JP7435573B2 - Radiation sensitive resin composition - Google Patents

Description

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

In recent years, liquid crystal display devices have become widely used as monitor devices for television receivers and personal computers. Liquid crystal display devices used for these applications are required to have a wide viewing angle so that the display screen can be viewed from all directions. As a liquid crystal display device that can obtain a wide viewing angle, for example, one using an MVA (Multi-domain Vertical Alignment) type liquid crystal display element is known. However, such a liquid crystal display device has disadvantages in that the response time of the liquid crystal is not sufficiently short and alignment is easily disturbed by finger pressure or the like.

Therefore, in liquid crystal display elements, a polymerizable liquid crystal composition that can be polymerized by light is used, and a polymer orientation support (PSA) is used that memorizes the tilt direction of the liquid crystal compound by applying a voltage and polymerizing the liquid crystal compound in a tilted state. The introduction of Polymer Sustained Alignment (Polymer Sustained Alignment) technology is being considered (see Japanese Patent Laid-Open No. 2003-149647). A liquid crystal display element using PSA technology has a strong alignment regulating force because a polymer film that memorizes 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 in orientation even by finger presses or the like.

Japanese Patent Application Publication No. 2003-149647

In manufacturing liquid crystal display elements using such PSA technology, a polymerizable liquid crystal composition that can be photopolymerized is injected between a pair of substrates (inside the cell), and the entire cell is irradiated with light to increase the polymerizability. This means that the liquid crystal compound or other polymerizable compound that has the liquid crystal compound or other polymerizable compound is polymerized. This light irradiation is performed at a high exposure amount of about 1 J, for example. However, if an interlayer insulating film made of an organic material is laminated between the wiring of the substrate and the pixel electrode, bubbling may occur due to the interlayer insulating film upon irradiation with light. If such bubbling occurs in the pixel region of the liquid crystal display element, the product will be defective. It is understood that this bubbling occurs when the organic substance forming the interlayer insulating film decomposes during light irradiation, and low-volume components that are the decomposed products evaporate. The above-mentioned low molecular weight components usually remain inside or on the surface of the interlayer insulating film due to adsorption, but when the liquid crystal display element is subjected to heat or impact, their desorption is accelerated and the low molecular weight components become bubbles. This is understood to appear in the pixel area as follows.

Further, the interlayer insulating film is generally required to have voltage holding rate, chemical resistance, and the like. Furthermore, when the interlayer insulating 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 was made based on the above-mentioned circumstances, and its purpose is to provide a liquid crystal display element that suppresses the generation of bubbles and satisfies general characteristics such as voltage holding rate, and such a liquid crystal display. An object of the present invention is to provide a method for manufacturing an element.

The invention made to solve the above problems includes two substrates arranged opposite to each other, an interlayer insulating film laminated on the inner surface side of at least one of the substrates, and a polymerizable liquid crystal disposed between the substrates. the interlayer insulating film is formed from a radiation-sensitive resin composition containing a radiation-sensitive compound and a polymerizable compound having two or more polymerizable groups and a ring structure; A liquid crystal display element in which the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a fused carbocyclic structure, or a combination thereof.

Another invention made to solve the above problems includes a step of forming an interlayer insulating film on the surface side of at least one of a pair of substrates, and a liquid crystal display 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 with the surfaces on which the liquid crystal alignment films are formed facing each other, and a polymerizable liquid crystal composition filled between the substrates. 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 interlayer insulating film comprising a step of forming a liquid crystal layer by irradiating an object with light. , a method for producing a liquid crystal display element in which the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a fused carbocyclic structure, or a combination thereof.

The present invention can provide a liquid crystal display element that suppresses the generation of bubbles and satisfies general characteristics such as voltage holding rate, and a method for manufacturing such a liquid crystal display element.

FIG. 1 is a schematic cross-sectional view of 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 the inner surface side of at least one of the substrates, and a liquid crystal layer disposed between the substrates. Equipped with.

In the liquid crystal display element, the liquid crystal mode is, for example, TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Planes Switching), VA (Vertical Alignment), FFS (Fringe ld Switching) and OCB (Optically Compensated Birefringence) ), etc. can be selected.

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

Further, the liquid crystal display element is preferably an active matrix type VA mode liquid crystal display element using PSA technology so that the effectiveness of the interlayer insulating film in which bubbling is suppressed is more significant. This VA mode liquid crystal display element also includes an MVA mode.

Hereinafter, as an example of the liquid crystal display element, an active matrix type VA mode liquid crystal display element using PSA technology will be described with reference to FIG. 1 as appropriate.

The liquid crystal display element 1 in 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 of a transmissive type and includes an array substrate 15 which is a display element substrate, and a color filter substrate 90 disposed opposite to the array substrate 15. The liquid crystal layer 10 is formed by sealing the liquid crystal composition between the substrates 15 and 90 using a sealing material (not shown) provided in the substrates 15 and 90.

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

In this way, on the substrate 21 constituting the array substrate 15, the TFT 29, which includes the semiconductor layer 23, the gate insulating film 24, and the gate electrode 25 and functions 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 drain electrode 35 made of the first wiring layer 61 are connected to the source/drain region of the semiconductor layer 23 via a contact hole 31f provided in the inorganic insulating film 41. Furthermore, the pixel electrode 36 is connected to the drain electrode 35 made of the first wiring layer 61 via a contact hole 31g provided in the interlayer insulating film 52.

Furthermore, in the pixel region, the color filter substrate 90 includes, on an insulating substrate 91, a black matrix 92 made of a light shielding member provided between each pixel, and red, green, and blue color filters provided for each pixel. 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.

To explain the liquid crystal display element 1 of FIG. 1 in more detail, the substrate 21 is not particularly limited, but for example, a glass substrate, a quartz substrate, a resin substrate made of acrylic resin, etc. are preferably used. Preferably, the substrate 21 is subjected to cleaning and pre-annealing as pre-treatments for configuring 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 plasma enhanced chemical vapor deposition (PECVD). can do. Examples of the raw material 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 Tetra Ethyl Ortho Silicate (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 made of low-temperature polysilicon.

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

Examples of the amorphous oxide applicable to the semiconductor layer 23 include amorphous oxides containing at least one element of indium (In), zinc (Zn), and tin (Sn).

Specific examples of amorphous oxides that can be applied 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 Examples include oxides, Sn--In--Zn oxides, In--Sn--Zn oxides (ITZO: indium tin zinc oxide), and the like. Note that in the above case, the composition ratio of the constituent materials does not necessarily have to be, for example, 1:1 or 1:1:1, and a composition ratio that achieves desired characteristics can be selected.

Patterning of the p-Si forming the semiconductor layer 23 can be performed by a known method, but for example, first, an amorphous silicon (a-Si) film with a thickness of 50 nm is formed by PECVD. Examples of the raw material 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 to reduce the hydrogen concentration in the a-Si film (dehydrogenation process) 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 example, an excimer laser can be used for laser annealing. To form a p-Si film, as a pretreatment for laser annealing, a metal catalyst such as nickel is applied without dehydrogenation (to form continuous grain silicon (CG-silicon)), and then hardened by heat treatment. Phase growth may also be performed. Further, as for crystallization of the a-Si film, only solid phase growth by heat treatment may be performed. Next, dry etching is performed using a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) to pattern the p-Si film and form a semiconductor layer 23. The thickness of the semiconductor layer 23 is preferably 20 nm to 100 nm.

A channel region, a source region, and a drain region (not shown) are formed in the semiconductor layer 23, but these are formed after forming a gate insulating film 24, which will be described later, or after forming a gate electrode, which will be described later. It is formed in layer 23.

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

Furthermore, the semiconductor layer 23 is doped with impurities such as phosphorus or boron 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, a thermal activation process is performed at about 700° C. for 6 hours to activate impurity ions existing in the semiconductor layer 23, thereby forming a source region and a drain region. Note that as a method of activating impurity ions, a method of irradiating with an excimer laser can also be mentioned.

The gate insulating film 24 can be, for example, a silicon oxide film with a thickness of 45 nm. For its 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. The raw material gases for forming the SiNx film and the SiON film include the same raw material gases as those described in the step of forming the base coat film 22. Further, the gate insulating film 24 may be a laminate made of the plurality of materials described above. The thickness of the gate insulating film 24 is preferably 30 nm to 150 nm.

The gate electrode 25 is formed by forming a tantalum nitride (TaN) film with a thickness of 30 nm and a tungsten (W) film with a thickness of 370 nm in this order using a sputtering method, and then forming a resist film as desired using a photolithography method. After forming a resist mask by patterning it _{in the shape of} It is formed by dry etching using an etching gas with an adjusted amount of mixed gas. Examples of the material for the gate electrode 25 include high melting point metals with flat surfaces and stable characteristics such as tantalum (Ta), molybdenum (Mo), and molybdenum tungsten (MoW), and low resistance metals such as aluminum (Al). . Further, the gate electrode 25 may be a laminate made of a plurality of the above-mentioned materials, and may further include a plurality of metals selected from, for example, Al, Cr, Ta, Mo, Ti, W, Cu, Nb, Mn, and Mg. It may be an alloy consisting of. The thickness of the gate electrode 25 is preferably 100 nm to 500 nm.

The inorganic insulating film 41 includes a SiNx film with a thickness of 100 nm to 400 nm, more preferably 200 nm to 300 nm, and a TEOS film with 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 (eg, TEOS film, etc.) of about 50 nm may be formed under the inorganic insulating film 41.

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

The source electrode 34 and the drain electrode 35 are made of the first wiring layer 61, and are formed by the steps shown below. That is, a titanium (Ti) film with a thickness of 100 nm, an aluminum (Al) film with a thickness of 500 nm, and a Ti film with a thickness of 100 nm 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 the Ti/Al/Ti metal laminated film is patterned by dry etching to form the first wiring layer 61. As a result, a source electrode 34 and a drain electrode 35 are formed. Note that as the metal constituting the first wiring layer 61, an Al--Si alloy or the like may be used instead of Al. In addition, although Al was used here to reduce the resistance of the wiring, if high heat resistance is required and a certain increase in resistance value is allowed (for example, when creating a short wiring structure), As the metal constituting the first wiring layer 61, the above-mentioned gate electrode materials (Ta, Mo, MoW, W, TaN, Al, etc.) may be used.

The interlayer insulating film 52 is formed from a radiation-sensitive resin composition described later. That is, the interlayer insulating film 52 is a layer in which a radiation-sensitive resin composition is cured. Specifically, a coating film is formed using a radiation-sensitive resin composition over the entire surface of the substrate 21 by a spin coating method using a spinner or the like. Next, after exposure through a photomask on which a light-shielding pattern of a desired shape is formed, etching (development treatment) is performed to remove the coating film in the area that will become the contact hole 31g, thereby forming a pattern. I do. Furthermore, the interlayer insulating film 52 is manufactured as a cured film in which the contact hole 31g is formed by heating at 200° C. for about 30 minutes, for example. The thickness of the interlayer insulating film 52 is preferably 1 μm to 5 μm, more preferably 2 μm to 3 μm, so as to fully exhibit its insulating and planarizing functions.

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

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

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

Since the liquid crystal alignment film 37 is a vertical alignment type liquid crystal alignment film, in combination with the liquid crystal having negative dielectric constant anisotropy of the liquid crystal layer 10, which will be described later, the liquid crystal display element 1 becomes a VA mode liquid crystal display element. can do.

Next, the substrate 91, black matrix 92, and color filter 93 that constitute the color filter substrate 90 will be explained.

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 red pigment is dispersed over the entire pixel area, and performing exposure, development, and baking (heat treatment). The green color filter 93 is formed by laminating a resin film in which green pigment is dispersed over the entire pixel area over the red color filter 93, and performing exposure, development, and baking (heat treatment). be. The blue color filter 93 is also formed similarly to the green color filter 93.

Note that the color filter substrate 90 can have a columnar spacer (not shown) made of a laminate of the above-mentioned light-shielding film and the above-mentioned resin film in a light-shielding region other than the pixel opening.

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.

Note that the color filter 93 of the color filter substrate 90 may be formed by a photolithography method using a color resist. Further, photo spacers may be formed on the color filter substrate 90 by a photolithography method using a color resist. Furthermore, the black matrix 92 may not be formed, and wiring such as the source line or CS line of the TFT substrate 15 may be used instead.

The liquid crystal display element 1 shown in FIG. A liquid crystal layer 10 is formed by filling and sealing a liquid crystal composition. The liquid crystal layer 10 is a layer formed by polymerizing at least a portion of a polymerizable liquid crystal composition.

The array substrate 15 and the color filter substrate 90 can be bonded together using a sealing material 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 constant anisotropy is dropped inside the sealing material using a dispenser or the like. The polymerizable liquid crystal composition will be described later.

Next, a color filter substrate 90 is bonded to the array substrate 15 onto which the polymerizable liquid crystal composition has been dropped. The steps up to this point are performed in a vacuum. Next, when both the bonded substrates 15 and 90 are returned to the atmosphere, the polymerizable liquid crystal composition is diffused between the bonded substrates 15 and 90 due to atmospheric pressure. Next, the sealant 39 is cured by irradiating the sealant 39 with UV (ultraviolet) light while moving the UV (ultraviolet) light source along the application area of the sealant 39 . In this way, the diffused polymerizable liquid crystal composition is filled and sealed between the pair of opposing substrates 15 and 90, and a layer of the polymerizable liquid crystal composition for forming the liquid crystal layer 10 is formed. .

Note that, as a method of injecting the 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 the polymerizable liquid crystal composition is injected from there. A method may also be used in which the composition is injected and then the polymerizable liquid crystal composition injection port is sealed with an ultraviolet curing resin or the like.

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

That is, after the array substrate 15 and the color filter substrate 90 are bonded together and a layer of the polymerizable liquid crystal composition is formed between both substrates 15 and 90, a voltage that turns on the TFT 29 is applied to the gate electrode 25. An alternating current 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 tilted orientation of the liquid crystal. That is, the polymerizable liquid crystal composition filled between the substrates is irradiated with light. The exposure amount of this UV light can be, for example, 50 mJ/cm ² or more and 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 a polymer that defines the pretilt angle of the liquid crystal is formed on the surface of the liquid crystal alignment films 37 and 95 on the liquid crystal layer 10 side. A union 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 in a tilted state, a polymer that remembers the direction in which the liquid crystal tilts when a voltage is applied can be provided on the array substrate 15, for example.

Thereafter, the liquid crystal display element 1 can be manufactured through a panel cutting process, a polarizing plate pasting process, an FCP board pasting process, a liquid crystal display panel and backlight unit combination process, 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, and cholesteric liquid crystal. As the liquid crystal compound, nematic liquid crystal is preferred. Furthermore, these liquid crystals may contain cholesteric liquid crystals, chiral nematic liquid crystals, chiral smectic liquid crystals, etc. or 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 contained in the liquid crystal compound having a polymerizable group include a vinyl group, (meth)acrylic group, (meth)acryloyl group, (meth)acrylamide group, styryl group, epoxy group, isocyanate group, etc. .

Examples of photopolymerizable compounds include styrene, chlorostyrene, α-methylstyrene, divinylbenzene;
As substituents, methyl group, ethyl group, propyl group, butyl group, amyl group, 2-ethylhexyl group, octyl group, nonyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, benzyl group, methoxyethyl group, butoxy Acrylates containing 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)acrylates or poly(meth)acrylates 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, vinylpyridine, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-hydroxymethylacrylamide or N-hydroxyethyl Methacrylamide and their alkyl ether compounds;
Diol di(meth)acrylate obtained by adding 2 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol;
Triol di- or tri(meth)acrylate obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane;
Diol di(meth)acrylate obtained by adding 2 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A;
reaction product of 1 mol of 2-hydroxyethyl (meth)acrylate and 1 mol of phenyl isocyanate or n-butyl isocyanate;
Dipentaerythritol poly(meth)acrylate;
Examples include oligomers such as caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate.

Examples of photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck's "Darocure 1173") and 1-hydroxycyclohexylphenyl ketone (Ciba-Geigy's "Irgacure 184"). ), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one (Merck's "Darocure 1116"), 2,2-dimethoxy-1,2-diphenylethan-1-one ( Ciba Geigy's "Irgacure 651"), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1 (Ciba-Geigy's "Irgacure 907"), 2,4-diethyl Mixture of thioxanthone (Nippon Kayaku Co., Ltd.'s "Kayacure DETX") and ethyl p-dimethylaminobenzoate (Nippon Kayaku Co., Ltd.'s "Kayacure-EPA"), isopropylthioxanthone (Ward Prekinsop Co., Ltd.'s "Cantacure ITX") and ethyl p-dimethylaminobenzoate.

<Radiation-sensitive resin composition>
The radiation-sensitive resin composition that forms the interlayer insulating film 52 will be explained in detail below. The radiation-sensitive resin composition includes a [B] radiation-sensitive compound and a polymerizable compound ([C] polymerizable compound) having two or more polymerizable groups and a cyclic structure. The above-mentioned radiation-sensitive resin composition usually contains the [A] polymer, and may further contain other components. In the liquid crystal display element, the interlayer insulating film is formed from the radiation-sensitive resin composition, thereby suppressing the generation of bubbles due to light irradiation when forming the liquid crystal layer. Further, according to the liquid crystal display element, the interlayer insulating film formed from the radiation-sensitive resin composition has excellent chemical resistance and voltage holding rate. Moreover, the radiation-sensitive resin composition also has good sensitivity and resolution.

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

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

(Structural unit (I))
Structural unit (I) is not particularly limited as long as it is a structural unit containing a carboxy group. Monomers providing this structural unit (IA) include, for example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their anhydrides, mono[(meth)acryloyloxyalkyl] esters of polyhydric carboxylic acids, carboxylic acids at both ends. Examples thereof include mono(meth)acrylates of polymers having a group and a hydroxyl group, unsaturated polycyclic compounds having a carboxy group, anhydrides thereof, and the like.

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

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

Examples of mono[(meth)acryloyloxyalkyl]esters of polyhydric carboxylic acids include mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, hexahydro Examples include mono[2-(meth)acryloyloxy)ethyl phthalate].

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

Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 5-carboxybicyclo[2.2.1]hept-2-ene, 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 acids and dicarboxylic acid anhydrides are preferred, and (meth)acrylic acid and maleic anhydride are more preferred in terms of copolymerization reactivity, solubility in alkaline aqueous solutions, and ease of availability. .

[A1] The lower limit of the content of the structural unit (I) in the polymer is preferably 1% by mass, more preferably 5% by mass, and 10% by mass with respect to all the structural units constituting the [A1] polymer. is even more preferable. On the other hand, the upper limit of this content is preferably 60% by mass, more preferably 40% by mass, and even more preferably 30% by mass. By setting the content ratio of the structural unit (I) within the above range, the solubility of the radiation-sensitive resin composition in the developer (alkali solubility) and the adhesion of the interlayer insulating film to the substrate etc. are improved. Note that the content ratio of the structural units can be considered to be the same as the charging ratio of the corresponding monomer (the same applies hereinafter).

(Structural unit (II))
The structural unit (II) is not particularly limited as long as it is a structural unit containing an epoxy group. Epoxy group refers to a group containing a cyclic ether structure, such as an oxiranyl group having a three-membered ring ether structure (1,2-epoxy structure), an oxetanyl group having a four-membered ring ether structure (1,3-epoxy structure), Examples include alicyclic epoxy groups. As the epoxy group, an oxiranyl group is preferred. By having such an epoxy group having crosslinking properties, 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 structural units represented by the following formula.

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

Monomers providing 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 of the structural unit (II) in the polymer is preferably 1% by mass, more preferably 5% by mass, and 10% by mass based on all structural units constituting the [A1] polymer. is even more preferable. On the other hand, the upper limit of this content is preferably 70% by mass, more preferably 60% by mass, and even more preferably 50% by mass. 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 a structural unit (IV) other than the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired. Note that the other structural units do not include the structural unit (III) having an acid-dissociable group, which will be described later. Moreover, the [A1] polymer may further have a structural unit (III) having an acid-dissociable group.

Examples of monomers providing other structural units include (meth)acrylic esters having an alcoholic hydroxyl group, (meth)acrylic acid chain alkyl esters, (meth)acrylic acid cyclic alkyl esters, and (meth)acrylic aryl esters. Examples include esters, unsaturated aromatic compounds, and conjugated dienes.

Examples of (meth)acrylic esters 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, and 6-hydroxyhexyl methacrylate.

Examples of (meth)acrylic acid chain alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and methacrylate. 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 tricyclo[5. 2.1.0 ^2,6 ]decane-8-yloxyethyl, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, Examples include tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxyethyl acrylate and isobornyl acrylate.

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

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

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

The lower limit of the content of the structural unit (IV) in the [A1] polymer is preferably 10% by mass, more preferably 30% by mass, based on all structural units constituting the [A1] polymer. On the other hand, this upper limit is preferably 80% by mass, more preferably 70% by mass. With such a content ratio, it is possible to obtain a radiation-sensitive resin composition that has optimized solubility in an alkaline aqueous solution and has excellent radiation sensitivity.

([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 that protects the carboxy group or phenolic hydroxyl group in the [A2] polymer. The [A2] polymer having such a protecting group is usually insoluble or sparingly soluble in an alkaline aqueous solution. Since the protective group in this [A2] polymer is an acid-dissociable group, the protective group is dissociated by the action of an acid, thereby making it soluble in an alkaline aqueous solution. When the radiation-sensitive resin composition contains the [A2] polymer, it is possible to achieve high radiation sensitivity and improve the stability of the pattern shape obtained by development and the like. [A2] The polymer is a so-called chemical amplification type 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 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of the hydrogen atom 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 an oxyhydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a part of the hydrogen atoms of a hydrocarbon group having 1 to 30 carbon atoms to a hydroxyl group, a halogen atom, or a cyano group. It is a group substituted with a group.

In the above formula (2), R ⁴ to R ¹⁰ are each independently a 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 linear or branched aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and 3 to 3 carbon atoms. ~30 alicyclic hydrocarbon groups, etc.

Examples of linear or branched aliphatic hydrocarbon groups 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, etc.

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, Examples include a cycloheptyl group and a 2-norbornyl group.

Examples of the oxyhydrocarbon group having 1 to 30 carbon atoms represented by R ³ in the above formula (1) include alkoxy groups having 1 to 30 carbon atoms such as methoxy group, ethoxy group, and propoxy group; cyclopentyloxy group, nor Cycloalkyloxy groups having 3 to 30 carbon atoms such as bornyloxy group; Aryloxy groups having 6 to 30 carbon atoms such as phenoxy, tolyloxy, and naphthyloxy groups; 7 carbon atoms such as benzyloxy and naphthylmethoxy groups -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 group having 1 to 30 carbon atoms represented by R ¹ to R ³ in the above formula (1). Among the exemplified groups, examples include those having 12 or less carbon atoms.

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 monomers providing structural units (III) represented by formulas (1-1) to (1-10) include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, and 1-(tritrimethacrylate). cyclodecanyloxy)ethyl, 1-(pentacyclopentadecanylmethyloxy)ethyl methacrylate, 1-(pentacyclopentadecanyloxy)ethyl methacrylate, 1-(tetracyclododecanylmethyloxy)ethyl methacrylate, Examples include 1-(adamantyloxy)ethyl methacrylate.

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.

The structural unit (III) represented by the above formula (2) is preferably a structural unit represented by the formula (2-3) obtained from tetrahydro-2H-pyran-2-yl methacrylate.

The content of the structural unit (III) is preferably 10% by mass, more preferably 25% by mass, and even more preferably 40% by mass, based on the total structural units constituting the [A2] polymer. On the other hand, the upper limit of this content is preferably 75% by mass, more preferably 65% by mass, and even more preferably 55% by mass. By setting the content ratio of the structural unit (III) within the above range, resolution can be further improved.

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

[A2] The lower limit of the content of structural unit (I) in the polymer is preferably 1% by mass, more preferably 3% by mass, and 5% by mass with respect to all the structural units constituting the [A2] polymer. is even more preferable. On the other hand, the upper limit of this content is preferably 50% by mass, more preferably 30% by mass, and even more preferably 15% by mass. By setting the content ratio of the structural unit (I) within the above range, the solubility of the radiation-sensitive resin composition in the developer (alkali solubility) and the adhesion of the interlayer insulating film to the substrate etc. are improved.

[A2] The lower limit of the content of structural unit (II) in the polymer is preferably 5% by mass, more preferably 10% by mass, and 25% by mass with respect to all structural units constituting the [A2] polymer. is even more preferable. On the other hand, the upper limit of this content is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass. By setting the content 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 monomers providing other structural units are as described above.

The lower limit of the content of the structural unit (IV) in the [A2] polymer is preferably 1% by mass, more preferably 3% by mass, based on all the structural units constituting the [A2] polymer. On the other hand, this upper limit is preferably 30% by mass, more preferably 10% by mass. With such a content ratio, it is possible to obtain a radiation-sensitive resin composition that has optimized solubility in an alkaline aqueous solution and has excellent radiation sensitivity.

(Method for synthesizing [A1] polymer and [A2] polymer)
The [A1] polymer and the [A2] polymer (hereinafter also referred to as "[A1] polymer, etc.") can be produced by, for example, monomers corresponding to predetermined structural units, using a radical polymerization initiator, in an appropriate manner. It can be synthesized by polymerization in a suitable solvent. [A1] Methods for synthesizing polymers include a method in which a solution containing a monomer and a radical initiator is dropped into a solution containing a reaction solvent to carry out a polymerization reaction, and a method in which a solution containing a 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, and a method in which a plurality of solutions containing each monomer and a solution containing a radical initiator are added dropwise to a solution containing a reaction solvent. A preferred method is to drop each component separately into a solution containing a reaction solvent and cause a polymerization reaction.

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

[A1] As the polymerization initiator used in the polymerization reaction of the polymer, those generally known as radical polymerization initiators can be used, such as 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, etc. , 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(methyl 2-methylpropionate) organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis-(t-butylperoxy)cyclohexane; and hydrogen peroxide.

[A1] In the polymerization reaction of the polymer, etc., a molecular weight regulator can also be used to adjust the molecular weight. Examples of molecular weight regulators include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, and thioglycolic acid; dimethyl Examples include 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 measured by gel permeation chromatography (GPC) of the polymer constituting the polymer, etc. is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and 5 More preferably .0×10 ³ or more and 5.0×10 ⁴ or less. [A1] By setting the Mw of the polymer constituting the polymer and the like within the above range, the radiation sensitivity and alkali developability of the radiation-sensitive resin composition can be improved.

[A1] The polystyrene equivalent number average molecular weight (Mn) determined by GPC of the polymer constituting the polymer is preferably 2.0 x 10 ³ or more and 1.0 x 10 ⁵ or less, and 5.0 x 10 ³ or more and 5.0 x 10 5 or less. More preferably, it is .0×10 ⁴ or less. [A1] By setting the Mn of the polymer constituting the polymer and the like within 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 is preferably 3.0 or less, more preferably 2.6 or less. [A1] By setting the Mw/Mn of the polymer constituting the polymer and the like to 3.0 or less, the developability of the coating film can be improved.

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

Here, the term "hydrolyzable silane compound" refers to a silanol compound that can be hydrolyzed into silanol groups by heating within a temperature range of room temperature (approximately 25 degrees Celsius) to approximately 100 degrees Celsius, usually in the absence of a catalyst and in the presence of excess water. Or it refers to a compound having a hydrolyzable group that produces a siloxane condensate. In addition, in the radiation-sensitive resin composition, some of the hydrolyzable silane compounds have some or all of the hydrolyzable groups in their molecules in an unhydrolyzed state, and other hydrolyzable silane compounds It may remain in a monomeric state without being condensed with. Furthermore, the term "hydrolyzed condensate" refers to a hydrolyzed condensate in which some silanol groups of a hydrolyzed silane compound are condensed together.

Examples of the hydrolyzable silane compound include a hydrolyzable silane compound represented by the following formula (S-1) (hereinafter also referred to as "(S1) compound") and/or a hydrolyzable silane compound 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]
The compound (S1) 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 from 1 to 3. From the viewpoint of progress of the hydrolytic condensation reaction, p is preferably 1 or 2, and more preferably 1. However, when there is a plurality of R ¹⁴ or R ¹⁵ , the plurality of R ¹⁴ or R ¹⁵ may be the same or different.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, and butyl group. Among these, methyl and ethyl groups are preferred from the viewpoint of ease of hydrolysis.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, and 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 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, 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 group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-heptadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Examples include groups. The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 1 to 3.

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

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

Examples of the (S1) compound where p is 2 include phenylmethyldimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, phenyltrifluoropropyldimethoxysilane, and the like. dialkoxysilane compounds.

Examples of the (S1) compound where p is 3 include 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, and dimethyltrifluoropropylmethoxysilane.

[(S2) Compound]
The compound (S2) 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 from 0 to 3. From the viewpoint of progress of the hydrolysis condensation reaction, q is preferably 1 or 2, and more preferably 1. However, when there is a plurality of R ¹⁶ or R ¹⁷ , the plurality of R ¹⁶ or R ¹⁷ may be the same or different. n is an integer from 0 to 6.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, and butyl group. Among these, methyl and ethyl groups are preferred from the viewpoint of ease of hydrolysis.

The compound (S2) 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 compound (S2) in which q is 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-tolyltrimethoxysilane, m-tolyltrimethoxysilane p-tolyltrimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxy Examples include trialkoxysilane compounds such as silane, trifluoropropyltriethoxysilane, trifluorobutyltrimethoxysilane, and 3-(trimethoxysilyl)propylsuccinic anhydride.

The compound (S2) in which q is 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-isocyanatepropylmethyldimethoxysilane.

The compound (S2) in which q is 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, and γ-isocyanatepropyldimethylmethoxysilane.

When both the (S1) compound and (S2) compound are used, the mixing ratio of the (S1) compound and (S2) compound is preferably such that the (S1) compound exceeds 5 mol%. When the amount of 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 etc. of the obtained protective film tends to be reduced.

([A3] Synthesis of polymer (hydrolytic condensation))
[A3] The polymer (polysiloxane) is usually heated within a temperature range of room temperature (approximately 25°C) to approximately 100°C in the presence of excess water and, if necessary, a solvent or catalyst, to add water. It can be synthesized by condensing silanol groups obtained by hydrolyzing a degradable silane compound.

As water for the hydrolytic condensation reaction, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation, or the like. 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, per 1 mol of the total amount of hydrolyzable groups of the above (S1) compound and (S2) compound. , particularly preferably from 0.5 mol to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolytic condensation can be optimized.

Examples of solvents for the hydrolytic condensation reaction include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether acetate. Examples include pionates, aromatic hydrocarbons, ketones, and other esters. 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 methoxy acetate are preferred, particularly diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, and butyl methoxyacetate are preferred.

As the catalyst for the hydrolysis condensation reaction, acid catalysts, base catalysts and alkoxides are preferred.

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 base catalysts include ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate. Salts; carboxylic acid salts such as sodium acetate; various Lewis bases, and the like.

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

From the viewpoint of promoting the hydrolytic condensation reaction, the amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0.2 mol, per 1 mol of the hydrolyzable silane compound monomer. It is 1 mole.

The polystyrene equivalent weight average molecular weight (Mw) of the [A3] polymer such as the hydrolyzed condensate by GPC is preferably 500 to 10,000, more preferably 2,000 to 7,000. [A3] By setting the Mw of the polymer to 500 or more, the film-forming properties of the radiation-sensitive resin composition can be improved. On the other hand, by setting the Mw of the [A3] polymer to 10,000 or less, it is possible to prevent a decrease in the developability of the radiation-sensitive resin composition.

[A3] The number average molecular weight (Mn) of the polymer measured by GPC in terms of polystyrene is preferably 300 to 5,000, more preferably 500 to 3,000. By setting Mn of the [A3] polymer within 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, more preferably 2.6 or less. [A3] By setting the 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 based on 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, the upper limit of this content is preferably 90% by mass, more preferably 70% by mass. [A] By setting the content of the polymer within the above range, an interlayer insulating film having good sensitivity, resolution, strength, etc. can be obtained.

[[B] Radiation-sensitive compound]
[B] Radiation-sensitive compounds include compounds that are sensitive to radiation and can generate radicals to initiate polymerization (i.e., [B-1] radical polymerization initiators), compounds that are sensitive to radiation and generate acids (i.e. , [B-2] acid generator), and a compound that generates a base in response to radiation (ie, [B-3] base generator). Among these, [B-1] radical polymerization initiator and [B-2] acid generator are preferred. Moreover, these may be used in combination of multiple types. Note that "radiation" is a concept that includes visible light, ultraviolet rays, far ultraviolet rays, 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 mass, more preferably 3 parts by mass, and even more preferably 5 parts by mass with respect to 100 parts by mass of the [A] polymer. On the other hand, this upper limit is preferably 40 parts by mass, more preferably 30 parts by mass. [B] By setting the usage ratio of the radiation-sensitive compound within the above range, the radiation-sensitive resin composition has high solvent resistance, high hardness, high adhesion, low foaming property, etc. even at low exposure doses. An interlayer insulating film having the following properties can be formed. The preferred content of [B-1] radical polymerization initiator or [B-2] acid generator will be described later.

([B-1] Radical polymerization initiator)
When the [B] radiation-sensitive compound contains the [B-1] radical polymerization initiator, it functions suitably as a negative-type radiation-sensitive resin composition in which the [C] polymerizable compound and the like in the exposed portion are 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 O-acyloxime compounds 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)-octan-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. -carbazol-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 α-aminoketone compounds and α-hydroxyketone compounds.

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

As the acetophenone compound, α-aminoketone compounds are preferred, particularly 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.

Biimidazole compounds include, for example, 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] Radical polymerization initiators can be used alone or in combination of two or more. [B-1] The lower limit of the content of the radical polymerization initiator is preferably 1 part by mass, more preferably 3 parts by mass, based on 100 parts by mass of the [A] polymer. The upper limit of this content is preferably 30 parts by mass, more preferably 10 parts by mass. [B-1] By setting the usage 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 low exposure doses. It is possible to form an interlayer insulating film having properties such as properties.

([B-2] Acid generator)
[B] When the radiation-sensitive compound contains a [B-2] acid generator and a [A-2] polymer, the acid-dissociable group of the [A-2] polymer is dissociated by the acid generated in the exposed area. Since the alkali solubility is increased, it functions suitably as a positive radiation-sensitive resin composition. In addition, when the [B-2] acid generator is a quinone diazide compound, the alkali solubility of the exposed portion increases regardless of the type of the [A] polymer, so that it functions suitably as a positive radiation-sensitive resin composition. . In addition, when the [B] radiation-sensitive compound contains a [B-2] acid generator and a [A-3] polymer, the acid generated in the exposed area causes the [A-3] polymer (polysiloxane) to Since the curing reaction progresses, 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, quinonediazide compounds, etc. . Note that these [B-2] photoacid generators may be used alone or in combination of two or more.

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (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 group having 6 to 20 carbon atoms. A group, or a group in which some or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups, and aryl groups are substituted with substituents.

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. This linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the above-mentioned substituents include alicyclic groups including bridged alicyclic groups such as alkoxy groups having 1 to 10 carbon atoms and 7,7-dimethyl-2-oxonorbornyl groups. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

The alicyclic hydrocarbon group represented by R ^A above is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. This 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, a halogen atom, etc. .

The aryl group represented by R ^A above 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 above-mentioned oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (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 sensitivity and solubility of the resulting radiation-sensitive resin composition can be improved.

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

Preferred onium salts include tetrahydrothiophenium salts and benzylsulfonium salts, including 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Phosphates are more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is even more preferred.

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

Examples of sulfonimide compounds 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)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide, and the like.

[B-2] By using a sulfonimide compound as an acid generator, the sensitivity and solubility of the resulting radiation-sensitive resin composition can be improved.

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

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

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

Examples of the above-mentioned core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other cores.

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.

(Polyhydroxyphenyl)alkanes include, for example, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, and 1,1,1-tris(p-hydroxyphenyl)methane. 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'-spirobiindene-5,6,7,5',6',7'- Examples include hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, and the like.

Other cores include, 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.

Among these cores, 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-naphthoquinonediazide sulfonic acid halide, 1,2-naphthoquinonediazide sulfonic acid chloride is preferred. Examples of the 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

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

In addition, examples of quinonediazide compounds include 1,2-naphthoquinonediazide sulfonic acid amides in which the ester bond in the mother nucleus is changed to an amide bond as exemplified above, 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, more preferably 3 parts by mass, per 100 parts by mass of the [A] polymer. [B-2] When the acid generator is a quinonediazide compound, the lower limit of this 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, more preferably 30 parts by mass, based on 100 parts by mass of the [A] polymer. [B-2] When the acid generator is the above-mentioned compound other than the quinonediazide compound, the upper limit is more preferably 10 parts by mass. [B-2] By using 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 low exposure doses. It is possible to form an interlayer insulating film having, etc.

([B-3] Base generator)
Specific examples of base generators include 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, and 2-benzyl-2-dimethyl. Heterocyclic group-containing radiation-sensitive base generators such as amino-1-(4-morpholinophenyl)-butanone, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, 1-(anthraquinon-2-yl)ethylimidazole carboxylate, etc. ;
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-tetramethylbiguanidium n-butyltriphenylborate Examples include.

[[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 fused carbocyclic structure, or a combination thereof. In an interlayer insulating film formed from a radiation-sensitive resin composition containing such a [C] polymerizable compound, the above-mentioned polymerizable groups of the [C] polymerizable compound cause the formation of oxidation between the [C] polymerizable compounds and others. A crosslinked structure is formed between the components. Here, it is presumed that when the [C] polymerizable compound has a ring structure including an aliphatic carbocyclic structure, a heterocyclic structure, or a fused carbocyclic structure, a film having a particularly dense crosslinked structure can be formed. It is thought that this dense crosslinked structure exhibits light resistance against high exposure doses and contributes to the reduction of foaming. Moreover, according to the radiation-sensitive resin composition that can form such a dense structure, the resulting interlayer insulating film can also have good chemical resistance and voltage holding rate.

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

Examples of the polymerizable groups include (meth)acryloyl groups, vinyl groups, epoxy groups, alkoxysilyl groups, styryl groups, and isocyanate groups. Among these, epoxy groups, (meth)acryloyloxy groups, alkoxysilyl groups, or combinations thereof are preferred. When the polymerizable group is one of these groups, a denser crosslinked structure is formed and foaming can be further suppressed.

Examples of the epoxy group include an oxiranyl group and an oxetanyl group, with an oxiranyl group (1,2-epoxy structure) being preferred.

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

[C] The number of polymerizable groups that the polymerizable compound has 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 structures, heterocyclic structures, fused carbocyclic structures, or a combination thereof in one molecule. [C] The number of the ring structures that the polymerizable compound has in one molecule is usually one.

The above-mentioned aliphatic carbocyclic structure refers to a carbocyclic ring that does not contain an aromatic ring. Examples of the aliphatic carbocyclic structure include aliphatic carbocyclic structures having 5 to 30 carbon atoms, and preferably aliphatic carbocyclic structures having 5 to 20 carbon atoms. 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 (a structure having a steroid skeleton). The aliphatic carbocyclic structure may be monocyclic or polycyclic.

The above-mentioned heterocyclic structure is a ring structure composed of carbon atoms and other atoms (eg, oxygen atoms, nitrogen atoms, sulfur atoms, 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 preferred. The triazine structure refers to a six-membered ring structure composed of three nitrogen atoms and three carbon atoms, and is a concept that includes a trione structure (isocyanuric acid structure). Among the above triazine structures, a trione structure (isocyanuric acid structure) is more preferable. The above-mentioned heterocyclic structure may be monocyclic or polycyclic.

The above-mentioned fused carbocyclic structure refers to a ring structure in which two or more carbon rings are bonded to each other by sharing two or more atoms. The above condensed carbocyclic structure may be a condensed ring of an aromatic ring and an alicyclic ring (aliphatic carbocyclic structure), or a condensed ring of aromatic rings, or a condensed ring of an aromatic ring and an alicyclic ring. A ring is preferred. Examples of the fused carbocyclic structure include a naphthalene structure, anthracene structure, acenaphthalene structure, and fluorene structure, with the fluorene structure being preferred.

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, it is possible to form an interlayer insulating film with a more dense crosslinked structure, and it is possible to further suppress foaming.

[C] The polymerizable compound may be a monomer or a polymer including an oligomer, but is preferably a monomer. By being a monomer, the structure formed by crosslinking becomes denser, thereby making it possible to further reduce foaming.

[C] The polymerizable compound is more preferably a compound represented by the following formula (C-1), (C-2) or (C-3). Note that the compound represented by the following formula (C-2) is a compound having a fluorene structure. Further, 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), R is each 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.

The above R's may each independently be a (meth)acryloyl group, a vinyl group, an epoxy group, or an alkoxysilyl group. The above R is preferably a group containing a (meth)acryloyl group or an epoxy group, and more preferably a (meth)acryloyl group and 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 (“A- BPEF), isocyanuric acid EO-modified di- and triacrylate (Toagosei Co., Ltd.'s "Aronix M-313"), triglydicyl isocyanurate (Nissan Chemical Co., Ltd.'s "TEPIC-S"), tris-(trimethoxysilylpropyl) Examples include 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 mass, more preferably 20 parts by mass, even more preferably 30 parts by mass, and particularly 40 parts by mass, based on 100 parts by mass of the [A] polymer. preferable. On the other hand, the upper limit of this content is preferably 150 parts by mass, more preferably 100 parts by mass, and even more preferably 80 parts by mass. [C] By setting the content of the polymerizable compound within the above range, the difference in solubility between the radiation irradiated area and the non-irradiated area in the alkaline aqueous solution serving as the developer is large, the patterning performance is good, and the resulting interlayer The light resistance and foaming suppression properties of the insulating film are also improved.

[[c] Other polymerizable compounds]
The radiation-sensitive resin composition may contain a polymerizable compound [c] other than the polymerizable compound [C]. [c] Other polymerizable compounds include difunctional or higher-functional (meth)acrylic esters that do not contain the above-mentioned specific ring structure.

As such (meth)acrylic esters,
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, Difunctional (meth)acrylic acid ester 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)acrylate 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 , trifunctional or higher functional (meth)acrylic acid esters such as succinic acid-modified dipentaerythritol penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate;
can be mentioned.

The upper limit of the content of the other polymerizable compound [c] in the radiation-sensitive resin composition can be 50 parts by mass, preferably 30 parts by mass, based on 100 parts by mass of the [A] polymer. In some cases.

Further, the lower limit of the content of the [C] polymerizable compound relative to the total content of the [C] polymerizable compound and [c] other polymerizable compounds may be, for example, 20% by mass, but may be 50% by mass. is preferable, and 65% by mass is more preferable. On the other hand, this upper limit may be 100% by mass. In this way, by increasing the content of the [C] polymerizable compound in the total polymerizable compounds, various properties of the radiation-sensitive resin composition, including foaming inhibiting properties, can be further improved.

[[F] Organic solvent]
The above-mentioned radiation-sensitive resin composition is usually prepared by mixing [F] an organic solvent with [A] a polymer, [B] a radiation-sensitive compound, [C] a polymerizable compound, and other optional components as necessary. It is prepared in a dissolved or dispersed state. [F] As the organic solvent, one that can uniformly dissolve or disperse each of the above components and does not react with each component is preferably used.

[F] Examples of organic solvents 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, ketones, and the like. These can be used alone or in combination of two or more.

The lower limit of the solid content concentration of the radiation-sensitive resin composition is, for example, 5% by mass, preferably 10% by mass, and more preferably 20% by mass. On the other hand, this upper limit is preferably 50% by mass, more preferably 40% by mass. By setting the solid content concentration within the above specific range, the occurrence of coating unevenness can be effectively suppressed.

[[D] Antioxidant]
The radiation-sensitive resin composition may contain [D] an antioxidant. [D] The antioxidant is a component that suppresses the cleavage of bonds in polymer molecules by capturing radicals generated by exposure or heating, or by decomposing peroxides generated by oxidation. When the radiation-sensitive resin composition contains an antioxidant, deterioration due to decomposition of 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 compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, and compounds having a thioether structure. Among these, the antioxidant is preferably a compound having a hindered phenol structure.

Examples of compounds having a hindered phenol structure (hindered phenol compounds) include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[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-hydroxyphenylpropionamide), 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-bis(octylthio)-1,3,5-triazin-2-ylamine)phenol, etc. .

The lower limit of the content of the antioxidant in the radiation-sensitive resin composition is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, based on 100 parts by mass of the [A] polymer. On the other hand, the upper limit may be 5 parts by weight, preferably 3 parts by weight, more preferably 1 part by weight, and even more preferably 0.3 parts by weight. Further, it may be preferable not to contain an antioxidant. If the content of antioxidant is high, sensitivity etc. may decrease.

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

The lower limit of the content of the [E] polymerization inhibitor in the radiation-sensitive resin composition is, for example, 0.01 part by mass. The upper limit is preferably 0.5 parts by mass, more preferably 0.3 parts by mass, per 100 parts by mass of the [A] polymer. [E] If the content of the polymerization inhibitor exceeds the above upper limit, the sensitivity of the radiation-sensitive resin composition may decrease and the pattern shape may deteriorate.

[Other optional ingredients]
The above-mentioned radiation-sensitive resin composition may contain other optional components as necessary within a range that does not impair the intended effect. Other optional components include surfactants, adhesion aids, 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 with the surfaces on which the liquid crystal alignment films are formed facing each other, and a liquid crystal layer formed by irradiating the polymerizable liquid crystal composition filled between the substrates with light. comprising a step of forming a
The interlayer insulating film is formed from a radiation-sensitive resin composition containing a radiation-sensitive compound and a polymerizable compound having two or more polymerizable groups and a ring structure,
The method for manufacturing a liquid crystal display element in which the ring structure is an aliphatic carbocyclic structure, a heterocyclic structure, a fused carbocyclic structure, or a combination thereof.

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

The process of forming an interlayer insulating film (method for forming an interlayer insulating film) will be described in detail below. Other steps are similar to known methods for manufacturing liquid crystal display elements using PSA technology. For example, the step of forming a liquid crystal alignment film can be performed by applying a liquid alignment agent and drying this coating film. Further, alignment treatment may be performed as necessary. Further, the step of filling the space between the substrates with the polymerizable liquid crystal composition may be performed by, for example, dropping the polymerizable liquid crystal composition onto one substrate, and then bonding the pair of substrates together and sealing them with a sealant. Can be done. The step of forming a liquid crystal layer by irradiating light can be performed by irradiating UV light while the liquid crystal compound is oriented obliquely by applying a voltage. The details of the method for manufacturing a liquid crystal display element, including each of these steps, have been appropriately explained together with the structure in the description of the liquid crystal display element 1 above, and therefore, repeated explanation will be omitted.

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

[Step (1)]
In step (1), after applying the composition or its solution or dispersion onto a substrate, the solvent is preferably removed by heating (pre-baking) the applied surface to form a coating film.

As a method for applying the composition solution or dispersion, an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, etc. can be adopted. Among these coating methods, spin coating or slit die coating is preferred.

Prebaking conditions vary depending on the type of each component, blending ratio, etc., but are preferably 60° C. to 120° C. for about 1 minute to 10 minutes. According to the composition, excellent pattern forming properties can be exhibited even under relatively low pre-bake conditions of, for example, 60° C. to 80° C.

<Step (2)>
In step (2), at least a portion of the formed coating film is exposed to light. In this case, when a part of the coating film is exposed to light, it is usually exposed through a photomask having a predetermined pattern. The radiation used for exposure is preferably the radiation used for photoacid generators. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet rays of 365 nm is particularly preferable.

The exposure amount is preferably 500 J/m ² to 6,000 J/m ² , more preferably 1,500 J as the value measured by the intensity of radiation at a wavelength of 365 nm using a luminometer (OAI model 356, manufactured by OAI Optical Associates). /m ² to 1,800J/m ² .

<Step (3)>
In step (3), the exposed coating film is developed to remove unnecessary portions and form a predetermined pattern. The developer used in the development step is preferably an alkaline aqueous solution. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and 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 may be added to the alkaline aqueous solution. The concentration of alkali in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. Examples of the developing method include a liquid piling method, a dipping method, a rocking immersion 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. Following such a development process, a desired pattern can be formed by, for example, washing with running water for 30 to 90 seconds, and then air drying with, for example, compressed air or compressed nitrogen.

<Step (4)>
In step (4), by heating the patterned thin film using a heating device such as a hot plate or an oven, the curing reaction of the [A] polymer can be promoted and an interlayer insulating film can be obtained. The heating temperature is, for example, 120°C to 250°C. The heating time varies depending on the type of heating device, but for example, it is 5 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 an oven. A step baking method or the like in which heating steps are performed two or more times can also be used. In this way, a patterned thin film corresponding to the intended interlayer insulating film can be formed on the surface of the substrate.

The present invention will be described in detail below based on Examples, but the present invention should not be construed as being limited by these Examples. In addition, the characteristics of the polymer obtained in the synthesis example were measured by 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) using Tosoh GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) under the following analysis conditions.
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 mass%
Sample injection volume: 100μL
Column temperature: 40℃
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 cooling tube 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 mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, 50 parts by mass of tricyclo[5.2.1.0 ^2,6 ]dec-8-yl methacrylate, 10 parts by mass of methyl methacrylate, and 0 parts by mass of α-methylstyrene dimer. After charging .5 parts by mass and purging with nitrogen, gentle stirring was started. 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 polymer (A-1). The Mw of the polymer (A-1) was 15,000, and the Mw/Mn was 2.0.

[Synthesis Example 2] (Synthesis of acrylic polymer (A-2))
A flask equipped with a cooling tube 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 mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 5 parts by mass of styrene, 9 parts by mass of N-cyclohexylmaleimide, and 34 parts by mass of methyl methacrylate were charged, and after purging with nitrogen, the solution was stirred gently. By raising the temperature to 70° C. and polymerizing by maintaining this temperature for 5 hours, a solution containing an acrylic polymer (A-2) as a polymer was obtained. Polymer (A-2) had Mw of 7,900, Mn of 3,200, and Mw/Mn of 2.5.

[Synthesis Example 3] (Synthesis of chemical amplification polymer (A-3))
A flask equipped with a cooling tube 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, 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 were charged and the mixture was replaced with nitrogen. Began stirring slowly. The temperature of the solution was raised to 70°C and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-3). Polymer (A-3) had Mw of 9,000, Mn of 3,600, and Mw/Mn of 2.5.

[Synthesis Example 4] (Synthesis of polysiloxane polymer (A-4))
In a container 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 added, heated to 75°C, and held for 4 hours. Further, the solution temperature was set to 40°C, and evaporation was performed while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolytic condensation. Through the above steps, a polysiloxane polymer (A-4) was obtained as a siloxane polymer which is a hydrolyzed condensate. Polymer (A-4) had Mw of 5,000, Mn of 2,500, and Mw/Mn of 2.0.

<Preparation of radiation-sensitive resin composition>
[A] Polymer, [B] Radiation-sensitive compound, [C] Polymerizable compound, [D] Antioxidant, [E] Polymerization inhibition used in the preparation of the radiation-sensitive resin compositions of Examples and Comparative Examples The agent and [F] organic solvent 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: ADEKA's "NCI-930" (photopolymerization initiator)
B-2: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product 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 multifunctional epoxy compound (“OGSOL EG-200” from Osaka Gas Chemical Co., Ltd.)
C-3: Isocyanuric acid EO modified di- and triacrylate (“Aronix M-313” manufactured by Toagosei Co., Ltd.)
C-4: Triglydicyl isocyanurate (Nissan Chemical Co., Ltd.'s "TEPIC-S")
C-5: Tris-(trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd.'s "KBM-9659")
c-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” from Nippon Kayaku Co., Ltd.)
c-2: Phenol novolak type liquid epoxy resin (Japan Epoxy Resin Co., Ltd.'s "jER 152")
c-3: Methacryloxypropyltrimethoxysilane (“XIAMETER(R) OFS-6030 SILANE” by Dow Corning Toray)

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

<[E] Polymerization inhibitor>
E-1: 2,5-di-t-butylhydroquinone (“2,5-di-t-butylhydroquinone” from 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 a polymerizable compound are added to the solution containing the polymer (A-1) in an amount equivalent to 100 parts by mass (solid content) Mix 20 parts by mass of compound (C-1), 40 parts by mass of another polymerizable compound (c-1), and 0.1 part by mass of polymerization inhibitor (E-1) to give a solid concentration of 30% by mass. The radiation-sensitive resin composition (S-1) was dissolved in a mixed solvent of organic solvent (F-1) and organic solvent (F-2) as shown in FIG. Prepared.

<Examples 2-25 Comparative Examples 1-16>
Radiation-sensitive resin compositions (S-2) to (S-25) and ( CS-1) to (CS-16) were prepared. Note that in Tables 1 and 2, "-" indicates that the corresponding component was not blended.

<Evaluation>
Interlayer insulating films were formed from the radiation-sensitive resin compositions of Examples 1 to 25 and Comparative Examples 1 to 16, and radiation sensitivity, resolution, foaming resistance, chemical resistance, and voltage holding rate were evaluated according to the method 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 onto a glass substrate using a spinner, it was prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with a thickness of 4.0 μm. Next, using an exposure machine (Canon Inc.'s "PLA-501F", which uses an ultra-high pressure mercury lamp), the coating film is exposed through a pattern mask having a plurality of rectangular light shielding areas (10 μm x 10 μm) by varying the exposure amount. Exposure was performed. Next, development was carried out at 25° C. by a piling method using an aqueous tetramethylammonium hydroxide solution (developer) having a concentration of 2.38% by mass. The development time was 100 seconds. After the development process, 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 at 230° C. for 30 minutes in a clean oven to obtain an interlayer insulating film. Regarding the film thickness of this interlayer insulating film, the sensitivity was determined as the exposure amount at which the remaining film rate (the ratio at which the patterned thin film remains properly) expressed by the following formula was 85% or more, and the sensitivity was evaluated according to the following criteria. .
Remaining film rate (%) = (film thickness after development / film thickness before development) x 100
(Evaluation criteria)
A: Less than 200 J/m ² B: 200 J/m ² or more and less than 400 J/m ² C: 400 J/m ² or more and less than 800 J/m ² D: 800 J/m ² or more

[Negative resolution (resolution)] (Examples 1 to 9, Comparative Examples 1 to 4)
An interlayer insulating film having through holes was formed in the same manner as in the evaluation of radiation sensitivity, except that the exposure amount was 200 J/m ² , and the minimum diameter of the through holes in this interlayer insulating film was observed using an optical microscope. Resolution (resolution) was evaluated according to the following criteria.
(Evaluation criteria)
A: The minimum diameter of the through hole is 10 μm or more. B: The minimum diameter of the through hole is 8 μm or more and less than 10 μm. C: The 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 film-formed glass substrate using a spinner, and heated at 60° C. for 1 minute (HMDS treatment). After this HMDS treatment, each of the positive radiation-sensitive compositions prepared as described above was applied onto the chromium-coated glass substrate using a spinner and prebaked at 90°C for 2 minutes to form a film with a thickness of 3.0 μm. A coating film was formed. Next, using an exposure machine (Canon Inc.'s "PLA-501F", which uses an ultra-high pressure mercury lamp), the exposure amount was varied and the film was exposed through a mask with a 60 μm line and space (10:1) pattern. Then, the coating film was exposed. Thereafter, it was developed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25° C. by a piling method. The development time was 80 seconds. Next, a pattern was formed on the chromium film-formed glass substrate after the HMDS treatment by washing with running ultrapure water for 1 minute and then drying. The entire surface of the coating film was exposed to light at 300 J/m ² , and the chromium-coated glass substrate was heated in a clean oven at 230° C. for 30 minutes to obtain an interlayer insulating film. The amount of exposure required to completely dissolve a 6 μm space pattern during development was investigated.
(Evaluation criteria)
A: Less than 200 J/m ² B: 200 J/m ² or more and less than 400 J/m ² C: 400 J/m ² or more and less than 800 J/m ² D: 800 J/m ² or more

<Manufacture of liquid crystal display elements and evaluation of foaming resistance>
[Evaluation of foaming resistance]
In this example, an active matrix VA mode color liquid crystal display element having the same structure as the liquid crystal display element 1 shown in FIG. 1 was manufactured using a known method as appropriate.

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

Next, the radiation-sensitive resin composition (S-1) prepared in Example 1 was applied onto the prepared substrate having the TFT using a slit die coater. Next, it was prebaked on a hot plate at 90° C. for 100 seconds to evaporate the organic solvent and the like to form a coating film. Next, 100 mJ of UV light was irradiated using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ) through a pattern mask capable of forming a predetermined pattern. Thereafter, a development process was performed at 25° C. for 100 seconds using an aqueous solution of tetramethylammonium hydroxide (developer) having a concentration of 2.38% by mass by a piling method. After the development process, the coating film was washed with running ultrapure water for 1 minute, dried to form a patterned coating film on the substrate, and then heated in an oven at 230°C for 30 minutes (post-baking). 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 via 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 grid pattern on a transparent glass substrate to form a color filter, and a color filter is formed on the color filter. In this case, an insulating film was formed to serve as a flattening layer of a color filter. Furthermore, a transparent common electrode made of ITO was formed on the insulating film.

Next, a liquid crystal alignment agent (trade name JALS2095-S2, manufactured by JSR Corporation) was applied using a spinner to the TFT arrangement surface of the manufactured array substrate and the color filter arrangement surface of the color filter substrate, respectively. By heating at 80° C. for 1 minute and then at 180° C. for 1 hour, an alignment film with a 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 curing sealant to the outer periphery of the pixel area of each substrate, a dispenser is used to apply a photopolymerizable nematic liquid crystal with negative dielectric anisotropy to the inside of the sealant. A polymerizable liquid crystal composition prepared by adding a polymerizable component was dropped.

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

Next, while applying a voltage that turns on the TFT on the array substrate to the gate electrode of the TFT, an AC voltage is applied between the source electrode of the TFT and the common electrode on the color filter substrate. The liquid crystals in the layer were tilted. Next, while maintaining the tilted orientation of the liquid crystal, the layer of polymerizable liquid crystal composition is irradiated with ultraviolet light from the array substrate side using an ultra-high pressure mercury lamp, so that the liquid crystal forms a pretilt angle in a predetermined direction. A liquid crystal layer which was aligned almost vertically was formed. In the manner described above, a VA mode color liquid crystal display element was manufactured.

Next, using the manufactured liquid crystal display element, impact was applied at a high temperature (80° C.) to check the presence or absence of bubbles in the pixels. Impact was applied to the liquid crystal display element by dropping a pachinko ball from 30 cm above the liquid crystal display element. When the impact was applied, no bubbles were generated in the pixels of the liquid crystal display element, which was evaluated as very good; cases where bubbles were formed but the density of the bubbles was low were evaluated as good; and cases where the density of bubbles was high were evaluated as poor. The evaluation results were marked A for very good, B for good, and C for poor.

[Chemical resistance]
The interlayer insulating film prepared in the radiation sensitivity evaluation above was immersed in N-methyl-2-pyrrolidone heated to 65°C for 6 minutes, and after immersion, the coating was washed with running ultrapure water for 5 seconds, and then dried. Ta. The thickness of the insulating film after the treatment was measured using a stylus-type film thickness meter. N-methyl-2-pyrrolidone swelling ratio (%) was calculated according to the following formula, and chemical resistance was evaluated according to the following criteria.
N-methyl-2-pyrrolidone swelling rate (%)
=100×(Remaining film after immersion (μm)/Remaining film (μm) rate before immersion (%) - 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 rate]
After each radiation-sensitive composition was spin-coated on a soda glass substrate on which a SiO ₂ film was formed to prevent the elution of sodium ions and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape, Prebaking was performed for 10 minutes in a clean oven at 90° C. to form a coating film with a thickness of 2.0 μm. The coating film was then exposed to light at an exposure dose of 500 J/m ² without using a photomask. Thereafter, post-baking was performed at 230° C. for 30 minutes to cure the coating film. Next, the substrate on which this pixel was formed and the substrate on which ITO electrodes were simply vapor-deposited in a predetermined shape were bonded together using a sealant mixed with 0.8 mm glass beads, and then Merck's liquid crystal MLC6608 was injected to form the liquid crystal. A cell was created. Further, the liquid crystal cell was placed in a constant temperature bath at 60° C., and the voltage retention rate of the liquid crystal cell was measured using a liquid crystal voltage retention rate measuring system (Model VHR-1A, Toyo Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. The voltage holding rate (%) is a value calculated from the following formula.
Voltage holding rate (%) = (Liquid crystal cell potential difference after 16.7 ms/voltage applied at 0 ms) x 100
If the voltage retention rate of the liquid crystal cell is less than 90%, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned, resulting in afterimage. There is a high risk of "burn-in" such as
(Evaluation criteria)
A: Less than 95% B: 90% or more but 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 radiation sensitivity, resolution, foaming resistance (low foaming), chemical resistance, and voltage holding rate. On the other hand, Examples 1 to 25 had good results in all the evaluations, including foaming resistance.

The liquid crystal display element of the present invention can be used in liquid crystal display devices such as television receivers and personal computer monitors.

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 (2)

A polymer having a structural unit containing a carboxyl group and a structural unit containing an epoxy group in the same or different polymer molecules;
A polymerizable compound represented by the following formula (C-3),
A bifunctional or higher functional (meth)acrylic ester that does not contain an isocyanuric acid structure,
containing a radiation-sensitive compound;
The content of the polymerizable compound is 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymer,
A radiation-sensitive resin composition for forming an interlayer insulating film.

(In formula (C-3), R is a (meth)acryloyloxy group. c is 2.) The radiation-sensitive resin composition according to claim 1 , wherein the radiation-sensitive compound is an acid generator, a radical polymerization initiator, or a combination thereof.

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