KR20180116742A - 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

The present invention is to provide a thin film transistor substrate having an interlayer insulating film which is hardly whitened at the time of high temperature treatment and in which the generation of outgas is suppressed; a liquid crystal display device or an organic EL element having the thin film transistor substrate; a radiation-sensitive resin composition capable of suitably forming the interlayer insulating film; and a method of manufacturing the thin film transistor substrate. The thin film transistor substrate comprises 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 includes a polymer having a structure represented by formula (1). In formula (1), R^1 represents a divalent linking group containing a hetero atom, R^2 represents a monovalent organic group containing an aromatic ring, and * represents the binding site.

Description

TECHNICAL FIELD [0001] The present invention relates to a thin film transistor substrate, a liquid crystal display device, an organic EL device, a radiation-sensitive resin composition, and a method of manufacturing a thin film transistor substrate using the thin film transistor substrate. FILM TRANSISTOR SUBSTRATE}

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

In recent years, display devices using liquid crystal, that is, liquid crystal display devices, have been actively developed due to advantages such as being thinner and lighter in weight as compared with conventional CRT-type display devices.

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

With the development of an active matrix system in which switching elements are arranged for each pixel in a liquid crystal display element, it is possible to realize a good image quality excellent in contrast ratio and response performance. In addition, liquid crystal display elements overcome the problems of high definition, colorization and enlargement of viewing angle. In recent years, liquid crystal display elements have been widely used as display devices for portable electronic devices such as smart phones and large and thin display devices for televisions Is being used.

In an active matrix type liquid crystal display device, gate wirings and signal wirings are provided in a lattice shape on one of a pair of substrates sandwiching a liquid crystal, and thin film transistors (for example, TFT: Thin Film Transistor) is formed. That is, in the active matrix type liquid crystal display element, one of the pair of substrates sandwiching the liquid crystal constitutes a thin film transistor substrate on which TFTs and the like are arranged.

The thin film transistor substrate typically includes a TFT as a switching element disposed on a substrate, a planarization film covering the TFT, an interlayer insulation film covering the planarization film, a pixel electrode arranged on the interlayer insulation film and connected to the TFT, And an auxiliary capacitance electrode disposed between the interlayer insulating film and the planarization film so as to face the pixel electrode through the interlayer insulating film.

There is a possibility that a high-temperature treatment (for example, 250 DEG C or more) may be performed on the interlayer insulating film from the viewpoint of improvement of reliability of future thin film transistor substrates. A radiation-sensitive resin composition in which the number of steps for forming a pattern is small and a high surface hardness can be obtained has been studied since the existing acrylic organic insulating film may be difficult to be applied from the viewpoint of lack of heat resistance and transparency. As such a resin composition, a siloxane-based photosensitive material has been proposed (Patent Document 1).

Japanese Patent Publication No. 4670693

It has been found that when a photosensitive agent having low compatibility with a polysiloxane such as a quinone diazide compound is used, the photosensitive siloxane material may cause whitening during formation of the interlayer insulating film due to low compatibility of the photosensitive agent and the polysiloxane have. On the other hand, as in Patent Document 1, it is a policy to increase the compatibility with the quinone diazide compound by introducing a phenyl group into the polysiloxane skeleton.

However, in the case of a photosensitive material using a polysiloxane in which a phenyl group is directly introduced into the polysiloxane skeleton, benzene is generated as an outgassing agent at the time of high temperature treatment of the interlayer insulating film, which may cause a pollution source 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 to provide a thin film transistor substrate having an interlayer insulating film which is hardly whitened at the time of high-temperature processing and in which the generation of outgas is suppressed, a liquid crystal display element and an organic EL element having the interlayer insulating film, A radiation sensitive resin composition capable of forming a radiation sensitive resin composition, and a method of manufacturing a thin film transistor substrate.

The present invention, in one aspect,

A 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,

Wherein the interlayer insulating film comprises a polymer having a structure represented by the following formula (1).

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

The present invention, in another aspect,

And a liquid crystal display element having a liquid crystal layer interposed between the thin film transistor substrate and the counter substrate, an opposite substrate having the 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 invention further provides, in a further aspect,

An organic EL device including the thin film transistor substrate, an interlayer insulating film, and a light emitting layer in this order.

The invention further provides, in yet another aspect,

[A] Polymer,

[B] Photosensitizer,

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

A substrate;

A thin film transistor disposed on the substrate;

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 the 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,

A substrate;

A thin film transistor disposed on the substrate;

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

[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 at least a part of the coating film formed in the step [1]

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

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

And a method of manufacturing the thin film transistor substrate.

According to the present invention, it is possible to provide a thin film transistor substrate having an interlayer insulating film which is hardly whitened at the time of high temperature treatment and in which the generation of outgas is suppressed, a liquid crystal display element and an organic EL element having the interlayer insulating film, And a method of 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 element according to a second embodiment of the present invention.
3 is a schematic cross-sectional view of a pixel portion in an example of the organic EL element according to the third embodiment of the present invention.

(Mode for carrying out the invention)

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate.

In the present invention, "radiation" irradiated at the time of exposure includes visible rays, ultraviolet rays, deep ultraviolet rays, X-rays and charged particle rays.

≪ 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 as a switching element disposed on the substrate 1, An interlayer insulating film 6 covering the planarizing film 5; a pixel electrode 7 disposed on the interlayer insulating film 6 to be connected to the TFT 2; an interlayer insulating film 6; And an auxiliary capacitance electrode 3 disposed between the interlayer insulating film 6 and the planarization film 5 so as to face the pixel electrode 7 through the interlayer insulating film 6. 1, the inorganic insulating film 4 may be formed between the TFT 2 and the planarization film 5 so as to cover and protect the TFT 2 .

On the arrangement surface of the TFT 2 of the substrate 1, various wirings such as gate wiring and signal wiring not shown are formed. The gate wirings and the signal wirings are provided in a lattice pattern, and the TFTs 2 are formed in each of the intersections thereof.

The substrate 1 is not particularly limited, and for example, a glass substrate, a quartz substrate, a resin substrate made of an acrylic resin, or the like is suitably used. In the substrate 1, cleaning and pre-annealing are preferably performed as a pre-treatment for forming the thin film transistor substrate 100.

The TFT 2 includes a gate electrode 10 formed on the substrate 1 as a switching element and forming a part of a gate wiring, a gate insulating film 11 covering the gate electrode 10, A source electrode 14 formed as a part of the signal wiring and connected to the semiconductor layer 12 and a source electrode 14 connected to the pixel electrode 7, And a 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 a vapor deposition method, a sputtering method, or the like, and patterning using an etching process. It is also possible to use a metal oxide conductive film or an organic conductive film by patterning.

Examples of the material of the metal thin film constituting the gate electrode 10 include aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium Au, tungsten (W) and silver (Ag), alloys of these metals, and alloys such as Al-Nd and APC alloys (silver, palladium and copper alloys). As the metal thin film, a laminated film composed of layers of different materials such as a laminated film of Al and Mo can be used.

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) have.

As the material of the organic conductive film constituting the gate electrode 10, a conductive organic compound such as polyaniline, polythiophene and polypyrrole, or a mixture thereof can be mentioned.

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

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

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

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

When p-Si is used for the semiconductor layer 12, impurities such as phosphorus (P) or boron (B) are doped into the semiconductor layer 12 to sandwich the channel region therebetween, It is preferable to form the drain region. It is preferable that an LDD (Lightly Doped Drain) layer is formed between the channel region of the semiconductor layer 12 and the source region and the drain region.

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, polycrystalline oxides, amorphous oxides, and mixtures thereof. Examples of polycrystalline oxides include zinc oxide (ZnO) and the like.

Examples of the amorphous oxide applicable to the semiconductor layer 12 include amorphous oxides composed of at least one kind of element selected from 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- In-Zn oxide, In-Zn oxide, Zn-Ga oxide, Sn-In-Zn oxide, and the like can be used as the oxide (ZTO), In oxide, Ga oxide, In-Sn oxide, In- . In addition, in such a case, the composition ratio of the constituent material does not necessarily have to be 1: 1, and it is possible to select a composition ratio that realizes desired characteristics.

When the amorphous oxide-based semiconductor layer 12 is formed using, for example, IGZO or ZTO, a semiconductor layer is formed by a sputtering method or a vapor deposition method using an IGZO target or a ZTO target, and a photolithography method or the like And patterning is performed by a resist process and an etching process. The thickness of the semiconductor layer 12 using the amorphous oxide is preferably 1 nm or more and 1000 nm or less, for example.

The source electrode 14 and the drain electrode 13 that are connected to the semiconductor layer 12 of the TFT 2 can be formed by a sputtering method, a CVD method, a vapor deposition method, or the like Method, and then patterning using a photolithography method or the like.

As the constituent material of the source electrode 14 and the drain electrode 13, for example, a metal such as Al, Cu, Mo, Cr, Ta, Ti, Au, W and Ag, 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 dope zinc oxide) and GZO (gallium doped zinc oxide), polyaniline, polythiophene and polypyrrole And the like. As the conductive film constituting these electrodes, a laminated film composed of layers of different materials such as a laminated film of Ti and Al may be used.

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

Further, the thin film transistor substrate 100 can form the inorganic insulating film 4 on the TFT 2 so as to cover it. The inorganic insulating film 4 can be formed, for example, by using a metal oxide such as SiO ₂ or a metal nitride such as SiN, either alone or in combination. The 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, for example, from being affected by humidity.

In the thin film transistor substrate 100, the inorganic insulating film 4 may not be formed. In this case, the planarizing film 5 formed between the pixel electrode 7 and the TFT 2 can be used also as a protection for the TFT 2.

The planarizing 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 planarizing film 5 has a function of flattening irregularities caused by the TFTs 2 formed on the substrate 1. [ The planarizing film 5 may be an insulating film formed using a radiation-sensitive resin composition. That is, the planarization film 5 may be an organic film formed using an organic material. For example, the planarizing film 5 may be a film made of an acrylic resin, a polyimide resin, a polysiloxane, and a novolac resin.

When the planarization film 5 is an organic film, the coupling capacitance between the pixel electrode 7 and other wirings such as gate wirings and signal wirings and electrodes can be reduced as described above. The thin film transistor substrate 100 can increase the area of the pixel electrode 7 in the pixel by having the planarization film 5, thereby improving the aperture ratio of the pixel.

The flattening film 5 preferably has a good function as a flattening film, and it is preferable that the film thickness is set in view of this. For example, the planarization film 5 can be formed with an average film thickness of 0.5 m to 6 m. It is also possible to set the respective film thicknesses so as to have an average film thickness of 1 占 퐉 to 6 占 퐉 in addition to the interlayer insulating film 6 so as to exhibit excellent planarization performance as well as the interlayer insulating film 6 to be described later.

When the flattening film 5 is formed using, for example, a radiation-sensitive resin composition as described above, the flattening film 5 is patterned by exposure and development according to a known method, followed by curing Can be easily formed.

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

Therefore, in the thin film transistor substrate 100, the above-described inorganic insulating film 4 covers the common wiring 17 in the region where the common wiring 17 is disposed, and the above- (17) and the inorganic insulating film (4).

A storage capacitor electrode 3 electrically connected to the common wiring 17 is disposed on the planarization film 5 through a contact hole 18 penetrating the planarization film 5 and the inorganic insulating film 4 do.

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

The interlayer insulating film 6 of the thin film transistor substrate 100 is disposed on the planarization film 5 so as to cover the planarization film 5. [ The auxiliary capacitance electrode 3 is formed so as to cover the auxiliary capacitance electrode 3 on the planarization film 5 and to cover the entire surface of the flattening film 5 and the auxiliary capacitance electrode 3, Respectively.

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 below. The interlayer insulating film 6 can be easily formed by applying the radiation sensitive resin composition of the fourth embodiment of the present invention, patterning by exposure and development, and 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 of the dielectric property is controlled to a desired value. For example, it is configured to have a higher dielectric constant than an ordinary organic film.

The interlayer insulating film 6 includes a polymer having a structure represented by the following formula (1).

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

In the polymer contained in the interlayer insulating film 6, since the aromatic ring is bonded to Si via a divalent linking group containing a hetero atom, outgas derived from an aromatic compound such as benzene can be suppressed. Although benzene is generated as an outgassing in an interlayer insulating film containing a polymer in which a conventional phenyl group is directly bonded to Si, the interlayer insulating film of the present embodiment can reduce or prevent such an event, The safety of the apparatus can be enhanced. Further, since the polymer contains an aromatic ring, its compatibility with a photosensitizer such as a quinone diazide compound is high, and whitening during the high-temperature treatment of the interlayer insulating film can be suppressed. Further, the interlayer insulating film has good solvent resistance.

The hetero atom constituting the divalent linking group containing a hetero atom includes, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specific examples of the linking group include -O-, -CO-, -S-, -CS-, -OCO-, -COO-, -NR'-, groups combining two or more of them, . R 'is a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, and examples of the monovalent chain hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i An alkenyl group such as a propenyl group or a butenyl group, an alkynyl group such as an ethynyl group, a propynyl group or a butynyl group, and the like.

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

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

(In the formula (2), R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a halogen atom. n represents an integer of 0 to 6. m represents 0 or 1.)

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

Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group.

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group and a methylnaphthyl group.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, 2-phenylethyl group, 2-phenyl-2-propyl group and the like.

The upper limit of n is preferably 4, more preferably 2. When m is 1, the effects and the like of the present invention may be sufficiently exhibited.

As the R ² represented by the formula (1), a group represented by the formula (2) is preferable. Specific examples of the group represented by the formula (2) include a benzyl group, a phenethyl group, and a naphthyl group.

The interlayer insulating film is preferably a polysiloxane film in view of ease of introduction of the structure represented by the above formula (1) or (2). The polysiloxane will be described later.

It is preferable that the content of an aromatic ring derived from the structure represented by the formula (1) in the interlayer insulating film is 1 mol% or more and 60 mol% or less with respect to Si atoms in the interlayer insulating film. The lower limit value of the content of the aromatic rings is more preferably 10 mol%, and still more preferably 30 mol%. The upper limit of the content of the aromatic ring is more preferably 50 mol%, and still more preferably 40 mol%. When the content of the aromatic ring is in the above range, it is possible to prevent whitening at the time of high-temperature treatment of the interlayer insulating film and suppress generation of outgas at a high level.

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

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

The polymer contained in the interlayer insulating film 6 further includes a structure in which the aryl group is bonded to the Si atom, so that the compatibility of the polymer and the photosensitizer is improved, and whitening during the high temperature treatment of the interlayer insulating film can be prevented.

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

When the polymer contained in the interlayer insulating film 6 has the structure represented by the above formula (a), the content ratio of the aromatic ring derived from the structure represented by the formula (a) in the interlayer insulating film is larger than the content ratio of the Si atoms in the interlayer insulating film By mole to 40% by mole or less. The lower limit of the content of the aromatic ring is more preferably 5 mol%, further preferably 10 mol%. The upper limit of the content of the aromatic ring is more preferably 30 mol%, further preferably 20 mol%. When the content of the aromatic ring is in the above range, it is possible to prevent whitening at the time of high-temperature treatment of the interlayer insulating film and suppress the generation of outgas at a higher level. The upper limit of the content of the aromatic ring derived from the structure represented by the above formula (a) is more preferably 10 mol%, and more preferably 5 mol%. By lowering the content of the aromatic ring derived from the structure represented by the above formula (a), generation of outgas is further suppressed and the solvent resistance of the interlayer insulating film tends to be increased.

The average film thickness of the interlayer insulating film 6 is preferably 0.3 mu m or more and 6 mu m or less, for example. It is also possible to set the respective film thicknesses so that the average film thickness is not less than 1 占 퐉 and not more than 6 占 퐉, in addition to the planarization film 5, as described above.

It is also considered that the interlayer insulating film 6 can be made of an inorganic film such as a SiN film in the same manner as the gate insulating film 11 and the inorganic insulating film 4. [ However, in order to form the interlayer insulating film made of such an inorganic film, vacuum film formation using a vacuum facility or dry etching is required, so that it can not be easily formed like the interlayer insulating film 6 which is an organic film. Therefore, it is preferable that the interlayer insulating film 6 is an organic film formed using the radiation sensitive resin composition of the fourth embodiment of the present invention. The interlayer insulating film 6 is formed using the radiation sensitive resin composition of the fourth embodiment of the present invention and has a higher permittivity than that of the conventional organic film constituting the conventional interlayer insulating film, And the like.

The pixel electrode 7 of the thin film transistor substrate 100 is provided on the interlayer insulating film 6 and has a contact hole 19 penetrating the interlayer insulating film 6, the planarizing film 5, and the inorganic insulating film 4 And is electrically connected to the drain electrode 13. [ In the thin film transistor substrate 100, the pixel electrode 7 and the storage capacitor electrode 3 are arranged to face each other through the interlayer insulating film 6.

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

The thin film transistor substrate 100 which is one example of the first embodiment of the present invention having the above configuration 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 A pixel electrode 7 and a storage capacitor 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 the auxiliary capacitance in the overlapping portion where the pixel electrode 7 and the auxiliary capacitance electrode 3 overlap each other in a plan view. The interlayer insulating film 6 sandwiched between the pixel electrode 7 and the storage capacitor electrode 3 is formed using the radiation sensitive resin composition of the fourth embodiment of the present invention as described above, And 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, the auxiliary capacitance generated in the overlapping portion where the pixel electrode 7 and the auxiliary capacitance electrode 3 overlap in plan view can have a high charge holding ability.

On the other hand, the thin film transistor substrate 100 has the planarization film 5 between the pixel electrode 7 and the TFT 2, as described above, It is possible to reduce the coupling capacity between the two.

The thin film transistor substrate 100 on which the storage capacitor is formed can form an alignment film on the surface of the substrate for the purpose of controlling alignment of the liquid crystal and can form a liquid crystal display element of the second embodiment of the present invention have. In the liquid crystal display element of the second embodiment of the present invention, by using the storage capacitor generated by the storage capacitor electrode 3, the interlayer insulating film 6, and the pixel electrode 7, The charge can be conserved with high efficiency even when the applied voltage ratio is non-applied. As a result, in the liquid crystal display element of the second embodiment of the present invention having the thin film transistor substrate 100, the driving of the liquid crystal can be maintained even when the voltage is not 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 lowering of the aperture ratio of the pixel 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 according to a second embodiment of the present invention.

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

The liquid crystal display element 200 is formed by using the thin film transistor substrate 100 which is one example of the first embodiment of the present invention described above and the thin film transistor substrate 100 and the counter substrate 110 with a sealing material And the liquid crystal is sealed between the two substrates to form the liquid crystal layer 111. [0156] Therefore, in the liquid crystal display element 200, the thin film transistor substrate 100 is common to the thin film transistor substrate 100, which is one example of the first embodiment of the present invention described above, And the description of duplication is omitted.

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

On the other hand, the thin film transistor substrate 100 has the planarization film 5 between the pixel electrode 7 and the TFT 2, as described above, It is possible to reduce the coupling capacity between the two.

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

An alignment film can be formed on the opposing surfaces of the thin film transistor substrate 100 and the counter substrate 110 for the purpose of controlling the alignment of the liquid crystal.

The liquid crystal layer 111 is formed of liquid crystals of vertically aligned type and is provided between the TFT 2 of the thin film transistor substrate 100 and the counter electrode of the counter substrate 110, By turning off the liquid crystal, alignment control of the liquid crystal is performed.

The liquid crystal display element 200 of the second embodiment of the present invention is formed by using the auxiliary capacitance generated by the auxiliary capacitance electrode 3 of the thin film transistor substrate 100, the interlayer insulating film 6 and the pixel electrode 7 , The charge can be conserved with high efficiency even when the voltage ratio of the applied voltage to the pixel is off. 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 the driving of the liquid crystal even when the voltage is not 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, the lowering of the aperture ratio of the pixel is suppressed. Therefore, the liquid crystal display element 200 according to 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 device)

3 is a cross-sectional view schematically showing the structure of the main part of the organic EL device 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 shape. The organic EL device 201 may be a top emission type or a bottom emission type. Properties of the materials constituting each member, for example, transparency are appropriately selected in accordance with the top emission type and the bottom emission type. The organic EL element 201 corresponds to the thin film transistor substrate of the first embodiment and includes a support substrate 202, a thin film transistor (TFT) 203, an inorganic insulating film 204, an interlayer insulating film 205, A luminescent layer 209, a cathode 210 as a second electrode, a passivation film 211, and an encapsulation substrate 212, which are provided with a positive electrode 206 as an electrode and a through hole 207, Respectively.

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

The present embodiment is not limited to a bottom gate type in which a gate insulating film and a semiconductor layer are provided on a gate electrode in this order, and 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 scanning signal line (not shown). The thickness of the gate electrode 230 is preferably 10 nm or more and 1000 nm or less. The gate insulating film 231 covers the gate electrode 230. The average film thickness of the gate insulating film 231 is preferably 10 nm or more and 10 占 퐉 or less. The source electrode 233 is an electrode serving as a carrier generation source. The source electrode 233 is a part of a video signal line (not shown), and is connected to the semiconductor layer 232. The drain electrode 234 receives the carrier moving through the semiconductor layer 232 (channel layer) and is connected to the semiconductor layer 232 like 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 through the gate insulating film 231. The semiconductor layer 232 is connected to the source electrode 233 and the drain electrode 234 to form a channel layer. The channel layer is a portion through which a carrier flows 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 the group consisting of In, Ga, Sn, and Zn. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, a mixture thereof, and the like.

The semiconductor layer 232 made of amorphous oxide using IGZO can be formed by forming a semiconductor layer using, for example, an IGZO target by a sputtering method or a vapor deposition method, and patterning by photolithography or the like using a resist process and an etching process . 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 prevent the semiconductor layer 232 from being affected by, for example, humidity to protect the semiconductor layer 232. 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 planarizing film that fulfills the role of flattening the surface unevenness of the TFT 203. [ The interlayer insulating film 205 is formed on the inorganic insulating film 204 so as to cover the entire TFT 203.

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

The average film thickness of the interlayer insulating film 205 is preferably 1 占 퐉 or more and 6 占 퐉 or less.

The through hole 207 is formed for connecting the anode 206 and the drain electrode 234. [ The through hole 207 is formed so as to penetrate the inorganic insulating film 204 underlying 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 the through hole of the desired shape. Here, the interlayer insulating film 205 can be formed using the radiation sensitive resin composition of the fourth embodiment of the present invention described later or a conventionally known radiation sensitive resin composition. Therefore, through-holes constituting the through-holes 207 can be formed by irradiating and developing the coating film made of these materials. Dry etching for the inorganic insulating film 204 can be performed using the interlayer insulating film 205 as a mask. A through hole communicating with the through hole of the interlayer insulating film 205 is formed in the inorganic insulating film 204 as a result of which a through hole 207 penetrating the interlayer insulating film 205 and the inorganic insulating film 204 is formed.

When the inorganic insulating film 204 is not disposed on the TFT 203, the through hole formed by the irradiation and development of the radiation to the interlayer insulating film 205 constitutes the through hole 207. As a result, the anode 206 covers a part of the interlayer insulating film 205, passes through the interlayer insulating film 205, passes through the through hole 207 formed in the interlayer insulating film 205, Can be connected.

The barrier rib 208 fulfills a role as a barrier rib (bank) having a recessed portion 80 defining an arrangement region of the light emitting layer 209. The partition 208 is formed so as to cover a part of the anode 206 while exposing a part of the anode 206.

It is preferable that the barrier rib 208 is 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" refers to a direction from the support substrate 202 to the sealing substrate 212.

Such barrier ribs 208 can be formed by a method described in a manufacturing method of a thin film transistor substrate using a known radiation sensitive resin composition. The partition walls 208 can be formed by patterning by exposure and development of a coating film so that a plurality of recesses 80 in which a light emitting layer 209 is formed are arranged in a matrix when viewed from a plane.

It is preferable that the barrier ribs 208 are formed so as to fill the through holes 207.

The lower limit of the average film thickness of the barrier ribs 208 (the distance between the uppermost surface of the barrier ribs 208 and the lowermost surface of the light emitting layer 209) is preferably 0.3 占 퐉 and more preferably 0.5 占 퐉. The upper limit of the average film thickness is preferably 25 占 퐉, and more preferably 20 占 퐉. If the average film thickness of the barrier ribs 208 exceeds the upper limit, there is a fear that the barrier ribs 208 come into contact with the sealing substrate 212. On the other hand, when the light emitting material composition is applied to the concave portion 80 of the partition 208 in the case of forming the light emitting layer 209 to be described later, if the average film thickness of the partition wall 208 does not reach the lower limit, There is a fear that the composition leaks from the concave portion 80. [

The light emitting layer 209 emits light by applying an electric field. The light emitting layer 209 is an organic light emitting layer including an electroluminescent material for electroluminescence. The light emitting layer 209 is formed in a region defined by the partition 208, that is, in the concave portion 80. By forming the light emitting layer 209 in the concave portion 80 as described above, the periphery of the light emitting layer 209 is surrounded by the partition wall 208, and a plurality of adjacent pixels can be partitioned.

The light emitting layer 209 is formed in contact with the anode 206 in the concave portion 80 of the partition 208. The thickness of the light emitting layer 209 is preferably 50 nm or more and 100 nm or less. 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 so as 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. The passivation film 211 is formed on the cathode 210.

The sealing substrate 212 encapsulates the main surface (the side opposite to the supporting substrate 202) where the light emitting layer 209 is disposed. The main surface on which the light emitting layer 209 is disposed is preferably sealed with the sealing substrate 212 via the sealing layer 213 using a sealant (not shown) coated near the outer peripheral end of the TFT substrate Do. The sealing layer 213 may be a layer of an inert gas such as a dried nitrogen gas or a layer of a filling material such as an adhesive.

In the organic EL device 201 of the present embodiment, the interlayer insulating film 205 and the barrier ribs 208 can be formed using a radiation-sensitive resin composition having low absorbability, and the interlayer insulating film 205, 208, it is possible to perform a treatment such as cleaning with a low-absorbency material. Therefore, it is possible to reduce the penetration of a small amount of water contained in the insulating film forming material into the light emitting layer 209 in the form of adsorbed material or the like, so that deterioration of the light emitting layer 209 and deterioration of the light emitting state can be reduced.

≪ 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 using its radiation sensitivity. The radiation sensitive resin composition according to the present embodiment is suitably used for forming the interlayer insulating film of a thin film transistor substrate having a substrate, a thin film transistor disposed on the substrate, and an interlayer insulating film disposed on the thin film transistor . That is, it is suitable for manufacturing the thin film transistor substrate of the first embodiment of the present invention described above, the liquid crystal display element of the second embodiment of the present invention, and the interlayer insulating film which is a main component of the organic EL element of the third embodiment of the present invention . By using the radiation-sensitive resin composition in forming the interlayer insulating film, the occurrence of whitening and outgas at the time of high temperature treatment is suppressed, and an interlayer insulating film having excellent solvent resistance is obtained. In addition, in the radiation-sensitive resin composition, storage stability can be improved by using an appropriate composition of components.

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

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

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

<[A] Polymer>

The polymer [A] is a component that becomes the base material of the resulting cured film. As the polymer [A], conventionally known polymers contained in the radiation-sensitive resin composition for forming a cured film may be used singly or in combination of two or more. The polymer [A] is preferably an alkali-soluble resin. As an alkali-soluble resin, patterning using an alkali developing solution becomes possible. As the polymer [A], polysiloxane can be suitably used.

(Polysiloxane)

The polysiloxane is not particularly limited as long as it is a polymer of a compound having a siloxane bond. This polysiloxane is usually cured by using, for example, an acid generated from the [B] photosensitive acid generator [B-2], which will be described later, or a base generated from the [B-3]

The polysiloxane is preferably a hydrolyzed condensate of a hydrolyzable silane compound represented by the following formula (4).

In the 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 there are plural R ²⁰ or R ²¹ , they may be the same or different.

Examples of the non-hydrolyzable organic group represented by R ²⁰ include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. These may be linear, branched, or cyclic. Some or all of the hydrogen atoms of these alkyl groups, aryl groups and aralkyl groups may be substituted with a vinyl group, a (meth) acryloyl group or an epoxy group.

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

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

As the silane compound substituted with four hydrolysable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,

As the silane compound substituted with one nonhydrolyzable group and three hydrolyzable groups, there may be mentioned methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyl triethoxy silane, ethyl tri-butoxy silane, butyl trimethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane , Vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like,

As the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane,

As the silane compound substituted with three nonhydrolyzable groups and one hydrolyzable group, tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, and the like can be given.

Of the hydrolyzable silane compounds represented by the above formula (4), silane compounds substituted with four hydrolyzable groups and silane compounds substituted with one nonhydrolyzable group and three hydrolyzable groups are preferred, and one nonhydrolyzable group A silane compound substituted with three hydrolyzable groups is more preferable. Specific examples of preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, butyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and And 3-methacryloxypropyltriethoxysilane. These hydrolyzable silane compounds may be used singly or in combination of two or more.

The condition for hydrolyzing and condensing the hydrolyzable silane compound represented by the formula (4) is that at least a part of the hydrolyzable silane compound represented by the formula (4) is hydrolyzed to convert the hydrolyzable group into a silanol group, But is not limited to, it can be carried out as an example as follows.

As the water used for the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (4), it is preferable to use water purified by reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, the side reaction can be suppressed and the reactivity of hydrolysis can be improved.

Examples of the solvent that can be used for the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (4) include, but are not limited to, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl Ethers, propylene glycol monoalkyl ether acetates, propionic acid esters, aryl alkanols, and aryloxy alkanols. Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, benzyl alcohol, Ol and phenoxyethanol are preferred. When a phenylalkanol or a phenoxyalkanol is used as the solvent, a phenylalkanol or a phenoxyalkanol is not used in the hydrolysis and condensation reaction but remains after the reaction. Therefore, the phenylalkanol or phenoxyalkanol contained in the solution after the hydrolysis and condensation reaction may be used as the [C] component.

The hydrolysis / condensation reaction of the hydrolyzable silane compound represented by the formula (4) is preferably carried out in the presence of an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, (For example, ammonia, a primary amine, a secondary amine, a tertiary amine, a nitrogen compound such as pyridine, a basic ion exchange resin, a hydroxide In the presence of a catalyst such as a hydroxide of sodium or the like, a carbonate such as potassium carbonate, a carbonate such as sodium acetate, various Lewis bases or the like) or an alkoxide (for example, zirconium alkoxide, titanium alkoxide or aluminum alkoxide).

The reaction temperature and the reaction time in the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (4) are suitably set. The reaction temperature is preferably 40 占 폚 to 200 占 폚. The reaction time is preferably 30 minutes to 24 hours.

The lower limit of the weight average molecular weight (Mw) of the hydrolyzed condensate of the hydrolyzable silane compound represented by the above formula (4) is usually preferably 500, more preferably 1000. On the other hand, as the upper limit, 20000 is preferable, and 10000 is more preferable.

The lower limit of the number average molecular weight (Mn) of the hydrolyzed condensate of the hydrolyzable silane compound represented by the above formula (4) is preferably 500, more preferably 1000, still more preferably 2500. By setting the number average molecular weight of the hydrolyzed condensate of the hydrolyzable silane compound represented by the formula (4) to be equal to or more than the lower limit described above, the effect of the present invention can be further enhanced and the storage stability and the solvent resistance of the obtained interlayer insulating film can be enhanced. On the other hand, the upper limit of the Mn is preferably 20000, more preferably 10,000, and still more preferably 5000.

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

The Mw and Mn of the polymer in the present specification are values measured by gel permeation chromatography (GPC) under the following conditions.

Device: "GPC-101" of Showa Denko

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

<Content of [A] Polymer>

The lower limit of the content of the polymer [A] in the radiation-sensitive resin composition is not particularly limited, but is preferably 50% by mass and 60% by mass in terms of solid content. On the other hand, the upper limit is preferably 99 mass%, more preferably 95 mass%.

<[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 a radical in response to radiation (i.e., a [B-1] photo radical polymerization initiator) , A compound capable of generating an acid upon exposure to radiation (i.e., a [B-2] photoacid generator), or a compound capable of generating a base in response to radiation (i.e., a [B-3] photobase generator) have.

Examples of such [B-1] photo radical polymerization initiators include O-acyloxime compounds, acetophenone compounds, imidazole compounds, and phosphine oxide compounds. These compounds may be used singly or as a mixture of two or more kinds.

Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone- 1- [ (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -octane-l- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, 1- [ ethane-1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol- Methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime), ethanone- 1- [ (9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone- 1- [ Dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyl Shim), and the like.

Among them, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], 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- } -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of the acetophenone compound include an? -Amino ketone compound and? -Hydroxy ketone compound.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) have.

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

As the acetophenone compound, an? -Amino ketone compound is preferable, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-l- On is preferred.

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

[B-1] The photoradical polymerization initiator may be used alone or as a mixture of two or more thereof, as described above. The lower limit of the content of the [B-1] photoradical polymerization initiator relative to 100 parts by mass of the component [A] is preferably 1 part by mass, more preferably 5 parts by mass. The upper limit of the content of the [B-1] photo radical polymerization initiator is preferably 40 parts by mass, more preferably 30 parts by mass. By setting the content of the [B-1] photo-radical polymerization 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 dose.

Next, examples of the [B-2] photoacid generator as the [B] photosensitizer of the radiation sensitive resin composition of the present embodiment include oxime sulfonate compounds, onium salts, sulfonimide compounds, quinone diazide compounds , Halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carbonic acid ester compounds. These [B-2] photo acid generators may be used singly or in combination of two or more kinds.

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

In formula (B1), R ^A represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, A group in which a part or all of the hydrogen atoms contained in the formula hydrocarbon group and the aryl group is substituted with a substituent.

As the alkyl group represented by R ^A in the above formula (B1), a linear or branched alkyl group having 1 to 12 carbon atoms is preferable. The straight 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-oxononorbornyl group and the like And an alicyclic group including a bridged alicyclic group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

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

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

The onium salts include, for example, diphenyl iodonium salts, triphenylsulfonium salts, benzylsulfonium salts, benzothiazonium salts, and tetrahydrothiophenium salts.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide , N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- - (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (Methanesulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) 1,8-naphthalimide, and the like.

Further, as described above, the radiation sensitive resin composition of the present embodiment may contain a quinone diazide compound as the [B-2] photoacid generator as the [B] photosensitizer. The radiation-sensitive resin composition of the present embodiment can be used as a positive radiation-sensitive resin composition by containing a quinone diazide compound. Then, the light shielding property of the cured film after formation can be imparted. In addition, it is possible to adjust the transmittance of light in the visible region of the cured film formed by the photo-bleaching performance.

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

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

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

Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4' -Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, .

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

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

(P-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1, 2-dihydroxyphenyl) methane, Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '- [1- {4- (1- [ } Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'- tetramethyl-1,1'-spirobindene- 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like.

Examples of the other parent nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- - (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1- methylethyl] -3- [1- {3- (4-hydroxyphenyl) -1-methylethyl} -1, 4-dihydroxyphenyl} -1- Dihydroxybenzene, and the like.

Among these nuclei, tetrahydroxybenzophenone and (polyhydroxyphenyl) alkane are preferable, 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 preferable.

As the 1,2-naphthoquinone diazidesulfonic 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. have. Of these, 1,2-naphthoquinonediazide-5-sulfonic chloride is more preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (mother nucleus) with 1,2-naphthoquinonediazide sulfonic acid halide, the condensation reaction is preferably carried out in an amount of 30 mol% to 85 mol% based on the number of OH groups in the phenolic compound or the alcoholic compound %, More preferably from 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonic acid halide. The condensation reaction can be carried out by a known method.

Examples of the quinone diazide compound include 1,2-naphthoquinone diazidesulfonic acid amides in which the ester bond of the mother nucleus is changed to an amide bond, for example, 2,3,4-triaminobenzophenone- 1,2-naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

These quinone diazide compounds may be used alone or in combination of two or more.

The content of the quinone diazide compound in the radiation-sensitive resin composition of the present embodiment can be set within a range described later. By setting the content in such a range, the irradiated portion of the aqueous solution of the alkaline compound, And the patterning performance can be improved. In addition, the cured film obtained by using the radiation sensitive resin composition may have good solvent resistance.

[B-2] As the photoacid generator, oxime sulfonate compounds, onium salts, sulfonimide compounds and quinone diazide compounds are preferable, and oxime sulfonate compounds and quinone diazide compounds are more preferable. Quinone diazide Compound is more preferable.

As the onium salt, a tetrahydrothiophenium salt or a benzylsulfonium salt is preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4 -Hydroxyphenylmethylsulfonium hexafluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable. [B-2] When the photoacid generator is used as the above compound, the resulting radiation sensitive resin composition of the present embodiment can improve sensitivity and solubility.

The lower limit of the content of [B-2] photoacid generator relative to 100 parts by mass of the component [A] is preferably 0.1 part by mass or more, more preferably 1 part by mass. The upper limit of the content of the [A] component is preferably 10 parts by mass, more preferably 5 parts by mass. [B-2] By setting the content of the photo-acid generator within the above range, it is possible to form a cured film having a high surface hardness by optimizing the sensitivity of the radiation sensitive resin composition of the present embodiment.

Next, the [B-3] photobase generator which is the photosensitive agent [B] of the radiation sensitive resin composition of the present embodiment is not particularly limited as long as it is a compound which generates a base (amine or the like) upon irradiation with radiation . [B-3] Examples of photobase generators include transition metal complexes such as cobalt, orthonitrobenzyl carbamates,?,? -Dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos have.

Examples of the above-mentioned transition metal complexes include bromopentaham ammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexammonium cobalt perchlorate, hexamethylamine cobalt perchlorate, Hexapropylamine cobalt perchlorate, and the like.

Examples of the orthonitrobenzylcarbamates include, for example, [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[ Benzyl) oxy] carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2- nitrobenzyl) oxy] carbonyl] aniline, [(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [ [(2-nitrobenzyl) oxy] carbonyl] piperazine, [(2-nitrobenzyl) oxy] carbonyl] diaminobenzyl) oxy] carbonyl] toluenediamine, bis [ [(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] propylamine, Carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[ [(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-methylpropyl) (2,6-dinitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [ Carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, and the like.

Examples of the?,? -dimethyl-3,5-dimethoxybenzylcarbamates include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[ carbonyl] hexylamine, [[(?,? - dimethyl-3,5-dimethoxybenzyl) oxy] dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl- dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperidine, bis [[(?,? -dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine, Bis [[(alpha, alpha -dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [ Dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(alpha, alpha -dimethyl-3,5-dimethoxybenzyl) oxy] Oxy] carbonyl] piperazine, and the like.

Examples of the acyloxyimines include propionyl acetophenone oxime, propionylbenzophenone oxime, propionylacetone oxime, butyryl acetophenone oxime, butyrylbenzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, Adipoyl benzophenone oxime, adipoyl acetone oxime, acryloyl acetophenone oxime, acryloylbenzophenone oxime, and acryloyl acetone oxime.

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

[B-3] The photobase generator may be used singly or in combination of two or more kinds. Furthermore, the [B-3] photo-base generator and the [B-2] photo-acid generator may be used in combination unless the effect of the present invention is adversely affected.

The lower limit of the content of [B-3] photo-base generator to 100 parts by mass of the component [A] is preferably 0.1 part by mass, more preferably 1 part by mass. The upper limit of the content of the [B-3] photo-nucleating agent is preferably 20 parts by mass, more preferably 10 parts by mass. [B-3] By setting the content of the photobase generator within the above range, it is possible to obtain a radiation-sensitive composition having a good balance of resistance to melt flow and heat resistance of a cured film to be formed, It is possible to prevent the occurrence of precipitates and to facilitate the formation of the coating film.

&Lt; Compound [C] >

The 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 the 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 component [C] of the radiation-sensitive resin composition of the present embodiment is a component that enables introduction of the structure represented by the formula (1) into the polymer [A] in the cured film formed using the radiation- Component. That is, in the interlayer insulating film of the thin film transistor substrate or the liquid crystal display element formed by using the radiation sensitive resin composition of the fourth embodiment of the present invention, the [C] component is introduced into the polymer to suppress the whitening . &Lt; / RTI &gt;

The monovalent organic group containing an aromatic ring is preferably a group corresponding to a monovalent organic group containing an aromatic ring in the polymer contained in the interlayer insulating film of the first embodiment. (B) a group generated by hydrolysis of a hydrolyzable group or a hydrolyzable group in the polysiloxane [component (A)] during the formation of the cured film (interlayer insulating film) using the radiation sensitive resin composition according to the present embodiment (1) of the polymer in the thin film transistor substrate according to the first embodiment can be efficiently introduced by the reaction between the [C] component and the [C] component.

Accordingly, specific examples of the monovalent organic group containing an aromatic ring of the [C] component include an aryl group and an aralkyl group which are described as monovalent organic groups in the polymer included in the interlayer insulating film of the first embodiment, Do.

As specific examples of the [C] component,

When X is a hydroxy group, phenol, naphthol, benzyl alcohol, phenoxyethanol, 2-phenylethyl alcohol,

When X is a thiol group, benzene thiol, naphthalene thiol,

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

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

.

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

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

In the radiation sensitive resin composition of the fourth embodiment of the present invention, the content of the [C] compound is not particularly limited, but the lower limit value thereof is preferably 10 parts by mass, more preferably 20 parts by mass per 100 parts by mass of the component [A] And the upper limit is preferably 400 parts by mass, more preferably 200 parts by mass, further preferably 100 parts by mass. If the content of the [C] compound is lower than the above lower limit value, the whitening inhibiting effect of the interlayer insulating film may not be sufficiently obtained. On the other hand, if the content of the [C] compound exceeds the upper limit value, there is a fear that the developability is deteriorated at the time of pattern formation.

In the radiation-sensitive resin composition of the present embodiment, the [C] compound is added as a component different from the [A] polymer, but the present invention is not limited thereto. May be added to introduce the structure of the formula (1) into the polymer [A]. Further, the [C] compound may be added to the polymer [A] during the synthesis of the polymer [A] to introduce the structure of the formula (1) into the polymer [A] .

&Lt; Other optional components >

The radiation sensitive resin composition of the embodiment of the present invention may contain a [D] compound having an action as a curing accelerator in addition to the above-mentioned [A] polymer, [B] photosensitive agent and [C] compound. The radiation-sensitive resin composition of the embodiment of the present invention may contain, in addition to the dispersant and the dispersion medium to be used together with the [C] compound, a surfactant, a storage stabilizer, , Heat resistance improver, and the like. Other optional components may be used singly or in combination of two or more. Each component will be described below.

[Surfactants]

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

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 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 , 1,2,2-tetrafluorobutyl) ether, and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, and perfluorododecylsulfonic acid Fluoroalkanes such as sodium, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, and 1,1,2,2,3,3-hexafluorodecane, Perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, Fluoroalkyls Tertiary and the like.

As commercially available products of these fluorinated surfactants, FEFOR (registered trademark) EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megapack (registered trademark) F171, 172, 173 (manufactured by DIC), FLORAD FC430, S-382, SC-101, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) FTX-218 (manufactured by NEOS), and the like.

Examples of the silicone surfactants include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH 8400 FLUID (Toray Dow Corning Silicone Co.), organosiloxane polymer KP341 (manufactured by Shinetsu Kagaku Kogyo Co., ) And the like.

When a surfactant is used as optional components, the lower limit of the content of the surfactant relative to 100 parts by mass of the component [A] is preferably 0.01 parts by mass, more preferably 0.05 parts by mass. The upper limit of the content of the surfactant is preferably 10 parts by mass, more preferably 5 parts by mass. By setting the content of the surfactant within the above range, the applicability of the radiation sensitive resin composition of the present embodiment can be optimized.

[Storage stabilizer]

Examples of the storage stabilizer include sulfur, a quinone, a hydroquinone, a polyoxy compound, an amine, and a nitrino nitro compound. More specifically, 4-methoxyphenol, N-nitroso- - phenylhydroxylamine aluminum and the like.

[Adhesion preparation]

The adhesion aid can be used for the purpose of further improving the adhesion between the interlayer insulating film obtained from the radiation sensitive resin composition of the present embodiment and the underlying layer, for example, an auxiliary capacity electrode or a planarizing film. As the adhesion 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 for example, trimethoxysilylbenzoic acid, Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane and the like.

&Lt; Preparation of radiation-sensitive resin composition >

The radiation-sensitive resin composition of the embodiment of the present invention may contain, in addition to the above-mentioned [A] polymer, the [B] photosensitizer and the [C] compound, a [D] compound or a surfactant, And mixed. At this time, in order to prepare the radiation-sensitive resin composition in the dispersion state, an organic solvent can be used. The organic solvents may be used alone or in combination of two or more.

Examples of the function of the organic solvent include adjusting the viscosity and the like of the radiation-sensitive resin composition to improve the applicability to, for example, a substrate, and improving the operability and the like. The lower limit of the viscosity measured by the E-type viscometer at 25 캜 of the radiation-sensitive resin composition realized by the incorporation of an organic solvent or the like is preferably 0.1 mPa · s, more preferably 0.5 mPa · s. The upper limit of the viscosity is preferably 50000 mPa · s, more preferably 10000 mPa · s.

Examples of the organic solvent usable in the radiation sensitive resin composition of the present embodiment include those which dissolve or disperse other contained components and do not react with other contained components.

Examples of the solvent include 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, Esters such as lactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and methyl-3-methoxypropionate, polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; .

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

As a dispersion method for preparing the radiation-sensitive resin composition in a dispersion state, a method of dispersing the radiation-sensitive resin composition is to use a paint shaker, an SC mill, an anilia type mill, a pin type mill, It may be done by the method which continues till the time. The duration time is usually several hours. In this dispersion, it is preferable to use dispersion beads such as glass beads and zirconia beads. The lower limit of the bead diameter is preferably 0.05 mm, more preferably 0.08 mm. The upper limit of the bead diameter is preferably 0.5 mm, more preferably 0.2 mm.

&Quot; Fifth Embodiment &

&Lt; Thin Film Transistor Substrate Manufacturing Method &

A method of manufacturing a thin film transistor substrate, which is an example of the fifth embodiment of the present invention, includes the steps of forming a cured film on a substrate using the radiation sensitive resin composition of the fourth embodiment of the present invention described above and forming the film as an interlayer insulating film Are included as main processes. In the manufacturing method of the thin film transistor substrate of the present embodiment, for example, the thin film transistor substrate 100 of the first embodiment of the present invention shown in Fig. 1 can be easily manufactured.

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

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

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

Processes [1] to [4] included in the method for manufacturing a thin film transistor substrate of this embodiment are as follows.

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

[3] A process for developing a coating film irradiated with radiation in the process [2] (hereinafter sometimes referred to as "[3] process"),

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

Hereinafter, the [1] step to [4] step will be described.

[Process [1]]

In this step, a coating film of the radiation sensitive resin composition of the fourth embodiment of the present invention is formed on the substrate 1. [ In this substrate 1, in addition to the TFT 2 serving as a switching element, various wirings such as a common wiring 17 and a gate wiring and a signal wiring not shown are formed. An inorganic insulating film 4 for protecting the TFT 2 is formed on the TFT 2. The inorganic insulating film 4 covers the common wiring 17 as well. A planarizing film 5 is formed on the inorganic insulating film 4 by patterning it according to a known method and forming a through hole forming a part of the contact hole 18. [ The planarizing 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 may be a film made of, for example, an acrylic resin, a polyimide resin, a polysiloxane, and a novolac resin.

A storage capacitor electrode 3 electrically connected to the common wiring 17 is disposed on the planarization film 5 through a contact hole 18 penetrating the planarization film 5 and the inorganic insulating film 4 . The contact hole 18 is formed by using a through hole formed by patterning of the planarization film 5. That is, the contact hole 18 is formed in the inorganic insulating film 4 with a through hole continuous with the through hole of the planarization film 5 by etching, using the planarization film 5 having the through hole formed by patterning as a mask The planarizing film 5, and the inorganic insulating film 4, as shown in Fig. The auxiliary capacitance electrode 3 is formed by forming a film made of a light-transmitting conductive material such as ITO on the planarization film 5 by sputtering or the like and patterning it by photolithography or the like .

In the planarizing film 5, it is preferable to form a through-hole which forms a part of the contact hole 19 when patterning the through-hole forming part of the contact hole 18. As will be described later, the through holes are formed so as to be continuous with the through holes formed in the interlayer insulating film 6, and can form part of the contact holes 19, respectively.

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

In this step, the radiation-sensitive resin composition of the fourth embodiment of the present invention is applied to the surface on which the TFT 2, the storage capacitor electrode 3, and the like are formed by using the aforementioned substrate 1, Baking is carried out to evaporate the solvent to form a coating film.

Examples of the constituent material of the above-mentioned substrate 1 include glass substrates such as soda lime glass and non-alkali glass, quartz substrates, silicon substrates, or acrylic resin, polyethylene terephthalate, polybutylene terephthalate , Polyether sulfone, polycarbonate, aromatic polyamide, polyamideimide, and polyimide. It is preferable that these substrates are subjected to a pretreatment such as cleaning or pre-annealing, if desired. Examples of the pretreatment of the substrate include chemical treatment with a silane coupling agent and the like, plasma treatment, ion plating, sputtering, gas phase reaction, 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) , An ink-jet coating method, and the like. Of these, a spin coating method or a slit coating method is preferable in that a film having a uniform thickness can be formed.

The above-mentioned prebaking condition is preferably carried out at a temperature of 70 to 120 캜, although it depends on the kind of each component constituting the radiation-sensitive resin composition, blending ratio, etc., Varies depending on the heating apparatus, but is about one minute to about 15 minutes. The lower limit of the average film thickness after prebaking of the coating film is preferably 0.3 탆, more preferably 1.0 탆. The upper limit of the average film thickness is preferably 10 占 퐉, and more preferably 7.0 占 퐉.

[Process [2]]

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

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

The lower limit of the radiation dose (also referred to as exposure dose) is preferably 10 J / m 2, as measured by a light meter (OAI model 356, manufactured by Optical Associates Inc.) at a wavelength of 365 nm, / M &lt; 2 &gt; is more preferable, and 200 J / m &lt; 2 &gt; The upper limit of the radiation dose is preferably 10,000 J / m 2, more preferably 5,000 J / m 2 or less, and still more preferably 3,000 J / m 2.

[Process [3]]

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

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

The developing method may be any of a puddle method, a dipping method, a shower method and a spraying method. The lower limit of the developing time is preferably 5 seconds at room temperature, more preferably 10 seconds, Is preferably 300 seconds, and more preferably 180 seconds. Following the development processing, for example, water-repellent cleaning is performed for 30 seconds or more for 90 seconds or less, followed by air drying with compressed air or compressed nitrogen, thereby obtaining a coating film having a desired pattern.

[Process [4]]

Subsequently, the coating film obtained in the step [3] is cured (also referred to as post-baking) by heating using a suitable heating apparatus such as a hot plate or an oven. As a result, 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.

The average film thickness of the interlayer insulating film 6 is preferably 0.3 탆 or more and 6 탆 or less.

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

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

The contact hole 19 is formed so as to be 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 formed with the through- 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.

Thereafter, the pixel electrode 7 is formed by, for example, forming a film made of a light-transmitting conductive material such as ITO on the interlayer insulating film 6 by sputtering or the like, And is performed by patterning. The formed pixel electrode 7 is connected to the TFT 2 through the contact hole 19 as described above.

The pixel electrode 7 and the storage capacitor electrode 3 are disposed on the substrate 1 so as to face each other through the interlayer insulating film 6.

As described above, a method of 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, An interlayer insulating film 6 covering the planarizing 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 The thin film transistor substrate 100 having the storage capacitor electrode 3 disposed between the interlayer insulating film 6 and the planarization film 5 can be manufactured so as to face the pixel electrode 7. [

In the manufactured thin film transistor substrate 100, an alignment film can be formed on the surface of the side where the TFT 2 or the like is disposed for the purpose of controlling the alignment of the liquid crystal.

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

[Example]

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzed 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 K.K.)

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

Mobile phase: tetrahydrofuran

<Synthesis Example of Hydrolysis-Condensate of Hydrolyzable 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 charged into a vessel equipped with a stirrer and heated until the solution temperature reached 60 캜. After the solution temperature reached 60 占 폚, a 4.4 mass% benzyl alcohol solution of oxalic acid was added and heated to 75 占 폚 and held for 3 hours. Methanol and ethanol generated in the ion-exchange water and the hydrolysis and condensation were removed by this distribution while maintaining the solution temperature at 40 占 폚 while maintaining this temperature. Subsequently, 80 g of benzyl alcohol was added to carry out this distribution again. After this distribution, benzyl alcohol was further added so that the solid content concentration became 40% by mass. Thus, a hydrolysis-condensation product (A-1) was obtained. The number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 2346 and the molecular weight distribution (Mw / Mn) was 2.2.

[Synthesis Example 2]

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

[Synthesis Example 3]

An experiment was carried out in the same manner except that the benzyl alcohol of Synthesis Example 1 was changed to 2-phenylethyl alcohol to obtain a hydrolysis-condensation product (A-3). The number-average molecular weight (Mn) of the obtained hydrolysis-condensation product 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 charged into a vessel equipped with a stirrer, and heated until the solution temperature reached 60 캜. After the solution temperature reached 60 占 폚, a 4.4 mass% propylene glycol monomethyl ether solution of oxalic acid was added, heated to 75 占 폚, and held for 3 hours. Methanol and ethanol generated in the ion-exchange water and the hydrolysis and condensation were removed by this distribution while maintaining the solution temperature at 40 占 폚 while maintaining this temperature. Subsequently, 80 g of propylene glycol monomethyl ether was added to carry out this distribution again. After this distribution, propylene glycol monomethyl ether was further added so that the solid content concentration became 40 mass%. Thus, a hydrolysis-condensation product (A-4) was obtained. The number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 2978 and the molecular weight distribution (Mw / Mn) was 3.7.

[Synthesis Example 5]

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 into a vessel equipped with a stirrer, The solution was heated until the solution temperature reached 60 占 폚. After the solution temperature reached 60 占 폚, a 4.4 mass% benzyl alcohol solution of oxalic acid was added and heated to 75 占 폚 and held for 3 hours. Methanol and ethanol generated in the ion-exchange water and the hydrolysis and condensation were removed by this distribution while maintaining the solution temperature at 40 占 폚 while maintaining this temperature. Subsequently, 80 g of benzyl alcohol was added to carry out this distribution again. After this distribution, benzyl alcohol was further added so that the solid content concentration became 40% by mass. Thus, a hydrolysis-condensation product (A-5) was obtained. The number-average molecular weight (Mn) of the obtained hydrolysis-condensation product was 2285 and the molecular weight distribution (Mw / Mn) was 2.1.

[Synthesis Example 6]

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

[Synthesis Example 7]

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

[Synthesis Example 8]

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

&Lt; Preparation of radiation-sensitive resin composition >

[Example 1]

An amount corresponding to 100 parts by mass (solid content) of the hydrolyzed condensate (A-1) and 150 parts by mass of benzyl alcohol as a component [C] containing the hydrolyzed condensate (A-1) obtained in Synthesis Example 1 (B-1) 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol ) And 0.1 part by mass of a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mole) and [F] surfactant (SH8400FLUID, manufactured by Toray Dow Corning) (Benzyl alcohol / propylene glycol monomethyl ether = 80/20 (mass%)) was added so that the amount of the solvent was 27% by mass, to prepare a radiation-sensitive resin composition. The solid content concentration in the present example means the concentration of the hydrolyzed condensates (A-1) to (A-8) (solid content), the photosensitizer (B-1 (C-1) to (C-4) and the 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 kind and amount of each component and the solid concentration were changed as shown in Table 1.

&Lt; Evaluation of physical properties &

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

[Evaluation of whitening of a cured film and transmittance thereof]

Each composition was coated on a glass substrate using a spinner and prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having an average film thickness of 3.0 mu m. The resulting coating film was exposed using a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. in such a manner that the cumulative dose was 3,000 J / m 2, and then heated in a clean oven at 230 ° C for 1 hour to obtain a cured film . In order to investigate the degree of whitening of this cured film, concavities and convexities of 3 mu m square were observed with an AFM &quot; Dimension 3100 &quot; (manufactured by Veeco). A "," 4 "Ra <7", "B", "7" Ra <10 "," C "and the case where the average roughness Ra is 1 ≦ Ra < Quot; D &quot; when 10 &amp;le; Ra. Quot; A &quot; to &quot; C &quot; were evaluated as good and the case of &quot; D &quot; The results are shown in Table 1.

The light transmittance of the glass substrate having the cured film was measured by using a spectrophotometer "150-20 type double beam" (manufactured by Hitachi, Ltd.) at a wavelength in the range of 300 to 500 nm. 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 is good.

[Evaluation of outgassing]

The composition solution was coated on a substrate and dried to form a film having an average film thickness of 6.0 mu m. Subsequently, headspace gas chromatography / mass spectrometry (mass spectrometry) was carried out on this film using n-octane as a standard substance (specific gravity = 0.701, injection amount, 0.02 μl) (JHS-100A manufactured by Nihon Bunseki Kogyo Co., Ltd., gas chromatography / mass spectrometer, JMS-AX505W type mass spectrometer manufactured by JEOL Corporation), and the peak area A derived from the compound having each aromatic ring was determined. The volatilization amount of a compound having an omnidirectional ring by n-octane conversion was calculated by a calculation formula, and the total amount was calculated as the volatilization amount (쨉 g) of the aromatic ring compound. When the volatilization amount exceeded 0.5., It was judged that the outgas component derived from the benzene ring was large.

Calculation of volatilization amount by n-octane conversion

Amount of volatiles (쨉 g) of compounds having aromatic rings = A 占 (amount of n-octane) (占 퐂) / (peak area of n-octane)

[Evaluation of solvent resistance]

The composition solution was coated on a substrate and then dried to form a coating film. The resulting coating film was exposed through a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so as to have an integrated irradiation amount of 3,000 J / m 2 without a pattern mask interposed therebetween. The silicon substrate was heated in a clean oven at 230 캜 for 30 minutes A cured film having an average film thickness of 3.0 탆 was obtained. The average film thickness (T1) of the cured film obtained here was measured. Then, the silicon substrate on which the cured film was formed was immersed in N-methyl-2-pyrrolidone controlled at 45 캜 for 6 minutes, and then the average film thickness t1 of the cured film was measured. The average film thickness 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, the solvent resistance is good.

[Evaluation of storage stability]

The composition solution was heated in an oven at 40 占 폚 for 1 week, and the resulting sample was coated on a substrate and dried to form a film. Subsequently, using an exposure apparatus ("MPA-600FA (ghi line mixing)" manufactured by Canon Inc.) and using a mask having a 10 μm line-and-space (one-to-one) pattern, And irradiated with radiation. Thereafter, the resist film was developed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 캜 for 80 seconds by a puddle method. Then, the substrate was subjected to water washing with ultra-pure water for 1 minute, and then dried to form a pattern on the glass substrate. At this time, the amount of exposure required to form a space pattern of 10 mu m was examined. The radiation sensitivity before and after heating was measured, and the rate of change (%) of the required exposure dose was determined to be an index of storage stability. The case where the rate of change is less than 5% is defined as &quot; A &quot;, the rate of change from 5% to less than 10% is defined as &quot; B &quot; The results are shown in Table 1.

In Table 1, the abbreviations of the [B] photosensitizer, the [C] compound and the [F] surfactant are as follows.

B-1: Synthesis of 4,4 '- [l- [4- [1- (4-hydroxyphenyl) -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediamine 5-sulfonic acid chloride (3.0 mol)

B-2: A 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 Incorporated

"-" in Table 1 indicates that the cured film was not measured because it was whitened. Further, the radiation-sensitive resin compositions of Examples 1 to 6 and 11 using a solution containing the hydrolysis-condensation product (A-1) further contained benzyl alcohol as a component [C] do. Similarly, the radiation-sensitive resin compositions of Examples 7 and 12 using the solution containing the hydrolyzed condensate (A-2) were prepared by adding 2-phenoxyethanol contained in this solution as the [C] component . The radiation-sensitive resin compositions of Examples 8 and 13 using the solution containing the hydrolyzed condensate (A-3) further contained 2-phenylethyl alcohol contained in the solution as the [C] component . The radiation-sensitive resin compositions of Examples 10 and 15 using the solution containing the hydrolysis-condensation product (A-5) further contained benzyl alcohol contained in the solution as the [C] component.

The abbreviations in Table 1 are as follows.

BnOH: benzyl alcohol

PhO (CH ₂ ) ₂ OH: 2-phenoxyethanol

Ph (CH ₂ ) ₂ OH: 2-phenylethyl alcohol

PGME: Propylene glycol monomethyl ether

EDM: diethylene glycol methyl ethyl ether

As shown in Table 1, the cured films formed by the radiation sensitive resin compositions of Examples 1 to 15 are excellent in light transmittance and solvent resistance as well as suppressed whitening of the cured film and volatilization of benzene. Further, by preparing a component composition, storage stability can be enhanced. Therefore, the cured film formed from these radiation sensitive resin compositions can be suitably used for an interlayer insulating film of a thin film transistor substrate, a liquid crystal display element using the same, and an organic EL element.

The present invention is not limited to the above-described embodiments, but may be modified in various ways within the scope not departing from the gist of the present invention.

1: substrate
2: TFT
3: auxiliary capacity electrode
4: Inorganic insulating film
5: Planarizing film
6: Interlayer insulating film
7:
10: gate electrode
11: Gate insulating film
12: semiconductor layer
13: drain electrode
14: source electrode
17: Common wiring
18, 19: Contact hole
80:
100: thin film transistor substrate
110: opposing substrate
111: liquid crystal layer
200: liquid crystal display element
201: Organic EL device
202: Support substrate
203: Thin Film Transistor (TFT)
204: inorganic insulating film
205: interlayer insulating film
206: anode (as the first electrode)
207: Through hole
208:
209: light emitting layer
210: cathode (as second electrode)
211: Passivation film
212: sealing substrate
213: sealing layer
230: gate electrode
231: Gate insulating film
232: semiconductor layer
233: source electrode
234: drain electrode

Claims (12)

A substrate;
A thin film transistor disposed on the substrate;
A thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,
Wherein the interlayer insulating film comprises a polymer having a structure represented by the following formula (1):

(In the formula (1), R ¹ represents a divalent linking group containing a hetero atom, R ² represents a monovalent organic group containing an aromatic ring;
* Indicates the binding site). The method according to claim 1,
R ¹ represents -O-, -S-, -OC (= O) - or -NH-. The method according to claim 1,
The content of an aromatic ring derived from the formula (1) in the interlayer insulating film is 1 mol% or more and 60 mol% or less with respect to Si atoms in the interlayer insulating film. The method according to claim 1,
Wherein the R ² represented by the formula (1) is represented by the following formula (2):

(In the formula (2), R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a halogen atom;
n represents an integer of 0 to 6;
m represents 0 or 1). The method according to claim 1,
Wherein the thin film transistor has a semiconductor layer formed using an oxide semiconductor. 6. The method of claim 5,
Wherein the semiconductor layer is formed of indium, gallium, and zinc oxide. The method according to claim 1,
Wherein the thin film transistor has a semiconductor layer formed using either amorphous silicon or crystalline silicon. The method according to claim 1,
Wherein the interlayer insulating film is a polysiloxane film. A liquid crystal display device comprising: the thin film transistor substrate according to any one of claims 1 to 8; an opposing substrate having opposing electrodes facing the thin film transistor substrate; and a liquid crystal layer disposed between the thin film transistor substrate and the opposing substrate Liquid crystal display element. An organic EL device comprising the thin film transistor substrate according to any one of claims 1 to 8, an interlayer insulating film, and a light emitting layer in this order. [A] Polymer,
[B] Photosensitizer,
[C] a compound represented by the following formula (3)
A radiation-sensitive resin composition,
A substrate;
A thin film transistor disposed on the substrate;
A radiation-sensitive resin composition used for forming the interlayer insulating film of a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor:

(In the 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). A substrate;
A thin film transistor disposed on the substrate;
A method of manufacturing a thin film transistor substrate having an interlayer insulating film disposed on the thin film transistor,
[1] A method for manufacturing a thin film transistor, comprising the steps of: forming a coating film of the radiation sensitive resin composition according to claim 11 on the substrate on which the thin film transistor is formed;
[2] a step of irradiating at least a part of the coating film formed in the step [1]
[3] a step of developing the coating film irradiated with the radiation in the step [2]
[4] Step of forming the interlayer insulating film by heating the developed coating film in the step [3]
Wherein the thin film transistor substrate has a thickness of 50 nm.

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