JP2018072523A - Liquid crystal display element and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display element that suppresses generation of air bubbles and has sufficient general characteristics such as a voltage retention rate, and a method for manufacturing the liquid crystal display element.SOLUTION: The liquid crystal display element includes two substrates disposed opposing to each other, an interlayer insulation film deposited on at least one inner surface side of the substrates, and a liquid crystal layer disposed between the substrates and formed of a polymerizable liquid crystal composition. The interlayer insulation film is formed of a radiation-sensitive resin composition comprising a polymerizable compound having at least two polymerizable groups and a ring structure and a radiation-sensitive compound; and the ring structure is an aliphatic carbon ring structure, a heterocyclic structure, a condensed carbon ring structure, or a combination of these structures.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a liquid crystal display element and a manufacturing method thereof.

  In recent years, liquid crystal display devices have been widely used as television receivers, monitor devices for personal computers, and the like. The liquid crystal display device used for these applications is required to have a wide viewing angle that allows the display screen to be viewed from all directions. As a liquid crystal display device capable of obtaining a wide viewing angle, for example, an apparatus using a MVA (Multi-domain Vertical Alignment) type liquid crystal display element is known. However, such a liquid crystal display device has a disadvantage that the response time of the liquid crystal is not sufficiently short, and the alignment is liable to be disturbed by finger pressing or the like.

  Therefore, a polymer liquid crystal composition that can be polymerized by light is used for the liquid crystal display element, and a polymer alignment support (PSA) that memorizes the tilt direction of the liquid crystal compound by applying a voltage to polymerize the liquid crystal compound in a tilted state. : Polymer Sustained Alignment) technology has been studied (see JP 2003-149647 A). A liquid crystal display element using the PSA technology has a strong alignment regulating force because a polymer film that stores the tilt direction of the liquid crystal compound is formed at the interface between the liquid crystal and the liquid crystal alignment film. Therefore, by using this PSA technology, it is possible to realize a liquid crystal display device that has a short response time and is less likely to be disturbed by finger pressing or the like.

JP 2003-149647 A

  In the manufacture of a liquid crystal display element using such a PSA technology, a polymerizable liquid crystal composition capable of photopolymerization is injected between a pair of substrates (inside the cell), and the entire cell is irradiated with light, thereby increasing the polymerizability. The liquid crystal compound or other polymerizable compound is polymerized. This light irradiation is performed with a high exposure amount of about 1 J, for example. However, when an interlayer insulating film formed of an organic material is stacked between the wiring of the substrate and the pixel electrode, foaming may occur due to the interlayer insulating film due to light irradiation. When such foaming occurs in the pixel region of the liquid crystal display element, a product defect occurs. It is understood that the foaming is caused by the decomposition of the organic substance forming the interlayer insulating film and the evaporation of the low-volume component which is the decomposition product during light irradiation. The low molecular weight component usually stays inside or on the surface of the interlayer insulating film as adsorbing, etc., but the desorption is accelerated when the liquid crystal display element is heated or shocked, and the low molecular weight component becomes a bubble. And appear in the pixel area.

  The interlayer insulating film is required to have a voltage holding ratio and chemical resistance as general characteristics. Furthermore, when the said interlayer insulation film is formed from a radiation sensitive resin composition, the sensitivity and resolution of this radiation sensitive resin composition are also required.

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide a liquid crystal display element that suppresses the generation of bubbles and satisfies general characteristics such as voltage holding ratio, and such a liquid crystal display. It is providing the manufacturing method of an element.

  In order to solve the above-mentioned problems, an invention is made by providing two substrates disposed opposite to each other, an interlayer insulating film laminated on at least one inner surface of the substrate, and a polymerizable liquid crystal disposed between the substrates. A liquid crystal layer formed from the composition, wherein the interlayer insulating film is formed from a radiation-sensitive resin composition containing a polymerizable compound having two or more polymerizable groups and a ring structure and a radiation-sensitive compound, A liquid crystal display element in which the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a condensed carbocyclic structure, or a combination thereof.

  Another invention made in order to solve the above-described problems includes a step of forming an interlayer insulating film on the surface side of at least one of the pair of substrates, a liquid crystal on the surface side of the interlayer insulating film and the surface side of the other substrate. A step of forming an alignment film, a step of filling a polymerizable liquid crystal composition between the substrates in a state where the surfaces on which the liquid crystal alignment film is formed are opposed to each other, and a polymerizable liquid crystal composition filled between the substrates And a step of forming a liquid crystal layer by irradiating light to an object, wherein the interlayer insulating film is formed from a radiation-sensitive resin composition containing a polymerizable compound having two or more polymerizable groups and a ring structure and a radiation-sensitive compound. The method for producing a liquid crystal display device, wherein the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a condensed carbocyclic structure, or a combination thereof.

  The present invention can provide a liquid crystal display element in which generation of bubbles is suppressed and general characteristics such as a voltage holding ratio are satisfied, and a method for manufacturing such a liquid crystal display element.

FIG. 1 is a schematic cross-sectional view in a pixel region of a liquid crystal display element according to an embodiment of the present invention.

<Liquid crystal display element>
A liquid crystal display element according to an embodiment of the present invention includes two substrates disposed opposite to each other, an interlayer insulating film laminated on at least one inner surface of the substrate, and a liquid crystal layer disposed between the substrates. Is provided.

  In the liquid crystal display element, the liquid crystal mode includes, for example, TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Aligned Swing), FFS (Fringed Field Swing). ) And the like can be selected.

  The liquid crystal display element is preferably an active matrix liquid crystal display element so that the interlayer insulating film in which foaming is suppressed effectively contributes to high image quality display by increasing the aperture ratio of the pixel.

  The liquid crystal display element is preferably an active matrix VA mode liquid crystal display element using PSA technology so that the effectiveness of the interlayer insulating film in which foaming is suppressed becomes more remarkable. The VA mode liquid crystal display element includes an MVA mode.

  Hereinafter, as an example of the liquid crystal display element, an active matrix VA mode liquid crystal display element using PSA technology will be described with reference to FIG.

  The liquid crystal display element 1 of FIG. 1 is a VA mode liquid crystal display element, and more specifically, is an active matrix type VA mode liquid crystal display element using PSA technology. The liquid crystal display element 1 is a transmissive type, and includes an array substrate 15 that is a display element substrate, and a color filter substrate 90 that is disposed so as to face the array substrate 15. The liquid crystal layer 10 is formed by sealing the liquid crystal composition between the substrates 15 and 90 with a sealing material (not shown) provided on the substrate.

  The array substrate 15 has a structure in which a substrate 21, an interlayer insulating film 52, and a pixel electrode 36 are provided in this order in a pixel region that is a display region in which a plurality of pixels are arranged. More specifically, the array substrate 15 includes a base coat film 22, a semiconductor layer 23, a gate insulating film 24, and an insulating substrate 21 in a pixel area that is a display area in which a plurality of pixels are arranged. The gate electrode 25, the inorganic insulating film 41, the source electrode 34 and the drain electrode 35 made of the first wiring layer 61, the interlayer insulating film 52, the pixel electrode 36 provided for each pixel, and the pixel region are covered. The provided liquid crystal alignment film 37 is stacked in this order from the substrate 21 side.

  As described above, on the substrate 21 constituting the array substrate 15, the TFT 29 including the semiconductor layer 23, the gate insulating film 24, and the gate electrode 25 and functioning as a pixel switching element is directly formed for each pixel. The TFT 29 constitutes a so-called top gate type TFT. The source electrode 34 and the drain electrode 35 made of the first wiring layer 61 are connected to the source / drain regions of the semiconductor layer 23 through contact holes 31 f provided in the inorganic insulating film 41. The pixel electrode 36 is connected to the drain electrode 35 formed of the first wiring layer 61 through a contact hole 31 g provided in the interlayer insulating film 52.

  The color filter substrate 90 includes a black matrix 92 made of a light-shielding member provided between the pixels and a red, green, and blue color filter provided for each pixel on the insulating substrate 91 in the pixel region. 93, a common electrode 94 made of a transparent conductive film, and a liquid crystal alignment film 95 are formed in this order from the substrate 91 side.

  The liquid crystal display element 1 of FIG. 1 will be described in more detail. The substrate 21 is not particularly limited, but for example, a glass substrate, a quartz substrate, a resin substrate made of an acrylic resin, or the like is preferably used. The substrate 21 is preferably subjected to cleaning and pre-annealing as pretreatment for constituting the array substrate 15.

The base coat film 22 on the substrate 21 is formed by, for example, forming a 50 nm thick SiON film and a 100 nm thick SiOx film in this order by a plasma enhanced chemical vapor deposition (PECVD) method. can do. Examples of the source gas for forming the SiON film include a mixed gas of monosilane (SiH ₄ ), nitrous oxide gas (N ₂ O), and ammonia (NH ₃ ). Note that the SiOx film is preferably formed using a tetraethyl orthosilicate (TEOS) gas as a source gas. Further, the base coat film 22 may include a silicon nitride (SiNx) film formed using a mixed gas of monosilane (SiH ₄ ) and ammonia (NH ₃ ) as a source gas. The thickness of the base coat film 22 is preferably 80 nm or more and 600 nm or less, that is, 80 nm to 600 nm.

  The semiconductor layer 23 can be formed by patterning a polysilicon (p-Si) film according to a known method. For example, the semiconductor layer 23 can be low-temperature polysilicon.

  The semiconductor layer 23 can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 23 of this embodiment include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  As an amorphous oxide applicable to the semiconductor layer 23, an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn) can be given.

  Specific examples of amorphous oxides applicable to the semiconductor layer 23 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, Sn—In—Zn oxide, In—Sn—Zn oxide (ITZO: indium tin zinc oxide), and the like can be given. In the above case, the composition ratio of the constituent materials does not necessarily need to be 1: 1 or 1: 1: 1, for example, and a composition ratio that realizes desired characteristics can be selected.

The p-Si patterning for forming the semiconductor layer 23 can be performed by a known method. For example, first, an amorphous silicon (a-Si) film having a thickness of 50 nm is formed by PECVD. Examples of the source gas for forming the a-Si film include SiH ₄ and disilane (Si ₂ H ₆ ). Since the a-Si film formed by the PECVD method contains hydrogen, a process (dehydrogenation process) for reducing the hydrogen concentration in the a-Si film is performed at about 500 ° C. Subsequently, laser annealing is performed to melt, cool, and crystallize the a-Si film, thereby forming a p-Si film. For laser annealing, for example, an excimer laser can be used. The p-Si film is formed by applying a metal catalyst such as nickel without dehydrogenation as a pretreatment for laser annealing (in order to make continuous grain boundary crystalline silicon (CG-silicon)), and solidifying by heat treatment. Phase growth may be performed. Further, as the crystallization of the a-Si film, only solid phase growth by heat treatment may be performed. Next, dry etching using a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) is performed, the p-Si film is patterned, and the semiconductor layer 23 is formed. The thickness of the semiconductor layer 23 is preferably 20 nm to 100 nm.

  In the semiconductor layer 23, a channel region, a source region, and a drain region (not shown) are formed. These are formed after forming a gate insulating film 24 described later or after forming a gate electrode described later. It is formed in the layer 23.

  That is, in the semiconductor layer 23, an impurity such as boron is doped through the gate insulating film 24 by an ion doping method, an ion implantation method, or the like in order to control the threshold voltage of the TFT 29, thereby forming a channel region.

  In the semiconductor layer 23, impurities such as phosphorus and boron are doped at a high concentration by an ion doping method, an ion implantation method, or the like using the gate electrode 25 as a mask. Next, in order to activate the impurity ions existing in the semiconductor layer 23, a thermal activation process is performed at about 700 ° C. for 6 hours, whereby a source region and a drain region are formed. As a method for activating the impurity ions, a method of irradiating an excimer laser can be used.

  The gate insulating film 24 may be a silicon oxide film having a thickness of 45 nm, for example. For the formation, TEOS gas can be used as a source gas. The material of the gate insulating film 24 is not particularly limited, and a SiNx film, a SiON film, or the like may be used. Examples of the source gas for forming the SiNx film and the SiON film include the same source gases as those described in the process for forming the base coat film 22. The gate insulating film 24 may be a stacked body made of the plurality of materials. The thickness of the gate insulating film 24 is preferably 30 nm to 150 nm.

As the gate electrode 25, a tantalum nitride (TaN) film having a thickness of 30 nm and a tungsten (W) film having a thickness of 370 nm are formed in this order by sputtering, and then a resist film is desired by photolithography. After forming a resist mask by patterning into a shape of, argon (Ar), sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), oxygen (O ₂ ), chlorine (Cl ₂ ), etc. It is formed by performing dry etching using an etching gas whose amount of mixed gas is adjusted. Examples of the material of the gate electrode 25 include a refractory metal having a flat surface and stable characteristics such as tantalum (Ta), molybdenum (Mo), and molybdenum tungsten (MoW), and a low resistance metal such as aluminum (Al). . Further, the gate electrode 25 may be a laminated body made of the above-mentioned plurality of materials, and further, for example, a plurality of metals selected from Al, Cr, Ta, Mo, Ti, W, Cu, Nb, Mn, and Mg. The alloy which consists of may be sufficient. The thickness of the gate electrode 25 is preferably 100 nm to 500 nm.

  The inorganic insulating film 41 is formed by forming a SiNx film having a thickness of 100 nm to 400 nm, more preferably 200 nm to 300 nm, and a TEOS film having a thickness of 500 nm to 1000 nm, more preferably 600 nm to 800 nm on the entire surface of the substrate 21 by PECVD. It is formed by forming a film. As the inorganic insulating film 41, a SiON film or the like may be used. Further, in order to stabilize the electrical characteristics of the TFT 29 as the characteristics of the TFT 29 deteriorate over time, a thin cap film (for example, a TEOS film) of about 50 nm may be formed below the inorganic insulating film 41.

  For the contact hole 31f, a resist mask is formed by patterning a resist film into a desired shape by photolithography, and then the gate insulating film 24 and the inorganic insulating film 41 are wet-etched using a hydrofluoric acid-based etching solution. Is formed. Note that dry etching may be used for the etching.

  The source electrode 34 and the drain electrode 35 are formed of the first wiring layer 61, and are formed by the following steps. That is, a 100 nm thick titanium (Ti) film, a 500 nm thick aluminum (Al) film, and a 100 nm thick Ti film are formed in this order by sputtering or the like. Next, a resist mask is formed by patterning the resist film into a desired shape by photolithography, and then a Ti / Al / Ti metal laminated film is patterned by dry etching to form the first wiring layer 61. Thereby, the source electrode 34 and the drain electrode 35 are formed. In addition, as a metal which comprises the 1st wiring layer 61, it may replace with Al and may use an Al-Si alloy. Here, Al is used for reducing the resistance of the wiring. However, when high heat resistance is required and a certain increase in resistance value is allowed (for example, in the case of a short wiring structure), As the metal constituting the first wiring layer 61, the gate electrode material (Ta, Mo, MoW, W, TaN, Al, etc.) described above may be used.

  The interlayer insulating film 52 is formed from a radiation sensitive resin composition to be described later. That is, the interlayer insulating film 52 is a layer obtained by curing the radiation sensitive resin composition. Specifically, the coating film is formed on the entire surface of the substrate 21 by a spin coating method using a spinner or the like using a radiation sensitive resin composition. Next, after exposure through a photomask in which a light-shielding pattern having a desired shape is formed, patterning is performed by, for example, removing a coating film in a region to be the contact hole 31g by performing etching (development processing). I do. Further, for example, heating is performed at 200 ° C. for about 30 minutes to manufacture the interlayer insulating film 52 as a cured film in which the contact holes 31g are formed. The film thickness of the interlayer insulating film 52 is preferably 1 μm to 5 μm, more preferably 2 μm to 3 μm, which can sufficiently exhibit the insulating function and the planarization function.

  Further, the contact hole 31g is formed by patterning a coating film of the radiation sensitive resin composition when the interlayer insulating film 52 is manufactured. A method for forming the interlayer insulating film 52 will be described in detail later.

  The pixel electrode 36 is formed with an ITO (Indium Tin Oxide) film or an IZO (Indium Zinc Oxide) film having a film thickness of 50 nm to 200 nm, more preferably 100 nm to 150 nm, by sputtering or the like. Thereafter, it is formed by patterning into a desired shape by photolithography.

  The liquid crystal alignment film 37 is formed on the surface in contact with the liquid crystal layer 10 of the array substrate 15 so as to cover at least the pixel region. The liquid crystal alignment film may be a vertical alignment liquid crystal alignment film formed using a polymer material such as polyimide, polysiloxane, or acrylic polymer. The vertically aligned liquid crystal alignment film aligns the liquid crystal so that the major axis direction of the liquid crystal of the liquid crystal layer 4 is perpendicular or substantially perpendicular to the substrate surface. The alignment of the liquid crystal in which the major axis direction of the liquid crystal is perpendicular or substantially perpendicular to the substrate surface is simply referred to as “substantially perpendicular alignment”. Such a liquid crystal alignment film 37 uses a liquid alignment agent prepared containing polyimide, polysiloxane, acrylic polymer, or a precursor thereof, for example, after forming the coating film by a printing method, and then drying by heating. In addition, after that, if necessary, it can be formed by performing an orientation treatment.

  Since the liquid crystal alignment film 37 is a vertical alignment type liquid crystal alignment film, the liquid crystal display element 1 is combined with a liquid crystal having negative dielectric anisotropy of the liquid crystal layer 10 to be described later. can do.

  Next, the substrate 91, the black matrix 92, and the color filter 93 constituting the color filter substrate 90 will be described.

  The substrate 91 is an insulating substrate similar to the substrate 21 constituting the array substrate 15.

  The black matrix 92 is formed by forming a light shielding film by sputtering and patterning the film.

  The color filter 93 includes a red color filter 93, a green color filter 93, and a blue color filter 93 as shown below. The red color filter 93 is formed by laminating a resin film (dry film) in which a red pigment is dispersed over the entire pixel region, and performing exposure, development, and baking (heat treatment). The green color filter 93 is formed by laminating a resin film in which a green pigment is dispersed over the red color filter 93 and laminating the entire pixel region, and then performing exposure, development, and baking (heating treatment). is there. The blue color filter 93 is formed in the same manner as the green color filter 93.

  The color filter substrate 90 can have columnar spacers (not shown) made of a laminate of the above-described light-shielding film and the above-described resin film in a light-shielding region other than the pixel openings.

  The common electrode 94 is formed by depositing ITO on the upper layer of the color filter 93.

  The liquid crystal alignment film 95 is a liquid crystal alignment film similar to the liquid crystal alignment film 37 of the array substrate 15 described above.

  The color filter 93 of the color filter substrate 90 may be formed by a photolithography method using a color resist. Photo spacers may be formed on the color filter substrate 90 by photolithography using a color resist. Further, instead of forming the black matrix 92, a wiring such as a source line or a CS line of the TFT substrate 15 may be substituted.

  The liquid crystal display element 1 shown in FIG. 1 is polymerized between the substrates 15 and 90 by a sealing material (not shown) provided around the array substrate 15 and the color filter substrate 90 disposed to face the array substrate 15. The liquid crystal layer 10 is formed by filling and sealing the liquid crystal composition. The liquid crystal layer 10 is a layer formed by polymerizing at least a part of the polymerizable liquid crystal composition.

  The bonding of the array substrate 15 and the color filter substrate 90 using the sealing material can be performed as follows. That is, after a sealing material is applied to the outer periphery of the pixel region of the array substrate 15, a polymerizable liquid crystal composition having negative dielectric anisotropy is dropped inside the sealing material using a dispenser or the like. The polymerizable liquid crystal composition will be described later.

  Next, the color filter substrate 90 is bonded to the array substrate 15 onto which the polymerizable liquid crystal composition has been dropped. The steps so far are performed in a vacuum. Next, when the bonded substrates 15 and 90 are returned to the atmosphere, the polymerizable liquid crystal composition diffuses between the bonded substrates 15 and 90 by atmospheric pressure. Next, UV (ultraviolet) light is irradiated to the sealing material 39 while moving the UV (ultraviolet) light source along the application region of the sealing material 39 to cure the sealing material 39. In this way, the diffused polymerizable liquid crystal composition is filled and sealed between a pair of opposing substrates 15 and 90 to form a layer of the polymerizable liquid crystal composition for forming the liquid crystal layer 10. .

  As a method for injecting a polymerizable liquid crystal composition between a pair of substrates, a polymerizable liquid crystal composition injection port is provided on one side of both the array substrate 15 and the color filter substrate 90, and a polymerizable liquid crystal is formed therefrom. A method of injecting the composition and then sealing the polymerizable liquid crystal composition injection port with an ultraviolet curable resin or the like may be used.

  Next, formation of the liquid crystal layer 10 filled and sealed between the array substrate 15 and the color filter substrate 90 can be performed as follows.

That is, after the array substrate 15 and the color filter substrate 90 are bonded together to form a layer of a polymerizable liquid crystal composition between the substrates 15 and 90, a voltage that turns on the TFT 29 is applied to the gate electrode 25. Then, an AC voltage is applied between the source electrode 34 and the common electrode 94 to tilt the liquid crystal compound. Next, the layer of the polymerizable liquid crystal composition is irradiated with UV light from the array substrate 15 side while maintaining the state in which the liquid crystal is tilted and aligned. That is, light irradiation is performed on the polymerizable liquid crystal composition filled between the substrates. The exposure of the UV light, for example, be a 50 mJ / cm ² or more 2,000 mJ / cm ² or less.

  By this UV light irradiation, the polymerizable liquid crystal compound or photopolymerizable compound contained in the polymerizable liquid crystal composition is polymerized, and the surface of the liquid crystal alignment films 37 and 95 on the liquid crystal layer 10 side is overlapped to define the pretilt angle of the liquid crystal. A coalescence is formed. That is, by polymerizing a polymerizable liquid crystal compound or the like while the liquid crystal of the liquid crystal layer 10 is tilted, a polymer storing the direction in which the liquid crystal tilts by voltage application can be provided on, for example, the array substrate 15.

  Thereafter, the liquid crystal display element 1 can be manufactured through a panel cutting step, a polarizing plate attaching step, an FCP substrate attaching step, a liquid crystal display panel and a backlight unit combining step, and the like.

(Polymerizable liquid crystal composition)
Examples of the polymerizable liquid crystal composition include (1) a composition containing a liquid crystal compound and a photopolymerizable compound, and (2) a composition containing a liquid crystal compound having a polymerizable group. These polymerizable liquid crystal compositions may contain a photopolymerization initiator.

  Examples of the liquid crystal compound include nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like. As the liquid crystal compound, nematic liquid crystal is preferable. In addition, these liquid crystals may contain cholesteric liquid crystals, chiral nematic liquid crystals, chiral smectic liquid crystals, and chiral compounds in order to improve performance.

  Specific liquid crystal compounds include, for example, 4-substituted benzoic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenyl ester, 4- ( 4-substituted cyclohexanecarbonyloxy) benzoic acid 4′-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4′-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4′-substituted cyclohexyl ester, 4-substituted 4′-substituted biphenyl, 4-substituted phenyl 4′-substituted cyclohexane, 4-substituted 4 ″ -substituted terphenyl, 4-substituted biphenyl 4′-substituted cyclohexane, 2- (4-substituted phenyl) -5 -Substituted pyrimidine and the like.

  Examples of the polymerizable group that the liquid crystal compound having a polymerizable group has include a vinyl group, a (meth) acryl group, a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, an epoxy group, and an isocyanate group. .

Examples of the photopolymerizable compound include styrene, chlorostyrene, α-methylstyrene, divinylbenzene;
As substituents, methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxy Acrylate having ethyl group, phenoxyethyl group, allyl group, methallyl group, glycidyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-chloro-2-hydroxypropyl group, dimethylaminoethyl group, diethylaminoethyl group, etc. , Methacrylate or fumarate;
Mono (meth) acrylate or poly (meta) such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and pentaerythritol ) Acrylate;
Vinyl acetate, vinyl butyrate, vinyl benzoate, acrylonitrile, cetyl vinyl ether, limonene, cyclohexene, diallyl phthalate, diallyl isophthalate, vinyl pyridine, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-hydroxymethylacrylamide or N-hydroxyethyl Methacrylamide and their alkyl ether compounds;
Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol;
Diol or tri (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane;
Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A;
Reaction product of 1 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of phenyl isocyanate or n-butyl isocyanate;
Poly (meth) acrylate of dipentaerythritol;
Examples include oligomers such as caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate.

  Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) ), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one ("Darocur 1116" from Merck), 2,2-dimethoxy-1,2-diphenylethane-1-one ( Ciba-Geigy "Irgacure 651"), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (Ciba-Geigy "Irgacure 907"), 2,4-diethyl Thioxanthone (“Kayacure DETX” from Nippon Kayaku) and ethyl p-dimethylaminobenzoate (from Nippon Kayaku) Kayacure -EPA ") a mixture of, a mixture of isopropylthioxanthone (word pre Kin Sop's" Kantakyua ITX ") and p- dimethylaminobenzoic acid ethyl.

<Radiation sensitive resin composition>
Below, the radiation sensitive resin composition which forms the interlayer insulation film 52 is explained in full detail. The radiation sensitive resin composition includes [B] a radiation sensitive compound and a polymerizable compound having two or more polymerizable groups and a cyclic structure ([C] polymerizable compound). The said radiation sensitive resin composition contains a [A] polymer normally, and also the other component may contain. In the liquid crystal display element, by forming the interlayer insulating film from the radiation-sensitive resin composition, generation of bubbles due to light irradiation when forming the liquid crystal layer is suppressed. Moreover, according to the said liquid crystal display element, it is excellent also in the chemical-resistance and voltage holding rate of the interlayer insulation film formed from the said radiation sensitive resin composition. Moreover, the said radiation sensitive resin composition also has a favorable sensitivity and resolution.

[[A] polymer]
[A] A polymer is a polymer which becomes a base of an interlayer insulation film. [A] The polymer is not particularly limited, but a polymer having a structural unit (I) containing a carboxy group and a structural unit (II) containing an epoxy group in the same or different polymer molecules ([A1] A polymer having a structural unit (III) containing an acid-dissociable group ([A2] polymer), a siloxane-based polymer ([A3] polymer), and the like.

([A1] polymer)
[A1] The polymer is a polymer having a structural unit (I) containing a carboxy group and a structural unit (II) containing an epoxy group in the same or different polymer molecules. Such [A1] polymer is a polymer containing both the structural unit (I) and the structural unit (II) in one molecule, or a polymer containing the structural unit (I) and the structural unit (II). It is a mixture with a polymer containing. [A1] The polymer is usually an acrylic polymer.

(Structural unit (I))
The structural unit (I) is not particularly limited as long as it is a structural unit containing a carboxy group. Monomers that give this structural unit (IA) include, for example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, and carboxy at both ends. And mono (meth) acrylate of a polymer having a group and a hydroxyl group, an unsaturated polycyclic compound having a carboxy group, and an anhydride thereof.

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

  Examples of unsaturated dicarboxylic acids and anhydrides thereof include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides thereof.

  Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], hexahydro And phthalic acid mono [2- (meth) acryloyloxy) ethyl].

  Examples of the mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate.

  Examples of unsaturated polycyclic compounds having a carboxy group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept. 2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy -6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2 .1] hept-2-ene anhydride and the like.

  Among these monomers, monocarboxylic acid and dicarboxylic acid anhydrides are preferable, and (meth) acrylic acid and maleic anhydride are more preferable in view of copolymerization reactivity, solubility in alkaline aqueous solution, and availability. .

  [A1] The lower limit of the content ratio of the structural unit (I) in the polymer is preferably 1% by mass, more preferably 5% by mass, and more preferably 10% by mass with respect to all the structural units constituting the [A1] polymer. Is more preferable. On the other hand, as an upper limit of this content rate, 60 mass% is preferable, 40 mass% is more preferable, and 30 mass% is further more preferable. By making the content rate of structural unit (I) into the said range, the solubility (alkali solubility) to the developing solution of a radiation sensitive resin composition and the adhesiveness to the board | substrate etc. of an interlayer insulation film improve. In addition, the content rate of a structural unit can be considered that it is the same as the preparation ratio of a corresponding monomer (hereinafter, it is the same).

(Structural unit (II))
The structural unit (II) is not particularly limited as long as it is a structural unit containing an epoxy group. The epoxy group refers to a group containing a cyclic ether structure, an oxiranyl group having a three-membered ether structure (1,2-epoxy structure), an oxetanyl group having a four-membered ether structure (1,3-epoxy structure), An alicyclic epoxy group etc. can be mentioned. As an epoxy group, an oxiranyl group is preferable. By having such a crosslinkable epoxy group, the strength of the interlayer insulating film formed from the radiation-sensitive resin composition can be further increased.

  Examples of the structural unit (II) include a structural unit represented by the following formula.

In the above formula, R ¹¹ is a hydrogen atom or a methyl group.

Monomers that give structural unit (II) include glycidyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo [5.2. 1.0 ^2.6 ] Decyl acrylate is preferred, and glycidyl methacrylate is more preferred.

  [A1] The lower limit of the content ratio of the structural unit (II) in the polymer is preferably 1% by mass, more preferably 5% by mass, and more preferably 10% by mass with respect to all the structural units constituting the [A1] polymer. Is more preferable. On the other hand, as an upper limit of this content rate, 70 mass% is preferable, 60 mass% is more preferable, and 50 mass% is further more preferable. By setting the content ratio of the structural unit (II) within the above range, the strength of the interlayer insulating film can be effectively increased.

(Other structural units (IV))
[A1] The polymer may have other structural units (IV) other than the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired. This other structural unit does not include the structural unit (III) having an acid dissociable group, which will be described later. [A1] The polymer may further have a structural unit (III) having an acid dissociable group.

  Other monomers that give structural units include, for example, (meth) acrylic acid ester having an alcoholic hydroxyl group, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl Examples include esters, unsaturated aromatic compounds, and conjugated dienes.

  Examples of the (meth) acrylic acid ester having an alcoholic hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, Examples include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

  Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, methacrylic acid. N-lauryl acid, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate , N-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate, and the like.

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

  Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-tolylmaleimide. N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  [A1] The lower limit of the content ratio of the structural unit (IV) in the polymer is preferably 10% by mass and more preferably 30% by mass with respect to all the structural units constituting the [A1] polymer. On the other hand, as this upper limit, 80 mass% is preferable and 70 mass% is more preferable. By setting it as such a content rate, while the solubility with respect to aqueous alkali solution is optimized, the radiation sensitive resin composition excellent in a radiation sensitivity is obtained.

([A2] polymer)
[A2] The polymer is a polymer having a structural unit (III) containing an acid dissociable group. This acid dissociable group acts as a protecting group for protecting the carboxy group or the phenolic hydroxyl group in the [A2] polymer. The [A2] polymer having such a protecting group is usually insoluble or hardly soluble in an aqueous alkali solution. Since the protective group is an acid-dissociable group, the [A2] polymer becomes soluble in an alkaline aqueous solution when the protective group is dissociated by the action of an acid. When the said radiation sensitive resin composition contains a [A2] polymer, it becomes possible to achieve high radiation sensitivity and to improve the stability of the pattern shape obtained by image development. [A2] The polymer is a so-called chemical amplification polymer.

(Structural unit (III))
As the structural unit (III), a structural unit containing a group represented by the following formula (1) or the following formula (2) is preferable.

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of hydrogen atoms possessed by a hydrocarbon group having 1 to 30 carbon atoms. A group substituted with a hydroxyl group, a halogen atom or a cyano group. However, there is no case where R ¹ and R ² are both hydrogen atoms. R ¹ and R ² may be bonded to each other to form an aliphatic carbocyclic structure having 4 to 30 carbon atoms together with the carbon atom to which they are bonded. R ³ is a hydroxyl group, a halogen atom or a cyano group in which a part of hydrogen atoms of an oxyhydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms is substituted. A group substituted with a group.

In the formula ^{(2), R} 4 ~R ¹⁰ are each independently hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{1 to} R ³ in the above formula (1) include, for example, a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and 3 carbon atoms. -30 alicyclic hydrocarbon groups etc. are mentioned.

  Examples of the linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- ( 4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- ( 3-methylpentyl) group and the like.

  Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, a 1- (2-cyclopentylethyl) group, a cyclohexyl group, a cyclohexylmethyl group, A cycloheptyl group, 2-norbornyl group, etc. can be mentioned.

Examples of the oxyhydrocarbon group having 1 to 30 carbon atoms represented by R ³ in the above formula (1) include an alkoxy group having 1 to 30 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; a cyclopentyloxy group, nor A cycloalkyloxy group having 3 to 30 carbon atoms such as bornyloxy group; an aryloxy group having 6 to 30 carbon atoms such as phenoxy group, tolyloxy group and naphthyloxy group; 7 carbon atoms such as benzyloxy group and naphthylmethoxy group -30 aralkyloxy groups and the like.

The hydrocarbon group having 1 to 12 carbon atoms represented by R ^{4 to} R ¹⁰ in the above formula (2) is a hydrocarbon having 1 to 30 carbon atoms represented by R ^{1 to} R ³ in the above formula (1). Among those exemplified as groups, those having 12 or less carbon atoms can be mentioned.

  Examples of the structural unit (III) having a group represented by the above formula (1) include those represented by the following formulas (1-1) to (1-10).

In the above formulas (1-1) to (1-10), R ¹² is a hydrogen atom or a methyl group.

  Examples of the monomer that gives the structural unit (III) represented by the formulas (1-1) to (1-10) include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, 1- (trimethyl methacrylate). Cyclodecanyloxy) ethyl, 1- (pentacyclopentadecanylmethyloxy) ethyl methacrylate, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) ethyl methacrylate, Examples include 1- (adamantyloxy) ethyl methacrylate and the like.

    Examples of the structural unit (III) having a group represented by the above formula (2) include structural units represented by the following formulas (2-1) to (2-5).

In the above formulas (2-1) to (2-5), R ¹³ represents a hydrogen atom or a methyl group.

  As the structural unit (III) represented by the above formula (2), a structural unit represented by the formula (2-3) given by tetrahydro-2H-pyran-2-yl methacrylate is preferable.

  As a content rate of structural unit (III), 10 mass% is preferable with respect to all the structural units which comprise a [A2] polymer, 25 mass% is more preferable, and 40 mass% is further more preferable. On the other hand, as an upper limit of this content rate, 75 mass% is preferable, 65 mass% is more preferable, and 55 mass% is further more preferable. By making the content rate of structural unit (III) into the said range, the resolution can be raised more.

(Structural unit (I) and structural unit (II))
[A2] The polymer preferably has a structural unit (I) containing a carboxy group and a structural unit (II) containing an epoxy group. The structural unit (I) and the structural unit (II) are as described above.

  [A2] The lower limit of the content ratio of the structural unit (I) in the polymer is preferably 1% by mass, more preferably 3% by mass, and more preferably 5% by mass with respect to all structural units constituting the [A2] polymer. Is more preferable. On the other hand, as an upper limit of this content rate, 50 mass% is preferable, 30 mass% is more preferable, and 15 mass% is further more preferable. By making the content rate of structural unit (I) into the said range, the solubility (alkali solubility) to the developing solution of a radiation sensitive resin composition and the adhesiveness to the board | substrate etc. of an interlayer insulation film improve.

  [A2] The lower limit of the content ratio of the structural unit (II) in the polymer is preferably 5% by mass, more preferably 10% by mass, and more preferably 25% by mass with respect to all the structural units constituting the [A2] polymer. Is more preferable. On the other hand, as an upper limit of this content rate, 60 mass% is preferable, 50 mass% is more preferable, and 40 mass% is further more preferable. By setting the content ratio of the structural unit (II) within the above range, the strength of the interlayer insulating film can be effectively increased.

(Other structural units (IV))
[A2] The polymer may have other structural units other than the structural unit (I), the structural unit (II) and the structural unit (III) as long as the effects of the present invention are not impaired. Specific examples of the monomer that gives other structural units are as described above.

  As a minimum of the content rate of structural unit (IV) in a [A2] polymer, 1 mass% is preferable with respect to all the structural units which comprise a [A2] polymer, and 3 mass% is more preferable. On the other hand, as this upper limit, 30 mass% is preferable and 10 mass% is more preferable. By setting it as such a content rate, while the solubility with respect to aqueous alkali solution is optimized, the radiation sensitive resin composition excellent in a radiation sensitivity is obtained.

([A1] Polymer and [A2] Polymer Synthesis Method)
As the [A1] polymer and the [A2] polymer (hereinafter also referred to as “[A1] polymer etc.”), for example, a monomer corresponding to a predetermined structural unit is used by using a radical polymerization initiator. Can be synthesized by polymerization in a solvent. [A1] As a method for synthesizing a polymer or the like, a solution containing a monomer and a radical initiator is dropped into a solution containing a reaction solvent to cause a polymerization reaction, a solution containing the monomer, and a radical A method in which a solution containing an initiator is separately dropped into a solution containing a reaction solvent to cause a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator A method in which a polymerization reaction is carried out by dropping into a solution containing a reaction solvent is preferable.

  [A1] Examples of the solvent used for the polymerization reaction of the polymer and the like include organic solvents exemplified as one component of the radiation-sensitive resin composition described later.

  [A1] As a polymerization initiator used in a polymerization reaction of a polymer or the like, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (methyl 2-methylpropionate) Azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide.

  [A1] In a polymerization reaction of a polymer or the like, a molecular weight modifier can be used to adjust 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; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[A1] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer constituting the polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, preferably 5 0.0 × 10 ³ or more and 5.0 × 10 ⁴ or less is more preferable. [A1] The radiation sensitivity and alkali developability of the radiation-sensitive resin composition can be increased by setting the Mw of the polymer constituting the polymer or the like in the above range.

[A1] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer constituting the polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and 5.0 × 10 ³ or more and 5 or less. 0.0 × 10 ⁴ or less is more preferable. [A1] By setting the Mn of the polymer constituting the polymer or the like in the above range, the curing reactivity during curing of the coating film of the radiation-sensitive resin composition can be improved.

  [A1] The molecular weight distribution (Mw / Mn) of the polymer constituting the polymer or the like is preferably 3.0 or less, and more preferably 2.6 or less. [A1] The developability of the coating film can be improved by setting the Mw / Mn of the polymer constituting the polymer or the like to 3.0 or less.

([A3] polymer)
[A3] The polymer is a so-called polysiloxane, and is preferably a hydrolyzed condensate of a hydrolyzable silane compound.

  Here, the “hydrolyzable silane compound” is usually hydrolyzed by heating within a temperature range from room temperature (about 25 ° C.) to about 100 ° C. in the coexistence of non-catalyst and excess water to form a silanol group. Or the compound which has a hydrolysis group which produces | generates a siloxane condensate. In addition, in the radiation-sensitive resin composition, some hydrolyzable silane compounds are in a state where some or all of the hydrolyzable groups in the molecule are not hydrolyzed, and other hydrolyzable silane compounds. It may remain in the monomer state without condensing with. The “hydrolysis condensate” means a hydrolysis condensate obtained by condensing some silanol groups of the hydrolyzed silane compound.

  As the hydrolyzable silane compound, a hydrolyzable silane compound represented by the following formula (S-1) (hereinafter also referred to as “(S1) compound”) and / or a hydrolyzate represented by the following formula (S-2). A hydrolyzable silane compound containing a decomposable silane compound (hereinafter also referred to as “(S2) compound”) is preferred.

[(S1) Compound]
(S1) The compound is a compound represented by the above formula (S-1). In the above formula ^{(S-1), R 14} is an alkyl group having 1 to 6 carbon atoms. R ¹⁵ is an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, a styryl group, or a vinyl group. p is an integer of 1 to 3. As this p, 1 or 2 is preferable from the viewpoint of the progress of hydrolysis condensation reaction, and 1 is more preferable. ^{However, if R 14} or ^{R 15} is plural, ^{R 14} or ^{R 15} may be different even in the same.

The alkyl group having 1 to 6 carbon atoms represented by R ^14, a methyl group, an ethyl group, n- propyl group, i- propyl group, a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. N-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl Group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1, 1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 4,4- Dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group, 1,3-dimethylpentyl group Group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethylbutyl group, 1,2, 3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1-methylheptyl group, 2-ethylhexyl Group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-heptadecyl group, n-he Sadeshiru group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like. As carbon number of a C1-C20 alkyl group, 1-10 are preferable and 1-3 are more preferable.

  Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a tetrafluoroethyl group, and a heptafluoropropyl group.

  Examples of the (S1) compound having p = 1 are phenyltrimethoxysilane, tolyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryl. Examples include trimethoxysilane, o-styryltriethoxysilane, m-styryltrimethoxysilane, m-styryltriethoxysilane, p-styryltrimethoxysilane, and p-styryltriethoxysilane.

  Examples of the (S1) compound having p of 2 include phenylmethyldimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, and phenyltrifluoropropyldimethoxysilane. Dialkoxysilane compounds.

  As the (S1) compound having p of 3, for example, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-methacryloxypropyldiphenylmethoxysilane, 3-acryloxypropyldiphenylmethoxysilane, 3,3′-dimethacryloxypropyldimethoxysilane, 3,3′-diacryloxypropyldimethoxysilane, 3,3 ′, 3 ″ -Trimethacryloxypropylmethoxysilane, 3,3 ', 3' '-triacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxysilane.

[(S2) Compound]
(S2) The compound is a compound represented by the above formula (S-2). In the above formula ^{(S-2), R 16} is an alkyl group having 1 to 6 carbon atoms. R ¹⁷ is a phenyl group, tolyl group, naphthyl group, epoxy group, amino group, isocyanate group, (meth) acryloyloxy group, 3,4-epoxycyclohexyl group, oxetanyl group, mercapto group or succinic anhydride group. q is an integer of 0-3. As this q, 1 or 2 is preferable from the viewpoint of progress of hydrolysis condensation reaction, and 1 is more preferable. ^{However, if R 16} or ^{R 17} is plural, ^{R 16} or ^{R 17} may be different even in the same. n is an integer of 0-6.

The alkyl group having 1 to 6 carbon atoms represented by R ^16, a methyl group, an ethyl group, n- propyl group, i- propyl group, a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis.

  The (S2) compound in which q is 0 is a silane compound substituted with four hydrolyzable groups. Examples of the silane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, and tetra-i-propoxysilane.

  The (S2) compound having q = 1 is a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups. Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, and ethyltributoxysilane. , Butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphthyltrimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane o-tolyl Limethoxysilane, m-tolyltrimethoxysilane, p-tolyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethyltripropoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 2-acrylic Loxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryl Roxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluorobutyltrimethoxysilane, 3- (trimethoxy And trialkoxysilane compounds such as silyl) propyl succinic anhydride.

  The (S2) compound having q of 2 is a silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups. Examples of the silane compound include 3-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane.

  The (S2) compound having q of 3 is a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group. Examples of the silane compound include 3-methacryloxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-isocyanatopropyldimethylmethoxysilane, and the like.

  When both the (S1) compound and the (S2) compound are used, the mixing ratio of the (S1) compound and the (S2) compound is preferably such that the (S1) compound exceeds 5 mol%. When the compound (S1) is 5 mol% or less, the exposure sensitivity when forming a protective film as a cured film is low, and the scratch resistance and the like of the resulting protective film tend to be reduced.

([A3] Polymer synthesis (hydrolytic condensation))
[A3] The polymer (polysiloxane) is usually heated in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of excess water and optionally in the presence of a solvent or a catalyst to It can be synthesized by condensing a silanol group obtained by hydrolysis of a decomposable silane compound.

  As water for the hydrolysis-condensation reaction, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 2 mol with respect to 1 mol of the total amount of hydrolyzable groups of the compound (S1) and (S2). Particularly preferred is 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

  Examples of the solvent for the hydrolysis condensation reaction include alcohols, ethers, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether Pionate, aromatic hydrocarbons, ketones, other esters and the like can be mentioned. These solvents may be used alone or in combination of two or more.

  Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether. Acetate, propylene glycol monomethyl ether, and butyl methoxyacetate are preferred.

  As a catalyst for hydrolysis condensation reaction, an acid catalyst, a base catalyst, and an alkoxide are preferable.

  Examples of the acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids, and the like.

  Examples of the base catalyst include ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine, basic ion exchange resins, hydroxides such as sodium hydroxide, and carbonates such as potassium carbonate. Salts; carboxylates such as sodium acetate; and various Lewis bases.

  Examples of the alkoxide include zirconium alkoxide, titanium alkoxide, aluminum alkoxide, and the like. Tri-i-propoxyaluminum can be used as the aluminum alkoxide.

  The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0.001 mol per mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction. 1 mole.

  The polystyrene-reduced weight average molecular weight (Mw) by GPC of the [A3] polymer such as a hydrolysis-condensation product is preferably 500 to 10,000, and more preferably 2,000 to 7,000. [A3] By setting the Mw of the polymer to 500 or more, the film formability of the radiation-sensitive resin composition can be improved. On the other hand, when the Mw of the [A3] polymer is 10,000 or less, the developability of the radiation sensitive resin composition can be prevented from being lowered.

  [A3] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is preferably 300 to 5,000, more preferably 500 to 3,000. By setting Mn of the [A3] polymer in such a range, the curing reactivity during curing of the coating film of the radiation sensitive resin composition is improved.

  [A3] The molecular weight distribution (Mw / Mn) of the polymer is preferably 3.0 or less, and more preferably 2.6 or less. [A3] By setting Mw / Mn of the polymer to 3.0 or less, the developability of the coating film can be improved.

([A] Polymer content)
The lower limit of the content of the [A] polymer with respect to the total solid content of the radiation-sensitive resin composition is, for example, 30% by mass, and preferably 50% by mass. On the other hand, as an upper limit of this content, 90 mass% is preferable and 70 mass% is more preferable. [A] By setting the content of the polymer in the above range, an interlayer insulating film having good sensitivity, resolution, strength and the like can be obtained.

[[B] Radiation sensitive compound]
[B] Radiation sensitive compounds include compounds capable of generating radicals in response to radiation (ie, [B-1] radical polymerization initiators), compounds generating acids in response to radiation (ie, And [B-2] acid generator), and a compound that generates a base in response to radiation (that is, [B-3] base generator). Among these, [B-1] radical polymerization initiator and [B-2] acid generator are preferable. Moreover, you may use these in combination of multiple types. The “radiation” is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  [B] The lower limit of the content of the radiation sensitive compound is preferably 1 part by weight, more preferably 3 parts by weight, and still more preferably 5 parts by weight with respect to 100 parts by weight of the [A] polymer. On the other hand, the upper limit is preferably 40 parts by mass, and more preferably 30 parts by mass. [B] By setting the use ratio of the radiation-sensitive compound in the above range, the radiation-sensitive resin composition has a high solvent resistance, a high hardness, a high adhesion, a low foaming property, etc. even at a low exposure amount. It is possible to form an interlayer insulating film having In addition, suitable content as a [B-1] radical polymerization initiator or a [B-2] acid generator is mentioned later.

([B-1] radical polymerization initiator)
[B] When the radiation sensitive compound contains a [B-1] radical polymerization initiator, it functions suitably as a negative radiation sensitive resin composition in which the [C] polymerizable compound or the like in the exposed portion is cured. [B-1] Examples of the radical polymerization initiator 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-methylbenzoyl). ) -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), and ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  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, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.

  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 and 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 and 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole is preferred. More preferred.

  [B-1] The radical polymerization initiators can be used alone or in admixture of two or more. [B-1] The lower limit of the content of the radical polymerization initiator is preferably 1 part by mass and more preferably 3 parts by mass with respect to 100 parts by mass of the polymer [A]. As an upper limit of this content, 30 mass parts is preferable and 10 mass parts is more preferable. [B-1] By setting the use ratio of the radical polymerization initiator within the above range, the radiation-sensitive resin composition has high solvent resistance, high hardness, high adhesion, and low foaming even at a low exposure amount. An interlayer insulating film having properties and the like can be formed.

([B-2] acid generator)
[B] When the radiation sensitive compound contains [B-2] acid generator and [A-2] polymer, the acid dissociable group of [A-2] polymer is dissociated by the acid generated in the exposed portion. Since alkali solubility is increased, it functions suitably as a positive radiation sensitive resin composition. In addition, when the [B-2] acid generator is a quinonediazide compound, the alkali solubility of the exposed portion is increased regardless of the type of the [A] polymer, and thus it functions suitably as a positive radiation sensitive resin composition. . In addition, when the [B] radiation sensitive compound contains the [B-2] acid generator and the [A-3] polymer, the [A-3] polymer (polysiloxane) of the [A-3] polymer (polysiloxane) is generated by the acid generated in the exposed portion. Since the curing reaction proceeds, it can function as a negative radiation sensitive resin composition.

  [B-2] Examples of the photoacid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinone diazide compounds. . In addition, these [B-2] photo-acid generators may be used independently and may mix and use 2 or more types.

  As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (B1) is preferable.

In the above formula (B1), 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. Group 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 (B1) 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. Examples of the substituent include an alicyclic group containing a bridged alicyclic group such as an alkoxy group having 1 to 10 carbon atoms and a 7,7-dimethyl-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.

The alicyclic hydrocarbon group represented by R ^A is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. 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.

  Examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene). -(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) -(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile and the like.

  [B-2] By using an oxime sulfonate compound as an acid generator, the resulting radiation-sensitive resin composition can improve sensitivity and solubility.

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

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

  [B-2] By using an onium salt as the acid generator, the obtained radiation-sensitive resin composition can improve sensitivity and solubility.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy). ) 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 monomer Imides, 4-methylphenyl-sulfonyloxy) diphenyl maleimide, and the like.

  [B-2] By using a sulfonimide compound as the acid generator, the obtained radiation-sensitive resin composition can improve sensitivity and solubility.

  As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

  [B-2] By using a sulfonic acid ester compound as an acid generator, the resulting radiation-sensitive resin composition can improve sensitivity and solubility.

  A quinonediazide compound is a compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

  Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

  Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, and the like.

  Examples of pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone.

  Examples of hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone and 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone.

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxy). Phenyl) 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'-spirobiy Den -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  As other mother nucleus, for example, 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.

  Of these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, and 4,4 ′-[1- {4- (1- [4-Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol is preferably used.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 85 mol%, more preferably 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide. -4-sulfonic acid amide and the like are also preferably used.

  These quinonediazide compounds can be used alone or in combination of two or more.

  [B-2] The lower limit of the content of the acid generator is preferably 1 part by mass and more preferably 3 parts by mass with respect to 100 parts by mass of the polymer [A]. [B-2] When the acid generator is a quinonediazide compound, the lower limit of the content is more preferably 10 parts by mass. On the other hand, the upper limit of the content of the [B-2] acid generator is preferably 40 parts by mass and more preferably 30 parts by mass with respect to 100 parts by mass of the [A] polymer. [B-2] When the acid generator is a compound other than the quinonediazide compound, the upper limit is more preferably 10 parts by mass. [B-2] By setting the use ratio of the acid generator in the above range, the radiation-sensitive resin composition has high solvent resistance, high hardness, high adhesion, and low foaming property even at a low exposure amount. Etc. can be formed.

([B-3] Base generator)
Specific examples of the base generator include, for example, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethyl Heterocyclic group-containing radiation-sensitive base generators such as amino-1- (4-morpholinophenyl) -butanone, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, 1- (anthraquinone-2-yl) ethylimidazolecarboxylate ;
2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, o -Carbamoylhydroxylamide, o-carbamoyloxime, hexaamminecobalt (III) tris (triphenylmethylborate), 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate Etc.

[[C] polymerizable compound]
[C] The polymerizable compound is a compound having two or more polymerizable groups and a ring structure. The ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a condensed carbocyclic structure, or a combination thereof. In the interlayer insulating film formed from such a radiation-sensitive resin composition containing a [C] polymerizable compound, the [C] polymerizable compound has the above-mentioned polymerizable group, [C] between the polymerizable compounds and others. A crosslinked structure is formed between these components. Here, it is presumed that a film having a particularly dense cross-linked structure can be formed when the [C] polymerizable compound has a ring structure including an aliphatic carbocyclic structure, a heterocyclic structure or a condensed carbocyclic structure. This dense cross-linked structure is considered to exhibit light resistance to high exposure doses and contribute to the reduction of foaming. Moreover, according to the said radiation sensitive resin composition which can form such a precise | minute structure, the chemical-resistance and voltage holding rate of the interlayer insulation film obtained can also be made favorable.

(Polymerizable group)
[C] The polymerizable compound has a plurality of polymerizable groups in one molecule. The plurality of polymerizable groups possessed by one molecule may be the same or different.

  Examples of the polymerizable group include a (meth) acryloyl group, a vinyl group, an epoxy group, an alkoxysilyl group, a styryl group, and an isocyanate group. Among these, an epoxy group, a (meth) acryloyloxy group, an alkoxysilyl group, or a combination thereof is preferable. When these polymerizable groups are these groups, a denser cross-linked structure is formed and foaming can be further suppressed.

  Examples of the epoxy group include an oxiranyl group and an oxetanyl group, and an oxiranyl group (1,2-epoxy structure) is preferable.

  Examples of the alkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.

  [C] The number of polymerizable groups possessed by the polymerizable compound is not particularly limited as long as it is 2 or more, and the upper limit is, for example, 10, 5, or 3.

(Ring structure)
[C] The polymerizable compound has one or more aliphatic carbocyclic structure, heterocyclic structure, condensed carbocyclic structure or a combination thereof in one molecule. [C] The polymerizable compound usually has one ring structure in one molecule.

  The aliphatic carbocyclic structure refers to a carbocyclic ring that does not contain an aromatic ring. As said aliphatic carbocyclic structure, a C5-C30 aliphatic carbocyclic structure can be mentioned, A C5-C20 aliphatic carbocyclic structure is preferable. Specific examples of the aliphatic carbocyclic structure include a cyclopentane structure, a cyclohexane structure, a dicyclopentadiene structure, a norbornane structure, an adamantane structure, and a steroid structure (structure having a steroid skeleton). The aliphatic carbocyclic structure may be monocyclic or polycyclic.

  The heterocyclic structure is a ring structure composed of carbon atoms and other atoms (for example, oxygen atom, nitrogen atom, sulfur atom, etc.). Examples of the heterocyclic structure include a furan structure, a thiophene structure, an oxane structure, a triazine structure, an imidazole structure, a pyrazole structure, an oxazole structure, an indole structure, a purine structure, and a carbazole structure. Among these, a triazine structure is preferable. The triazine structure refers to a six-membered ring structure composed of three nitrogen atoms and three carbon atoms, and is a concept including a trione structure (isocyanuric acid structure). Among the triazine structures, a trione structure (isocyanuric acid structure) is more preferable. The heterocyclic structure may be monocyclic or polycyclic.

  The condensed carbocyclic structure refers to a ring structure in which two or more carbocycles are bonded by sharing two or more atoms. The condensed carbocyclic structure may be a condensed ring of an aromatic ring and an aliphatic ring (aliphatic carbocyclic structure), or may be a condensed ring of aromatic rings, but the condensed aromatic ring and aliphatic ring. A ring is preferred. Examples of the condensed carbocyclic structure include a naphthalene structure, an anthracene structure, an acenaphthalene structure, a fluorene structure, and the like, and a fluorene structure is preferable.

  The ring structure is preferably a fluorene structure, a triazine structure, an aliphatic carbocyclic structure having 5 to 20 carbon atoms, or a combination thereof. With these structures, an interlayer insulating film having a denser cross-linked structure can be formed, and foaming can be further suppressed.

  [C] The polymerizable compound may be a monomer or a polymer containing an oligomer, but is preferably a monomer. By being a monomer, foaming can be further reduced due to the denser structure formed by crosslinking.

  [C] The polymerizable compound is more preferably a compound represented by the following formula (C-1), (C-2) or (C-3). In addition, the compound represented by the following formula (C-2) is a compound having a fluorene structure. Moreover, the compound represented by the following formula (C-3) is a compound having a triazine structure (isocyanuric acid structure).

  In the above formulas (C-1), (C-2) and (C-3), each R is independently a group containing a (meth) acryloyl group, a vinyl group, an epoxy group or an alkoxysilyl group. a, b and c are each independently an integer of 1 to 10.

  Each R may independently be a (meth) acryloyl group, a vinyl group, an epoxy group, or an alkoxysilyl group. R is preferably a (meth) acryloyl group or a group containing an epoxy group, more preferably a (meth) acryloyl group or an epoxy group. The epoxy group is preferably an oxiranyl group (1,2-epoxy structure).

  [C] Specific examples of the polymerizable compound include dicyclopentadienyl di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (“N- BPEF ”), isocyanuric acid EO-modified di- and triacrylate (“ Aronix M-313 ”from Toa Gosei Co., Ltd.), triglycidyl isocyanurate (“ TEPIC-S ”from Nissan Chemical Co., Ltd.), tris- (trimethoxysilylpropyl) And isocyanurate (“KBM-9659” manufactured by Shin-Etsu Chemical Co., Ltd.).

  [C] The lower limit of the content of the polymerizable compound is preferably 10 parts by weight, more preferably 20 parts by weight, further preferably 30 parts by weight, and particularly preferably 40 parts by weight with respect to 100 parts by weight of the polymer [A]. preferable. On the other hand, the upper limit of the content is preferably 150 parts by mass, more preferably 100 parts by mass, and still more preferably 80 parts by mass. [C] By setting the content of the polymerizable compound in the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained interlayer The light resistance and foaming suppression property of the insulating film are also improved.

[[C] Other polymerizable compounds]
The radiation sensitive resin composition may contain [c] other polymerizable compounds other than the [C] polymerizable compound. [C] Examples of other polymerizable compounds include bifunctional or higher functional (meth) acrylic acid esters that do not contain the specific ring structure.

As such (meth) acrylic acid ester,
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Bifunctional (meth) acrylic acid esters such as 1,9-nonanediol di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; dipentaerythritol penta (meth) Mixture of acrylate and dipentaerythritol hexa (meth) acrylate; ethylene oxide modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, succinic acid modified pentaerythritol tri (meth) acrylate , Succinic acid modified dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripenta Trifunctional or more (meth) acrylic acid esters such as Risuri Torr octa (meth) acrylate;
Can be mentioned.

  As an upper limit of content of [c] other polymeric compounds in the said radiation sensitive resin composition, it can be 50 mass parts with respect to 100 mass parts of [A] polymers, and 30 mass parts is preferable. In some cases.

  Moreover, as a minimum of content of [C] polymeric compound with respect to the total content of [C] polymeric compound and [c] other polymeric compounds, for example, 20 mass% may be sufficient, but 50 mass% Is preferable, and 65 mass% is more preferable. On the other hand, this upper limit may be 100% by mass. As described above, by increasing the content ratio of the [C] polymerizable compound in the total polymerizable compound, it is possible to further improve various characteristics of the radiation sensitive resin composition including foaming suppression.

[[F] Organic solvent]
The radiation-sensitive resin composition is usually a mixture of [F] organic solvent with [A] polymer, [B] radiation-sensitive compound, [C] polymerizable compound, and other optional components as necessary. To prepare a dissolved or dispersed state. [F] As the organic solvent, those that uniformly dissolve or disperse the above components and do not react with the components are preferably used.

  [F] Examples of the organic solvent include alcohols, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, Examples include dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, amides, and ketones. These can be used alone or in combination of two or more.

  The minimum of the solid content concentration of the said radiation sensitive resin composition is 5 mass%, for example, 10 mass% is preferable and 20 mass% is more preferable. On the other hand, this upper limit is preferably 50% by mass, and more preferably 40% by mass. By setting the solid content concentration within the specific range, it is possible to effectively suppress the occurrence of coating unevenness.

[[D] Antioxidant]
The radiation sensitive resin composition may contain [D] an antioxidant. [D] The antioxidant is a component that suppresses the breakage of the bond of the polymer molecule by capturing radicals generated by exposure or heating or by decomposing a peroxide generated by oxidation. When the radiation-sensitive resin composition contains an antioxidant, the degradation degradation of the polymer molecules in the formed interlayer insulating film is suppressed, and durability and the like can be improved. Antioxidants can be used alone or in combination of two or more.

  Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among these, the antioxidant is preferably a compound having a hindered phenol structure.

  Examples of the compound having a hindered phenol structure (hindered phenol compound) include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di- tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N '-Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxy Phenylpropionamide), 3,3 ′, 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -M-tolyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy -2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6- Scan (octylthio) -1,3,5-triazin-2-ylamine) phenol, and the like.

  As a minimum of content of the antioxidant in the said radiation sensitive resin composition, 0.01 mass part is preferable with respect to 100 mass parts of [A] polymers, and 0.05 mass part is more preferable. On the other hand, the upper limit may be 5 parts by mass, preferably 3 parts by mass, more preferably 1 part by mass, and still more preferably 0.3 parts by mass. Moreover, it may be preferable not to contain antioxidant. When there is much content of antioxidant, a sensitivity etc. may fall.

[[E] polymerization inhibitor]
The said radiation sensitive resin composition can contain a [E] polymerization inhibitor. [E] Examples of the polymerization inhibitor include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, p-methoxyphenol, N-nitroso-N-phenylhydroxyl. Examples include amine aluminum.

  As a minimum of content of [E] polymerization inhibitor in the above-mentioned radiation sensitive resin composition, it is 0.01 mass part, for example. As this upper limit, 0.5 mass part is preferable with respect to 100 mass parts of [A] polymer, and 0.3 mass part is more preferable. [E] If the content of the polymerization inhibitor exceeds the above upper limit, the sensitivity of the radiation-sensitive resin composition may be lowered and the pattern shape may be deteriorated.

[Other optional ingredients]
The said radiation sensitive resin composition can contain another arbitrary component as needed in the range which does not impair the expected effect. Examples of other optional components include surfactants, adhesion assistants, basic compounds, storage stabilizers, heat resistance improvers, and the like. Other optional components can be used alone or in combination of two or more.

<Method for manufacturing liquid crystal display element>
A method for manufacturing a liquid crystal display element according to an embodiment of the present invention includes:
Forming an interlayer insulating film on the surface side of at least one of the pair of substrates;
Forming a liquid crystal alignment film on the surface side of the interlayer insulating film and the surface side of the other substrate;
A step of filling a polymerizable liquid crystal composition between the substrates in a state in which the surfaces on which the liquid crystal alignment film is formed are opposed to each other; and a liquid crystal layer by light irradiation on the polymerizable liquid crystal composition filled between the substrates Comprising the step of forming
Forming the interlayer insulating film from a radiation sensitive resin composition comprising a polymerizable compound having two or more polymerizable groups and a ring structure and a radiation sensitive compound;
In the method for producing a liquid crystal display device, the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a condensed carbocyclic structure, or a combination thereof.

  According to the manufacturing method, by forming the interlayer insulating film from the radiation-sensitive resin composition, as described above, the generation of bubbles is also suppressed by light irradiation when forming the liquid crystal layer. Moreover, according to the manufacturing method, the chemical resistance and voltage holding ratio of the interlayer insulating film are excellent. Furthermore, according to the said manufacturing method, an interlayer insulation film can be formed with favorable sensitivity and resolution by using the said radiation sensitive resin composition.

  Hereinafter, the step of forming the interlayer insulating film (method for forming the interlayer insulating film) will be described in detail. Other processes are the same as those of a known method for manufacturing a liquid crystal display element using PSA technology. For example, the step of forming the liquid crystal alignment film can be performed by applying a liquid alignment agent and drying the coating film. Moreover, you may perform an orientation process as needed. The step of filling the polymerizable liquid crystal composition between the substrates is performed, for example, by dropping the polymerizable liquid crystal composition on one substrate, then bonding the pair of substrates, and sealing with a sealing material. Can do. The step of forming the liquid crystal layer by light irradiation can be performed by irradiating UV light in a state where the liquid crystal compound is tilted and aligned by applying a voltage. Details of the description of the manufacturing method of the liquid crystal display element including these steps are appropriately described together with the structure in the description of the liquid crystal display element 1, and thus the repeated description is omitted.

<Method for forming interlayer insulating film>
The method of forming the interlayer insulating film is as follows:
(1) The process of forming the coating film of the said radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3).

[Step (1)]
In the step (1), after coating the composition or the solution or dispersion on the substrate, the solvent is removed by heating (pre-baking) the coated surface, thereby forming a coating film.

  As a method for applying the composition solution or the dispersion, 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 the like can be employed. Among these coating methods, a spin coating method or a slit die coating method is preferable.

  The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but preferably 60 to 120 ° C. for about 1 minute to 10 minutes. According to the composition, even when the prebake conditions are relatively low, such as 60 ° C. to 80 ° C., excellent pattern formability can be exhibited.

<Step (2)>
In the step (2), at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed through a photomask having a predetermined pattern. As the radiation used for exposure, the radiation used for the photoacid generator is suitable. 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 exposure dose is preferably 500 J / m ^{2 to} 6,000 J / m ² , more preferably 1,500 J as a value measured with a luminometer (OAI model 356, manufactured by OAI Optical Associates) for the intensity of radiation at a wavelength of 365 nm. / M ^{2 to} 1,800 J / m ² .

<Step (3)>
In step (3), the coated film after exposure is developed to remove unnecessary portions and form a predetermined pattern. As the developer used in the development step, an alkaline aqueous solution is preferable. Examples of the alkali 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. .

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the radiation-sensitive composition, but is preferably about 10 seconds to 180 seconds. Subsequent to 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.

<Process (4)>
In the step (4), the patterned thin film is heated using a heating device such as a hot plate or an oven, whereby the curing reaction of the [A] polymer is promoted to obtain an interlayer insulating film. As heating temperature, it is 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, 5 minutes to 30 minutes when the heating process is performed on a hot plate, and 30 minutes to 90 minutes when the heating process is performed in the oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly by this Example. In addition, the characteristic of the polymer obtained by a synthesis example was measured with the following method.

[Weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw / Mn)]
Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following analytical conditions using Tosoh GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL).
The degree of dispersion (Mw / Mn) was calculated from the measurement results of Mw and Mn.
(Analysis conditions)
Elution solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Column temperature: 40 ° C
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Synthesis of polymer>
[Synthesis Example 1] (Synthesis of acrylic polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 5.2 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, 20 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, 50 parts by weight of tricyclo [5.2.1.0 ^2,6 ] dec-8-yl methacrylate, 10 parts by weight of methyl methacrylate, and α-methylstyrene dimer 0 After charging 5 parts by mass and substituting with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain an acrylic polymer solution containing the polymer (A-1). Mw of the polymer (A-1) was 15,000, and Mw / Mn was 2.0.

[Synthesis Example 2] (Synthesis of acrylic polymer (A-2))
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 12 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 9 parts by weight of N-cyclohexylmaleimide and 34 parts by weight of methyl methacrylate were charged, and after nitrogen substitution, the solution was stirred gently. The temperature was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution containing an acrylic polymer (A-2) as a polymer. Mw of the polymer (A-2) was 7,900, Mn was 3,200, and Mw / Mn was 2.5.

[Synthesis Example 3] (Synthesis of Chemically Amplified Polymer (A-3))
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 diethylene glycol ethyl methyl ether. Subsequently, after adding 50 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 35 parts by mass of glycidyl methacrylate, 5 parts by mass of dodecyl methacrylate, 10 parts by mass of methacrylic acid and 3 parts by mass of α-methylstyrene dimer, the nitrogen substitution was performed. Stirring was started gently. 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-3). Mw of the polymer (A-3) was 9,000, Mn was 3,600, and Mw / Mn was 2.5.

[Synthesis Example 4] (Synthesis of polysiloxane polymer (A-4))
In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane, and heated until the solution temperature reached 60 ° C. . After the solution temperature reached 60 ° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 4 hours. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As a result, a polysiloxane polymer (A-4) was obtained as a siloxane polymer which is a hydrolysis-condensation product. Mw of the polymer (A-4) was 5,000, Mn was 2,500, and Mw / Mn was 2.0.

<Preparation of radiation-sensitive resin composition>
[A] Polymer, [B] Radiation Sensitive Compound, [C] Polymerizable Compound, [D] Antioxidant, [E] Polymerization Inhibition Used in Preparation of Radiation Sensitive Resin Compositions of Examples and Comparative Examples Agents and [F] organic solvents are shown below.

<[A] polymer>
A-1, A-2, A-3 and A-4: Polymers synthesized in Synthesis Examples 1 to 4, respectively

<[B] Radiation sensitive compound>
B-1: “NCI-930” from ADEKA (photopolymerization initiator)
B-2: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol) B-3: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

<[C] polymerizable compound>
C-1: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (“A-BPEF” from Shin-Nakamura Chemical Co., Ltd.)
C-2: Fluorene skeleton polyfunctional epoxy compound ("OGSOL EG-200" from Osaka Gas Chemical Company)
C-3: EO modified diisocyanate and triacrylate (“Aronix M-313” manufactured by Toa Gosei Co., Ltd.)
C-4: Triglycidyl isocyanurate (Nissan Chemical's “TEPIC-S”)
C-5: Tris- (trimethoxysilylpropyl) isocyanurate (“KBM-9659” from Shin-Etsu Chemical Co., Ltd.)
c-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” from Nippon Kayaku Co., Ltd.)
c-2: Phenol novolac type liquid epoxy resin (“jER 152” of Japan Epoxy Resin)
c-3: Methacryloxypropyltrimethoxysilane ("XIAMETER (R) OFS-6030 SILANE" manufactured by Dow Corning Toray)

<[D] Antioxidant>
D-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (ADEKA, ADK STAB AO-60)

<[E] Polymerization inhibitor>
E-1: 2,5-di-t-butylhydroquinone (“2,5-di-t-butylhydroquinone” manufactured by Wako Pure Chemical Industries, Ltd.)

<[F] Organic solvent>
F-1: Methyl 3-methoxypropionate F-2: Propylene glycol monomethyl ether acetate

<Example 1>
In a solution containing the polymer (A-1), 5 parts by mass of the radiation-sensitive compound (B-1) and polymerizability with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer (A-1). 20 parts by mass of the compound (C-1), 40 parts by mass of the other polymerizable compound (c-1) and 0.1 parts by mass of the polymerization inhibitor (E-1) are mixed, and the solid content concentration becomes 30% by mass. Thus, after making it melt | dissolve in the mixed solvent of an organic solvent (F-1) and an organic solvent (F-2), it filters with a membrane filter with a hole diameter of 0.2 micrometer, and makes a radiation sensitive resin composition (S-1). Prepared.

<Examples 2-25 Comparative Examples 1-16>
Except having used each component of the kind and compounding quantity which are shown to following Table 1 and Table 2, it operated similarly to Example 1 and the radiation sensitive resin composition (S-2)-(S-25) and ( CS-1) to (CS-16) were prepared. In Tables 1 and 2, “-” indicates that the corresponding component was not blended.

<Evaluation>
An interlayer insulating film is formed from the radiation-sensitive resin compositions of Examples 1 to 25 and Comparative Examples 1 to 16, and the radiation sensitivity, resolution, foam resistance, chemical resistance and voltage holding ratio are set according to the methods described below. evaluated. The evaluation results are shown in Tables 1 and 2.

[Negative radiation sensitivity] (Examples 1 to 9, Comparative Examples 1 to 4)
After applying the radiation sensitive resin composition on a glass substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. Next, using an exposure machine ("PLA-501F" manufactured by Canon Inc .: using an ultra-high pressure mercury lamp), the amount of exposure was changed, and the coating film was passed through a pattern mask having a plurality of rectangular light shielding portions (10 μm × 10 μm). Exposure was performed. Next, a development process was performed at 25 ° C. by a liquid piling method using a tetramethylammonium hydroxide aqueous solution (developer) having a concentration of 2.38 mass%. The development processing time was 100 seconds. After the development treatment, the coating film was washed with running ultrapure water for 1 minute and dried to form a pattern on the glass substrate. This glass substrate was heated in a clean oven at 230 ° C. for 30 minutes to obtain an interlayer insulating film. With respect to the film thickness of the interlayer insulating film, the exposure amount at which the remaining film ratio (ratio in which the patterned thin film remains properly) represented by the following formula is 85% or more was obtained as sensitivity, and the sensitivity was evaluated according to the following criteria. .
Residual film ratio (%) = (film thickness after development / film thickness before development) × 100
(Evaluation criteria)
A: 200J / ^{m 2} less B: 200J / ^{m 2} or more 400 J / ^{m 2} less than C: 400J / ^{m 2} or more 800 J / ^{m 2} less than D: 800J / ^{m 2} or more

[Negative Resolution (Resolution)] (Examples 1 to 9, Comparative Examples 1 to 4)
An interlayer insulating film having a through hole was formed in the same manner as the evaluation of radiation sensitivity except that the exposure amount was 200 J / m ^2, and the minimum diameter of the through hole of this interlayer insulating film was observed with an optical microscope. The resolution (resolution) was evaluated according to the following criteria.
(Evaluation criteria)
A: Minimum diameter of the through hole is 10 μm or more B: Minimum diameter of the through hole is 8 μm or more and less than 10 μm C: Minimum diameter of the through hole is 5 μm or more and less than 8 μm D: No through hole is formed

[Positive Radiation Sensitivity] (Examples 10 to 25, Comparative Examples 5 to 16)
Hexamethyldisilazane (HMDS) was applied onto a chromium-deposited glass substrate using a spinner and heated at 60 ° C. for 1 minute (HMDS treatment). Each positive radiation-sensitive composition prepared as described above is applied onto the chromium-deposited glass substrate after the HMDS treatment using a spinner and pre-baked at 90 ° C. for 2 minutes to obtain a film thickness of 3.0 μm. The coating film was formed. Subsequently, using an exposure machine ("PLA-501F" manufactured by Canon Inc .: using an ultra-high pressure mercury lamp), the exposure amount was changed and passed through a mask having a 60 μm line and space (10 to 1) pattern. Then, the coating film was exposed. Then, it developed with the puddle method at 25 degreeC with 2.38 mass% tetramethylammonium hydroxide aqueous solution. The development time was 80 seconds. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. The entire surface of the coating film was exposed to 300 J / m ² , and this chromium film-formed glass substrate was heated in a clean oven at 230 ° C. for 30 minutes to obtain an interlayer insulating film. The amount of exposure necessary to completely dissolve the 6 μm space pattern during development was examined.
(Evaluation criteria)
A: 200J / ^{m 2} less B: 200J / ^{m 2} or more 400 J / ^{m 2} less than C: 400J / ^{m 2} or more 800 J / ^{m 2} less than D: 800J / ^{m 2} or more

<Manufacture of liquid crystal display elements and evaluation of foam resistance>
[Evaluation of foaming resistance]
In this example, an active matrix type VA mode color liquid crystal display device having the same structure as that of the liquid crystal display device 1 shown in FIG.

  First, an array substrate constituting a liquid crystal display element was manufactured. First, according to a known method, a semiconductor layer made of p-Si is formed on an insulating glass substrate made of non-alkali glass so that the array substrate to be manufactured has the same TFT as the TFT 29 of FIG. 1 described above. A substrate having TFTs was prepared by arranging TFTs having electrodes, electrodes and wirings, and an inorganic insulating film made of SiN. Therefore, in this embodiment, the TFT of the array substrate is formed on the glass substrate according to a known method by repeating normal semiconductor film formation, known insulating layer formation, etc., and etching by photolithography. It has been done.

  Subsequently, the radiation sensitive resin composition (S-1) prepared in Example 1 was used, and it apply | coated with the slit die coater on the board | substrate which has the prepared TFT. Subsequently, it prebaked on a hot plate at 90 ° C. for 100 seconds to evaporate an organic solvent and the like to form a 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. Then, the development process for 100 second was performed at 25 degreeC by the liquid piling method using the tetramethylammonium hydroxide aqueous solution (developer) of a density | concentration of 2.38 mass%. After development, the coating film is washed with ultrapure water for 1 minute, dried to form a patterned coating film on the substrate, and then heated (post-baked) at 230 ° C. for 30 minutes in an oven. It was cured and a cured film was formed on the substrate to form an interlayer insulating film. Contact holes were formed in the interlayer insulating film on the substrate by patterning.

  Next, a film made of ITO was formed on the interlayer insulating film using a sputtering method, and a pixel electrode was formed by patterning using a photolithography method. The formed pixel electrode was connected to the TFT through a contact hole.

  Next, a color filter substrate manufactured by a known method was prepared. In this color filter substrate, a red color filter, a green color filter, a blue color filter, and a black matrix are arranged in a lattice pattern on a transparent glass substrate, and a color filter is formed on the color filter. Was formed with an insulating film to be a flattening layer of the color filter. Furthermore, a transparent common electrode made of ITO was formed on the insulating film.

  Next, a liquid crystal aligning agent (trade name JALS2095-S2, manufactured by JSR Co., Ltd.) is applied to the TFT placement surface of the manufactured array substrate and the color filter placement surface of the color filter substrate, respectively, using a spinner. By heating at 80 ° C. for 1 minute and then at 180 ° C. for 1 hour, an alignment film with a film thickness of 60 nm was formed, and an array substrate with an alignment film and a color filter substrate with an alignment film were manufactured.

  Next, after applying an ultraviolet curable sealing material to the outer periphery of the pixel region of each substrate, a nematic liquid crystal having negative dielectric anisotropy is photopolymerizable inside the sealing material using a dispenser. A polymerizable liquid crystal composition prepared by adding a polymerizable component was dropped.

  Thereafter, the color filter substrate was bonded to the array substrate onto which the polymerizable liquid crystal composition was dropped in a vacuum. Next, UV (ultraviolet) light was irradiated to the sealing material while moving the UV (ultraviolet) light source along the application area of the sealing material, and the sealing material was cured. In this manner, the polymerizable liquid crystal composition was filled and sealed between the opposing array substrate and the color filter substrate to form a layer of the polymerizable liquid crystal composition.

  Next, an AC voltage is applied between the source electrode of the TFT and the common electrode on the color filter substrate in a state where a voltage for turning on the TFT of the array substrate is applied to the gate electrode of the TFT, and the polymerizable liquid crystal composition The liquid crystal in the layer was tilted. Next, while maintaining the state in which the liquid crystal is tilted and aligned, an ultrahigh pressure mercury lamp is used to irradiate the polymerizable liquid crystal composition layer with ultraviolet light from the array substrate side, and the liquid crystal forms a pretilt angle in a predetermined direction. Thus, a liquid crystal layer having a substantially vertical alignment was formed. As described above, a VA mode color liquid crystal display element was manufactured.

  Next, using the manufactured liquid crystal display element, the impact was given in the state of high temperature (80 degreeC), and the presence or absence of the foam in a pixel was confirmed. The impact was applied to the liquid crystal display element by dropping a pachinko ball from 30 cm above the liquid crystal display element. A pixel in a liquid crystal display element that was not subjected to foaming by applying an impact was evaluated as being very good, a foaming one having a low bubble density, and a bubble having a high bubble density as bad. As a result of the evaluation, very good was marked as A, good as B, and bad as C.

[Chemical resistance]
The interlayer insulating film prepared in the above evaluation of radiation sensitivity is immersed in N-methyl-2-pyrrolidone heated to 65 ° C. for 6 minutes, and after immersion, the coating film is washed with running ultrapure water for 5 seconds and dried. It was. The thickness of the insulating film after the treatment was measured using a stylus type film thickness meter. N-methyl-2-pyrrolidone swelling rate (%) was calculated according to the following formula, and chemical resistance was evaluated according to the following criteria.
N-methyl-2-pyrrolidone swelling rate (%)
= 100 × (residual film after immersion (μm) / remaining film before immersion (μm) rate (%) − 1)
(Evaluation criteria)
A: Less than 3% B: 3% or more and less than 5% C: 5% or more and less than 7% D: 7% or more

[Voltage holding ratio]
After spin-coating each radiation-sensitive composition on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface and further depositing an ITO (indium-tin oxide alloy) electrode in a predetermined shape, Pre-baking was performed for 10 minutes in a 90 ° C. clean oven to form a coating film having a thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, the coating film was cured by post-baking at 230 ° C. for 30 minutes. Next, the substrate on which the pixels are formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 is injected into the liquid crystal. A cell was produced. Further, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio (%) is a value obtained from the following formula.
Voltage holding ratio (%) = (potential difference of liquid crystal cell after 16.7 milliseconds / voltage applied at 0 milliseconds) × 100
If the voltage holding ratio of the liquid crystal cell is less than 90%, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing "burn-in".
(Evaluation criteria)
A: Less than 95% B: 90% or more and less than 95% C: Less than 90%

  The radiation sensitive resin compositions and interlayer insulating films of Comparative Examples 1 to 16 were inferior in any of radiation sensitivity, resolution, foam resistance (low foamability), chemical resistance and voltage holding ratio. On the other hand, in Examples 1 to 25, in addition to foaming resistance, all evaluated were good results.

  The liquid crystal display element of the present invention can be used in a liquid crystal display device such as a television receiver or a monitor device of a personal computer.

DESCRIPTION OF SYMBOLS 1 Liquid crystal display element 10 Liquid crystal layer 15 TFT substrate 21, 91 Substrate 22 Base coat film 23 Semiconductor layer 24 Gate insulating film 25 Gate electrode 29 TFT
31f, 31g Contact hole 34 Source electrode 35 Drain electrode 36 Pixel electrode 37, 95 Liquid crystal alignment film 41 Inorganic insulating film 52 Interlayer insulating film 61 First wiring layer 90 Color filter substrate 92 Black matrix 93 Color filter 94 Common electrode

Claims (6)

Two substrates placed opposite each other,
An interlayer insulating film laminated on at least one inner surface of the substrate; and a liquid crystal layer disposed between the substrates and formed from a polymerizable liquid crystal composition,
The interlayer insulating film is formed from a radiation-sensitive resin composition containing a polymerizable compound having two or more polymerizable groups and a ring structure and a radiation-sensitive compound,
A liquid crystal display device, wherein the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a condensed carbocyclic structure, or a combination thereof. The radiation sensitive resin composition is
The liquid crystal display element according to claim 1, further comprising a polymer having a structural unit containing a carboxy group and a structural unit containing an epoxy group in the same or different polymer molecules.   The liquid crystal display element according to claim 1, wherein the radiation sensitive compound is an acid generator, a radical polymerization initiator, or a combination thereof.   The liquid crystal display element according to claim 1, wherein the polymerizable group is an epoxy group, a (meth) acryloyloxy group, an alkoxysilyl group, or a combination thereof.   The liquid crystal display element according to any one of claims 1 to 4, wherein the ring structure is a fluorene structure, a triazine structure, an aliphatic carbocyclic structure having 5 to 20 carbon atoms, or a combination thereof. Forming an interlayer insulating film on the surface side of at least one of the pair of substrates;
Forming a liquid crystal alignment film on the surface side of the interlayer insulating film and the surface side of the other substrate;
A step of filling a polymerizable liquid crystal composition between the substrates in a state in which the surfaces on which the liquid crystal alignment film is formed are opposed to each other; and a liquid crystal layer by light irradiation on the polymerizable liquid crystal composition filled between the substrates Comprising the step of forming
Forming the interlayer insulating film from a radiation sensitive resin composition comprising a polymerizable compound having two or more polymerizable groups and a ring structure and a radiation sensitive compound;
A method for producing a liquid crystal display device, wherein the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a condensed carbocyclic structure, or a combination thereof.

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