preferable to be within a range of ˜50% by mass or less, and it is more preferable to be within a range of 10% by mass to 40% by mass. When the compound [D] is contained in the above range, excellent patterning performance can be realized in the radiation-sensitive resin composition, and at the same time, a cured film having an improved relative dielectric constant can be obtained.

<Other optional components>
The radiation-sensitive resin composition of the embodiment of the present invention can contain a [D] compound in addition to the above-mentioned [A] polymer, [B] photosensitizer and [C] compound. Furthermore, the radiation-sensitive resin composition of the embodiment of the present invention includes, in addition to the dispersant and dispersion medium used together with the [C] compound, a surfactant, if necessary, within a range not impairing the effects of the present invention. Other optional components such as a storage stabilizer, an adhesion aid, and a heat resistance improver can be contained. Other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described.

[Surfactant]
The surfactant that can be contained in the radiation-sensitive resin composition of the present embodiment is added to improve the coating property of the radiation-sensitive resin composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. Can do. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

Commercially available products of these fluorosurfactants include Ftop (registered trademark) EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFac (registered trademark) F171, 172, and 173 (DIC Corporation). Manufactured), FLORARD FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG (registered trademark) 710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC-101, 102, 103, 104 , 105, 106 (manufactured by AGC Seimi Chemical Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.), and the like.
Examples of silicone-based surfactants are commercially available under the trade names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.).

  In addition, when using a surfactant as an optional component, the content thereof is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 100 parts by mass of the [A] polymer. 5 parts by mass. By making the usage-amount of surfactant into 0.01 mass part-10 mass parts, the applicability | paintability of the radiation sensitive resin composition of this embodiment can be optimized.

[Storage stabilizer]
Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum. Etc.

[Adhesion aid]
The adhesion assistant can be used for the purpose of further improving the adhesion between the insulating film obtained from the radiation-sensitive resin composition of the present embodiment and a layer, a substrate, or the like disposed under the insulating film. As the adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferably used. For example, trimethoxysilylbenzoic acid, γ-methacrylic acid is used. Roxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Is mentioned.

<Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition according to the embodiment of the present invention includes the [A] polymer, the [B] photosensitizer, and the [C] compound as well as the [D] compound and a multi-option thereof as necessary. It is prepared by mixing a component surfactant or the like. At this time, an organic solvent can be used to prepare a radiation-sensitive resin composition in a dispersion state. An organic solvent can be used individually or in mixture of 2 or more types.

  Examples of the function of the organic solvent include adjusting the viscosity and the like of the radiation-sensitive resin composition to improve operability and the like in addition to improving applicability to a substrate and the like. As a viscosity of the radiation sensitive resin composition implement | achieved by containing organic solvents etc., 0.1 mPa * s-50000 mPa * s (25 degreeC) are preferable, for example, More preferably, 0.5 mPa * s-10000 mPa * are preferable. s (25 ° C.).

  Examples of the organic solvent that can be used in the radiation-sensitive resin composition of the present embodiment include those that dissolve or disperse other components and that do not react with other components.

  For example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene Esters such as glycol monoethyl ether acetate and methyl-3-methoxypropionate; ethers such as polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether; benzene, Aromatic hydrocarbons such as toluene and xylene; dimethylformamide, di Chill acetamide, etc. amides such as N- methylpyrrolidone.

  The content of the organic solvent used in the radiation sensitive resin composition of the present embodiment can be appropriately determined in consideration of viscosity and the like.

  As a dispersion method when preparing a radiation-sensitive resin composition in a dispersion state, the particle speed is usually 5 m / s to 15 m / s using a paint shaker, SC mill, annular mill, pin mill, etc. It is good to carry out by the method of continuing until the fall of a diameter is no longer observed. This duration is usually several hours. In this dispersion, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is preferably 0.05 mm to 0.5 mm, more preferably 0.08 mm to 0.5 mm, and still more preferably 0.08 mm to 0.2 mm.

  Next, the display element of the embodiment of the present invention including an insulating film formed from the radiation-sensitive resin composition of the embodiment of the present invention will be described.

<Liquid crystal display element>
As described above, the display element according to the embodiment of the present invention includes an insulating film formed from the radiation-sensitive resin composition according to the embodiment of the present invention. The liquid crystal display element of the present embodiment is configured using the array substrate of the embodiment of the present invention including the insulating film of the embodiment of the present invention, for example, an active matrix type FFS mode color liquid crystal display element. it can.

  The liquid crystal display element of this embodiment includes an array substrate of an embodiment of the present invention in which active elements used for switching, electrodes, insulating films and the like are formed, and a color filter substrate configured with a colored pattern, It can be set as the structure which opposes through a liquid-crystal layer. A plurality of pixels have a display area arranged in a dot matrix.

  FIG. 1 is a plan view schematically showing a main structure of a pixel portion of an array substrate according to an embodiment of the present invention.

  FIG. 2 is a diagram schematically showing a cross-sectional structure along the line A-A ′ of FIG. 1.

  In FIG. 1, a planar common electrode 14 and a gate insulating film 31 described later are omitted.

  1 and 2, the array substrate 1 has a structure in which an active element 8 is disposed on one surface of a transparent substrate 4. The active element 8 includes a gate electrode 7a that forms part of the scanning signal line 7 disposed on the substrate 4, a semiconductor layer 8a disposed on the gate electrode 7a via a gate insulating film 31, and a semiconductor layer 8a. And a second source-drain electrode 5a that forms part of the video signal line 5 and is connected to the semiconductor layer 8a. As a whole, a thin film transistor (TFT: Thin Film) is provided. (Transistor).

  The semiconductor layer 8a is made of, for example, silicon (such as amorphous a-Si (amorphous-silicon)) or p-Si (polysilicon) obtained by crystallizing a-Si by excimer laser or solid phase growth. It can be formed by using Si) material.

  When a-Si is used for the semiconductor layer 8a, the thickness of the semiconductor layer 8a is preferably 30 nm to 500 nm. Further, an n + Si layer (not shown) for making ohmic contact is formed with a thickness of 10 nm to 150 nm between the semiconductor layer 8a and the first source-drain electrode 6 or the second source-drain electrode 5a. It is preferable.

  The semiconductor layer 8a can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 8a include single crystal oxide, polycrystalline oxide, amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  Examples of the amorphous oxide applicable to the semiconductor layer 8a include an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn).

  Specific examples of amorphous oxides applicable to the semiconductor layer 8a include Sn—In—Zn oxide, In—Ga—Zn oxide (IGZO: indium gallium zinc oxide), and In—Zn—Ga—Mg oxide. Zn-Sn oxide (ZTO: zinc tin oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga An oxide, a Sn—In—Zn oxide, and the like can be given. In the above case, the composition ratio of the constituent materials is not necessarily 1: 1, and a composition ratio that realizes desired characteristics can be selected.

  For example, when the semiconductor layer 8a using an amorphous oxide is formed using IGZO or ZTO, a layer is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method or the like is performed. By using this, patterning is performed by a resist process and an etching process. The thickness of the semiconductor layer 8a using an amorphous oxide is preferably 1 nm to 1000 nm.

  By using the oxides exemplified above, the semiconductor layer 8a having high mobility can be formed at a low temperature, and the active element 8 having excellent performance can be provided.

  As oxides particularly preferable for forming the semiconductor layer 8a of the active element 8, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (ZIO) are exemplified. be able to.

  By using these oxides, the active element 8 has the semiconductor layer 8a having excellent mobility formed at a lower temperature, and can exhibit a high ON / OFF ratio.

The gate insulating film 31 disposed so as to cover the gate electrode 7a can be formed of, for example, a metal oxide such as SiO ₂ (silicon dioxide) or a metal nitride such as SiN (silicon nitride).

  An inorganic insulating film 32 is provided on the active element 8 so as to cover the active element 8. The inorganic insulating film 32 is a third insulating film, which is a different insulating film from the organic insulating film 12 that is the first insulating film and the insulating film 33 that is the second insulating film. In addition, the insulating film 33 which is a 2nd insulating film is an insulating film of embodiment of this invention formed from the radiation sensitive resin composition of embodiment of this invention mentioned above.

The inorganic insulating film 32 can be formed of, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. The inorganic insulating film 32 is provided to prevent the semiconductor layer 8a from being affected by humidity. In the array substrate 1 of the present embodiment, it is possible not to provide the inorganic insulating film 32 that is the third insulating film. That is, the array substrate 1 may have a structure in which the organic insulating film 12 that is the first insulating film is disposed on the active element 8.

  On the active element 8, the organic insulating film 12 that is the first insulating film is disposed so as to cover the inorganic insulating film 32. The organic insulating film 12 is an insulating film formed using an organic insulating film forming composition, and is an organic insulating film formed using an organic material. In the present embodiment, the organic insulating film 12 preferably has a function as a planarizing film, and is preferably formed thick from this viewpoint. For example, in the case of the active element 8 having a general structure, the organic insulating film 12 can be formed with a film thickness of 1 μm to 6 μm.

  In the organic insulating film 12 of the array substrate 1 of the present embodiment, the organic insulating film forming composition is applied onto the substrate 4 on which the video signal lines 5 and the active elements 8 are formed, and the contact holes 17 are formed. After the necessary patterning, it is formed by heat curing.

  The organic insulating film forming composition used for forming the organic insulating film 12 is a radiation-sensitive resin composition comprising [X] alkali-soluble resin as an essential component so as to have patternability. [X] The alkali-soluble resin is not limited as long as it is a resin having alkali developability. The [X] alkali-soluble resin is preferably a resin containing a structural unit having a carboxyl group and a structural unit having a polymerizable group, or a polyimide resin obtained by dehydrating and ring-closing polyamic acid to imidize.

  The organic insulating film-forming composition can be either a positive type or a negative type, but when it is a positive type radiation-sensitive resin composition, it preferably contains a [Y] quinonediazide compound as an essential component. In the case of a negative radiation sensitive resin composition, it is preferable to contain a [Z] polymerizable compound and a [W] radiation sensitive polymerization initiator.

  And. In the present embodiment, for example, in the organic insulating film 12 using a positive type organic insulating film forming composition, when it is sensitive to radiation, the solubility in a developer increases and the sensitive part is removed. Therefore, when a positive organic insulating film forming composition is used, the desired contact hole 17 can be formed relatively easily by irradiating the contact hole 17 forming portion of the organic insulating film 12 with radiation. Can do.

  Also,. In the present embodiment, in the organic insulating film 12 using the negative organic insulating film forming composition, the solubility in the developer is lowered when sensitive to radiation, and therefore the non-sensitive part is removed. Therefore, when a negative type organic insulating film forming composition is used, the desired contact hole 17 can be formed by irradiating the portion other than the contact hole 17 forming portion of the organic insulating film 12 with radiation. Compared to the positive type, there is a disadvantage that it becomes difficult to control the shape of the contact hole 17, but there are advantages in terms of transparency and heat resistance of the organic insulating film 12 to be obtained.

  As described above, the organic insulating film-forming composition contains an alkali-soluble resin for both positive and negative types. This alkali-soluble resin can be, for example, a polymer containing a structural unit having a carboxyl group and a structural unit having a polymerizable group. When the alkali-soluble resin is a polymer containing a structural unit having a carboxyl group and a structural unit having a polymerizable group, after forming a pattern by irradiating the coating film formed from the organic insulating film-forming composition with radiation, It can be cured by heating. That is, in a resin having a polymerizable group, the polymerizable group is cross-linked by reacting with heating, and a cured film in which a highly crosslinked network is formed can be formed. Even if such a cured film is further heated thereafter, since the expansion and contraction of the film is small, the stress applied to the film formed thereon can be minimized. Therefore, after the organic insulating film 12 is formed, even if the organic insulating film 12 is further subjected to heat treatment in the curing process of other films provided thereon, the variation in the size of the organic insulating film 12 due to this is minimized. Can be suppressed. Thereby, the stress applied to the common electrode 14 and the insulating film 33 on the organic insulating film 12 can be reduced.

  As described above, since the expansion and contraction of the film due to the heating of the organic insulating film 12 is small, it is possible to prevent the peeling between the common electrode 14 made of ITO or the like and the insulating film 33 disposed thereon. it can.

  A contact hole 17 penetrating the organic insulating film 12 is formed in the organic insulating film 12 in order to connect a pixel electrode 9 described later and the first source-drain electrode 6. The contact hole 17 is formed so as to penetrate the inorganic insulating film 32 under the organic insulating film 12. The organic insulating film 12 is formed using an organic insulating film forming composition that is a radiation-sensitive resin composition. Accordingly, for example, after forming a through hole by irradiating the organic insulating film 12 with radiation, the contact hole 17 is formed by performing dry etching on the inorganic insulating film 32 using the organic insulating film 12 as a mask. Can do. In the case where the array substrate 1 has a structure that does not have the inorganic insulating film 32, a through hole formed by irradiating the organic insulating film 12 with radiation serves as the contact hole 17.

  The upper surface of the organic insulating film 12 is flat, and a common electrode 14 (not shown in FIG. 1) is provided thereon. The common electrode 14 is formed in a planar shape, and is formed on the entire surface so as to avoid the contact hole 17.

  For the common electrode 14, for example, a film made of a transparent conductive material such as ITO is formed using a sputtering method or the like. Then, patterning is performed using a photolithography method or the like, and an opening is provided so as to surround the contact hole 17. Thereby, the common electrode 14 having the structure of FIG. 2 can be formed.

  On the organic insulating film 12 and the common electrode 14, an insulating film 33 according to the embodiment of the present invention is provided as a second insulating film covering them. This insulating film 33 is a coating-type organic insulating film formed from the radiation-sensitive resin composition of the above-described embodiment of the present invention. The insulating film 33 replaces the above-described conventional interlayer insulating film made of SiN, and is a main component of the array substrate 1 of the present embodiment.

  The insulating film 33 of this embodiment has an opening at the same position as the contact hole 17 of the organic insulating film 12 described above. Therefore, the contact hole 17 of the organic insulating film 12 is not blocked by the insulating film 33, and the first source-drain electrode 6 connected to the pixel electrode 9 on the insulating film 33 described later and the semiconductor layer 8a. Allows electrical connection between the two. At this time, it is sufficient that the contact hole 17 is opened at the top and bottom and penetrates the organic insulating film 12, and at least a part of the inner wall of the contact hole 17 may be covered with the insulating film 33. .

  As described above, the insulating film 33 according to the embodiment of the present invention, which is the second insulating film, replaces the conventional interlayer insulating film made of SiN or the like, and is a coating type organic insulating film using an organic material. It is. The insulating film 33 is formed by performing coating film formation by coating using the radiation-sensitive resin composition of the embodiment of the present invention and performing predetermined patterning using a photolithography method or the like.

  In the photolithography method, a resist composition is formed by applying a resist composition to the surface of a substrate to be processed or processed, and a resist pattern is formed by exposing a predetermined resist pattern by irradiation with light or an electron beam. An exposure step for forming a pattern latent image, a heat treatment step if necessary, a development step for developing the pattern to form a desired fine pattern, and a process such as etching on the substrate using the fine pattern as a mask. The process to perform is included.

  The radiation-sensitive resin composition of the embodiment of the present invention is optimal in composition so that the insulating film 33 of the present embodiment can achieve the desired dielectric constant and refractive index in the array substrate 1 of the present embodiment. Has been made. That is, the radiation-sensitive resin composition of the present embodiment contains a component for increasing the dielectric constant so that the insulating film 33 can be controlled to increase the dielectric constant. For example, the radiation-sensitive resin composition of the present embodiment includes at least one metal selected from the group consisting of [C] titanium oxide and barium, strontium, calcium, magnesium, zirconium and lead as the [C] component. A compound containing an element is included. In addition, as described above, the radiation-sensitive resin composition of the present embodiment includes, as the [D] component, a polymer having at least one of [D] urethane bond and amide bond, and urethane bond and amide bond. At least one selected from the group consisting of (meth) acrylate compounds having at least one of them can be included.

  Furthermore, the radiation-sensitive resin composition according to the embodiment of the present invention contains the [C] compound, so that the insulating film 33 formed using the compound can have a high refractive index. For example, the refractive index of the insulating film 33 can be controlled within the range of 1.55 to 1.85.

  And the radiation sensitive resin composition of this embodiment is excellent in patterning property, combined use of the [C] component and the [D] component, etc. so as to show high curing performance and excellent insulation. Optimal composition design is possible.

  As a result, the array substrate 1 is configured such that the dielectric constant and the like of the insulating film 33 are adjusted, and can be easily replaced with a conventional inorganic interlayer insulating film made of SiN.

  The film thickness of the insulating film 33 is not particularly limited, but it is preferable that the insulating film 33 has a thickness suitable for ensuring insulation between the common electrode 14 and the pixel electrode 9 and realizing a desired capacitance. The thickness of the insulating film 33 is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

  Further, like the organic insulating film 12, the common electrode 14, and the pixel electrode 9, the insulating film 33 is required to have excellent visible light transmittance as a component constituting the array substrate 1. The insulating film 33 of this embodiment formed from the radiation sensitive resin composition of this embodiment has excellent transparency. As a result, the insulating film 33 can have a light transmittance of a wavelength of 400 nm of 85% or more, and can be 90% or more by selecting a component composition.

  The insulating film 33 of the present embodiment described above is patterned so as not to block the contact hole 17 of the organic insulating film 12 and is disposed so as to cover the common electrode 14.

  On the insulating film 33 of the present embodiment, the pixel electrode 9 is provided. The pixel electrode 9 is a transparent electrode and has a portion formed in a comb shape (hereinafter, simply referred to as “comb shape” or “comb shape”). The pixel electrode 9 having a comb-like shape (hereinafter may be simply referred to as “comb shape”) is connected to the first source-drain electrode 6 connected to the semiconductor layer 8 a through the contact hole 17. To do. With such a structure, the aperture ratio of the pixel can be improved, and a pixel structure that provides high-luminance display can be realized.

  The array substrate 1 of the embodiment of the present invention including the insulating film 33 of the embodiment of the present invention is used for the configuration of the liquid crystal display element of the embodiment of the present invention. Then, by applying a voltage between the comb-like pixel electrode 9 and the solid common electrode 14 described above, a component parallel to the surface of the substrate 4 is formed between the pixel electrode 9 and the common electrode 14. An electric field is formed. As a result, in the liquid crystal display element of this embodiment, the liquid crystal molecules in the liquid crystal layer can be rotated (aligned) in a plane parallel to the plane of the substrate 4.

  The pixel electrode 9 can be formed as follows. For example, a film made of a transparent conductive material such as ITO (Indium Tin Oxide) is formed using a sputtering method or the like. Next, patterning is performed using a photolithography method or the like to form comb-shaped electrodes.

  An alignment film 10 can be provided on the pixel electrode 9 so as to cover the pixel electrode 9. The alignment film 10 controls the alignment of the liquid crystal layer. More specifically, the alignment film 10 controls the alignment of the liquid crystal molecules constituting the liquid crystal layer in the liquid crystal display element of the present embodiment formed using the array substrate 1, and thus controls the alignment of the liquid crystal layer. .

  The alignment film 10 includes (1) a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group (hereinafter, simply referred to as (1) liquid crystal alignment agent) or (2) photo-alignment. It can be obtained by using a liquid crystal aligning agent containing polyimide not having a functional group (hereinafter, simply referred to as (2) liquid crystal aligning agent). (1) The liquid crystal aligning agent is a resin composition, which is an organic insulating film forming composition used for forming the organic insulating film 12 and a radiation sensitive resin composition of the present embodiment used for forming the insulating film 33. Although it is different, it is cured by low-temperature heat treatment at 200 ° C. or lower. Further, (2) the polyimide contained in the liquid crystal aligning agent is a solvent-soluble polyimide, and (2) the liquid crystal aligning agent is cured by a heat treatment at 200 ° C. or lower as in (1). Therefore, by forming the alignment film 10 with these liquid crystal aligning agents, the influence of the heating in the formation process of the alignment film 10 on the organic insulating film 12 and the insulating film 33 of the present embodiment can be minimized. . For example, the expansion and contraction of the organic insulating film 12 that may be caused by heating in the step of forming the alignment film 10 can be minimized. In addition, since the heat treatment at 200 ° C. or less is possible, a preferable method for manufacturing an array substrate can be provided from the viewpoint of energy saving.

  In the array substrate 1 having the above structure, the video signal lines 5 and the scanning signal lines 7 are arranged in a matrix. The active element 8 is provided in the vicinity of the intersection of the video signal line 5 and the scanning signal line 7, and they constitute each pixel partitioned on the array substrate 1.

  FIG. 3 is a schematic cross-sectional view of a liquid crystal display element using the array substrate of the embodiment of the present invention.

  As shown in FIG. 3, the liquid crystal display element 41 is an active matrix type FFS mode color liquid crystal display element including the array substrate 1 shown in FIGS. 1 and 2 and the color filter substrate 22. The liquid crystal display element 41 has a structure in which the array substrate 1 and the color filter substrate 22 face each other with the liquid crystal layer 23 aligned in parallel to the substrate 4 and the substrate 11.

  As shown in FIG. 3, the array substrate 1 has active elements 8 used for switching on the surface of the transparent substrate 4 on the liquid crystal layer 23 side. As described above, the active element 8 includes the gate electrode 7a, the gate insulating film 31, the semiconductor layer 8a, the first source-drain electrode 6, and the second source-drain electrode 5a. As shown in FIG. On the array substrate 1, the video signal line 5 (not shown in FIG. 3) connected to the second source-drain electrode 5a and the scanning signal line 7 connected to the gate electrode 7a (not shown in FIG. 3). Are arranged in a matrix. The active element 8 is provided in the vicinity of the intersection of the video signal line 5 and the scanning signal line 7, and constitutes each pixel partitioned on the array substrate 1.

  An inorganic insulating film 32 that is a third insulating film can be provided on the active element 8, and the organic insulating film 12 that is the first insulating film is disposed so as to cover the inorganic insulating film 32. As described above, the organic insulating film 12 is formed using the organic insulating film forming composition, and is formed thick so as to have a function as a planarizing film.

  A solid common electrode 14 is disposed on the organic insulating film 12 so as to avoid the contact hole 17. On the common electrode 14 and the organic insulating film 12, the insulating film 33 of the present embodiment, which is a second insulating film, is disposed. As described above, the insulating film 33 of the present embodiment is an organic insulating film provided by replacing the conventional interlayer insulating film made of SiN using the radiation-sensitive resin composition of the embodiment of the present invention. This is a main component of the liquid crystal display element 41 of the present embodiment.

  On the insulating film 33 of this embodiment, the pixel electrode 9 which is a transparent electrode and has a comb-shaped portion is disposed. In addition, a contact hole 17 is formed in the organic insulating film 12 so as to penetrate the organic insulating film 12 and further penetrate the inorganic insulating film 32 therebelow. The pixel electrode 9 is connected to the first source-drain electrode 6 connected to the semiconductor layer 8 a through the contact hole 17. An alignment film 10 that controls the alignment of the liquid crystal layer 23 is provided on the pixel electrode 9.

  The color filter substrate 22 is provided on the surface of the transparent substrate 11 on the liquid crystal layer 23 side. Further, the color filter substrate 22 is configured by arranging the coloring pattern 15 and the black matrix 13. In the coloring pattern 15, red, green, and blue minute patterns are arranged in a regular shape such as a lattice shape. The color of the colored pattern 15 is not limited to the above three colors of red, green, and blue, but other colors can be selected, or yellow can be added to form a four-color colored pattern. Is also possible. These color patterns can be arranged to constitute a color filter substrate.

  An alignment film 10 similar to that of the array substrate 1 is provided on the surface of the color filter substrate 22 that is in contact with the liquid crystal layer 23. Note that a planarizing film may be formed between the alignment film 10 and the color filter substrate 22 for the purpose of planarizing unevenness on the surface of the color filter substrate 22.

  As described above, in the liquid crystal display element 41 of the present embodiment, the alignment film 10 is provided on the surface of the array substrate 1 and the color filter substrate 22 in contact with the liquid crystal layers 23. The alignment film 10 is subjected to an alignment process such as rubbing, if necessary, to realize uniform parallel alignment of the liquid crystal layer 23 sandwiched between the array substrate 1 and the color filter substrate 22.

  The distance between the array substrate 1 and the color filter substrate 22 facing each other through the liquid crystal layer 23 is held at a predetermined value by a spacer (not shown), and is usually 2 μm to 10 μm. In addition, the array substrate 1 and the color filter substrate 22 are fixed to each other by a sealing material (not shown) provided in the peripheral portion thereof.

  In the array substrate 1 and the color filter substrate 22, polarizing plates 28 are respectively arranged on the side opposite to the side in contact with the liquid crystal layer 23.

  In FIG. 3, reference numeral 27 denotes backlight light emitted toward the liquid crystal layer 23 from a backlight unit (not shown) serving as a light source of the liquid crystal display element 41.

  As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. A backlight unit using a white LED as a light source can also be used. As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, and a white light that is obtained by mixing a blue LED, a red LED, and a green light emitting phosphor. White LED, blue LED, white LED that obtains white light by color mixing by combining red light emitting phosphor and green light emitting phosphor, white LED that obtains white light by color mixture of blue LED and YAG phosphor A white LED, an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor that combine a blue LED, an orange light-emitting phosphor, and a green light-emitting phosphor to obtain white light by mixing colors. A white LED that obtains white light by color mixing in combination can be exemplified.

  As described above, the liquid crystal display element 41 of this embodiment has a configuration in which the liquid crystal layer 23 is sandwiched between the array substrate 1 of this embodiment and the color filter substrate 22. In the array substrate 1, the electrical connection between the pixel electrode 9 and the first source-drain electrode 6 is realized through the contact hole 17 provided through the organic insulating film 12 and the inorganic insulating film 32. Then, a signal voltage from the video signal line 5 is applied to the pixel electrode 9. As a result, a lateral electric field generated between the pixel electrode 9 and the common electrode 14, that is, a component parallel to the substrates 4 and 11 of the electric field generated between the pixel electrode 9 and the common electrode 14, causes the liquid crystal layer 23 to The liquid crystal molecules can be rotated (aligned) in a plane parallel to the substrates 4 and 11. The liquid crystal display element 41 forms an image by controlling the light transmission characteristics of the liquid crystal layer 23 for each pixel by using the rotation operation of the liquid crystal molecules in the plane of the substrates 4 and 11.

  Here, the liquid crystal display element 41 is an FFS mode liquid crystal display element in which the liquid crystal molecules of the liquid crystal layer 23 rotate in the plane of the substrates 4 and 11, and the operation of the liquid crystal molecules is different from the conventional TN mode or the like. Yes. That is, the liquid crystal display element 41 has little change in the tilt angle of the liquid crystal molecules with respect to the substrates 4 and 11 that sandwich the liquid crystal layer. Therefore, the liquid crystal display element 41 is a display element that realizes a wide viewing angle characteristic and can display an image with high image quality.

  Further, the liquid crystal display element 41 of the present embodiment has a structure in which the insulating film 33 of the embodiment of the present invention is provided on the common electrode 14, and the comb-shaped pixel electrode 9 is further disposed on the insulating film 33. Have According to this structure, the aperture ratio of the pixels is improved, and high-luminance image display is realized.

  In the liquid crystal display element 41, the insulating film 33 of the present embodiment is a coating-type organic insulating film made of an organic material and formed using the radiation-sensitive resin composition of the present embodiment described above. That is, the insulating film 33 according to the embodiment of the present invention can be formed using a coating method and patterned using a photolithography method. As a result, the insulating film 33 of this embodiment can be formed with high throughput, and high productivity can be realized. In addition, the liquid crystal display element 41 is designed with components that enable control to increase the dielectric constant in the insulating film 33 using an organic material. Therefore, the liquid crystal display element 41 of the present embodiment can replace the insulating film 33 of the present embodiment instead of the conventional inorganic interlayer insulating film made of SiN, and can perform excellent image display similar to the conventional one. Become.

  As described above, the liquid crystal display element of this embodiment has high productivity, excellent image quality, and high reliability. In realizing such performance, the array substrate of the present embodiment is an important component, and in particular, the characteristics of the insulating film of the present embodiment, which is the second insulating film of the array substrate, are important. While the insulating film of the present embodiment formed using the radiation-sensitive resin composition of the embodiment of the present invention described above is configured using an organic material, the dielectric constant is controlled so as to have desirable dielectric characteristics. The conventional inorganic interlayer insulating film made of SiN can be easily replaced.

  Next, a method for manufacturing the insulating film according to the present embodiment and a method for manufacturing the array substrate according to the present embodiment will be described.

<Insulating film and array substrate manufacturing method>
In the manufacturing process of the array substrate of the embodiment of the present invention, the radiation sensitive resin composition of the embodiment of the present invention described above is used to form the insulating film of the embodiment of the present invention which is the second insulating film described above. This process is included as a main process.

  And the process of forming the organic insulating film which is a 1st insulating film using the organic insulating film formation composition mentioned above can be included. Furthermore, in the manufacturing process of the array substrate of this embodiment, in order to form the alignment film on the array substrate, a process of forming the alignment film from the liquid crystal aligning agent can be included as described above.

  In the array substrate manufacturing method of the present embodiment, the organic insulating film, the insulating film of the present embodiment, and the alignment film are formed in this order, and an organic insulating film is first formed on the substrate. Therefore, the array substrate manufacturing method of the present embodiment preferably includes the following steps [1] to [4] in this order. Next, the following steps [5] to [7] are performed in this order so that the insulating film of this embodiment is formed between the common electrode and the pixel electrode on the substrate on which the organic insulating film is formed. It is preferable to contain. Furthermore, it is preferable to include the step [8] so as to form an alignment film on the array substrate on which the organic insulating film and the insulating film of this embodiment are formed.

  Steps [1] to [8] included in the method for manufacturing an array substrate of the present embodiment are as follows.

  [1] A step of forming a coating film of an organic insulating film forming composition on a substrate on which an active element used for switching is formed (hereinafter, sometimes referred to as “step [1]”).

  An electrode or the like may be formed on the substrate. Hereinafter, active elements and electrodes, that is, semiconductor layers, gate electrodes, gate insulating films, source-drain electrodes, video signal lines, scanning signal lines and the like already described are collectively referred to as “active elements”. There is.

[2] A step of irradiating at least a part of the coating film of the organic insulating film forming composition formed in the step [1] (hereinafter sometimes referred to as “step [2]”).
[3] A step of developing the coating film irradiated with radiation in the step [2] (hereinafter sometimes referred to as “step [3]”).
[4] A step of curing the coating film developed in step [3] to form an insulating film (hereinafter sometimes referred to as “step [4]”).
[5] A step of forming a coating film of the radiation sensitive resin composition of the embodiment of the present invention on a substrate having an organic insulating film formed through the steps [1] to [4] (hereinafter referred to as “step [ 5] ").
[6] A step of irradiating at least a part of the coating film formed in step [5] (hereinafter sometimes referred to as “step [6]”).
[7] A step of developing the coating film irradiated with radiation in step [6] (hereinafter sometimes referred to as “step [7]”).
[8] A substrate having a coating film of a liquid crystal aligning agent, an organic insulating film formed through steps [1] to [4], and an insulating film formed through steps [5] to [7]. And forming the alignment film by heating the coating film (hereinafter sometimes referred to as “process [8]”).

  It is preferable that a step of providing a common electrode on the organic insulating film formed in the step [4] is provided between the step [4] and the step [5]. It is preferable that a step of providing a comb-like pixel electrode on the insulating film formed in the step [7] is provided between the step [7] and the step [8]. In each step between the step [4] and the step [5] and between the step [7] and the step [8], a common electrode and a pixel electrode are formed using a known technique.

  According to process [1]-process [4], an organic insulating film can be formed on a substrate in which an active element etc. were formed using the organic insulating film formation composition mentioned above. The organic insulating film formed on the substrate has a contact hole. In addition, this organic insulating film has a reduced expansion / contraction rate of the film by the subsequent heat treatment.

  Then, according to the steps [5] to [7], the radiation-sensitive resin composition according to the embodiment of the present invention is used to place the active element on the substrate on which the organic insulating film, the common electrode, etc. are formed. The insulating film of the embodiment of the invention can be formed. Then, as described above, by providing the comb-shaped pixel electrode on the insulating film, the insulating film of the embodiment of the present invention can be disposed between the common electrode and the pixel electrode.

  The formed insulating film of the embodiment of the present invention is a coating type insulating film that can be easily formed and patterned by a coating method or the like. The insulating film according to the present embodiment is made of an organic material and exhibits excellent adhesive strength with a common electrode made of ITO or the like. Moreover, the insulating film of this embodiment is excellent in curability, and as a result, exhibits excellent insulating properties. Further, the dielectric constant is controlled to a desired value and the capacitance is controlled, and the interlayer insulating film made of SiN, which is the conventional technique, can be substituted and used suitably for display elements.

  Further, according to the step [8], the alignment film can be formed on the substrate by, for example, low temperature curing using the liquid crystal aligning agent described above.

  Therefore, according to the steps [1] to [8], a coating type provided with a highly reliable organic insulating film provided with a contact hole at a predetermined position, and a desired dielectric constant and excellent insulating properties. The array substrate of this embodiment having the insulating film of this embodiment is manufactured.

  Hereinafter, the above-described step [1] to step [4], step [5] to step [7], and step [8] will be described in more detail.

[Step [1]]
In this step, a coating film of the organic insulating film forming composition described above is formed on the substrate. On this substrate, active elements, electrodes and the like for use in switching are formed. These active elements and the like are formed in accordance with a known method on a substrate by repeating normal semiconductor film formation, known insulating layer formation, etc., and etching by photolithography. As the substrate, it is also possible to use a substrate in which an inorganic insulating film made of a metal oxide such as SiO ₂ or a metal nitride such as SiN is formed on a switching active element or the like.

  After applying the above-mentioned organic insulating film forming composition to the surface of the substrate on which the active elements and the like are formed, pre-baking is performed to evaporate the solvent and form a coating film.

  Examples of the substrate material include glass substrates such as soda lime glass and alkali-free glass, silicon substrates, and resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, and polyimide. Etc. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.

  As a coating method of the organic insulating film forming composition, for example, a spray method, a roll coating method, a spin coating method (sometimes called a spin coating method or a spinner method), a slit coating method (slit die coating method). An appropriate method such as a bar coating method or an ink jet coating method can be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

  The prebaking conditions described above vary depending on the types and blending ratios of the components constituting the organic insulating film forming composition, but it is preferably performed at a temperature of 70 ° C. to 120 ° C., and the time is such as a hot plate or oven. Although it differs depending on the heating device, it is about 1 to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.

[Step [2]]
Next, radiation is applied to at least a part of the coating film formed in the step [1]. At this time, in order to irradiate only a part of the coating film, for example, it is performed through a photomask having a pattern corresponding to formation of a desired contact hole.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

Radiation dose (also referred to as exposure.), As a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. ^{Inc.), 10J / m 2 ~10000J} / m 2 100 J / m ^{2 to} 5000 J / m ² is preferable, and 200 J / m ^{2 to} 3000 J / m ² is more preferable.

[Step [3]]
Next, the coating film after irradiation in the step [2] is developed to remove unnecessary portions, and a coating film in which contact holes of a predetermined shape are formed is obtained.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline, An aqueous solution of an alkaline compound such as 8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, the surfactant can be used alone or in combination with the addition of the above-mentioned water-soluble organic solvent.

  The developing method may be any of a liquid filling method, a dipping method, a shower method, a spraying method, etc., and the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[Step [4]]
Next, the coating film obtained in the step [3] is cured (also referred to as post-baking) by heating using an appropriate heating device such as a hot plate or an oven. Thereby, the organic insulating film mentioned above is obtained as a cured film. The thickness of the organic insulating film after curing is preferably 1 μm to 5 μm. Contact holes arranged at desired positions are formed in the organic insulating film by the step [3].

  After forming the organic insulating film in the step [4], it is preferable to have a step of providing a common electrode which is a transparent electrode as the first electrode on the organic insulating film. For example, a transparent conductive layer made of ITO can be formed on the organic insulating film using a sputtering method or the like. Next, this transparent conductive layer is etched using a photolithography method, and a solid common electrode can be formed as a transparent electrode in a region where the contact hole on the organic insulating film is not disposed.

[Step [5]]
In this step, the substrate with an organic insulating film obtained in step [4] is used, and the radiation-sensitive resin composition of the present embodiment is applied onto the substrate. Next, the coated surface is preferably heated (prebaked), and when the solvent is contained in the coating film, the solvent is removed to form the coating film.

  It does not specifically limit as a coating method of the radiation sensitive resin composition of this embodiment. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C. for 1 to 10 minutes.

[Step [6]]
Next, in this step, at least a part of the coating film on the substrate formed in step [5] is irradiated with radiation. In this case, when a part of the coating film is irradiated with radiation, it is preferably performed through a photomask having a predetermined pattern. As radiation used for radiation irradiation, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is particularly preferable.

The dose of radiation in the step [6], the intensity at the wavelength 365nm radiation, as measured by a luminometer (OAI model356, OAI Optical Associates Ltd. Inc.), preferably ^{100J / m 2 ~10000J / m 2} , more preferably ^{500J / m 2 ~6000J / m 2} .

[Step [7]]
Next, in this step, by developing the coating film after irradiation obtained in step [6], unnecessary portions (in the case where the radiation-sensitive resin composition is a negative type, non-irradiation of the coating film) And a predetermined pattern is formed.

  As the developer used in the development step of step [7], it is preferable to use an alkali developer composed of an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline developer. The concentration of alkali in the alkali developer is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation-sensitive resin composition of the present embodiment, but is preferably about 10 seconds to 180 seconds. Following such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

  As described above, the insulating film of the embodiment of the present invention on the substrate formed by the steps [5] to [7] has high transparency and exhibits a high dielectric constant of about 5 to 10. Can do. Further, since it has excellent curability and insulating properties, it can be made into a thin film. Therefore, film thickness adjustment such as thinning can be performed together, and the control can be performed so as to have the same capacitance characteristics as in the case of using a conventional interlayer insulating film made of SiN.

  Furthermore, the insulating film of this embodiment has a higher refractive index than a normal organic film. The insulating film formed from the radiation-sensitive resin composition of the present embodiment can have a high refractive index of 1.50 or more, further 1.55 or more, although it varies depending on the blending ratio of each component. . Therefore, the difference in refractive index with respect to ITO or the like constituting the pixel electrode, which will be described later, can be reduced, and a reduction in display quality due to the difference in refractive index can be suppressed.

  The thickness of the insulating film of this embodiment is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and further preferably 0.1 μm to 4 μm.

  As described above, after forming the insulating film of this embodiment, it is preferable to have a step of providing a comb-shaped pixel electrode as the second electrode on the insulating film. For example, a transparent conductive layer made of ITO can be formed on the insulating film of the present embodiment using a sputtering method or the like. Next, this transparent conductive layer is etched using a photolithography method, and a comb-like pixel electrode can be formed as a transparent electrode on the insulating film. The pixel electrode enables electrical connection with the switching active element on the substrate through the contact hole of the organic insulating film described above.

  In addition, the common electrode and the pixel electrode can be configured using a transparent material having high transmittance and conductivity with respect to visible light in addition to ITO. For example, it can be configured using IZO (Indium Zinc Oxide), ZnO (zinc oxide), tin oxide, or the like.

[Step [8]]
A pixel electrode is formed on the insulating film on the common electrode as described above using the organic insulating film obtained in the step [7] and the substrate provided with the insulating film of the present embodiment, and then on the pixel electrode. The liquid crystal aligning agent described above is applied. Examples of the coating method include a roll coater method, a spinner method, a printing method, and an ink jet method.

  Next, the substrate coated with the liquid crystal aligning agent is pre-baked and then post-baked to form a coating film.

  Prebaking conditions are, for example, 40 ° C. to 120 ° C. for 0.1 minute to 5 minutes. The temperature of the post-bake conditions is preferably 120 ° C to 230 ° C, more preferably 150 ° C to 200 ° C, and further preferably 150 ° C to 180 ° C. Moreover, although the time of post-baking changes with heating apparatuses, such as a hotplate and oven, Usually, it is preferably 5 minutes-200 minutes, More preferably, it is 10 minutes-100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

  The solid content concentration of the liquid crystal aligning agent used when applying the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) takes viscosity, volatility, etc. into consideration However, it is preferably 1 to 10% by weight.

  When a liquid crystal aligning agent containing (1) a radiation-sensitive polymer having a photo-aligning group is used as the liquid crystal aligning agent, radiation that is linearly polarized or partially polarized, or non-polarized radiation is applied to the coating film. By irradiating, the liquid crystal alignment ability is imparted. Such irradiation of polarized radiation corresponds to the alignment treatment of the alignment film.

  Here, as the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In particular, it is preferable to use ultraviolet rays including light having a wavelength of 300 nm to 400 nm as radiation. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.

The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10000 J / ^{m 2,} more preferably ^{10J / m 2 ~3000J / m 2} .

  When a liquid crystal aligning agent containing (2) polyimide having no photo-alignable group is used as the liquid crystal aligning agent, the post-baked coating film can be used as the alignment film. And, if necessary, the coating film after post-baking is subjected to a rubbing process (rubbing process) with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, etc. Can be given.

  As described above, when the alignment film is formed on the array substrate of the present embodiment, the above-described liquid crystal aligning agent is used. The alignment film can be formed at a suitable heating temperature of 180 ° C. or less. By setting the curing temperature in the alignment film forming step to such a low temperature, the organic insulating film formed in the steps [1] to [4] and the present invention formed in the steps [5] to [7]. The insulating film of the embodiment can be prevented from being exposed to a high temperature state in the alignment film forming step.

  Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.

<[A] Synthesis of polymer>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (a-1) 20.0 parts by mass of methacrylic acid, (a-2) 10 parts by mass of glycidyl methacrylate, (a-3) 40.0 parts by mass of styrene, (a-4) tricyclo [5.2. 1.0 ^2,6 ] Deca-8-yl methacrylate was charged in 30 parts by mass and purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1) as a copolymer (solid content concentration = 29.1% by mass). Mw = 6800, Mw / Mn = 1.8). As a result of ¹³ C-NMR analysis, (a-1) structural unit derived from (a-1), (a-2) structural unit derived from (a-2), (a-3) derived from (a-3) -3) The contents of the structural unit and (a-4) structural unit derived from (a-4) were 24.1 mol%, 7.2 mol%, 38.6 mol%, and 13.7 mol%, respectively. It was. Further, the contents of unreacted (a-1), (a-2), (a-3), and (a-4) are 4.1 mol%, 1.3 mol%, and 8.1 mol%, respectively. It was 2.9 mol%. These contents were determined by ¹ H-NMR, ¹³ C-NMR, FT-IR, and pyrolysis gas chromatography mass spectrometry.

<Preparation of [C] compound dispersion>
In a plastic bottle or glass bottle, 25 parts by mass of (C-1) as a [C] compound, 5 parts by weight of (I-1) as a [I] dispersant, and 70 parts by mass of (G-2) as a solvent Then, 0.1 μm zirconia beads were added for 3.5 times the charged weight and sealed, and the mixture was lightly stirred to blend the solvent, particle component, and organic component. This was set in a paint shaker, dispersed for 3 hours, and zirconia beads were removed with a mesh filter to obtain a [C] compound dispersion (C-1).

<Synthesis of [D] Compound (Polymer Having [D-6] Amide Bond)>
[Synthesis Example 2]
Into the flask, 8 parts by mass of methacrylic acid, 36 parts by mass of benzyl methacrylate, 50 parts by mass of dimethylacrylamide, 4 parts by mass of azobisisobutyronitrile, 2 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) are charged. 1-Methoxy-2-propanol was added so that the M ratio was 2. Next, the mixture was stirred at room temperature under a nitrogen atmosphere, and after all the above monomers had dissolved, the temperature of the solution was raised to 90 ° C. and held for 5 hours under a nitrogen atmosphere, whereby [D- 6] A polymer having an amide bond was obtained.

<Synthesis of [J] comparative component ([J-3] acrylic polymer having neither urethane bond nor amide bond)>
[Synthesis Example 3]
A flask is charged with 8 parts by weight of methacrylic acid, 36 parts by weight of benzyl methacrylate, 50 parts by weight of isobutyl methacrylate, 4 parts by weight of azobisisobutyronitrile, and 2 parts by weight of pentaerythritol tetrakis (3-mercaptobutyrate). 1-Methoxy-2-propanol was added so that the M ratio was 2. Next, the mixture was stirred at room temperature under a nitrogen atmosphere, and after all the monomers were dissolved, the temperature of the solution was raised to 90 ° C. and held for 5 hours under a nitrogen atmosphere, thereby [J] [J as a comparative component] -3] An acrylic polymer having neither a urethane bond nor an amide bond was obtained.

<Preparation of radiation-sensitive resin composition>
[Example 1]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of the agent (B-1), 100 parts by weight (solid content) of the [C] compound dispersion (C-1), 100 parts by weight of (D-1) as a compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 1) was prepared.

[Example 2]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of the agent (B-1), 100 parts by weight (solid content) of the [C] compound dispersion (C-1), 100 parts by weight of (D-2) as a compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 2) was prepared.

[Example 3]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of agent (B-1), 100 parts by weight (solid content) of [C] compound dispersion (C-1), 100 parts by weight of (D-3) as a compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 3) was prepared.

[Example 4]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of agent (B-1), 100 parts by weight (solid content) of [C] compound dispersion (C-1), 100 parts by weight of (D-4) as compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 4) was prepared.

[Example 5]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of the agent (B-1), 100 parts by weight (solid content) of the [C] compound dispersion (C-1), 100 parts by weight of (D-5) as a compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 5) was prepared.

[Example 6]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of the agent (B-1), 100 parts by weight (solid content) of the [C] compound dispersion (C-1), 100 parts by weight of (D-6) as a compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 6) was prepared.

[Example 7]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of agent (B-1), 75 parts by weight (solid content) of [C] compound dispersion (C-1), 100 parts by weight of (D-1) as compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 7) was prepared.

[Example 8]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of the agent (B-1), 75 parts by weight (solid content) of the [C] compound dispersion (C-1), 100 parts by weight of (D-2) as a compound [D] which is a high dielectric organic component, [E] 5 parts by mass of (E-1) as an adhesion aid and 0.10 parts by mass of (F-1) as a [F] surfactant are mixed, and the solid content concentration becomes 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition (S- 8) was prepared.

[Comparative Example 1]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. Agent (B-1) 10 parts by mass, [C] Compound dispersion (C-1) 100 parts by mass (solid content), [J] 100 parts by mass as comparative component (J-1), [E] Adhesion assistant 5 parts by weight of (E-1) as an agent and 0.10 parts by weight of (F-1) as a [F] surfactant are mixed together so that the solid concentration is 30% by weight [G]. After dissolving and dispersing in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition (CS-1). .

[Comparative Example 2]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. Agent (B-1) 10 parts by mass, [C] Compound dispersion (C-1) 100 parts by mass (solid content), [J] 100 parts by mass as comparative component (J-2), [E] Adhesion assistant 5 parts by weight of (E-1) as an agent and 0.10 parts by weight of (F-1) as a [F] surfactant are mixed together so that the solid concentration is 30% by weight [G]. After dissolving and dispersing in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition (CS-2). .

[Comparative Example 3]
[A] Into the solution containing (A-1) as a polymer, [B] Radiation-sensitive polymerization as a photosensitizer starts with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. Agent (B-1) 10 parts by weight, [C] Compound dispersion (C-1) 100 parts by weight (solid content), [J] 100 parts by weight as comparative component (J-3), [E] Adhesion assistant 5 parts by weight of (E-1) as an agent and 0.10 parts by weight of (F-1) as a [F] surfactant are mixed together so that the solid concentration is 30% by weight [G]. After dissolving and dispersing in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition (CS-3). .

Details of each component used in Examples and Comparative Examples are shown below.
<[B] Radiation sensitive polymerization initiator>
B-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Ciba Specialty Chemicals, Irgacure ( Registered trademark) OXE02)

<[C] Compound>
C-1: BaTiO ₃ (powder) (Toda Kogyo Co., Ltd., T-BTO-020)

<[D] Compound>
D-1: 6-functional urethane acrylate (Negami Kogyo Co., Ltd., Art Resin UN-906)
D-2: Bifunctional polyester urethane acrylate (Negami Kogyo Co., Ltd., Art Resin UN-9200A)
D-3: Ethoxylated isocyanuric acid triacrylate (Shin Nakamura Chemical Co., A-9300)
D-4: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (Shin Nakamura Chemical Co., A-9300-1CL)
D-5: Polyurethane resin (Arakawa Chemical Industries, Juliano KL-422)
D-6: Polymer having an amide bond as described in Synthesis Example 2 above

<[E] Adhesion aid>
E-1: γ-Glycidoxypropyltrimethoxysilane (Chisso Corporation, S-510)
<[F] Surfactant>
F-1: Silicone surfactant (Toray Dow Corning Silicone, SH28PA)

<[G] Organic solvent>
G-1: Ethyl 3-methoxypropionate G-2: 1-methoxy-2-propanol <[I] dispersant>
I-1: Phosphate ester salt (Big Chemie Japan, BYK-102)

<[J] Comparative component>
[J] A polymer having an ester bond or an acrylate was used as a comparative component.

J-1: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (pentaerythritol triacrylate content: about 60%) (Shin Nakamura Chemical Co., Ltd., NK Ester A-TMM-3LM-N)
J-2: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (dipentaerythritol pentaacrylate content 50%) (Shin Nakamura Chemical Co., Ltd., NK Ester A-9550)
J-3: Acrylic polymer having neither urethane bond nor amide bond described in Synthesis Example 3

<Evaluation of physical properties of radiation-sensitive resin composition and insulating film>
An insulating film was formed from the radiation-sensitive resin composition prepared as described above, and the physical properties were evaluated. The results are also shown in Table 1.

[Preparation of patterning evaluation substrate]
Using the radiation sensitive resin compositions (S-1) to (S-8) and (CS-1) to (CS-3) described in Examples and Comparative Examples, each was cured on a Si (silicon) wafer. After coating with a spin coater so as to have a post film thickness of 0.5 μm, it was pre-baked on a hot plate at 90 ° C. for 100 seconds, and the organic solvent was evaporated to form each coating film. Next, using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), 100 mJ of UV light was irradiated through a pattern mask capable of forming a predetermined pattern. Thereafter, using a tetramethylammonium hydroxide aqueous solution (developer) having a concentration of 2.38% by mass, development processing was performed at 25 ° C. for 100 seconds by a liquid piling method. After development processing, each coating film is washed with running water for 1 minute with ultrapure water, dried to form a pattern on the wafer, and then cured by heating (post-baking) at 230 ° C. for 30 minutes in an oven, An insulating film was formed on the Si wafer.

[Evaluation of patterning properties]
The penetrating 20 μm × 20 μm hole formed in the insulating film formed as described above was observed with an optical microscope, and the degree of residue was evaluated. The patterning property was evaluated as A when the residue could not be confirmed, B when the residue could be confirmed slightly, C when the residue could be clearly confirmed, and D when the residue could be confirmed in large quantities.

[Fabrication of electrical property evaluation board]
Using the radiation sensitive resin compositions (S-1) to (S-8) and (CS-1) to (CS-3) described in Examples and Comparative Examples, each is a glass substrate with an ITO film. After coating on an ITO substrate with a spin coater so as to have a film thickness of 1 μm, it was pre-baked on a hot plate at 90 ° C. for 100 seconds, and the organic solvent was evaporated to form each coating film. Next, as an electrode extraction site for measuring electrical characteristics, a part of the end of the substrate coated with the radiation-sensitive resin composition was wiped with acetone to expose the underlying ITO. Next, UV light is irradiated by 100 mJ with a UV exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), and then cured by heating (post-baking) at 230 ° C. for 30 minutes in an oven to form an insulating film on the ITO substrate. Formed.

[Measurement of dielectric constant]
An Al (aluminum) electrode for measuring the capacitance is formed on a vacuum deposition apparatus (JEOL VACUUM) on the insulating film of each electrical property evaluation substrate produced by the method described in [Production of electrical property evaluation substrate]. It was prepared using EVAPROTOR JEE-420). Next, a lead wire for electrode connection is soldered to the ITO portion of each substrate that has been exposed in advance, and the lead wire and an Al electrode produced by a vacuum deposition apparatus are respectively connected to an LCR meter (HEWRET PACKARD 4284A PRECISION LCR METER). The capacitance C of the insulating film was measured under the conditions of an applied voltage of 100 mV and a frequency of 1000 Hz. The value of the dielectric constant ε was obtained by substituting the measured value of the capacitance C, the area S (m ² ) of the Al electrode, and the thickness d (m) of the cured film into the following equation.

<Measurement method of leakage current>
Leakage current measurement box in which each substrate (lead wire and Al electrode) measured for the dielectric constant in [Measurement of dielectric constant] described above is connected to an electrometer (KEITHLEY 6517A ELECTROMETER / HIGH REISTANCE METER) The leakage current was measured by applying a voltage between the electrodes sandwiching the insulating film so that the electric field strength was 50 V / μm, and the terminal was connected to the terminal of (KEITHLEY 8002A HIGH RESISTANCE TEST FIXTURE). Since the value of the leak current varies immediately after the start of measurement, the value 1 minute after the start of measurement was evaluated as the leak current value.

  As is clear from Table 1, the radiation-sensitive resin compositions (S-1 to S-6) described in Examples 1 to 6 contain [C] compounds, and the insulating films formed using them are high. The dielectric constant ε was indicated.

  And the radiation sensitive resin composition (S-1 to S-6) as described in Examples 1-6 contains the [D] compound of a compound which has a urethane bond or an amide bond with a [C] compound. As a result, the insulating film formed from the radiation sensitive resin compositions (S-1 to S-6) of Examples 1 to 6 does not contain the [D] compound and has neither a urethane bond nor an amide bond. [J] The value of dielectric constant ε is improved by about 0.5 as compared with the insulating film formed from the radiation sensitive resin composition (CS-1 to CS-3) described in Comparative Examples 1 to 3 including the comparative component. Was. From this result, it is considered that the dielectric constant of the insulating film containing them is improved by urethane bonds and amide bonds which are easily polarized.

  Moreover, the radiation sensitive resin compositions (S-7 and S-8) described in Example 7 and Example 8 were the radiation sensitive resin compositions (S-1 and S-8) described in Example 1 and Example 2. Compared with S-2), the amount of the [C] compound is reduced by 25%. This is because the insulating film formed from the radiation-sensitive resin compositions (S-7 and S-8) is from the radiation-sensitive resin compositions (CS-1 to CS-3) described in Comparative Examples 1 to 3. This is because the components are prepared so as to have a dielectric constant equivalent to that of the formed insulating film.

As a result, in the insulating film formed from the radiation sensitive resin compositions (CS-1 to CS-3) described in Comparative Examples 1 to 3, the leakage current value was on the order of 10 ^−7. In the insulating film formed from the radiation-sensitive resin composition (S-7 and S-8) described in Example 7 and Example 8, the leakage current value can be suppressed to a value on the order of 10 ^−8. did it. As a result, it is considered that the occurrence of a leak path in the insulating film is suppressed by reducing the content of the [C] compound that is the metal oxide particles, which leads to suppression of the leak current.

  Furthermore, the insulating film formed from the radiation-sensitive resin compositions (S-7 and S-8) described in Example 7 and Example 8 is metal oxide particles that are difficult to dissolve in the developer [C]. By reducing the content of the compound, it was possible to suppress the occurrence of a residual, and the patterning property was improved.

  From the above results, the radiation-sensitive resin composition containing the [A] polymer, [B] radiation-sensitive polymerization initiator, and [C] compound contains the [D] compound having a urethane bond or an amide bond as a component. By containing, the relative dielectric constant of the insulating film formed therefrom could be further improved. In addition, the amount of the [C] compound, which is a metal particle oxide added for increasing the dielectric constant, can be reduced. As a result, it was possible to improve the patterning property and suppress the leakage current in the formed insulating film.

  The radiation-sensitive resin composition of the present invention can form a highly reliable insulating film that is simply patterned, and can provide an array substrate including the insulating film. And the liquid crystal display element manufactured using this array substrate has high reliability. Therefore, a liquid crystal display element including an insulating film formed using the radiation-sensitive resin composition of the present invention is suitable for applications such as large liquid crystal televisions that require excellent image quality and reliability.

1 array substrate 4, 11 substrate 5 video signal line 5a second source-drain electrode 6 first source-drain electrode 7 scanning signal line 7a gate electrode 8 active element 8a semiconductor layer 9 pixel electrode 10 alignment film 12 organic insulating film 13 Black matrix 14 Common electrode 15 Colored pattern 17 Contact hole 22 Color filter substrate 23 Liquid crystal layer 27 Backlight 28 Polarizing plate 31 Gate insulating film 32 Inorganic insulating film 33 Insulating film 41 Liquid crystal display element

Claims (8)

[A] polymer,
[B] a photosensitive agent, and [C] a radiation-sensitive resin composition comprising a compound containing titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium, and lead. Because
[C] A radiation-sensitive resin composition, wherein the compound has a particle size in the range of 0.01 μm to 0.1 μm and a c / a axial ratio of 1.0025 to 1.010.   [A] The radiation-sensitive resin composition according to claim 1, wherein the polymer is a polymer containing a structural unit having a carboxyl group.   [B] The radiation-sensitive resin composition according to claim 1 or 2, wherein the photosensitive agent contains at least one selected from a photo radical polymerization initiator and a photo acid generator.   The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the [C] compound is barium titanate.   [D] includes at least one selected from the group consisting of a polymer having at least one of a urethane bond and an amide bond, and a (meth) acrylate compound having at least one of a urethane bond and an amide bond. The radiation sensitive resin composition of any one of Claims 1-4 characterized by the above-mentioned.   The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition is used for forming an insulating film of a display element.   It forms using the radiation sensitive resin composition of any one of Claims 1-5, The insulating film characterized by the above-mentioned.   The display element characterized by including the insulating film formed from the radiation sensitive resin composition of any one of Claims 1-5.

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