TW201533524A - Method for forming insulating film and device using insulating film - Google Patents

Abstract

A display or illuminating device of the invention includes: a thin film transistor (TFT) substrate; a first electrode, disposed on the TFT substrate and connected to a TFT; an insulating film, formed on the first electrode to partially expose the first electrode, a total light transmittance of which is in a range of 0%-15% in a wavelength of 300 nm-400 nm; and a second electrode, disposed opposite to the first electrode. The insulating film is formed with a radiation-sensitive material. The radiation-sensitive material includes (A) a polymer, (B) a photosensitizer and (C) a resin such as novolak resin. The content of the resin (C) in the radiation-sensitive material is 2-200 parts by weight with respect to 100 parts by weight of the polymer (A).

Description

Display or illumination device and method of forming insulating film

The present invention relates to a display or illumination device and a method of forming an insulating film. More specifically, the present invention relates to an insulating film having a substrate, a first electrode provided on the substrate, and a first electrode partially exposed to expose the first electrode, and a first electrode The display or illumination device of the second electrode and the method of forming the insulating film are provided.

As a flat panel display, a non-emissive liquid crystal display (LCD) is popularized. Further, in recent years, an electroluminescent display (ELD) as a self-luminous display has been known. In particular, an organic electroluminescence (EL) element that emits light by an electric field of an organic compound is expected as a light-emitting element provided in a display device of the next generation, and is expected as a light-emitting element provided in a next-generation illumination device. .

For example, an organic EL display or illumination device has an insulating film such as a planarizing film and a partition wall separating pixels (light emitting elements). Such an insulating film is usually formed using a radiation-sensitive resin composition (see, for example, Patent Document 1 and Patent Document 2).

These flat panel displays operate by applying a voltage or a current between the opposing first and second electrodes. However, at this time, the electric field tends to concentrate on the edge portion of the electrode having a small radius of curvature, so that an undesirable phenomenon such as insulation breakdown or leakage current is likely to occur at the edge portion.

In order to solve this problem, it is disclosed that the thickness of the insulating film at the boundary portion where the first electrode is exposed by the insulating film is gradually increased from the central portion of the first electrode toward the edge portion, and the cross section is set to A technique of a positive conical shape (for example, refer to Patent Document 3).

Further, in recent years, studies on thin film transistors (TFTs) using an oxide semiconductor layer have been actively conducted. Patent Document 4 proposes an example in which a polycrystalline thin film containing an oxide of In, Ga, or Zn (hereinafter also referred to as "Indium Gallium Zinc Oxide (IGZO)") is used for a semiconductor layer of a TFT. Patent Document 4 and Patent Document 5 propose an example in which an amorphous thin film of IGZO is used for a semiconductor layer of a TFT.

However, for IGZO, photodegradation caused by natural light, lighting, manufacturing steps, and the like is known. Therefore, when a TFT including a semiconductor layer containing a substance having a large photodegradation such as IGZO is used as a driving element of a display or illumination device, particularly a driving element of an organic EL element, the viewpoint of preventing photodegradation of IGZO is considered. It is required to impart a light-shielding property to ultraviolet to visible light as a characteristic of the insulating film. However, the insulating film currently used is, for example, mostly transparent in a wavelength region of 300 to 400 nm, and is required to impart a light blocking property.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-107476

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-237310

[Patent Document 3] Japanese Patent No. 4982927

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-103957

[Patent Document 5] International Publication No. 2005/088726

An object of the present invention is to provide a display or illumination device having a thin film transistor as a driving element, the thin film transistor containing a semiconductor layer containing a substance having a large photodegradation such as IGZO, and in the display or illumination device, Photodegradation of the substance accompanying the use of such devices is suppressed.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that the above problems can be solved by adopting the following constitution, and the present invention has been completed. The present invention relates to, for example, the following [1] to [19].

[1] A display or illumination device comprising: a TFT substrate, wherein a semiconductor layer constituting the TFT includes an oxide semiconductor, and the oxide semiconductor contains one or more selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn. An element; the first electrode is provided on the TFT substrate and connected to the TFT; and the insulating film is formed on the first electrode so that the first electrode is partially exposed, and the total light transmittance is at a wavelength of 300 nm to 400 nm. In the range of 0% to 15%; and the second electrode, and the first electric The insulating film is an insulating film formed of a radiation-sensitive material containing (A) a polymer other than the following resin (C), (B) a sensitizer, and (C) at least one resin selected from the group consisting of a phenol aldehyde resin, a resol phenol resin, and a resol phenol resin, and a resin (C) in the radiation sensitive material with respect to 100 parts by mass of the polymer (A) The content is 2 parts by mass to 200 parts by mass.

[2] The display or illumination device according to [1], wherein the polymer (A) is selected from the group consisting of polyimine (A1), a precursor of the polyimine (A2), and an acrylic resin. (A3), polyoxyalkylene (A4), polybenzoxazole (A5-1), precursor of the polybenzoxazole (A5-2), polyolefin (A6) and cardo resin (A7) At least one of them.

[3] The display or illumination device according to [1], wherein the polymer (A) is selected from the group consisting of polyoxyalkylene (A4), polybenzoxazole (A5-1), and the polybenzoic acid. At least one of a precursor of oxazole (A5-2), a polyolefin (A6), and a cardo resin (A7).

[4] The display or illumination device according to [2], wherein the polyimine (A1) contains a structural unit represented by the formula (A1),

[In the formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group].

[5] The display or illumination device according to [2] or [3] wherein the polyoxyalkylene (A4) is a polyoxyalkylene obtained by reacting an organodecane represented by the formula (a4),

In the formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a carbon number of 2 to 15. The epoxy ring-containing group or a group obtained by substituting one or two or more hydrogen atoms contained in the alkyl group with a substituent may be the same or different when R ^{1 is} present in plurality R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, and may be the same or different when R ^{2 is} present in plurality; n is an integer from 0 to 3.].

[6] The display or illumination device according to [2] or [3] wherein the polybenzoxazole (A5-1) contains a structural unit represented by the formula (a5-1),

[In the formula (a5-1), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group].

[7] The display or illumination device according to [2] or [3] wherein the precursor of the polybenzoxazole (A5-2) contains the structural unit represented by the formula (a5-2),

[In the formula (a5-2), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group].

[8] The display or illumination device according to any one of [1] to [7] wherein the photosensitive agent (B) is a photoacid generator or a photoradical polymerization initiator.

[9] The display or illumination device according to any one of [1] to [8] wherein the resin (C) is a novolac resin.

[10] The display or illumination device according to any one of the above [1], wherein the insulating film has a cross-sectional shape of a boundary portion of the insulating film in which the first electrode is exposed is a regular conical shape .

[11] The display or illumination device according to any one of [1] to [10] wherein the insulating film has a film thickness of 0.3 μm to 15.0 μm.

[12] The display or illumination device according to any one of [1], wherein the insulating film is formed to cover at least an edge portion of the first electrode, and the insulating film The cross-sectional shape of the boundary portion is a regular conical shape.

[13] The display or illumination device according to any one of [1] to [12] wherein the insulating film is a partition wall that partitions a surface of the TFT substrate into a plurality of regions, and The display or illumination device has pixels respectively formed in the plurality of regions.

[14] The display or illumination device according to [13], wherein the organic EL device includes a first electrode provided on the TFT substrate and connected to the TFT, and is formed in the The organic light-emitting layer formed on the first electrode and the second electrode provided on the organic light-emitting layer in the region partitioned by the partition wall.

[15] The display or illumination device according to [14], wherein the TFT substrate has a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a TFT covered a planarization layer, wherein the partition wall covers at least an edge portion of the first electrode, and the partition wall is formed on the planarization layer so as to be disposed at least above the semiconductor layer of the TFT .

[16] The display or illumination device according to [15], wherein the first electrode is formed on the planarization layer, and the first electrode is formed through a through hole penetrating the planarization layer. The wiring is connected to the TFT.

The display or illumination device according to any one of the above aspects, wherein the insulating film is formed on the TFT substrate so as to be disposed at least over the semiconductor layer. When viewed from above the TFT substrate, 50% or more of the area of the semiconductor layer overlaps with the insulating film.

[18] A method of forming an insulating film, which comprises the insulating film of the display or illumination device according to [1], and the method for forming the insulating film comprises the following steps: Step 1, using the patent application scope The radiation sensitive material according to the first aspect forms a coating film on the TFT substrate; in step 2, at least a part of the coating film is irradiated with radiation; in step 3, the radiation-coated coating film is developed; and step 4 The developed coating film is heated to form an insulating film having a total light transmittance in a range of 0% to 15% at a wavelength of 300 nm to 400 nm.

[19] The method for forming an insulating film according to [18], wherein the heating temperature in the step 1 is 60 ° C to 130 ° C, and the heating temperature in the step 4 is more than 130 ° C and 300 ° C or less.

According to the present invention, there can be provided a display or illumination device having a thin film transistor as a driving element, the thin film transistor containing a semiconductor layer containing a substance having a large photodegradation such as IGZO, and in the display or illumination device, Photodegradation of the substance accompanying the use of such devices is suppressed.

1‧‧‧Organic EL device

2‧‧‧Support substrate

3‧‧‧TFT

4‧‧‧1st insulating film (planar film)

5‧‧‧Anode

6‧‧‧through holes

7‧‧‧2nd insulating film (wall)

8‧‧‧Organic light-emitting layer

9‧‧‧ cathode

10‧‧‧ Passivation film

11‧‧‧Seal substrate

12‧‧‧ Sealing layer

70‧‧‧ recess

100‧‧‧TFT substrate

110‧‧‧1st electrode

111‧‧‧The opening of the insulating film

112‧‧‧The edge of the first electrode

113‧‧‧1st electrode face

120‧‧‧Insulation film

121‧‧‧Slope of insulating film

Θ‧‧‧ angle (cone angle)

FIG. 1 is a plan view showing an example of the shape of an insulating film.

2(a) and 2(b) are cross-sectional views showing a regular conical shape as a cross-sectional shape of an insulating film.

3 is a schematic cross-sectional view showing the configuration of a main part of an organic EL device.

The display or illumination device of the present invention includes a TFT substrate, and the semiconductor layer constituting the TFT is a layer containing an oxide semiconductor containing one or more selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn. The first electrode is provided on the TFT substrate and is connected to the TFT; the insulating film is formed on the first electrode so that the first electrode is partially exposed; and the second electrode and the first electrode Set relative to each other. Here, the total light transmittance of the insulating film is 0% to 15% at a wavelength of 300 nm to 400 nm.

Hereinafter, the display or illumination device will be collectively referred to as "device".

The display device of the present invention may, for example, be a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescent display (ELD), or particularly an organic EL display. The illuminating device of the present invention is exemplified by organic EL illumination.

In the device of the present invention, the specific examples (support substrate, TFT, anode, and cathode) described in the column of [organic EL display device and organic EL illumination device] to be described later can be exemplified, for example, in the TFT substrate, the first electrode, and the second electrode. ).

In the device of the present invention, the insulating film is formed to cover at least a part of the first electrode and partially expose the first electrode. It is preferable that the insulating film is formed so as to cover the edge portion of the first electrode.

An example of the shape of the insulating film is shown in FIG. A first electrode 110 formed in a stripe shape is formed on the TFT substrate 100. The insulating film 120 is formed on the TFT substrate 100 and the first electrode 110 so that the first electrode 110 is partially exposed. The exposed portion of the electrode 110 is also referred to as an "opening portion 111". Here, the insulating film 120 is formed to cover the edge portion 112 of the first electrode 110. The opening portion 111 can correspond to one light-emitting region, that is, a pixel, for example, in an organic EL device.

The cross-sectional shape of the insulating film is preferably a regular conical shape in a boundary portion where the first electrode is exposed. Here, the "normally conical shape" corresponds to an angle θ between the inclined surface 121 of the boundary portion where the first electrode 110 is exposed in the insulating film 120 and the first electrode surface 113, for example, FIG. 2(a) and FIG. The angle θ in 2(b) is less than 90°. Hereinafter, the angle θ is also referred to as a "cone angle θ". The taper angle θ is preferably 80° or less, more preferably 5° to 60°, still more preferably 10° to 45°.

For example, in the case of the organic EL device, when the cross-sectional shape of the insulating film at the boundary portion is a regular conical shape, even when the organic light-emitting layer and the second electrode are formed after the formation of the insulating film, it is also in the boundary portion. By smoothly forming the films, it is possible to reduce the film thickness unevenness caused by the step, and to obtain a light-emitting device having stable characteristics.

The film thickness of the insulating film is not particularly limited, and is preferably from 0.3 μm to 15.0 μm, more preferably from 0.5 μm to 10.0 μm, even more preferably 1.0 μm, in view of light blocking property and easiness of film formation or patterning. 5.0 μm.

The insulating film is formed, for example, so as to straddle the adjacent first electrodes. Therefore, good electrical insulation is required for the insulating film. The volume resistivity of the insulating film is preferably 10 ¹⁰ μΩ. More than cm, more preferably 10 ¹² μΩ. More than cm.

The total light transmittance of the insulating film at a wavelength of 300 nm to 400 nm is 0% to 15%, preferably 0% to 10%, and particularly preferably 0% to 6%. That is, the maximum value of the total light transmittance at a wavelength of 300 nm to 400 nm is 15% or less, preferably 10% or less, and particularly preferably 6% or less. The total light transmittance can be measured, for example, by using a spectrophotometer ("150-20 type double beam" manufactured by Hitachi, Ltd.).

The insulating film is, for example, a partition wall that partitions the surface of the TFT substrate into a plurality of regions, and pixels are formed in the plurality of regions. The insulating film (partition wall) is preferably formed on the TFT substrate so as to be disposed at least above the semiconductor layer from the viewpoint of light shielding properties of the semiconductor layer included in the TFT. Here, "above" means a direction from the TFT substrate toward the second electrode. In the case of projecting from above the TFT substrate, an example in which the area of the semiconductor layer is 50% or more and the insulating film (partition wall) is repeated, and in particular, 80% or more of the area of the semiconductor layer, and further More than 90%, especially 100%, overlaps with the insulating film (wall).

As described above, in the device of the present invention, the insulating film that exposes the first electrode has light blocking properties at the wavelength. By providing such an insulating film, even if the thin film transistor including the semiconductor layer is used as a device for driving, and the semiconductor layer contains a substance having large photodegradation such as IGZO, the insulating film functions as a light shielding film. It is possible to suppress photodegradation of the semiconductor layer accompanying use of the device or the like.

For example, the semiconductor layer constituting the TFT is a layer containing an oxide semiconductor containing an oxide selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn. More than one element. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture of these oxides.

Examples of the oxide semiconductor containing one or more elements selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn include quaternary metal oxides such as In-Sn-Ga-Zn-O-based oxide semiconductors. In-Ga-Zn-O-based oxide semiconductor, In-Sn-Zn-O-based oxide semiconductor, In-Al-Zn-O-based oxide semiconductor, Sn-Ga-Zn-O-based oxide semiconductor, Al a ternary metal oxide such as a -Ga-Zn-O-based oxide semiconductor or a Sn-Al-Zn-O-based oxide semiconductor; an In-Zn-O-based oxide semiconductor, and a Sn-Zn-O-based oxide semiconductor; Binary of Al-Zn-O-based oxide semiconductor, Zn-Mg-O-based oxide semiconductor, Sn-Mg-O-based oxide semiconductor, In-Mg-O-based oxide semiconductor, or In-Ga-O-based material A metal oxide; a monovalent metal oxide such as an In—O based oxide semiconductor, a Sn—O based oxide semiconductor, or a Zn—O based oxide semiconductor.

In the present invention, even when the semiconductor layer constituting the TFT is the oxide semiconductor layer, particularly in the case of an oxide semiconductor layer including an In—Ga—Zn—O-based oxide semiconductor (IGZO semiconductor), Prevent its light from deteriorating.

The apparatus of the present invention is preferably an organic EL device having an organic EL element having a first electrode provided on the TFT substrate and connected to the TFT, and being formed by the partition wall An organic light-emitting layer formed on the first electrode and a second electrode provided on the organic light-emitting layer.

The TFT substrate has, for example, a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a planarization layer covering the TFT. For example, the first electrode is formed on the planarization layer and is passed through A wiring formed in the through hole of the planarization layer is connected to the TFT. Moreover, it is preferable that the insulating film (partition wall) having a light-shielding property is formed on the first electrode and the planarization layer so that the first electrode is partially exposed.

The insulating film that exposes the first electrode can be formed, for example, using a radiation sensitive material. Among the radiation sensitive materials, there are a positive type in which the solubility in the developer is increased by exposure, a positive type in which the exposed portion is removed, and a negative type which is cured by exposure and removes the non-exposed portion. When the coating film formed of the radiation sensitive material is exposed, light is strongly absorbed on the surface portion of the coating film, and the amount of absorption tends to decrease toward the inside of the coating film. Therefore, in the case of a positive type, the solubility of the surface part of the coating film is larger than the internal solubility, and in the case of a negative type, it is the opposite tendency. In the present invention, since the cross-sectional shape of the boundary portion of the insulating film is preferably set to a regular conical shape, it is preferable to form the pattern by using a positive-type radiation-sensitive material.

[radial sensing material]

The radiation sensitive material can be used to form the insulating film in the display or illumination device of the present invention. The radiation sensitive material is preferably a resin (C) containing at least one of a polymer (A), a photosensitizer (B), and a condensate selected from the group consisting of a novolak resin, a resol resin, and a resol resin.

The radiation sensitive material may further contain a crosslinking agent (D) as a preferred component, and may further contain a solvent (E) as a preferred component. Further, the radiation sensitive material may contain other optional components within a range that does not impair the effects of the present invention.

The radiation sensitive agent material has high radiation sensitivity, and by using the material, an insulating film having an excellent pattern shape can be formed, and the narrow pitch of the pattern can be Respond to the requirements. Further, by using the material, an insulating film having low water absorbability can also be formed.

Hereinafter, each component will be described in detail.

[Polymer (A)]

The polymer (A) is preferably an alkali-soluble polymer other than the resin (C). The term "base soluble" in the polymer (A) means that it can be dissolved in an alkali solution, for example, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

The polymer (A) may, for example, be selected from the group consisting of polyimine (A1), a precursor of the polyimine (A2), an acrylic resin (A3), a polyoxyalkylene (A4), and polybenzazole. At least one of azole (A5-1), a precursor of the polybenzoxazole (A5-2), a polyolefin (A6), and a cardo resin (A7).

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A) is preferably 2,000 to 500,000, more preferably 3,000, as measured by a gel permeation chromatography (GPC) method. ~100,000, and then 4,000~50,000. When Mw is at least the lower limit of the above range, an insulating film having sufficient mechanical properties tends to be obtained. When Mw is at most the upper limit of the above range, the polymer (A) tends to be excellent in solubility in a solvent or a developing solution.

The content of the polymer (A) is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and further preferably 30% by mass based on 100% by mass of the total solid content in the radiation sensitive material. ~60% by mass.

Polyethylenimine (A1)

The polyimine (A1) preferably contains a structural unit represented by the formula (A1).

In the formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group.

R ^{1 is,} for example, a divalent group represented by the formula (a1).

In the formula (a1), R ² is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group or a bis(trifluoromethyl)methylene group; and R ^{3 is} independently The ground is a hydrogen atom, a decyl group, a fluorenyl group or an alkyl group. Among them, at least one of R ³ is a hydrogen atom. N1 and n2 are each independently an integer of 0-2. Wherein at least one of n1 and n2 is 1 or 2. When the total of n1 and n2 is 2 or more, a plurality of R ^{3 's} may be the same or different.

Examples of the fluorenyl group in R ³ include a group having 2 to 20 carbon atoms such as an ethyl group, a propyl group, a butyl group, and an isobutyl group; and examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. A group having 1 to 20 carbon atoms such as a group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group or n-dodecyl group.

The divalent group represented by the formula (a1) is preferably a divalent group having 1 to 4 hydroxyl groups, more preferably a divalent group having 2 hydroxyl groups. The divalent group having one to four hydroxyl groups represented by the formula (a1) is, for example, a divalent group represented by the following formula. Further, in the following formula, two "-" extending from the aromatic ring represent a bond.

The tetravalent organic group represented by X may, for example, be a tetravalent aliphatic hydrocarbon group or a tetravalent group. An aromatic hydrocarbon group or a group represented by the following formula (1). X is preferably a tetravalent organic group derived from a tetracarboxylic dianhydride. Among these groups, a group represented by the following formula (1) is preferred.

In the formula (1), Ar is each independently a trivalent aromatic hydrocarbon group, and A is a direct bond or a divalent group. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis(trifluoromethyl)methylene group.

The tetravalent aliphatic hydrocarbon group has a carbon number of usually 4 to 30, preferably 8 to 24. The carbon number of the tetravalent aromatic hydrocarbon group and the trivalent aromatic hydrocarbon group in the formula (1) is usually 6 to 30, preferably 6 to 24.

Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aliphatic hydrocarbon group containing an aromatic ring in at least one part of the molecular structure.

Examples of the tetravalent chain hydrocarbon group include a tetravalent group derived from a chain hydrocarbon such as n-butane, n-pentane, n-hexane, n-octane, n-decane or n-dodecane.

Examples of the tetravalent alicyclic hydrocarbon group include a tetravalent group derived from a hydrocarbon such as cyclobutane, cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, cyclohexene, cyclooctane or the like. Hydrocarbon; bicyclo[2.2.1]heptane, bicyclo[3.1.1]heptane, bicyclo[3.1.1]hept-2-ene, bicyclo[2.2.2]octane, bicyclo[2.2.2]xin- a bicyclic hydrocarbon such as 5-ene; tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[5.2.1.0 ^2,6 ]non-4-ene, adamantane, tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] A tricyclic or higher hydrocarbon such as dodecane.

The aliphatic hydrocarbon group containing an aromatic ring in at least a part of the molecular structure is preferably, for example, a group having a number of benzene nuclei contained in the group of 3 or less, and particularly preferably a number of benzene nuclei is one. Group. More specifically, a tetravalent group derived from 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene or 1-ethyl-1,2,3,4-tetrahydronaphthalene .

In the above description, the tetravalent group derived from the hydrocarbon is a tetravalent group formed by removing four hydrogen atoms from the hydrocarbon. The portion where the four hydrogen atoms are removed is a portion where the tetracarboxylic dianhydride structure can be formed when the four hydrogen atoms are substituted with four carboxyl groups.

The tetravalent aliphatic hydrocarbon group is preferably a tetravalent group represented by the following formula. Further, in the following formula, four "-" extending from the chain hydrocarbon group and the alicyclic ring represent a bond.

Examples of the tetravalent aromatic hydrocarbon group and the group represented by the formula (1) include the following A tetravalent group represented by the formula. In the following formula, four "-" extending from the aromatic ring represent a bond.

The polyimine (A1) can be obtained by imidization of ruthenium of the polyimine precursor (A2) which will be described below. The ruthenium iodization here can be carried out completely or locally. That is, the sulfhydrylation rate may not be 100%. Therefore, the polyimine (A1) may further contain at least one selected from the structural unit represented by the formula (A2-1) and the structural unit represented by the formula (A2-2) which will be described below.

In the polyimine (A1), the ruthenium amination ratio is preferably 5% or more, more preferably 7.5% or more, and still more preferably 10% or more. The upper limit of the sulfhydrylation ratio is preferably 50%, more preferably 30%. When the imidization ratio is within the above range, heat resistance and solubility of the exposed portion in the developer are preferred.

The hydrazine imidation ratio can be measured, for example, as follows. First, the measurement of infrared absorption spectrum of polyimide was confirmed acyl imine absorption peak caused by the polyimide (near 1780 cm ^-1, near 1377 cm ^-1) exists. Then, the polyimide was subjected to heat treatment at 350 ° C for 1 hour, and then the infrared absorption spectrum was measured again. The peak intensity near 1377 cm ^-1 before and after the heat treatment was compared. The ruthenium imidization ratio of the heat-treated polyimine was set to 100%, and the oxime imidization ratio of the polyimine before heat treatment was determined = {peak intensity near 1377 cm ^-1 before heat treatment / after heat treatment Peak intensity near 1377 cm ^-1 × 100 (%). For the measurement of the infrared absorption spectrum, for example, "NICEIT 6700 Fourier Transform Infrared (FT-IR)" (manufactured by Thermo Electron) is used.

In the polyimine (A1), the total content of the structural units represented by the formula (A1), the formula (A2-1), and the formula (A2-2) is usually 50% by mass or more, preferably 60% by mass or more. More preferably, it is 70% by mass or more, and particularly preferably 80% by mass or more.

Polyethylenimine precursor (A2)

The polyimine precursor (A2) is a polyfluorene (A1) which can be formed by dehydration or cyclization (imidization), preferably containing a structural unit represented by the formula (A1). A compound of the amine (A1). The polyimine precursor (A2) may, for example, be a polyamic acid or a poly-proline derivative.

(polyglycine)

The polyamic acid contains a structural unit represented by the formula (A2-1).

In the formula (A2-1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. The divalent group having a hydroxyl group represented by R ¹ and the tetravalent organic group represented by X are the same as those exemplified as R ¹ and X in the formula (A1).

In the polyamic acid, the content of the structural unit represented by the formula (A2-1) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. .

(polyproline derivatives)

The polyproline derivative is a derivative synthesized by esterification or the like of polyproline. The polyamine derivative is, for example, a polymer obtained by substituting a hydrogen atom of a carboxyl group in a structural unit represented by the formula (A2-1) contained in the polyamic acid with another group, and preferably a polyfluorene. Amine ester.

The polyglycolate is an esterified polymer of at least a portion of a carboxyl group possessed by polyphthalic acid. The polyperactamate is a polymer containing a structural unit represented by the formula (A2-2) which can form a polyimine (A1) containing a structural unit represented by the formula (A1).

In the formula (A2-2), R ¹ is a divalent group having a hydroxyl group, X is a tetravalent organic group, and R ^{4 is} each independently an alkyl group having 1 to 5 carbon atoms. The divalent group having a hydroxyl group represented by R ¹ and the tetravalent organic group represented by X are the same as those exemplified as R ¹ and X in the formula (A1). Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, and a propyl group.

In the polyphthalate, the content of the structural unit represented by the formula (A2-2) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. .

"Synthesis method of polyimine (A1) and polyimine precursor (A2)"

The polyamic acid as the polyimine precursor (A2) can be obtained, for example, by polymerizing a tetracarboxylic dianhydride with a diamine including a diamine having a hydroxyl group and optionally other diamines. . The ratio of use of these compounds is, for example, 0.3 mol to 4 mol, preferably substantially equimolar, relative to 1 mol of the tetracarboxylic dianhydride. In the polymerization, it is preferred to heat the mixed solution of the tetracarboxylic dianhydride and the all diamines at 50 ° C to 200 ° C for 1 hour to 24 hours.

Hereinafter, the tetracarboxylic dianhydride and the diamine having a hydroxyl group are also referred to as "acid dianhydride (A1-1) and "diamine (A1-2)", respectively, and the other diamines are also referred to as It is "diamine (A1-2')".

The synthesis of polylysine can be carried out by dissolving the diamine (A1-2) in the polymerization solvent, and then reacting the diamine (A1-2) with the acid dianhydride (A1-1), or by After the acid dianhydride (A1-1) is dissolved in a polymerization solvent, the acid dianhydride (A1-1) is reacted with a diamine (A1-2).

The polyphthalic acid derivative which is a polyimine precursor (A2) can be synthesized by esterifying the carboxyl group of the polyamic acid. The method of esterification is not particularly limited, and a known method can be applied.

The polyimine (A1) can be synthesized, for example, by synthesizing polylysine by the method, and then dehydrating and cyclizing the polyamic acid; or by the following Synthetic method: After synthesizing the polyaminic acid derivative by the method, the polyaminic acid derivative is imidized.

A known method such as heating a ruthenium imidization reaction or a chemical hydrazine imidization reaction can be applied to the ruthenium iodide reaction of poly-proline and poly-proline derivatives. In the case of heating the hydrazine imidization reaction, it is preferred to heat the solution containing the polyamic acid and/or the poly-proline derivative at 120 ° C to 210 ° C for 1 hour to 16 hours. The hydrazine imidization reaction may be carried out by removing the water in the system while using an azeotropic solvent such as toluene, xylene or mesitylene.

Further, when a diamine is used excessively with respect to the tetracarboxylic dianhydride, a dicarboxylic acid anhydride such as maleic anhydride may be used as the polyimine, polylysine, and poly-proline derivative. End capping end capping agent.

The acid dianhydride (A1-1) is, for example, an acid dianhydride represented by the formula (a2).

In the formula (a2), X is a tetravalent organic group. The tetravalent organic group represented by X may be the same as the group exemplified as X in the formula (A1).

The diamine (A1-2) is, for example, a diamine represented by the formula (a3).

H ₂ N-R ₁ -NH ₂    (a3)

In the formula (a3), R ¹ is a divalent group having a hydroxyl group. The divalent group having a hydroxyl group represented by R ¹ may be the same as the group exemplified as R ¹ in the formula (A1).

Other diamines (A1-2') other than the (A1-2) may be used together with the diamine (A1-2). The other diamine (A1-2') may, for example, be at least one diamine selected from the group consisting of an aromatic diamine and an aliphatic diamine having no hydroxyl group.

Polyimide (A1) may also have more formula (A1), the formula (A2-1) and the formula (A2-2) R ¹ is changed to the other residue of a diamine (A1-2 ') of Structural unit. Likewise, the polyimide precursor (A2) may be more in the formula (A2-1) and the formula (A2-2) R ¹ is changed to the other residue of a diamine (A1-2 ') of Structural unit.

The polymerization solvent for synthesizing the polyimine (A1) and the polyimide precursor (A2) is preferably such that the raw materials for synthesis or the (A1) and (A2) are soluble in water absorption. Solvent. As the polymerization solvent, the same solvent as the solvent exemplified as the solvent (E) to be described later can be used.

By using the same solvent as the solvent (E) as a polymerization solvent, it is not necessary to separate the polymer after the synthesis of the polyimine (A1) or the polyimide precursor (A2), and to dissolve after separation. The steps in other solvents. Thereby, the productivity of the apparatus of the present invention can be improved.

The polyimine (A1) and the polyimine precursor (A2) preferably have the specific structure having a hydroxyl group, thereby having excellent solubility in a solvent (E) to be described later. Therefore, these polymers are also dissolved in a low water-absorbent solvent other than N-methyl pyrrolidone (NMP), for example, a solvent (E) to be described later. As a result, for example, by using a solvent other than NMP as a polymerization solvent for obtaining the polymer (A), the insulating film formed of the radiation sensitive material can be made lower in water absorption.

Acrylic Resin (A3)

Examples of the monomer constituting the acrylic resin (A3) include an alicyclic group-containing ester of (meth)acrylic acid, an alicyclic group-containing ester of (meth)acrylic acid, and an aryl ester of (meth)acrylic acid. At least one monomer A.

Further, examples of the monomer constituting the above (A3) include at least one acid group-containing monomer B selected from the group consisting of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated dicarboxylic anhydride.

Further, the monomer constituting the (A3) may also be exemplified by (meth)acrylic acid. At least one functional group-containing monomer C of a hydroxyalkyl ester, an epoxy group-containing (meth)acrylic acid ester, and an oxetanyl ester of (meth)acrylic acid.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and dibutyl (meth)acrylate. Isopropyl acrylate, tert-butyl (meth)acrylate; alicyclic ester of (meth)acrylic acid, for example, cyclohexyl (meth)acrylate, 2-methyl (meth)acrylate a monocyclic hydrocarbon ester such as cyclohexyl ester, a polycycloalkane ester such as dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate or isobornyl (meth)acrylate Examples of the aryl group-containing ester of (meth)acrylic acid include phenyl (meth)acrylate and benzyl (meth)acrylate.

Examples of the unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, and 2-(meth)acryloxyethyl succinic acid; and examples of the unsaturated dicarboxylic acid include maleic acid and fumaric acid. And citraconic acid, mesaconic acid, itaconic acid; and unsaturated dicarboxylic anhydride, for example, maleic anhydride and itaconic anhydride are mentioned.

Examples of the hydroxyalkyl ester of (meth)acrylic acid include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and examples of the epoxy group-containing ester of (meth)acrylic acid include: Glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-butyl butyl (meth)acrylate , (meth)acrylic acid-6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, (meth)acrylic acid-3,4-epoxycyclohexyl methyl ester; Examples of the oxyheterocyclic butyl ester of acrylic acid include 3-methyl-3-(methyl)propenyloxymethyloxetane and 3-ethyl-3-(methyl)propene.醯oxymethyloxetane, 3- Methyl-3-(methyl)propenyloxyethyloxetane, 3-ethyl-3-(methyl)propenyloxyethyloxetane.

In the acrylic resin (A3), the content of the structural unit derived from the monomer A is usually 5% by mass or more, preferably 10% by mass to 85% by mass, more preferably 15% by mass to 75% by mass, based on the source. The content of the structural unit of the acid group-containing monomer B is usually 5% by mass to 70% by mass, preferably 10% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, based on the The content of the structural unit of the functional group-containing monomer C is usually 90% by mass or less, preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass.

In particular, in the acrylic resin (A3), the total content of the structural unit derived from the (meth)acrylic acid-containing epoxy group-containing (meth)acrylic acid-containing oxetanyl ester is preferably 10% by mass. 70% by mass, more preferably 20% by mass to 50% by mass. When the structural unit is in the above range, the curing reaction proceeds sufficiently during heating of the coating film formed of the radiation sensitive material, and the heat resistance and surface hardness of the obtained pattern tend to be sufficient, and radiation is also felt. The storage stability of the material is also excellent.

Further, as the monomer constituting the acrylic resin (A3), a diester of an unsaturated dicarboxylic acid such as diethyl maleate, diethyl fumarate or diethyl itaconate; styrene or ? a styrene monomer such as methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene or p-methoxy styrene.

Examples of the solvent used in the synthesis of the acrylic resin (A3) include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether and propylene glycol monomethyl. Glycol ethers such as ether; glycol ether acetates such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; and aromatic hydrocarbons, ketones, and esters.

The acrylic resin (A3) can be synthesized, for example, by radical polymerization of the monomer. As the polymerization catalyst in the radical polymerization, a usual radical polymerization initiator can be used, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis-(2,4-di). Azo compounds such as methylvaleronitrile and 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, peroxidation An organic peroxide such as tributyl methacrylate or 1,1-bis-(t-butylperoxy)cyclohexane and hydrogen peroxide. In the case where a peroxide is used for the radical polymerization initiator, a peroxide and a reducing agent may be combined to form a redox type initiator.

Polyoxane (A4)

The polyoxyalkylene (A4) is, for example, a polyoxyalkylene obtained by reacting the organodecane represented by the formula (a4).

In the formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a carbon number of 2 to 15 The group of the epoxy ring or a group (substituent) obtained by substituting one or two or more hydrogen atoms contained in the alkyl group as a substituent may be the same when R ^{1 is} present in plurality R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms. When R ^{2 is} present, the same may be used. Can be different; n is an integer from 0 to 3.

The substituent is, for example, at least one selected from the group consisting of a halogen atom, an amine group, a hydroxyl group, a mercapto group, an isocyanate group, and a (meth)acryloxy group.

Examples of the alkyl group and the substituent thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2, 2, 2 -Trifluoroethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatepropyl, 3-(methyl)propenyloxypropyl.

The alkenyl group is, for example, a vinyl group.

Examples of the aryl group-containing group include an aryl group such as a phenyl group, a tolyl group, and a naphthyl group; a hydroxyaryl group such as a p-hydroxyphenyl group; an aralkyl group such as a benzyl group or a phenethyl group; and a 1-(p-hydroxyphenyl group). Ethyl, hydroxyarylalkyl such as 2-(p-hydroxyphenyl)ethyl; 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl.

Examples of the epoxy ring-containing group include 3-glycidoxypropyl group and 2-(3,4-epoxycyclohexyl)ethyl group.

The mercapto group is exemplified by an ethyl group.

Examples of the aryl group include a phenyl group.

n in the formula (a4) is an integer of 0 to 3. The case of n=0 is a tetrafunctional decane, the case of n=1 is a trifunctional decane, the case of n=2 is a difunctional decane, and the case of n=3 is a monofunctional decane.

Examples of the organic decane include tetramethoxy decane and tetraethoxy decane. Tetrafunctional decane such as tetraethoxydecane or tetraphenoxydecane; methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane , ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane , n-butyl trimethoxy decane, n-butyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, benzene Trimethoxy decane, phenyl triethoxy decane, p-hydroxyphenyl trimethoxy decane, 1-(p-hydroxyphenyl)ethyl trimethoxy decane, 2-(p-hydroxyphenyl)ethyltrimethoxy Baseline, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltri Oxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyl Trifunctional such as trimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane Hydrazine; dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldiethoxydecane, di-n-butyldimethoxydecane, diphenyldimethoxydecane, etc. Difunctional decane; monofunctional decane such as trimethyl methoxy decane or tri-n-butyl ethoxy decane. Among these organic decanes, trifunctional decane is preferred in terms of crack resistance and hardness of the insulating film.

The organic decane may be used alone or in combination of two or more.

In terms of the crack resistance and hardness of the insulating film, the content of the phenyl group contained in the polyoxyalkylene (A4) is preferably 20 mol to 70 mol with respect to 100 mol of the Si atom. More preferably 35 moles ~ 55 moles. When the content of the phenyl group is at most the above-described upper limit value, an insulating film having a high hardness tends to be obtained. When the content of the phenyl group is at least the lower limit value, an insulating film having high crack resistance can be obtained. Propensity. The content of the phenyl group is, for example, a ²⁹ Si-nuclear magnetic resonance spectrum for measuring polyadenine (A4), and is obtained from the ratio of the peak area of Si bonded to the phenyl group to the peak area of Si in which the phenyl group is not bonded. .

The polyoxyalkylene (A4) can be obtained, for example, by subjecting the organodecane to hydrolysis and partial condensation. The usual method can be used for the hydrolysis and partial condensation. For example, a solvent, water, and an optional catalyst are added to the organic decane, and heating and stirring are carried out. During the stirring, a hydrolysis by-product such as an alcohol or a condensation by-product such as water may be distilled off by distillation if necessary. The reaction temperature is not particularly limited, and is usually in the range of 0 ° C to 150 ° C. The reaction time is also not particularly limited, and is usually in the range of 1 hour to 10 hours.

Examples of the solvent include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, and 4- a hydroxyl group-containing ketone such as hydroxy-4-methyl-2-pentanone (diacetone alcohol); ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol. Among these solvents, diacetone alcohol is particularly preferably used. The solvent may be used alone or in combination of two or more.

The amount of the solvent added is preferably 10% based on 100 parts by mass of the organic decane. Parts by mass to 1000 parts by mass. Further, the amount of water used for the hydrolysis reaction is preferably from 0.5 mol to 2 mol per mol of the hydrolyzable group.

Examples of the catalyst include an acid catalyst and an alkali catalyst. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof, and an ion exchange resin. The base catalyst may, for example, be triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide or potassium hydroxide. An alkoxy decane having an amine group, an ion exchange resin, or the like. The amount of the catalyst added is preferably from 0.01 part by mass to 10 parts by mass per 100 parts by mass of the organic decane.

Polybenzoxazole (A5-1)

The polybenzoxazole (A5-1) preferably contains a structural unit represented by the formula (a5-1). Hereinafter, the structural unit represented by the formula (a5-1) is also referred to as "structural unit (a5-1)".

In the formula (a5-1), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group.

In the formula (a5-1), X ^{1 is} preferably a tetravalent group containing at least one aromatic ring, more preferably a group having a linear structure, and further preferably a group having 1 to 4 aromatic rings. More preferably, it is a group having two aromatic rings. The polybenzoxazole (A5-1) having such a structure is excellent in rigidity.

Further, the aromatic ring contained in X ¹ may be either a substituted or unsubstituted ring. Examples of the substituent include -OH, -COOH, an alkyl group, an alkoxy group, and an alicyclic hydrocarbon group. Bonded to the O ¹ X N, for example, bonded to adjacent carbon atoms of X ¹ on the aromatic ring, form a benzoxazole ring.

When two or more aromatic rings are contained in X ¹ , the plurality of aromatic rings may form any one of a polycyclic ring system and a condensed polycyclic ring structure, and it is preferred to form a bonded polycyclic ring structure. The polybenzoxazole (A5-1) having such a structure is excellent in both light-shielding property and rigidity.

The total carbon number of X ¹ is preferably from 6 to 24, more preferably from 6 to 20, and even more preferably from 6 to 18. Thereby, the effect can be exerted more prominently.

The structure of X ^{1 is} , for example, a monocyclic structure such as a benzene ring, a condensed polycyclic structure such as a naphthalene ring, or a group represented by the formula (g1), and a polycyclic structure. Among these structures, a group represented by the formula (g1) is preferred.

In the formula (g1), Ar ^{1 is} each independently a trivalent aromatic hydrocarbon group, and R ¹ is a direct bond or a divalent group. The trivalent aromatic hydrocarbon group may, for example, be a benzene ring, or may have a substituent such as an alkyl group, an alkoxy group or an alicyclic hydrocarbon group, and the substituents in the two Ar ¹ may be bonded to each other to form two Ar groups. ^A cross-linked carbonyl group or the like. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group, a bis(trifluoromethyl)methylene group, and a phenylene group.

Specific examples of the structure of X ¹ include, for example, a tetravalent group represented by the following formula. Further, in the following formula, four "-" extending from the aromatic ring represent a bonding bond.

In the formula (a5-1), Y ^{1 is} preferably a divalent group containing at least one ring selected from the group consisting of an alicyclic ring and an aromatic ring, and more preferably a group having 1 to 4 aromatic rings. More preferably, it is a group having two aromatic rings. Polybenzoxazole (A5-1) having such a structure is excellent in rigidity and light resistance.

Further, the alicyclic ring and the aromatic ring contained in Y ¹ may be either a substituted or unsubstituted ring. Examples of the substituent include -OH, -COOH, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alicyclic hydrocarbon group.

In the case where two or more of the rings are contained in Y ¹ , a plurality of the rings may form any one of a structure in which a polycyclic ring system and a condensed polycyclic ring system are bonded, and it is preferred to form a bonded polycyclic ring structure. The polybenzoxazole (A5-1) having such a structure is excellent in both light-shielding property and rigidity.

The total carbon number of Y ¹ is preferably 4 to 24, more preferably 4 to 15, and further preferably 6 to 12. Thereby, the effect can be exerted more prominently.

The structure of Y ^{1 is} , for example, a monocyclic structure such as a benzene ring, a condensed polycyclic structure such as a naphthalene ring, or a group represented by the formula (g2), and the like, and an aromatic structure such as a polycyclic structure; Ring structure. Among these structures, a group represented by the formula (g2) is preferred.

In the formula (g2), Ar ^{2 is} each independently a divalent aromatic hydrocarbon group, and R ² is a direct bond or a divalent group. The divalent aromatic hydrocarbon group may, for example, be a benzene ring, or may have a substituent such as an alkyl group, an alkoxy group or an alicyclic hydrocarbon group, and the substituents in the two Ar ² may be bonded to each other to form two Ar groups. ^{2 a} cross-linked carbonyl group or the like. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group, a bis(trifluoromethyl)methylene group, and a phenylene group.

Specific examples of the structure of Y ¹ include a divalent group represented by the following formula. Further, in the following formula, two "-" extending from the aromatic ring and the alicyclic ring indicate a bond.

Polybenzoxazole (A5-1) can be obtained by a cyclization reaction of a polybenzoxazole precursor (A5-2) which will be described below. The cyclization reaction here can be carried out completely or Performed locally. That is, the cyclization rate may not be 100%. Therefore, the polybenzoxazole (A5-1) may further contain a structural unit represented by the formula (a5-2) which will be described below. Hereinafter, the structural unit represented by the formula (a5-2) is also referred to as "structural unit (a5-2)".

In the polybenzoxazole (A5-1), the cyclization ratio is preferably 5% or more, more preferably 7.5% or more, and still more preferably 10% or more. The upper limit of the cyclization rate is preferably 50%, more preferably 30%. When the cyclization ratio is within the above range, heat resistance and solubility of the exposed portion in the developer are preferable.

The cyclization rate can be measured, for example, as follows. First, polybenzoxazole measuring the infrared absorption spectrum, absorption of the benzoxazole ring peak (1557cm ^-1 vicinity, 1574cm ^-1) is present. Then, the polybenzoxazole was heat-treated at 350 ° C for 1 hour, and then the infrared absorption spectrum was measured again. The peak intensity near 1554 cm ^-1 before and after the heat treatment was compared. The cyclization ratio of polybenzoxazole after heat treatment was set to 100%, and the cyclization ratio of polybenzoxazole before heat treatment was determined = {peak intensity at around 1554 cm ^-1 before heat treatment / 1554 cm after heat treatment ^- The peak intensity near ^{1 is} ×100 (%). For the measurement of the infrared absorption spectrum, for example, "NICOLET 6700 FT-IR" (manufactured by Thermo Electron Co., Ltd.) is used.

In the polybenzoxazole (A5-1), the total content of the structural unit (a5-1) and the structural unit (a5-2) is usually 50% by mass or more, preferably 60% by mass or more, and more preferably 70%. The mass% or more is more preferably 80% by mass or more.

Polybenzoxazole Precursor (A5-2)

The polybenzoxazole precursor (A5-2) is a polybenzoxazole which can be formed by dehydration or cyclization to form polybenzoxazole (A5-1), preferably containing structural unit (a5-1). (A5-1) compound of. The precursor (A5-2) contains, for example, a structural unit represented by the formula (a5-2).

In the formula (a5-2), X ¹ is a tetravalent organic group having an aromatic ring, and preferably a tetravalent group containing at least one aromatic ring. N and OH bonded to X ¹ are bonded to adjacent carbon atoms on the same aromatic ring.

In the formula (a5-2), Y ¹ is a divalent organic group, and preferably a divalent group containing at least one ring selected from the group consisting of an alicyclic ring and an aromatic ring.

The tetravalent organic group represented by X ¹ and the divalent organic group represented by Y ¹ are the same as those exemplified as X ¹ and Y ¹ in the formula (a5-1).

In the polybenzoxazole precursor (A5-2), the content of the structural unit (a5-2) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass. More than % by mass.

"Synthesis method of polybenzoxazole (A5-1) and its precursor (A5-2)"

The polybenzoxazole precursor (A5-2) can be obtained, for example, by subjecting at least one selected from the group consisting of a dicarboxylic acid, a diester thereof and a dihalide thereof to a diamine having two hydroxyl groups. polymerization. Further, in order to increase the reaction yield, an active ester type dicarboxylic acid derivative obtained by reacting a dicarboxylic acid with 1-hydroxybenzotriazole or the like in advance may also be used. The organism acts as a diester.

With respect to the use ratio, for example, 1 mol relative to the total amount of the dicarboxylic acid and the diester body and the dihalide, the diamine is 0.5 mol to 4 mol, preferably 1 mol. 2 Mo Er. In the polymerization, it is preferred to heat the mixed solution at 50 ° C to 200 ° C for 1 hour to 72 hours.

Polybenzoxazole (A5-1) can be synthesized, for example, by synthesizing a polybenzoxazole precursor (A5-2) by the method described above, and then using the polybenzoxazole precursor (A5-2) ) Dehydration and cyclization.

A known method can be applied to the cyclization reaction of the polybenzoxazole precursor (A5-2). In the case of heating the cyclization reaction, it is preferred to heat the solution containing the polybenzoxazole precursor (A5-2) at 150 ° C to 400 ° C for 1 hour to 16 hours. The cyclization reaction may be carried out while removing water in the system by using an azeotropic solvent such as toluene, xylene or mesitylene as needed.

Further, from the viewpoint of storage stability, it is preferred to terminate the terminal groups of the polybenzoxazole and its precursor. Examples of the blocking agent include dicarboxylic anhydrides such as maleic anhydride and 5-norbornene-2,3-dicarboxylic anhydride. For example, after synthesizing a polybenzoxazole precursor containing a structural unit represented by the formula (a5-2), the terminal amine group contained in the precursor is blocked with a guanamine using a blocking agent. .

"Polyolefin (A6)"

The polyolefin (A6) is, for example, a cyclic olefin polymer having a protic polar group. The so-called protic polar group refers to an atomic group in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. Belong to the 15th family of the periodic table or The atom of Group 16 is preferably an atom belonging to the second or third cycle of Group 15 or Group 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, and particularly preferably an oxygen atom.

Examples of the protic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group or a phosphoric acid group; a primary amino group, a secondary amino group, a primary guanamine group, and a second guanamine group ( a polar group containing a nitrogen atom such as a quinone imino group; a polar group containing a sulfur atom such as a thiol group. Among these groups, a polar group having an oxygen atom is preferred, and a hydroxyl group or a carboxyl group is more preferred. Further, a phenolic hydroxyl group or a carboxyl group is preferred, and a carboxyl group is particularly preferred.

In the following description, examples of the polar group other than the protic polar group include a decyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a cyano group, an alkoxy group, and a tertiary amino group. Alkyl fluorenyl, carbonyl, sulfonyl, N-substituted quinone imine, epoxy, carbonyloxycarbonyl (dicarboxylic acid anhydride structure). Among these groups, a decyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an N-substituted fluorenylene group, a halogen atom and a cyano group are preferred, and a decyloxy group, an alkoxycarbonyl group and a aryl group are more preferred. The oxycarbonyl group and the N-substituted quinone imine group are particularly preferably N-substituted quinone imine groups.

The cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin having a cyclic structure such as an alicyclic ring or an aromatic ring and a carbon-carbon double bond. The cyclic olefin polymer may also contain structural units derived from monomers other than cyclic olefins.

Hereinafter, the structural unit derived from the monomer A is also referred to as a "monomer A unit".

In all the structural units of the cyclic olefin polymer, the content of the cyclic olefin unit is usually from 30% by mass to 100% by mass, preferably from 50% by mass to 100% by mass. The amount % is more preferably 70% by mass to 100% by mass.

The ratio of the monomer unit having a protic polar group to the other monomer unit in the cyclic olefin polymer having a protic polar group (monomer unit having a protic polar group / other monomer unit) The mass ratio is usually 100/0 to 10/90, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

In the cyclic olefin polymer having a protic polar group, the protic polar group may be bonded to the cyclic olefin unit, or may be bonded to a monomer unit other than the cyclic olefin, preferably bonded to the cyclic olefin unit. .

Examples of the monomer which forms the cyclic olefin polymer having a protic polar group include a cyclic olefin having a protic polar group (a), a cyclic olefin having a polar group other than a protic polar group (b), and a cyclic olefin (c) having a polar group or a monomer (d) other than a cyclic olefin. The monomer (d) may have a protic polar group or a polar group other than the above, or may have no polar group at all. The cyclic olefin (a) to the cyclic olefin (c) are also referred to as "monomer (a) to monomer (c)", respectively.

The cyclic olefin polymer having a protic polar group is preferably composed of a monomer (a), at least one selected from the group consisting of monomer (b) and monomer (c), and optionally monomer (d). More preferably, it consists of a monomer (a), a monomer (b), and an optional monomer (d).

The monomer (a) is, for example, a cyclic olefin represented by the following formula.

In the formula (a6-1), R ^a1 to R ^a4 are each independently a hydrogen atom or -X _n -R ^a5 . X is a divalent organic group. n is 0 or 1. R ^a5 is an alkyl group, an aromatic group or the protic polar group, and the alkyl group and the aromatic group may each have a substituent. At least one of R ^a1 to R ^a4 is a -X _n -R ^a5 group in which R ^a5 is a protic polar group. m is an integer of 0 to 2, preferably 0 or 1. Examples of the divalent organic group of X include an alkylene group having 1 to 18 carbon atoms such as a methylene group and an exoethyl group, and a aryl group having 6 to 24 carbon atoms such as a phenyl group.

The alkyl group of R ^{a5 is} , for example, a linear or branched alkyl group having 1 to 18 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. The aromatic group of R ⁵ is, for example, an aromatic group having 6 to 24 carbon atoms, and specific examples thereof include an aryl group such as a phenyl group or an aralkyl group such as a benzyl group.

R ^{a1 is} preferably a hydroxyaryl group having 6 to 24 carbon atoms such as a carboxyl group or a hydroxyphenyl group, more preferably a carboxyl group. R ^{a2 is} preferably an alkyl group having 1 to 18 carbon atoms such as a hydrogen atom or a methyl group, or a carboxyalkyl group having 2 to 18 carbon atoms such as a carboxymethyl group. R ^a3 and R ^{a4 are} preferably a hydrogen atom.

Examples of the monomer (a) include 8-carboxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene.

The monomer (a) may be used alone or in combination of two or more.

The monomer (b) is, for example, a cyclic olefin represented by the following formula.

In the formula (b6-1), R ^b1 is a polar group other than the protic polar group, and preferably a decyloxy group having 2 to 12 carbon atoms such as an ethoxycarbonyl group, a methoxycarbonyl group or an ethoxycarbonyl group; Alkoxycarbonyl group having 2 to 12 carbon atoms such as n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group or 2,2,2-trifluoroethoxycarbonyl group, carbon number such as phenoxycarbonyl group ~24 aryloxycarbonyl, halogen atom such as cyano or chlorine atom. R ^b2 is an alkyl group having 1 to 18 carbon atoms such as a hydrogen atom or a methyl group. R ^b3 and R ^b4 are a hydrogen atom. m is an integer of 0 to 2, preferably 0 or 1.

Further, R ^b1 to R ^b4 may form a heterocyclic ring structure of 3 to 5 members containing an oxygen atom or a nitrogen atom as a ring-constituting atom together with the two carbon atoms to be bonded in any combination.

The three-membered heterocyclic ring structure may, for example, be an epoxy structure. The 5-membered heterocyclic structure can be exemplified by a structure of a dicarboxylic anhydride [-C(=O)-OC(=O)-], a dicarboxy quinone imine structure [-C(=O)-NR ^b5 -C(=O) -]Wait. R ^b5 is an aryl group having 6 to 24 carbon atoms such as a phenyl group, a naphthyl group or a fluorenyl group. Among these structures, a dicarboxy quinone imine structure is preferred.

Examples of the monomer (b) include N-phenyl-(5-norbornene-2,3-dicarboxyinlimine).

The monomer (b) may be used alone or in combination of two or more.

Examples of the monomer (c) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo[2.2.1] hept-2-ene, 5-butyl group. -bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methine-bicyclo[2.2.1]hept-2-ene, 5 -vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene (common name: dicyclopentadiene), tetracyclic [8.4. 0.1 ^11,14 .0 ^3,7 ] fifteen-3,5,7,12,11-pentene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]癸-3-ene (custom name: Tetracyclododecene), 8-methyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^Dodec -3-ene, 8-methine-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^dode -3-ene, 8-ethylene-tetracyclo[4.4. 0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-vinyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-propenyl-four Ring [4.4.0.1 ^2,5 .1 ^7,10 ] dode-3-ene, pentacyclic [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] fifteen-3,10-diene Cyclopentene, cyclopentadiene, 1,4-methyl bridge-1,4,4a,5,10,10a-hexahydroindole, 8-phenyl-tetracyclo[4.4.0.1 ^2,5 .1 ^{7 , 10]} dodeca-3-ene, tetracyclo [9.2.1.0 ^2,10 .0 ^3,8] -3,5,7,12- fourteen tetraene ( 1,4-bridged referred -1,4,4a, 9a- tetrahydro -9H- fluorene), pentacyclo [7.4.0.1 ^3,6 .1 ^10,13 .0 ^2,7] -4 fifteen, 11-diene, pentacyclo[9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] fifteen-5,12-diene.

The monomer (c) may be used alone or in combination of two or more.

The monomer (d) other than the cyclic olefin is, for example, a chain olefin. Examples of the chain olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl group. 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentyl Alkene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octene, 1-hexene, etc., 2 to 20 carbon atoms; 1,4-hexadiene, 4-methyl a non-conjugated diene such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,5-hexadiene or 1,7-octadiene.

The monomer (d) may be used alone or in combination of two or more.

The cyclic olefin polymer having a protic polar group can be obtained by polymerizing the monomer (a) as needed with at least one monomer selected from the group consisting of the monomer (b) to the monomer (d). The polymer obtained by the polymerization can also be further hydrogenated. The hydrogenated polymer is also included in the cyclic olefin polymer having a protic polar group.

The polymerization method for polymerizing the monomer (a) together with at least one monomer selected from the group consisting of the monomer (b) to the monomer (d) as needed may be carried out according to a usual method, and examples thereof include ring-opening polymerization. Method and addition polymerization method.

As the polymerization catalyst, for example, a metal complex of molybdenum, rhodium, ruthenium or the like can be preferably used. These polymerization catalysts may be used alone or in combination of two or more.

The amount of the polymerization catalyst is usually from 1:100 to 1:2,000,000, preferably from 1:500 to 1:1,000,000, more preferably 1 in terms of the molar ratio of the metal compound: cyclic olefin in the polymerization catalyst. : The range of 1,000~1:500,000.

The hydrogenation of the polymer obtained by polymerizing the monomer is usually carried out using a hydrogenation catalyst. The hydrogenation catalyst can be used, for example, in the usual case of hydrogenation of an olefin compound. Specific examples include a Ziegler-type homogeneous phase catalyst, a noble metal complex catalyst, and a supported noble metal catalyst.

Among these hydrogenation catalysts, it is preferable that the noble metal such as ruthenium or osmium is misaligned in terms of side reactions such as no functional group modification and selective hydrogenation of carbon-carbon unsaturated bonds in the polymer. Catalyst, especially a nitrogen-containing heterocyclic carbene with high electron donation a carbene compound or a phosphine-coordinated ruthenium catalyst.

The cyclic olefin polymer having a protic polar group can also be obtained by introducing a protic polar group into a cyclic olefin polymer having no protic polar group by using a known modifier, and hydrogenating as necessary. . Hydrogenation can also be carried out on the polymer before the introduction of the protic polar group. Further, the cyclic olefin polymer having a protic polar group may be further modified to introduce a protic polar group.

The cyclic olefin polymer having no protic polar group can be obtained, for example, by polymerizing at least one monomer selected from the group consisting of monomer (b) to monomer (c) with an optional monomer (d).

As the modifier for introducing a protic polar group, a compound having a protonic polar group and a reactive carbon-carbon unsaturated bond in one molecule can be usually used. Examples of such a compound include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, and sulphate ( Brassic acid), maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid and other unsaturated carboxylic acids; allyl alcohol, methyl vinyl alcohol, Crotonol, methyl allyl alcohol, 1-phenylvinyl-1-ol, 2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl- 3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol An unsaturated alcohol such as 4-penten-1-ol, 4-methyl-4-penten-1-ol or 2-hexen-1-ol.

The reforming reaction of the cyclic olefin polymer using the modifier may be carried out in accordance with a usual method, and the reaction is usually carried out in the presence of a radical generator.

The cyclic olefin polymer having a protic polar group is preferably contained, for example. The polymer of the structural unit represented by the formula (A6-1) is more preferably a polymer containing the structural unit represented by the formula (A6-1) and the structural unit represented by the formula (A6-2).

In the formula (A6-1), R ^a1 to R ^a4 and m have the same meanings as in the formula (a6-1). In the formula (A6-2), R ^b1 to R ^b4 and m have the same meanings as in the formula (b6-1).

Cardo Resin (A7)

The cardo resin (A7) is a resin having a cardo structure. The cardo structure refers to a skeleton structure in which two cyclic structures are bonded to a ring carbon atom constituting a cyclic structure. The general structure of the cardo structure is a structure in which two aromatic rings (for example, a benzene ring) are bonded to a carbon atom at the 9-position of the anthracene ring.

From the viewpoint of alkali solubility, the cardo resin is preferably a cardo resin having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group.

Specific examples of the skeleton structure in which two cyclic structures are bonded to a ring carbon atom constituting the cyclic structure include a 9,9-bis(phenyl)fluorene skeleton and 9,9-bis(hydroxyphenyl). Anthracene skeleton, 9,9-bis(cyanophenyl or aminoalkylphenyl)fluorene skeleton, 9,9-bis(phenyl)fluorene skeleton having an epoxy group, 9 having a (meth)acryl group , 9-bis(phenyl)anthracene skeleton.

The cardo resin is formed by polymerization of a skeleton having the structure of the card by polymerization or the like between the functional groups bonded thereto. The cardo resin has, for example, a structure in which a main chain and a cyclic structure as a large-volume side chain are connected by one element (cardo structure), and has a ring structure in a substantially vertical direction with respect to the main chain.

The cardo resin is, for example, a polymer obtained by polymerizing a monomer having a cardo structure, or a copolymer with other copolymerizable monomers. The polymerization method of the monomer may be carried out according to a usual method, and for example, a ring-opening polymerization method or an addition polymerization method may be employed.

The cardo resin may, for example, be a polymer of a monomer having a cardo structure.

Examples of the monomer having a cardo structure include 9,9-bis(4-glycidoxyphenyl)fluorene, 9,9-bis[4-(2-glycidoxyethoxy)phenyl] An epoxy compound containing a cardo structure; a (meth)acrylic compound containing a cardo structure such as a compound represented by the following formula; 9,9-bis(4-hydroxyphenyl)anthracene, 9,9- A bisphenol having a cardo structure such as bis(4-hydroxy-3-methylphenyl)anthracene.

In the formula, A is an alkyl group having 2 to 6 carbon atoms such as an ethyl group and a propyl group, and the alkyl group may have a hydroxyl group, and examples thereof include a 2-hydroxy-1,3-propanediyl group, and R is A hydrogen atom or a methyl group, and p and q are integers of 1 to 30.

From the viewpoint of alkali solubility, the monomer having a cardo structure exemplified above may also have a carboxyl group and a phenolic hydroxyl group on an anthracene ring or an aromatic ring bonded to a carbon atom at the 9-position of the anthracene ring. At least one group.

Commercially available products can also be used for the cardo resin. For example, Ogsol CR-TR1, Ogsol CR-TR2, Ogsol CR-TR3, Ogsol CR- manufactured by Osaka Gas Chemical Co., Ltd. A polyester compound having a cardo structure such as TR4, Ogsol CR-TR5, Ogsol CR-TR6 or the like.

[sensitizer (B)]

Examples of the photosensitive agent (B) include a photoacid generator and a photoradical polymerization initiator. The radiation sensitive material can exhibit radiation sensitivity characteristics by containing the photosensitive agent (B), and can have good radiation sensitivity.

The sensitizer (B) may be used alone or in combination of two or more.

The content of the photosensitive agent (B) in the radiation sensitive material is usually 5 parts by mass to 100 parts by mass, preferably 10 parts by mass to 65 parts by mass, more preferably 15 parts by mass based on 100 parts by mass of the polymer (A). ~60 parts by mass. By setting the content of the photosensitive agent (B) to the above range, the difference in solubility between the irradiated portion of the radiation and the non-irradiated portion in the aqueous alkaline solution or the like to be used as the developing solution can be increased, and the patterning performance can be improved.

Photoacid generator

The photoacid generator is a compound which generates an acid by a treatment including irradiation of radiation. Examples of the radiation include visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

The photoacid generator may, for example, be a quinonediazide compound, an oxime sulfonate compound, a phosphonium salt, an N-sulfonyloxy quinone compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, or a sulfonate compound. , a carboxylate compound. By using these compounds, a material that exhibits positive radiation characteristics can be obtained.

The photoacid generator is preferably a quinonediazide compound, an oxime sulfonate compound, a sulfonium salt or a sulfonate compound, more preferably a quinonediazide compound or an oxime sulfonate compound, and particularly preferably a quinonediazide compound. .

<醌diazide compound>

The quinonediazide compound produces a carboxylic acid by treatment including irradiation with radiation and development using an aqueous alkaline solution. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother core") and 1,2-naphthoquinonediazidesulfonium halide.

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

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

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.

Examples of the hexahydroxybenzophenone include 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxydiene. Benzophenone.

Examples of the poly(hydroxyphenyl)alkane include bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tri ( p-Hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tri 2,5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl) Phenyl}ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1, 1'-spirobi-5,6,7,5',6'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan.

Other parent cores include, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 1-[1- {3-(1-[4-Hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]-3-[1-{3-(1 -[4-hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]benzene, 4,6-bis{1-(4-hydroxyphenyl) )-1-methylethyl}-1,3-dihydroxybenzene.

Among these cores, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, 4,4'-[1-{ 4-(1-[4-Hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol.

The 1,2-naphthoquinonediazidesulfonium halide is preferably 1,2-naphthoquinonediazidesulfonium chloride. 1,2-naphthoquinonediazidesulfonium chloride, for example, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2- Naphthoquinonediazide-5-sulfonyl chloride, preferably 1,2-naphthoquinonediazide-5-sulfonyl chloride.

In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) with a 1,2-naphthoquinonediazidesulfonium halide, it is preferably used in comparison with the number of OH groups in the phenolic compound or the alcoholic compound. It is a 1,2-naphthoquinonediazide sulfonium halide of 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol%. The condensation reaction can be carried out by a known method.

The quinonediazide compound may also preferably be a phthalamide of 1,2-naphthoquinonediazidesulfonate, such as 2,3,4-triamine, which changes the ester bond of the nucleus exemplified to a guanamine bond. Dibenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid decylamine and the like.

<Other examples>

Specific examples of the oxime sulfonate compound include the compounds described in the publications of JP-A-2011-227106, JP-A-2012-234148, and JP-A-2013-054125. Specific examples of the onium salt include, for example, Japanese Patent No. 5,208, 573, Japanese Patent No. 5,397, 152, Japanese Patent No. 5,413,124, Japanese Patent Laid-Open No. 2004-2110525, Japanese Patent Laid-Open No. 2008-129423, and Japanese Patent Publication No. 2010 A compound described in the publication of Japanese Laid-Open Patent Publication No. Hei. No. Hei.

Specific examples of the other acid generators include, for example, Japanese Patent No. 49242256, Japanese Patent Laid-Open No. 2011-064770, Japanese Patent Laid-Open No. 2011-232648, Japanese Patent Laid-Open No. 2012-185430, and Japanese Patent Laid-Open No. 2013- A compound described in the publication of No. 242540 or the like.

"Photoradical polymerization initiator"

By using a photoradical polymerization initiator as the photosensitive agent (B) and using a crosslinking agent (D) such as a compound containing a polymerizable carbon-carbon double bond described later, a material exhibiting negative radiation sensitivity can be obtained. .

The photoradical polymerization initiator may, for example, be 2,2'-bis(2,4-dichlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorobenzene -4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dimethylphenyl)-4,5,4', 5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-methylphenyl)-4,5,4',5'-tetraphenyl-1,2'-linked Imidazole, 2,2'-diphenyl-4,5,4',5'-tetraphenyl-1,2'-biimidazole and the like biimidazole compound; diethoxyacetophenone, 2-(dimethyl Alkylphenone compound such as arylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 2,4 a mercaptophosphine oxide compound such as 6-trimethylbenzimidyldiphenylphosphine oxide; 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1, a triazine compound such as 3,5-triazine or 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine; and a benzoin compound such as benzoin; A benzophenone compound such as benzophenone, methyl ortho-benzoylbenzoate or 4-phenylbenzophenone.

[resin (C)]

The resin (C) is at least one selected from the group consisting of a phenol novolak resin, a resol resin, and a phenol resin. Among these resins, a novolak resin is preferred in terms of having good alkali solubility (developability).

The resin (C) is a substance which is colored by heating. In the method for forming an insulating film to be described later, the coating film formed of the radiation-sensitive material containing the resin (C) before exposure does not have a light-shielding property at a wavelength of 300 nm to 400 nm, but The resin (C) is ketylated by heating after exposure and development, and the obtained insulating film has light blocking properties at the above wavelength. By using such a resin (C), the radiation-sensitive material can simultaneously impart light-shielding property and alkali developability.

For example, the light-shielding property may not be imparted to the heating temperature at the time of pre-baking, that is, about 60 to 130 ° C, and the light-shielding property may be given at a heating temperature at the time of post-baking, that is, more than 130 ° C and not more than 300 ° C.

The novolac resin is, for example, a novolac resin containing a structural unit represented by the formula (C1).

In the formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, and carbon. a group represented by a 7- to 30-membered aralkyl group or a -R ² -Ar-R ² - (Ar is a divalent aromatic group, and R ^{2 is} independently a methylene group or a carbon number of 2 to 20 alkyl). Further, one hydrogen atom of the methylene group may be substituted with a cyclopentadienyl group, an aromatic ring, an aromatic ring-containing group, or a hetero ring containing a nitrogen atom, a sulfur atom or an oxygen atom.

Examples of the alkylene group having 2 to 30 carbon atoms in R ¹ include an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a hydrazine group, a hydrazine group, and a decene group. Alkyl, tetradecyl, tetradecyl, hexadecyl, octadecyl, hexadecyl, eicosyl, octadecyl, and twenty-two Alkyl, tetracosyl, tetracosyl, tetradecyl, hexadecyl, hexadecyl, octadecyl, hexadecane Base, stretch thirty alkyl.

Examples of the divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms in R ¹ include a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms in R ¹ include a benzyl group, a phenethyl group, a benzyl group, and a naphthyl group.

The group represented by -R ² -Ar-R ² - in R ¹ may, for example, be a group represented by -CH ₂ -Ph-CH ₂ - (Ph is a stretching phenyl group).

Examples of the divalent aromatic group having a phenolic hydroxyl group in A include a benzene ring having a phenolic hydroxyl group and a condensed polycyclic aromatic group having a phenolic hydroxyl group. The condensed polycyclic aromatic group having a phenolic hydroxyl group is, for example, a group obtained by substituting a part or all of a hydrogen atom bonded to an aromatic ring carbon contained in a condensed polycyclic aromatic hydrocarbon group with a hydroxyl group. Examples of the condensed polycyclic aromatic hydrocarbon group include a naphthalene ring, an anthracene ring, and a phenanthrene ring.

The divalent aromatic group having a phenolic hydroxyl group is specifically preferably a divalent group represented by the formula (c1-1), the formula (c1-2), the formula (c1-3) or the formula (c1-4).

The meanings of the symbols in the formulae (c1-1) to (c1-4) are as follows.

A1 is an integer from 1 to 4. B1 is an integer from 0 to 3. A2~a5 and b2~b5 are each independently an integer of 0-4. A6 and b6 are integers from 0 to 2.

Here, a2+a3 is an integer of 1 or more and 6 or less, b2+b3 is an integer of 0 or more and 5 or less, and a2+a3+b2+b3 is an integer of 1 or more and 6 or less; a4+a5+a6 is 1 or more. An integer of 8 or less, b4+b5+b6 is an integer of 0 or more and 7 or less, and a4+a5+a6+b4+b5+b6 is an integer of 1 or more and 8 or less. In addition, 1≦a1+b1≦4, a2+b2≦4, a3+b3≦4, a4+b4≦4, a5+b5≦4, a6+b6≦2.

A1, a2+a3, and a4+a5+a6 are each preferably an integer of 1 to 3.

R is a hydrocarbon group having a carbon number of 1 to 20, preferably a carbon number of 1 to 10, or a carbon number of 1~ 20. Preferably, the alkoxy group having 1 to 10 carbon atoms may be the same or different when R is present in plurality. Examples of the hydrocarbon group include an alkyl group such as a methyl group, a propyl group, an isopropyl group or a tributyl group. The alkoxy group is exemplified by a methoxy group.

In the formula (c1-1) to the formula (c1-4), the bonding positions of -OH and -R are not particularly limited, and the bonding positions of the two -R ¹ - are also not particularly limited. For example, two -R ¹ - may be bonded to different benzene nuclei (for example, the following formula (1)), or may be bonded to the same benzene nucleus (for example, the following formula (2)). Where * is a bond. The following formulas (1) and (2) are specific examples of the formula (c1-2), and the formula (c1-3) and the formula (c1-4) are also the same. Further, for the sake of convenience, the substituent on the benzene nucleus is omitted.

In the above A, the bonding position with -R ¹ - is preferably, for example, an ortho and/or para position with respect to the hydroxyl group contained in the A.

The A is preferably a group represented by the formula (c1-2), the formula (c1-3) or the formula (c1-4) from the viewpoint of imparting light-shielding property or heat resistance and alkali developability, and more preferably It is a group represented by the formula (c1-2) or the formula (c1-3).

For the aspect of having good alkali solubility (developability), the resin (C) A novolak resin is preferred. By containing an alkali-soluble novolac resin in the radiation sensitive material, a radiation sensitive material having good analytical properties can be obtained.

The novolak resin can be obtained, for example, by condensing a phenol with an aldehyde in the presence of an acid catalyst, and distilling off the unreacted component as needed. With respect to the reaction conditions, the phenols and the aldehydes are usually reacted in a solvent at 60 ° C to 200 ° C for about 1 hour to 20 hours. For example, it can be synthesized by the method described in JP-A-47-15111, JP-A-63-238129, and the like.

The resol resin can be obtained, for example, by condensing a phenol with an aldehyde in the presence of a base catalyst, and distilling off the unreacted component as needed. With respect to the reaction conditions, the phenols and the aldehydes are usually reacted in a solvent at 40 ° C to 120 ° C for about 1 hour to 20 hours. Thus, for example, a soluble ring derived from a phenol may be bonded to a group derived from an aldehyde (for example, -R ¹ -OH, and R ¹ has the same meaning as R ¹ in the formula (C1)). Phenolic Resin. The condensate of the resol resin can be obtained by heating or adding an acid to the resol resin, thereby performing a dehydration condensation reaction. This reaction is carried out by dehydration condensation of an aldehyde-derived group contained in the resol resin. When the reaction is carried out by heating, the resol resin or a solution thereof is usually reacted at 60 ° C to 200 ° C for about 1 hour to 20 hours. The resole phenolic resin and the condensate thereof can be synthesized, for example, by the method described in Japanese Patent No. 3889274, Japanese Patent No. 4013111, and Japanese Patent Laid-Open No. 2010-111013.

Examples of the phenols include compounds having a hydroxyl group number of 1 to 4, preferably 1 to 3, and a benzene core number of 1, and specifically Phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol , 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-tert-butylphenol, 3 -T-butylphenol, 4-tert-butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-tert-butyl-o-benzene Diphenol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2-methoxy-5- Methylphenol, 2-tert-butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 5-isopropyl-2-methylphenol; having a hydroxyl number of 1 to 6, preferably a compound having 1 to 3 and a nucleus number of 2 (naphthyl type compound), specifically 1-hydroxynaphthalene such as 1-naphthol or 2-naphthol, 1,2-dihydroxynaphthalene or 1,3-dihydroxynaphthalene , 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2 a dihydroxynaphthalene such as 6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene; the number of hydroxyl groups is 1-8, preferably 1-3, and the number of benzene nuclei a compound of 3 (an quinoid compound or a phenanthrene compound), specifically a monohydroxy hydrazine such as 1-hydroxyindole, 2-hydroxyindole or 9-hydroxyindole, 1,4-dihydroxyindole, 9,10-dihydroxyindole Others such as dihydroxyindole, 1,2,10-trihydroxyindole, 1,8,9-trihydroxyindole, 1,2,7-trihydroxyindole, etc., trihydroxyindole, 1-hydroxyphenanthrene and the like.

Examples of the aldehydes include formaldehyde, trioxane, acetaldehyde, benzaldehyde, and terephthalaldehyde.

In the synthesis of the resin (C), the amount of the aldehyde used is usually 0.3 mol or more, preferably 0.4 mol to 3 mol, more preferably 0.5, based on 1 mol of the phenol. Mo Er ~ 2 Mo Er.

Examples of the acid catalyst in the synthesis of the novolak resin include hydrochloric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. Examples of the alkali catalyst in the synthesis of the resol phenol resin include ammonia water and tertiary amine.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (C) is usually from 100 to 50,000, preferably from 150 to 10,000, more preferably measured by a gel permeation chromatography (GPC) method. 500~6,000. The resin (C) having an Mw within the above range is preferable in terms of light shielding property and resolution. For example, the Mw of the novolac resin is preferably from 500 to 50,000, more preferably from 700 to 5,000, and still more preferably from 800 to 3,000.

The resin (C) may be used alone or in combination of two or more.

In the radiation sensitive material, the content of the resin (C) is usually 2 parts by mass to 200 parts by mass, preferably 3 parts by mass to 160 parts by mass, more preferably 4 parts by mass, per 100 parts by mass of the polymer (A). ~140 parts by mass, particularly preferably from 10 parts by mass to 100 parts by mass. When the content of the resin (C) is at least the lower limit of the above range, the effect of imparting light shielding properties and developability by the resin (C) is easily exhibited. When the content of the resin (C) is at most the upper limit of the above range, the deterioration of the low water absorbability of the insulating film and the possibility of deterioration of heat resistance are small.

[Crosslinking agent (D)]

The crosslinking agent (D) is a compound having a crosslinkable functional group. The crosslinking agent (D) is, for example, a compound having two or more crosslinkable functional groups in one molecule.

An insulating film containing a radiation sensitive material is used as an organic EL element In the case of the constituent elements, in the organic EL device, if the organic light-emitting layer is in contact with moisture, it deteriorates. Therefore, it is preferred to use a crosslinking agent (D) to reduce the water absorption of the insulating film. Further, a negative radiation sensitive material can be obtained by using a photoradical polymerization initiator as the photosensitive agent (B) and using a compound containing a polymerizable carbon-carbon double bond as the crosslinking agent (D).

Examples of the crosslinkable functional group include an isocyanate group and a blocked isocyanate group, an oxetanyl group, a glycidyl ether group, a glycidyl ester group, a glycidylamine group, a methoxymethyl group, an ethoxymethyl group, and a benzyl group. Oxymethyl, ethoxymethyl, benzyl methoxymethyl, methionyl, ethenyl, dimethylaminomethyl, diethylaminomethyl, dimethylolamine Methyl, dihydroxyethylaminomethyl, morpholinylmethyl; a group having a polymerizable carbon-carbon double bond such as a vinyl group, a vinylidene group or a (meth)acryloyl group.

Examples of the crosslinking agent (D) include an oxetanyl group-containing compound, a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, and a novolak resin epoxy compound. a resol phenol resin epoxy compound, a poly(hydroxystyrene) epoxy compound, a methoxymethyl group-containing phenol compound, a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing phenol compound, an alkoxyalkyl group-containing melamine compound, an alkoxyalkyl group-containing benzoguanamine compound, an alkoxyalkyl group-containing urea compound, Alkoxyalkyl phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine Compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxymethyl group-containing phenol compound, polymerizable carbon-carbon A compound with a double bond.

Examples of the oxetane-containing compound include 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl and 3,7-bis(3-oxeine). -5-oxaxane, 3,3'-[1,3-(2-methylenyl)propanediylbis(oxymethylene)]bis(3-ethyloxetane ), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,2-bis[(3-ethyl-3-oxetanyl) Methoxymethyl]ethane, 1,3-bis[(3-ethyl-3-oxetanyl)methoxymethyl]propane, ethylene glycol bis[(3-ethyl-3- Oxecyclobutyl)methyl]ether, dicyclopentenyl bis[(3-ethyl-3-oxetanyl)methyl]ether, triethylene glycol bis[(3-ethyl-3) -oxetanyl)methyl]ether, tetraethylene glycol bis[(3-ethyl-3-oxetanyl)methyl]ether, tricyclodecanediyldimethylene bis[( 3-ethyl-3-oxetanyl)methyl]ether, trimethylolpropane tris[(3-ethyl-3-oxetanyl)methyl]ether, 1,4-double [ (3-ethyl-3-oxetanyl)methoxy]butane, 1,6-bis[(3-ethyl-3-oxetanyl)methoxy]hexane, pentaerythritol III [(3-ethyl-3-oxetanyl)methyl]ether, pentaerythritol tetrakis[(3-ethyl-3-oxetanyl)methyl]ether Polyethylene glycol bis[(3-ethyl-3-oxetanyl)methyl]ether, dipentaerythritol hexa[(3-ethyl-3-oxetanyl)methyl]ether, dipentaerythritol Penta[(3-ethyl-3-oxetanyl)methyl]ether, dipentaerythritol tetrakis[(3-ethyl-3-oxetanyl)methyl]ether.

The oxetane-containing compound may furthermore be a reaction product of dipentaerythritol hexa[(3-ethyl-3-oxetanyl)methyl]ether and caprolactone, dipentaerythritol five [(3-ethyl) Reaction product of benzyl-3-oxetanyl)methyl]ether with caprolactone, di-trimethylolpropane tetra[(3-ethyl-3-oxetanyl)methyl]ether, Reaction product of bisphenol A bis[(3-ethyl-3-oxetanyl)methyl]ether with ethylene oxide, bisphenol A bis[(3-ethyl-3-oxa) Reaction product of cyclobutyl)methyl]ether with propylene oxide, reaction product of hydrogenated bisphenol A bis[(3-ethyl-3-oxetanyl)methyl]ether with ethylene oxide, hydrogenation Reaction product of bisphenol A bis[(3-ethyl-3-oxetanyl)methyl]ether with propylene oxide, bisphenol F bis[(3-ethyl-3-oxetanyl) The reaction product of methyl]ether and ethylene oxide.

The crosslinking agent (D) may, for example, be a compound having a group blocked by a protecting group with an isocyanate group. The compound is also referred to as a "blocking isocyanate compound". A group in which an isocyanate group is blocked by a protecting group is also referred to as a "blocking isocyanate group".

Examples of the blocked isocyanate compound include, for example, Japanese Patent Laid-Open No. Hei. No. 2013-225031, Japanese Patent No. 5,132,096, Japanese Patent No. 5,071,686, Japanese Patent Laid-Open Publication No. No. No. No. No. No. No. No. No. No. No. The compound described in JP-A-2003-41185, Japanese Patent No. 4879557, and JP-A-2006-119441.

Examples of the compound containing a polymerizable carbon-carbon double bond include a polyfunctional (meth) acrylate, and specific examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and poly Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(a) Acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trishydroxyl Methylpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition di-trimethylolpropane tetra(meth)acrylate, epoxy Ethane addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth) acrylate, propylene oxide addition trimethylolpropane tri(meth) acrylate, propylene oxide Addition of di-trimethylolpropane tetra(meth) acrylate, propylene oxide addition pentaerythritol tetra(meth) acrylate, propylene oxide addition dipentaerythritol hexa(meth) acrylate, ε-cap Ester addition trimethylolpropane tri(meth) acrylate, ε-caprolactone addition di-trimethylolpropane tetra(meth) acrylate, ε-caprolactone addition pentaerythritol tetra (methyl Acrylate and ε-caprolactone are added to dipentaerythritol hexa(meth)acrylate.

The crosslinking agent (D) may be used alone or in combination of two or more.

In the radiation sensitive material, the content of the crosslinking agent (D) is usually from 1 part by mass to 210 parts by mass, preferably from 4 parts by mass to 160 parts by mass, more preferably 10%, based on 100 parts by mass of the polymer (A). The mass portion is -150 parts by mass, and further preferably 15 parts by mass to 100 parts by mass. When the content of the crosslinking agent (D) is at least the lower limit of the above range, the low water absorption of the insulating film tends to be improved. When the content of the crosslinking agent (D) is at most the upper limit of the above range, the heat resistance of the insulating film tends to be improved.

[solvent (E)]

The solvent (E) can be used to make the radiation sensitive material into a liquid form.

The solvent (E) is preferably diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkane. Ethyl acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether propionate, triethylene glycol dialkyl ether, hydroxyl group-containing ketone, cyclic ether or ring ester.

Examples of the diethylene glycol monoalkyl ether include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether.

Examples of the diethylene glycol dialkyl ether include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

Examples of the ethylene glycol monoalkyl ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

Examples of the ethylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate.

Examples of the diethylene glycol monoalkyl ether acetate include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate.

Examples of the triethylene glycol dialkyl ether include triethylene glycol dimethyl ether.

Examples of the hydroxy group-containing ketone include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, and 4- Hydroxy-4-methyl-2-pentanone (diacetone alcohol).

Examples of the cyclic ether or cyclic ester include γ-butyrolactone, tetrahydrofuran, and dioxane.

The solvent (E) may further be exemplified by a guanamine-based solvent such as N,N,2-trimethylpropanamide, 3-butoxy-N,N-dimethylpropane decylamine, 3-methoxy- N,N-dimethylpropane decylamine, 3-hexyloxy-N,N-dimethylpropane decylamine, isopropoxy-N-isopropyl-propionamide, n-butoxy-N -isopropyl-propionamide and the like.

The solvent (E) is preferably propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA (Propyleneglycol monomethylether acetate)"), propylene glycol monomethyl ether (hereinafter also referred to as "PGME (Propyleneglycol monomethylether)"), and diethylene glycol. Alcohol ethyl methyl ether (hereinafter also referred to as "EDM (Diethyleneglycol ethylmethylether)"), diacetone alcohol (hereinafter also referred to as "DAA (Diacetonalcohol)"), γ-butyrolactone (hereinafter also referred to as "BL (γ) -butyrolactone)").

Further, in one embodiment, the solvent (E) is preferably a γ-butyrolactone, preferably a mixed solvent containing BL. The content of the BL is preferably 70% by mass or less, and more preferably 20% by mass to 60% by mass based on 100% by mass of the total amount of the solvent (E). BL is preferably used in combination with at least one selected from the group consisting of PGMEA, PGME, EDM, and DAA. By setting the content of BL to the above range, there is a tendency that the dissolved state of the polymer (A) in the radiation sensitive material can be preferably maintained.

The solvent (E) may be used in combination with an alcohol solvent such as methanol, ethanol, propanol or butanol, or an aromatic hydrocarbon such as toluene or xylene, in addition to the above-exemplified solvent. Agents, etc.

The solvent exemplified as the solvent (E) is lower in water absorbability than NMP. Therefore, the material can be prepared using a solvent having low water absorbability without using a highly water-absorbing NMP. As a result, the material can exhibit low water absorption. The solvent exemplified as the solvent (E) has high safety, so that the safety of the material can be improved.

In the case of using the solvent exemplified as the solvent (E), the insulating film formed of the material can be made low in water absorbability. Therefore, the material can be preferably used to form an insulating film which the organic EL element has.

The solvent (E) may be used alone or in combination of two or more.

In the radiation sensitive material, the content of the solvent (E) is usually 5% by mass to 60% by mass, preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, based on the solid content of the material. The amount. The solid component herein means all components other than the solvent (E). When the content of the solvent (E) is set to the above range, the developability is not impaired, and the low water absorbability of the insulating film formed of the material tends to be improved.

[Other optional ingredients]

The radiation sensitive material may contain other optional components such as an adhesion aid (F) and a surfactant (G), as needed, in addition to the essential components and preferred components, without departing from the effects of the present invention. . The other optional components may be used singly or in combination of two or more.

<Intimate Auxiliary (F)>

The adhesion aid (F) is a component that improves the adhesion between the film formation target such as a substrate and the insulating film. In particular, in order to improve the adhesion between the inorganic substrate and the insulating film, the adhesion aid (F) is useful. Examples of the inorganic material include ruthenium compounds such as ruthenium, iridium oxide, and ruthenium nitride; and metals such as gold, copper, and aluminum.

The adhesion aid (F) is preferably a functional decane coupling agent. Examples of the functional decane coupling agent include decane having a reactive substituent such as a carboxyl group, a halogen atom, a vinyl group, a methacryl fluorenyl group, an isocyanate group, an epoxy group, an oxetanyl group, an amine group or a thiol group. Coupling agent.

Examples of the functional decane coupling agent include N-phenyl-3-aminopropyltrimethoxydecane, trimethoxydecylbenzoic acid, γ-methylpropenyloxypropyltrimethoxydecane, and vinyl group. Triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl alkyl dioxane Oxydecane, γ-chloropropyltrialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. Among these compounds, preferred are N-phenyl-3-aminopropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylalkyldialkyloxy Basear, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane.

The content of the adhesion aid (F) in the radiation sensitive material is preferably 20 parts by mass or less, more preferably 0.01 parts by mass to 20 parts by mass, per 100 parts by mass of the polymer (A). By setting the content of the adhesion aid (F) to the above range, the adhesion between the formed insulating film and the substrate is further improved.

<Surfactant (G)>

The surfactant (G) is a component that enhances the coating film formability of the radiation sensitive material. Since the radiation sensitive material contains the surfactant (G), the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the insulating film can be further improved. Examples of the surfactant (G) include a fluorine-based surfactant and an anthrone-based surfactant.

Specific examples of the surfactant (G) include those described in JP-A-2003-015278 and JP-A-2013-231869.

The content of the surfactant (G) in the radiation sensitive material is preferably 20 parts by mass or less, more preferably 0.01 parts by mass to 15 parts by mass, even more preferably 0.05 parts by mass, based on 100 parts by mass of the polymer (A). ~10 parts by mass. By setting the content of the surfactant (G) to the above range, the film thickness uniformity of the formed coating film can be further improved.

[Preparation method of radiation sensitive material]

The radiation sensitive material can be prepared, for example, by mixing necessary components such as the polymer (A), the photosensitive agent (B), and the resin (C) in the solvent (E), and other optional components. Further, in order to remove foreign matter, the components may be uniformly mixed, and the resulting mixture may be filtered by a filter or the like.

[Method of Forming Insulating Film Using Radiation-Tensor Material]

The method for forming an insulating film of the display or illumination device of the present invention comprises the steps of: step 1, forming a coating film on the substrate using the radiation sensitive material; and step 2, irradiating at least a portion of the coating film with radiation; Step 3, developing the radiation-coated coating film; and Step 4, performing the developed coating film heating.

According to the method for forming an insulating film, an insulating film having excellent light-shielding properties and a regular conical shape at the boundary portion can be formed on the TFT substrate. Further, since the material has excellent radiation sensitivity, the pattern is formed by exposure, development, and heating using the characteristics, whereby an insulating film having a fine and delicate pattern can be easily formed.

"step 1"

In the step 1, the radiation sensitive material is applied onto the surface of the substrate, preferably by prebaking to remove the solvent (E), thereby forming a coating film. The film thickness of the coating film can be preferably from 0.3 μm to 15.0 μm, more preferably from 0.5 μm to 10.0 μm, even more preferably from 1.0 μm to 5.0 μm, after prebaking.

Examples of the substrate include a resin substrate, a glass substrate, and a tantalum wafer. In the organic EL element in the middle of the production, for example, a TFT substrate in which a TFT or a wiring thereof is formed is exemplified. In the case of manufacturing the device of the present invention, the coating film is formed particularly on a TFT substrate.

Examples of the coating method of the radiation sensitive material include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an inkjet method. Among these coating methods, a spin coating method and a slit die coating method are preferred.

The prebaking conditions vary depending on the composition of the radiation-sensitive material, for example, the heating temperature is set to 60 ° C to 130 ° C, and the heating time is set to about 30 seconds to 15 minutes. The prebaking is preferably carried out at a temperature at which the coating film is not provided with the light blocking property based on the resin (C).

Step 2

In the step 2, the coating film formed in the step 1 is irradiated with radiation by interposing a mask having a predetermined pattern. Examples of the radiation used at this time include visible light, ultraviolet light, far ultraviolet light, X-ray, and charged particle beam. Examples of the visible light rays include g rays (wavelength: 436 nm) and h rays (wavelength: 405 nm). Examples of the ultraviolet light include an i-ray (wavelength: 365 nm). The far ultraviolet rays include, for example, laser light of a KrF excimer laser. Examples of the X-rays include synchrotron radiation. The charged particle beam is exemplified by an electron beam.

Among these radiations, visible light rays and ultraviolet rays are preferable, and radiation containing g rays and/or i rays is particularly preferable among visible rays and ultraviolet rays. In the case of using radiation containing i-rays, the exposure amount is preferably 6000 mJ/cm ² or less, preferably 20 mJ/cm ² to 2000 mJ/cm ² .

Step 3

In the step 3, the coating film irradiated with radiation in the step 2 is developed. Thereby, for example, in the case of using a positive-type radiation sensitive material, the irradiated portion of the radiation can be removed, and in the case of using a negative-type radiation-sensitive material, the non-irradiated portion of the radiation can be removed to form a desired pattern. . The developer used in the development treatment is preferably an alkaline aqueous solution.

Examples of the basic compound contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and diethylamino group. Ethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diaza Bicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5- Decane. The concentration of the basic compound in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability.

The developer may be used by adding an appropriate amount of an aqueous solution of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an alkaline aqueous solution, or a small amount of an aqueous solution containing various organic solvents having a radiation-sensitive radiation-sensitive material in an alkaline aqueous solution. . The organic solvent in the latter aqueous solution may be the same solvent as the solvent (E) used to obtain the polymer (A) or the radiation-sensitive material.

Examples of the development method include a liquid-filling method, a dipping method, a shaking dipping method, and a shower method. The development time varies depending on the composition of the radioactive linear material, and is usually about 10 seconds to 180 seconds. Following such development processing, for example, a running water rinse is performed for 30 seconds to 90 seconds, and then air-dried using, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

Step 4

In the step 4, an insulating film is obtained by performing a heat treatment (post-baking treatment) on the coating film by using a heating means such as a hot plate or an oven after the step 3. The heating temperature in the heat treatment is, for example, more than 130 ° C and 300 ° C or less, and the heating time varies depending on the type of the heating device, and is, for example, 5 minutes to 90 minutes. In this case, a step bake method or the like which performs a heating step of 2 or more times may be used. For the heat treatment, for example, a hot plate or an oven can be used.

By the heat treatment in the temperature range, the insulating film is provided with a light transmittance of 15% or less, preferably 10% or less, and particularly preferably 6% or less at a wavelength of 300 nm to 400 nm. Thus, the target pattern can be formed on the substrate. Marginal membrane.

In the step 4, the patterned coating film may be subjected to a rinsing treatment or a decomposition treatment before the heating of the coating film. In the rinsing treatment, it is preferred to wash the coating film with a solvent having low water absorption as exemplified as the solvent (E). In the decomposition treatment, the photosensitive agent (B) remaining in the coating film can be decomposed by irradiating the entire surface with radiation (post exposure) such as a high pressure mercury lamp. The exposure amount of the post exposure is preferably about 1000 mJ/cm ² to 5000 mJ/cm ² .

The insulating film thus obtained has light-shielding properties for light having a wavelength of 300 nm to 400 nm, and has a low water absorption structure because of a low water absorption structure of the constituent material, and can be treated with a compound having low water absorbability in the production step. Further, the insulating film exhibits excellent characteristics in terms of heat resistance, patterning property, radiation sensitivity, resolution, and the like. Therefore, the insulating film can be preferably used as an insulating film as a protective film or a planarizing film, in addition to, for example, an insulating film which is a partition wall which the organic EL element or the like has.

[Organic EL display device and organic EL illumination device]

Hereinafter, an organic EL display or an illumination device will be described as a specific example of the display or illumination device of the present invention with reference to FIG. 3. 3 is a cross-sectional view schematically showing a configuration of a main part of an organic EL display or illumination device (hereinafter also simply referred to as an "organic EL device") of the present invention.

The organic EL device 1 of FIG. 3 is an active matrix type organic EL device having a plurality of pixels formed in a matrix. The organic EL device 1 may be of a top emission type or a bottom emission type. Composition The properties of the material of the member, for example, transparency, are appropriately selected depending on the top emission type and the bottom emission type.

The organic EL device 1 includes a support substrate 2, a thin film transistor (hereinafter also referred to as "TFT") 3, a first insulating film 4, an anode 5 as a first electrode, a through hole 6, a second insulating film 7, and an organic light emitting layer. 8. The cathode 9, the passivation film 10, and the sealing substrate 11 as the second electrode. The insulating film is used as the second insulating film 7.

The support substrate 2 is formed of an insulating material. When the organic EL device 1 is of the bottom emission type, high transparency is required for the support substrate 2. Therefore, the insulating material is preferably a transparent resin such as polyethylene terephthalate having high transparency, polyethylene naphthalate or polyimine, or a glass material such as alkali-free glass. On the other hand, when the organic EL device 1 is of the top emission type, any insulating material can be used as the insulating material, and the above-mentioned transparent resin or glass material can be used.

The TFT 3 is an active element of each pixel portion and is formed on the support substrate 2. The TFT 3 includes a gate electrode, a gate insulating film, a semiconductor layer, a source electrode, and a drain electrode. In the present invention, it is not limited to the bottom gate type in which the gate insulating film and the semiconductor layer are sequentially provided on the gate electrode, and the top gate type in which the gate insulating film and the gate electrode are sequentially provided on the semiconductor layer. .

The semiconductor layer can be formed using the oxide semiconductor containing one or more elements selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn. In the organic EL device 1, since the second insulating film 7 (isolation wall) has light blocking properties, it is possible to prevent or reduce the light generated by the organic light-emitting layer 8 from reaching the semiconductor layer. Therefore, a semiconductor layer containing IGZO or the like which is easily photodegraded can be used.

The first insulating film 4 is a planarizing film that functions to flatten the surface unevenness due to the TFT 3 . The first insulating film 4 is formed to cover the entire TFT 3 . The first insulating film 4 can be formed using the radiation sensitive material, or can be formed using a conventionally known radiation sensitive material. The thickness of the first insulating film 4 is preferably large to exhibit an excellent function as a planarizing film. The film thickness of the first insulating film 4 is preferably 1 μm to 5 μm. The first insulating film 4 can be formed by a method or the like described in the method of forming the insulating film.

The anode 5 forms a pixel electrode. The anode 5 is formed on the first insulating film 4 by a conductive material. In the case where the organic EL device 1 is of the bottom emission type, the anode 5 is required to be transparent. Therefore, the material of the anode 5 is preferably Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), or tin oxide having high transparency. When the organic EL device 1 is of the top emission type, the anode 5 is required to have light reflectivity. Therefore, the material of the anode 5 is preferably an APC alloy (an alloy of silver, palladium, and copper) having high light reflectivity, an alloy of ARA (an alloy of silver, iridium, and gold), MoCr (an alloy of molybdenum and chromium), and NiCr (nickel and nickel). Chromium alloy).

The through hole 6 is formed to connect the anode 5 to the drain electrode of the TFT 3. The anode 5 is connected to the drain electrode of the TFT 3 by a wiring formed in the through hole 6.

The second insulating film 7 functions as a partition wall (bank) having a concave portion 70 that defines an arrangement region of the organic light-emitting layer 8. The second insulating film 7 is formed to cover a part of the anode 5 and expose a part of the anode 5 on the other hand. Further, a boundary portion of the second insulating film 7 where the anode 5 is exposed The cross-sectional shape is a regular conical shape. The second insulating film 7 can be formed using the radiation sensitive material by a method or the like described in the method of forming an insulating film.

The second insulating film 7 is patterned by exposure and development of the coating film, whereby the plurality of concave portions 70 in which the organic light-emitting layer 8 is formed can be arranged in a matrix in a plan view.

Further, the second insulating film 7 is preferably formed to fill the through holes 6. With such a configuration, the insulating film formed on the first insulating film 4 and the insulating film formed in the through hole 6 serve as a defensive wall for preventing or reducing the light generated by the organic light-emitting layer 8 from reaching the semiconductor layer of the TFT 3. In addition, when two or more through holes 6 are provided corresponding to one TFT 3, it is possible to further prevent or reduce the light generated by the organic light-emitting layer 8 from reaching the semiconductor layer of the TFT 3.

The second insulating film 7 is formed on the first insulating film 4 so as to be disposed at least above the semiconductor layer included in the TFT 3 . Here, "above" refers to a direction in which the self-supporting substrate 2 faces the sealing substrate 11. Since the second insulating film 7 has a light-shielding property, it is possible to prevent or reduce the light generated by the organic light-emitting layer 8 from reaching the semiconductor layer.

The film thickness of the second insulating film 7 (the distance between the uppermost surface of the second insulating film 7 and the lowermost portion of the organic light-emitting layer 8) is preferably 0.3 μm to 15.0 μm, more preferably 0.5 μm to 10.0 μm, and still more preferably 1.0. Mm~5.0μm.

The organic light-emitting layer 8 is applied with an electric field to emit light. The organic light-emitting layer 8 is a layer containing an organic light-emitting material that emits electric field. The organic light-emitting layer 8 is formed on the anode 5 in a region defined by the second insulating film 7, that is, in the recess 70. Thus, by forming the organic light-emitting layer 8 in the recess 70, the periphery of the organic light-emitting layer 8 is insulated by the second Surrounded by the film 7, a plurality of adjacent pixels can be separated from each other.

The organic light-emitting layer 8 is formed in contact with the anode 5 in the concave portion 70 of the second insulating film 7. The thickness of the organic light-emitting layer 8 is preferably from 50 nm to 100 nm. Here, the thickness of the organic light-emitting layer 8 means the distance from the bottom surface of the organic light-emitting layer 8 on the anode 5 to the upper surface of the organic light-emitting layer 8 on the anode 5.

Further, a hole injection layer and/or a hole transport layer may be disposed between the anode 5 and the organic light-emitting layer 8, or an electron transport layer and/or an electron injection layer may be disposed between the organic light-emitting layer 8 and the cathode 9.

The cathode 9 is formed by collectively covering a plurality of pixels, and forms a common electrode of the organic EL device 1. The cathode 9 contains a conductive member. When the organic EL device 1 is of a top emission type, the cathode 9 is preferably a visible light transmissive electrode, and examples thereof include an ITO electrode or an IZO electrode. When the organic EL device 1 is of the bottom emission type, the cathode 9 does not need to be a visible light transmitting electrode. In this case, examples of the constituent material of the cathode 9 include barium (Ba), barium oxide (BaO), aluminum (Al), and an alloy containing Al.

The passivation film 10 suppresses penetration of moisture or oxygen into the organic EL element. The passivation film 10 is provided on the cathode 9.

The sealing substrate 11 seals the main surface on which the organic light-emitting layer 8 is disposed (the surface on the opposite side of the TFT substrate from the support substrate 2). The sealing substrate 11 is a glass substrate such as an alkali-free glass substrate. The main surface on which the organic light-emitting layer 8 is disposed is preferably sealed with a sealing agent applied to the vicinity of the outer peripheral end portion of the TFT substrate, and sealed by the sealing substrate 11 via the sealing layer 11. The sealing layer 12 can be set, for example, to an inert gas such as dried nitrogen. a layer of a bulk, or a layer of a filler such as an adhesive.

In the organic EL device 1 of the present embodiment, the second insulating film 7 has light-shielding properties for light having a wavelength of 300 nm to 400 nm, so that photodegradation of the semiconductor layer accompanying use of the device or the like can be suppressed. Further, the first insulating film 4 and the second insulating film 7 can be formed using a low-absorption radiation sensitive material, and in the step of forming the insulating film 4 and the insulating film 7, a material having low water absorbability can be used. Cleaning and other processing. Therefore, it is possible to reduce the infiltration of a small amount of water contained in the insulating film forming material into the organic light-emitting layer 8 in the form of adsorbed water or the like, and it is possible to reduce the deterioration of the organic light-emitting layer 8 and the deterioration of the light-emitting state.

[Examples]

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to the examples. In the following examples and the like, "parts" are "parts by mass" unless otherwise specified.

[GPC Analysis]

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer (A) and the resin (C) were measured by a gel permeation chromatography (GPC) method under the following conditions.

. Standard material: polystyrene conversion

. Device: Tosoh (stock) manufacturing, trade name: HLC-8020

. Pipe column: The guard column H _XL -H, TSK gel G7000H _XL , TSK gel GMH _XL 2 and TSK gel G2000H _XL manufactured by Tosoh (stock) are sequentially connected.

. Solvent: tetrahydrofuran

. Sample concentration: 0.7% by mass

. Injection volume: 70μL

. Flow rate: 1mL/min

[NMR analysis]

The content of the phenyl group in the polyoxyalkylene (A1) is measured by using "JNM-ECS400" (manufactured by JEOL Ltd.) to determine the ²⁹ Si-nuclear magnetic resonance spectrum, based on the peak area of Si bonded to the phenyl group. The ratio of the peak areas of Si in which the phenyl group was not bonded was determined.

<Synthesis of Polymer (A)>

[Synthesis Example A1] Synthesis of Polymer (A-1) (Polyimine)

After adding 390 g of γ-butyrolactone as a polymerization solvent to a three-necked flask, 120 g of 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a diamine compound was added to a polymerization solvent. . After dissolving the diamine compound in a polymerization solvent, 71 g of 4,4'-oxydiphthalic dianhydride as an acid dianhydride was added. Thereafter, after reacting at 60 ° C for 1 hour, 19 g of maleic anhydride as a terminal blocking agent was added, and the mixture was further reacted at 60 ° C for 1 hour, and then heated and reacted at 180 ° C for 4 hours. About 600 g of a polyimine solution containing a solid content of the polymer (A-1) of about 35% by mass was obtained. The Mw of the obtained polymer (A-1) was 8,000.

[Synthesis Example A2] Synthesis of Polymer (A-2) (Acrylic Polymer)

After the inside of the flask was purged with nitrogen, 250.0 g of a propylene glycol monomethyl ether acetate solution in which 5.0 g of 2,2'-azobisisobutyronitrile was dissolved was added. Then 20.0 g of methacrylic acid, 45.0 g of dicyclopentanyl methacrylate and 3-ethyl-3-methylpropenyloxymethyl group were added. After 30.0 g of oxetane, stirring was started slowly. The temperature of the solution was raised to 80 ° C, the temperature was maintained for 5 hours, and then heated at 100 ° C for 1 hour to complete the polymerization. Thereafter, the reaction-forming solution was added dropwise to a large amount of methanol to solidify the reactant. The coagulum was washed with water, dissolved in 200 g of tetrahydrofuran, and solidified again with a large amount of methanol.

After the re-dissolution-solidification operation was carried out for a total of three times, the obtained coagulum was vacuum dried at 60 ° C for 48 hours to obtain a target copolymer. Thereafter, a copolymer solution was prepared using propylene glycol monomethyl ether acetate so that the solid content concentration became about 35% by mass. The obtained polymer (A-2) had a weight average molecular weight (Mw) of 10,000.

[Synthesis Example A3] Synthesis of Polymer (A-3) (Acrylic Polymer)

In addition to 20.0 g of 2-methylpropenyloxyethyl succinic acid, 45.0 g of dicyclopentanyl methacrylate and 30.0 g of 3,4-epoxycyclohexylmethyl methacrylate as monomers, and synthesis Example A2 was operated in the same manner. The obtained polymer (A-3) had a weight average molecular weight (Mw) of 20,000.

[Synthesis Example A4] Synthesis of Polymer (A-4) (Polybenzoxazole Precursor)

443.2g (0.90 mole) of hexacarboxylic acid derivative obtained by reacting 1 molar of diphenyl ether-4,4'-dicarboxylic acid with 1-hydroxybenzotriazole 2, hexafluoro-2, 366.3 parts (1.00 mol) of 2-bis(3-amino-4-hydroxyphenyl)propane was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube, and N- was added thereto. 3000 parts of methyl-2-pyrrolidone and dissolved. Thereafter, it was reacted at 75 ° C for 16 hours using an oil bath.

Then, add 5-dext dissolved in 100 parts of N-methyl-2-pyrrolidone 32.8 parts (0.20 mol) of borneol-2,3-dicarboxylic anhydride was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water/isopropyl alcohol = 3/1 (mass ratio), and the precipitate was collected by filtration and thoroughly washed with water, and dried under vacuum to obtain polybenzoic acid. Azole precursor (A-4). Γ-butyrolactone was added so that the concentration of the polymer (A-4) was 35% by mass to obtain a γ-butyrolactone solution of the polymer (A-4). The obtained polymer (A-4) had a weight average molecular weight (Mw) of 15,000.

[Synthesis Example A5] Synthesis of Polymer (A-5) (Polyoxane)

To a 500 mL three-necked flask, 63.39 parts (0.55 mol) of methyltrimethoxydecane, 69.41 parts (0.35 mol) of phenyltrimethoxydecane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy group were added. 24.64 parts (0.1 mol) of decane and 150.36 parts of diacetone alcohol, and the mixture was stirred at room temperature, and added to 55.8 parts of water, and 0.338 parts of phosphoric acid (0.2 mass% with respect to the monomer added) was dissolved in 55.8 parts of water for 10 minutes. Aqueous solution. Thereafter, the flask was immersed in an oil bath of 70 ° C and stirred for 1 hour, and then the oil bath was heated to 115 ° C over 30 minutes. One hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C, and then the mixture was heated and stirred for 2 hours (the internal temperature was 100 ° C to 110 ° C). In the reaction, 115 parts of methanol and a hydrate as a by-product were distilled off. Diacetone alcohol was added to the diacetone alcohol solution of the obtained polymer (A-5) so that the concentration of the polymer (A-5) was 35% by mass to obtain a diacetone alcohol solution of the polymer (A-5). . The obtained polymer (A-5) had a weight average molecular weight (Mw) of 5,000 and a phenyl content of 35 mol with respect to 100 mol of Si atom.

[Synthesis Example A6] Synthesis of Polymer (A-6) (Polyolefin)

In a 1000 mL autoclave purged with nitrogen, add 8-carboxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene 60 parts, N-phenyl-(5-norbornene- 2,3-dicarboxy quinone imine) 40 parts, 1,5-hexadiene 2.8 parts, di(1,3-d-trimethylphenylimidazolidin-2-ylidene) (tricyclohexylphosphine) 0.05 parts of benzalkonium hydride and 400 parts of diethylene glycol ethyl methyl ether were subjected to polymerization at 80 ° C for 2 hours with stirring to obtain a polymer solution containing the polymer (A-6'). To the polymer solution, 0.1 part of dichlorobis(tricyclohexylphosphine)ethoxymethylene fluorene as a hydrogenation catalyst was added, and hydrogen was dissolved at a pressure of 4 MPa for 5 hours, and after hydrogenation reaction, activated carbon powder 1 was added. The hydrogen was dissolved at a pressure of 4 MPa for 3 hours while stirring at 150 °C. Then, the solution was taken out, and the activated carbon was separated by filtration using a fluororesin filter having a pore size of 0.2 μm to obtain 490 parts of a hydrogenation reaction solution containing the polymer (A-6) as a hydride of the polymer (A-6'). . The solid content concentration of the hydrogenation reaction solution containing the polymer (A-6) obtained here was 21% by mass, and the yield of the polymer (A-6) was 102 parts. The hydrogenation reaction solution of the obtained polymer (A-6) was concentrated by a rotary evaporator, and the solid content concentration was adjusted to 35% by mass to obtain a solution of the polymer (A-6). The obtained polymer (A-6) had a weight average molecular weight (Mw) of 4,000.

[Preparation Example A7] Polymer (A-7) (Cardo Resin)

The propylene glycol monomethyl ether solution CR-TR5 (manufactured by Osaka Gas Chemical Co., Ltd.) of the cardo resin is a product having a solid content of 52.7 mass% and a solid component acid value of 135 KOHmg/g. 100 parts of CR-TR5 was metered, and 50.57 parts of propylene glycol monomethyl ether was added and stirred. Thus, a cardo resin solution (A-7) having a solid content concentration of 35 mass% was obtained.

<Synthesis of Resin (C)>

[Synthesis Example C1] Synthesis of Novolak Resin (C-1)

In a flask equipped with a thermometer, a condenser, a fractionation tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 96 g of water, and 32.6 g of 92% by mass of paraformaldehyde were added ( It is 1.0 mole in terms of formaldehyde. Then, 3.4 g of p-toluenesulfonic acid was added while stirring. Thereafter, the reaction was carried out at 100 ° C for 8 hours. After the completion of the reaction, 200 g of pure water was added, and the solution in the system was transferred to a separatory funnel, and the aqueous layer was separated and removed from the organic layer. After washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 140 g of a novolak resin (C-1) containing a structural unit represented by the following formula. The obtained novolak resin (C-1) had a weight average molecular weight (Mw) of 2,000.

According to the measurement spectrum of the Fourier Transform Infrared (FT-IR), the absorption of the stretching derived from the methylene bond (2800 cm ^-1 to 3000 cm ^-1 ) was confirmed as compared with the raw material, and it was impossible to find It is derived from the absorption of aromatic ether (1000 cm ^-1 ~ 1200 cm ^-1 ). According to these results, in the present synthesis example, the dehydration etherification reaction (hydroxy group disappearance) of the hydroxyl groups did not occur, and a novolak resin having a methylene bond was obtained. The same was found in the following Synthesis Examples C2 to C5.

[Synthesis Example C2] Synthesis of Novolak Resin (C-2)

In a flask equipped with a thermometer, a condenser, a fractionation tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol, 134.1 g (1.0 mol) of terephthalaldehyde, and 3.0 g of trifluoromethanesulfonic acid were charged. The reaction was carried out at 150 ° C to 160 ° C for 4 hours while stirring. After the completion of the reaction, 200 g of pure water was added, and the solution in the system was transferred to a separatory funnel, and the aqueous layer was separated and removed from the organic layer. After washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 220 g of a novolak resin (C-2) containing a structural unit represented by the following formula. The obtained novolak resin (C-2) had a weight average molecular weight (Mw) of 1,500.

[Synthesis Example C3] Synthesis of Novolak Resin (C-3)

The raw material component and 134.1 g (1.0 mol) of terephthalaldehyde and 160.2 g (1.0 mol) of 1,6-dihydroxynaphthalene and 3.0 g of trifluoromethanesulfonic acid were used as an acid catalyst, and the synthesis and synthesis were carried out. Example C2 was synthesized in the same manner. 230 g of a novolak resin (C-3) containing a structural unit represented by the following formula was obtained. The weight of the obtained novolak resin (C-3) The amount average molecular weight (Mw) was 1,000.

[Synthesis Example C4] Synthesis of Novolak Resin (C-4)

In addition to using 194.2 g (1.0 mol) of 1-hydroxyindole as a raw material component, 400 g of methyl isobutyl ketone, 96 g of water, and 32.6 g of trioxane of 92% by mass (1.0 mol in terms of formaldehyde), The synthesis was carried out in the same manner as in Synthesis Example C1. 180 g of a novolak resin (C-4) containing a structural unit represented by the following formula was obtained. The obtained novolak resin (C-4) had a weight average molecular weight (Mw) of 2,000.

[Synthesis Example C5] Synthesis of Novolak Resin (C-5)

In addition to using 1,4-dihydroxyindole as a raw material component, 210.2 g (1.0 mol), The synthesis was carried out in the same manner as in Synthesis Example C1 except that 400 g of methyl isobutyl ketone, 96 g of water, and 32.6 g of 92% by mass of paraformaldehyde (1.0 mol in terms of formaldehyde) were used. 190 g of a novolak resin (C-5) containing a structural unit represented by the following formula was obtained. The obtained novolak resin (C-5) had a weight average molecular weight (Mw) of 3,000.

<Preparation of radiation sensitive materials>

The polymer (A) used for the preparation of the radiation sensitive material is the polymer (A-1) to the polymer (A-7) of Synthesis Example A1 to Synthesis Example A6 and Preparation Example A7, and the resin (C) is Synthesis Example C1. ~Novolak resin (C-1) to novolak resin (C-5), sensitizer (B), crosslinker (D), solvent (E), adhesion aid (F) and interfacial activity of Synthesis Example C5 The agent (G) is as follows.

Photosensitive agent (B)

B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) (Toyo Synthetic Industry Co., Ltd.)

B-2: 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene -1-butanone ("IRG-379EG" by BASF)

Crosslinking agent (D)

D-1: 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl ("OXBP" by Ube Industries Co., Ltd.)

D-2: "C-357" of Qunrong Chemical Industry Co., Ltd.

D-3: "M-405" of East Asia Synthesis Corporation

Solvent (E)

E-1: mixed solvent of γ-butyrolactone (BL), propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in a mass ratio of 30:20:50

DAA: Diacetone alcohol

EDM: diethylene glycol ethyl methyl ether

Adhesion aid (F)

F-1: N-phenyl-3-aminopropyltrimethoxydecane

("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.)

Surfactant (G)

G-1: anthrone-based surfactant

("SH8400" manufactured by Toray-Dow Corning Co., Ltd.)

[Preparation Example 1]

In the polymer solution containing the polymer (A-1) of Synthesis Example A1 (corresponding to the amount of 25 parts (solid content) of the polymer (A-1)), 10 parts (B-1) were mixed (C-). 1) 40 parts, (D-1) 15 parts, (D-2) 5 parts, (F-1) 4 parts, (G-1) 1 part and (E-1), the solid concentration is 25 mass % mode is set, and the caliber is A 0.2 μm membrane filter was filtered to prepare a positive material 1.

[Preparation Example 2 to Preparation Example 33]

In the same manner as in Preparation Example 1, a positive material 2 to a positive material 23, a positive material 30 to a positive material 31, and a negative material 24 to a negative type were prepared in the same manner as in the preparation example 1 except that each component of the type and the amount shown in Table 1 was used. Material 29 and negative material 32 to negative material 33.

[Examples and Comparative Examples]

Using the radiation sensitive material 1 to the radiation sensitive material 33 of Preparation Examples 1 to 33, an insulating film and an organic EL device were produced by the method described below. The patterning property, line width roughness (LWR), light blocking property, cone angle, water absorption and heat resistance of the obtained insulating film, and the element characteristics of the obtained organic EL device were evaluated by the following methods, respectively. .

<patterning>

The coatings obtained in Preparation Example 1 to Preparation Example 23 and Preparation Example 30 to Preparation Example 31 were coated on a tantalum substrate using a Clean Track (manufactured by Tokyo Electron Co., Ltd.: Mark VZ). After the positive material, it was prebaked on a hot plate at 120 ° C for 2 minutes to form a coating film. An exposure machine (ikon stepping machine "NSR-2005i10D" of Nikon Corporation) was used for the coating film, and the pattern mask having a predetermined pattern was exposed to light at an exposure amount of 100 mJ/cm ² at a wavelength of 365 nm. Thereafter, development was carried out by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 80 seconds by a liquid-filling method, followed by washing with ultrapure water for 1 minute, and drying to form a 5 μm on a crucible substrate. A square coating film having a plurality of through holes arranged in a row pattern, and the coating film is baked on a hot plate at 250 ° C for 60 minutes to form a film having the pattern and the film thickness shown in Table 2. Insulating film.

Further, using a gel tracker (manufactured by Tokyo Electron Co., Ltd.: Mark VZ), Coating Example 24 to Preparation Example 29 and Preparation Example 32 to Preparation Example 33 were coated on a ruthenium substrate. After the obtained negative material was prebaked on a hot plate at 120 ° C for 2 minutes to form a coating film. An exposure machine (Nikon stepping machine "NSR-2005i10D" manufactured by Nikon Corporation) was used for the coating film, and the pattern mask having a predetermined pattern was exposed to an exposure amount of 300 mJ/cm ² at a wavelength of 365 nm. Thereafter, development was carried out by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 120 seconds by a liquid-filling method, followed by washing with ultrapure water for 1 minute, and drying to form a 5 μm on a crucible substrate. A plurality of through-holes of the square are arranged in a line-like pattern. The coating film was baked on a hot plate at 250 ° C for 60 minutes, and an insulating film having the above-described pattern and the film thickness shown in Table 2 was formed.

At this time, in the case of the positive film, in the case of the positive film, it was confirmed whether or not the exposed portion after development was completely dissolved, and in the case of the negative material, it was confirmed whether or not the non-exposed portion after development was completely dissolved. When a pattern of 5 μm square was formed and the insulating film was not peeled off or the residue was developed to form an insulating film, it was evaluated as "excellent", and a pattern of 5 μm square was formed, and the insulating film was not peeled off, but the development residue was slightly evaluated. In the case of "good", it was evaluated that the pattern of 5 μm square or the peeling of the insulating film was not formed.

<LWR>

Using a scanning electron microscope (SEM, "SU3500" by Hitachi High-Tech Co., Ltd.), the line width of the coating film before post-baking formed in the <patterning property> was 5 μm. The square pattern was observed from the upper portion of the pattern, and the line width was measured at any 10 points. The 3σ value (deviation) of the measured value of the line width was defined as LWR (μm). When the value of LWR is 0.4 μm or less, it is evaluated as "excellent", and when it is more than 0.4 μm and 0.8 μm or less, it is evaluated as "good", and when it is more than 0.8 μm, it is evaluated as "not". good".

<shading>

The preparation was coated on a glass substrate (Corning 7059, Corning) using a Clean track (manufactured by Tokyo Electron Co., Ltd.: Mark VZ). The radiation sensitive material obtained in the example was prebaked on a hot plate at 120 ° C for 2 minutes, and then baked on a hot plate at 250 ° C for 60 minutes to form a film thickness as shown in Table 2. Insulating film.

The glass substrate having an insulating film was measured for total light transmittance in a wavelength range of 300 nm to 780 nm using a spectrophotometer ("150-20 type double beam" manufactured by Hitachi, Ltd.). The total light transmittance at a wavelength of 300 nm to 400 nm. The light-shielding property is evaluated as "excellent" when the maximum total light transmittance is 6% or less at a wavelength of 300 nm to 400 nm, and is considered to be "good" when it exceeds 6% and is 10% or less. When it is 15% or less, it is evaluated as "slightly good", and when it is more than 15%, it is evaluated as "poor".

<cone angle and film thickness>

In the insulating film of the <patterning property>, a vertical cross-sectional shape of a plurality of through holes in a direction orthogonal to the line was observed by SEM ("SU3500" of Hitachi High-Tech Co., Ltd.). The cone angle of the insulating film is determined based on the SEM image. In each evaluation, the film thickness of the insulating film was determined in the same manner from the SEM image.

<Water absorption>

Using a gel tracker (manufactured by Tokyo Electron Co., Ltd.: Mark VZ), the radiation sensitive material obtained in the preparation example was coated on a tantalum substrate, and then placed on a hot plate. After prebaking at 120 ° C for 2 minutes, it was post-baked on a hot plate at 250 ° C for 60 minutes to form an insulating film having a film thickness of 3.0 μm.

The insulating film was subjected to thermal desorption spectroscopy ("ESC" company "TDS1200"), and the temperature was raised to 200 at a heating rate of 30 ° C/min from a normal temperature at a vacuum of 1.0 × 10 ^-9 Pa. °C. The gas separated from the surface of the sample and the sample at this time was measured in the form of a detected value of the peak value of water (M/z = 18) using a mass spectrometer ("Agilent Technology""5973N"). Take the integral value of the total peak intensity from 60 ° C to 200 ° C [A. Sec], evaluation of water absorption. Regarding water absorption, the integral value of the total peak intensity at 60 ° C ~ 200 ° C [A. When sec] is 3.0 × 10 ^-8 or less, it is evaluated as "excellent", and when it is more than 3.0 × 10 ^-8 and 5.0 × 10 ^-8 or less, it is evaluated as "good", and when it is more than 5.0 × 10 ^-8 In the case of the situation, it was evaluated as "bad".

<heat resistance>

In the same manner as the evaluation of the "water absorption property", an insulating film was formed using a radiation sensitive material, and the insulating film was subjected to a thermogravimetric measuring apparatus (TA Instruments (TA), "TGA 2950"), and was carried out at 100 ° C to 500 ° C. The thermogravimetric analysis (TGA) was measured (air temperature, heating rate: 10 ° C / min), thereby obtaining a 5% weight loss temperature. About heat resistance, at 5% weight When the temperature was more than 350 ° C, the evaluation was "excellent", and when it was 350 ° C to 330 ° C, it was evaluated as "good", and when it was 330 ° C or lower, it was evaluated as "poor".

"Component Characteristics Evaluation"

A TFT substrate on which a TFT was formed on the glass substrate was produced using a glass substrate (Corning 7059) of Corning Co., Ltd., and an insulating film was formed on the TFT substrate to prepare an evaluation element. The evaluation element was evaluated for the element characteristics.

The TFT substrate is formed in the following order. First, a molybdenum film is formed by sputtering on a glass substrate, and a gate electrode is formed by photolithography and etching using a resist. Then, a ruthenium oxide film is formed as a gate insulating film by sputtering on the entire surface of the glass substrate and the upper layer of the gate electrode. An InGaZnO-based amorphous oxide film (InGaZnO ₄ ) is formed on the gate insulating film by sputtering, and a semiconductor layer is formed by photolithography and etching using a resist. A molybdenum film is formed by sputtering on the upper layer of the semiconductor layer, and a source electrode and a drain electrode are formed by photolithography and etching using a resist. Finally, a ruthenium oxide film was formed as a passivation film by sputtering on the entire surface of the substrate, the source electrode, and the upper electrode of the drain electrode to obtain a TFT substrate.

Using a gel tracker (manufactured by Tokyo Electron Co., Ltd.: Mark VZ), the radiation sensitive material obtained in the preparation example was coated on a TFT substrate, and then dried on a hot plate. After prebaking at 120 ° C for 2 minutes, it was baked at 250 ° C for 60 minutes on a hot plate to form an insulating film having the film thickness shown in Table 2.

<Switch Response Characteristics>

The component characteristics were evaluated by the switching response characteristics. The switch response characteristics were evaluated by measuring the ON/OFF ratio. The ON/OFF ratio was calculated by measuring the current flowing between the source electrode and the drain electrode in a state where a voltage was applied to the gate electrode using a probe and a semiconductor parameter analyzer. Specifically, the gate electrode is set to be positive under the condition that the semiconductor layer is irradiated with white light having an illuminance of 30,000 lux centering on the wavelength of 450 nm or 500 nm from the insulating film formed of the radiation sensitive material. When 10 V and the source electrode are set to 0 V, the ratio of the current value when the voltage applied to the gate electrode is positive 10 V and negative 10 V is set as the ON/OFF ratio. The switch response characteristic, that is, the element characteristics, was evaluated as "good" when the ON/OFF ratio was 1.0 × 10 ⁵ or more, and "bad" when it was less than 1.0 × 10 ⁵ .

<TFT reliability>

The TFT reliability was evaluated by changing the Id-Vg characteristics when electric stress was applied between the gate electrode and the source electrode during light irradiation and non-light irradiation of the evaluation element. The amount of change in voltage Vth is compared.

(Id-Vg characteristics and determination of threshold voltage Vth)

The application of the electrical stress is performed by holding the potential of the source electrode of the evaluation element at 0 V, maintaining the potential of the drain electrode at +10 V, and applying a voltage between the source electrode and the drain electrode. Next, the potential Vg of the gate electrode is changed from -20V to +20V. When the potential Vg of the gate electrode is changed in this manner, the Id-Vg characteristic is obtained by plotting the current Id flowing between the drain electrode and the source electrode. In the Id-Vg characteristic, the voltage at which the current value becomes ON is set as the threshold. Voltage Vth.

(Measurement of the amount of change in the threshold voltage Vth)

The electrical stress is imparted by applying a positive voltage of +20 V and a negative voltage of -20 V every 12 hours between the gate electrode and the source electrode. Such electrical stress is applied under the following conditions: the semiconductor layer of the evaluation element is irradiated with white light having an illuminance of 30000 lux centering on a wavelength of 450 nm or 500 nm from above the insulating film formed of the radiation sensitive material. Under the conditions, and under the condition that the semiconductor layer is not irradiated with light. The amount of change in the threshold voltage Vth is calculated based on the Id-Vg characteristics under the light irradiation conditions and the non-light irradiation conditions, respectively. In addition, when the amount of change in the threshold voltage Vth at the time of light irradiation is less than 1.3 times the amount of change in the threshold voltage Vth at the time of non-light irradiation, the reliability of the evaluation TFT is "excellent", and is suppressed by 1.3 times. When the ratio is less than 1.6 times, the reliability of the TFT is evaluated as "good", and when the voltage is suppressed to 1.6 times or more and less than 2 times, the reliability of the TFT is evaluated to be "slightly good", and when the voltage is twice or more, the TFT is evaluated to be reliable. Sex is "bad".

As shown in Table 2, the radiation sensitive materials of Preparation Examples 1 to 29 were excellent in patterning property, pattern shape, low water absorbability, and heat resistance. In addition, the insulating film formed in the first to the third embodiments is excellent in light-shielding property and has a true conical shape, and the element characteristics (switching response characteristics) of the element using the insulating film and the semiconductor layer which is easily photo-degraded even in a light irradiation environment , TFT reliability) is also excellent. On the other hand, the insulating film formed in Comparative Example 1 was inferior in light shielding property, and the insulating film formed in Comparative Example 2 and Comparative Example 4 was inferior in patterning property, pattern shape, light blocking property, low water absorbability, and heat resistance, and Comparative Example 3 and The insulating film formed in Comparative Example 5 is inferior in patterning property, pattern shape, and low water absorbability, and the element characteristics (switching response characteristics, TFT reliability) in the light irradiation environment using the insulating film and the semiconductor layer which is easily photodegraded. difference.

100‧‧‧TFT substrate

110‧‧‧1st electrode

111‧‧‧The opening of the insulating film

112‧‧‧The edge of the first electrode

120‧‧‧Insulation film

Claims (19)

A display or illumination device comprising: a thin film transistor substrate; the semiconductor layer constituting the thin film transistor contains an oxide semiconductor containing at least one selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn The first electrode is disposed on the thin film transistor substrate and is connected to the thin film transistor; the insulating film is formed on the first electrode such that the first electrode is partially exposed. The total light transmittance is in the range of 0% to 15% at a wavelength of 300 nm to 400 nm; and the second electrode is disposed opposite to the first electrode; and the insulating film is formed of a radiation sensitive material An insulating film comprising: (A) a polymer other than the following resin (C), (B) a sensitizer, and (C) selected from the group consisting of a novolak resin, a resol resin, and a resol resin. The content of the resin (C) in the radiation sensitive material is from 2 parts by mass to 200 parts by mass based on 100 parts by mass of the polymer (A). The display or illumination device of claim 1, wherein the polymer (A) is selected from the group consisting of polyimine (A1), a precursor of the polyimine (A2), and an acrylic resin (A3). ), polyoxyalkylene (A4), polybenzoxazole (A5-1), At least one of a precursor of polybenzoxazole (A5-2), a polyolefin (A6), and a cardo resin (A7). The display or illumination device of claim 1, wherein the polymer (A) is selected from the group consisting of polyoxyalkylene (A4), polybenzoxazole (A5-1), and the polybenzoxazole. At least one of the precursor (A5-2), the polyolefin (A6), and the cardo resin (A7). The display or illumination device according to claim 2, wherein the polyimine (A1) contains a structural unit represented by the formula (A1), [In the formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group]. The display or illumination device of claim 2, wherein the polyoxyalkylene (A4) is a polyoxyalkylene obtained by reacting an organodecane represented by the formula (a4), In the formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a carbon number of 2 to 15. The epoxy ring-containing group or a group obtained by substituting one or two or more hydrogen atoms contained in the alkyl group with a substituent may be the same or different when R ^{1 is} present in plurality R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms. When R ^{2 is} present in a plurality of cases, they may be the same or different. n is an integer from 0 to 3.]. The display or illumination device of claim 2, wherein the polybenzoxazole (A5-1) contains a structural unit represented by the formula (a5-1), [In the formula (a5-1), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group]. The display or illumination device according to claim 2, wherein the precursor of polybenzoxazole (A5-2) contains a structural unit represented by formula (a5-2), [In the formula (a5-2), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group]. The display or illumination device according to any one of claims 1 to 7, wherein the sensitizer (B) is a photoacid generator or a photoradical polymerization initiator. The display or illumination device according to any one of claims 1 to 8, wherein the resin (C) is a novolac resin. The display or illumination device according to any one of the items 1 to 9, wherein the insulating film has a cross-sectional shape of a boundary portion of the insulating film in which the first electrode is exposed is a regular conical shape . The display or illumination device according to any one of claims 1 to 10, wherein the insulating film has a film thickness of 0.3 μm to 15.0 μm. The display or illumination device according to any one of claims 1 to 11, wherein the insulating film is formed to cover at least an edge portion of the first electrode, the insulating film The cross-sectional shape of the boundary portion is a regular conical shape. The display or illumination device according to any one of claims 1 to 12, wherein the insulating film is a partition wall that partitions a surface of the thin film transistor substrate into a plurality of regions, and has The pixels formed in the plurality of regions, respectively. The display or illumination device of claim 13, comprising an organic electroluminescence device, the organic electroluminescence device comprising: the first electrode disposed on the thin film transistor substrate and a thin film transistor is connected; an organic light emitting layer is formed in a region partitioned by the partition wall and formed on the first electrode; and the second electrode is provided on the organic light emitting layer. The display or illumination device of claim 14, wherein the thin film transistor substrate is provided with a support substrate, and the thin film electricity is disposed on the support substrate corresponding to the organic electroluminescent element. a crystal, and a thin film transistor substrate covering a planarization layer of the thin film transistor, wherein the partition wall covers at least an edge portion of the first electrode, and the partition wall is disposed at least on the thin film transistor The upper surface of the semiconductor layer is formed on the planarization layer. The display or illumination device according to claim 15, wherein the first electrode is formed on the planarization layer, and the first electrode is formed through a through hole penetrating the planarization layer. Wiring is connected to the thin film transistor. The display or illumination device according to any one of claims 1 to 16, wherein the insulating film is formed on the thin film transistor substrate in such a manner as to be disposed at least over the semiconductor layer. When the film is projected from above the thin film transistor substrate, 50% or more of the area of the semiconductor layer overlaps with the insulating film. A method of forming an insulating film, which comprises forming an insulating film of a display or illumination device according to claim 1, and the method for forming the insulating film comprises the following steps: Step 1, using No. 1 of the patent application scope The radiation sensitive material according to the invention forms a coating film on the thin film transistor substrate; in step 2, at least a part of the coating film is irradiated with radiation; in step 3, the radiation-coated coating film is developed; and step 4 The developed coating film is heated to form an insulating film having a total light transmittance in a range of 0% to 15% at a wavelength of 300 nm to 400 nm. The method for forming an insulating film according to claim 18, wherein the heating temperature in the step 1 is 60 ° C to 130 ° C, and the heating temperature in the step 4 is more than 130 ° C and 300 ° C or less.