JP5613851B1 - Display or lighting device - Google Patents

Abstract

In a display or lighting device having, as a driving element, a thin film transistor including a semiconductor layer made of a material having high photodegradation, such as IGZO, the display or illumination in which the photodegradation of the material accompanying use of these devices is suppressed Providing the device. A semiconductor layer constituting a TFT includes a TFT substrate containing an oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn, and is provided on the TFT substrate, and the TFT A first electrode connected to the first electrode, an insulating film formed on the first electrode so as to partially expose the first electrode, and having a total light transmittance of 0 to 15% at a wavelength of 300 to 400 nm; A display or illumination device comprising: a second electrode provided opposite to the first electrode. [Selection figure] None

Description

  The present invention relates to a display or lighting device. More specifically, the present invention is directed to a substrate, a first electrode provided on the substrate, an insulating film formed on the first electrode so as to partially expose the first electrode, and the first electrode. The present invention relates to a display or illumination device having a second electrode provided in the same manner.

  As a flat panel display, a liquid crystal display (LCD) which is a non-light-emitting type is widespread. In recent years, an electroluminescent display (ELD) which is a self-luminous display is known. In particular, an organic electroluminescence (EL) element using electroluminescence by an organic compound is expected as a light emitting element provided in a next-generation lighting device in addition to a light emitting element provided in a display.

  For example, an organic EL display or lighting device has an insulating film such as a planarization film and a partition wall that partitions pixels (light emitting elements). Such an insulating film is generally formed using a radiation sensitive resin composition (see, for example, Patent Documents 1 and 2).

  These flat panel displays operate by applying a voltage between the first electrode and the second electrode facing each other, or by passing a current. However, at this time, since the electric field tends to concentrate on the edge portion of the electrode having a small radius of curvature, an undesirable phenomenon such as dielectric breakdown or generation of leakage current tends to occur at the edge portion.

  In order to solve this problem, the film thickness of the insulating film at the boundary where the insulating film exposes the first electrode is gradually increased from the center of the first electrode toward the edge, that is, the cross section is in order. A technique for forming a taper is disclosed (see, for example, Patent Document 3).

  In recent years, research on thin film transistors (TFTs) using an oxide semiconductor layer has been actively conducted. Patent Document 4 proposes an example in which a polycrystalline thin film of an oxide made of In, Ga, and Zn (hereinafter also abbreviated as “IGZO”) is used as a semiconductor layer of a TFT. In Patent Documents 4 and 5, an amorphous IGZO film is proposed. An example in which a thin film is used for a semiconductor layer of a TFT has been proposed.

  However, IGZO is known to suffer light degradation due to natural light, lighting, manufacturing processes, and the like. For this reason, when a TFT including a semiconductor layer made of a material having a large light deterioration such as IGZO is used as a driving element for a display or lighting device, particularly a driving element for an organic EL element, from the viewpoint of preventing light deterioration of IGZO, As a characteristic of the above-described insulating film, it is required to impart light shielding properties from ultraviolet to visible light. However, many insulating films that are currently used are transparent in the wavelength region of, for example, 300 to 400 nm, and a light-shielding function is required.

JP 2011-107476 A JP 2010-237310 A Japanese Patent No. 498927 JP 2004-103957 A International Publication No. 2005/088726 Pamphlet

  The present invention relates to a display or lighting device having, as a driving element, a thin film transistor including a semiconductor layer made of a material having high photodegradation, such as IGZO, or the like. It is an object to provide a lighting device.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention. The present invention relates to the following [1] to [13], for example.

[1] A TFT substrate in which the semiconductor layer constituting the TFT contains an oxide semiconductor containing one or more elements selected from In, Ga, Sn and Zn;
A first electrode provided on the TFT substrate and connected to the TFT;
An insulating film formed on the first electrode so as to partially expose the first electrode and having a total light transmittance in a range of 0 to 15% at a wavelength of 300 to 400 nm;
A display or lighting device having a second electrode provided to face the first electrode.

[2] The display or illumination device according to [1], wherein the insulating film exposes the first electrode, and a cross-sectional shape at a boundary portion of the insulating film is a forward tapered shape.
[3] The display or illumination device according to any one of [1] to [2], wherein the insulating film has a thickness of 0.3 to 15.0 μm.

[4] The display or illumination device according to any one of [1] to [3], wherein the insulating film is an insulating film formed of a positive radiation sensitive material.
[5] The positive radiation sensitive material is selected from (A) a polyimide (A1) having a structural unit represented by the formula (A1), the polyimide precursor (A2), and an acrylic resin (A3). [4] The display or illumination device according to [4] above, which contains at least one polymer and (B) a radiation-sensitive acid generator.

［式（Ａ１）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基である。］

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

[6] The display or illumination device of [5], wherein (B) is a quinonediazide compound.
[7] The display or illumination device of [5] or [6], wherein the positive radiation sensitive material further contains (C) a novolac resin.
[8] The display or lighting device of [7], wherein the novolak resin (C) is a resin containing a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group.

[9] The display or illumination device according to [7] or [8], wherein the content of the novolak resin (C) is 2 to 200 parts by mass with respect to 100 parts by mass of the polymer (A).
[10] Any one of [1] to [9], wherein the insulating film is formed so as to cover at least an edge portion of the first electrode, and a cross-sectional shape at a boundary portion of the insulating film is a forward tapered shape. Display or lighting device.

  [11] The insulating film is formed of a positive radiation sensitive material, and is a partition partitioning the surface of the TFT substrate into a plurality of regions, and includes pixels respectively formed in the plurality of regions. [1] The display or illumination device according to any one of [10].

  [12] A first electrode provided on the TFT substrate and connected to the TFT; an organic EL layer formed on the first electrode in a region partitioned by the partition; and provided on the organic EL layer [11] The display or illumination device according to [11], further including an organic EL element including the second electrode.

  [13] The TFT substrate is a TFT substrate having a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a planarizing layer covering the TFT, and the partition wall The at least edge portion of the first electrode is covered, and the partition is formed on the planarizing layer so as to be disposed at least above the semiconductor layer of the TFT. The display or illumination device according to [12].

  According to the present invention, for example, in a display or lighting device having, as a driving element, a thin film transistor including a semiconductor layer made of a material with large photodegradation such as IGZO, the photodegradation of the material with use of these devices is suppressed. A display or lighting device can be provided.

FIG. 1 is a plan view showing an example of the shape of the insulating film. FIG. 2 is a cross-sectional view illustrating a forward tapered shape as a cross-sectional shape of the insulating film. FIG. 3 is a cross-sectional view schematically showing the structure of the main part of the organic EL device.

  The display or lighting device of the present invention includes a TFT substrate in which a semiconductor layer constituting a TFT includes an oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn, and a TFT substrate. A first electrode provided on the TFT and connected to the TFT; an insulating film formed on the first electrode so as to partially expose the first electrode; and a first electrode opposed to the first electrode. A second electrode. Here, the total light transmittance of the insulating film is 0 to 15% at a wavelength of 300 to 400 nm.

Hereinafter, the display or lighting device is also collectively referred to as “device”.
Examples of the display device of the present invention include a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescent display (ELD), and particularly an organic EL display. As an illuminating device of this invention, organic EL illumination is mentioned, for example.

  In the device of the present invention, the TFT substrate, the first electrode, and the second electrode are, for example, specific examples described in the column of “organic EL display device and organic EL lighting device” described later (support substrate and TFT, anode, cathode). ) Can be exemplified.

  In the device of the present invention, the insulating film covers at least a part of the first electrode and is formed so as to partially expose the first electrode. In particular, the insulating film is preferably 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, and an insulating film 120 is formed on the TFT substrate 100 and the first electrode 110 so as to partially expose the first electrode 110. The exposed portion of the first electrode 110 is also referred to as “opening 111”. Here, the insulating film 120 is formed so as to cover the edge portion 112 of the first electrode 110. For example, in the organic EL device, the opening 111 can correspond to one light emitting region, that is, a pixel.

  The cross-sectional shape of the insulating film is preferably a forward taper at the boundary portion where the first electrode is exposed. Here, the “forward taper shape” means that an angle θ formed by the slope 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, the angle θ in FIG. 2 is less than 90 °. Corresponds to Hereinafter, the angle θ is also referred to as “taper angle θ”. The taper angle θ is preferably 80 ° or less, more preferably 5 to 60 °, and more preferably 10 to 45 °.

  For example, in the case of an organic EL device, when the cross-sectional shape of the insulating film at the boundary portion is a forward taper shape, even when the organic light emitting layer and the second electrode are formed after the insulating film is formed, these films are smooth at the boundary portion. Thus, unevenness of the film thickness due to the level difference can be reduced, and a light-emitting device having stable characteristics can be obtained.

  The thickness of the insulating film is not particularly limited, but is preferably 0.3 to 15.0 μm, more preferably 0.5 to 10.0 μm, considering light shielding properties and ease of film formation and patterning. More preferably, the thickness is 1.0 to 5.0 μm.

The insulating film is formed so as to straddle adjacent first electrodes, for example. For this reason, the insulating film is required to have good electrical insulation. The volume resistivity of the insulating film is preferably 10 ¹⁰ μΩ · cm or more, more preferably 10 ¹² μΩ · cm or more.

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

  The insulating film is, for example, a partition that partitions the surface of the TFT substrate into a 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 with respect to the semiconductor layer included in the TFT. Here, “upward” is a direction from the TFT substrate toward the second electrode. As an example, when projected from the top of the TFT substrate, an aspect in which 50% or more of the area of the semiconductor layer overlaps with the insulating film (partition wall), particularly 80% or more of the area of the semiconductor layer, Further, an embodiment in which 90% or more, particularly 100%, overlaps with the insulating film (partition wall) can be mentioned.

  As described above, in the device of the present invention, the insulating film exposing the first electrode has a light shielding property at the wavelength. By providing such an insulating film, for example, even in a device having a thin film transistor including a semiconductor layer made of a material with high photodegradation such as IGZO as a driving element, the insulating film functions as a light-shielding film. Photodegradation of the semiconductor layer due to use or the like can be suppressed.

  As an oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn, for example, a quaternary metal oxide such as an In—Sn—Ga—Zn—O-based oxide semiconductor; 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-Ga- Ternary metal oxides such as Zn-O-based oxide semiconductor and Sn-Al-Zn-O-based oxide semiconductor; In-Zn-O-based oxide semiconductor, Sn-Zn-O-based oxide semiconductor, Al- 2 such as a Zn-O-based oxide semiconductor, a Zn-Mg-O-based oxide semiconductor, a Sn-Mg-O-based oxide semiconductor, an In-Mg-O-based oxide semiconductor, an In-Ga-O-based material, etc. Binary metal oxides: In-O oxide semiconductors, Sn-O oxide semiconductors, Zn O-based oxide 1-component metal oxide such as a semiconductor and the like.

  In the present invention, even when the semiconductor layer constituting the TFT is the oxide semiconductor layer, particularly when the semiconductor layer is an oxide semiconductor layer made of an In—Ga—Zn—O-based oxide semiconductor (IGZO semiconductor), Photodegradation can be prevented.

  The apparatus of the present invention includes a first electrode provided on the TFT substrate and connected to the TFT, an organic EL layer formed on the first electrode in a region partitioned by the partition, and an organic EL layer An organic EL device having an organic EL element including the second electrode provided on the top is preferable.

  The TFT substrate includes, for example, a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a planarization layer that covers the TFT. For example, the first electrode is formed on the planarization layer, and is connected to the TFT through a through hole penetrating the planarization layer. The insulating film (partition wall) having a light shielding property is preferably formed on the first electrode and the planarization layer so as to partially expose the first electrode.

  The insulating film exposing the first electrode can be formed using a radiation sensitive material. The radiation-sensitive material includes a positive type in which the solubility in a developer is increased by exposure and the exposed part is removed, and a negative type in which the exposed part is cured and the non-exposed part is removed. When a coating film formed from a radiation-sensitive material is exposed, usually, light is strongly absorbed at the surface portion of the coating film, and the amount of absorption tends to decrease toward the inside of the coating film. For this reason, in the positive type, the solubility of the surface portion of the coating film is larger than the internal solubility, and in the negative type, the opposite tendency tends to occur. In the present invention, since the cross-sectional shape of the boundary portion of the insulating film is preferably forward tapered, it is preferable to form a pattern using a positive radiation sensitive material.

[Positive radiation sensitive material]
The positive radiation sensitive material can be suitably used for forming the insulating film in the display or illumination device of the present invention. The positive radiation sensitive material (A) is at least selected from a polyimide (A1) having a structural unit represented by the formula (A1), a precursor (A2) of the polyimide, and an acrylic resin (A3). A material containing one kind of polymer and (B) a radiation sensitive acid generator is preferred.

  The positive radiation sensitive material preferably further contains a novolac resin (C). Moreover, you may contain the crosslinking agent (D) and the solvent (E) as a suitable component. Moreover, the said positive type radiation sensitive material may contain another arbitrary component in the range which does not impair the effect of this invention.

  The positive-type radiation sensitive material has high radiation sensitivity, and by using the material, an insulating film having an excellent pattern shape can be formed, and it is possible to meet the demand for narrowing the pattern pitch. Further, an insulating film having low water absorption can be formed by using the above material.

Hereinafter, each component will be described in detail.
[Polymer (A)]
Examples of the polymer (A) include at least one selected from a polyimide (A1) having a structural unit represented by the formula (A1), a precursor of the polyimide (A2), and an acrylic resin (A3). . Hereinafter, the polyimide is also referred to as “polyimide (A1)”, and the precursor is also referred to as “polyimide precursor (A2)”.

  The insulating film formed from polyimide (A1) and / or its precursor (A2) is excellent in heat resistance. For this reason, as a polymer (A), it is preferable to use a polyimide (A1) and / or its precursor (A2), and it is more preferable to use a polyimide (A1).

  The weight average molecular weight (Mw) in terms of polystyrene of the polymer (A) is preferably 2,000 to 500,000, preferably 3,000 to 100,000, as measured by gel permeation chromatography (GPC). More preferred is 4,000 to 5,000. When Mw is not less than the lower limit of the above range, an insulating film having sufficient mechanical properties tends to be obtained. When the Mw is not more than the upper limit of the above range, the solubility of the polymer (A) in the solvent or developer tends to be excellent.

  The content of the polymer (A) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and more preferably 30 to 60% by mass with respect to 100% by mass of the total solid content in the positive radiation sensitive material. Is more preferable.

<< Polyimide (A1) >>
The polyimide (A1) has a structural unit represented by the formula (A1).

式（Ａ１）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基である。
Ｒ¹としては、例えば、式（ａ１）で表される２価の基が挙げられる。

In formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group.
Examples of R ¹ include a divalent group represented by the formula (a1).

式（ａ１）中、Ｒ²は、単結合、酸素原子、硫黄原子、スルホン基、カルボニル基、メチレン基、ジメチルメチレン基またはビス（トリフルオロメチル）メチレン基であり；Ｒ³は、それぞれ独立に水素原子、ホルミル基、アシル基またはアルキル基である。ただし、Ｒ³の少なくとも１つは水素原子である。ｎ１およびｎ２は、それぞれ独立に０〜２の整数である。ただし、ｎ１およびｎ２の少なくとも一方は１または２である。ｎ１とｎ２との合計が２以上の場合、複数のＲ³は同一でも異なっていてもよい。

In formula (a1), R ² is a single bond, oxygen atom, sulfur atom, sulfone group, carbonyl group, methylene group, dimethylmethylene group or bis (trifluoromethyl) methylene group; R ³ is independently A hydrogen atom, a formyl group, an acyl group or an alkyl group; However, at least one of R ³ is a hydrogen atom. n1 and n2 are each independently an integer of 0-2. However, at least one of n1 and n2 is 1 or 2. When the total of n1 and n2 is 2 or more, the plurality of R ³ may be the same or different.

Examples of R ³ include a formyl group, and examples of the acyl group include groups having 2 to 20 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group; examples of the alkyl group include a methyl group. Groups having 1 to 20 carbon atoms such as ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, etc. Is mentioned.

  The divalent group represented by the formula (a1) is preferably a divalent group having 1 to 4 hydroxyl groups, and more preferably a divalent group having 2 hydroxyl groups. Examples of the divalent group having 1 to 4 hydroxyl groups represented by the formula (a1) include a divalent group represented by the following formula. In the following formula, two “-” extending from the aromatic ring represent a bond.

  Examples of the tetravalent organic group represented by X include a tetravalent aliphatic hydrocarbon group, a tetravalent aromatic hydrocarbon group, and two aromatic hydrocarbon groups A bonded directly or through a linking group. The group which consists of. Carbon number of a tetravalent aliphatic hydrocarbon group is 4-30 normally, Preferably it is 8-24. Carbon number of a tetravalent aromatic hydrocarbon group and the said aromatic hydrocarbon group A is 6-30 normally, Preferably it is 6-24. Among these, a group in which two aromatic hydrocarbon groups A are bonded directly or by a linking group is preferable.

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 a part of the molecular structure.
Examples of the chain hydrocarbon of the mother skeleton that forms the tetravalent chain hydrocarbon group include n-butane, n-pentane, n-hexane, n-octane, n-decane, and n-dodecane.

Examples of the alicyclic hydrocarbon of the mother skeleton that forms the tetravalent alicyclic hydrocarbon group include monocyclic hydrocarbons such as cyclobutane, cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, cyclohexene, and cyclooctane; 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] Bicyclic hydrocarbons such as octa-5-ene; tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [5.2.1.0 ^2,6 ] dec-4-ene, adamantane , Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] tricyclic or higher hydrocarbons such as dodecane.

  As the compound of the mother skeleton that forms an aliphatic hydrocarbon group containing an aromatic ring in at least a part of the molecular structure, for example, those in which the number of benzene nuclei contained in one molecule is 3 or less are preferable, One is particularly preferred. More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene and the like can be mentioned.

  The tetravalent aliphatic hydrocarbon group is preferably a tetravalent group represented by the following formula. In the following formula, four “-” s extending from a chain hydrocarbon group having 4 carbon atoms and an alicyclic ring represent a bond.

  Examples of the tetravalent aromatic hydrocarbon group and the group formed by bonding two aromatic hydrocarbon groups A by a direct bond or a linking group include a tetravalent group represented by the following formula. Examples of the linking group include an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. In the following formula, four “-” extending from the aromatic ring represent a bond.

  In the polyimide (A1), the content of the structural unit represented by the formula (A1) is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more. When the content is in the above range, it is preferable from the viewpoint of heat resistance and solubility of the exposed portion in the developer.

  A polyimide (A1) can be obtained by imidation of the polyimide precursor (A2) demonstrated below. The imidization here may proceed completely or partially. In other words, the imidation ratio may not be 100%. Therefore, the polyimide (A1) further has 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. May be. In the polyimide (A1), the total content of the structural units represented by the formula (A1), formula (A2-1), and formula (A2-2) is usually 50% by mass or more, preferably 60% by mass or more. Preferably it is 70 mass% or more, Most preferably, it is 80 mass% or more.

<< Polyimide precursor (A2) >>
A polyimide precursor (A2) is a compound which can produce | generate the polyimide (A1) which has a structural unit represented by Formula (A1) by dehydration and cyclization (imidization). Examples of the polyimide precursor (A2) include polyamic acid and polyamic acid derivatives.

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

式（Ａ２−１）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基である。Ｒ¹で表される水酸基を有する２価の基およびＸで表される４価の有機基としては、各々式（Ａ１）中のＲ¹およびＸとして例示した基と同様なものが挙げられる。

In formula (A2-1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. Examples of the divalent group having a hydroxyl group represented by R ¹ and the tetravalent organic group represented by X include the same groups 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. is there.

(Polyamic acid derivative)
The polyamic acid derivative is a derivative synthesized by esterification of polyamic acid or the like. As a polyamic acid derivative, the polymer which substituted the hydrogen atom of the carboxyl group in the structural unit represented by the formula (A2-1) which a polyamic acid has with another group is mentioned, for example, A polyamic acid ester is preferable.

  The polyamic acid ester is a polymer in which at least a part of the carboxyl group of the polyamic acid is esterified. Examples of the polyamic acid ester include a polymer having a structural unit represented by the formula (A2-2) that can produce a polyimide (A1) having the structural unit represented by the formula (A1).

式（Ａ２−２）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基であり、Ｒ⁴はそれぞれ独立に炭素数１〜５のアルキル基である。Ｒ¹で表される水酸基を有する２価の基およびＸで表される４価の有機基としては、各々式（Ａ１）中のＲ¹およびＸとして例示した基と同様なものが挙げられる。Ｒ⁴で表される炭素数１〜５のアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。

In formula (A2-2), R ¹ is a divalent group having a hydroxyl group, X is a tetravalent organic group, and R ⁴ is independently an alkyl group having 1 to 5 carbon atoms. Examples of the divalent group having a hydroxyl group represented by R ¹ and the tetravalent organic group represented by X include the same groups 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 polyamic acid ester, 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. It is.

<< Synthesis Method of Polyimide (A1) and Polyimide Precursor (A2) >>
The polyamic acid which is a polyimide precursor (A2) can be obtained, for example, by polymerizing a tetracarboxylic dianhydride, a diamine having a hydroxyl group and a diamine containing another diamine as required. The proportion of these used is, for example, 0.3 to 4 mol, preferably approximately equimolar, with respect to 1 mol of the tetracarboxylic dianhydride. In the polymerization, the mixed solution of the tetracarboxylic dianhydride and the total diamine is preferably heated 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.

  The synthesis of polyamic acid may be carried out by dissolving diamine (A1-2) in a polymerization solvent and then reacting diamine (A1-2) with acid dianhydride (A1-1). You may carry out by making an acid dianhydride (A1-1) and diamine (A1-2) react after melt | dissolving an anhydride (A1-1) in a polymerization solvent.

  The polyamic acid derivative which is the polyimide precursor (A2) can be synthesized by esterifying the carboxyl group of the polyamic acid. There is no limitation in particular as a method of esterification, A well-known method is applicable.

  The polyimide (A1) can be synthesized, for example, by synthesizing a polyamic acid by the above method and then dehydrating and cyclizing (imidizing) the polyamic acid; and a polyamic acid derivative is synthesized by the above method. Then, it can also synthesize | combine by imidating this polyamic acid derivative.

  As the imidization reaction of the polyamic acid and the polyamic acid derivative, known methods such as a heat imidization reaction and a chemical imidation reaction can be applied. In the case of the heating imidization reaction, it is preferable to heat a solution containing a polyamic acid and / or a polyamic acid derivative at 120 ° C. to 210 ° C. for 1 hour to 16 hours. The imidization reaction may be carried out while removing water in the system using an azeotropic solvent such as toluene, xylene, mesitylene or the like, if necessary.

Moreover, when diamine is used excessively with respect to tetracarboxylic dianhydride, for example, dicarboxylic acid such as maleic anhydride is used as an end-capping agent for sealing the end groups of polyimide, polyamic acid and polyamic acid derivatives. Anhydrides may be used.
Acid dianhydride (A1-1) is an acid dianhydride represented by the formula (a2).

式（ａ２）中、Ｘは４価の有機基である。Ｘで表される４価の有機基としては、式（Ａ１）中のＸとして例示した基と同様なものが挙げられる。
ジアミン（Ａ１−２）は、式（ａ３）で表されるジアミンである。

In the formula (a2), X is a tetravalent organic group. Examples of the tetravalent organic group represented by X include the same groups as those exemplified as X in formula (A1).
Diamine (A1-2) is a diamine represented by formula (a3).

式（ａ３）中、Ｒ¹は水酸基を有する２価の基である。Ｒ¹で表される水酸基を有する２価の基としては、式（Ａ１）中のＲ¹として例示した基と同様なものが挙げられる。

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, include those similar to the groups exemplified as R ¹ in the formula (A1).

  Other diamines other than (A1-2) may be used together with diamine (A1-2). Examples of the other diamine include at least one diamine selected from an aromatic diamine and an aliphatic diamine having no hydroxyl group.

The polyimide (A1) may further have a structural unit in which R ¹ in the formulas (A1), (A2-1) and (A2-2) is replaced with the residue of the other diamine. Similarly, the polyimide precursor (A2) may further have a structural unit in which R ¹ in the formulas (A2-1) and (A2-2) is replaced with the residue of the other diamine.

  Examples of other aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, , 4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1 , 3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5 -Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1 , 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) Phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl Is mentioned.

Examples of aliphatic diamines that are other diamines include metaxylylenediamine, paraxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine , hexahydro-4,7-meth Noin mite range diamine, tricyclo [6.2.1.0 ^2,7] - undecylenate range methyl diamine, 4,4'-methylenebis (cyclohexylamine) is ani It is.

  As a polymerization solvent used for the synthesis of the polyimide (A1) and the polyimide precursor (A2), these synthesis raw materials and the above (A1) and (A2) can be dissolved, and a low water-absorbing solvent is preferable. . As a polymerization solvent, the solvent similar to the solvent illustrated as the solvent (E) mentioned later can be used.

  By using the same solvent as the solvent (E) as the polymerization solvent, the step of isolating these polymers after synthesizing the polyimide (A1) or the polyimide precursor (A2), and reusing the solvent again after the isolation. The step of dissolving can be eliminated. Thereby, the productivity of the apparatus of the present invention can be improved.

  The polyimide (A1) and the polyimide precursor (A2) have excellent solubility in the solvent (E) described later due to the specific structure having a hydroxyl group. For this reason, these polymers are also soluble in a low water-absorbing solvent other than N-methylpyrrolidone (NMP), for example, the solvent (E) described later. As a result, by using a solvent other than NMP as the polymerization solvent for obtaining the polymer (A), it is possible to reduce the water absorption of the insulating film formed from the positive radiation sensitive material.

<< Acrylic resin (A3) >>
The monomer constituting the acrylic resin (A3) is, for example, at least selected from (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic group-containing ester, and (meth) acrylic acid aryl group-containing ester. One monomer A is mentioned.

  Moreover, as a monomer which comprises the said (A3), the at least 1 sort (s) of acid group containing monomer B chosen from unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated dicarboxylic acid anhydride is also mentioned.

  Moreover, as a monomer which comprises the said (A3), at least 1 chosen from the hydroxyalkyl ester of (meth) acrylic acid, the epoxy-group-containing ester of (meth) acrylic acid, and the oxetanyl group-containing ester of (meth) acrylic acid. Also included are the functional group-containing monomers C of the species.

  Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl ( Examples of the alicyclic group-containing ester of (meth) acrylic acid include monocyclic hydrocarbon group-containing esters such as cyclohexyl (meth) acrylate and 2-methylcyclohexyl (meth) acrylate, diesters, and the like. Examples thereof include polycyclic group-containing esters such as cyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and isoboronyl (meth) acrylate; examples of aryl group-containing esters of (meth) acrylic acid include , Phenyl (meth) acryl Over DOO, benzyl (meth) acrylate.

  Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, and 2- (meth) acryloyloxyethyl succinic acid; examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, and citracone. Acid, mesaconic acid, itaconic acid; unsaturated dicarboxylic acid anhydrides include, for example, maleic anhydride and itaconic anhydride.

  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 (meth) acrylate. , Glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxy Heptyl, α-ethylacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexylmethyl (meth) acrylate; oxetanyl group-containing esters of (meth) acrylic acid include, for example, 3-methyl-3 -(Meth) acryloyloxymethyloxetane 3-ethyl-3- (meth) acryloyloxy methyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane and the like.

  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 to 85% by mass, more preferably 15 to 75% by mass, and the acid group-containing monomer. The content of the structural unit derived from B is usually 5 to 70% by mass, preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and the content of the structural unit derived from the functional group-containing monomer C. The amount is usually 90% by mass or less, preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.

  In particular, in the acrylic resin (A3), the total content of structural units derived from the epoxy group-containing ester of (meth) acrylic acid and the oxetanyl group-containing ester of (meth) acrylic acid is 10 to 70% by mass. Is more preferable, and it is 20-50 mass% more preferably. When this structural unit is in the above range, the curing reaction proceeds sufficiently when the coating film formed from the positive radiation sensitive material is heated, and the resulting pattern tends to have sufficient heat resistance and surface hardness. Also, the storage stability of the positive radiation sensitive material tends to be excellent.

  Other monomers constituting the acrylic resin (A3) include diesters of unsaturated dicarboxylic acids such as diethyl maleate, diethyl fumarate and diethyl itaconate; styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene. , Styrene monomers such as p-methylstyrene, vinyltoluene, and p-methoxystyrene can also be used.

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

  The acrylic resin (A3) can be synthesized, for example, by radical polymerization of the above monomer. As a polymerization catalyst in radical polymerization, a normal radical polymerization initiator can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2 Azo compounds such as' -azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis- (t-butylperoxy) cyclohexane, etc. Examples include organic peroxides and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide and a reducing agent may be combined to form a redox type initiator.

[Radiosensitive acid generator (B)]
The radiation sensitive acid generator (B) is a compound that generates an acid upon irradiation with radiation. Examples of radiation include visible light, ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. By containing the radiation-sensitive acid generator (B), the positive radiation-sensitive material can exhibit positive radiation-sensitive characteristics and can have good radiation sensitivity.

  The content of the radiation sensitive acid generator (B) in the positive radiation sensitive material is usually 5 to 100 parts by weight, preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the polymer (A). More preferably, it is 15-40 mass parts. By setting the content of the radiation-sensitive acid generator (B) within the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to an alkaline aqueous solution or the like serving as a developer is increased, and the patterning performance is improved. be able to.

  Examples of the radiation sensitive acid generator (B) include quinonediazide compounds, oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. Is mentioned. The radiation sensitive acid generator (B) may be used alone or in combination of two or more.

<Quinonediazide compound>
A quinonediazide compound generates a carboxylic acid upon irradiation with radiation. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “host nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide.

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

Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.
Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, Examples include 3,4,2′-tetrahydroxy-4′-methylbenzophenone and 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone.

Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone.
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone and 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone.

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

  Examples of other mother nuclei include 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 mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- {4- (1- [ 4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol is preferred.

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

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the exemplified ester bond of the mother nucleus is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4- Sulfonamide and the like are also preferably used.

<Oxime sulfonate compound>
As the oxime sulfonate compound, for example, a compound having an oxime sulfonate group represented by the formula (B1) is preferable.

式（Ｂ１）中、Ｒ^B1は、アルキル基、１価の脂環式炭化水素基、アリール基、またはこれらのアルキル基、１価の脂環式炭化水素基、アリール基が有する水素原子の一部もしくは全部を置換基で置換した基である。

In Formula (B1), R ^B1 represents an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or an alkyl group, a monovalent alicyclic hydrocarbon group, or an aryl group. It is a group in which part or all is substituted with a substituent.

  As the alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable. As an alicyclic hydrocarbon group, a C4-C12 alicyclic hydrocarbon group is preferable. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are more preferable.

  Examples of the compound containing an oxime sulfonate group represented by formula (B1) include oxime sulfonate compounds represented by formulas (B1-1) to (B1-3).

式（Ｂ１−１）〜式（Ｂ１−３）中、Ｒ^B1は式（Ｂ１）と同義である。式（Ｂ１−１）〜式（Ｂ１−２）中、Ｒ^B2は、炭素数１〜１２のアルキル基または炭素数１〜１２のフルオロアルキル基である。式（Ｂ１−３）中、Ｘ^B1は、アルキル基、アルコキシ基またはハロゲン原子である。ｍは、０〜３の整数である。ただし、ｍが２または３の場合、複数のＸ^B1は、同一でも異なっていてもよい。

In formula (B1-1) to formula (B1-3), R ^B1 has the same meaning as formula (B1). In Formula (B1-1) to Formula (B1-2), R ^B2 is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms. In formula (B1-3), X ^B1 represents an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when m is 2 or 3, the plurality of X ^B1 may be the same or different.

The alkyl group represented by X ^B1 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms; and the alkoxy group is a linear or branched alkoxy group having 1 to 4 carbon atoms. Preferably, the halogen atom is preferably a chlorine atom or a fluorine atom.
Examples of the oxime sulfonate compound represented by the formula (B1-3) include compounds represented by the formulas (B1-3-1) to (B1-3-5).

《Onium salt》
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluoro Examples thereof include tansulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, and bis (4-t-butylphenyl) iodonium camphorsulfonic acid. It is done.

  Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, and triphenyl. And sulfonium butyl tris (2,6-difluorophenyl) borate.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4 Examples include-(benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, and dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxy. Phenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxy Examples include phenylmethylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenyl. Sulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl -4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenyl. Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3 -Chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy). Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate.

  Examples of the tetrahydrothiophenium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoro. L-methanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1, 1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxy) Bicyclo [2.2.1] heptan-2-yl) -1,1 2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptane-2- Yl) -1,1,2,2-tetrafluoroethanesulfonate.

<< N-sulfonyloxyimide compound >>
Examples of the N-sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoro). Methylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) ) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) Diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) ) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro) Butanesulfonyloxy) bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphor Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) Xyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimi N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3 -Dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboximide, N- (camphorsulfonyloxy) naphthyl dicarboximide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboximide, N- (phenyl Sulfonyloxy) naphthyl dicarboximide, N- (2-trifluoromethylpheny Sulfonyloxy) naphthyl dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboximide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboximide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboximide N- (nonafluorobutylsulfonyloxy) naphthyl dicarboximide, N- (ethylsulfonyloxy) naphthyl dicarboximide, N- (propylsulfonyloxy) naphthyl dicarboximide, N- (butylsulfonyloxy) naphthyl dicarboximide N- (pentylsulfonyloxy) naphthyl dicarboximide, N- (hexylsulfonyloxy) naphthyl dicarboximide, N- (heptylsulfonyloxy) naphth Examples thereof include tildicarboximide, N- (octylsulfonyloxy) naphthyldicarboximide, and N- (nonylsulfonyloxy) naphthyldicarboximide.

<Halogen-containing compound>
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

《Diazomethane compound》
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Is mentioned.

<< sulfone compound >>
Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and diaryldisulfone compounds.

<< Sulfonate compound >>
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates, and specific examples include N-hydroxynaphthalimide-trifluoromethane sulfonic acid ester.

<< carboxylic acid ester compound >>
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

<< Preferred example of radiation sensitive acid generator (B) >>
As the radiation sensitive acid generator (B), a quinonediazide compound, an oxime sulfonate compound, an onium salt, and a sulfonate compound are preferable, a quinonediazide compound and an oxime sulfonate compound are more preferable, and a quinonediazide compound is particularly preferable.

  As the oxime sulfonate compound, a compound having an oxime sulfonate group represented by the formula (B1) is preferable, and compounds represented by the formulas (B1-3-1) to (B1-3-5) are more preferable.

  As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Phosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferred. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

[Novolac resin (C)]
Examples of the novolak resin (C) include novolak resins including a structural unit having at least one selected from 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 in which part or all of the hydrogen atoms bonded to the aromatic ring carbon contained in the condensed polycyclic aromatic hydrocarbon group are substituted with hydroxyl groups. is there. Examples of the condensed polycyclic aromatic hydrocarbon group include a naphthalene ring, an anthracene ring, and a phenanthrene ring.

  The novolac resin (C) is a substance that develops color when heated. In the insulating film forming method described later, the coating film itself formed from the positive type material containing the novolak resin (C) does not have a light-shielding property at a wavelength of 300 to 400 nm before the exposure. It is presumed that the novolac resin (C) is ketoized and the obtained insulating film has a light shielding property at the wavelength.

  For example, when the heating temperature is about 60 to 130 ° C., which is the heating temperature during pre-baking, the above light-shielding property is not imparted, and the heating temperature during post-baking. A novolac resin capable of imparting the above-described light shielding property at a temperature exceeding 130 ° C. and not higher than 300 ° C. is preferred.

  Examples of the novolak resin (C) include a structural unit represented by the formula (C1), a structural unit represented by the formula (C2-1), a structural unit represented by the formula (C2-2), and a formula ( And a resin having at least one selected from structural units represented by C3).

式（Ｃ１）〜式（Ｃ３）中、Ｒ¹は、炭素数１〜２０のアルキル基または炭素数１〜２０のアルコキシ基であり；Ｒ²は、メチレン基、炭素数２〜３０のアルキレン基、炭素数４〜３０の２価の脂環式炭化水素基，炭素数７〜３０のアラルキレン基または−Ｒ³−Ａｒ−Ｒ³−で表される基（Ａｒは２価の芳香族基であり、Ｒ³はそれぞれ独立にメチレン基または炭素数２〜２０のアルキレン基である）であり；ｎ１は１〜４の整数であり、ｎ２は０〜３の整数であり、ｎ１＋ｎ２≦４であり、ａ〜ｈは、それぞれ独立に０〜２の整数であり、但し、ａおよびｂが共に０である場合はなく、ｃ〜ｅの全てが０である場合はなく、ｆ〜ｈの全てが０である場合はない。ａ＋ｂ、ｃ＋ｄ＋ｅ、ｆ＋ｇ＋ｈは、各々、好ましくは１〜３の整数である。式（Ｃ１）〜式（Ｃ３）において、−ＯＨ、−Ｒ¹および−Ｒ²−の結合位置は特に限定されない。

In formulas (C1) to (C3), R ¹ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; R ² is a methylene group or an alkylene group having 2 to 30 carbon atoms. , A divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms or a group represented by —R ³ —Ar—R ³ — (Ar is a divalent aromatic group). Each of R ³ is independently a methylene group or an alkylene group having 2 to 20 carbon atoms; n1 is an integer of 1 to 4, n2 is an integer of 0 to 3, and n1 + n2 ≦ 4 , A to h are each independently an integer of 0 to 2, provided that a and b are not both 0, c to e are not all 0, and all of f to h are There is no case of zero. a + b, c + d + e, and f + g + h are each preferably an integer of 1 to 3. In Formula (C1) to Formula (C3), the bonding position of —OH, —R ¹ and —R ² — is not particularly limited.

Examples of the alkylene group having 2 to 30 carbon atoms in R ² include ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene. Group, octadecylene group, nonadecylene group, icosylene group, henicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacosylene group, octacosylene group, nonacosylene group, triaconylene group.

Examples of the divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms in R ² include a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.

Examples of the aralkylene group having 7 to 30 carbon atoms in R ² include a benzylene group, a phenethylene group, a benzylpropylene group, and a naphthylene methylene group.
Examples of the group represented by —R ³ —Ar—R ³ — in R ² include a group represented by —CH ₂ —Ph—CH ₂ — (Ph is a phenylene group).

  As the novolak resin (C), a resin having alkali solubility is preferable. By containing the alkali-soluble novolak resin (C) in the positive radiation sensitive material, a radiation sensitive material having good resolution can be obtained.

  The novolak resin (C) is, for example, a condensed polycyclic aromatic compound having phenols or a phenolic hydroxyl group and an aldehyde are condensed in the presence of an acid catalyst, and unreacted components are distilled off if necessary. Can be obtained. For example, methods described in JP-B-47-15111 and JP-A-63-238129 can be referred to.

  Examples of phenols include phenol, orthocresol, metacresol, paracresol, 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-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresorcinol 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2- Meto Shi-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, include Isochimoru.

  Examples of condensed polycyclic aromatic compounds having a phenolic hydroxyl group include compounds having 1 to 6 hydroxyl groups, preferably 1 to 3 and 2 to 3 rings. Is monohydroxynaphthalene such as 1-naphthol and 2-naphthol; 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1 , 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like; 1-hydroxyanthracene, 2-hydroxyanthracene, 9- Monohydroxy such as hydroxyanthracene 1,4-dihydroxyanthracene, dihydroxyanthracene such as 9,10-dihydroxyanthracene; 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, 1,2,7-trihydroxyanthracene, etc. Trihydroxyanthracene; and hydroxyphenanthrenes such as 1-hydroxyphenanthrene.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and terephthalaldehyde.
In the synthesis of the novolak resin (C), the amount of the phenols or condensed polycyclic aromatic compounds having a phenolic hydroxyl group is usually 0.5 mol or more, preferably 0, per 1 mol of aldehydes. .8 to 3.0 moles. Examples of the acid catalyst include hydrochloric acid, paratoluenesulfonic acid, and trifluoromethanesulfonic acid.

  The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the novolak resin (C) is usually 500 to 50,000, preferably 700 to 5,000, more preferably 800 to 3,000. The novolak resin (C) having Mw in the above range is preferable in terms of light shielding properties.

  In the positive radiation sensitive material, the content of the novolak resin (C) is usually 2 to 200 parts by weight, preferably 3 to 160 parts by weight, more preferably 100 parts by weight of the polymer (A). It is 4-140 mass parts, Most preferably, it is 10-100 mass parts. When the content of the novolak resin (C) is not less than the lower limit of the above range, the light shielding effect based on the novolak resin (C) is easily exhibited. When the content of the novolak resin (C) is not more than the upper limit of the above range, there is little possibility that the low water absorption and the heat resistance of the insulating film are deteriorated.

[Crosslinking agent (D)]
A crosslinking agent (D) is a compound which has a crosslinkable functional group, for example, is a compound which has a cationically polymerizable group. Examples of the crosslinking agent (D) include compounds having two or more crosslinkable functional groups in one molecule, for example, compounds having two or more oxetanyl groups in one molecule. In addition, the compound applicable to both an acrylic resin (A3) and a crosslinking agent (D) is classified into an acrylic resin (A3).

  Examples of the crosslinkable functional group include oxetanyl group, glycidyl ether group, glycidyl ester group, glycidylamino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, acetoxymethyl group, benzoyloxymethyl group, formyl group, Examples include acetyl group, vinyl group, isopropenyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, and morpholinomethyl group.

  Examples of the compound having an oxetanyl group include 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl, 3,7-bis (3-oxetanyl) -5-oxanonane, and 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-oxetanyl) methyl ] Ether, dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether, triethylene glycol bis [( -Ethyl-3-oxetanyl) methyl] ether, tetraethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclodecanediyldimethylenebis [(3-ethyl-3-oxetanyl) methyl] ether, Trimethylolpropane tris [(3-ethyl-3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] butane, 1,6-bis [(3-ethyl-3- Oxetanyl) methoxy] hexane, pentaerythritol tris [(3-ethyl-3-oxetanyl) methyl] ether, pentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, polyethylene glycol bis [(3-ethyl-3 -Oxetanyl) methyl] ether, di Ntaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol tetrakis [(3-ethyl-3-oxetanyl) ) Methyl] ether.

  Examples of the compound having an oxetanyl group include a reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone, dipentaerythritol pentakis [(3-ethyl-3- Oxetanyl) methyl] ether and caprolactone reaction product, ditrimethylolpropane tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide Reaction product of bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether with propylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and Ethylene oxide Reaction product with id, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, bisphenol F bis [(3-ethyl-3-oxetanyl) methyl] ether And a reaction product of ethylene oxide.

  Examples of the crosslinking agent (D) include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds, poly (hydroxystyrene) epoxy compounds, and methoxy. Methyl group-containing phenol compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound , Alkoxyalkyl group-containing phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxy Methyl group-containing urea resins, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, may be mentioned carboxymethyl group-containing phenol compound.

  In the positive radiation sensitive material, the content of the crosslinking agent (D) is usually 1 to 200 parts by weight, preferably 4 to 160 parts by weight, more preferably 100 parts by weight of the polymer (A). 5 to 70 parts by mass. When the content of the crosslinking agent (D) is not less than 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 not more than 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 positive radiation sensitive material liquid.
As the solvent (E), diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol Monoalkyl ether propionate and triethylene glycol dialkyl ether are preferred.

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.
As the solvent (E), amide solvents such as N, N, 2-trimethylpropionamide, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3- Examples also include hexyloxy-N, N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like.

  As the solvent (E), propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), propylene glycol monomethyl ether (hereinafter also referred to as “PGME”), and diethylene glycol ethyl methyl ether (hereinafter also referred to as “EDM”) are particularly preferable.

  As the solvent (E), γ-butyrolactone (hereinafter also referred to as “BL”) is preferably used, and a mixed solvent containing BL is preferable. As content of BL, 70 mass% or less is preferable in the total amount of 100 mass% of a solvent (E), and 20-60 mass% is more preferable. BL is preferably used in combination with at least one selected from PGMEA, PGME and EDM. By setting the BL content in the above range, the polymer (A) dissolved state in the positive radiation sensitive material tends to be suitably maintained.

  As the solvent (E), in addition to the solvents exemplified above, alcohol solvents such as methanol, ethanol, propanol and butanol; aromatic hydrocarbon solvents such as toluene and xylene can be used in combination as necessary.

  The solvent exemplified above as the solvent (E) has a low water absorption compared to NMP. Therefore, the positive radiation sensitive material can be prepared using a low water absorption solvent without using NMP having high water absorption. As a result, the positive radiation sensitive material can exhibit low water absorption. Moreover, since the solvent illustrated above as a solvent (E) has high safety | security, the safety | security of positive type radiation sensitive material can be improved.

  When the solvent exemplified above is used as the solvent (E), the insulating film formed from the positive radiation sensitive material can have low water absorption. Therefore, this positive radiation sensitive material can be suitably used for forming an insulating film of an organic EL element.

A solvent (E) may be used individually by 1 type, or may use 2 or more types together.
In the positive radiation sensitive material, the content of the solvent (E) is such that the solid content concentration of the radiation sensitive material is usually 5 to 60 mass%, preferably 10 to 50 mass%, more preferably 15 to 40 mass%. Is the amount. Here, solid content means all components other than a solvent (E). By setting the content of the solvent (E) in the above range, the low water absorption of the insulating film formed from the positive radiation sensitive material tends to be improved without impairing the developability.

[Other optional ingredients]
In addition to the above essential components and preferred components, the positive type radiation sensitive material is within the range not impairing the effects of the present invention, and other optional components such as an adhesion assistant (F) and a surfactant (G) as necessary. It may contain. Other optional components may be used alone or in combination of two or more.

<Adhesion aid (F)>
The adhesion aid (F) is a component that improves the adhesion between a film forming object such as a substrate and the insulating film. The adhesion assistant (F) is particularly useful for improving the adhesion between the inorganic substrate and the insulating film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride; and metals such as gold, copper, and aluminum.

  As the adhesion assistant (F), a functional silane coupling agent is preferable. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxy groups, halogen atoms, vinyl groups, methacryloyl groups, isocyanate groups, epoxy groups, oxetanyl groups, amino groups, and thiol groups. Can be mentioned.

  Examples of the functional silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ- Isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane. Among these, N-phenyl-3-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane and γ-methacryloxypropyltrimethoxysilane are preferred.

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

<Surfactant (G)>
Surfactant (G) is a component that enhances the film-forming property of the positive radiation sensitive material. By containing the surfactant (G), the positive radiation sensitive material can improve the surface smoothness of the coating film, and as a result, the film thickness uniformity of the cured film can be further improved. Examples of the surfactant (G) include a fluorine-based surfactant and a silicone-based surfactant.

As surfactant (G), the specific example described in Unexamined-Japanese-Patent No. 2003-015278 and Unexamined-Japanese-Patent No. 2013-231869 can be mentioned, for example.
The content of the surfactant (G) in the positive radiation sensitive material is preferably 10 parts by mass or less, more preferably 0.01 to 7.5 parts by mass, with respect to 100 parts by mass of the polymer (A). More preferably, it is 0.05-5 mass parts. By making content of surfactant (F) into the said range, the film thickness uniformity of the coating film formed can be improved more.

[Preparation method of positive radiation sensitive material]
The positive-type radiation-sensitive material includes, for example, a solvent (E), a polymer (A), a radiation-sensitive acid generator (B), a suitable component such as a novolac resin (C), and other optional components as necessary. It can be prepared in a dissolved or dispersed state by mixing.

[Method of forming insulating film using positive radiation sensitive material]
The method for forming an insulating film included in the display or lighting device of the present invention includes the step 1 of forming a coating film on a substrate using the positive radiation-sensitive material described above, and irradiating at least a part of the coating film with radiation. Step 2, Step 3 for developing the coating film irradiated with the radiation, and Step 4 for heating the developed coating film.

  According to the method for forming an insulating film, an insulating film having excellent light shielding properties and a forward tapered shape at the boundary can be formed on the TFT substrate. Since the above-mentioned positive radiation sensitive material is excellent in radiation sensitivity, an insulating film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development, and heating utilizing the characteristics. Can do.

<< Process 1 >>
In step 1, a positive radiation sensitive material is applied to the substrate surface, and the coating film is formed by removing the solvent (E), preferably by pre-baking. As a film thickness of the said coating film, it is 0.3-15.0 micrometers normally as a value after prebaking, Preferably it is 0.5-10.0 micrometers, More preferably, it can be 1.0-5.0 micrometers.

  Examples of the substrate include a resin substrate, a glass substrate, and a silicon wafer. Examples of the substrate further include a TFT substrate and a wiring substrate in which TFTs and wirings thereof are formed in an organic EL element being manufactured. When manufacturing the device of the present invention, the coating film is formed on the TFT substrate.

  Examples of the application method of the positive 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 ink jet method. Among these coating methods, spin coating and slit die coating are preferable.

  The pre-baking conditions vary depending on the composition of the positive radiation sensitive material, but for example, the heating temperature is 60 to 130 ° C. and the heating time is about 30 seconds to 15 minutes. Pre-baking is preferably performed at a temperature at which the light-shielding property based on the novolak resin (C) is not imparted to the coating film.

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

Among these radiations, visible light and ultraviolet light are preferable, and among visible light and ultraviolet light, radiation containing g-line and / or i-line is particularly preferable. As an exposure amount, 6000 mJ / cm < ² > or less is preferable and 20-2000 mJ / cm < ² > is preferable. This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).

<< Process 3 >>
In step 3, the coating film irradiated with radiation in step 2 is developed. Thereby, the irradiation part of a radiation can be removed and a desired pattern can be formed. As the developer used for the development treatment, an alkaline aqueous solution is preferable.

  Examples of the alkaline compound contained in the aqueous alkaline solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 -Diazabicyclo [4,3,0] -5-nonane. The concentration of the alkaline compound in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability.

  As the developer, an aqueous solution in which an appropriate amount of a water-soluble organic solvent or a surfactant such as methanol or ethanol is added to an alkaline aqueous solution, or an aqueous solution in which various organic solvents for dissolving a positive radiation sensitive material are added in an alkaline aqueous solution. It can also be used. As the organic solvent in the latter aqueous solution, the same solvent as the solvent (E) for obtaining the polymer (A) and the positive radiation sensitive material can be used.

  Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the positive radiation sensitive material, but is usually about 10 seconds to 180 seconds. Subsequent to such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

<< Process 4 >>
In step 4, after step 3, using a heating device such as a hot plate or an oven, the coating film is cured by a heat treatment (post-bake treatment) on the coating film to obtain an insulating film. The heating temperature in this heat treatment is, for example, more than 130 ° C. and not more than 300 ° C., and the heating time varies depending on the type of heating equipment, but for example, 5 minutes to 30 when performing the heat treatment on a hot plate. In the case of performing heat treatment in an oven for 30 minutes, it is 30 minutes to 90 minutes. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used.

  By the heat treatment in the above temperature range, the insulating film is provided with a light shielding property that the total light transmittance at a wavelength of 300 to 400 nm is 0 to 15%. In this manner, an insulating film having a target pattern can be formed on the substrate.

In step 4, before the coating film is heated, the patterned coating film may be rinsed or decomposed. In the rinse treatment, it is preferable to wash the coating film using the low water-absorbing solvent mentioned as the solvent (E). In the decomposition treatment, the radiation sensitive acid generator (B) such as a quinonediazide compound remaining in the coating film can be decomposed by irradiating the entire surface with radiation (post-exposure) from a high pressure mercury lamp or the like. The exposure amount in this post-exposure is preferably about 1000 to 5000 mJ / cm ² .

  The insulating film thus obtained has a light-shielding property with respect to light having a wavelength of 300 to 400 nm, and has a low water absorption property because the constituent material has a low water absorption structure. It is possible to treat with the compound. In addition, the insulating film exhibits good characteristics in terms of heat resistance, patterning properties, radiation sensitivity, resolution, and the like. For this reason, the said insulating film can be used suitably as an insulating film as a protective film or a planarization film | membrane other than the insulating film as a partition which an organic EL element etc. have, for example.

[Organic EL display device and organic EL lighting device]
Hereinafter, an organic EL display or lighting device will be described as a specific example of the display or lighting device of the present invention with reference to FIG. FIG. 3 is a cross-sectional view schematically showing the structure of the main part of the organic EL display or illumination device (hereinafter also simply referred to as “organic EL device”) according to the present invention.

  The organic EL device 1 of FIG. 3 is an active matrix organic EL device having a plurality of pixels formed in a matrix. The organic EL device 1 may be either a top emission type or a bottom emission type. The organic EL device 1 includes a support substrate 2, a thin film transistor (hereinafter also referred to as "TFT") 3, an inorganic insulating film 4, a first insulating film 5, an anode 6 as a first electrode, a through hole 7, and a second insulating film. 8, an organic light emitting layer 9, a cathode 10 as a second electrode, a passivation film 11, and a sealing substrate 12.

<Support substrate>
The support substrate 2 is made of an insulating material. The insulating material may be selected depending on whether the organic EL device 1 is a top emission type or a bottom emission type, that is, whether the support substrate 2 is required to be transparent. When the organic EL device 1 is a bottom emission type, the support substrate 2 is required to have high transparency. Therefore, as the insulating material, for example, transparent resins such as highly transparent polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI), and glass materials such as alkali-free glass are preferable. On the other hand, when the organic EL device 1 is a top emission type, an arbitrary insulator can be used as the insulating material, and a glass material such as non-alkali glass can be used as in the bottom emission type.

<TFT>
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 30, a gate insulating film 31, a semiconductor layer 32, a source electrode 33 and a drain electrode 34.

  The present invention 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 may be the top gate type in which the gate insulating film and the gate electrode are sequentially provided on the semiconductor layer.

<Gate electrode>
The gate electrode 30 forms part of a scanning signal line (not shown). The gate electrode 30 may be formed as a single layer film or a multilayer film. The thickness of the gate electrode 30 is preferably 10 to 1000 nm.

The gate electrode 30 can be formed by forming a metal thin film on the support substrate 2 by vapor deposition or sputtering, and performing patterning using an etching process.
Examples of the material for the metal thin film include aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), gold (Au), tungsten (W) and Examples thereof include metals such as silver (Ag), alloys of these metals, and alloys such as Al—Nd and APC alloys (alloys of silver, palladium, and copper). When the gate electrode 30 is formed as a multilayer film, the metal thin film can be formed as a laminated film in which thin films of different materials are laminated, such as a laminated film of an Al thin film and a Mo thin film.

  The gate electrode 30 can be formed by patterning a metal oxide conductive film or an organic conductive film instead of the metal thin film. Examples of the material for the metal oxide conductive film include tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide), and indium zinc oxide (IZO). Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, and mixtures thereof.

<Gate insulation film>
The gate insulating film 31 covers the gate electrode 30. The gate insulating film 31 can be formed by forming an oxide film or a nitride film by sputtering, CVD, vapor deposition or the like.

The gate insulating film 31 is formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. The gate insulating film 31 may be a single insulating film or a stacked film in which a plurality of insulating films are stacked. The gate insulating film 31 can also be formed from an organic material such as a polymer material.

  The film thickness of the gate insulating film 12 is preferably 10 nm to 10 μm, particularly preferably 10 nm to 1000 nm when an inorganic material such as a metal oxide is used, and preferably 50 nm to 10 μm when an organic material is used.

<Semiconductor layer>
The semiconductor layer 32 is disposed on the gate electrode 30 via the gate insulating film 31. The semiconductor layer 32 is connected to the source electrode 33 and the drain electrode 34 and constitutes a channel layer. The channel layer is a portion where carriers flow and is controlled by the gate electrode 30.

  The semiconductor layer 32 can be formed using the above-described oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof.

  For the semiconductor layer 32 made of amorphous oxide using IGZO, for example, a semiconductor layer is formed by sputtering or vapor deposition using an IGZO target, and patterning is performed by a resist process and an etching process using a photolithography method or the like. Is formed. In this case, the thickness of the semiconductor layer 32 is preferably 1 nm to 1000 nm.

When the semiconductor layer 32 is formed as an oxide layer, a protective layer (not shown) made of SiO ₂ having a thickness of, for example, 5 nm to 80 nm is provided in a region of the semiconductor layer 32 where the source electrode 33 and the drain electrode 34 are not formed. Is preferred. This protective layer may be referred to as an etching stop layer, a stop layer, or the like.

  In the organic EL device 1, since the second insulating film 8 (partition wall) has a light shielding property, the light generated from the organic light emitting layer 9 can be prevented or reduced from reaching the semiconductor layer 32. Therefore, it is possible to use a semiconductor layer made of IGZO or the like that is easily photodegraded.

<< Source and drain electrodes >>
The source electrode 33 is an electrode serving as a carrier generation source. The source electrode 33 forms part of a video signal line (not shown) and is connected to the semiconductor layer 32. The drain electrode 34 is a part that receives carriers moving through the semiconductor layer 32 (channel layer), and is connected to the semiconductor layer 32 in the same manner as the source electrode 33.

  Whether it is the source electrode 33 or the drain electrode 34 is determined by, for example, the conductivity type (p-type or n-type) of the semiconductor layer 32, whether it is the high voltage side or the low voltage side when a voltage is applied, etc. The

  The source electrode 33 and the drain electrode 34 may be formed as a single layer film or a multilayer film. The thickness of the source electrode 33 and the drain electrode 34 is preferably 10 nm to 1000 nm.

  The source electrode 33 and the drain electrode 34 can be formed by forming a conductor film by a printing method, a coating method, a sputtering method, a CVD method, a vapor deposition method, or the like, and then patterning using a photolithography method or the like. it can.

  Examples of the constituent material of the source electrode 33 and the drain electrode 34 include metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W, and Ag, alloys of these metals, alloys such as Al-Nd and APC, and the like. The metal material is mentioned. When the source electrode 33 and the drain electrode 34 are formed as multilayer films, they can be formed as a laminated film in which thin films of different materials are laminated, such as a laminated film of a Ti thin film and an Al thin film.

  As a constituent material of the source electrode 33 and the drain electrode 34, a conductive metal oxide or a conductive organic compound can be used instead of the metal material. Examples of the conductive metal oxide include tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum doped zinc oxide), and GZO (gallium doped zinc oxide). Examples of the conductive organic compound include polyaniline, polythiophene, and polypyrrole.

<Inorganic insulating film>
The inorganic insulating film 4 is provided to protect the semiconductor layer 32, for example, to prevent the semiconductor layer 32 from being affected by humidity. The inorganic insulating film 4 is formed so as to cover the entire TFT 3.

The inorganic insulating film 4 is formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. The inorganic insulating film 4 may be a single insulating film or a laminated film in which a plurality of insulating films are laminated. The inorganic insulating film 4 can be omitted when the first insulating film 5 is provided.

<First insulating film>
The first insulating film 5 is a planarizing film that plays a role of planarizing the surface irregularities of the TFT 3. The first insulating film 5 is formed on the inorganic insulating film 4 so as to cover the entire TFT 3.

The first insulating film 5 may be formed using the positive radiation sensitive material described above, or may be formed using a conventionally known radiation sensitive resin composition. These materials may be selected depending on whether the organic EL device 1 is a top emission type or a bottom emission type. The first insulating film 5 is formed as an organic insulating film because these materials are organic materials. The first insulating film 5 can be formed by the method described in [Method of forming insulating film] described above.
The film thickness of the first insulating film 5 is preferably increased so as to exhibit an excellent function as a planarizing film. The film thickness of the first insulating film 5 is preferably 1 μm to 6 μm.

<Anode>
The anode 6 forms a pixel electrode. The anode 6 is formed on the first insulating film 5 with a conductive material. The conductive material may be selected depending on whether the organic EL device 1 is a top emission type or a bottom emission type, that is, whether the anode 6 is required to be transparent or light reflective.

In the case of the bottom emission type, the anode 6 is required to be transparent. Therefore, the material of the anode 6 is preferably highly transparent ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or tin oxide. On the other hand, when the organic EL device 1 is a top emission type, the anode 6 is required to have light reflectivity. Therefore, as the material of the anode 6, APC alloy (silver, palladium, copper alloy), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium alloy), NiCr (nickel and nickel) having high light reflectivity are used. Chromium alloys) are preferred.
The thickness of the anode 6 is preferably 100 nm to 500 nm.

<Through hole>
The through hole 7 is formed to connect the anode 6 and the drain electrode 34. In addition to the first insulating film 5, the through hole 7 is formed so as to penetrate the inorganic insulating film 4 under the first insulating film 5.

  The through hole 7 can be formed by dry etching the inorganic insulating film 4 after forming the first insulating film 5 having a through hole having a desired shape. Here, the first insulating film 5 is formed by using the above-described positive-type radiation-sensitive material or a conventionally known radiation-sensitive resin composition, and a method similar to the method described in [Method of forming insulating film]. Can be formed. Therefore, the through-hole which comprises the through hole 7 can be formed by irradiation and development with respect to the coating film which consists of these materials. Dry etching on the inorganic insulating film 4 can be performed using the first insulating film 5 as a mask. As a result, a through hole communicating with the through hole of the first insulating film 5 is formed in the inorganic insulating film 4, and as a result, a through hole 7 penetrating the first insulating film 5 and the inorganic insulating film 4 is formed.

  Note that, when the inorganic insulating film 4 is not disposed on the TFT 3, the through hole formed by the irradiation and development of radiation to the first insulating film 5 constitutes the through hole 7. As a result, the anode 6 covers a part of the first insulating film 5 and the drain electrode 34 through the through hole 7 provided in the first insulating film 5 so as to penetrate the first insulating film 5. Can be connected with.

<Second insulating film>
The second insulating film 8 serves as a partition (bank) having a recess 80 that defines the arrangement region of the organic light emitting layer 9. The second insulating film 8 is formed so as to cover a part of the anode 6 and to expose a part of the anode 6. Further, the second insulating film has a forward tapered shape in cross section at the boundary portion where the anode 6 is exposed.

  The second insulating film 8 is preferably formed on the first insulating film 5 so as to be disposed at least above the semiconductor layer 32 of the TFT 3. Here, “upward” is a direction from the support substrate 2 toward the sealing substrate 12. Since the second insulating film 8 has a light shielding property, light generated from the organic light emitting layer 9 can be prevented or reduced from reaching the semiconductor layer 32.

  Such a second insulating film 8 can be formed by using the above-described positive radiation sensitive material by the method described in [Method of forming insulating film]. The second insulating film 8 can be formed as a plurality of concave portions 80 in which the organic light emitting layer 9 is formed arranged in a matrix in a plan view by patterning by exposing and developing the coating film. .

  The second insulating film 8 is preferably formed so as to fill the through hole 7. By adopting such a configuration, the insulating film formed on the first insulating film 5 and the insulating film formed in the through hole 7 cause the light generated from the organic light emitting layer 9 to be emitted from the semiconductor layer 32 of the TFT 3. It becomes a defensive wall that prevents or reduces reaching.

  As will be described later, an ink-like luminescent material composition is applied to the recess 80 by, for example, an ink jet method. In this case, it is desired that at least the inner surface of the recess 80 of the second insulating film 8 has low wettability (high water repellency). Examples of a method for improving the wettability of the second insulating film 8 include a method of plasma-treating the second insulating film 8 with fluorine gas and a method of improving the liquid repellency of the positive radiation sensitive material. Among these methods, since the plasma treatment may adversely affect other components of the organic EL device 1, a method of increasing the liquid repellent of the positive radiation sensitive material is preferable.

  The thickness T1 of the second insulating film 8 (distance between the uppermost surface of the second insulating film 8 and the lowermost surface of the organic light emitting layer 9) is preferably 0.3 μm or more and 15.0 μm or less, and more preferably 0.5 μm or more. 10.0 μm or less is more preferable, and 1.0 μm or more and 5.0 μm or less is particularly preferable. If the thickness of the second insulating film 8 exceeds 15.0 μm, the second insulating film 8 may come into contact with the sealing substrate 12. On the other hand, if the thickness of the second insulating film 8 is less than 0.3 μm, the light shielding property may not be sufficiently provided, or the concave portion of the second insulating film 8 is formed when the organic light emitting layer 9 described later is formed. When the light emitting material composition is applied to 80, the light emitting material composition may leak from the recess 80.

<Organic light emitting layer>
The organic light emitting layer 9 emits light when an electric field is applied. The organic light emitting layer 9 is a layer containing an organic light emitting material that emits electroluminescence. The organic light emitting layer 9 is formed in a region defined by the second insulating film 8, that is, a recess 80. In this manner, by forming the organic light emitting layer 9 in the recess 80, the periphery of the organic light emitting layer 9 is surrounded by the second insulating film 8, and a plurality of adjacent pixels can be partitioned.

  The organic light emitting layer 9 is formed by filling the concave portion 80 of the second insulating film 8 with an organic light emitting material. A method for filling the recess 80 with the organic light emitting material is not particularly limited, but an inkjet method is preferable.

The organic light-emitting material may be a low-molecular organic light-emitting material or a polymer organic light-emitting material, and examples thereof include materials obtained by doping quinacridone or coumarin on a base material such as Alq ₃ or BeBq _3. It is done. When the organic light emitting material is filled by the ink jet method, a polymer organic light emitting material is preferable. Examples of the polymer organic light-emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene (Polyacetylene), derivatives thereof, polyphenylene (Polyphenylene), derivatives thereof, polyparaphenyleneethylene (Poly (phenylene-ethylene)), derivatives thereof, Examples thereof include poly (3-hexylthiophene) (P3HT), derivatives thereof, polyfluorene (PF), derivatives thereof, and the like.

  The organic light emitting layer 9 is formed in contact with the anode 6 at the recess 80 of the second insulating film 8. The thickness T2 of the organic light emitting layer 9 is preferably 50 nm to 100 nm. Here, the thickness T2 of the organic light emitting layer 9 means the distance from the bottom surface of the organic light emitting layer 9 on the anode 6 to the top surface of the organic light emitting layer 9 on the anode 6.

  A hole injection layer and / or an intermediate layer may be disposed between the anode 6 and the organic light emitting layer 9. When the hole injection layer and the intermediate layer are disposed between the anode 6 and the organic light emitting layer 9, the hole injection layer is disposed on the anode 6, the intermediate layer is disposed on the hole injection layer, and An organic light emitting layer 9 is disposed on the intermediate layer. Further, the hole injection layer and the intermediate layer may be omitted as long as holes can be efficiently transported from the anode 6 to the organic light emitting layer 9.

<Cathode>
The cathode 10 is formed so as to cover a plurality of pixels in common, and serves as a common electrode of the organic EL device 1. The cathode 10 is made of a conductive member. The material for forming the cathode 10 may be selected depending on whether the organic EL device 1 is a top emission type or a bottom emission type, that is, whether the cathode 10 is required to be transparent. In the case of the top emission type, the cathode 10 is preferably an ITO electrode or an IZO electrode that constitutes a visible light transmissive electrode. On the other hand, when the organic EL device 1 is a bottom emission type, the cathode 10 does not have to be visible light transmissive. In that case, the constituent material of the cathode 10 is not particularly limited as long as it is conductive. For example, barium (Ba), barium oxide (BaO), aluminum (Al), and an alloy containing Al can be selected. is there.
An electron injection layer made of, for example, barium (Ba), lithium fluoride (LiF), or the like may be disposed between the cathode 10 and the organic light emitting layer 9.

<Passivation film>
The passivation film 11 suppresses entry of moisture and oxygen into the organic EL element. The passivation film 11 is provided on the cathode 11. The passivation film 11 is formed using a metal nitride such as SiN or aluminum nitride (AlN). The passivation film 11 may be a single insulating film or a laminated film in which a plurality of insulating films are laminated.

<Sealing substrate>
The sealing substrate 12 seals the main surface (the side opposite to the support substrate 2) on which the organic light emitting layer 9 is disposed. As the sealing substrate 12, a glass substrate such as non-alkali glass can be used. The main surface on which the organic light emitting layer 9 is disposed can be sealed with the sealing substrate 12 through the sealing layer 13 using a sealing agent (not shown) applied in the vicinity of the outer peripheral edge of the TFT substrate. preferable. The sealing layer 13 can be a layer of an inert gas such as a dried nitrogen gas or a layer of a filling material such as an adhesive.

  In the organic EL device 1 of the present embodiment, since the second insulating film 8 has a light shielding property with respect to light having a wavelength of 300 to 400 nm, it suppresses light deterioration of the semiconductor layer 32 due to use of the device or the like. Can do. Further, the first insulating film 5 and the second insulating film 8 can be formed using a positive radiation sensitive material having low water absorption, and in the process of forming these insulating films 5 and 8, Processing such as cleaning using a low water-absorbing material is possible. Therefore, it is possible to reduce a slight amount of moisture contained in the insulating film forming material in the form of adsorbed water from gradually entering the organic light emitting layer 9, and to reduce deterioration of the organic light emitting layer 9 and deterioration of the light emitting state. .

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” means “part 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) are determined by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020). And measured in terms of polystyrene under conditions of tetrahydrofuran (THF) solvent.
・ Measuring method: Gel permeation chromatography (GPC) method ・ Standard material: polystyrene conversion ・ Device: manufactured by Tosoh Corporation, trade name: HLC-8020
Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected Solvent: Tetrahydrofuran Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1mL / min

<Synthesis of polymer (A)>
[Synthesis Example A1] Synthesis of Polymer (A-1) After adding 390 g of γ-butyrolactone as a polymerization solvent to a three-necked flask, 2,2′-bis (3-amino-4-hydroxyphenyl as a diamine compound was added. ) 120 g of hexafluoropropane was added to the polymerization solvent. After the diamine compound was dissolved in the polymerization solvent, 71 g of 4,4′-oxydiphthalic dianhydride as an acid dianhydride was added. Then, after making it react at 60 degreeC for 1 hour, 19 g of maleic anhydride as a terminal blocker was added, and it was made to react at 60 degreeC for further 1 hour, Then, it heated up and made it react at 180 degreeC for 4 hours. About 600 g of a polyimide solution having a solid content concentration of about 35% by mass including the polymer (A-1) was obtained. Mw of the obtained polymer (A-1) was 8000.

[Synthesis Example A2] Synthesis of Polymer (A-2) The flask was purged with nitrogen and charged with 250.0 g of a propylene glycol monomethyl ether acetate solution in which 5.0 g of 2,2′-azobisisobutyronitrile was dissolved. It is. Subsequently, 20.0 g of methacrylic acid, 45.0 g of dicyclopentanyl methacrylate, and 30.0 g of 3-ethyl-3-methacryloyloxymethyloxetane were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 100 ° C. for 1 hour to complete the polymerization. Thereafter, the reaction product solution was dropped into a large amount of methanol to solidify the reaction product. The coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of methanol.

  After this re-dissolution / coagulation operation was performed three times in total, the obtained coagulated product was vacuum-dried at 60 ° C. for 48 hours to obtain the desired copolymer. Thereafter, a copolymer solution was prepared using propylene glycol monomethyl ether acetate so that the solid content concentration was about 35% by mass. The weight average molecular weight (Mw) of the obtained polymer (A-2) was 10,000.

[Synthesis Example A3] Synthesis of Polymer (A-3) 20.0 g of 2-methacryloyloxyethyl succinic acid, 45.0 g of dicyclopentanyl methacrylate and 30.0 g of 3,4-epoxycyclohexylmethyl methacrylate were used as monomers. The procedure was the same as in Synthesis Example A2 except that The weight average molecular weight (Mw) of the obtained polymer (A-3) was 20000.

<Synthesis of novolac resin (C)>
[Synthesis Example C1] Synthesis of Novolak Resin (C-1) In a flask equipped with a thermometer, a condenser tube, a fractionating 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 mass% paraformaldehyde (1.0 mol in terms of formaldehyde) were charged. Subsequently, 3.4 g of paratoluenesulfonic acid was added with stirring. Then, it was made to react at 100 degreeC for 8 hours. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separating funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water became neutral, the solvent was removed from the organic layer under heating and reduced pressure to obtain 140 g of a novolak resin (C-1) composed of a structural unit represented by the following formula. The obtained novolak resin (C-1) had a weight average molecular weight (Mw) of 2000.

From the measurement chart using a Fourier transform infrared spectrophotometer (FT-IR), absorption (2800 to 3000 cm ⁻¹ ) derived from expansion and contraction due to a methylene bond can be confirmed as compared with the raw material, and further, absorption derived from aromatic ether (1000 ˜1200 cm ⁻¹ ) could not be found. From these results, it was presumed that no dehydration etherification reaction between hydroxyl groups (hydroxyl disappearance) occurred in this synthesis example, and a novolak resin having a methylene bond was obtained. These estimations are the same 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 tube, a fractionating tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol and 134.1 g of terephthalaldehyde were added. (1.0 mol) and 3.0 g of trifluoromethanesulfonic acid were charged and reacted at 150 to 160 ° C. for 4 hours while stirring. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separating funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, 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) comprising a structural unit represented by the following formula. The obtained novolak resin (C-2) had a weight average molecular weight (Mw) of 1500.

[Synthesis Example C3] Synthesis of Novolak Resin (C-3) 134.1 g (1.0 mol) of terephthalaldehyde and 160.2 g (1.0 mol) of 1,6-dihydroxynaphthalene as raw material components and acid catalyst, trifluoro The same procedure as in Synthesis Example C2 was performed except that 3.0 g of methanesulfonic acid was used. 230 g of novolak resin (C-3) comprising a structural unit represented by the following formula was obtained. The obtained novolak resin (C-3) had a weight average molecular weight (Mw) of 1000.

[Synthesis Example C4] Synthesis of Novolak Resin (C-4) 194.2 g (1.0 mol) of 1-hydroxyanthracene, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92% by mass paraformaldehyde (in terms of formaldehyde) 1.0 mol) was used in the same manner as in Synthesis Example C1. 180 g of novolak resin (C-4) composed of a structural unit represented by the following formula was obtained. The obtained novolak resin (C-4) had a weight average molecular weight (Mw) of 2000.

[Synthesis Example C5] Synthesis of Novolak Resin (C-5) As raw material components, 210.2 g (1.0 mol) of 1,4-dihydroxyanthracene, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92 mass% paraformaldehyde ( The same procedure as in Synthesis Example C1 was conducted except that 1.0 mol in terms of formaldehyde was used. 190 g of novolak resin (C-5) comprising a structural unit represented by the following formula was obtained. The obtained novolak resin (C-5) had a weight average molecular weight (Mw) of 3000.

<Preparation of positive radiation sensitive material>
The polymer (A) used for the preparation of the positive radiation sensitive material is the polymers (A-1) to (A-3) of Synthesis Examples A1 to A3, and the novolak resin (C) is the Synthesis Examples C1 to C5. Novolak resins (C-1) to (C-5), and a radiation-sensitive acid generator (B), a crosslinking agent (D), a solvent (E), an adhesion assistant (F) and a surfactant (G ) Is as follows.
Radiation sensitive acid generator (B)
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol) ("MILNESS-AC" from Toyo Gosei Co., Ltd.)
Cross-linking agent (D)
D-1: 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl
("OXBP" from Ube Industries)
D-2: “C-357” from Gunei Chemical Co., Ltd.
Solvent (E)
E-1: Mixed solvent of 30:20:50 by mass ratio of γ-butyrolactone (BL), propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME)
Adhesion aid (F)
F-1: N-phenyl-3-aminopropyltrimethoxysilane
(Shin-Etsu Chemical's “KBM-573”)
Surfactant (G)
G-1: Toray Dow Corning's silicone surfactant “SH8400”

[Preparation Example 1]
As a radiation-sensitive acid generator (B), a polymer solution containing the polymer (A-1) of Synthesis Example A1 (amount corresponding to 25 parts (solid content) of polymer (A-1)) is used as (B- 1) 10 parts, 40 parts of (C-1) as novolak resin (C), 15 parts of (D-1) as crosslinking agent (D), 5 parts of (D-2), (F- 1) 4 parts, (G-1) 1 part as a surfactant (G), and (E-1) as a solvent (E) are mixed so that the solid content concentration is 25% by mass. A positive radiation sensitive material 1 was prepared by filtration through a 0.2 μm membrane filter.

[Preparation Examples 2 to 11]
Positive type radiation sensitive materials 2 to 11 were prepared in the same manner as in Preparation Example 1 except that the components of the types and blending amounts shown in Table 2 were used.

[Examples and Comparative Examples]
Using positive type radiation-sensitive materials 1 to 11 of Preparation Examples 1 to 11, an insulating film and an organic EL element were produced by the method described below. These insulating films and organic EL elements were evaluated as follows.

<Evaluation of insulating film characteristics>
The insulating film patterning property, light shielding property, taper angle, water absorption and heat resistance were evaluated.
<Patternability>
Using a spinner or a slit die coater, the positive radiation sensitive material obtained in the above preparation example was applied on a silicon substrate and then pre-baked on a hot plate at 120 ° C. for 2 minutes to form a coating film. . This coating film was exposed at an exposure amount of 100 mJ / cm ² at a wavelength of 365 nm through a pattern mask using an exposure machine (“MPA-6000” manufactured by Canon Inc.). Thereafter, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washed with running ultrapure water for 1 minute, dried, and dried on a silicon substrate having a diameter of 5 μm. A coating film having a pattern in which a plurality of through holes are arranged in a line was formed. This coating film was cured by heating at 250 ° C. for 45 minutes in a clean oven to form an insulating film having the film thickness shown in Table 2 having the pattern.

  At this time, it is confirmed whether or not the exposed portion after development is completely dissolved in the coating film, a pattern of 5 μm is formed, and the insulating film is formed without peeling off or developing residue. Although the pattern was formed and the insulating film was not peeled off, the case where there was a slight development residue was “good”, and the case where the pattern of 5 μm could not be formed or the insulating film was peeled off was regarded as “bad”.

<Light shielding>
Using a spinner or a slit die coater, the positive radiation sensitive material obtained in the above preparation example was applied on a glass substrate (Corning “Corning 7059”), and then on a hot plate at 120 ° C. for 2 minutes. After pre-baking, it was post-baked at 250 ° C. for 45 minutes in a clean oven to form an insulating film having a film thickness shown in Table 2.

  For the glass substrate having this insulating film, the total light transmittance was measured in the 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 400 nm was determined. The light shielding property is “excellent” when the maximum total light transmittance at a wavelength of 300 to 400 nm is 6% or less, “good” when it exceeds 6% and 15% or less, and “good” when it exceeds 15%. “Bad”.

<Taper angle>
In the <patterning> insulating film, the vertical cross-sectional shape in the direction perpendicular to the plurality of through-hole lines was observed with SEM (Hitachi High-Technology “SU3500”).

<Water absorption>
After applying the positive radiation sensitive material obtained in the above-mentioned preparation example on a silicon substrate using a spinner or a slit die coater, prebaking on a hot plate at 120 ° C. for 2 minutes and then 250 in a clean oven. Post-baking was performed at 45 ° C. for 45 minutes to form an insulating film having a film thickness shown in Table 2. The insulation film is desorbed from the sample surface and the sample when the temperature is raised from room temperature to 200 ° C. at a vacuum degree of 1.0 × 10 ⁻⁹ Pa using Thermal Desorption Spectroscopy (“TDS1200” from ESCO). The detected value of the water peak (M / z = 18) was measured with a mass spectrometer (“5973N” manufactured by Agilent Technologies). The integrated value of the total peak intensity from 60 ° C. to 200 ° C. was taken to evaluate the water absorption. The water absorption is “excellent” when the integrated value of the total peak intensity from 60 ° C. to 200 ° C. is 3.0 × 10 ⁻⁸ or less, exceeding 3.0 × 10 ⁻⁸ and 5.0 × 10 ^−8. “Good” in the following cases.

<Heat resistance>
In the same manner as in the evaluation of <water absorption>, an insulating film was formed using a positive radiation-sensitive material, and this insulating film was measured at 100 ° C. using a thermogravimetric apparatus (“TGA2950” manufactured by TA Instruments). To 500 ° C., 5% weight loss temperature was determined by TGA measurement (in air, temperature rising rate 10 ° C./min). The heat resistance was “excellent” when the 5% weight loss temperature exceeded 350 ° C., and “good” when the temperature was 350 to 330 ° C.

<Evaluation of device characteristics>
Using a glass substrate (Corning “Corning 7059”), a TFT substrate having TFTs formed on the glass substrate was prepared, and then an insulating film was formed on the TFT substrate to prepare an evaluation element. The element characteristics were evaluated for this evaluation element.

The TFT substrate was formed by the following procedure. First, a molybdenum film was formed on a glass substrate by sputtering, and a gate electrode was formed by photolithography using a resist and etching. Next, a silicon oxide film was formed by sputtering on the entire surface of the glass substrate and on the upper layer of the gate electrode to form a gate insulating film. An InGaZnO-based amorphous oxide film (InGaZnO ₄ ) was formed on the gate insulating film by sputtering, and a semiconductor layer was formed by photolithography and etching using a resist. A molybdenum film was formed on the semiconductor layer by sputtering, and a source electrode and a drain electrode were formed by photolithography and etching using a resist. Finally, a silicon oxide film was formed by sputtering on the entire surface of the substrate and on the upper layer of the source electrode and drain electrode to obtain a passivation film, thereby obtaining a TFT substrate.

  After applying the positive radiation sensitive material obtained in the above preparation example on the TFT substrate using a spinner or slit die coater, pre-baking on a hot plate at 120 ° C. for 2 minutes and then in a clean oven. An insulating film having a film thickness shown in Table 2 was formed by post-baking at 45 ° C. for 45 minutes.

<Switching response characteristics>
The device characteristics were evaluated as switching response characteristics. The switching response characteristic was 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 with a voltage applied to the gate electrode using a prober and a semiconductor parameter analyzer. Specifically, the drain electrode under the condition that the semiconductor layer is irradiated with white light (illuminance 30000 lux) centered at a wavelength of 450 nm or 500 nm from above the insulating film formed of the positive radiation sensitive material. The ratio of the current value when the voltage applied to the gate electrode is plus 10 V and minus 10 V when the source electrode is plus 10 V and the source electrode is 0 V is the ON / OFF ratio. The switching response characteristic, that is, the element characteristic, was “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>
TFT reliability refers to changes in Id-Vg characteristics (amount of change in threshold voltage Vth) when an electrical stress is applied between the gate electrode and the source electrode, when the evaluation element is irradiated with light and when light is not irradiated. It was evaluated by comparing with.

(Measurement of Id-Vg characteristics and threshold voltage Vth)
The electrical stress is applied by keeping the potential of the source electrode of the evaluation element at 0 V, the potential of the drain electrode at +10 V, and applying the voltage between the source electrode and the drain electrode, and the potential Vg of the gate electrode at −20 V. To + 20V. In this way, when the potential Vg of the gate electrode is changed, the current Id flowing between the drain electrode and the source electrode is plotted to obtain the Id-Vg characteristic. In this Id-Vg characteristic, the voltage at which the current value is ON is set to the threshold voltage Vth.

(Measurement of change in threshold voltage Vth)
Electrical stress was applied by applying a positive voltage of +20 V and a negative voltage of −20 V for 12 hours between the gate electrode and the source electrode. Such electrical stress was performed under the condition where the semiconductor film of the evaluation element was irradiated with light from above and under the condition where the semiconductor film was not irradiated with light. The amount of change in the threshold voltage Vth was calculated from the Id-Vg characteristic for each of the light irradiation condition and the light non-irradiation condition. When the amount of change in the threshold voltage Vth during light irradiation is suppressed to less than 1.5 times the amount of change in the threshold voltage Vth during non-light irradiation, the TFT reliability is assumed to be “excellent”. The TFT reliability is determined to be “good” when it is suppressed to 5 to 2 times, and the TFT reliability is determined to be “bad” when it exceeds 2 times.

  As shown in Table 2, the positive radiation sensitive materials 1 to 11 of Preparation Examples 1 to 11 were excellent in patterning property, pattern shape, low water absorption and heat resistance. Moreover, the insulating film formed in Examples 1 to 15 has a light-shielding property and has a forward tapered shape. An element using the insulating film and a semiconductor layer that is easily deteriorated by light has element characteristics (even in a light irradiation environment). Excellent switching response characteristics and TFT reliability). On the other hand, the insulating film formed in Comparative Example 1 is inferior in light-shielding property, and an element using this insulating film and a semiconductor layer that is susceptible to photodegradation has element characteristics (switching response characteristics, TFTs) in a light irradiation environment. The reliability was inferior.

  DESCRIPTION OF SYMBOLS 1 ... Organic EL device, 2 ... Support substrate, 3 ... TFT, 30 ... Gate electrode, 31 ... Gate insulating film, 32 ... Semiconductor layer, 33 ... Source electrode, 34 ... Drain electrode, 4 ... Inorganic insulating film, 5 ... 1st DESCRIPTION OF SYMBOLS 1 insulating film (flattening film), 6 ... anode, 7 ... through hole, 8 ... 2nd insulating film (partition), 80 ... recessed part, 9 ... organic light emitting layer, 10 ... cathode, 11 ... passivation film, 12 DESCRIPTION OF SYMBOLS ... Sealing substrate, 13 ... Sealing layer, 100 ... TFT substrate, 110 ... 1st electrode, 111 ... Opening part of insulating film, 112 ... Edge part of 1st electrode, 113 ... 1st electrode surface, 120 ... Insulating film 121: Insulating film slope

Claims (12)

A TFT substrate in which the semiconductor layer constituting the TFT contains an oxide semiconductor containing one or more elements selected from In, Ga, Sn and Zn;
A first electrode provided on the TFT substrate and connected to the TFT;
An insulating film formed on the first electrode so as to partially expose the first electrode and having a total light transmittance in a range of 0 to 15% at a wavelength of 300 to 400 nm;
A display or lighting device having a second electrode provided opposite to the first electrode ,
The insulating film is an insulating film formed from a positive radiation sensitive material,
The positive radiation sensitive material is (A) at least one selected from polyimide (A1) having a structural unit represented by formula (A1), precursor of polyimide (A2), and acrylic resin (A3). A polymer of (B), a radiation sensitive acid generator, and (C) a novolac resin,
The content of the novolac resin (C) in the positive radiation sensitive material is 2 to 200 parts by mass with respect to 100 parts by mass of the polymer (A).
Display or lighting device .

[In Formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. ]   The display or lighting device according to claim 1, wherein a cross-sectional shape at a boundary portion of the insulating film where the insulating film exposes the first electrode is a forward tapered shape.   The display or lighting device according to claim 1, wherein a thickness of the insulating film is 0.3 to 15.0 μm. The display or lighting device according to claim 1, wherein (B) is a quinonediazide compound. The display or lighting device according to any one of claims 1 to 4, wherein the novolac resin (C) is a resin containing a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group. Wherein the insulating film is formed so as to cover at least an edge portion of the first electrode, wherein any one of the display or lighting device according to claim 1 to 5 cross-sectional shape is a forward tapered at the boundary portion of the insulating film. The insulating film is a partition wall for partitioning the upper surface of the front Symbol TFT substrate into a plurality of regions,
Any one of a display or lighting device according to claim 1-6 having pixels formed respectively on the plurality of regions. A first electrode provided on the TFT substrate and connected to the TFT; an organic EL layer formed on the first electrode in a region partitioned by the partition; a first electrode provided on the organic EL layer; The display or illumination device according to claim 7 , comprising an organic EL element including two electrodes. The TFT substrate is a TFT substrate having a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a planarization layer covering the TFT,
The partition is formed on the planarization layer so as to cover at least the edge portion of the first electrode, and the partition is disposed at least above the semiconductor layer of the TFT. 9. A display or illumination device according to claim 8 characterized in that: The insulating film is formed on the TFT substrate so as to be disposed at least above the semiconductor layer, and 50% or more of the area of the semiconductor layer when projected from above the TFT substrate The display or lighting device according to any one of claims 1 to 9, which overlaps with the insulating film. The process 1 which forms a coating film on a TFT substrate using the positive radiation sensitive material of Claim 1, The process 2 which irradiates a radiation to at least one part of the said coating film, The coating film which the said radiation irradiated The method according to claim 1, further comprising a step 3 for developing the film and a step 4 for heating the developed coating film to form an insulating film having a total light transmittance in the range of 0 to 15% at a wavelength of 300 to 400 nm. A method for forming an insulating film included in the display or lighting device. The method for forming an insulating film according to claim 11, wherein the heating temperature in step 1 is 60 to 130 ° C, and the heating temperature in step 4 is higher than 130 ° C and not higher than 300 ° C.

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