JP2018182305A - Thin-film transistor substrate, liquid crystal display element, organic el element, radiosensitive resin composition, and manufacturing method of thin-film transistor substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a thin-film transistor substrate having an interlayer insulation film which is hard to cause the whitening in a high-temperature treatment and in which the occurrence of outgassing is suppressed; a liquid crystal display element and an organic EL element, each including the thin-film transistor substrate; a radiosensitive resin composition which enables the suitable formation of the interlayer insulation film as described above; and a method for manufacturing the thin-film transistor substrate.SOLUTION: A thin-film transistor substrate comprises: a substrate; a thin-film transistor disposed on the substrate; and an interlayer insulation film disposed on the thin-film transistor. The interlayer insulation film includes a polymer having a structure represented by the formula (1) below. (In the formula (1), Rrepresents a divalent coupling group including a heteroatom, Rrepresents a monovalent organic group including an aromatic ring, and * represents a coupling portion.)SELECTED DRAWING: None

Description

  The present invention relates to a thin film transistor substrate, a liquid crystal display element, an organic EL element, a radiation sensitive resin composition, and a method of manufacturing a thin film transistor substrate.

  In recent years, development of a display element using liquid crystal, that is, a liquid crystal display element has been actively promoted from advantages such as reduction in thickness and weight and the like as compared with a conventional CRT type display device.

  The liquid crystal display element has, for example, a structure in which liquid crystal is sandwiched between a pair of substrates such as a transparent glass substrate. An alignment film can be provided on the surface of these substrates for the purpose of controlling the alignment of the liquid crystal. Further, the pair of substrates is held, for example, by a pair of polarizing plates. Then, by applying an electric field between the substrates, alignment change occurs in the liquid crystal, and light is partially transmitted or blocked. The liquid crystal display element can display an image using such characteristics.

  With the development of an active matrix system in which a switching element is disposed for each pixel, the liquid crystal display element can realize good image quality with excellent contrast ratio and response performance. Furthermore, the liquid crystal display device overcomes the problems such as high definition, colorization and widening of the viewing angle, and is recently used as a display device of a portable electronic device such as a smartphone or a large thin television display device. It has

  In the active matrix liquid crystal display element, gate wiring and signal wiring are arranged in a grid shape on one of a pair of substrates sandwiching liquid crystal, and, as their switching elements, for example, Thin film transistors (TFTs) are provided. That is, in the active matrix liquid crystal display element, one of the pair of substrates sandwiching the liquid crystal constitutes a thin film transistor substrate in which a TFT or the like is disposed.

  The thin film transistor substrate is typically disposed on a substrate and a TFT which is a switching element disposed on the substrate, a planarizing film covering the TFT, an interlayer insulating film covering the planarizing film, and an interlayer insulating film, It has a pixel electrode connected to the TFT, and a storage capacitance electrode disposed between the interlayer insulating film and the planarization film so as to face the pixel electrode via the interlayer insulating film.

  From the viewpoint of improving the reliability of the thin film transistor substrate in the future, the interlayer insulating film may be subjected to a high temperature treatment (for example, 250 ° C. or more). Since there is a possibility that application may become difficult in the viewpoint of heat resistance and lack of transparency in the existing organic insulating film of acrylic type, the number of processes for forming a pattern is small, and radiation sensitivity that high surface hardness can be obtained Resin compositions are being considered. A siloxane-based photosensitive material has been proposed as such a resin composition (Patent Document 1).

Patent No. 4670693 gazette

  When the photosensitive siloxane material is a photosensitive agent having low compatibility with a polysiloxane such as a quinonediazide compound, whitening occurs when the interlayer insulating film is formed due to the low compatibility between the photosensitive agent and the polysiloxane. It turns out that there are things. On the other hand, it is possible to introduce a phenyl group into the polysiloxane skeleton as in Patent Document 1 to enhance the compatibility with the quinone diazide compound as one measure.

  However, in a photosensitive material using polysiloxane in which a phenyl group is directly introduced into the polysiloxane skeleton, benzene may be generated as an outgas during high-temperature processing of the interlayer insulating film, which may cause contamination with respect to the manufacturing process and the environment. It is done.

  The present invention has been made in view of the above problems. That is, the object of the present invention is to preferably use a thin film transistor substrate provided with an interlayer insulating film which is hard to whiten during high temperature processing and from which the outgassing is suppressed, a liquid crystal display element or organic EL element provided with the same, and the interlayer insulating film. It is an object of the present invention to provide a radiation-sensitive resin composition that can be formed as well as a method of manufacturing a thin film transistor substrate.

（式（１）中、Ｒ^１は、ヘテロ原子を含む２価の連結基を示し、Ｒ^２は、芳香環を含む１価の有機基を示す。＊は結合部位を示す。） The present invention, in one aspect, comprises
A substrate and a thin film transistor disposed on the substrate;
A thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor, the thin film transistor substrate comprising:
The present invention relates to a thin film transistor substrate in which the interlayer insulating film includes a polymer having a structure represented by the following formula (1).

(In formula (1), R ¹ represents a divalent linking group containing a hetero atom, R ² represents a monovalent organic group containing an aromatic ring, and * represents a binding site.)

The invention, in another aspect, comprises
The present invention relates to a liquid crystal display device having the above thin film transistor substrate, a counter substrate having a counter electrode facing the thin film transistor substrate, and a liquid crystal layer disposed between the thin film transistor substrate and the counter substrate.

In still another aspect of the present invention,
The present invention relates to an organic EL element including the thin film transistor substrate, an interlayer insulating film, and a light emitting layer in this order.

（式（３）中、Ｘは、ヒドロキシ基、チオール基、カルボキシ基又はアミノ基を示し、Ｒ^４は、芳香環を含む１価の有機基を示す。） In still yet another aspect of the present invention,
[A] Polymer,
A radiation sensitive resin composition comprising: [B] a photosensitizer, and [C] a compound represented by the following formula (3),
A substrate,
A thin film transistor disposed on the substrate;
The present invention relates to a radiation sensitive resin composition used for forming the interlayer insulating film of a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor.

(In formula (3), X represents a hydroxy group, a thiol group, a carboxy group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring.)

The invention, in another aspect, comprises
A substrate,
A thin film transistor disposed on the substrate;
A method of manufacturing a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor, comprising:
[1] A process of forming a coating film of the radiation sensitive resin composition according to claim 11 on the substrate on which the thin film transistor is formed,
[2] irradiating at least a part of the coating film formed in the step [1] with radiation;
[3] a process of developing the coating film irradiated with radiation in the process [2], and a process of heating the coating film developed in the [4] process [3] to form the interlayer insulating film The present invention relates to a method of manufacturing a thin film transistor substrate.

  According to the present invention, a thin film transistor substrate provided with an interlayer insulating film which is not easily whitened during high temperature processing and in which generation of outgas is suppressed, a liquid crystal display element or an organic EL element provided with the same, and the interlayer insulating film are suitably formed. The present invention can provide a radiation sensitive resin composition that can be used as well as a method of manufacturing a thin film transistor substrate.

FIG. 3 is a schematic cross-sectional view of a pixel portion in an example of a thin film transistor substrate according to the first embodiment of the present invention. It is a typical sectional view of a pixel part in an example of a liquid crystal display element concerning a 2nd embodiment of the present invention. It is a schematic cross section of the pixel part in an example of the organic EL element concerning a 3rd embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described using drawings as appropriate.

  In the present invention, the “radiation” irradiated at the time of exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

First Embodiment
(Thin film transistor substrate)
FIG. 1 is a schematic cross-sectional view of a pixel portion in an example of a thin film transistor substrate according to a first embodiment of the present invention.

  A thin film transistor substrate 100 as an example of the first embodiment of the present invention shown in FIG. 1 includes a substrate 1, a TFT 2 as a switching element disposed on the substrate 1, a planarizing film 5 covering the TFT 2, and a planarizing film 5. Interlayer insulating film 6 disposed on the interlayer insulating film 6 to cover the pixel electrode 7 connected to the TFT 2, and the interlayer insulating film 6 so as to face the pixel electrode 7 via the interlayer insulating film 6 And a storage capacitor electrode 3 disposed between the membrane 5 and the storage capacitor. The thin film transistor substrate 100 can be provided with an inorganic insulating film 4 between the TFT 2 and the planarizing film 5 so as to cover and protect the TFT 2 as shown in FIG.

  On the surface of the substrate 1 on which the TFTs 2 are disposed, various wirings such as gate wirings and signal wirings not shown are formed. The gate wiring and the signal wiring are arranged in a lattice, and the TFT 2 is provided at each of the intersections thereof.

  The substrate 1 is not particularly limited. For example, a glass substrate, a quartz substrate, a resin substrate made of an acrylic resin or the like is preferably used. The substrate 1 is preferably subjected to cleaning and pre-annealing as pretreatment for forming the thin film transistor substrate 100.

  As described above, the TFT 2 is a switching element, and is formed on the substrate 1 to form a part of the gate wiring, the gate electrode 10, the gate insulating film 11 covering the gate electrode 10, and the gate insulating film 11. It has a semiconductor layer 12 disposed, a source electrode 14 forming a part of the signal wiring to be connected to the semiconductor layer 12, and a drain electrode 13 connected to the pixel electrode 7 and connected to the semiconductor layer 12 on the other side. Is configured.

  The gate electrode 10 of the TFT 2 can be formed by forming a metal thin film on the substrate 2 by a vapor deposition method, a sputtering method, or the like, and performing patterning using an etching process. Moreover, it is also possible to pattern and use a metal oxide conductive film or an organic conductive film.

  Examples of the material of the metal thin film constituting the gate electrode 10 include aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), gold (Au), and the like. Mention may be made of metals such as tungsten (W) and silver (Ag), alloys of these metals, and alloys such as Al-Nd and APC alloys (alloys of silver, palladium, copper). As the metal thin film, it is also possible to use a laminated film made of layers of different materials, such as a laminated film of Al and Mo.

  As a material of the metal oxide conductive film constituting the gate electrode 10, metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide: indium-doped tin oxide) and zinc indium oxide (IZO) Can be mentioned.

  Moreover, as a material of the organic conductive film which comprises the gate electrode 10, electroconductive organic compounds, such as polyaniline, polythiophene, and polypyrrole, or these mixtures can be mentioned.

  The thickness of the gate electrode 10 can be, for example, 10 nm to 1000 nm.

The gate insulating film 11 of the TFT ₂ can be formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN, either alone or by laminating them. The thickness of the gate insulating film 11 can be, for example, 100 nm to 1000 nm.

  The semiconductor layer 12 of the TFT 2 may be, for example, a-Si (amorphous silicon) in an amorphous state, or p-Si (polysilicon) obtained by crystallizing a-Si with an excimer laser or solid phase growth. It can be formed by using a silicon (Si) material.

  When a-Si is used for the semiconductor layer 12, the thickness of the semiconductor layer 12 is preferably 30 nm or more and 500 nm or less. Further, an n + Si layer (not shown) for achieving ohmic contact is preferably formed between the semiconductor layer 12 and the source electrode 14 and the drain electrode 13 with a thickness of 10 nm or more and 150 nm or less.

  When p-Si is used for the semiconductor layer 12, the semiconductor layer 12 is doped with an impurity such as phosphorus (P) or boron (B) to form a source region and a drain region across the channel region. It is preferable to do. Further, it is preferable to form a lightly doped drain (LDD) layer between the channel region of the semiconductor layer 12 and the source and drain regions.

  The semiconductor layer 12 of the TFT 2 can be formed using an oxide. Oxides applicable to the semiconductor layer 12 include single crystal oxides, polycrystalline oxides, and amorphous oxides, and mixtures thereof. As a polycrystalline oxide, zinc oxide (ZnO) etc. can be mentioned, for example.

  Examples of the amorphous oxide applicable to the semiconductor layer 12 include an amorphous oxide including at least one element of indium (In), zinc (Zn) and tin (Sn).

  Specific examples of the amorphous oxide applicable to the semiconductor layer 12 include Sn-In-Zn oxide, In-Ga-Zn oxide (IGZO: indium oxide gallium gallium zinc), 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 oxide, Sn-In-Zn oxide, etc. can be mentioned. In the above case, the composition ratio of the constituent materials does not necessarily have to be 1: 1, and it is possible to select a composition ratio that achieves desired characteristics.

  For example, when the semiconductor layer 12 using an amorphous oxide is formed using IGZO or ZTO, the semiconductor layer is formed by sputtering or evaporation using an IGZO target or ZTO target, and a photolithography method or the like is performed. It is formed by patterning using a resist process and an etching process. The thickness of the semiconductor layer 6 using an amorphous oxide is preferably, for example, 1 nm or more and 1000 nm or less.

  The source electrode 14 and the drain electrode 13 connected to the semiconductor layer 12 of the TFT 2 are formed of conductive films constituting these electrodes using a method such as a sputtering method, a CVD method, or an evaporation method in addition to the printing method and the coating method. After that, patterning can be performed using a photolithography method or the like.

  As a constituent material of the source electrode 14 and the drain electrode 13, for example, metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W and Ag, alloys of these metals, and alloys such as Al-Nd and APC Can be mentioned. Also, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum-doped zinc oxide) and GZO (gallium-doped zinc oxide), polyaniline, polythiophene and polypyrrole. And conductive organic compounds such as And as a conductive film which constitutes those electrodes, it is also possible to use a lamination film which consists of layers of different materials, such as a lamination film of Ti and Al.

  The thickness of each of the source electrode 14 and the drain electrode 13 is preferably 10 nm or more and 1000 nm or less, for example.

In addition, the thin film transistor substrate 100 can provide the inorganic insulating film 4 on the TFT 2 so as to cover it. The inorganic insulating film 4 can be formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN, either alone or as a laminate. The inorganic insulating film 4 is provided to cover and protect the TFT 2. More specifically, the inorganic insulating film 4 covers the TFT 2 to protect the semiconductor layer 12 and can be prevented from being affected by humidity, for example.

  In the thin film transistor substrate 100, the inorganic insulating film 4 may not be provided. In that case, the flattening film 5 provided between the pixel electrode 7 and the TFT 2 can also be used to protect the TFT 2.

  The planarizing film 5 of the thin film transistor substrate 100 is provided on the inorganic insulating film 4 so as to cover the TFT 2 from above. The planarization film 5 has a function of planarizing the unevenness due to the TFT 2 formed on the substrate 1. The planarization film 5 can be an insulating film formed using a radiation sensitive resin composition. That is, the planarization film 5 can be an organic film formed using an organic material. For example, the planarizing film 5 can be a film made of an acrylic resin, a polyimide resin, a polysiloxane, and a novolac resin.

  When the planarization film 5 is an organic film, as described above, the coupling capacitance between the pixel electrode 7 and another wiring such as a gate wiring or a signal wiring can be reduced. The thin film transistor substrate 100 can increase the area of the pixel electrode 7 in the pixel and can improve the aperture ratio of the pixel by including the planarizing film 5.

  The planarization film 5 preferably has an excellent function as a film for planarization, and from this viewpoint, the film thickness is preferably set. For example, the planarization film 5 can be formed with an average film thickness of 0.5 μm to 6 μm. Also, each film thickness is set such that the average film thickness combined with interlayer insulating film 6 is 1 μm to 6 μm so that the excellent planarization ability can be exhibited in combination with interlayer insulating film 6 described later. It is also possible.

  As described above, when the planarization film 5 is formed using, for example, a radiation sensitive resin composition, patterning is performed by exposure and development after application according to a known method, and curing is performed, It can be easily formed.

  Further, in the thin film transistor substrate 100, the common wire 17 to which a common voltage is applied is disposed on the gate insulating film 11.

  Therefore, in the thin film transistor substrate 100, the inorganic insulating film 4 described above covers the common wiring 17 in the arrangement region of the common wiring 17, and the planarization film 5 described above covers the common wiring 17 and the inorganic insulating film 4. It is configured.

  Then, the auxiliary capacitance electrode 3 electrically connected to the common wiring 17 is disposed on the planarization film 5 via the contact hole 18 penetrating the planarization film 5 and the inorganic insulating film 4.

  The storage capacitor electrode 3 is made of a light-transmitting conductive material, and is, for example, a transparent electrode made of ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide, or the like. The thickness of the storage capacitor electrode 3 is preferably 100 nm or more and 500 nm or less, which is effective for achieving both light transmittance and conductive characteristics.

  The interlayer insulating film 6 of the thin film transistor substrate 100 is disposed on the planarization film 5 so as to cover the planarization film 5. Then, in the arrangement region of the above-mentioned storage capacitance electrode 3, it is formed so as to cover the storage capacitance electrode 3 on the planarization film 5 and is disposed so as to cover the entire surface of the planarization film 5 and the storage capacitance electrode 3. .

  The interlayer insulating film 6 is an organic film formed using the radiation sensitive resin composition of the fourth embodiment of the present invention described later. The interlayer insulating film 6 can be easily formed by performing patterning by exposure and development after application of the radiation sensitive resin composition of the fourth embodiment of the present invention, and curing. The interlayer insulating film 6 is formed using the radiation sensitive resin composition of the fourth embodiment of the present invention, whereby the dielectric constant as the dielectric characteristic is controlled to a desired value. For example, it is configured to have a high dielectric constant as compared to a normal organic film.

（式（１）中、Ｒ^１は、ヘテロ原子を含む２価の連結基を示し、Ｒ^２は、芳香環を含む１価の有機基を示す。＊は結合部位を示す。） The interlayer insulating film 6 includes a polymer having a structure represented by the following formula (1).

(In formula (1), R ¹ represents a divalent linking group containing a hetero atom, R ² represents a monovalent organic group containing an aromatic ring, and * represents a binding site.)

  In the polymer contained in the interlayer insulating film 6, since the aromatic ring is bonded to Si through the divalent linking group containing a hetero atom, generation of outgassing derived from an aromatic compound such as benzene is suppressed be able to. Although benzene is generated as an outgas in the conventional interlayer insulating film containing a polymer in which a phenyl group is directly bonded to Si, in the interlayer insulating film of this embodiment, such an event is reduced or prevented to produce a manufacturing process. And improve the safety to the environment. Further, since the polymer contains an aromatic ring, the compatibility with a photosensitizer such as a quinonediazide compound is high, and whitening can be suppressed during high-temperature treatment of the interlayer insulating film. In addition, the interlayer insulating film has good solvent resistance.

  As a hetero atom which comprises the bivalent coupling group containing a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom etc. are mentioned, for example. As a specific example of the said coupling group, the group which combined 2 or more of these, for example -O-, -CO-, -S-, -CS-, -OCO-, -COO-, -NR'-, is mentioned. Etc. R 'is a hydrogen atom or a C1-C10 monovalent hydrocarbon group. As a C1-C10 monovalent hydrocarbon group, a C1-C10 monovalent | monohydric chain hydrocarbon group is mentioned, As a C1-C10 monovalent | monohydric chain hydrocarbon group, it is mentioned. For example, alkyl groups such as methyl group, ethyl group, n-propyl group and i-propyl group, alkenyl groups such as ethenyl group, propenyl group and butenyl group, and alkynyl groups such as ethynyl group, propynyl group and butynyl group can be mentioned. .

Among them, R ¹ preferably represents —O—, —S—, —O—C (= O) — or —NH— from the viewpoint of chemical stability, synthesis ease, and the like. Among these, from the viewpoint of further enhancing the effect of the present invention, -O-, -S-,-or -NH- is preferable, and -O- is more preferable. Moreover, the content ratio of -O-, -S- and -NH- occupied in all R ¹ in the polymer having the structure represented by the above formula (1), particularly -O- occupied in all R ¹ The lower limit of the content is preferably 90 mol%, more preferably 95 mol%, and still more preferably 99 mol%.

  The monovalent organic group containing an aromatic ring is, for example, an aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylnaphthyl group, anthryl group, methylanthryl group, 4- (2-phenyl) And phenoxyalkyl groups such as -2-propyl) phenyl group, phenoxymethyl group and phenoxyethyl group; groups represented by the following formula (2); and aralkyl groups such as naphthylmethyl group and anthrylmethyl group. One or more hydrogen atoms of these groups may be substituted.

（式（２）中、Ｒ^１は、―Ｏ−、―Ｓ−、−Ｏ−Ｃ（＝Ｏ）−又は−ＮＨ−を示し、Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基又はハロゲン原子を示す。ｎは０から６の整数を示す。ｍは０又は１を示す。）

(In formula (2), R ¹ represents —O—, —S—, —O—C (= O) — or —NH—, and R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms And an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a halogen atom, n represents an integer of 0 to 6. m represents 0 or 1 .)

  Examples of the alkyl group having 1 to 12 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl and i-propyl, alkenyl groups such as ethenyl, propenyl and butenyl, ethynyl and propynyl And alkynyl groups such as butynyl group.

  As a C1-C12 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a phenoxy group etc. are mentioned, for example.

  As a C6-C12 aryl group, a phenyl group, a tolyl group, xylyl group, mesityl group, a naphthyl group, a methyl naphthyl group etc. are mentioned, for example.

  As a C7-C12 aralkyl group, a benzyl group, 2-phenylethyl group, 2-phenyl 2-propyl group etc. are mentioned, for example.

  As an upper limit of said n, 4 is preferable and 2 is more preferable. When m is 1, the effects of the present invention may be exhibited more sufficiently.

As R ² shown by the said Formula (1), group shown by the said Formula (2) is preferable. Specifically as a group shown by the said Formula (2), a benzyl group, a phenethyl group, a naphthyl group etc. are mentioned, for example.

  The interlayer insulating film is preferably a polysiloxane film from the viewpoint of easiness of introduction of the structure represented by the formula (1) or (2). The polysiloxane will be described later.

  In the interlayer insulating film, the content of the aromatic ring derived from the structure represented by the formula (1) is preferably 1 mol% to 60 mol% with respect to Si atoms in the interlayer insulating film. . 10 mol% is more preferable, and, as for the lower limit of the content rate of the said aromatic ring, 30 mol% is more preferable. As for the upper limit of the content rate of the said aromatic ring, 50 mol% is more preferable, and 40 mol% is further more preferable. When the content rate of the aromatic ring is in the above range, it is possible to achieve the prevention of whitening and the suppression of the generation of outgassing at the high level in the high temperature treatment of the interlayer insulating film.

  The polymer contained in the interlayer insulating film 6 may further have a structure represented by the following formula (a).

（式（ａ）中、Ｒ^ａは、アリール基を示す。）

(In formula (a), R ^a represents an aryl group.)

  By further including a structure in which the polymer contained in the interlayer insulating film 6 has a structure in which an aryl group is bonded to a Si atom, the compatibility between the polymer and the photosensitizer becomes higher, and the high temperature processing of the interlayer insulating film is performed. Whitening can be prevented.

The aryl group represented by R ^a, such monovalent those exemplified as the organic group and similar groups containing an aromatic ring in R ² can be mentioned.

  When the polymer contained in the interlayer insulating film 6 has a structure represented by the above formula (a), the content of the aromatic ring derived from the structure represented by the above formula (a) in the interlayer insulating film is the above interlayer It is preferable that it is 1 mol% or more and 40 mol% or less with respect to the Si atom in an insulating film. As for the lower limit of the content rate of the said aromatic ring, 5 mol% is more preferable, and 10 mol% is further more preferable. As for the upper limit of the content rate of the said aromatic ring, 30 mol% is more preferable, and 20 mol% is further more preferable. When the content rate of the aromatic ring is in the above range, it is possible to achieve the prevention of whitening and the suppression of the generation of outgassing at the high level in the high temperature processing of the interlayer insulating film. In addition, the upper limit value of the content of the aromatic ring derived from the structure represented by the above-mentioned formula (a) may be more preferably 10 mol%, and even more preferably 5 mol%. As described above, by reducing the content of the aromatic ring derived from the structure represented by the above formula (a), the generation of outgassing is further suppressed, and the solvent resistance of the interlayer insulating film tends to be enhanced.

  The average film thickness of the interlayer insulating film 6 is preferably, for example, 0.3 μm or more and 6 μm or less. Moreover, as described above, it is also possible to set each film thickness so that the average film thickness combined with the planarization film 5 is 1 μm or more and 6 μm or less.

  The interlayer insulating film 6 can be considered to be an inorganic film such as a SiN film as well as the gate insulating film 11 and the inorganic insulating film 4. However, in order to form an interlayer insulating film made of such an inorganic film, vacuum film formation using a vacuum facility or dry etching is required, and it is easily formed like the interlayer insulating film 6 which is an organic film. It is not possible. Therefore, the interlayer insulating film 6 is preferably an organic film formed using the radiation sensitive resin composition of the fourth embodiment of the present invention. The interlayer insulating film 6 is formed using the radiation sensitive resin composition according to the fourth embodiment of the present invention, and has a dielectric constant higher than that of a conventional organic film constituting a conventional interlayer insulating film, for example, It can have the same dielectric constant as an inorganic film such as a SiN film.

  The pixel electrode 7 of the thin film transistor substrate 100 is disposed on the interlayer insulating film 6 and electrically connected to the drain electrode 13 through the contact hole 19 penetrating the interlayer insulating film 6, the planarization film 5 and the inorganic insulating film 4. Be done. In the thin film transistor substrate 100, the pixel electrode 7 and the auxiliary capacitance electrode 3 are configured to face each other through the interlayer insulating film 6.

  The pixel electrode 7 is made of a light-transmitting conductive material, and is a transparent electrode made of, for example, ITO, IZO, or tin oxide. The thickness of the pixel electrode 7 is preferably 100 nm or more and 500 nm or less, which is effective for achieving both light transmittance and conductive characteristics.

  The thin film transistor substrate 100, which is an example of the first embodiment of the present invention having the above configuration, is provided on one surface side of the interlayer insulating film 6, and is connected to the pixel electrode 7 electrically connected to the drain electrode 13 of the TFT 2. And a storage capacitance electrode 3 provided on the other surface side of interlayer insulating film 6 and electrically connected to common wiring 17.

  As a result, in the thin film transistor substrate 100, the storage capacitance electrode 3 can generate a storage capacitance at an overlapping portion where the pixel electrode 7 and the storage capacitance electrode 3 overlap in plan view. Then, as described above, the interlayer insulating film 6 sandwiched between the pixel electrode 7 and the storage capacitance electrode 3 is formed using the radiation sensitive resin composition of the fourth embodiment of the present invention, and the dielectric constant is desired. It is controlled by the value of. The interlayer insulating film 6 is configured to have, for example, a dielectric constant higher than that of a normal organic film. Therefore, in plan view, the auxiliary capacitance generated at the overlapping portion where the pixel electrode 7 and the auxiliary capacitance electrode 3 overlap can have high charge retention ability.

  On the other hand, as described above, the thin film transistor substrate 100 has the planarizing film 5 between the pixel electrode 7 and the TFT 2 to reduce the coupling capacitance between the pixel electrode 7 and other wirings and electrodes. can do.

  An alignment film can be provided on the surface of the thin film transistor substrate 100 in which the storage capacitance is generated for the purpose of controlling the alignment of the liquid crystal, and the liquid crystal display element of the second embodiment of the present invention described later can be configured. it can. The liquid crystal display device according to the second embodiment of the present invention utilizes the auxiliary capacitance generated by the auxiliary capacitance electrode 3, the interlayer insulating film 6, and the pixel electrode 7, and the voltage applied to the pixel is turned off. Even at the time of application, charge can be held with high efficiency. As a result, the liquid crystal display element of the second embodiment of the present invention having the thin film transistor substrate 100 can maintain the driving of the liquid crystal even when no voltage is applied due to the function of the storage capacitance.

  At this time, the storage capacitor electrode 3 is a transparent electrode made of a light-transmitting conductive material, and in the liquid crystal display element of the second embodiment of the present invention described later, the decrease in the aperture ratio of the pixel is suppressed. Therefore, the liquid crystal display device of the second embodiment of the present invention having the thin film transistor substrate 100 can display an image of excellent display quality.

Second Embodiment
(Liquid crystal display element)
FIG. 2 is a schematic cross-sectional view of a pixel portion in an example of a liquid crystal display device according to a second embodiment of the present invention.

  A liquid crystal display element 200 which is an example of the second embodiment of the present invention shown in FIG. 2 is a thin film transistor substrate 100 which is an example of the first embodiment of the present invention described above, an opposing substrate 110, a thin film transistor substrate 100 and an opposing substrate And a liquid crystal layer 111 disposed between them.

  The liquid crystal display element 200 uses the thin film transistor substrate 100 which is an example of the first embodiment of the present invention described above, and bonds the thin film transistor substrate 100 and the counter substrate 110 using a sealing material not shown. A liquid crystal is sealed between the substrates to form a liquid crystal layer 111. Therefore, in the liquid crystal display element 200, the thin film transistor substrate 100 is in common with the thin film transistor substrate 100 which is an example of the first embodiment of the present invention described above, and the components are denoted by the same reference numerals as those described above. Duplicate descriptions will be omitted.

  In the liquid crystal display element 200, the thin film transistor substrate 100 can generate a storage capacitance at an overlapping portion where the pixel electrode 7 and the storage capacitance electrode 3 overlap in plan view by the storage capacitance electrode 3. Then, the interlayer insulating film 6 sandwiched between the pixel electrode 7 and the auxiliary capacitance electrode 3 is formed using the radiation sensitive resin composition of the fourth embodiment of the present invention described later, and the dielectric constant has a desired value. It is controlled. The interlayer insulating film 6 is configured to have, for example, a dielectric constant higher than that of a normal organic film. Therefore, in plan view, the auxiliary capacitance generated at the overlapping portion where the pixel electrode 7 and the auxiliary capacitance electrode 3 overlap can have high charge retention ability.

  On the other hand, as described above, the thin film transistor substrate 100 has the planarizing film 5 between the pixel electrode 7 and the TFT 2 to reduce the coupling capacitance between the pixel electrode 7 and other wirings and electrodes. can do.

  In the liquid crystal display element 200, on the counter substrate 110, a counter electrode, a color filter (all not shown), and the like are provided.

  Then, an alignment film can be provided on the opposing surfaces of the thin film transistor substrate 100 and the counter substrate 110 for the purpose of controlling the alignment of the liquid crystal.

  The liquid crystal layer 111 is made of, for example, a vertical alignment type liquid crystal, and alignment control of the liquid crystal is performed by turning on / off voltage application between the TFT 2 of the thin film transistor substrate 100 and the counter electrode of the counter substrate 110.

  The liquid crystal display element 200 according to the second embodiment of the present invention utilizes the storage capacitance generated by the storage capacitance electrode 3 of the thin film transistor substrate 100, the interlayer insulating film 6 and the pixel electrode 7, and the voltage applied to the pixel is turned off. The charge can be held at high efficiency even when no voltage is applied. As a result, the liquid crystal display element 200 of the second embodiment of the present invention having the thin film transistor substrate 100 can maintain the driving of the liquid crystal even when no voltage is applied.

  At this time, the storage capacitor electrode 3 of the thin film transistor substrate 100 is a transparent electrode made of a light transmitting conductive material, and in the liquid crystal display element 200, the decrease in the aperture ratio of the pixel is suppressed. Therefore, the liquid crystal display element 200 of the second embodiment of the present invention having the thin film transistor substrate 100 can display an image of excellent display quality.

Third Embodiment
(Organic EL element)
FIG. 3 is a cross-sectional view schematically showing the structure of the main part of the organic EL element according to this embodiment.

  The organic EL element 201 in FIG. 3 is an active matrix organic EL element having a plurality of pixels formed in a matrix. The organic EL element 201 may be either a top emission type or a bottom emission type. The property of the material constituting each member, for example, the transparency, is appropriately selected according to the top emission type and the bottom emission type. The organic EL element 201 corresponds to the thin film transistor substrate of the first embodiment, and includes a support substrate 202, a thin film transistor (TFT) 203, an inorganic insulating film 204, an interlayer insulating film 205, an anode 206 as a first electrode, and a through hole 207. And the partition wall 208, the light emitting layer 209, the cathode 210 as the second electrode, the passivation film 211, and the sealing substrate 212 disposed thereon.

  The TFT 203 is an active element of each pixel portion, and is formed on the support substrate 202. The TFT 203 includes a gate electrode 230, a gate insulating film 231, a semiconductor layer 232, a source electrode 233, and a drain electrode 234.

  The present embodiment is not limited to the bottom gate type in which the gate insulating film and the semiconductor layer are sequentially provided on the gate electrode, but may be top gate type in which the gate insulating film and the gate electrode are sequentially provided on the semiconductor layer.

  The gate electrode 230 forms a part of a scanning signal line (not shown). The thickness of the gate electrode 230 is preferably 10 nm or more and 1000 nm or less. The gate insulating film 231 covers the gate electrode 230. The average film thickness of the gate insulating film 231 is preferably 10 nm or more and 10 μm or less. The source electrode 233 is an electrode serving as a carrier generation source. The source electrode 233 forms a part of a video signal line (not shown), and is connected to the semiconductor layer 232. The drain electrode 234 is a portion that receives carriers moving through the semiconductor layer 232 (channel layer), and is connected to the semiconductor layer 232 similarly to the source electrode 233. The thickness of the source electrode 233 and the drain electrode 234 is preferably 10 nm or more and 1000 nm or less.

  The semiconductor layer 232 is disposed on the gate electrode 230 via the gate insulating film 231. The semiconductor layer 232 is connected to the source electrode 233 and the drain electrode 234, and forms a channel layer. The channel layer is a portion where carriers flow and is controlled by the gate electrode 230.

  The semiconductor layer 232 can be formed using the above-described oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn. Examples of the oxide in this case include single crystal oxides, polycrystalline oxides, amorphous oxides, and mixtures thereof.

  The semiconductor layer 232 made of an amorphous oxide using IGZO forms a semiconductor layer by sputtering or evaporation using an IGZO target, for example, and performs patterning by a resist process and an etching process using a photolithography method or the like. It is formed by The thickness of the semiconductor layer 232 in this case is preferably 1 nm or more and 1000 nm or less.

  The inorganic insulating film 204 is provided to protect the semiconductor layer 232, for example, to prevent the semiconductor layer 232 from being affected by humidity. The inorganic insulating film 204 is formed to cover the entire TFT 203.

  The interlayer insulating film 205 can also function as a planarizing film that plays a role in planarizing the surface unevenness of the TFT 203. The interlayer insulating film 205 is formed on the inorganic insulating film 204 so as to cover the whole of the TFT 203.

  The interlayer insulating film 205 is an organic film formed using the radiation sensitive resin composition of the fourth embodiment of the present invention described later. These materials may be selected according to whether the organic EL element 201 is of top emission type or bottom emission type. The interlayer insulating film 205 is formed as an organic insulating film because these materials are organic materials. The interlayer insulating film 205 can be formed by the method described in the section of the method of manufacturing a thin film transistor substrate described later.

  The average film thickness of the interlayer insulating film 205 is preferably 1 μm to 6 μm.

  The through hole 207 is formed to connect the anode 206 and the drain electrode 234. The through hole 207 is formed to penetrate the inorganic insulating film 204 in the lower layer of the interlayer insulating film 205 in addition to the interlayer insulating film 205.

  The through hole 207 can be formed by dry etching the inorganic insulating film 204 after forming the interlayer insulating film 205 having a through hole of a desired shape. Here, the interlayer insulating film 205 can be formed using the radiation sensitive resin composition of the fourth embodiment of the present invention described later or a conventionally known radiation sensitive resin composition. Therefore, the through holes constituting the through holes 207 can be formed by irradiation and development of radiation to the coating film made of these materials. Dry etching of the inorganic insulating film 204 can be performed using the interlayer insulating film 205 as a mask. As a result, a through hole communicating with the through hole of the interlayer insulating film 205 is formed in the inorganic insulating film 204, and as a result, a through hole 207 penetrating the interlayer insulating film 205 and the inorganic insulating film 204 is formed.

  When the inorganic insulating film 204 is not disposed on the TFT 203, the through holes formed by irradiation and development of radiation on the interlayer insulating film 205 form the through holes 207. As a result, the anode 206 can be connected to the drain electrode 234 through a through hole 207 provided in the interlayer insulating film 205 so as to cover a part of the interlayer insulating film 205 and to penetrate the interlayer insulating film 205. .

  The partition wall 208 serves as a partition (bank) having a recess 80 that defines the arrangement region of the light emitting layer 209. The partition wall 208 is formed to cover a portion of the anode 206 while exposing a portion of the anode 206.

  The partition wall 208 is preferably formed on the interlayer insulating film 205 so as to be disposed at least above the semiconductor layer 232 of the TFT 203. Here, “upper” is a direction from the support substrate 202 toward the sealing substrate 212.

  Such a partition wall 208 can be formed by a method described in the section of the method of manufacturing a thin film transistor substrate using a known radiation sensitive resin composition. The partition wall 208 can be formed as a plurality of concave portions 80 in which the light emitting layer 209 is formed in a matrix shape in plan view by patterning the partition wall by exposure and development of a coating film.

  The partition wall 208 is preferably formed to fill the through hole 207.

  The lower limit of the average film thickness of the partition wall 208 (the distance between the uppermost surface of the partition wall 208 and the lowermost surface of the light emitting layer 209) is preferably 0.3 μm, and more preferably 0.5 μm. As a maximum of the above-mentioned average film thickness, 25 micrometers is preferred and 20 micrometers is more preferred. When the average film thickness of the partition wall 208 exceeds the above upper limit, the partition wall 208 may come in contact with the sealing substrate 212. On the other hand, when the light emitting layer 209 to be described later is formed when the average film thickness of the partition wall 208 is less than the above lower limit, when the light emitting material composition is applied to the recess 80 of the partition 208 May leak from the

  The light emitting layer 209 emits light when an electric field is applied. The light emitting layer 209 is an organic light emitting layer containing an organic light emitting material that emits light in an electric field. The light emitting layer 209 is formed in the region defined by the partition wall 208, that is, in the recess 80. Thus, by forming the light emitting layer 209 in the recess 80, the periphery of the light emitting layer 209 is surrounded by the partition wall 208, and a plurality of adjacent pixels can be partitioned.

  The light emitting layer 209 is formed in contact with the anode 206 at the recess 80 of the partition wall 208. The thickness of the light emitting layer 209 is preferably 50 nm or more and 100 nm or less. Here, the thickness of the light emitting layer 209 means the distance from the bottom surface of the light emitting layer 209 on the anode 206 to the top surface of the light emitting layer 209 on the anode 206.

  The anode 206 forms a pixel electrode. The anode 206 is formed on the interlayer insulating film 205 by a conductive material. The cathode 210 is formed to cover a plurality of pixels in common, and forms a common electrode of the organic EL element 201. The passivation film 211 suppresses the infiltration of moisture and oxygen into the organic EL element. The passivation film 211 is provided on the cathode 210.

  The sealing substrate 212 seals the main surface (the opposite side to the supporting substrate 202) on which the light emitting layer 209 is disposed. The main surface on which the light emitting layer 209 is disposed may be sealed by the sealing substrate 212 via the sealing layer 213 using a sealing agent (not shown) applied near the outer peripheral end of the TFT substrate. preferable. The sealing layer 213 can be a layer of an inert gas such as dried nitrogen gas or a layer of a filling material such as an adhesive.

  In the organic EL element 201 of the present embodiment, the interlayer insulating film 205 and the partition wall 208 can be formed using a radiation-sensitive resin composition with low water absorption, and the interlayer insulating film 205 and the partition wall 208 In the forming step, processing such as washing using a low water absorption material is possible. Therefore, it is possible to reduce the gradual infiltration of a slight amount of water contained in the insulating film formation material into the light emitting layer 209 in the form of adsorbed water or the like, and to reduce the deterioration of the light emitting layer 209 and the deterioration of the light emitting state.

Fourth Embodiment
Radiation-sensitive resin composition
The radiation sensitive resin composition of 4th Embodiment of this invention can form the cured film patterned using the radiation sensitivity. The radiation sensitive resin composition according to the present embodiment is suitable for forming the interlayer insulating film of a thin film transistor substrate having a substrate, a thin film transistor disposed on the substrate, and an interlayer insulating film disposed on the thin film transistor Used for That is, manufacturing of the thin film transistor substrate of the first embodiment of the present invention, the liquid crystal display element of the second embodiment of the present invention, and the interlayer insulating film which is the main component of the organic EL element of the third embodiment of the present invention Are preferably used. By using the said radiation sensitive resin composition for formation of the said interlayer insulation film, the whitening in the case of high temperature processing and generation | occurrence | production of an outgas are suppressed, and an interlayer insulation film favorable also in solvent resistance is obtained. Moreover, in the said radiation sensitive resin composition, storage stability can also be improved by setting it as a suitable component composition.

（式（３）中、Ｘは、ヒドロキシ基、チオール基、カルボキシ基又はアミノ基を示し、Ｒ^４は、芳香環を含む１価の有機基を示す。） The radiation sensitive resin composition of the fourth embodiment of the present invention is also referred to as [A] polymer (hereinafter, also simply referred to as [A] component) and [B] photosensitizer (hereinafter, simply as [B] component). And [C] a compound represented by the following formula (3) (hereinafter, also simply referred to as [C] component or [C] compound) is contained as an essential component.

(In formula (3), X represents a hydroxy group, a thiol group, a carboxy group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring.)

  Moreover, in addition to [A] component, [B] component, and [C] component, you may contain other arbitrary components, unless the effect of this invention is impaired. For example, it can contain the below-mentioned [D] compound (Hereafter, it is also only mentioned [D] ingredient.) Which functions as a hardening accelerator.

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

<[A] polymer>
[A] A polymer is a component used as the base material of the cured film obtained. As the polymer [A], generally, known polymers contained in a radiation sensitive resin composition for forming a cured film can be used singly or in combination of two or more. [A] The polymer is preferably an alkali-soluble resin. By using an alkali-soluble resin, patterning using an alkali developer becomes possible. As the polymer [A], polysiloxane can be suitably used.

(Polysiloxane)
The polysiloxane is not particularly limited as long as it is a polymer of a compound having a siloxane bond. This polysiloxane is usually cured using, for example, an acid generated from the photoacid generator [B-2], which is a photosensitive agent to be described later, or a base generated from the photobase generator [B-3], as a catalyst. Do.

  As polysiloxane, it is preferable that it is a hydrolysis condensation product of the hydrolysable silane compound shown by following formula (4).

Wherein ^{(4), R 20} is a non-hydrolyzable organic group having 1 to 20 carbon atoms. R ²¹ is an alkyl group having 1 to 4 carbon atoms. q is an integer of 0 to 3; When R ²⁰ or R ²¹ is plural, these may be the same or different.

As a C1-C20 nonhydrolyzable organic group represented by said R ²⁰ , a C1-C12 alkyl group, a C6-C12 aryl group, a C7-C12 aralkyl group etc. are mentioned. Can be mentioned. They may be linear, branched or cyclic. In addition, some or all of the hydrogen atoms of these alkyl groups, aryl groups and aralkyl groups may be substituted with vinyl groups, (meth) acryloyl groups or epoxy groups.

The alkyl group having 1 to 4 carbon atoms represented by R ^21, a methyl group, an ethyl group, n- propyl group, i- propyl group, a butyl group. q is an integer of 0 to 3, but is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 1. When q is the above numerical value, the progress of the hydrolysis / condensation reaction becomes easier, and as a result, the speed of the curing reaction becomes larger, and the strength, adhesion, etc. of the resulting cured film can be improved.

As a specific example of the hydrolysable silane compound represented by such said Formula (4),
Examples of silane compounds substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, etc.
As a silane compound substituted with one nonhydrolyzable group and three hydrolysable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-glycidoxy pro Le trimethoxysilane, .gamma.-glycidoxypropyl triethoxy silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like,
Examples of silane compounds substituted by two nonhydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, etc.
Examples of silane compounds substituted with three nonhydrolyzable groups and one hydrolyzable group include tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane and the like.

Among the hydrolyzable silane compounds represented by the above formula (4), a silane compound substituted with 4 hydrolyzable groups, and 1 non-hydrolyzable group and 3 hydrolyzable groups And a silane compound substituted with one nonhydrolyzable group and three hydrolyzable groups is more preferable. Specific examples of preferable hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Ethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane can be mentioned. Such hydrolyzable silane compounds may be used alone or in combination of two or more.
You may

  The conditions for hydrolytic condensation of the hydrolyzable silane compound represented by the above formula (4) include hydrolysis of at least a part of the hydrolyzable silane compound represented by the above formula (4) to form a hydrolyzable group. Is not particularly limited as long as it converts the compound into a silanol group to cause a condensation reaction, but can be carried out, for example, as follows.

  It is preferable to use the water refine | purified by methods, such as a reverse osmosis membrane process, an ion exchange process, a distillation, as water used for the hydrolysis condensation of the hydrolysable silane compound represented by said Formula (4). By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.

  The solvent that can be used for the hydrolytic condensation of the hydrolyzable silane compound represented by the above formula (4) is not particularly limited, and for example, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, Propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propionic acid esters, arylalkanols, aryloxyalkanols and the like can be mentioned. Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, benzyl alcohol, 2-phenylethyl alkanol and phenoxyethanol are preferable. When phenylalkanol or phenoxyalkanol is used as the above-mentioned solvent, phenylalkanol or phenoxyalkanol is not used in the above-mentioned hydrolytic condensation reaction and remains as it is after the reaction. For this reason, you may use the phenyl alkanol or phenoxy alkanol contained in the solution after the said hydrolysis condensation reaction as a [C] component.

  The hydrolysis / condensation reaction of the hydrolyzable silane compound represented by the above formula (4) is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, Phosphoric acid, acidic ion exchange resin, various Lewis acids etc., base catalyst (eg ammonia, primary amines, secondary amines, tertiary amines, nitrogen containing compounds such as pyridine, etc., basic ion exchange resin, hydroxylated In the presence of a catalyst such as a hydroxide such as sodium, a carbonate such as potassium carbonate, a carboxylate such as sodium acetate, various Lewis bases, etc. or an alkoxide (eg, zirconium alkoxide, titanium alkoxide, aluminum alkoxide etc.) It will be.

  The reaction temperature and the reaction time in the hydrolysis and condensation of the hydrolyzable silane compound represented by the above formula (4) are appropriately set. The reaction temperature is preferably 40 ° C. or more and 200 ° C. or less. The reaction time is preferably 30 minutes or more and 24 hours or less.

  The lower limit of the weight average molecular weight (Mw) of the hydrolytic condensate of the hydrolyzable silane compound represented by the above formula (4) is usually preferably 500, and more preferably 1,000. On the other hand, as this upper limit, 20000 is preferable and 10000 is more preferable.

  The lower limit of the number average molecular weight (Mn) of the hydrolytic condensate of the hydrolyzable silane compound represented by the above formula (4) is usually preferably 500, more preferably 1000, and still more preferably 2500. By setting the number average molecular weight of the hydrolytic condensate of the hydrolyzable silane compound represented by the above formula (4) to the above lower limit or more, the effects of the present invention are further enhanced, and the storage stability and the obtained interlayer insulating film are obtained. Solvent resistance can be enhanced. On the other hand, the upper limit of the Mn is preferably 20000, more preferably 10000, and still more preferably 5000.

  The lower limit of the molecular weight distribution (Mw / Mn) of the hydrolytic condensate of the hydrolyzable silane compound represented by the above formula (4) is usually 1.1, preferably 2 and more preferably 3 Sometimes it is preferable. By setting the molecular weight distribution of the hydrolytic condensate of the hydrolyzable silane compound represented by the above formula (4) to the above lower limit or more, the effect of the present invention is further enhanced, and the storage stability, the interlayer insulating film obtained, Solvent resistance can be enhanced. On the other hand, the upper limit of the molecular weight distribution is, for example, 5 and 4 is preferable.

In addition, Mw and Mn of the polymer in this specification are taken as the value measured by the gel permeation chromatography (GPC) on condition of the following.
Device: Showa Denko "GPC-101"
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804. Mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential Refractometer Standard: Monodispersed polystyrene

<[A] Content of Polymer>
The lower limit of the content of the polymer [A] in the radiation sensitive resin composition is not particularly limited, but is, for example, 50% by mass, preferably 60% by mass in terms of solid content. On the other hand, as this upper limit, 99 mass% is preferred, and 95 mass% is more preferred.

<[B] Photosensitizer
As the [B] photosensitizer contained in the radiation sensitive resin composition of the fourth embodiment of the present invention, a compound capable of generating radicals and initiating polymerization in response to radiation (that is, [B-1] photoradicals A polymerization initiator), a compound that responds to radiation to generate an acid (ie, [B-2] photoacid generator), or a compound that responds to radiation to generate a base (ie, [B-3] light Base generators) can be mentioned.

  As such [B-1] photo-radical polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, a phosphine oxide compound etc. are mentioned. These compounds may be used singly or in combination of two or more.

  As an O-acyl oxime compound, for example, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl] Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -octan-1-one oxime-O-acetate 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2- Ethyl benzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetraphenyl) Rofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyl oxime) etc. are mentioned.

  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) -9H-carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyl oxime) is preferred.

  As an acetophenone compound, the alpha-amino ketone compound and the alpha-hydroxy ketone compound are mentioned, for example.

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

  As the α-hydroxy ketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and the like.

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

  As a biimidazole compound, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5, 5'-Tetraphenyl-1,2'-biimidazole is preferred, among which 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- More preferred is biimidazole.

  [B-1] The radical photopolymerization initiator may be used alone or in combination of two or more, as described above. As a minimum of content of [B-1] radical photopolymerization initiator to 100 mass parts of [A] ingredient, 1 mass part is preferred and 5 mass parts is more preferred. As a maximum of content of the above-mentioned [B-1] radical photopolymerization initiator, 40 mass parts is preferred, and 30 mass parts is more preferred. [B-1] By setting the content of the photo radical polymerization initiator in the above range, the radiation sensitive resin composition has high solvent resistance, high hardness and high adhesion even with a low exposure amount. A cured film can be formed.

  Next, as the photoacid generator [B-2], which is the [B] photosensitizer of the radiation sensitive resin composition of this embodiment, for example, an oxime sulfonate compound, an onium salt, a sulfone imide compound, a quinonediazide compound, a halogen Included compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds and the like. In addition, these [B-2] photo-acid generators may be used individually by 1 type, and may mix and use 2 or more types.

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

In the above formula (B1), R ^A represents 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, and an aryl having 6 to 20 carbon atoms And a group or a group in which part or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups and aryl groups are substituted with a substituent.

As an alkyl group represented by ^RA in the said Formula (B1), a C1-C12 linear or branched alkyl group is preferable. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted by a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, and 7,7-dimethyl-. Alicyclic groups containing a bridged alicyclic group such as 2-oxonorbornyl group and the like can be mentioned. A trifluoromethyl group, a pentafluoroethyl group, a heptyl fluoropropyl group etc. are mentioned as a C1-C12 fluoroalkyl group.

The alicyclic hydrocarbon group represented by R ^A, preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted by a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like. .

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

  Examples of the onium salt include diphenyl iodonium salt, triphenyl sulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt and the like.

  Examples of sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl) Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenyl maleimide, N- (camphorsulfonyloxy) diphenyl Reimido, 4-methylphenyl sulfonyloxy) diphenyl maleimide, N- (trifluoromethylsulfonyloxy) -1,8-naphthalimide, and the like.

  Moreover, the radiation sensitive resin composition of this embodiment can contain a quinone diazide compound as a [B-2] photo-acid generator which is a [B] photosensitive agent as mentioned above. The radiation sensitive resin composition of the present embodiment can be used as a positive type radiation sensitive resin composition by containing a quinone diazide compound. And the light shielding property of the cured film after formation can be provided. Furthermore, it is possible to adjust the light transmittance of the visible light region of the formed cured film by the photobleaching performance.

  [B-2] A quinone diazide compound that can be used as a photoacid generator is a quinone diazide compound that generates a carboxylic acid upon irradiation with radiation. As the quinone diazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as "mother core") and 1,2-naphthoquinone diazide sulfonic acid halide can be used.

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

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

  Examples of tetrahydroxybenzophenones include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, 3,4,2'-tetrahydroxy-4'-methyl benzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxy benzophenone etc. are mentioned.

  Examples of pentahydroxybenzophenones include 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like.

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

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-). Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-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′-spirobi Nden -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  As another mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [1- [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 mother nuclei, (polyhydroxyphenyl) alkane is preferable, and 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '-[4 More preferred is 1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol.

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

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

  Moreover, as the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2-naphtho Quinonediazide-4-sulfonic acid amide and the like are also suitably used.

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

  The content of the quinone diazide compound in the radiation sensitive resin composition of the present embodiment can be in the range described later, but by setting the content to such a range, a portion irradiated with radiation to the aqueous solution of the alkali compound to be a developer can be obtained. The patterning performance can be improved by increasing the difference in solubility between and the unirradiated portion. Moreover, the solvent resistance of the cured film obtained using this radiation sensitive resin composition can also be made favorable.

  [B-2] The photoacid generator is preferably an oxime sulfonate compound, an onium salt, a sulfone imide compound, or a quinone diazide compound, more preferably an oxime sulfonate compound or a quinone diazide compound, and still more preferably a quinone diazide compound.

Moreover, as the above onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium hexame ate. Fluorophosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferred. As said sulfonic acid ester compound, haloalkyl sulfonic acid ester is preferable and N-hydroxy naphthalimide trifluoromethane sulfonic acid ester is more preferable. [B-2] By making a photo-acid generator into the said compound, the radiation sensitive resin composition of this embodiment obtained can improve a sensitivity and solubility.

  As a minimum of content of [B-2] photo-acid generator with respect to 100 mass parts of [A] component, 0.1 mass part or more is preferable, and 1 mass part is more preferable. As an upper limit of content of the said [A] component, 10 mass parts is preferable, and 5 mass parts is more preferable. [B-2] By making content of a photo-acid generator into the said range, the sensitivity of the radiation sensitive resin composition of this embodiment can be optimized, and a cured film with high surface hardness can be formed.

  Next, as the [B-3] photosensitizer, which is the [B] photosensitizer of the radiation sensitive resin composition of the present embodiment, as long as it is a compound that generates a base (such as an amine) upon irradiation with radiation, It is not particularly limited. [B-3] Examples of photobase generators include transition metal complexes such as cobalt, ortho-nitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like .

  As the above-mentioned transition metal complex, for example, bromopentaammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine Cobalt perchlorate, hexapropylamine cobalt perchlorate and the like can be mentioned.

  Examples of ortho-nitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy] Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-nitrobenzyl) oxy Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2, 6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[2, 6- dinitro benzyl) oxy] carbonyl] hexamethylene diamine, bis [[(2, 6- dinitro benzyl) Oxy] carbonyl] phenylene diamine, bis [ (2,6-Dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine and the like Can be mentioned.

  Examples of α, α-dimethyl-3,5-dimethoxybenzyl carbamates include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl)] 3,5-Dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5 -Dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] ] Carbonyl] piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] Samethylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluene Diamines, bis [[(. Alpha.,. Alpha.-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(. Alpha.,. Alpha.-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, etc. It can be mentioned.

  As acyloxyiminos, for example, propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acroyl acetophenone oxime, acroyl benzophenone oxime, acroyl acetone oxime and the like can be mentioned.

  [B-3] As other examples of the photobase generator, 2-nitrobenzylcyclohexylcarbamate, O-carbamoylhydroxyamide and O-carbamoylhydroxyamide are particularly preferable.

  [B-3] The photobase generator may be used alone or in combination of two or more. Moreover, as long as the effect of this invention is not impaired, you may use together a [B-3] photobase generator and a [B-2] photoacid generator.

  As a minimum of content of [B-3] a photobase generator to 100 mass parts of [A] ingredient, 0.1 mass part is preferred, and 1 mass part is more preferred. As an upper limit of content of said [B-3] photobase generator, 20 mass parts is preferable, and 10 mass parts is more preferable. [B-3] By setting the content of the photobase generator in the above range, it is possible to obtain a radiation sensitive composition excellent in melt flow resistance and heat resistance of the formed cured film in a well-balanced manner, Moreover, it becomes possible to prevent generation | occurrence | production of a precipitate in the formation process of a coating film, and to make coating film formation easy.

（式（３）中、Ｘは、ヒドロキシ基、チオール基、カルボキシ基又はアミノ基を示し、Ｒ^４は、芳香環を含む１価の有機基を示す。） <[C] compound>
The [C] component of the radiation sensitive resin composition of the fourth embodiment of the present invention is a compound represented by the following formula (3).

(In formula (3), X represents a hydroxy group, a thiol group, a carboxy group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring.)

  The component [C] of the radiation sensitive resin composition of the present embodiment is the introduction of the structure represented by the above formula (1) to the polymer [A] in a cured film formed using the radiation sensitive resin composition Component that makes it possible. That is, the [C] component is introduced into a polymer in an interlayer insulating film of a thin film transistor substrate or a liquid crystal display element formed using the radiation sensitive resin composition of the fourth embodiment of the present invention and subjected to high temperature treatment. It is a component that makes it possible to suppress the whitening of

  The monovalent organic group containing an aromatic ring is preferably a group corresponding to a monovalent organic group containing an aromatic ring in the polymer contained in the interlayer insulating film of the first embodiment. At the time of prebaking in forming a cured film (interlayer insulating film) using the radiation sensitive resin composition according to the present embodiment, hydrolysis of the hydrolyzable group or hydrolyzable group in the polysiloxane which is the component [A] A predetermined structure represented by the above formula (1) possessed by the polymer in the thin film transistor substrate according to the first embodiment is efficiently introduced by the reaction between the resulting group (for example, a hydroxy group etc.) and the [C] component. be able to.

  Therefore, as a specific example of the monovalent organic group containing the aromatic ring of the [C] component, the aryl described as the monovalent organic group containing the aromatic ring in the polymer contained in the interlayer insulating film of the first embodiment Preferred are groups and aralkyl groups.

Specific examples of the component [C]
When X is a hydroxy group, phenol, naphthol, benzyl alcohol, phenoxyethanol, 2-phenylethyl alcohol, etc.
When X is a thiol group, benzenethiol, naphthalenethiol, etc.
When X is a carboxy group, benzoic acid, carboxymethyl benzene and the like,
When X is an amino group, aniline, benzylamine and the like can be mentioned.

  These [C] compounds may be used alone or in combination of two or more.

  [C] The compound preferably includes a compound in which X in the above formula (3) is a hydroxy group, a thiol group or an amino group, and includes a compound in which X in the above formula (3) is a hydroxy group More preferable. [C] 90 mol% as a lower limit of the content ratio of the compound in which X in the above formula (3) in the compound is a hydroxy group, a thiol group or an amino group, particularly the compound in which X is a hydroxy group Is preferable, 95 mol% is more preferable, and 99 mol% is more preferable. The effect of the present invention can be further enhanced by containing a compound in which X in the above formula (3) is a hydroxy group, a thiol group or an amino group at a high ratio as the compound [C].

  Although it does not specifically limit as content of a [C] compound in the radiation sensitive resin composition of 4th Embodiment of this invention, The lower limit is 10 mass parts with respect to 100 mass parts of [A] components. Is preferable, 20 parts by mass is more preferable, 400 parts by mass is preferable, 200 parts by mass is more preferable, and 100 parts by mass is more preferable. [C] If the content of the compound is less than the above lower limit value, the whitening inhibitory effect of the interlayer insulating film may not be sufficiently obtained. On the other hand, when the content of the [C] compound exceeds the above upper limit value, the developability may be lowered at the time of pattern formation.

  In addition, in the radiation sensitive resin composition of this embodiment, although the [C] compound is added as a component different from the [A] polymer, it is not limited to this, but in the case of the synthesis of the [A] polymer [C] compound may be added to the [A] polymer to introduce the structure of the above formula (1) into the [A] polymer. In addition, a [C] compound is added in the synthesis of the [A] polymer, and the structure of the above formula (1) is introduced into the [A] polymer, and further, as a component other than this polymer [ C] compounds may be contained.

<Other optional components>
The radiation sensitive resin composition according to the embodiment of the present invention contains, in addition to the aforementioned [A] polymer, [B] photosensitizer and [C] compound, a [D] compound having an action as a curing accelerator. be able to. Furthermore, the radiation sensitive resin composition according to the embodiment of the present invention may optionally contain a surfactant, as long as the effects of the present invention are not impaired, in addition to the dispersant and the dispersion medium used together with the [C] compound. Other optional components such as storage stabilizers, adhesion promoters, heat resistance improvers, etc. can be contained. The other optional components may be used alone or in combination of two or more. Each component will be described below.

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

  As a fluorine-based surfactant, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octal Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2 Fluoroethers such as 2, 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as fluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkyloxyethylene ethers, fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols, perfluoroalkyl alkoxylates And fluorine-based alkyl esters.

  As commercially available products of these fluorine-based surfactants, F-Top (registered trademark) EF 301, 303, 352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafuck (registered trademark) F 171, 172, 173 (manufactured by DIC Corporation), Florard FC430, 431 (manufactured by Sumitomo 3M), Asahi Guard AG (registered trademark) 710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC-101, 102, 103, 104, 105, 106 (AGC Seimi Chemical Co., Ltd.) Company company), FTX-218 (made by Neos company), etc. can be mentioned.

  As examples of silicone surfactants, commercially available trade names are SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH 8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP 341 (Shin-Etsu Co., Ltd.) And the like.

  When a surfactant is used as another optional component, the lower limit of the content of the surfactant relative to 100 parts by mass of the component [A] is preferably 0.01 parts by mass, and more preferably 0.05 parts by mass. As an upper limit of content of the said surfactant, 10 mass parts is preferable, and 5 mass parts is more preferable. By making content of surfactant into the said range, the applicability of the radiation sensitive resin composition of this embodiment can be optimized.

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

[Adhesive agent]
The adhesion aiding agent is for the purpose of further improving the adhesion between the interlayer insulating film obtained from the radiation sensitive resin composition of the present embodiment and, for example, the auxiliary capacitance electrode or the flattening film disposed therebelow. It can be used. As the adhesion assistant, functional silane coupling agents having reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group, oxiranyl group are preferably used, and examples thereof include trimethoxysilylbenzoic acid and γ-methacrylic acid. Roxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Can be mentioned.

<Preparation of radiation sensitive resin composition>
The radiation sensitive resin composition according to the embodiment of the present invention may optionally contain, in addition to the aforementioned [A] polymer, [B] photosensitizer, and [C] compound, a [D] compound or a plurality of optional compounds thereof. It is prepared by mixing the component surfactant and the like. At this time, an organic solvent can be used to prepare the radiation sensitive resin composition in a dispersion state. The organic solvents can be used singly or in combination of two or more.

  Examples of the function of the organic solvent include adjusting the viscosity of the radiation sensitive resin composition to improve the coatability to the substrate and the like, as well as improving the operability and the like. The lower limit of the viscosity measured by an E-type viscometer at 25 ° C. of the radiation sensitive resin composition realized by the inclusion of an organic solvent or the like is preferably 0.1 mPa · s, more preferably 0.5 mPa · s. The upper limit of the viscosity is preferably 50000 mPa · s, more preferably 10000 mPa · s.

  As an organic solvent which can be used for the radiation sensitive resin composition of this embodiment, while melt | dissolving or disperse | distributing other containing components, the thing which does not react with other containing components can be mentioned.

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

  Content of the organic solvent used in the radiation sensitive resin composition of this embodiment can be suitably determined in consideration of viscosity etc.

  As a dispersion method for preparing the radiation sensitive resin composition in the dispersion state, particles are usually prepared at a peripheral velocity of 5 m / s to 15 m / s using a paint shaker, SC mill, annular mill, pin mill or the like. It may be done by a method that continues until no reduction in diameter is observed. The duration is usually several hours. Moreover, it is preferable to use dispersion beads, such as a glass bead and a zirconia bead, in the case of this dispersion | distribution. As a minimum of this bead diameter, 0.05 mm is preferred and 0.08 mm is more preferred. As a maximum of the above-mentioned bead diameter, 0.5 mm is preferred and 0.2 mm is more preferred.

Fifth Embodiment
<Method of manufacturing thin film transistor substrate>
In a method of manufacturing a thin film transistor substrate which is an example of the fifth embodiment of the present invention, a cured film is formed on a substrate using the above-described radiation sensitive resin composition of the fourth embodiment of the present invention, and an interlayer insulating film is formed. The constituent steps are included as the main steps. Then, in the method of manufacturing the thin film transistor substrate according to the present embodiment, for example, the thin film transistor substrate 100 according to the first embodiment of the present invention shown in FIG. 1 can be easily manufactured.

  Hereinafter, a method of manufacturing a thin film transistor substrate which is an example of the fifth embodiment of the present invention will be described by taking a method of manufacturing the thin film transistor substrate 100 of the first embodiment of the present invention shown in FIG. 1 as an example.

  In the method of manufacturing the thin film transistor substrate 100 of the present embodiment, as shown in FIG. 1, the interlayer insulating film 6 is formed on the substrate 1 on which the TFT 2, the planarization film 5 and the auxiliary capacitance electrode 3 are provided. Then, an inorganic insulating film 4 can be provided between the TFT 2 on the substrate 1 and the planarization film 5 so as to cover and protect the TFT 2. The inorganic insulating film 4 also covers the common wiring 17 electrically connected with the storage capacitor electrode 3 together with the TFT 2 on the substrate 1.

  In order to form the interlayer insulation film 6 on the above-mentioned board | substrate 1, it is preferable that the manufacturing method of the thin-film transistor board | substrate of this embodiment includes following process [1]-process [4] in this order. After that, the pixel electrode 7 can be formed on the interlayer insulating film 6 according to a known method on the substrate 1 on which the interlayer insulating film 6 is formed, and the thin film transistor substrate 100 can be manufactured.

  Steps [1] to [4] included in the method of manufacturing a thin film transistor substrate according to the present embodiment are as follows.

[1] A process of forming a coating film of the radiation sensitive resin composition of the fourth embodiment of the present invention on the substrate 1 (hereinafter, may be referred to as "[1] process")
[2] A step of irradiating at least a part of the coating of the radiation sensitive resin composition formed in the step (1) (hereinafter, may be referred to as a "2 step")
[3] A step of developing a coating film irradiated with radiation in the step (hereinafter may be referred to as a “[3] step”)
[4] [3] A step of heating the coating film developed in the step (hereinafter, may be referred to as a “[4] step”)

  The steps [1] to [4] will be described below.

[Step [1]]
In this step, the coating film of the radiation sensitive resin composition of the fourth embodiment of the present invention is formed on the substrate 1. In addition to the TFT 2 which is a switching element, the substrate 1 is provided with common wires 17 and various wires such as gate wires and signal wires not shown. Then, the inorganic insulating film 4 for protecting the TFT 2 is provided on the TFT 2, and the inorganic insulating film 4 also covers the common wiring 17. Further, on the inorganic insulating film 4, the planarizing film 5 is formed which is patterned according to a known method to form a through hole which is a part of the contact hole 18. The planarization film 5 is an insulating organic film formed by patterning using a radiation sensitive resin composition according to a known method. As described above, the planarizing film 5 can be a film made of, for example, an acrylic resin, a polyimide resin, a polysiloxane, and a novolac resin.

  An auxiliary capacitance electrode 3 electrically connected to the common wiring 17 is disposed on the planarizing film 5 via a contact hole 18 penetrating the planarizing film 5 and the inorganic insulating film 4. The contact holes 18 are provided utilizing through holes formed by patterning the planarization film 5. That is, the contact hole 18 is planarized by forming, in the inorganic insulating film 4, a through hole continuous with the through hole of the planarizing film 5 by using the planarizing film 5 in which the through hole is formed by patterning as a mask and etching. It is provided as a through hole penetrating the oxide film 5 and the inorganic insulating film 4. The storage capacitor electrode 3 is formed, for example, by depositing a film made of a light-transmitting conductive material such as ITO on the planarization film 5 using a sputtering method or the like, and patterning using a photolithographic method or the like It is formed.

  In the planarization film 5, it is preferable to form a through hole forming a part of the contact hole 19 at the same time as patterning for forming a through hole forming a part of the contact hole 18. The through holes are formed so as to be continuous with the through holes formed in the interlayer insulating film 6, as described later, and can form a part of the contact holes 19, respectively.

  As described above, the TFT 2, the common wiring 17, etc., the inorganic insulating film 4, the flattening film 5, and the auxiliary capacitance electrode 3 provided on the substrate 1 use the well-known manufacturing method of the thin film transistor substrate as described above. It is formed. For example, the TFT 2 is formed on the substrate 1 according to a known method by repeating normal semiconductor film formation, known insulating layer formation, and the like and etching by photolithography. The common wiring 17 and the like, the inorganic insulating film 4, the planarizing film 5 and the auxiliary capacitance electrode 3 and the like are also formed according to known methods. Thus, a more detailed description of their formation is omitted.

  In this step, the radiation sensitive resin composition of the fourth embodiment of the present invention is applied to the surface on which the TFT 2 and the auxiliary capacitance electrode 3 and the like are formed using the substrate 1 described above, and then prebaked to obtain a solvent. Evaporate to form a coating.

  In the substrate 1 described above, as a constituent material thereof, for example, a glass substrate such as soda lime glass and non-alkali glass, a quartz substrate, a silicon substrate, or an acrylic resin, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, Resin substrates, such as aromatic polyamide, polyamide imide, and a polyimide, etc. are mentioned. In addition, it is preferable that these substrates be subjected to pretreatment such as cleaning and pre-annealing, if desired. Examples of pretreatment of the substrate include chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, a gas phase reaction method, vacuum deposition, and the like.

  As a method of applying the radiation sensitive resin composition, for example, a spray method, a roll coating method, a spin coating method (sometimes referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method) A suitable method such as a bar coating method or an inkjet coating method can be adopted. Among these, the spin coating method or the slit coating method is preferable in that a film having a uniform thickness can be formed.

  Although the conditions of the above-mentioned prebaking differ depending on the kind of each component which constitutes the radiation sensitive resin composition, the compounding ratio, etc., it is preferable to carry out at a temperature of 70 ° C. to 120 ° C. Although it changes with heating apparatuses, it is about 1 minute-about 15 minutes. As a lower limit of the average film thickness after prebaking of a coating film, 0.3 micrometer is preferable and 1.0 micrometer is more preferable. As a maximum of the above-mentioned average film thickness, 10 micrometers is preferred and 7.0 micrometers is more preferred.

[Step [2]]
Next, radiation is applied to at least a part of the coating film formed in step [1]. At this time, in order to irradiate only a part of the coating film, for example, it is performed through a photomask of a pattern corresponding to the formation of the desired contact hole 19.

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

The lower limit of the radiation dose (also referred to as the exposure dose) is preferably 10 J / m ² as a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation to be applied using a luminometer (OAI model 356, manufactured by Optical Associates Inc.) And 100 J / m ² is more preferable, and 200 J / m ² is more preferable. As an upper limit of the said radiation dose, 10000 J / m < ² > is preferable, 5000 J / m < ² > or less is more preferable, 3000 J / m < ² > is more preferable.

[Step [3]]
Next, the coating film after the radiation irradiation in the step [2] is developed to remove an unnecessary portion, and a coating film after patterning in which a through hole having a predetermined shape which forms a part of the contact hole 19 is formed is obtained. . The through holes of the coating film formed in this step are formed to be continuous with the through holes forming a part of the contact holes 19 formed in the above-described planarization film 5.

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

  The developing method may be any of a liquid deposition method, a dipping method, a shower method, a spray method, etc. The lower limit of the development time is preferably 5 seconds at normal temperature, more preferably 10 seconds, and the normal temperature as an upper limit of development time. Is preferably 300 seconds, more preferably 180 seconds. Following the development process, for example, after performing washing with running water for at least 30 seconds and not more than 90 seconds, a coating film having a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[Step [4]]
Next, the coated film obtained in step [3] is cured (also referred to as post-baking) by heating using a suitable heating device such as a hot plate or an oven. Thereby, the interlayer insulating film 6 is formed on the substrate 1 as a cured film.

The interlayer insulating film 6 is formed using the radiation sensitive resin composition of the fourth embodiment of the present invention as described above, and the dielectric constant is controlled to a desired value. The interlayer insulating film 6 can be configured, for example, to have a dielectric constant higher than that of a normal organic film.
The average film thickness of the interlayer insulating film 6 is preferably 0.3 μm or more and 6 μm or less.

  In the method of manufacturing the thin film transistor substrate of the present embodiment, the pixel electrode 7 is formed on the interlayer insulating film 6 formed on the substrate 1 after the step [4]. The pixel electrode 7 is connected to the TFT 2 by being electrically connected to the drain electrode 13 of the TFT 2 through a contact hole 19 penetrating the interlayer insulating film 6, the planarization film 5 and the inorganic insulating film 4.

  At this time, the contact hole 19 is formed, for example, using the through hole formed by the patterning of the planarizing film 5 and the through hole formed by the patterning of the interlayer insulating film 6 after the step [4]. Ru. That is, for the formation of the contact hole 19, a through hole formed to continuously penetrate the planarization film 5 and the interlayer insulating film 6 is used.

  The contact hole 19 uses as a mask the planarizing film 5 and the interlayer insulating film 6 in which the through holes are formed continuously penetrating so as to be continuous with the planarizing film 5 and the through holes of the interlayer insulating film by etching. , The inorganic insulating film 4 is formed by forming a through hole. That is, the contact hole 19 is formed as a through hole which continuously penetrates the interlayer insulating film 6, the planarizing film 5 and the inorganic insulating film 4 in this order.

  Thereafter, the pixel electrode 7 is formed, for example, by depositing a film made of a light-transmissive conductive material such as ITO on the interlayer insulating film 6 using a sputtering method or the like, and patterning using a photolithographic method or the like It is done by doing. The formed pixel electrode 7 is connected to the TFT 2 through the contact hole 19 as described above.

  The pixel electrode 7 and the auxiliary capacitance electrode 3 are disposed on the substrate 1 so as to face each other via the interlayer insulating film 6.

  As described above, in the method of manufacturing the thin film transistor substrate according to the fifth embodiment of the present invention, the substrate 1, the TFT 2 disposed on the substrate 1, the planarizing film 5 covering the TFT 2, and the planarizing film The interlayer insulating film 6 covering 5 and the pixel electrode 7 disposed on the interlayer insulating film 6 and connected to the TFT 2 and planarized with the interlayer insulating film 6 so as to face the pixel electrode 7 via the interlayer insulating film 6 A thin film transistor substrate 100 having a storage capacitor electrode 3 disposed between the film 5 and the thin film transistor 5 can be manufactured.

The manufactured thin film transistor substrate 100 can be provided with an alignment film on the surface on which the TFT 2 and the like are disposed, in order to control the alignment of the liquid crystal.
The thin film transistor substrate 100 can be configured as the liquid crystal display element according to the second embodiment of the present invention described above.

  EXAMPLES The present invention will be described more specifically by showing synthesis examples and examples below, but the present invention is not limited to the following examples.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the hydrolytic condensate of the hydrolyzable silane compound obtained from each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Device: GPC-101 (manufactured by Showa Denko)
Column: 1, combined GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko) Mobile phase: tetrahydrofuran

<Synthesis Example of Hydrolysis Condensate of Hydrolyzable Silane Compound of Component [A]>
Synthesis Example 1
In a container equipped with a stirrer, 63.0 g (0.46 mol) of methyltrimethoxysilane, 96.3 g (0.46 mol) of tetraethoxysilane and 47.3 g of ion exchanged water are charged, and the solution temperature is 60 ° C. It was heated until it became. After the solution temperature reached 60 ° C., a 4.4% by mass benzyl alcohol solution of oxalic acid was charged, heated to 75 ° C., and held for 3 hours. The solution temperature was further raised to 40 ° C., and evaporation was carried out while maintaining this temperature to remove ion-exchanged water and methanol and ethanol generated by hydrolytic condensation. Then, 80 g of benzyl alcohol was added and evaporation was performed again. After evaporation, benzyl alcohol was further added to a solid concentration of 40% by mass. By the above, a hydrolysis condensation product (A-1) was obtained. The number average molecular weight (Mn) of the obtained hydrolytic condensate was 2346, and the molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 2
An experiment was conducted in the same manner as in Synthesis Example 1 except that benzyl alcohol was changed to phenoxyethanol, to obtain a hydrolysis condensate (A-2). The number average molecular weight (Mn) of the obtained hydrolytic condensate was 1623 and the molecular weight distribution (Mw / Mn) was 1.4.

Synthesis Example 3
An experiment was conducted in the same manner as in Synthesis Example 1 except that benzyl alcohol was changed to 2-phenylethyl alcohol, to obtain a hydrolysis condensate (A-3). The number average molecular weight (Mn) of the obtained hydrolytic condensate was 1450, and the molecular weight distribution (Mw / Mn) was 1.3.

Synthesis Example 4
In a container equipped with a stirrer, 89.7 g (0.66 mol) of methyltrimethoxysilane, 68.5 g (0.33 mol) of tetraethoxysilane and 48.1 g of ion-exchanged water are charged, and the solution temperature is 60 ° C. It was heated until it became. After the solution temperature reached 60 ° C., a 4.4 mass% propylene glycol monomethyl ether solution of oxalic acid was charged, heated to 75 ° C., and held for 3 hours. The solution temperature was further raised to 40 ° C., and evaporation was carried out while maintaining this temperature to remove ion-exchanged water and methanol and ethanol generated by hydrolytic condensation. Then, 80 g of propylene glycol monomethyl ether was added and evaporation was performed again. After evaporation, propylene glycol monomethyl ether was further added to a solid concentration of 40% by mass. By the above, a hydrolysis condensation product (A-4) was obtained. The number average molecular weight (Mn) of the obtained hydrolyzed condensate was 2978, and the molecular weight distribution (Mw / Mn) was 3.7.

Synthesis Example 5
In a container equipped with a stirrer, 28.3 g (0.14 mol) of phenyltrimethoxysilane, 95.6 g (0.70 mol) of methyltrimethoxysilane, 41.8 g (0.20 mol) of tetraethoxysilane and ions 47.0 g of exchange water was charged and heated until the solution temperature reached 60.degree. After the solution temperature reached 60 ° C., a 4.4% by mass benzyl alcohol solution of oxalic acid was charged, heated to 75 ° C., and held for 3 hours. The solution temperature was further raised to 40 ° C., and evaporation was carried out while maintaining this temperature to remove ion-exchanged water and methanol and ethanol generated by hydrolytic condensation. Then, 80 g of benzyl alcohol was added and evaporation was performed again. After evaporation, benzyl alcohol was further added to a solid concentration of 40% by mass. By the above, a hydrolysis condensation product (A-5) was obtained. The number average molecular weight (Mn) of the obtained hydrolytic condensate was 2285, and the molecular weight distribution (Mw / Mn) was 2.1.

Synthesis Example 6
An experiment was conducted in the same manner as in Synthesis Example 1 except that the benzyl alcohol was changed to propylene glycol monomethyl ether, to obtain a hydrolysis condensate (A-6). The number average molecular weight (Mn) of the obtained hydrolytic condensate was 1450, and the molecular weight distribution (Mw / Mn) was 1.3.

Synthesis Example 7
An experiment was carried out in the same manner as in Synthesis Example 1 except that benzyl alcohol was changed to diethylene glycol methyl ethyl ether, to obtain a hydrolysis condensate (A-7). The number average molecular weight (Mn) of the obtained hydrolytic condensate was 2561 and the molecular weight distribution (Mw / Mn) was 2.6.

Synthesis Example 8
An experiment was conducted in the same manner as in Synthesis Example 5 except that the benzyl alcohol was changed to propylene glycol monomethyl ether, to obtain a hydrolysis condensate (A-8). The number average molecular weight (Mn) of the obtained hydrolytic condensate was 2706, and the molecular weight distribution (Mw / Mn) was 2.6.

<Preparation of radiation sensitive resin composition>
Example 1
A solution containing the hydrolytic condensate (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by mass (solid content) of the hydrolytic condensate (A-1), 150 parts by mass of benzyl alcohol [C] (B-1) 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1. 20 parts by mass of a condensation product of 0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol), [F] "SH8400FLUID" manufactured by Toray Dow Corning as a surfactant, 0.1 A mass part was added, and a solvent (benzyl alcohol / propylene glycol monomethyl ether = 80/20 (mass%)) was added so that solid content concentration might be 27 mass%, and the radiation sensitive resin composition was prepared. In addition, with solid content concentration in a present Example, hydrolysis condensation products (A-1)-(A-8) (solid content) with respect to the mass of all the components (radiation sensitive resin composition), a photosensitive agent (B) -1) to (B-2), the compounds (C-1) to (C-4), and the surfactant (F-1), the ratio of the total mass.

[Examples 2 to 15 and Comparative Examples 1 to 6]
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the types and amounts of each component and the solid content concentration were as described in Table 1.

<Physical evaluation>
Using the radiation-sensitive resin composition prepared as described above, various properties of the composition and a cured film formed from the composition were evaluated as follows.

[Evaluation of whitening and transmittance of cured film]
After applying each composition on a glass substrate using a spinner, a coating film having an average film thickness of 3.0 μm was formed by prebaking on a hot plate at 90 ° C. for 2 minutes. The obtained coating film is exposed to an integrated irradiation dose of 3,000 J / m ² using a PLA-501F exposure apparatus (super high pressure mercury lamp) manufactured by CANON CO., LTD. A cured film was obtained by heating at 230 ° C. for 1 hour. In order to check the degree of whitening of the cured film, the unevenness of 3 μm square was observed by AFM “Dimension 3100” (manufactured by Veeco). From the correlation with the degree of whitening visually, "A" is the case where average roughness Ra is 1 ≦ Ra <4, “B” when 4 ≦ Ra <7, and “C” when 7 ≦ Ra <10. The case of 10 ≦ Ra is “D”. The cases of “A” to “C” were evaluated as good, and the case of “D” was evaluated as poor. The results are shown in Table 1.
Moreover, the light transmittance of the glass substrate which has this cured film was measured by the wavelength of the range of 300-500 nm using spectrophotometer "150-20 type | mold double beam" (made by Hitachi, Ltd.). The values of the lowest light transmittance at that time are shown in Table 1. When the lowest light transmittance is 95% or more, it can be said that the light transmittance is good.

[Evaluation of outgassing]
The composition solution was applied onto a substrate and then dried to form a film having an average film thickness of 6.0 μm. After that, for this film, head space gas chromatography / mass using n-octane as a standard substance (specific gravity = 0.701, injection amount, 0.02 μl) and a purge condition of 100 ° C./10 min. Analysis (head space sampler: JHS-100A manufactured by Japan Analytical Industry Co., Ltd., gas chromatography / mass spectrometer, JMS-AX505W mass spectrometer manufactured by JEOL), and peak area A derived from compounds having each aromatic ring The volatilized amount of the compound having each aromatic ring was calculated by n-octane conversion according to the following formula, and the total of these was defined as the volatilized amount (μg) of the aromatic ring compound. When this volatilization amount exceeded 0.5 μg, it was judged that the outgas component derived from the benzene ring was large.
Calculation formula of volatilization amount by n-octane conversion Volatilization amount (μg) of compound having aromatic ring (A) (quantity of n-octane) (μg) / (peak area of n-octane)

[Evaluation of solvent resistance]
The composition solution was applied onto a substrate and then dried to form a film. The obtained coating film is exposed to an integrated irradiation dose of 3,000 J / m ^{2 using a} PLA-501F exposure apparatus (super high pressure mercury lamp) manufactured by Canon without using a pattern mask, and this silicon substrate is cleaned in a clean oven The film was heated at 230 ° C. for 30 minutes to obtain a cured film having an average thickness of 3.0 μm. The average film thickness (T1) of the cured film obtained here was measured. Then, after immersing the silicon substrate on which the cured film is formed in N-methyl-2-pyrrolidone whose temperature is controlled at 45 ° C. for 6 minutes, the average film thickness (t1) of the cured film is measured, and The average film thickness change rate {| t1−T1 | / T1} × 100 [%] was calculated. The results are shown in Table 1 as solvent resistance. When this value is 5% or less, it can be said that the solvent resistance is good.

[Evaluation of storage stability]
The above composition solution was heated in an oven at 40 ° C. for one week, and the obtained sample was applied on a substrate and then dried to form a film. Subsequently, using a light exposure machine (“MPA-600FA (Ghi line mixed)” from Canon Inc.), the exposure dose to the coating film is obtained through a mask having a 10 μm line and space (1 to 1) pattern. Radiation was used as a variable. Thereafter, it was developed by immersion in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 80 seconds. Subsequently, the pattern was formed on the glass substrate by performing flowing-water washing | cleaning with ultrapure water for 1 minute, and drying after that. At this time, the exposure amount required to form a 10 μm space pattern was examined. The radiation sensitivities before and after heating were measured, and the change rate (%) of the required exposure was determined to be an index of storage stability. If the rate of change is less than 5%, "A", if the rate of change is 5% or more and less than 10%, "B", if the rate of change is 10% or more is "C". The stability was evaluated as good. The results are shown in Table 1.

  In Table 1, abbreviations for [B] photosensitizer, [C] compound, and [F] surfactant respectively represent the following.

B-1: 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 Condensation products with sulfonic acid chloride (3.0 mol) B-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (3.0 mol) C-1: Naphthol C-2: 2- (4'-hydroxyphenyl) -2-phenylpropane C-3: Benzoic acid C-4: Benzene thiol F-1: Toray Dow Corning's SH8400FLUID

  "-" In Table 1 indicates that the measurement was not performed because the cured film turned white. In addition, the radiation sensitive resin composition of Examples 1-6 and 11 using the solution containing a hydrolysis-condensation product (A-1) adds the benzyl alcohol contained in this solution further as a [C] component. Including. Similarly, the radiation sensitive resin compositions of Examples 7 and 12 using a solution containing the hydrolytic condensate (A-2) further contain phenoxyethanol contained in this solution as a component [C]. The radiation sensitive resin composition of Examples 8 and 13 using the solution containing the hydrolytic condensate (A-3) further contains 2-phenylethyl alcohol contained in this solution as a [C] component. . The radiation sensitive resin composition of 10 and 15 using the solution containing a hydrolysis condensation product (A-5) further contains the benzyl alcohol contained in this solution as a [C] component.

The abbreviations in Table 1 are as follows.
BnOH: benzyl alcohol PhO (CH ₂ ) ₂ OH: 2-phenoxyethanol Ph (CH ₂ ) ₂ OH: 2-phenylethyl alcohol PGME: propylene glycol monomethyl ether EDM: diethylene glycol methyl ethyl ether

  As Table 1 shows, while the whitening of a cured film and evaporation of benzene are suppressed, the cured film formed with the radiation sensitive resin composition of Examples 1-15 is excellent in light transmittance and solvent tolerance. Moreover, storage stability can also be improved by preparing a component composition. For this reason, the cured film formed of these radiation sensitive resin compositions can be suitably used for an interlayer insulating film of a thin film transistor substrate, a liquid crystal display element using the same, and an organic EL element.

  The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention.

  In the liquid crystal display device of the present invention, an interlayer insulating film is formed using the radiation sensitive resin composition of the present invention, enabling high-quality display and exhibiting high reliability, and being simple. It can be manufactured. Therefore, the liquid crystal display element of the present invention is suitable for use as a display element of a portable information device such as a smart phone recently required to achieve low power consumption and high image quality, in addition to applications such as large liquid crystal TVs. is there.

1 substrate 2 TFT
Reference Signs List 3 auxiliary capacitance electrode 4 inorganic insulating film 5 planarization film 6 interlayer insulating film 7 pixel electrode 10 gate electrode 11 gate insulating film 12 semiconductor layer 13 drain electrode 14 source electrode 17 common wiring 18 and 19 contact hole 80 recessed portion 100 thin film transistor substrate 110 facing Substrate 111 Liquid crystal layer 200 Liquid crystal display element 201 Organic EL element 202 Support substrate 203 Thin film transistor (TFT)
204 inorganic insulating film 205 interlayer insulating film 206 anode (as first electrode) anode 207 through hole 208 partition wall 209 light emitting layer 210 cathode as second electrode 211 passivation film 212 sealing substrate 213 sealing layer 230 gate electrode 231 gate Insulating film 232 Semiconductor layer 233 Source electrode 234 Drain electrode

Claims (12)

A substrate and a thin film transistor disposed on the substrate;
A thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor, the thin film transistor substrate comprising:
The thin-film transistor substrate in which the said interlayer insulation film contains the polymer which has a structure shown by following formula (1).

(In formula (1), R ¹ represents a divalent linking group containing a hetero atom, R ² represents a monovalent organic group containing an aromatic ring, and * represents a binding site.) The thin film transistor substrate according to claim 1, wherein R ¹ represents —O—, —S—, —O—C (= O) — or —NH—.   The content ratio of the aromatic ring derived from the formula (1) in the interlayer insulating film is 1 mol% or more and 60 mol% or less with respect to the Si atom in the interlayer insulating film. The thin film transistor substrate according to claim 1. The thin film transistor substrate according to claim 1, 2 or 3, wherein R ² represented by the formula (1) is represented by the following formula (2).

(In Formula (2), R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. Represents an integer of 6. m represents 0 or 1.)   The thin film transistor substrate according to any one of claims 1 to 4, wherein the thin film transistor has a semiconductor layer formed using an oxide semiconductor.   The thin film transistor substrate according to claim 5, wherein the semiconductor layer is formed of indium gallium gallium zinc.   The thin film transistor substrate according to any one of claims 1 to 4, wherein the thin film transistor has a semiconductor layer formed using any of amorphous silicon and crystalline silicon.   The thin film transistor substrate according to any one of claims 1 to 7, wherein the interlayer insulating film is a polysiloxane film.   A thin film transistor substrate according to any one of claims 1 to 8, a counter substrate having a counter electrode facing the thin film transistor substrate, and a liquid crystal layer disposed between the thin film transistor substrate and the counter substrate. The liquid crystal display element which it has.   An organic EL device comprising the thin film transistor substrate according to any one of claims 1 to 8 and a light emitting layer in this order. [A] Polymer,
A radiation sensitive resin composition comprising: [B] a photosensitizer, and [C] a compound represented by the following formula (3),
A substrate,
A thin film transistor disposed on the substrate;
The radiation sensitive resin composition used for formation of this interlayer insulation film of the thin-film transistor board | substrate which has an interlayer insulation film arrange | positioned on the said thin-film transistor.

(In formula (3), X represents a hydroxy group, a thiol group, a carboxy group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring.) A substrate,
A thin film transistor disposed on the substrate;
A method of manufacturing a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor, comprising:
[1] A process of forming a coating film of the radiation sensitive resin composition according to claim 11 on the substrate on which the thin film transistor is formed,
[2] irradiating at least a part of the coating film formed in the step [1] with radiation;
[3] a process of developing the coating film irradiated with radiation in the process [2], and a process of heating the coating film developed in the [4] process [3] to form the interlayer insulating film Method of manufacturing a thin film transistor substrate

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