KR102482590B1 - Thin film transistor substrate, liquid crystal display device, organic el device, radiation-sensitive resin composition and process for producing the thin film transistor substrate - Google Patents

Abstract

(식 (1) 중, R¹은, 헤테로 원자를 포함하는 2가의 연결기를 나타내고, R²는, 방향환을 포함하는 1가의 유기기를 나타낸다. *는 결합 부위를 나타낸다.)(Problem) A thin film transistor substrate having an interlayer insulating film that is difficult to whiten during high-temperature treatment and the generation of outgas is suppressed, a liquid crystal display element or an organic EL element having the same, and a feeling capable of suitably forming the interlayer insulating film A radioactive resin composition and a method for manufacturing a thin film transistor substrate are provided.
(Solution means) 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, wherein the interlayer insulating film has a polymer having a structure represented by the following formula (1) It relates to a thin film transistor substrate comprising

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

Description

Thin film transistor substrate, liquid crystal display device, organic EL device, radiation-sensitive resin composition, and method for manufacturing a thin film transistor substrate FILM TRANSISTOR SUBSTRATE}

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

In recent years, development of a display element using a liquid crystal, that is, a liquid crystal display element, is actively progressing due to advantages such as being able to reduce the thickness and weight compared to the conventional CRT type display device.

A liquid crystal display element has a structure in which a liquid crystal is sandwiched between a pair of substrates, such as a transparent glass substrate, for example. An alignment film can be formed on the surface of these substrates for the purpose of controlling the alignment of liquid crystals. In addition, these pair of substrates are held by a pair of polarizing plates, for example. Then, by applying an electric field between the substrates, an alignment change occurs in the liquid crystal, and light is partially transmitted or shielded. In a liquid crystal display element, images can be displayed using these characteristics.

With the development of an active matrix method in which a switching element is arranged for each pixel of a liquid crystal display element, it has become possible to realize good image quality with excellent contrast ratio and response performance. In addition, the liquid crystal display element overcomes problems such as high definition, colorization, widening of the viewing angle, and the like, and has recently been used as a display element for portable electronic devices such as smartphones and a display element for large and thin televisions. is about to be used.

In an active matrix liquid crystal display element, gate wiring and signal wiring are provided in a lattice shape on one of a pair of substrates holding liquid crystal, and the above-described switching element is used at the intersection between them, for example, a thin film transistor ( TFT: Thin Film Transistor) is formed. That is, in an active matrix type liquid crystal display element, one of a pair of substrates sandwiching a liquid crystal constitutes a thin film transistor substrate on which a TFT or the like is disposed.

A thin film transistor substrate typically includes a substrate and a TFT as a switching element disposed on the substrate, a planarization film covering the TFT, an interlayer insulating film covering the planarization film, a pixel electrode disposed on the interlayer insulating film and connected to the TFT, An auxiliary capacitance electrode is disposed between the interlayer insulating film and the planarization film to face the pixel electrode through the interlayer insulating film.

From the standpoint of improving the reliability of future thin film transistor substrates, there is a possibility that high-temperature treatment (eg, 250° C. or higher) is performed on the interlayer insulating film. Since application of existing acrylic organic insulating films may be difficult from the standpoint of lack of heat resistance or transparency, a radiation-sensitive resin composition capable of obtaining a high surface hardness with a small number of steps for forming a pattern has been studied. As such a resin composition, a siloxane-based photosensitive material has been proposed (Patent Document 1).

Japanese Patent Publication No. 4670693

As for the photosensitive siloxane material, when a photosensitizer having low compatibility with polysiloxane such as a quinonediazide compound is used, it has been found that whitening may occur during formation of an interlayer insulating film due to low compatibility between the photosensitizer and polysiloxane. there is. In contrast, as in Patent Document 1, introducing a phenyl group into the polysiloxane backbone to enhance compatibility with the quinonediazide compound may be one measure.

However, in photosensitive materials using polysiloxane in which a phenyl group is directly introduced into the polysiloxane backbone, benzene is generated as an outgas during high-temperature treatment of an interlayer insulating film, and there is a concern that it becomes a pollutant to the manufacturing process and the environment.

The present invention has been made in view of the above problems. That is, an object of the present invention is a thin film transistor substrate provided with an interlayer insulating film that is difficult to whiten during high-temperature treatment and the generation of outgas is suppressed, a liquid crystal display element or organic EL element provided with the thin film transistor substrate, and the interlayer insulating film suitably It is providing the manufacturing method of the radiation sensitive resin composition which can be formed, and a thin film transistor board|substrate.

The present invention, in one aspect,

substrate,

a thin film transistor disposed on the substrate;

A thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,

It is related with the thin film transistor substrate in which the said interlayer insulating film contains the polymer which has a structure represented by following formula (1).

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

The present invention, in another aspect,

It relates to a liquid crystal display element comprising the 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.

The present invention, in a further other aspect,

It is related with the organic electroluminescent element provided with the said thin film transistor substrate, an interlayer insulating film, and a light emitting layer in this order.

The present invention, in a further other aspect,

[A] polymer,

[B] a photosensitizer and,

[C] A radiation-sensitive resin composition containing a compound represented by the following formula (3),

substrate,

a thin film transistor disposed on the substrate;

It relates to a radiation-sensitive resin composition used for forming an 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 hydroxyl group, a thiol group, a carboxyl group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring)

The present invention, in another aspect,

substrate,

a thin film transistor disposed on the substrate;

As a method of manufacturing a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,

[1] a step of forming a coating film of the radiation-sensitive resin composition on the substrate on which the thin film transistor is formed;

[2] a step of irradiating radiation to at least a part of the coating film formed in step [1];

[3] a step of developing the coating film irradiated with radiation in step [2]; and

[4] A step of forming the interlayer insulating film by heating the coating film developed in step [3]

It relates to a method for manufacturing a thin film transistor substrate having a.

According to the present invention, it is possible to suitably form a thin film transistor substrate having an interlayer insulating film that is resistant to whitening during high-temperature treatment and suppresses generation of outgas, a liquid crystal display element or organic EL element including the same, and the interlayer insulating film. It is possible to provide a radiation-sensitive resin composition, and a method for manufacturing a thin film transistor substrate.

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.
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.
3 is a schematic cross-sectional view of a pixel portion in an example of an organic EL device according to a third embodiment of the present invention.

(Mode for implementing the invention)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described using drawings suitably.

In the present invention, "radiation" irradiated during exposure includes visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

≪First Embodiment≫

(thin film transistor substrate)

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, which is an example of the first embodiment of the present invention shown in FIG. 1, includes a substrate 1, a TFT 2 disposed on the substrate 1 as a switching element, and covering the TFT 2. A planarization film 5, an interlayer insulating film 6 covering the planarization film 5, a pixel electrode 7 disposed on the interlayer insulating film 6 and connected to the TFT 2, and an interlayer insulating film 6 An auxiliary capacitance electrode 3 is disposed between the interlayer insulating film 6 and the planarization film 5 so as to face the pixel electrode 7 through the . In the thin film transistor substrate 100, as shown in FIG. 1, an inorganic insulating film 4 can be formed between the TFT 2 and the flattening film 5 so as to cover and protect the TFT 2. .

On the surface on which the TFTs 2 are placed on the substrate 1, various wirings such as gate wirings and signal wirings, which are not shown, are formed. Gate wiring and signal wiring are provided in a lattice shape, and TFTs 2 are formed at each of their intersections.

Although not particularly limited as the substrate 1, for example, a glass substrate, a quartz substrate, a resin substrate made of acrylic resin or the like is preferably used. In addition, in the substrate 1, it is preferable that cleaning and pre-annealing are performed as pre-processes for forming the thin film transistor substrate 100.

As described above, the TFT 2 is a switching element, and includes a gate electrode 10 formed on the substrate 1 and forming a part of the gate wiring, a gate insulating film 11 covering the gate electrode 10, The semiconductor layer 12 disposed on the gate insulating film 11, the source electrode 14 that forms part of the signal wiring and is connected to the semiconductor layer 12, and the pixel electrode 7 are connected to the other side. It is structured with the drain electrode 13 connected to the semiconductor layer 12.

The gate electrode 10 of the TFT 2 can be formed by forming a metal thin film on the substrate 1 by evaporation or sputtering, and patterning using an etching process. It is also possible to pattern and use a metal oxide conductive film or an organic conductive film.

As the material of the metal thin film constituting the gate electrode 10, for example, aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), gold ( Au), 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, and copper). And, as the metal thin film, it is also possible to use a laminated film composed of layers of different materials, such as a laminated film of Al and Mo.

Examples of the material of the metal oxide conductive film constituting the gate electrode 10 include metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). there is.

In addition, as a material of the organic conductive film constituting the gate electrode 10, conductive organic compounds, such as polyaniline, polythiophene, and polypyrrole, or mixtures thereof are exemplified.

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 singly 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 is, for example, a-Si (amorphous silicon) in an amorphous state or p-Si (polysilicon) obtained by crystallizing a-Si by excimer laser or solid-state growth. etc., can be formed by using a silicon (Si) material.

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

Further, 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), and a channel region is sandwiched therebetween, and a source region and It is preferable to form a drain region. In addition, it is preferable to form an LDD (Lightly Doped Drain) layer between the channel region, the source region, and the drain region of the semiconductor layer 12 .

In addition, the semiconductor layer 12 of the TFT 2 can be formed using an oxide. Examples of oxides applicable to the semiconductor layer 12 include single-crystal oxides, poly-crystal oxides, amorphous oxides, and mixtures thereof. As a polycrystal oxide, zinc oxide (ZnO) etc. are mentioned, for example.

Examples of the amorphous oxide applicable to the semiconductor layer 12 include an amorphous oxide composed of 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 gallium zinc oxide), In-Zn-Ga-Mg oxide, and 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 heard 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 realizing desired characteristics.

The semiconductor layer 12 using an amorphous oxide is, for example, when it is formed using IGZO or ZTO, the semiconductor layer is formed by a sputtering method or a vapor deposition method using an IGZO target or a ZTO target, photolithography method, etc. is formed by performing patterning by a resist process and an etching process. It is preferable to set the thickness of the semiconductor layer 12 using an amorphous oxide to, 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 by using a sputtering method, CVD method, evaporation method, etc. After forming using a method, it may be formed by performing patterning using a photolithography method or the like.

Examples of materials constituting the source electrode 14 and the drain electrode 13 include metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W, and Ag, alloys of these metals, and Al-Nd. and alloys such as APC. In addition, 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 Conductive organic compounds, such as these, are mentioned. And, as the conductive film constituting these electrodes, it is also possible to use a laminated film composed of layers of different materials such as a laminated film of Ti and Al.

It is preferable that the thickness of the source electrode 14 and the drain electrode 13 be, for example, 10 nm or more and 1000 nm or less, respectively.

In the thin film transistor substrate 100, an inorganic insulating film 4 can be formed 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 individually or by laminating them. An inorganic insulating film 4 is formed to cover the TFT 2 and protect it. More specifically, the inorganic insulating film 4 covers the TFT 2 and protects the semiconductor layer 12, so that it can be prevented from being affected by, for example, humidity.

In addition, in the thin film transistor substrate 100, it is also possible to set it as the structure which does not form the inorganic insulating film 4. In that case, the flattening film 5 formed between the pixel electrode 7 and the TFT 2 can also be used for protection of the TFT 2 .

The flattening film 5 of the thin film transistor substrate 100 is formed on the inorganic insulating film 4 so as to cover the TFT 2 from above. The flattening film 5 has a function of flattening irregularities caused by the TFTs 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 flattening film 5 can be made of a film made of acrylic resin, polyimide resin, polysiloxane, or novolac resin.

And, when the planarization film 5 is made of an organic film, as described above, the coupling capacitance between the pixel electrode 7 and other wires or electrodes such as gate wires and signal wires can be reduced. Since the thin film transistor substrate 100 has the planarization film 5, the area of the pixel electrode 7 in the pixel can be increased, and the aperture ratio of the pixel can be improved.

The planarization film 5 preferably has an excellent function as a planarization film, and from this point of view, it is preferable to set the film thickness. For example, the planarization film 5 can be formed with an average film thickness of 0.5 μm to 6 μm. In addition, it is also possible to set each film thickness so that the average film thickness together with the interlayer insulating film 6 is 1 µm to 6 µm so as to exhibit excellent planarization capability together with the interlayer insulating film 6 described later.

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

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

Therefore, in the thin film transistor substrate 100, in the area where the common wiring 17 is arranged, the inorganic insulating film 4 described above covers the common wiring 17, and the planarization film 5 described above further covers the common wiring. (17) and the inorganic insulating film (4).

On top of the planarization film 5, an auxiliary capacitance electrode 3 electrically connected to the common wiring 17 via a contact hole 18 passing through the planarization film 5 and the inorganic insulating film 4 is disposed. do.

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

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 . Further, in the above-mentioned storage capacitance electrode 3 arrangement area, the storage capacitance electrode 3 on the planarization film 5 is formed to cover the entire surface of the planarization film 5 and the storage capacitance electrode 3. placed to cover

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 applying the radiation-sensitive resin composition of the fourth embodiment of the present invention, then patterning by exposure and development, followed by curing. Then, the interlayer insulating film 6 is formed using the radiation-sensitive resin composition of the fourth embodiment of the present invention, so that the dielectric constant, which is a dielectric characteristic, is controlled to a desired value. For example, it is configured to have a higher permittivity than a normal organic film.

The interlayer insulating film 6 contains 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, and R ² represents a monovalent organic group containing an aromatic ring. * indicates a bonding site.)

In the polymer included in the interlayer insulating film 6, since the aromatic ring is bonded to Si via a divalent linking group containing a hetero atom, generation of outgas derived from aromatic compounds such as benzene can be suppressed. Although benzene is generated as an outgas in a conventional interlayer insulating film containing a polymer in which a phenyl group is directly bonded to Si, the interlayer insulating film of the present embodiment reduces or prevents such an event, thereby improving the manufacturing process and the environment. safety can be increased. Moreover, since the said polymer contains an aromatic ring, compatibility with photosensitizers, such as a quinonediazide compound, is high, and whitening at the time of high-temperature treatment of an interlayer insulating film can be suppressed. In addition, the interlayer insulating film has good solvent resistance.

As a hetero atom which comprises the divalent coupling group containing a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom etc. are mentioned, for example. Specific examples of the linking group include -O-, -CO-, -S-, -CS-, -OCO-, -COO-, and -NR'-, groups combining two or more of these, and the like. can R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group of 1 to 10 carbon atoms include monovalent chain hydrocarbon groups of 1 to 10 carbon atoms, and examples of the monovalent chain hydrocarbon group of 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i - alkyl groups such as propyl groups; alkenyl groups such as ethenyl, propenyl and butenyl groups; alkynyl groups such as ethynyl, propynyl and butynyl groups; and the like.

Among them, R ¹ preferably represents -O-, -S-, -OC(=O)-, or -NH- from the viewpoint of chemical stability and ease of synthesis. 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. In addition, as the lower limit of the content ratio of -O-, -S- and -NH- occupied in all R ¹ in the polymer having the structure represented by the formula (1), particularly the content ratio of -O- occupied in all R ¹ , 90 mol% is preferable, 95 mol% is more preferable, and 99 mol% is still more preferable.

Examples of the monovalent organic group containing an aromatic ring include aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl naphthyl group, anthryl group and methyl anthryl group, 4-(2- Phenoxyalkyl groups, such as a phenyl-2-propyl) phenyl group, a phenoxymethyl group, and a phenoxyethyl group, and aralkyl groups, such as a group represented by following formula (2), a naphthylmethyl group, and an anthrylmethyl group, etc. are mentioned. One or more hydrogen atoms in these groups may be substituted.

(In Formula (2), R ³ represents a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a halogen atom. n represents an integer from 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 groups, alkenyl groups such as ethenyl, propenyl and butenyl, ethynyl, propynyl and butynyl groups, etc. The alkynyl group of , etc. are mentioned.

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, a xylyl group, a 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. In addition, when the said m is 1, the effect of this invention etc. may be exhibited more fully.

As R ² represented by the formula (1), a group represented by the formula (2) is preferable. As group represented by said formula (2), a benzyl group, a phenethyl group, a naphthyl group etc. are mentioned specifically, for example.

It is preferable that the said interlayer insulating film is a polysiloxane film from the point of the ease of introduction of the structure represented by said formula (1) or (2). Polysiloxane is described later.

It is preferable that the content rate of the aromatic ring derived from the structure represented by the said formula (1) in the said interlayer insulating film is 1 mol% or more and 60 mol% or less with respect to Si atoms in the said 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 still more preferable. 50 mol% is more preferable, and, as for the upper limit of the content rate of the said aromatic ring, 40 mol% is still more preferable. When the aromatic ring content is within the above range, it is possible to achieve a high level of prevention of whitening and suppression of outgassing during high-temperature treatment of the interlayer insulating film.

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

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

When the polymer included in the interlayer insulating film 6 further includes a structure in which an aryl group is bonded to a Si atom, compatibility between the polymer and the photosensitizer is further increased, and whitening of the interlayer insulating film during high-temperature treatment can be prevented.

Examples of the aryl group represented by R ^a include the same groups as those exemplified as the monovalent organic group containing an aromatic ring for R ² .

When the polymer contained in the interlayer insulating film 6 has the structure represented by the formula (a), the content of aromatic rings derived from the structure represented by the formula (a) in the interlayer insulating film is relative to the Si atoms in the interlayer insulating film. , it is preferably 1 mol% or more and 40 mol% or less. 5 mol% is more preferable, and, as for the lower limit of the content rate of the said aromatic ring, 10 mol% is still more preferable. 30 mol% is more preferable, and, as for the upper limit of the content rate of the said aromatic ring, 20 mol% is still more preferable. When the aromatic ring content is within the above range, it is possible to achieve a higher level of prevention of whitening and suppression of outgassing during high-temperature treatment of the interlayer insulating film. Moreover, as for the upper limit of the content rate of the aromatic ring derived from the structure represented by the said formula (a), 10 mol% is more preferable in some cases, and 5 mol% is more preferable in some cases. In this way, by lowering the content of the aromatic ring derived from the structure represented by the above formula (a), the generation of outgas is more suppressed, and the solvent resistance of the interlayer insulating film tends to increase.

As an average film thickness of the interlayer insulating film 6, 0.3 micrometer or more and 6 micrometer or less are preferable, for example. In addition, as described above, it is also possible to set each film thickness so that the average film thickness together with the flattening film 5 is 1 µm or more and 6 µm or less.

In addition, about the interlayer insulating film 6, it is thought that it is also possible to set it as an inorganic film, such as a SiN film, similarly to the gate insulating film 11 and the inorganic insulating film 4. However, forming an interlayer insulating film made of such an inorganic film requires vacuum film formation using vacuum equipment or dry etching, and cannot be formed as easily as the interlayer insulating film 6 which is an organic film. 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. And, the interlayer insulating film 6 is formed using the radiation-sensitive resin composition of the fourth embodiment of the present invention, and has a higher dielectric constant than a normal organic film constituting a conventional interlayer insulating film, for example, a SiN film. It may have the same permittivity as that of an inorganic film such as

The pixel electrode 7 of the thin film transistor substrate 100 is disposed on the interlayer insulating film 6 and has a contact hole 19 penetrating the interlayer insulating film 6, the planarization film 5, and the inorganic insulating film 4. It is electrically connected to the drain electrode 13 through In the thin film transistor substrate 100, the pixel electrode 7 and the storage capacitance electrode 3 are configured to face each other via 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 effective for achieving both light transmittance and electrical conductivity.

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

As a result, in the thin film transistor substrate 100, the auxiliary capacitance electrode 3 can generate auxiliary capacitance at an overlapping portion where the pixel electrode 7 and the auxiliary capacitance electrode 3 overlap in plan view. And, as described above, the interlayer insulating film 6 sandwiched by 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 has a high dielectric constant. It is controlled to a desired value. The interlayer insulating film 6 is configured to have a higher dielectric constant than, for example, a normal organic film. Therefore, in plan view, the storage capacitance generated at the overlapping portion where the pixel electrode 7 and the storage capacitance electrode 3 overlap can have a high charge holding capacity.

On the other hand, the thin film transistor substrate 100, as described above, has a flattening film 5 between the pixel electrode 7 and the TFT 2, so that the pixel electrode 7 and other wiring or electrode coupling capacitance between them can be reduced.

The thin film transistor substrate 100 on which this auxiliary capacitance is generated can form an alignment film on the surface of the substrate for the purpose of controlling the alignment of liquid crystals, and can constitute a liquid crystal display device of a second embodiment of the present invention described later. there is. Further, in the liquid crystal display element according to the second embodiment of the present invention, the voltage applied to the pixel is turned off by using the auxiliary capacitance generated by the auxiliary capacitance electrode 3, the interlayer insulating film 6, and the pixel electrode 7. Even when the applied voltage is not applied, the electric 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 driving of the liquid crystal even when no voltage is applied due to the function of the auxiliary capacitance.

At this time, the auxiliary capacitance 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 aperture ratio of the pixels is suppressed. Therefore, the liquid crystal display element 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)

2 is a schematic cross-sectional view of a pixel portion in an example of a liquid crystal display element of 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, includes a thin film transistor substrate 100, a counter substrate 110, and a thin film that are an example of the first embodiment of the present invention described above. A liquid crystal layer 111 is disposed between the transistor substrate 100 and the counter substrate 110 .

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 the thin film transistor substrate 100 and the counter substrate 110 are formed by using a sealing material (not shown). It is constituted by bonding using and bonding, encapsulating liquid crystal between the two substrates, and forming the liquid crystal layer 111. Therefore, in the liquid crystal display device 200, the thin film transistor substrate 100 is common to the thin film transistor substrate 100 as an example of the first embodiment of the present invention described above, and its components are the same as those described above. Symbols are attached, and redundant descriptions are omitted.

In the liquid crystal display device 200, in the thin film transistor substrate 100, the auxiliary capacitance electrode 3 forms an auxiliary capacitance at an overlapping portion where the pixel electrode 7 and the auxiliary capacitance electrode 3 overlap in plan view. can create Then, 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 described later, and has a dielectric constant of a desired value. is controlled by The interlayer insulating film 6 is configured to have a higher dielectric constant than, for example, a normal organic film. Therefore, in plan view, the storage capacitance generated at the overlapping portion where the pixel electrode 7 and the storage capacitance electrode 3 overlap can have a high charge holding capacity.

On the other hand, the thin film transistor substrate 100, as described above, has a flattening film 5 between the pixel electrode 7 and the TFT 2, so that the pixel electrode 7 and other wiring or electrode coupling capacitance between them can be reduced.

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

Alignment films may be formed on opposite surfaces of the thin film transistor substrate 100 and the counter substrate 110 for the purpose of controlling alignment of liquid crystals.

Further, the liquid crystal layer 111 is made of, for example, vertically aligned liquid crystal, and between the TFT 2 of the thin film transistor substrate 100 and the counter electrode of the counter substrate 110, voltage application is turned on. • By OFF, orientation control of the liquid crystal is performed.

The liquid crystal display device 200 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 of the thin film transistor substrate 100. , charge can be held with high efficiency even when the voltage applied to the pixel is turned off and the voltage is not applied. As a result, the liquid crystal display element 200 according to the second embodiment of the present invention having the thin film transistor substrate 100 can maintain driving of the liquid crystal even when no voltage is applied.

At this time, the auxiliary capacitance 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, a decrease in the aperture ratio of the pixels 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)

3 is a cross-sectional view schematically showing the structure of a main part of the organic EL element according to the present embodiment.

The organic EL element 201 in Fig. 3 is an active matrix type organic EL element having a plurality of pixels formed in a matrix. This 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, transparency, is appropriately selected according to the top emission type or 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, a first An anode 206 as an electrode and a through hole 207 are provided, and a barrier rib 208 provided thereon, a light emitting layer 209, a cathode 210 as a second electrode, a passivation film 211, and a sealing substrate 212 to provide

The TFT 203 is an active element of each pixel portion and is formed on the support substrate 202 . This 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.

In this embodiment, it is not limited to a bottom gate type in which a gate insulating film and a semiconductor layer are sequentially provided on a gate electrode, but a top gate type in which a gate insulating film and a gate electrode are sequentially provided on a semiconductor layer may be used.

The gate electrode 230 forms a part of a scan 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 constitutes 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 in the same way as 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 constitutes a channel layer. The channel layer is a portion through which carriers flow and is controlled by the gate electrode 230 .

The semiconductor layer 232 can be formed using an oxide semiconductor containing at least one element selected from In, Ga, Sn, and Zn, as described above. Examples of oxides in this case include single crystal oxides, polycrystal oxides, amorphous oxides, and mixtures thereof.

The semiconductor layer 232 made of an amorphous oxide using IGZO is patterned by, for example, a resist process and an etching process by forming a semiconductor layer by a sputtering method or a vapor deposition method using an IGZO target and using a photolithography method or the like. is formed by doing 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 formed 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 so as to cover the entire TFT 203 .

The interlayer insulating film 205 can also function as a planarization film that serves to flatten surface irregularities of the TFT 203 . An interlayer insulating film 205 is formed on the inorganic insulating film 204 so as to cover the entire TFT 203 .

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

As an average film thickness of the interlayer insulating film 205, 1 micrometer or more and 6 micrometers or less are preferable.

The through hole 207 is formed to connect the anode 206 and the drain electrode 234. The through hole 207 is formed so as to pass through the inorganic insulating film 204 under 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 desired shape through hole. 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 hole constituting the through hole 207 can be formed by irradiation and development of radiation to a 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. Accordingly, 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.

In the case where the inorganic insulating film 204 is not disposed on the TFT 203, a through hole formed by irradiation and development of radiation to the interlayer insulating film 205 constitutes a through hole 207. As a result, the anode 206 covers a part of the interlayer insulating film 205 and passes through the drain electrode 234 through the through hole 207 formed in the interlayer insulating film 205 so as to pass through the interlayer insulating film 205. can connect

The barrier rib 208 serves as a barrier rib (bank) having a concave portion 80 defining an area where the light-emitting layer 209 is placed. The barrier rib 208 is formed so as to expose a part of the anode 206 while covering a part of the anode 206 .

The barrier rib 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, "upward" is a direction from the support substrate 202 toward the sealing substrate 212 .

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

In addition, it is preferable that the barrier rib 208 is formed so as to fill the through hole 207 .

The lower limit of the average film thickness of the barrier rib 208 (the distance between the uppermost surface of the barrier rib 208 and the lowermost surface of the light emitting layer 209) is preferably 0.3 µm, and more preferably 0.5 µm. As an upper limit of the said average film thickness, 25 micrometers are preferable and 20 micrometers are more preferable. If the average film thickness of the barrier rib 208 exceeds the above upper limit, there is a possibility that the barrier rib 208 comes into contact with the sealing substrate 212 . On the other hand, if the average film thickness of the barrier rib 208 is less than the lower limit, when the light emitting layer 209 described later is formed, and when the light emitting material composition is applied to the concave portion 80 of the barrier rib 208, the light emitting material There is a possibility that the composition may leak from the concave portion 80 .

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 electroluminescence. The light emitting layer 209 is formed in a region defined by the barrier rib 208, that is, in the concave portion 80. In this way, by forming the light emitting layer 209 in the concave portion 80, the periphery of the light emitting layer 209 is surrounded by the barrier rib 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 concave portion 80 of the barrier rib 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 surface of the light emitting layer 209 on the anode 206 .

The anode 206 constitutes 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 penetration of moisture or oxygen into the organic EL element. This passivation film 211 is formed on the cathode 210 .

The sealing substrate 212 seals the main surface on which the light emitting layer 209 is disposed (opposite to the supporting substrate 202). It is preferable to seal the main surface on which the light emitting layer 209 is disposed with a sealing substrate 212 via a sealing layer 213 using a sealant (not shown) applied near the outer circumferential end of the TFT substrate. Do. 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 barrier rib 208 can be formed using a low-absorbent radiation-sensitive resin composition, and these interlayer insulating film 205, the barrier rib ( In the formation step of 208), a treatment such as washing using a low-absorbent material is possible. Therefore, it is possible to reduce the gradual intrusion of a small amount of moisture contained in the insulating film forming material in the form of an adsorbate or the like into the light emitting layer 209, thereby reducing deterioration of the light emitting layer 209 and deterioration of the light emitting state.

«Fourth Embodiment»

(Radiation-sensitive resin composition)

The radiation-sensitive resin composition of the fourth embodiment of the present invention can form a patterned cured film by utilizing its radiation-sensitive properties. The radiation-sensitive resin composition according to the present embodiment is suitably used for forming an 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. . That is, it is suitable for manufacturing an interlayer insulating film, which is a main component of the thin film transistor substrate of the first embodiment of the present invention, the liquid crystal display of the second embodiment of the present invention, and the organic EL element of the third embodiment of the present invention. it is used By using the radiation-sensitive resin composition for forming the interlayer insulating film, whitening and outgassing during high-temperature treatment are suppressed, and an interlayer insulating film having good solvent resistance is obtained. Moreover, in the said radiation-sensitive resin composition, storage stability can also be improved by setting it as an appropriate component composition.

The radiation-sensitive resin composition of the fourth embodiment of the present invention includes [A] polymer (hereinafter, simply referred to as component [A]), [B] photosensitizer (hereinafter, also referred to simply as component [B]), and [C] A compound represented by the following formula (3) (hereinafter, simply referred to as a [C] component or a [C] compound) is contained as an essential component.

(In Formula (3), X represents a hydroxyl group, a thiol group, a carboxyl group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring.)

In addition to component [A], component [B], and component [C], other optional components may be contained as long as the effect of the present invention is not impaired. For example, the compound [D] described later (hereinafter, simply referred to as component [D]) functioning as a curing accelerator may be contained.

Hereinafter, each component contained in the radiation-sensitive resin composition of the present embodiment is described in detail.

<[A] Polymer>

[A] A polymer is a component used as a base material of the cured film obtained. [A] As a polymer, normally, the well-known polymer contained in the radiation-sensitive resin composition for cured film formation can be used individually or in mixture of 2 or more types. [A] The polymer is preferably an alkali-soluble resin. By being an alkali-soluble resin, patterning using an alkali developing solution becomes possible. [A] As the polymer, polysiloxane can be suitably used.

(Polysiloxane)

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 a photoacid generator [B-2], which is the photosensitizer described later, or a base generated from a photobase generator [B-3] as a catalyst, for example.

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

In Formula (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, they may be the same or different.

Examples of the non-hydrolyzable organic group of 1 to 20 carbon atoms represented by R ²⁰ include an alkyl group of 1 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, and an aralkyl group of 7 to 12 carbon atoms. These 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.

As a C1-C4 alkyl group represented by said R< ²¹ >, a methyl group, an ethyl group, n-propyl group, i-propyl group, a butyl group, etc. are mentioned. q is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 and 1, 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 increases, and the strength, adhesion and the like of the resulting cured film can be improved.

As specific examples of the hydrolyzable silane compound represented by the above formula (4),

As a silane compound substituted with four hydrolysable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, etc.

As a silane compound substituted with one non-hydrolysable group and three hydrolysable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

As a silane compound substituted with two non-hydrolysable groups and two hydrolysable groups, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, etc.

Examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include tributyl methoxysilane, trimethyl methoxysilane, trimethyl ethoxysilane, and tributyl ethoxysilane.

Among these hydrolysable silane compounds represented by the above formula (4), silane compounds substituted with four hydrolysable groups and silane compounds substituted with one non-hydrolysable group and three hydrolysable groups are preferable, and one non-hydrolyzable group A silane compound substituted with three hydrolysable groups is more preferred. Specific examples of preferred hydrolysable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, and ethyltrimethyx. Toxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyl triethoxysilane is mentioned. These hydrolyzable silane compounds may be used individually by 1 type, or may be used in combination of 2 or more types.

The conditions for hydrolytic condensation of the hydrolysable silane compound represented by the above formula (4) are to hydrolyze at least a part of the hydrolyzable silane compound represented by the above formula (4) to convert the hydrolysable group into a silanol group, thereby starting a condensation reaction. It is not particularly limited as long as it is caused, but as an example, it can be implemented as follows.

It is preferable to use water purified by methods such as reverse osmosis membrane treatment, ion exchange treatment, and distillation as the water used for hydrolytic condensation of the hydrolyzable silane compound represented by the above 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 hydrolytic condensation of the hydrolyzable silane compound represented by the above formula (4) is not particularly limited, but examples thereof include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, and propylene glycol monoalkyl. ethers, propylene glycol monoalkyl ether acetates, propionic acid esters, arylalkanols, aryloxyalkanols and the like. Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 3-methoxymethylpropionate, benzyl alcohol, 2-phenylethylalkane Ol and phenoxyethanol are preferred. In the case where phenylalkanol or phenoxyalkanol is used as the solvent, the phenylalkanol or phenoxyalkanol is not used in the hydrolytic condensation reaction and remains after the reaction. For this reason, you may use phenylalkanol or phenoxyalkanol contained in the solution after the said hydrolytic condensation reaction as component [C].

The hydrolysis/condensation reaction of the hydrolyzable silane compound represented by the above formula (4) is preferably performed using 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 resins, various Lewis acids, etc.), base catalysts (eg, ammonia, primary amines, secondary amines, tertiary amines, nitrogen compounds such as pyridine, basic ion exchange resins, hydroxides) Hydroxides such as sodium, carbonates such as potassium carbonate, carbonates such as sodium acetate, various Lewis bases, etc.) or alkoxides (eg, zirconium alkoxide, titanium alkoxide, aluminum alkoxide, etc.).

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

As a lower limit of the weight average molecular weight (Mw) of the hydrolytic condensation product of the hydrolysable silane compound represented by said formula (4), 500 is preferable normally, and 1000 is more preferable. On the other hand, as this upper limit, 20000 is preferable and 10000 is more preferable.

As a lower limit of the number average molecular weight (Mn) of the hydrolyzed condensate of the hydrolyzable silane compound represented by the formula (4), usually 500 is preferable, 1000 is more preferable, and 2500 is still more preferable. By setting the number average molecular weight of the hydrolyzed condensate of the hydrolyzable silane compound represented by the formula (4) above the lower limit, the effect of the present invention can be further enhanced, storage stability and solvent resistance of the obtained interlayer insulating film can be improved. On the other hand, as an upper limit of this Mn, 20000 is preferable, 10000 is more preferable, and 5000 is still more preferable.

As 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), 1.1 is usually preferable, 2 is more preferable in some cases, and 3 is more preferable in some cases. By setting the molecular weight distribution of the hydrolyzed condensate of the hydrolyzable silane compound represented by the formula (4) above the lower limit, the effect of the present invention can be further enhanced, storage stability and solvent resistance of the obtained interlayer insulating film can be further improved. On the other hand, as an upper limit of this molecular weight distribution, it is 5, for example, and 4 is preferable.

In addition, Mw and Mn of the polymer in this specification are taken as values measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: Showa Denko's "GPC-101"

Column: combine 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 material: monodisperse polystyrene

<[A] content of polymer>

Although it does not specifically limit as a lower limit of content of the [A] polymer in a radiation sensitive resin composition, It is 50 mass %, for example in conversion of solid content, and 60 mass % is preferable. On the other hand, as this upper limit, 99 mass % is preferable and 95 mass % is more preferable.

<[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 initiating polymerization by generating radicals in response to radiation (namely, [B-1] photo-radical polymerization initiator) , a compound that generates an acid in response to radiation (ie, [B-2] photoacid generator), or a compound that generates a base in response to radiation (ie, [B-3] photobase generator). there is.

Examples of such a [B-1] radical photopolymerization initiator include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and phosphine oxide compounds. These compounds may be used individually by 1 type, and may mix and use 2 or more types.

Examples of the O-acyloxime compound include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-octane-1- Onoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-oneoxime-O-benzoate, 1-[9- n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2- Methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetra Hydropyranylbenzoyl) -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- dioxolanil) methoxybenzoyl} -9H-carbazol-3-yl] -1-(O-acetyloxime); and the like.

Among these, 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole-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-acetyloxime) is preferable.

Examples of the acetophenone compound include α-amino ketone compounds and α-hydroxy ketone compounds.

As an α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl) -1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, etc. there is.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropane. -1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned.

As the acetophenone compound, an α-amino ketone compound is preferable, particularly 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-( 4-Methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1- On is preferred.

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

[B-1] Radical photopolymerization initiator can be used individually or in mixture of 2 or more types as mentioned above. As a lower limit of the content of the radical photopolymerization initiator [B-1] with respect to 100 parts by mass of the [A] component, 1 part by mass is preferable, and 5 parts by mass is more preferable. As an upper limit of content of the said radical photopolymerization initiator [B-1], 40 mass parts is preferable and 30 mass parts is more preferable. [B-1] By setting the content of the radical photopolymerization initiator within the above range, the radiation-sensitive resin composition can form a cured film having high solvent resistance, high hardness and high adhesion even at a low exposure amount.

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

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

In the above formula (B1), R ^A is an alkyl group of 1 to 12 carbon atoms, a fluoroalkyl group of 1 to 12 carbon atoms, an alicyclic hydrocarbon group of 4 to 12 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an alkyl group or an alicyclic group of these groups. It is a group in which some or all of the hydrogen atoms of the formula hydrocarbon group and aryl group are substituted with substituents.

As the alkyl group represented by R ^A in the formula (B1), a linear or branched alkyl group having 1 to 12 carbon atoms is preferable. This 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, a 7,7-dimethyl-2-oxonorbornyl group, and the like. and an alicyclic group including a bridged alicyclic group of . As a C1-C12 fluoroalkyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptylfluoropropyl group, etc. are mentioned.

As an alicyclic hydrocarbon group represented by said R ^A , a C4-C12 alicyclic hydrocarbon group is preferable. This C4-C12 alicyclic hydrocarbon group may be substituted by the substituent, and as said substituent, a C1-C5 alkyl group, an alkoxy group, a halogen atom etc. are mentioned, for example.

As the aryl group represented by R ^A , an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group, a naphthyl group, a tolyl group, and 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, and a halogen atom.

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

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(4-methylphenylsulfonyloxy)succinimide. , N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N -(Camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoro Methylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)- 1, 8- naphthalimide etc. are mentioned.

In addition, as described above, the radiation-sensitive resin composition of the present embodiment can contain a quinonediazide compound as the [B-2] photoacid generator that is the [B] photosensitizer. The radiation-sensitive resin composition of this embodiment can be used as a positive radiation-sensitive resin composition by containing a quinonediazide compound. And the light-shielding property of the cured film after formation can be provided. In addition, it is possible to adjust the transmittance of light in the visible region of the formed cured film by the photobleach performance.

[B-2] A quinonediazide compound that can be used as a photoacid generator is a quinonediazide compound that generates carbonic acid when irradiated with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother core") and a 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

As trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc. are mentioned, for example.

As tetrahydroxybenzophenone, for example, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4' -Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc. can

As pentahydroxy benzophenone, 2,3,4,2', 6'- pentahydroxy benzophenone etc. are mentioned, for example.

As hexahydroxybenzophenone, for example, 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxy Benzophenone etc. are mentioned.

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'-spirobiindene- 5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc. are mentioned.

As other mother nuclei, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 1-[1-{3 -(1-[4-hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]-3-[1-{3-(1-[4-hydroxy Phenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1, 3-dihydroxybenzene etc. are mentioned.

Among these parent nuclei, tetrahydroxybenzophenone and (polyhydroxyphenyl)alkane are preferred, and 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl) Ethane and 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol are more preferred.

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

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

Moreover, as a quinonediazide compound, the 1, 2- naphthoquinonediazide sulfonic acid amides which changed the ester bond of the parent nucleus into an amide bond exemplified above, for example, 2,3,4-triaminobenzophenone- 1,2-naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

These quinonediazide compounds can be used individually or in combination of 2 or more types.

Although the content of the quinonediazide compound in the radiation-sensitive resin composition of the present embodiment can be set within the range described later, by setting it in such a range, the irradiated portion and the unirradiated portion of the radiation to the aqueous solution of the alkali compound serving as the developing solution By increasing the difference in solubility of , it is possible to improve patterning performance. Moreover, the solvent resistance of the cured film obtained using this radiation-sensitive resin composition can also be made favorable.

[B-2] As the photoacid generator, oxime sulfonate compounds, onium salts, sulfonimide compounds, and quinonediazide compounds are preferable, oxime sulfonate compounds and quinonediazide compounds are more preferable, and quinonediazide compounds are more preferred.

As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4 -Hydroxyphenylmethylsulfonium hexafluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is still more preferable. As the sulfonic acid ester compound, a haloalkyl sulfonic acid ester is preferable, and an N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable. [B-2] By using the compound as the photoacid generator, the radiation-sensitive resin composition of the present embodiment obtained can improve sensitivity and solubility.

As a lower limit of the content of the [B-2] photoacid generator with respect to 100 parts by mass of the [A] component, 0.1 parts by mass or more is preferable, and 1 part by mass 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 is optimized, and a cured film with high surface hardness can be formed.

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

Examples of the above transition metal complex include bromopentammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate, Hexapropylamine cobalt perchlorate etc. are mentioned.

As orthonitrobenzyl carbamates, for example, [[(2-nitrobenzyl)oxy]carbonyl]methylamine, [[(2-nitrobenzyl)oxy]carbonyl]propylamine, [[(2-nitrobenzyl)oxy]carbonyl] Benzyl)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-dinitrobenzyl)oxy]carbonyl]hexamethylenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbo Nyl]phenylenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]toluenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl)oxy]carbonyl]piperazine etc. are mentioned.

Examples of α,α-dimethyl-3,5-dimethoxybenzylcarbamates 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]hexamethylenediamine, Bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]phenylenediamine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl] Toluenediamine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]diaminodiphenylmethane, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine and the like.

Examples of acyloxyiminos include 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, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime, etc. are mentioned.

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

[B-3] The photobase generator may be used individually by 1 type, or may be used in mixture of 2 or more types. Further, the [B-3] photobase generator and the [B-2] photobase generator may be used together as long as the effects of the present invention are not impaired.

The lower limit of the content of the [B-3] photobase generator relative to 100 parts by mass of the component [A] is preferably 0.1 part by mass, more preferably 1 part by mass. As an upper limit of content of the 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 within the above range, it is possible to obtain a radiation-sensitive composition excellent in balance in melt flow resistance and heat resistance of the cured film to be formed, and also in the formation step of the coating film. It becomes possible to prevent the generation of precipitates and to facilitate the formation of a coating film.

<[C] compound>

Component [C] 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 hydroxyl group, a thiol group, a carboxyl group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring.)

Component [C] of the radiation-sensitive resin composition of the present embodiment enables introduction of the structure represented by the formula (1) into [A] polymer in a cured film formed using the radiation-sensitive resin composition. become an ingredient. That is, component [C] is introduced into a polymer in the interlayer insulating film of a thin film transistor substrate or liquid crystal display element formed using the radiation-sensitive resin composition of the fourth embodiment of the present invention to suppress whitening during high-temperature treatment. becomes a component that enables

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 included in the interlayer insulating film of the first embodiment. During prebaking at the time of forming a cured film (interlayer insulating film) using the radiation-sensitive resin composition according to the present embodiment, a hydrolyzable group in polysiloxane, which is component [A], or a group generated by hydrolysis of a hydrolyzable group (eg For example, a hydroxyl group) and component [C] can efficiently introduce a predetermined structure represented by the formula (1) of the polymer in the thin film transistor substrate according to the first embodiment.

Therefore, as a specific example of the monovalent organic group containing an aromatic ring of component [C], the aryl group, aralkyl group, etc. described as the monovalent organic group containing an aromatic ring in the polymer included in the interlayer insulating film of the first embodiment are preferable. Do.

As a specific example of component [C],

When X is a hydroxyl group, phenol, naphthol, benzyl alcohol, phenoxyethanol, 2-phenylethyl alcohol, etc.;

When X is a thiol group, benzenethiol, naphthalenethiol, etc.

When X is a carboxyl group, benzoic acid, carboxymethylbenzene, etc.

When X is an amino group, aniline, benzylamine, etc.

can be heard

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

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

In the radiation-sensitive resin composition of the fourth embodiment of the present invention, the content of compound [C] is not particularly limited, but the lower limit thereof is preferably 10 parts by mass with respect to 100 parts by mass of component [A], and 20 Part by mass is more preferable, and the upper limit is preferably 400 parts by mass, more preferably 200 parts by mass, and still more preferably 100 parts by mass. When the content of the [C] compound is less than the lower limit, the effect of suppressing whitening of the interlayer insulating film may not be sufficiently obtained. Conversely, when the content of the compound [C] exceeds the above upper limit, there is a possibility that the developability may decrease during pattern formation.

In addition, in the radiation-sensitive resin composition of the present embodiment, although the [C] compound is added as a component different from the [A] polymer, it is not limited to this, and the [C] compound at the time of synthesizing the [A] polymer may be added to introduce the structure of the above formula (1) into the [A] polymer. In addition, at the time of synthesizing polymer [A], compound [C] is added, the structure of the above formula (1) is introduced into polymer [A], and compound [C] is further contained as a component different from this polymer. You can do it.

<Other optional ingredients>

The radiation-sensitive resin composition of the embodiment of the present invention may contain a [D] compound having a function as a curing accelerator in addition to the above-described [A] polymer, [B] photosensitizer, and [C] compound. In addition, the radiation-sensitive resin composition of the embodiment of the present invention, in addition to the dispersant and dispersion medium used together with the [C] compound, a surfactant, a storage stabilizer, and an adhesion promoter as necessary within a range that does not impair the effects of the present invention , and other optional components such as a heat resistance improver. Other arbitrary components may be used individually by 1 type, and may mix and use 2 or more types. Hereinafter, each component is demonstrated.

[Surfactants]

The surfactant that can be contained in the radiation-sensitive resin composition of the present embodiment can be added to improve the applicability of the radiation-sensitive resin composition, to reduce the application unevenness, and to improve the developability of the radiation-irradiated portion. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

Examples of the fluorochemical surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 Fluoroethers such as 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecylsulfonic acid Fluoroalkanes such as sodium, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonates, fluoroalkyloxyethylene ethers, fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols, perfluoroalkylalkoxylates, Fluorine-type alkyl esters etc. are mentioned.

As commercially available products of these fluorine-based surfactants, Ftop (registered trademark) EF301, 303, 352 (manufactured by Shin-Akitaka Chemical Co., Ltd.), Megapack (registered trademark) F171, 172, 173 (manufactured by DIC Corporation), Florad FC430, 431 ( Sumitomo 3M Co.), Asahi Guard AG (registered trademark) 710 (Asahi Glass Co., Ltd.), Saffron (registered trademark) S-382, SC-101, 102, 103, 104, 105, 106 (AGC Seimi Chemical Co., Ltd.) manufacture), FTX-218 (manufactured by Neos), and the like.

Examples of silicone surfactants are commercially available trade names, namely SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH 8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ) and the like.

In the case of using a surfactant as the other optional component, the lower limit of the content of the surfactant with respect to 100 parts by mass of the [A] component is preferably 0.01 part by mass, more preferably 0.05 part 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|paintability of the radiation-sensitive resin composition of this embodiment can be optimized.

[Preservation 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. are mentioned.

[Adhesion aid]

The adhesion promoter can be used for the purpose of further improving adhesion between an interlayer insulating film obtained from the radiation-sensitive resin composition of the present embodiment and an auxiliary capacitance electrode, a planarization film, or the like, disposed under the interlayer insulating film. As the adhesive aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferably used, and examples thereof include trimethoxysilylbenzoic acid, γ- Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclo Hexyl) ethyltrimethoxysilane etc. are mentioned.

<Preparation of radiation-sensitive resin composition>

In the radiation-sensitive resin composition of the embodiment of the present invention, in addition to the above-described [A] polymer, [B] photosensitizer, and [C] compound, if necessary, a [D] compound, a surfactant as other optional components, and the like prepared by mixing. At this time, an organic solvent can be used to prepare the radiation-sensitive resin composition in a dispersion state. An organic solvent can be used individually by 1 type or in mixture of 2 or more types.

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

Examples of the organic solvent that can be used in the radiation-sensitive resin composition of the present embodiment include those that do not react with other contained components while dissolving or dispersing other contained components.

For example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, ethyl lactate, and γ-butyro Lactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, esters such as methyl-3-methoxypropionate, polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethers such as propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. can

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

As a dispersion method for preparing the radiation-sensitive resin composition in a dispersion state, a decrease in particle size is not observed at a circumferential speed of 5 m/s to 15 m/s using a paint shaker, SC mill, anura type mill, pin type mill, etc. It is good if it is done by a method that continues until As this duration, it is usually several hours. In this dispersion, it is preferable to use dispersion beads such as glass beads and zirconia beads. As a lower limit of this bead diameter, 0.05 mm is preferable and 0.08 mm is more preferable. As an upper limit of the said bead diameter, 0.5 mm is preferable and 0.2 mm is more preferable.

<<Fifth Embodiment>>

<Method of manufacturing thin film transistor substrate>

A method for manufacturing a thin film transistor substrate, which is an example of the fifth embodiment of the present invention, is a step of forming a cured film on a substrate using the radiation-sensitive resin composition of the fourth embodiment described above and configuring it as an interlayer insulating film. It is included as this main process. And, in the manufacturing method of the thin film transistor substrate of this embodiment, the thin film transistor substrate 100 of the 1st embodiment of this invention shown in FIG. 1 can be manufactured easily, for example.

Hereinafter, a method of manufacturing a thin film transistor substrate as an example of the fifth embodiment of the present invention will be described by taking the 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 manufacturing method of the thin film transistor substrate 100 of this embodiment, as shown in FIG. 1 , an interlayer insulating film is formed on the substrate 1 on which the TFT 2, the planarization film 5, and the storage capacitance electrode 3 are formed. (6) is formed. Then, between the TFT 2 and the flattening film 5 on the substrate 1, an inorganic insulating film 4 can be formed to cover and protect the TFT 2. This inorganic insulating film 4 also covers the common wiring 17 to which the auxiliary capacitance electrode 3 electrically connects with the TFT 2 on the substrate 1 .

The manufacturing method of the thin film transistor substrate of the present embodiment preferably includes the following steps [1] to steps [4] in this order in order to form the interlayer insulating film 6 on the above-described substrate 1. . After that, on the substrate 1 on which the interlayer insulating film 6 is formed, the pixel electrode 7 can be formed on the interlayer insulating film 6 according to a known method, and the thin film transistor substrate 100 can be manufactured. there is.

Step [1] to step [4] included in the method for manufacturing a thin film transistor substrate of the present embodiment are as shown below.

[1] A step of forming a coating film of the radiation-sensitive resin composition according to the fourth embodiment of the present invention on the substrate 1 (hereinafter sometimes referred to as “step [1]”)

[2] A step of irradiating radiation to at least a part of the coating film of the radiation-sensitive resin composition formed in the [1] step (hereinafter sometimes referred to as “[2] step”)

[3] Step of developing the coating film irradiated with radiation in step [2] (hereinafter, sometimes referred to as "step [3]")

[4] Step of heating the coating film developed in step [3] (hereinafter sometimes referred to as "step [4]")

Hereinafter, the [1] process - [4] process are demonstrated.

[Process [1]]

In this step, a coating film of the radiation-sensitive resin composition according to the fourth embodiment of the present invention is formed on the substrate 1. In addition to the TFT 2 as a switching element, a common wiring 17 and various types of wiring such as gate wiring and signal wiring not shown are formed on the substrate 1. Then, an inorganic insulating film 4 is formed on the TFT 2 to protect it, and the inorganic insulating film 4 also covers the common wiring 17 . Further, on the inorganic insulating film 4, a planarization film 5 formed with through-holes forming part of the contact holes 18, patterned according to a known method, is disposed. 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 planarization film 5 can be made of, for example, a film made of acrylic resin, polyimide resin, polysiloxane, or novolak resin.

On top of the planarization film 5, an auxiliary capacitance electrode 3 electrically connected to a common wiring 17 via a contact hole 18 passing through the planarization film 5 and the inorganic insulating film 4 is disposed. . The contact hole 18 is formed using a through hole formed by patterning the planarization film 5 . That is, the contact hole 18 is formed by forming a through hole continuous with the through hole of the planarization film 5 in the inorganic insulating film 4 by etching using the planarization film 5 in which the through hole is formed by patterning as a mask. , formed as a through hole penetrating the planarization film 5 and the inorganic insulating film 4. Then, the auxiliary capacitance electrode 3 is formed by forming a film made of, for example, a light-transmitting conductive material such as ITO on the planarization film 5 by using a sputtering method or the like, and then patterning it by using a photolithography method or the like. is formed by

Further, in the planarization film 5, it is preferable to also form a through hole forming a part of the contact hole 19 at the time of patterning to form a through hole forming a part of the contact hole 18. As will be described later, these through holes are formed so as to be continuous with the through holes formed in the interlayer insulating film 6, and each can form a part of the contact hole 19.

As described above, the TFT 2, the common wiring 17, etc., the inorganic insulating film 4, the planarization film 5, and the storage capacitance electrode 3 formed on the substrate 1 are, as described above, known It is formed using a method for manufacturing a thin film transistor substrate. For example, the TFT 2 is formed on the substrate 1 by a known method, such as by repeating a normal semiconductor film formation, a known insulating layer formation, and the like, and etching by a photolithography method. The common wiring 17 and the like, the inorganic insulating film 4, the planarization film 5, the auxiliary capacitance electrode 3, and the like are also formed by known methods. Therefore, a more detailed description of their formation is omitted.

In this step, using the substrate 1 described above, the radiation-sensitive resin composition of the fourth embodiment of the present invention is applied to the surface on which the TFTs 2, storage capacitance electrodes 3, etc. are formed, and then free Baking is performed to evaporate the solvent to form a coating film.

In the substrate 1 described above, as the constituent material, for example, a glass substrate such as soda-lime glass or non-alkali glass, a quartz substrate, a silicon substrate, or an acrylic resin, polyethylene terephthalate, or polybutylene terephthalate , resin substrates such as polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide and polyimide; and the like. In addition, it is preferable to give pre-processing, such as washing|cleaning and pre-annealing, to these board|substrates if desired. Examples of the pretreatment of the substrate include chemical treatment using a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, and the like.

Examples of the application method of the radiation-sensitive resin composition include a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method), and a bar coating method. , an appropriate method such as an inkjet coating method can be employed. Among these, a spin coating method or a 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 type of each component constituting the radiation-sensitive resin composition, the blending ratio, etc., it is preferable to carry out at a temperature of 70 ° C. to 120 ° C., and the time is such as a hot plate or oven. Although it differs depending on the heating device, it is about 1 minute to 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 an upper limit of the said average film thickness, 10 micrometers are preferable and 7.0 micrometers are more preferable.

[Process [2]]

Next, radiation is irradiated 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, it is carried out through a photomask having a pattern corresponding to the formation of the desired contact hole 19, for example.

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

The lower limit of the radiation dose (also referred to as exposure dose) is a value obtained by measuring the intensity of the irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), preferably 10 J/m 2 , and 100 J /m 2 is more preferable, and 200 J/m 2 is even 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, and 3000 J/m<2> is still more preferable.

[Process [3]]

Next, the coating film after radiation irradiation in step [2] is developed to remove unnecessary portions, and a patterned coating film in which through-holes of a predetermined shape constituting a part of the contact hole 19 are formed is obtained. In addition, the through hole of the coating film formed in this step is formed so as to be continuous with the through hole forming a part of the contact hole 19 formed in the above-mentioned planarization film 5.

Examples of the developing solution used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline and 1,8- Aqueous solutions of alkaline compounds such as 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 above aqueous solution of the alkaline compound before use. In addition, a surfactant may be used alone or in an appropriate amount together with the above-described water-soluble organic solvent.

The developing method may be any of a puddle method, a dipping method, a shower method, a spray method, and the like. The lower limit of the developing time is preferably 5 seconds at room temperature, more preferably 10 seconds, and the upper limit of the developing time is room temperature. 300 seconds is preferable, and 180 seconds is more preferable. After the developing treatment, for example, running water washing is performed for 30 seconds or more and 90 seconds or less, and then air-dried with compressed air or compressed nitrogen to obtain a coating film having a desired pattern.

[Process [4]]

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

As described above, the interlayer insulating film 6 is formed using the radiation-sensitive resin composition of the fourth embodiment of the present invention, and the dielectric constant is controlled to a desired value. The interlayer insulating film 6 can be configured to have a higher dielectric constant than, for example, a normal organic film.

As for the average film thickness of the interlayer insulating film 6, 0.3 micrometer or more and 6 micrometers or less are preferable.

In the manufacturing method of the thin film transistor substrate of this embodiment, the pixel electrode 7 is formed on the interlayer insulating film 6 formed on the board|substrate 1 after process [4]. The pixel electrode 7 is 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, thereby Connect to TFT(2).

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

Then, the contact hole 19 is continuous with the through hole of the planarization film 5 and the interlayer insulating film by etching using the planarization film 5 and the interlayer insulating film 6 as a mask, in which through holes continuously pass through are formed, It is formed by forming a through hole in the inorganic insulating film 4. That is, the contact hole 19 is formed as a through hole that continuously passes through the interlayer insulating film 6, the planarization film 5, and the inorganic insulating film 4 in this order.

After that, the formation of the pixel electrode 7 is performed by forming a film made of a light-transmitting conductive material such as ITO on the interlayer insulating film 6 by using a sputtering method or the like, and then using a photolithography method or the like. It is done by patterning. The formed pixel electrode 7 is connected to the TFT 2 via the contact hole 19 as described above.

Further, the pixel electrode 7 and the storage capacitance electrode 3 are arranged to face each other on the substrate 1 via the interlayer insulating film 6 .

As described above, the method for manufacturing a thin film transistor substrate, which is an example of the fifth embodiment of the present invention, includes a substrate 1, a TFT 2 disposed on the substrate 1, and flattening covering the TFT 2 film 5, the interlayer insulating film 6 covering the planarization film 5, the pixel electrode 7 disposed on the interlayer insulating film 6 and connected to the TFT 2, and the interlayer insulating film 6 The thin film transistor substrate 100 having the storage capacitance electrode 3 disposed between the interlayer insulating film 6 and the planarization film 5 to face the pixel electrode 7 can be manufactured.

An alignment film may be formed on the surface of the manufactured thin film transistor substrate 100 on the side where the TFTs 2 and the like are disposed for the purpose of controlling alignment of liquid crystals.

And, the thin film transistor substrate 100 can constitute the liquid crystal display element of the second embodiment of the present invention described above.

[Example]

Synthesis examples and examples are shown below to explain the present invention more specifically, 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.

Apparatus: GPC-101 (manufactured by Showa Denko)

Column: 1, a combination of GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko)

Mobile phase: tetrahydrofuran

<Synthesis example of hydrolytic condensation product of hydrolysable silane compound of component [A]>

[Synthesis Example 1]

63.0 g (0.46 mol) of methyltrimethoxysilane, 96.3 g (0.46 mol) of tetraethoxysilane, and 47.3 g of ion-exchanged water were put into a container with a stirrer, and it was heated until the solution temperature reached 60°C. After the solution temperature reached 60°C, a 4.4% by mass benzyl alcohol solution of oxalic acid was introduced, heated until it reached 75°C, and held for 3 hours. Furthermore, the temperature of the solution was set to 40°C, and ion-exchanged water and methanol and ethanol generated by hydrolytic condensation were removed by subjecting the solution to evaporation while maintaining this temperature. Next, 80 g of benzyl alcohol was added and the distribution was repeated again. After evaporation, benzyl alcohol was further added so that the solid content concentration might be 40% by mass. By the above, the hydrolysis condensation product (A-1) was obtained. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 2346, and the molecular weight distribution (Mw/Mn) was 2.2.

[Synthesis Example 2]

A hydrolysis condensate (A-2) was obtained in the same experiment except that benzyl alcohol in Synthesis Example 1 was replaced with 2-phenoxyethanol. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 1623, and the molecular weight distribution (Mw/Mn) was 1.4.

[Synthesis Example 3]

A hydrolysis condensate (A-3) was obtained in the same experiment except that benzyl alcohol in Synthesis Example 1 was replaced with 2-phenylethyl alcohol. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 1450, and the molecular weight distribution (Mw/Mn) was 1.3.

[Synthesis Example 4]

89.7 g (0.66 mol) of methyltrimethoxysilane, 68.5 g (0.33 mol) of tetraethoxysilane, and 48.1 g of ion-exchanged water were put into a container with a stirrer, and heated until the solution temperature reached 60°C. After the solution temperature reached 60°C, a 4.4% by mass propylene glycol monomethyl ether solution of oxalic acid was introduced, heated until it reached 75°C, and held for 3 hours. Furthermore, the temperature of the solution was set to 40°C, and ion-exchanged water and methanol and ethanol generated by hydrolytic condensation were removed by subjecting the solution to evaporation while maintaining this temperature. Next, 80 g of propylene glycol monomethyl ether was added, and the distribution was repeated again. After evaporation, propylene glycol monomethyl ether was further added so that the solid content concentration would be 40% by mass. By the above, the hydrolysis condensation product (A-4) was obtained. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 2978, and the molecular weight distribution (Mw/Mn) was 3.7.

[Synthesis Example 5]

Into a container 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 47.0 g of ion-exchanged water were charged, It was heated until the solution temperature became 60 degreeC. After the solution temperature reached 60°C, a 4.4% by mass benzyl alcohol solution of oxalic acid was introduced, heated until it reached 75°C, and held for 3 hours. Furthermore, the temperature of the solution was set to 40°C, and ion-exchanged water and methanol and ethanol generated by hydrolytic condensation were removed by subjecting the solution to evaporation while maintaining this temperature. Next, 80 g of benzyl alcohol was added and the distribution was repeated again. After evaporation, benzyl alcohol was further added so that the solid content concentration might be 40% by mass. By the above, the hydrolysis condensation product (A-5) was obtained. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 2285, and the molecular weight distribution (Mw/Mn) was 2.1.

[Synthesis Example 6]

A hydrolysis condensate (A-6) was obtained in the same experiment except that benzyl alcohol in Synthesis Example 1 was replaced with propylene glycol monomethyl ether. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 1450, and the molecular weight distribution (Mw/Mn) was 1.3.

[Synthesis Example 7]

A hydrolysis condensate (A-7) was obtained in the same experiment except that benzyl alcohol in Synthesis Example 1 was replaced with diethylene glycol methyl ethyl ether. The number average molecular weight (Mn) of the obtained hydrolysis condensate was 2561, and the molecular weight distribution (Mw/Mn) was 2.6.

[Synthesis Example 8]

A hydrolysis condensate (A-8) was obtained in the same experiment except that benzyl alcohol in Synthesis Example 5 was replaced with propylene glycol monomethyl ether. The number average molecular weight (Mn) of the obtained hydrolysis 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 hydrolysis-condensation product (A-1) obtained in Synthesis Example 1 (amount corresponding to 100 parts by mass (solid content) of the hydrolysis-condensation product (A-1), containing 150 parts by mass of benzyl alcohol as component [C]) ), as [B] component (B-1) 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol ) and 20 parts by mass of a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol), and 0.1 part by mass of "SH8400FLUID" manufactured by Toray Dow Corning as [F] surfactant, the solid content concentration is A solvent (benzyl alcohol/propylene glycol monomethyl ether = 80/20 (mass %)) was added so as to become 27 mass %, and a radiation-sensitive resin composition was prepared. In addition, the solid content concentration in this Example refers to the mass of all components (radiation-sensitive resin composition), hydrolysis condensates (A-1) to (A-8) (solid content), photosensitizer (B-1 ) to (B-2), compounds (C-1) to (C-4), and surfactant (F-1).

[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 type and amount of each component and the solid content concentration were set as shown in Table 1.

<Evaluation of physical properties>

Using the radiation-sensitive resin composition prepared as described above, various properties of the composition and cured films formed from the composition were evaluated as follows.

[Evaluation of Whitening and Transmittance of Cured Film]

On a glass substrate, after apply|coating each composition using a spinner, it prebaked on a hot plate at 90 degreeC for 2 minute(s), and the coating film of average film thickness of 3.0 micrometer was formed. The obtained coating film was exposed using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc., so that the cumulative irradiation amount was 3,000 J/m 2 , and then heated at 230° C. for 1 hour in a clean oven to obtain a cured film. . In order to investigate the degree of whitening of this cured film, irregularities of 3 µm square were observed by AFM "Dimension 3100" (manufactured by Veeco). From the correlation with the degree of whitening with the naked eye, "A" when the average roughness Ra is 1 ≤ Ra < 4, "B" when 4 ≤ Ra < 7, "C" when 7 ≤ Ra < 10, The case of 10≤Ra was set as "D". The case of "A" to "C" was evaluated as good, and the case of "D" was evaluated as poor. The results are shown in Table 1.

In addition, the light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 300 to 500 nm using a spectrophotometer "150-20 type double beam" (manufactured by Hitachi, Ltd.). Table 1 shows the values of the lowest light transmittance at that time. When the minimum light transmittance is 95% or more, the light transmittance can be said to be good.

[Evaluation of outgas]

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, n-octane was used as a standard substance (specific gravity = 0.701, injection amount, 0.02 μl), and the purge conditions were 100 ° C. / 10 minutes, and head space gas chromatography / mass spectrometry (head space gas chromatography / mass spectrometry (head Space sampler: JHS-100A manufactured by Nippon Bunseki Kogyo Co., Ltd., gas chromatography/mass spectrometer, JMS-AX505W mass spectrometer manufactured by JEOL), and the peak area A derived from the compound having each aromatic ring was determined, The volatilization amount of the compound having each aromatic ring in terms of n-octane was calculated by the calculation formula, and the sum of these was taken as the volatilization amount (μg) of the aromatic ring compound. When this volatilization amount exceeded 0.5 microgram, 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 an aromatic ring = A×(amount of n-octane) (μg)/(peak area of n-octane)

[Evaluation of solvent resistance]

After coating the composition solution on a substrate, it was dried to form a film. The obtained coating film was exposed to light with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation amount was 3,000 J/m 2 without a pattern mask interposed therebetween, and the silicon substrate was heated at 230° C. for 30 minutes in a clean oven. A cured film having an average film thickness of 3.0 μm was obtained. The average film thickness (T1) of the cured film obtained here was measured. And, after immersing the silicon substrate with this cured film formed in N-methyl-2-pyrrolidone temperature-controlled at 45 degreeC for 6 minutes, the average film thickness (t1) of this cured film was measured, and the average film thickness by immersion was measured. The rate of change {|t1-T1|/T1} x 100 [%] was calculated. The results are shown in Table 1 as solvent resistance. When this value is 8% or less, it can be said that solvent resistance is good.

[Evaluation of storage stability]

The composition solution was heated in an oven at 40° C. for one week, and the obtained sample was applied onto a substrate and then dried to form a film. Then, using an exposure machine ("MPA-600FA (ghi line mixing)" manufactured by Canon Inc.), the exposure amount to the coating film was varied through a mask having a 10 µm line-and-space (1 to 1) pattern. was irradiated with radiation. Then, it developed by the puddle method for 80 second in 25 degreeC in 2.38 mass % tetramethylammonium hydroxide aqueous solution. Next, a pattern was formed on the glass substrate by performing flowing water washing with ultrapure water for 1 minute and drying after that. At this time, the exposure amount necessary for forming a 10 μm space pattern was investigated. The radiation sensitivity before and after warming was measured, and the rate of change (%) of the required exposure amount was determined, which was used as an index of storage stability. The case where the change rate was less than 5% was set as "A", the case where the change rate was 5% or more and less than 10% was set as "B", and the case where the change rate was 10% or more was set as "C". The results are shown in Table 1.

In Table 1, the abbreviations of [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-naphthoquinonedia Condensate of zide-5-sulfonic acid chloride (3.0 mol)

B-2: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol)

C-1: naphthol

C-2: 2-(4'-hydroxyphenyl)-2-phenylpropane

C-3: benzoic acid

C-4: benzenethiol

F-1: "SH8400FLUID" manufactured by Toray Dow Corning

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

The symbol in Table 1 is 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, the cured films formed from the radiation-sensitive resin compositions of Examples 1 to 15 are excellent in light transmittance and solvent resistance while suppressing whitening of the cured films and volatilization of benzene. 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 used suitably for the interlayer insulating film of a thin film transistor board|substrate, the liquid crystal display element using this, and organic electroluminescent element.

The present invention is not limited to each embodiment described above, and can be implemented with various modifications within a range not departing from the gist of the present invention.

1: Substrate
2 : TFT
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, 19: contact hole
80: recess
100: thin film transistor substrate
110: counter 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)
207: through hole
208: bulkhead
209: light emitting layer
210: cathode (as second electrode)
211: passivation film
212: encapsulation substrate
213: encapsulation layer
230: gate electrode
231: gate insulating film
232: semiconductor layer
233: source electrode
234: drain electrode

Claims (14)

substrate,
a thin film transistor disposed on the substrate;
A thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,
A thin film transistor substrate in which the interlayer insulating film contains 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, and R ² represents a monovalent organic group containing an aromatic ring;
* indicates a binding site). According to claim 1,
A thin film transistor substrate in which R ¹ represents -O-, -S-, -OC(=O)-, or -NH-. According to claim 1,
The thin film transistor substrate in which the content rate of the aromatic ring derived from said Formula (1) in the said interlayer insulating film is 1 mol% or more and 60 mol% or less with respect to Si atoms in the said interlayer insulating film. According to claim 1,
A thin film transistor substrate in which R ² represented by the above formula (1) is represented by the following formula (2):

(In Formula (2), R ³ represents a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a halogen atom;
n represents an integer from 0 to 6;
m represents 0 or 1). According to claim 1,
The thin film transistor is a thin film transistor substrate having a semiconductor layer formed using an oxide semiconductor. According to claim 5,
The semiconductor layer is formed using an oxide, and the oxide is selected from a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. According to claim 5,
The thin film transistor substrate of claim 1 , wherein the semiconductor layer includes an amorphous oxide comprising at least one element selected from indium (In), zinc (Zn), and tin (Sn). According to claim 5,
The semiconductor layer includes Sn-In-Zn oxide, In-Ga-Zn oxide (IGZO: indium gallium oxide zinc), In-Zn-Ga-Mg oxide, Zn-Sn oxide (ZTO: zinc tin oxide), Thin film transistor substrate comprising an amorphous oxide including In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga oxide or Sn-In-Zn oxide . According to claim 1,
The thin film transistor substrate having a semiconductor layer formed using either amorphous silicon or crystalline silicon. According to claim 1,
The thin film transistor substrate wherein the interlayer insulating film is a polysiloxane film. The thin film transistor substrate according to any one of claims 1 to 10, 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 Liquid crystal display element. An organic EL device comprising the thin film transistor substrate according to any one of claims 1 to 10, an interlayer insulating film, and a light emitting layer in this order. [A] polymer,
[B] a photosensitizer and,
[C] A compound represented by the following formula (3)
As a radiation-sensitive resin composition comprising a,
substrate,
a thin film transistor disposed on the substrate;
It is used for forming an interlayer insulating film of a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,
The interlayer insulating film is a radiation-sensitive resin composition containing a polymer having a structure represented by the following formula (1):

(In Formula (3), X represents a hydroxy group, a thiol group, a carboxyl group or an amino group, and R ⁴ represents a monovalent organic group containing an aromatic ring);

(In Formula (1), R ¹ represents a divalent linking group containing a hetero atom, and R ² represents a monovalent organic group containing an aromatic ring;
* indicates a binding site). substrate,
a thin film transistor disposed on the substrate;
As a method of manufacturing a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,
[1] a step of forming a coating film of the radiation-sensitive resin composition according to claim 13 on the substrate on which the thin film transistor is formed;
[2] a step of irradiating radiation to at least a part of the coating film formed in step [1];
[3] a step of developing the coating film irradiated with radiation in step [2]; and
[4] A step of forming the interlayer insulating film by heating the coating film developed in step [3]
Method for manufacturing a thin film transistor substrate having a.

Images