CN105874882A - Display or illumination device, and method for forming insulating film - Google Patents

Abstract

The present invention provides a display or lighting device using, as a driving element, a thin film transistor including a semiconductor layer containing a substance having a large photodegradation, and photodegradation of the substance accompanying the use of these devices is suppressed . The display or lighting device of the present invention has: a TFT substrate; a first electrode provided on the TFT substrate and connected to the TFT; an insulating film formed on the first electrode so that the first electrode is partially exposed, and the entire The light transmittance is in the range of 0% to 15% at a wavelength of 300nm to 400nm; and the second electrode is arranged opposite to the first electrode; and the insulating film is an insulating film formed of a radiation-sensitive material, The radiation-sensitive material contains resins such as (A) polymer, (B) sensitizer and (C) novolac resin, and relative to 100 parts by mass of the polymer (A), the resin in the radiation-sensitive material ( The content of C) is 2 to 200 parts by mass.

Description

Display or lighting device and method for forming insulating film

technical field

The invention relates to a display or lighting device and a method for forming an insulating film. More specifically, the present invention relates to a substrate having a substrate, a first electrode provided on the substrate, an insulating film formed on the first electrode so that the first electrode is partially exposed, and a substrate facing the first electrode. A display or lighting device provided with a second electrode and a method of forming the insulating film.

Background technique

As a flat panel display (flat panel display), a non-luminous liquid crystal display (Liquid Crystal Display, LCD) is becoming more and more popular. In addition, in recent years, electroluminescent displays (Electroluminescent Displays, ELDs), which are self-luminous displays, have become known. In particular, an organic electroluminescence (EL) element utilizing electroluminescence of an organic compound is expected not only as a light-emitting element installed in a display, but also as a light-emitting element installed in a next-generation lighting device. .

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

These flat panel displays operate by applying a voltage or passing a current between opposing first electrodes and second electrodes. However, in this case, the electric field tends to concentrate on the edge portion of the electrode with a small curvature radius, so that undesirable phenomena such as dielectric breakdown and leakage current are likely to occur at the edge portion.

In order to solve this problem, the following technology is disclosed: the film thickness of the insulating film at the boundary portion where the insulating film exposes the first electrode is set so that it gradually becomes thicker from the center portion of the first electrode toward the edge portion, so-called cross-sectional design. A technology defined as a right conical shape (for example, refer to Patent Document 3).

In addition, in recent years, research on a thin film transistor (Thin Film Transistor, TFT) using an oxide semiconductor layer has been actively conducted. Patent Document 4 proposes an example in which a polycrystalline thin film containing oxides of In, Ga, and Zn (hereinafter also simply referred to as "Indium Gallium Zinc Oxide, IGZO") is used for a semiconductor layer of a TFT, Patent Document 4 and Patent Document 5 propose examples in which an amorphous thin film of IGZO is used for a semiconductor layer of a TFT.

However, IGZO is known to suffer from photodegradation due to natural light, lighting, manufacturing steps, and the like. Therefore, when a TFT containing a semiconductor layer containing a substance with large optical degradation such as IGZO is used as an element for driving a display or lighting device, especially an element for driving an organic EL element, from the viewpoint of preventing the optical degradation of IGZO , it is required to impart light-shielding properties to ultraviolet to visible light as a characteristic of the insulating film. However, most insulating films currently used are transparent in the wavelength region of 300 nm to 400 nm, for example, and are required to provide a light-shielding function.

[Prior art literature]

[Patent Document]

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

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

[Patent Document 3] Japanese Patent No. 4982927

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

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

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide a display or lighting device, which has a thin film transistor including a semiconductor layer containing a substance having a large photodegradation such as IGZO as a driving element, and in the display or lighting device, accompanied by The photodegradation of the materials associated with the use of these devices is suppressed.

technical means to solve problems

The inventors of the present invention have diligently studied to solve the above-mentioned problems. As a result, the inventors have found that the above-mentioned problems can be solved by employing the following configurations, and completed the present invention. The present invention relates to, for example, the following [1] to [19].

[1] A display or lighting device comprising: a TFT substrate, a semiconductor layer constituting the TFT contains an oxide semiconductor, and the oxide semiconductor contains one selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn The above elements; the first electrode is arranged on the TFT substrate and connected to the TFT; the insulating film is formed on the first electrode in a manner that the first electrode is partially exposed, and the total light transmittance is at a wavelength of 300nm～ In the range of 0% to 15% at 400nm; and the second electrode is arranged opposite to the first electrode; and the insulating film is an insulating film formed of a radiation-sensitive material, and the radiation-sensitive material contains (A) a polymer other than the following resin (C), (B) a photosensitive agent, and (C) at least one resin selected from the group consisting of novolak resins, resole resins, and condensates of resole resins, and relatively The content of the resin (C) in the radiation sensitive material is 2 to 200 parts by mass based on 100 parts by mass of the polymer (A).

[2] The display or lighting device according to the above [1], wherein the polymer (A) is selected from polyimide (A1), the precursor (A2) of the polyimide, and an acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5-1), the precursor (A5-2) of said polybenzoxazole, polyolefin (A6) and cardo resin (cardo resin) (A7).

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

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

[chemical 1]

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

[5] The display or lighting device according to the above [2] or [3], wherein the polysiloxane (A4) is a polysiloxane obtained by reacting an organosilane represented by the formula (a4),

[Chem 2]

[In formula (a4), R ¹ is a hydrogen atom, an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons, an aryl-containing group with 6 to 15 carbons, an aryl group with 2 to 15 carbons A group containing an epoxy ring or a group obtained by substituting one or more hydrogen atoms contained in the alkyl group as substituents may be the same or different when there are a plurality of R ¹ ; R2 is a ^hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons, or an aryl group with 6 to 15 carbons, and when there are multiple ^R2s , they can be the same or different; n is an integer of 0 to 3].

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

[Chem 3]

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

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

[chemical 4]

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

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

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

[10] The display or lighting device according to any one of the above [1] to [9], wherein the cross-sectional shape of the boundary portion of the insulating film where the first electrode is exposed is a right conical shape. .

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

[12] The display or lighting device according to any one of [1] to [11], wherein the insulating film is formed to cover at least an edge portion of the first electrode, and the insulating film The cross-sectional shape of the boundary part is a right conical shape.

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

[14] The display or lighting device according to the above [13], comprising an organic EL element including a first electrode provided on the TFT substrate and connected to the TFT, formed on the The organic light-emitting layer formed on the first electrode in the region separated by the partition wall, and the second electrode disposed on the organic light-emitting layer.

[15] The display or lighting device according to [14], wherein the TFT substrate has a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a TFT covering the TFT. A planarization layer, and the partition wall covers at least the edge portion of the first electrode, and the partition wall is formed on the planarization layer in such a manner that it is disposed at least above the semiconductor layer included in the TFT. .

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

[17] The display or lighting device according to any one of [1] to [16], wherein the insulating film is formed on the TFT substrate so as to be disposed at least above the semiconductor layer, When projected and viewed from above the TFT substrate, 50% or more of the area of the semiconductor layer overlaps with the insulating film.

[18] A method for forming an insulating film, forming the insulating film included in the display or lighting device described in [1], and the method for forming the insulating film includes the following steps: Step 1, using the following steps: The radiation-sensitive material described in 1 forms a coating film on the TFT substrate; step 2, irradiating radiation to at least a part of the coating film; step 3, developing the coating film irradiated with radiation; and step 4, irradiating The developed coating film is heated to form an insulating film with a total light transmittance in the range of 0% to 15% at a wavelength of 300nm to 400nm.

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

The effect of the invention

According to the present invention, it is possible to provide a display or lighting device having, as a driving element, a thin film transistor including a semiconductor layer containing a substance having a large photodegradation such as IGZO, and in the display or lighting device, accompanied by The photodegradation of the materials associated with the use of these devices is suppressed.

Description of drawings

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

FIG. 2 is a cross-sectional view illustrating a right conical shape as a cross-sectional shape of an insulating film.

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

Reference signs:

detailed description

The display or lighting device of the present invention has: a TFT substrate, and the semiconductor layer constituting the TFT is a layer containing an oxide semiconductor containing one selected from In, Ga, Sn, Ti, Nb, Sb, and Zn. The above elements; the first electrode is provided on the TFT substrate and is connected to the TFT; the insulating film is formed on the first electrode so that the first electrode is partially exposed; and the second electrode is connected to the first electrode. The electrodes are arranged facing each other. Here, the total light transmittance of the insulating film is 0% to 15% at a wavelength of 300 nm to 400 nm.

Hereinafter, display and lighting devices are collectively referred to as "device".

The display device of the present invention includes, for example, a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescence display (ELD), and particularly an organic EL display. The lighting device of the present invention includes, for example, organic EL lighting.

In the device of the present invention, the TFT substrate, the first electrode, and the second electrode, for example, can respectively illustrate specific examples (supporting substrate, TFT, anode, cathode).

In the device of the present invention, the insulating film is formed to cover at least a part of the first electrode and partially expose the first electrode. 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. 1 . The first electrodes 110 formed in stripes are formed on the TFT substrate 100, and the insulating film 120 is formed on the TFT substrate 100 and the first electrodes 110 so that the first electrodes 110 are partially exposed. The exposed portion of the electrode 110 is also referred to as an “opening portion 111 ”. Here, the insulating film 120 is formed to cover the edge portion 112 of the first electrode 110 . The opening 111 can correspond to one light-emitting region, that is, a pixel, for example, in an organic EL device.

The cross-sectional shape of the insulating film is preferably a true conical shape at the boundary portion where the first electrode is exposed. The so-called "positive conical shape" here corresponds to the following situation: the 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 smaller than 90°. Hereinafter, the angle θ is also referred to as "cone angle θ". The cone 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, if the cross-sectional shape of the insulating film at the boundary portion is a right conical shape, even when the organic light-emitting layer and the second electrode are formed into films after the insulating film is formed, the By forming these films smoothly, unevenness in film thickness due to step differences can be reduced, and a light-emitting device having stable characteristics can be obtained.

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

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

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

The insulating film is, for example, a partition wall that partitions the surface of the TFT substrate into a plurality of regions in which pixels are formed. From the viewpoint of light-shielding properties of the semiconductor layer included in the TFT, the insulating film (partition wall) is preferably formed on the TFT substrate so as to be disposed at least above the semiconductor layer. Here, "upward" refers to the direction from the TFT substrate toward the second electrode. As an example, in the case of projecting observation from above 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, and further An aspect in which 90% or more, especially 100%, overlaps with the insulating film (partition wall).

Thus, in the device of the present invention, the insulating film exposing the first electrode has light-shielding properties at the above-mentioned wavelength. By providing such an insulating film, even if it is a device having a thin film transistor including a semiconductor layer containing a substance having a large photodegradation such as IGZO, for example, as a driving element, the insulating film functions as a light shielding film. Photodeterioration of the semiconductor layer accompanying use of the device and the like is suppressed.

For example, the semiconductor layer constituting the TFT is a layer containing an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn. The oxide in this case includes, for example, a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture of these oxides.

Examples of oxide semiconductors containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn include; quaternary metal oxides such as In-Sn-Ga-Zn-O oxide semiconductors material; In-Ga-Zn-O oxide semiconductor, In-Sn-Zn-O oxide semiconductor, In-Al-Zn-O oxide semiconductor, Sn-Ga-Zn-O oxide semiconductor, Al-Ga-Zn-O-based oxide semiconductors, Sn-Al-Zn-O-based oxide semiconductors and other ternary metal oxides; In-Zn-O-based oxide semiconductors, Sn-Zn-O-based oxide semiconductors , Al-Zn-O-based oxide semiconductors, Zn-Mg-O-based oxide semiconductors, Sn-Mg-O-based oxide semiconductors, In-Mg-O-based oxide semiconductors or In-Ga-O-based materials, etc. Elementary metal oxides; In-O-based oxide semiconductors, Sn-O-based oxide semiconductors, Zn-O-based oxide semiconductors, and other unary metal oxides.

In the present invention, even when the semiconductor layer constituting the TFT is the above-mentioned oxide semiconductor layer, especially in the case of an oxide semiconductor layer including an In-Ga-Zn-O-based oxide semiconductor (IGZO semiconductor), the prevent its photodegradation.

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

The TFT substrate includes, for example, a support substrate, TFTs provided on the support substrate corresponding to the organic EL elements, and a planarization layer covering the TFTs. For example, the first electrode is formed on the planarization layer, and is connected to the TFT through a wiring formed in a via hole penetrating the planarization layer. In addition, an insulating film (partition wall) having light-shielding properties is preferably formed on the first electrode and the planarization layer so that the first electrode is partially exposed.

The insulating film exposing the first electrode can be formed using a radiation-sensitive material, for example. Radiation-sensitive materials include a positive type that increases solubility in a developer by exposure and removes exposed parts, and a negative type that hardens by exposure and removes non-exposed parts. When exposing a coating film formed of a radiation-sensitive material, light is generally strongly absorbed on the surface of the coating film, and the amount of light absorbed tends to decrease toward the inside of the coating film. Therefore, in the case of a positive type, the solubility of the surface portion of the coating film is greater than the solubility of the interior, and in the case of a negative type, the tendency is opposite. In the present invention, it is preferable to set the cross-sectional shape of the boundary portion of the insulating film into a right conical shape, so it is preferable to perform patterning using a positive radiation-sensitive material.

[radiation sensitive material]

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

The said radiation sensitive material may contain a crosslinking agent (D) as a preferable component, and may also contain a solvent (E) as a preferable component. Moreover, the said radiation sensitive material may contain other arbitrary components in the range which does not impair the effect of this invention.

The radiation sensitivity of the radiation-sensitive agent material is high, and by using the material, an insulating film with an excellent pattern shape can be formed, and it is possible to meet the demand for narrowing the pitch of the pattern. Furthermore, by using such a material, an insulating film having low water absorption can also be formed.

Each component will be described in detail below.

[Polymer (A)]

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

Examples of the polymer (A) include polyimide (A1), the precursor (A2) of the polyimide, acrylic resin (A3), polysiloxane (A4), polybenzoxane At least one polymer selected from the azole (A5-1), the precursor of the polybenzoxazole (A5-2), the polyolefin (A6) and the cardo resin (A7).

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A) is preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and further Preferably it is 4,000 to 50,000. There exists a tendency for the insulating film which has sufficient mechanical characteristics to be obtained as Mw is more than the lower limit value of the said range. When Mw is below the upper limit of the said range, there exists a tendency for the solubility of a polymer (A) to a solvent or a developing solution to be excellent.

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

《Polyimide (A1)》

It is preferable that a polyimide (A1) contains the structural unit represented by a formula (A1).

[chemical 5]

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

R ¹ includes, for example, a divalent group represented by formula (a1).

[chemical 6]

In formula (a1), R ² is a single bond, oxygen atom, sulfur atom, sulfonyl, carbonyl, methylene, dimethylmethylene or bis(trifluoromethyl) methylene; R ³ are independently is a hydrogen atom, formyl, acyl or alkyl. Wherein, at least one of ^R3 is a hydrogen atom. n1 and n2 are each independently an integer of 0-2. Wherein, at least one of n1 and n2 is 1 or 2. When the total of n1 and n2 is 2 or more, a plurality of R ³ may be the same or different.

In ^R3 , the acyl group includes, for example: acetyl, propionyl, butyryl, isobutyryl and other groups with 2 to 20 carbon atoms; the alkyl group includes, for example, methyl, ethyl, n-propyl, isopropyl , n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl and other groups having 1 to 20 carbon atoms.

The divalent group represented by formula (a1) is preferably a divalent group having 1 to 4 hydroxyl groups, 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 divalent groups represented by the following formulas. In addition, in the following formula, two "-" protruding from an aromatic ring represent a bond.

[chemical 7]

[chemical 8]

[chemical 9]

[chemical 10]

The tetravalent organic group represented by X includes, for example, a tetravalent aliphatic hydrocarbon group, a tetravalent aromatic hydrocarbon group, and a group represented by the following formula (1). X is preferably a tetravalent organic group derived from tetracarboxylic dianhydride. Among these groups, a group represented by the following formula (1) is preferable.

[chemical 11]

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

The carbon number of a tetravalent aliphatic hydrocarbon group is 4-30 normally, Preferably it is 8-24. The carbon numbers of the tetravalent aromatic hydrocarbon group and the trivalent aromatic hydrocarbon group in the formula (1) are usually 6-30, preferably 6-24.

As a tetravalent aliphatic hydrocarbon group, a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aliphatic hydrocarbon group containing an aromatic ring in at least a part of molecular structure are mentioned, for example.

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

Quaternary alicyclic hydrocarbon groups include, for example, tetravalent groups derived from the following hydrocarbons: monocyclic groups such as cyclobutane, cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, cyclohexene, and cyclooctane. Formula hydrocarbons; Bicyclic hydrocarbons such as 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 ] Dodecane and other hydrocarbons with tricyclic or higher types.

An aliphatic hydrocarbon group containing an aromatic ring in at least a part of its molecular structure is, for example, preferably a group in which the number of benzene nuclei contained in the group is 3 or less, particularly preferably a group in which the number of benzene nuclei is 1. group. More specifically, quaternary groups derived from 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene, etc. .

In the description above, the tetravalent group derived from the hydrocarbon is a tetravalent group formed by removing 4 hydrogen atoms from the hydrocarbon. The removal site of four hydrogen atoms is a site which can form a tetracarboxylic dianhydride structure when these four hydrogen atoms are substituted with four carboxyl groups.

The tetravalent aliphatic hydrocarbon group is preferably a tetravalent group represented by the following formula. In addition, in the following formulae, four "-" protruding from the chain hydrocarbon group and the alicyclic ring represent bonding bonds.

[chemical 12]

As a tetravalent aromatic hydrocarbon group and the group represented by said formula (1), the tetravalent group represented by the following formula is mentioned, for example. In the following formulae, four "-" protruding from the aromatic ring represent bonding bonds.

[chemical 13]

A polyimide (A1) can be obtained by imidation of the polyimide precursor (A2) demonstrated below. The imidization here may proceed completely or partially. That is, the imidation ratio does not need to be 100%. Therefore, polyimide (A1) may further contain at least 1 sort(s) chosen from the structural unit represented by the formula (A2-1) demonstrated below, and the structural unit represented by formula (A2-2).

In the polyimide (A1), the imidization ratio is preferably 5% or more, more preferably 7.5% or more, and still more preferably 10% or more. The upper limit of the imidization ratio is preferably 50%, more preferably 30%. If the imidization rate is in the said range, it is preferable from the viewpoint of heat resistance and the solubility in a developing solution of an exposed part.

The imidation rate can be measured as follows, for example. First, the infrared absorption spectrum of the polyimide was measured to confirm the presence of absorption peaks (around 1780 cm ^-1 and around 1377 cm ^-1 ) of the imide structure due to the polyimide. Next, after heat-processing this polyimide at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again. Compare the peak intensity around 1377cm ^-1 before heat treatment and after heat treatment. Set the imidization rate of polyimide after heat treatment to 100%, and obtain the ^imidization rate of polyimide before heat treatment = {peak strength around 1377 cm before heat treatment/after heat treatment The peak intensity around 1377cm ^-1 }×100(%). In the measurement of the infrared absorption spectrum, for example, "NICOLET6700 Fourier Transform Infrared (FT-IR)" (manufactured by Thermoelectron Co., Ltd.) is used.

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

《Polyimide Precursor (A2)》

The polyimide precursor (A2) can generate polyimide (A1) by dehydration, cyclization (imidation), preferably the polyimide containing the structural unit represented by formula (A1) ( Compounds of A1). As a polyimide precursor (A2), polyamic acid and a polyamic acid derivative are mentioned, for example.

(polyamic acid)

Polyamic acid contains the structural unit represented by formula (A2-1).

[chemical 14]

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

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

(polyamic acid derivative)

A polyamic acid derivative is a derivative synthesize|combined by esterification etc. of polyamic acid. 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) contained in a polyamic acid with another group is mentioned, for example, Polyamic acid ester is preferable.

Polyamic acid ester is the polymer which esterified at least a part of the carboxyl group which polyamic acid has. As a polyamic acid ester, the polymer containing the structural unit represented by a formula (A2-2) which produces|generates the polyimide (A1) containing a structural unit represented by a formula (A1) is mentioned.

[chemical 15]

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

In polyamic acid ester, content of the structural unit represented by formula (A2-2) is 50 mass % or more normally, Preferably it is 60 mass % or more, More preferably, it is 70 mass % or more, Especially preferably, it is 80 mass % or more.

"Synthetic method of polyimide (A1) and polyimide precursor (A2)"

The polyamic acid which is a polyimide precursor (A2) can be obtained by polymerizing tetracarboxylic dianhydride, diamine containing diamine which has a hydroxyl group, and other diamine as needed, for example. The use ratio of these compounds is, for example, 0.3 mol to 4 mol of all the diamines with respect to 1 mol of the tetracarboxylic dianhydride, preferably substantially equimolar. In the said superposition|polymerization, it is preferable to heat the mixed solution of the said tetracarboxylic dianhydride and all the said diamines at 50 degreeC - 200 degreeC for 1 hour - 24 hours.

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

The synthesis of polyamic acid can be carried out by dissolving the diamine (A1-2) in the polymerization solvent, and then reacting the diamine (A1-2) with the acid dianhydride (A1-1), or by making the acid dianhydride (A1-1) is performed by making acid dianhydride (A1-1) and diamine (A1-2) react after dissolving in a polymerization solvent.

About the polyamic-acid derivative which is a polyimide precursor (A2), it can esterify the carboxyl group of the said polyamic acid, etc., and can synthesize|combine. The method of esterification is not specifically limited, A well-known method can be applied.

Polyimide (A1) can be synthesized, for example, by the following method: after the polyamic acid is synthesized by the method described above, the polyamic acid is dehydrated and cyclized (imidized); in addition, it can also be synthesized by using After the polyamic acid derivative is synthesized by the method, the polyamic acid derivative is imidized.

For the imidation reaction of polyamic acid and polyamic acid derivatives, known methods such as thermal imidation reaction and chemical imidation reaction can be applied. In the case of heat imidation reaction, it is preferable to heat the solution containing a polyamic acid and/or a polyamic acid derivative at 120 degreeC - 210 degreeC for 1 hour - 16 hours. If necessary, the imidization reaction may be performed while removing water in the system using an azeotropic solvent such as toluene, xylene, and mesitylene.

In addition, when diamine is used in excess relative to tetracarboxylic dianhydride, dicarboxylic anhydrides such as maleic anhydride can also be used as terminal groups for polyimide, polyamic acid, and polyamic acid derivatives. Capped capping agent.

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

[chemical 16]

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

Diamine (A1-2) is, for example, diamine represented by formula (a3).

[chemical 17]

H ₂ N—R ¹ —NH ₂ (a3)

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

Other diamines (A1-2') other than this (A1-2) can also be used together with diamine (A1-2). As other diamine (A1-2'), the at least 1 sort(s) of diamine selected from the group which does not have a hydroxyl group and is chosen from the aromatic diamine and aliphatic diamine is mentioned, for example.

The polyimide (A1) may also have a residue in which R ¹ in the formula (A1), formula (A2-1) and formula (A2-2) is changed to the other diamine (A1-2′) structural unit. Similarly, the polyimide precursor (A2) may also have a residue in which R in the formula (A2-1) and the formula ( ^A2-2 ) is changed to the other diamine (A1-2′) structural unit.

It is preferable that the polymerization solvent used for synthesizing a polyimide (A1) and a polyimide precursor (A2) is a low water-absorbing solvent which can dissolve the raw material for these synthesis, or the said (A1) and (A2). As the polymerization solvent, the same solvents as those exemplified as the solvent (E) described 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 polyimide (A1) or polyimide precursor (A2), and dissolving them in other step in solvent. Thereby, the productivity of the apparatus of this invention can be improved.

It is preferable that a polyimide (A1) and a polyimide precursor (A2) contain the said specific structure which has a hydroxyl group, and it has excellent solubility in the solvent (E) mentioned later by this. Therefore, these polymers are also dissolved in low water-absorbing solvents other than N-methylpyrrolidone (NMP), such as the solvent (E) described later. As a result, for example, by using a solvent other than NMP as a polymerization solvent for obtaining the polymer (A), the insulating film formed of the radiation-sensitive material can be lowered in water absorption.

"Acrylic resin (A3)"

Examples of monomers constituting the acrylic resin (A3) include those selected from alkyl (meth)acrylates, alicyclic group-containing esters of (meth)acrylic acid, and aryl-group-containing esters of (meth)acrylic acid. at least one monomer A of

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

In addition, examples of monomers constituting the above-mentioned (A3) include hydroxyalkyl (meth)acrylic acid esters, epoxy group-containing esters of (meth)acrylic acid, and oxetane-containing (meth)acrylic acid esters. At least one functional group-containing monomer C in the base ester.

Examples of alkyl (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylate Isopropyl acrylate, tert-butyl (meth)acrylate; alicyclic group-containing esters of (meth)acrylic acid include, for example, cyclohexyl (meth)acrylate, 2-methylcyclo(meth)acrylate Monocyclic hydrocarbyl esters such as hexyl ester, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate and other polycyclic esters; ( As for the aryl group-containing ester of meth)acrylic acid, phenyl (meth)acrylate and benzyl (meth)acrylate are mentioned, for example.

Examples of unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, and 2-(meth)acryloyloxyethylsuccinic acid; examples of unsaturated dicarboxylic acids include maleic acid and fumaric acid , citraconic acid, mesaconic acid, and itaconic acid; examples of unsaturated dicarboxylic anhydrides include maleic anhydride and itaconic anhydride.

The hydroxyalkyl ester of (meth)acrylic acid can enumerate, for example, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-2-hydroxypropyl ester; base) glycidyl acrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, (meth)acrylate-3,4-epoxybutyl , (meth)acrylate-6,7-epoxyheptyl ester, α-ethylacrylate-6,7-epoxyheptyl ester, (meth)acrylate-3,4-epoxycyclohexylmethyl ester; (form Base) Oxetanyl esters of acrylic acid include, for example, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)propene Acyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetanes.

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

In particular, in the acrylic resin (A3), the total content of the structural units derived from the epoxy group-containing ester of (meth)acrylic acid and the oxetanyl ester of (meth)acrylic acid is preferably 10% by mass to 70%. % by mass, more preferably 20% by mass to 50% by mass. If the structural unit is within the above range, the hardening reaction will proceed sufficiently when the coating film formed by the radiation-sensitive material is heated, and the heat resistance and surface hardness of the obtained pattern will tend to be sufficient, and there will also be a tendency for the radiation-sensitive There is also a tendency that the storage stability of the active material is excellent.

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

Examples of solvents used in 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; Glycol ether acetates such as acetate and propylene glycol monomethyl ether acetate; in addition, aromatic hydrocarbons, ketones, and esters are exemplified.

Acrylic resin (A3) can be synthesize|combined by radical polymerization of the said monomer, for example. As a polymerization catalyst during radical polymerization, a common radical polymerization initiator can be used, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethyl valeronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, lauroyl peroxide, trimethyl peroxide tert-butyl acetate, 1,1-bis-(tert-butylperoxy)cyclohexane and other organic peroxides and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a redox (Redox) type initiator may be obtained by combining a peroxide and a reducing agent.

"Polysiloxane (A4)"

As polysiloxane (A4), the polysiloxane obtained by making the organosilane represented by a formula (a4) react is mentioned, for example.

[chemical 18]

In formula (a4), R ¹ is a hydrogen atom, an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons, an aryl-containing group with 6 to 15 carbons, an aryl-containing group with 2 to 15 carbons A group of an epoxy ring or a group (substituent) obtained by substituting one or more hydrogen atoms contained in the alkyl group (substituent) may be the same when there are a plurality of R ¹ It can also be different; R2 is a ^hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons, or an aryl group with 6 to 15 carbons. When there are multiple ^R2s , they can be the same or can be different; n is an integer of 0-3.

The substituent is, for example, at least one selected from a halogen atom, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, and a (meth)acryloyloxy group.

Examples of the alkyl group and its substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-decyl, trifluoromethyl, 2,2,2- Trifluoroethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatopropyl, 3-(meth)acryloyloxypropyl.

As an alkenyl group, a vinyl group is mentioned, for example.

Examples of aryl-containing groups include: aryl groups such as phenyl, tolyl, and naphthyl; hydroxyaryl groups such as p-hydroxyphenyl; aralkyl groups such as benzyl and phenethyl; 1-(p-hydroxyphenyl) hydroxyaralkyl groups such as ethyl and 2-(p-hydroxyphenyl)ethyl; 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl.

Examples of epoxy ring-containing groups include 3-glycidyloxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.

As an acyl group, an acetyl group is mentioned, for example.

As an aryl group, a phenyl group is mentioned, for example.

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

Examples of organosilanes include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, Methyltriisopropoxysilane, Methyltri-n-butoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltriisopropoxysilane, Ethyltri-n-butoxysilane , n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, Decyltrimethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxy phenylsilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyl Trimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane , Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-shrink Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxy Trifunctional silanes such as trifunctional silane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethylsilane Difunctional silanes such as oxysilane and monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane. Among these organosilanes, trifunctional silanes are preferable from the viewpoint of the crack resistance and hardness of the insulating film.

Organosilanes may be used alone or in combination of two or more.

In terms of both crack resistance and hardness of the insulating film, the content of the phenyl group contained in the polysiloxane (A4) is preferably 20 mol to 70 mol, more preferably 35 moles to 55 moles. When the phenyl group content is below the upper limit, an insulating film with high hardness tends to be obtained, and when the phenyl group content is above the lower limit, an insulating film with high crack resistance may be obtained. Propensity. The phenyl group content is obtained by measuring the ²⁹ Si-NMR spectrum of polysiloxane (A4), for example, from the ratio of the peak area of Si to which the phenyl group is bonded to the peak area of Si to which the phenyl group is not bonded. .

Polysiloxane (A4) can be obtained by hydrolyzing and partially condensing the said organosilane, for example. A usual method can be used for hydrolysis and partial condensation. For example, a solvent, water, and optionally a catalyst are added to organosilane, followed by heating and stirring. During stirring, hydrolysis by-products such as alcohol and condensation by-products such as water may be distilled off as necessary. The reaction temperature is not particularly limited, but is usually in the range of 0°C to 150°C. The reaction time is also not particularly limited, and is usually in the range of 1 hour to 10 hours.

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

It is preferable that the addition amount of a solvent is 10 mass parts - 1000 mass parts with respect to 100 mass parts of organosilanes. Moreover, it is preferable that the addition amount of the water used for a hydrolysis reaction is 0.5 mol - 2 mol with respect to 1 mol of hydrolyzable groups.

As a catalyst, an acid catalyst and an alkali catalyst are mentioned, for example. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or its anhydride, ion exchange resin, and the like. Examples of base catalysts include: triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, Alkoxysilanes having amino groups, ion exchange resins, and the like. It is preferable that the addition amount of a catalyst is 0.01 mass part - 10 mass parts with respect to 100 mass parts of organosilanes.

"Polybenzoxazole (A5-1)"

It is preferable that polybenzoxazole (A5-1) contains the structural unit represented by formula (a5-1). Hereinafter, the structural unit represented by formula (a5-1) is also called "structural unit (a5-1)".

[chemical 19]

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

In formula (a5-1), X1 is preferably ^a tetravalent group containing at least one aromatic ring, more preferably a group with a linear structure, further preferably a group with 1 to 4 aromatic rings, especially It is preferably a group having two aromatic rings. Polybenzoxazole (A5-1) having such a structure is excellent in rigidity.

In addition, the aromatic ring contained in X1 may be either ^a substituted or unsubstituted ring. Examples of substituents include -OH, -COOH, alkyl, alkoxy, and alicyclic hydrocarbon groups. N and O bonded to X ¹ are, for example, bonded to adjacent carbon atoms on the aromatic ring in X ¹ to form a benzoxazole ring.

When X1 contains two or more aromatic rings, the plurality ^of aromatic rings may form either a linked polycyclic ring system or a condensed polycyclic ring system, preferably a linked polycyclic ring system structure. The polybenzoxazole (A5-1) which has such a structure is excellent in both light-shielding property and rigidity.

The total carbon number of X ¹ is preferably 6-24, more preferably 6-20, and still more preferably 6-18. Thereby, the said effect can be exhibited more notably.

The structure of X1 includes, for example, ^a monocyclic structure such as a benzene ring, a condensed polycyclic structure such as a naphthalene ring, and a linked polycyclic structure such as a group represented by the formula (g1). Among these structures, the group represented by the formula (g1) is preferable.

[chemical 20]

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

Specific examples ^of the structure of X1 include, for example, a tetravalent group represented by the following formula. In addition, in the following formula, four "-" protruding from an aromatic ring represent a bond.

[chem 21]

In formula (a5-1), Y ¹ is preferably a divalent group containing at least one ring selected from alicyclic rings and aromatic rings, more preferably a group with 1 to 4 aromatic rings, especially It is preferably a group having two aromatic rings. Polybenzoxazole (A5-1) having such a structure is excellent in rigidity and light resistance.

In addition, the alicyclic ring and aromatic ring contained in ^Y1 may be either substituted or unsubstituted rings. Examples of substituents include -OH, -COOH, alkyl, alkoxy, alkoxycarbonyl, and alicyclic hydrocarbon groups.

When ^Y1 contains two or more of the above rings, the plurality of rings may form either a linked polycyclic ring system or a condensed polycyclic ring system, preferably a linked polycyclic ring system structure. The polybenzoxazole (A5-1) which has such a structure is excellent in both light-shielding property and rigidity.

The total carbon number of ^Y1 is preferably 4-24, more preferably 4-15, and still more preferably 6-12. Thereby, the said effect can be exhibited more notably.

The structure of ^Y1 includes, for example, aromatic structures such as monocyclic structures such as benzene rings, condensed polycyclic structures such as naphthalene rings, and linked polycyclic structures such as groups represented by formula (g2); Alicyclic structure. Among these structures, the group represented by the formula (g2) is preferable.

[chem 22]

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

Specific examples of the structure of ^Y1 include, for example, divalent groups represented by the following formulas. In addition, in the following formula, two "-" protruding from an aromatic ring and an alicyclic ring represent a bond.

[chem 23]

[chem 24]

The polybenzoxazole (A5-1) can be obtained by the cyclization reaction of the polybenzoxazole precursor (A5-2) demonstrated below. The cyclization reaction here can proceed completely or partially. That is, the cyclization rate may not be 100%. Therefore, polybenzoxazole (A5-1) may further contain the structural unit represented by the formula (a5-2) demonstrated below. Hereinafter, the structural unit represented by formula (a5-2) is also called "structural unit (a5-2)".

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

The cyclization rate can be measured, for example, as follows. First, the infrared absorption spectrum of polybenzoxazole was measured to confirm the presence of the absorption peak of the benzoxazole ring (near 1557 cm ^-1 , 1574 cm ^-1 ). Next, after heat-processing this polybenzoxazole at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again. Compare the peak intensity around 1554 cm ^-1 before heat treatment and after heat treatment. Set the cyclization rate of polybenzoxazole after heat treatment to 100%, and calculate the cyclization rate of polybenzoxazole before heat treatment = {peak intensity around 1554 cm ⁻¹ before heat treatment/1554 cm after heat treatment Peak intensity around ^-1 }×100(%). In the measurement of the infrared absorption spectrum, for example, "NICOLET6700FT-IR" (manufactured by Thermoelectron Co., Ltd.) is used.

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

"Polybenzoxazole Precursor (A5-2)"

The polybenzoxazole precursor (A5-2) can generate polybenzoxazole (A5-1) by dehydration and cyclization, preferably polybenzoxazole (A5-1) containing structural unit (a5-1). - Compounds of 1). The precursor (A5-2) contains, for example, a structural unit represented by the formula (a5-2).

[chem 25]

In the formula (a5-2), X1 is ^a tetravalent organic group having an aromatic ring, preferably a tetravalent group containing at least one aromatic ring. N and OH bonded to X1 are bonded to adjacent carbon atoms ^on the same aromatic ring.

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

The tetravalent organic group represented by X1 and the divalent organic group represented by ^Y1 include the same groups as those exemplified as X1 and ^Y1 in the formula ( ^{a5-1 )} , respectively.

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

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

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

The usage ratio is, for example, 0.5 mol to 4 mol of the diamine, preferably 1 mol to 2 mol, based on 1 mol of the total amount of the dicarboxylic acid, the diester body, and the dihalide. In the polymerization, it is preferable to heat the mixed solution at 50° C. to 200° C. for 1 hour to 72 hours.

The polybenzoxazole (A5-1) can be synthesized, for example, by synthesizing the polybenzoxazole precursor (A5-2) by the method described above, and then the polybenzoxazole precursor (A5-2) Carry out dehydration and cyclization.

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

Moreover, it is preferable to block the terminal group of polybenzoxazole and its precursor from a viewpoint of storage stability. Examples of the end-blocking agent include dicarboxylic anhydrides such as maleic anhydride and 5-norbornene-2,3-dicarboxylic anhydride. For example, after synthesizing a polybenzoxazole precursor containing a structural unit represented by formula (a5-2), it is preferable to block the terminal amino group contained in the precursor as an amide using a blocking agent.

"Polyolefin (A6)"

The polyolefin (A6) includes, for example, a cyclic olefin polymer having a protic polar group. The term "protic polar group" refers to an atomic group in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. The atom belonging to the 15th or 16th group of the periodic table is preferably an atom belonging to the 2nd or 3rd period of the 15th or 16th group of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, especially It is preferably an oxygen atom.

The protic polar group can enumerate, for example: polar groups containing oxygen atoms such as hydroxyl, carboxyl (hydroxycarbonyl), sulfonic acid group, phosphoric acid group; primary amino group, secondary amino group, primary amido group, secondary amido group ( Polar groups containing nitrogen atoms such as imide groups); polar groups containing sulfur atoms such as thiol groups. Among these groups, polar groups containing oxygen atoms are preferred, hydroxyl groups and carboxyl groups are more preferred, phenolic hydroxyl groups and carboxyl groups are further preferred, and carboxyl groups are especially preferred.

In addition, in the following description, polar groups other than protic polar groups include, for example, acyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, halogen atoms, cyano groups, alkoxy groups, tertiary amino groups, ( Meth)acryloyl group, carbonyl group, sulfonyl group, N-substituted imide group, epoxy group, carbonyloxycarbonyl group (dicarboxylic acid anhydride structure). Among these groups, acyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, N-substituted imide groups, halogen atoms, and cyano groups are preferred, and acyloxy groups, alkoxycarbonyl groups, and aryloxy groups are more preferred. A carbonyl group and an N-substituted imide group are particularly preferably an N-substituted imide group.

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

Hereinafter, the structural unit derived from monomer A is also called "monomer A unit".

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

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

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

Examples of monomers forming a cyclic olefin polymer having a protic polar group include: a cyclic olefin (a) having a protic polar group, a cyclic olefin having a polar group other than a protic polar group ( b) Cyclic olefins (c) having no polar groups, and monomers (d) other than cyclic olefins. The monomer (d) may have a protic polar group or other polar groups, or may not have a polar group at all. Said cyclic olefin (a) - cyclic olefin (c) are also called "monomer (a) - monomer (c)", respectively.

The cyclic olefin polymer having a protic polar group preferably contains monomer (a), at least one selected from monomer (b) and monomer (c), and optionally monomer (d), Furthermore, it is preferable to contain a monomer (a), a monomer (b), and an optional monomer (d).

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

[chem 26]

In formula (a6-1), R ^a1 to R ^a4 are each independently a hydrogen atom or -X _n -R ^a5 . X is a divalent organic group. n is 0 or 1. R ^a5 is an alkyl group, an aromatic group, or the aforementioned protic polar group, and each of the alkyl group and the aromatic group may have a substituent. At least one of R ^a1 to R ^a4 is a -X _n -R ^a5 group in which R ^a5 is a protic polar group. m is an integer of 0-2, preferably 0 or 1. The divalent organic group of X includes, for example, an alkylene group having 1 to 18 carbons such as a methylene group or an ethylene group, and an arylene group having 6 to 24 carbons such as a phenylene group.

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

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

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

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

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

[chem 27]

In formula (b6-1), R ^b1 is a polar group other than the protonic polar group, preferably an acyloxy group having 2 to 12 carbons such as acetoxy, methoxycarbonyl, ethoxycarbonyl, Alkoxycarbonyl with 2 to 12 carbons such as n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, etc., and 7 carbons such as phenoxycarbonyl ~24 aryloxycarbonyl groups, halogen atoms such as cyano groups or chlorine atoms. R ^b2 is a hydrogen atom or an alkyl group having 1 to 18 carbons such as a methyl group. R ^b3 and R ^b4 are hydrogen atoms. m is an integer of 0-2, preferably 0 or 1.

In addition, R ^b1 to R ^b4 can form a 3- to 5-membered heterocyclic ring structure containing an oxygen atom or a nitrogen atom as a ring-forming atom together with these two bonded carbon atoms in any combination.

As a three-membered heterocyclic structure, an epoxy structure etc. are mentioned. Examples of 5-membered heterocyclic structures include: dicarboxylic acid anhydride structure [-C(=O)-OC(=O)-], dicarboxylic imide structure [-C(=O)-NR ^b5 -C(=O) -]Wait. R ^b5 is an aryl group having 6 to 24 carbons such as phenyl, naphthyl, anthracenyl and the like. Among these structures, a dicarboximide structure is preferable.

As the monomer (b), N-phenyl-(5-norbornene-2,3-dicarboxyimide) is mentioned, for example.

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

Examples of the monomer (c) include: bicyclo[2.2.1]hept-2-ene (common name: norbornene), 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl -bicyclo[2.2.1]hept-2-ene, 5-ethylene-bicyclo[2.2.1]hept-2-ene, 5-methine-bicyclo[2.2.1]hept-2-ene, 5 -Vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 ^2,5 ]dec-3,7-diene (common name: dicyclopentadiene), tetracyclo[8.4. 0.1 11, ¹⁴ .0 3, 7] pentadec-3, 5, 7, 12, 11- ^pentaene , tetracyclo [4.4.0.1 ^{2, 5} .1 ⁷ , 10] dec-3-ene (common name: Tetracyclododecene), 8-methyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dode-3-ene, 8-methine-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dode-3-ene, 8-ethylene-tetracyclo[4.4. 0.1 ^2,5 .1 ^7,10 ]dode-3-ene, 8-vinyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene, 8-propenyl-tetracyclo Cyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ]pentadeca-3,10-diene , cyclopentene, cyclopentadiene, 1,4-methylbridge-1,4,4a,5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo[4.4.0.1 ^2,5 .1 ^{7 , 10} ] dode-3-ene, tetracyclo [9.2.1.0 ² , 10 .0 ^{3, 8} ] tetradeca-3, 5, 7, 12-tetraene (also known as 1,4-methylbridge-1 , 4,4a,9a-tetrahydro-9H-fluorene), pentacyclo[7.4.0.1 ^3,6 .1 ^10,13 .0 ^2,7 ]pentadeca-4,11-diene, pentacyclo[9.2. 1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] Pentadec-5,12-diene.

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

Monomers (d) other than cyclic olefins include, for example, chain olefins. Examples of chain olefins include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene ene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, α-olefins with 2 to 20 carbons such as 1-octadecene and 1-eicosene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1, Non-conjugated dienes such as 4-hexadiene, 1,5-hexadiene, and 1,7-octadiene.

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

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

The polymerization method for polymerizing the monomer (a) together with optionally at least one monomer selected from the monomer (b) to monomer (d) may be carried out according to a conventional method, for example, ring-opening Polymerization and addition polymerization.

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

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

Hydrogenation of the polymer obtained by polymerizing the monomer is usually performed using a hydrogenation catalyst. As the hydrogenation catalyst, for example, those generally used in the hydrogenation of olefin compounds can be used. Specific examples thereof include Ziegler-type homogeneous catalysts, noble metal complex catalysts, and supported noble metal catalysts.

Among these hydrogenation catalysts, noble metal complex catalysts such as rhodium and ruthenium are preferred in that they do not cause side reactions such as functional group modification and can selectively hydrogenate the carbon-carbon unsaturated bonds in the polymer. Particularly preferred are nitrogen-containing heterocyclic carbene compounds or phosphine-coordinated ruthenium catalysts with high electron-donating properties.

A cyclic olefin polymer having a protic polar group can also be obtained by introducing a protic polar group into a cyclic olefin polymer having no protic polar group using a known modifier, and optionally carry out hydrogenation. Hydrogenation can also be performed on the polymer before introduction of the protic polar group. In addition, the cyclic olefin polymer having a protic polar group may be further modified to introduce a protic polar group.

The cyclic olefin polymer not having a protic polar group can be obtained, for example, by polymerizing at least one monomer selected from monomers (b) to (c) and optionally monomer (d). .

As a modifying agent for introducing a protic polar group, generally, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule can be used. Examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, and brassic acid. acid), maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid and other unsaturated carboxylic acids; allyl alcohol, methyl vinyl methanol, croton Alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3 -buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, Unsaturated alcohols such as 4-penten-1-ol, 4-methyl-4-penten-1-ol, and 2-hexen-1-ol.

The modification reaction of the cyclic olefin polymer using the modifier may be carried out according to a conventional method, and the reaction is usually carried out in the presence of a radical generating agent.

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

[chem 28]

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

"Cardo Resin (A7)"

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

As the cardo resin, it is preferable to use a cardo resin having at least one group selected from carboxyl groups and phenolic hydroxyl groups from the viewpoint of alkali solubility.

Specific examples of the skeleton structure in which two ring structures are bonded to ring carbon atoms constituting the ring structure include: 9,9-bis(phenyl)fluorene skeleton, 9,9-bis(hydroxyphenyl)fluorene Skeleton, 9,9-bis(cyanophenyl or aminoalkylphenyl)fluorene skeleton, 9,9-bis(phenyl)fluorene skeleton with epoxy group, 9,9-bis(phenyl)fluorene skeleton with (meth)acrylic group - Bis(phenyl)fluorene skeleton.

The cardo resin is formed by polymerizing the skeleton having the cardo structure through a reaction or the like between functional groups bonded thereto. The cardo resin has, for example, a structure in which a main chain and a cyclic structure as a bulky side chain are linked via one element (cardo structure), and has a cyclic structure in a direction substantially perpendicular to the main chain.

The cardo resin is, for example, a polymer obtained by polymerizing a monomer having a cardo structure, and may be a copolymer with other copolymerizable monomers. The polymerization method of the said monomer should just follow a conventional method, for example, a ring-opening polymerization method, an addition polymerization method, etc. can be used.

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

Examples of monomers having a cardo structure include: 9,9-bis(4-glycidyloxyphenyl)fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)phenyl] Cardo structure-containing epoxy compounds such as fluorene; (meth)acrylic compounds containing cardo structures such as compounds represented by the following formula; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9- Cardo-containing bisphenols such as bis(4-hydroxy-3-methylphenyl)fluorene.

[chem 29]

In the formula, A is an alkylene group with 2 to 6 carbons such as ethylene group and propylene group, and the alkylene group may also have a hydroxyl group, such as 2-hydroxyl-1,3-propanediyl group, etc., and R is hydrogen atom or methyl group, p and q are integers of 1-30.

From the viewpoint of alkali solubility, the above-exemplified monomers having a cardo structure may also have a carboxyl group and a phenolic hydroxyl group selected from the fluorene ring or the aromatic ring bonded to the carbon atom at the 9-position of the fluorene ring. at least one group.

As the cardo resin, a commercially available product can also be used. Examples include: Ogsol CR-TR1, Ogsol CR-TR2, Ogsol CR-TR3, Ogsol CR-TR3 manufactured by Osaka Gas Chemical Co., Ltd. Polyester compounds with cardo structure, such as TR4, Ogsol CR-TR5, Ogsol CR-TR6, etc.

[Sensitizer (B)]

As a photosensitive agent (B), a photoacid generator and a photoradical polymerization initiator are mentioned, for example. When the radiation-sensitive material contains a photosensitizer (B), it can exhibit radiation-sensitive characteristics and can have favorable radiation sensitivity.

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

The content of the photosensitizer (B) in the radiation-sensitive material is usually 5 to 100 parts by mass, preferably 10 to 65 parts by mass, more preferably 15 parts by mass relative to 100 parts by mass of the polymer (A). ~60 parts by mass. By setting the content of the photosensitizer (B) within the above range, the difference in solubility between the portion irradiated with radiation and the portion not irradiated with an alkaline aqueous solution or the like as a developing solution can be increased, thereby improving patterning performance.

"Photoacid Generator"

A photoacid generator is a compound that generates an acid by treatment including irradiation with radiation. Examples of radiation include visible rays, ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams.

Examples of photoacid generators include quinone diazide compounds, oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, and sulfonate esters. Compounds, Carboxylate Compounds. By using these compounds, a material exhibiting positive radiation-sensitive properties can be obtained.

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

<Quinone diazide compound>

A quinonediazide compound generates a carboxylic acid by a treatment including irradiation with radiation and development using an aqueous alkaline solution. As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "core") and a 1,2-naphthoquinonediazidesulfonyl halide is exemplified.

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

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

Tetrahydroxybenzophenones include, for example: 2,2′,4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4 '-Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxydi Benzophenone.

Pentahydroxybenzophenone includes, for example, 2,3,4,2',6'-pentahydroxybenzophenone.

Examples of hexahydroxybenzophenone include: 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxydiphenone Benzophenone.

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

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

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

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

In the condensation reaction of phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinone diazide sulfonyl halide, with respect to the OH group in phenolic compound or alcoholic compound, can use the equivalent preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonyl halide. The condensation reaction can be implemented by a known method.

As the quinonediazide compound, 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the illustrated core is changed to an amide bond, such as 2,3,4-triaminobenzidine, can also be preferably used. Ketone-1,2-naphthoquinonediazide-4-sulfonic acid amide, etc.

<Other examples>

Specific examples of the oxime sulfonate compound include compounds described in publications such as JP 2011-227106, JP 2012-234148, and JP 2013-054125. Specific examples of onium salts include, for example, Japanese Patent No. 5208573, Japanese Patent No. 5397152, Japanese Patent No. 5413124, Japanese Patent Laid-Open No. 2004-2110525, Japanese Patent Laid-Open No. 2008-129423, and Japanese Patent Laid-Open No. 2010. Compounds described in publications such as -215616 and Japanese Patent Laid-Open No. 2013-228526.

Specific examples of other acid generators include, for example, Japanese Patent No. 49242256, Japanese Patent Laid-Open No. 2011-064770, Japanese Patent Laid-Open No. 2011-232648, Japanese Patent Laid-Open No. 2012-185430, Japanese Patent Laid-Open No. 2013- Compounds described in publications such as No. 242540.

"Photo Radical Polymerization Initiator"

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

Examples of photoradical polymerization initiators include: 2,2'-bis(2,4-dichlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl )-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dimethylphenyl)-4,5,4',5 '-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-methylphenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole , 2,2'-diphenyl-4,5,4',5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; diethoxyacetophenone, 2-(dimethyl Amino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkyl phenone compounds; 2,4,6 -Acylphosphine oxide compounds such as trimethylbenzoyldiphenylphosphine oxide; 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5- Triazine compounds such as triazine and 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine; and benzoin compounds such as benzoin; benzophenone , methyl phthaloylbenzoate, 4-phenylbenzophenone and other benzophenone compounds.

[Resin (C)]

The resin (C) is at least one selected from the group consisting of novolak resins, resol resins, and condensates of resol resins. Among these resins, novolak resins are preferable at the point of having good alkali solubility (developability).

The resin (C) is a substance that develops color by heating. It is presumed that in the method of forming an insulating film described later, the coating film itself formed of a radiation-sensitive material containing resin (C) before exposure does not have light-shielding properties at a wavelength of 300nm to 400nm, but after exposure and development, the coating film itself does not have light-shielding properties. The resin (C) is ketoneized by heating, and the resulting insulating film has light-shielding properties at the above-mentioned wavelength. By using such a resin (C), the radiation-sensitive material can realize the provision of light-shielding property and alkali developability simultaneously.

For example, the light-shielding property may not be imparted at a heating temperature of about 60°C to 130°C during pre-baking, and the light-shielding property may be imparted at a heating temperature of about 130°C to 300°C or lower during post-baking.

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

[chem 30]

In the formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, R1 is ^a methylene group, an alkylene group with 2 to 30 carbons, a divalent alicyclic hydrocarbon group with 4 to 30 carbons, carbon An aralkylene group with a number of 7 to 30 or a group represented by -R ² -Ar-R ² - (Ar is a divalent aromatic group, R ² is independently a methylene group or a methylene group with a carbon number of 2 to 20 alkyl). In addition, one hydrogen atom of the methylene group may be substituted with a cyclopentadienyl group, an aromatic ring, a group containing an aromatic ring, or a heterocyclic ring containing a nitrogen atom, a sulfur atom, an oxygen atom, or the like.

Examples of alkylene groups with ² to 30 carbon atoms in R1 include: ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, and undecane Base, Dodecyl, Tetradecyl, Hexadecyl, Octadecyl, Nonadecyl, Eicosanyl, Icodecyl, Docosane group, triacyl, tetracosyl, pentapentacyl, hexadecyl, heptacyl, octadecyl, nonacacyl , Triadylene.

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

Examples of the aralkylene group having 7 to 30 carbon atoms in R ¹ include benzylidene group, phenylethylene group, benzylpropylene group, and naphthylenemethylene group.

The group represented by -R ² -Ar-R ² - in R ¹ includes, for example, a group represented by -CH ₂ -Ph-CH ₂ - (Ph is phenylene).

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

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

[chem 31]

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

a1 is an integer of 1-4. b1 is an integer of 0-3. a2-a5 and b2-b5 are each independently an integer of 0-4. a6 and b6 are integers of 0-2.

Among them, a2+a3 is an integer between 1 and 6, b2+b3 is an integer between 0 and 5, a2+a3+b2+b3 is an integer between 1 and 6, and a4+a5+a6 is 1 or more , an integer of 8 or less, b4+b5+b6 is an integer of 0 to 7, and a4+a5+a6+b4+b5+b6 is an integer of 1 to 8. In addition, 1≤a1+b1≤4, a2+b2≤4, a3+b3≤4, a4+b4≤4, a5+b5≤4, a6+b6≤2.

a1, a2+a3, and a4+a5+a6 are each preferably an integer of 1-3.

R is a hydrocarbon group having 1 to 20 carbons, preferably a hydrocarbon group having 1 to 10 carbons, or an alkoxy group having 1 to 20 carbons, preferably alkoxy having 1 to 10 carbons, and when there are multiple Rs, they may be the same or different. . Examples of the hydrocarbon group include alkyl groups such as methyl, propyl, isopropyl, and tert-butyl. As an alkoxy group, a methoxy group is mentioned, for example.

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

[chem 32]

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

From the viewpoint of imparting light-shielding properties, heat resistance, and alkali developability, the above-mentioned A is preferably a group represented by formula (c1-2), formula (c1-3) or formula (c1-4), more preferably is a group represented by formula (c1-2) or formula (c1-3).

The resin (C) is preferably a novolac resin at the point of having good alkali solubility (developability). By making the radiation sensitive material contain an alkali-soluble novolak resin, a radiation sensitive material with good resolution can be obtained.

The novolac resin can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst, and distilling off unreacted components if necessary. Regarding the reaction conditions, phenols and aldehydes are reacted in a solvent, usually at 60° C. to 200° C. for about 1 hour to 20 hours. For example, it can be synthesized by the methods described in JP-A-47-15111, JP-A-63-238129, and the like.

The resol resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a base catalyst, and distilling off unreacted components if necessary. Regarding the reaction conditions, phenols and aldehydes are reacted in a solvent usually at 40° C. to 120° C. for about 1 hour to 20 hours. In this way, for example, a soluble compound in which a group derived from an aldehyde (for example, -R ¹ -OH, R ¹ has the same meaning as R ¹ in formula (C1)) is bonded to an aromatic ring contained in phenols can be obtained. Phenolic Resin. The condensate of the resol resin can be obtained by heating or adding an acid to the resol resin to perform a dehydration condensation reaction. This reaction proceeds by dehydration condensation of groups derived from aldehydes contained in the resole resin. When performing the said reaction by heating, a resole phenolic resin or its solution is made to react at 60 degreeC - 200 degreeC normally for 1 hour - about 20 hours. The resole resin and its condensate can be synthesized by methods described in, for example, JP 3889274, JP 4013111, JP 2010-111013 and the like.

Examples of phenols include:

Compounds having 1 to 4 hydroxyl groups, preferably 1 to 3, and 1 benzene nucleus, specifically phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5 -Dimethylphenol, 3,4-Dimethylphenol, 3,5-Dimethylphenol, 2,4-Dimethylphenol, 2,6-Dimethylphenol, 2,3,5-Trimethylphenol phenylphenol, 2,3,6-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-methylresorcinol, 4-methylresorcinol Diphenol, 5-methylresorcinol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propyl Phenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 5-isopropyl -2-Methylphenol;

Compounds (naphthalene-type compounds) having 1 to 6 hydroxyl groups, preferably 1 to 3, and 2 benzene nuclei, specifically monohydroxynaphthalene such as 1-naphthol and 2-naphthol, and 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 other dihydroxynaphthalene;

Compounds with 1 to 8 hydroxyl groups, preferably 1 to 3, and 3 benzene nuclei (anthracene-type compounds or phenanthrene-type compounds), specifically, monohydroxyl groups such as 1-hydroxyanthracene, 2-hydroxyanthracene, and 9-hydroxyanthracene Anthracene, 1,4-dihydroxyanthracene, 9,10-dihydroxyanthracene, 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, 1,2,7-trihydroxyanthracene Anthracene and other trihydroxy anthracene, 1-hydroxy phenanthrene and other hydroxy phenanthrene.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and terephthalaldehyde.

When synthesizing the resin (C), the usage-amount of aldehydes is 0.3 mol or more normally with respect to 1 mol of phenols, Preferably it is 0.4 mol-3 mol, More preferably, it is 0.5 mol-2 mol.

As an acid catalyst at the time of synthesis|combination of a novolac resin, hydrochloric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid are mentioned, for example. As an alkali catalyst at the time of synthesis|combination of a resol resin, ammonia water and a tertiary amine are mentioned, for example.

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

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

In the radiation-sensitive material, the content of the resin (C) is usually 2 to 200 parts by mass, preferably 3 to 160 parts by mass, more preferably 4 to 100 parts by mass relative to 100 parts by mass of the polymer (A). 140 parts by mass, especially preferably 10 to 100 parts by mass. When content of resin (C) is more than the lower limit of the said range, the effect of light-shielding property and developability provision by resin (C) will be exhibited easily. When content of resin (C) is below the upper limit of the said range, there will be little possibility of causing the deterioration of the low water absorption property of an insulating film, and the fall of heat resistance.

[Crosslinking agent (D)]

The crosslinking agent (D) is a compound having a crosslinkable functional group. As a crosslinking agent (D), the compound which has 2 or more crosslinkable functional groups in one molecule is mentioned, for example.

In the case of using an insulating film containing a radiation-sensitive material as a constituent of an organic EL element, in the organic EL element, if the organic light-emitting layer is in contact with moisture, it will deteriorate, so it is preferable to use a crosslinking agent (D) to reduce the insulating film. water absorption of the membrane. In addition, a negative radiation-sensitive material can be obtained by using a photoradical polymerization initiator as the photosensitizer (B) and a polymerizable carbon-carbon double bond-containing compound as the crosslinking agent (D).

Examples of crosslinkable functional groups include: isocyanate group and blocked isocyanate group, oxetanyl group, glycidyl ether group, glycidyl ester group, glycidyl amino group, methoxymethyl group, ethoxymethyl group, benzyloxy Acylmethyl, Acetoxymethyl, Benzoyloxymethyl, Formyl, Acetyl, Dimethylaminomethyl, Diethylaminomethyl, Dihydroxymethylaminomethyl, Dihydroxyethyl Aminomethyl group, morpholinomethyl group; groups having polymerizable carbon-carbon double bonds, such as vinyl group, vinylidene group and (meth)acryloyl group.

Examples of the crosslinking agent (D) include oxetanyl group-containing compounds, bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, and novolac resin-based epoxy compounds. , Resole resin-based epoxy compounds, poly(hydroxystyrene)-based epoxy compounds, methoxymethyl-containing phenol compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, Methylol-containing urea compounds, methylol-containing phenol compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing urea compounds, Alkoxyalkyl phenolic compounds, carboxymethyl-containing melamine resins, carboxymethyl-containing benzoguanamine resins, carboxymethyl-containing urea resins, carboxymethyl-containing phenol resins, carboxymethyl-containing melamine Compounds, carboxymethyl-containing benzoguanamine compounds, carboxymethyl-containing urea compounds, carboxymethyl-containing phenol compounds, polymerizable carbon-carbon double bond-containing compounds.

Examples of oxetanyl-containing compounds include: 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 3,7-bis(3-oxetane Base)-5-oxanonane, 3,3′-[1,3-(2-methenyl)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 [(3-ethyl-3 -oxetanyl)methyl]ether, tetraethylene glycol bis[(3-ethyl-3-oxetanyl)methyl]ether, tricyclodecanediyl dimethylenebis[( 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, dipentaerythritol hexa[(3-ethyl-3-oxetanyl)methyl]ether, dipentaerythritol penta[(3-ethyl- 3-oxetanyl)methyl]ether, dipentaerythritol tetrakis[(3-ethyl-3-oxetanyl)methyl]ether.

The oxetanyl-containing compound further includes: the reaction product of dipentaerythritol hexa[(3-ethyl-3-oxetanyl)methyl] ether and caprolactone, dipentaerythritol penta[(3-ethyl The reaction product of base-3-oxetanyl)methyl]ether and caprolactone, di-trimethylolpropane tetrakis[(3-ethyl-3-oxetanyl)methyl]ether, The reaction product of bisphenol A bis[(3-ethyl-3-oxetanyl)methyl]ether and ethylene oxide, bisphenol A bis[(3-ethyl-3-oxetanyl) ) methyl] ether and propylene oxide reaction product, hydrogenated bisphenol A bis[(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide reaction product, hydrogenated bisphenol A The reaction product of bis[(3-ethyl-3.-oxetanyl)methyl]ether and propylene oxide, bisphenol F bis[(3-ethyl-3-oxetanyl)methyl ] The reaction product of ether and ethylene oxide.

As the crosslinking agent (D), for example, a compound having an isocyanate group blocked with a protecting group is also exemplified. Such compounds are also referred to as "blocked isocyanate compounds". A group in which an isocyanate group is blocked with a protecting group is also referred to as a "blocked isocyanate group".

Blocked isocyanate compounds include, for example, Japanese Patent Laid-Open No. 2013-225031, Japanese Patent No. 5132096, Japanese Patent No. 5071686, Japanese Patent Laid-Open No. 2013-223859, Japanese Patent No. 5199752, Japanese Patent No. Compounds described in Japanese Patent Laid-Open No. 2003-41185, Japanese Patent No. 4879557, and Japanese Patent Laid-Open No. 2006-119441.

Compounds containing polymerizable carbon-carbon double bonds include, for example, polyfunctional (meth)acrylates, specifically: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, poly Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate base) acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trihydroxy Methylpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, cyclo Oxygen addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition di-trimethylolpropane tetra(meth)acrylate, ethylene oxide addition pentaerythritol tetra(meth)acrylate ) acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition di-trimethylolpropane Tetra(meth)acrylate, propylene oxide added pentaerythritol tetra(meth)acrylate, propylene oxide added dipentaerythritol hexa(meth)acrylate, ε-caprolactone added trimethylolpropane trimethylolpropane (Meth)acrylate, ε-caprolactone-added di-trimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone Addition of dipentaerythritol hexa(meth)acrylate.

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

In the radiation-sensitive material, the content of the crosslinking agent (D) is usually 1 to 210 parts by mass, preferably 4 to 160 parts by mass, more preferably 10 parts by mass relative to 100 parts by mass of the polymer (A). 150 parts by mass, more preferably 15 parts by mass to 100 parts by mass. There exists a tendency for the low water absorption of an insulating film to improve that content of a crosslinking agent (D) is more than the lower limit of the said range. There exists a tendency for the heat resistance of an insulating film to improve that content of a crosslinking agent (D) is below the upper limit of the said range.

[Solvent (E)]

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

The solvent (E) is preferably 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, triethylene glycol dialkyl ether, hydroxyl-containing ketone, cyclic ether or cyclic ester .

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

Diethylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

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

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

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

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

Examples of 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.

As triethylene glycol dialkyl ether, triethylene glycol dimethyl ether is mentioned, for example.

Hydroxyl-containing ketones include, for example, acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4- Hydroxy-4-methyl-2-pentanone (diacetone alcohol).

Examples of cyclic ethers or cyclic esters include γ-butyrolactone, tetrahydrofuran, and dioxane.

The solvent (E) further includes amide solvents such as N,N,2-trimethylpropanamide, 3-butoxy-N,N-dimethylpropaneamide, 3-methoxy-N,N -Dimethylpropaneamide, 3-hexyloxy-N,N-dimethylpropaneamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide Wait.

The solvent (E) is particularly preferably propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA (Propyleneglycol monomethylether acetate)"), propylene glycol monomethyl ether (hereinafter also referred to as "PGME (Propyleneglycol monomethylether)"), diethylene glycol ethylene Ethyl methyl ether (hereinafter also referred to as "EDM (Diethyleneglycolethylmethylether)"), diacetone alcohol (hereinafter also referred to as "DAA (Diacetone alcohol)"), γ-butyrolactone (hereinafter also referred to as "BL (γ-butyrolactone) ").

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

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

As the solvent (E), the above-mentioned exemplified solvent has lower water absorption than NMP. Therefore, the material can be prepared using a solvent with low water absorption without using NMP with high water absorption. As a result, the material can exhibit low water absorption. Since the solvents exemplified as the solvent (E) are highly safe, the safety of the materials can be improved.

When using the above-mentioned illustrated solvent as the solvent (E), the insulating film formed of the above-mentioned material can be made to have low water absorption. Therefore, the material can be preferably used to form an insulating film of an organic EL element.

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

In the radiation-sensitive material, the content of the solvent (E) is such that the solid content concentration of the material is usually 5% by mass to 60% by mass, preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass. quantity. The term "solid content" here refers to all components other than the solvent (E). By making content of a solvent (E) into the said range, it exists in the tendency for the low water absorption of the insulating film formed from the said material to improve without impairing developability.

[other optional ingredients]

The radiation sensitive material may contain other arbitrary components, such as an adhesion aid (F) and a surfactant (G), as needed, in addition to the said essential component and preferable component, within the range which does not impair the effect of this invention. Other arbitrary components may be used alone or in combination of two or more.

<Adhesion aid (F)>

Adhesion assistant (F) is a component which improves the adhesiveness of a film formation target object, such as a board|substrate, and an insulating film. In particular, the adhesion aid (F) is useful for improving the adhesion between an inorganic substrate and an insulating film. Examples of inorganic substances include silicon compounds such as silicon, silicon oxide, and silicon nitride; and metals such as gold, copper, and aluminum.

The adhesion aid (F) is preferably a functional silane coupling agent. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, halogen atoms, vinyl groups, methacryloyl groups, isocyanate groups, epoxy groups, oxetanyl groups, amino groups, and thiol groups. .

Functional silane coupling agents include, for example: N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, Acetoxysilane, Vinyltrimethoxysilane, γ-Isocyanatopropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropylalkyldialkoxy ylsilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Among these compounds, N-phenyl-3-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane.

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

<Surfactant (G)>

Surfactant (G) is a component which improves the coating film formability of a radiation sensitive material. When the radiation-sensitive material contains the surfactant (G), the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the insulating film can be further improved. Surfactant (G) is mentioned, for example, a fluorine-type surfactant and a silicone-type surfactant.

As surfactant (G), the specific example described in Unexamined-Japanese-Patent No. 2003-015278 and Unexamined-Japanese-Patent No. 2013-231869 is mentioned, for example.

The content of the surfactant (G) in the radiation-sensitive material is preferably 20 parts by mass or less, more preferably 0.01 parts by mass to 15 parts by mass, and still more preferably 0.05 parts by mass to 100 parts by mass of the polymer (A). 10 parts by mass. By making content of surfactant (G) into the said range, the film thickness uniformity of the formed coating film can be improved more.

[Preparation method of radiation-sensitive material]

The radiation-sensitive material can be prepared by mixing essential components such as a polymer (A), a photosensitizer (B), and a resin (C) and other optional components in a solvent (E), for example. Moreover, after mixing each component uniformly, you may filter the obtained mixture with a filter etc. in order to remove a foreign substance.

[Formation method of insulating film using radiation-sensitive material]

The method for forming the insulating film of the display or lighting device of the present invention comprises the following steps: step 1, using the radiation-sensitive material to form a coating film on the substrate; step 2, irradiating radiation to at least a part of the coating film; Step 3, developing the coating film irradiated with radiation; and Step 4, heating the developed coating film.

According to the method of forming the insulating film, an insulating film having excellent light-shielding properties and having a right conical boundary portion can be formed on the TFT substrate. In addition, since the material is excellent in radiation sensitivity, it is possible to easily form an insulating film having a fine and delicate pattern by forming a pattern by exposure, development, and heating utilizing this characteristic.

"step 1"

In step 1, the radiation-sensitive material is coated on the surface of the substrate, and the solvent (E) is preferably removed by prebaking, thereby forming a coating film. The film thickness of the coating film can be set to a value after prebaking, preferably 0.3 μm to 15.0 μm, more preferably 0.5 μm to 10.0 μm, and still more preferably 1.0 μm to 5.0 μm.

As a substrate, a resin substrate, a glass substrate, and a silicon wafer are mentioned, for example. The substrate further includes, for example, a TFT substrate on which TFTs or wiring thereof are formed in an organic EL element in the process of being manufactured. In the case of manufacturing the device of the present invention, the coating film is formed especially on the TFT substrate.

As for the coating method of a radiation sensitive material, a spray method, the roll coater method, the spin coater method, the slit die coater method, the bar coater method, and the inkjet method are mentioned, for example. Among these coating methods, the spin coating method and the slit die coating method are preferable.

Prebaking conditions also vary depending on the composition of the radiation-sensitive material, for example, the heating temperature is set to 60° C. to 130° C., and the heating time is set to about 30 seconds to 15 minutes. It is preferable to perform prebaking at the temperature which does not provide the light-shielding property by resin (C) to a coating film.

"Step 2"

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

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

"Step 3"

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

Examples of basic compounds contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol , di-n-propylamine, 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. From the viewpoint of obtaining appropriate developability, the concentration of the basic compound in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less.

The developer can also be used: an aqueous solution in which an appropriate amount of water-soluble organic solvents such as methanol and ethanol or surfactants are added to an alkaline aqueous solution, or a small amount of various organic solvents that dissolve radioactive materials are added to an alkaline aqueous solution. aqueous solution. As the organic solvent in the latter aqueous solution, the same solvent as the solvent (E) used to obtain the polymer (A) or the radiation-sensitive material can be used.

As an image development method, the soaking method, the dipping method, the shaking dipping method, and the shower method are mentioned, for example. The development time varies depending on the composition of the radiation-sensitive material, but is usually about 10 seconds to 180 seconds. After such developing treatment, for example, running water washing is performed for 30 seconds to 90 seconds, and air drying is performed with, for example, compressed air or compressed nitrogen to form a desired pattern.

"Step 4"

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

Heat treatment in the above temperature range imparts light-shielding properties to the insulating film with a total light transmittance of 15% or less, preferably 10% or less, particularly preferably 6% or less, at a wavelength of 300 nm to 400 nm. In this way, an insulating film of a desired pattern can be formed on the substrate.

In Step 4, the patterned coating film may be rinsed or decomposed before heating the coating film. In the rinsing process, it is preferable to wash the coating film using a low water-absorbing solvent listed as the solvent (E). In the decomposition treatment, the photosensitive agent (B) remaining in the coating film can be decomposed by irradiating the entire surface with radiation such as a high-pressure mercury lamp (post-exposure). The exposure amount of this post-exposure is preferably about 1000 mJ/cm ² to 5000 mJ/cm ² .

The insulating film obtained in this way has light-shielding properties against light with a wavelength of 300nm to 400nm, and has low water absorption because the constituent materials have a low water absorption structure, and can be treated with a low water absorption compound in the production process. In addition, the insulating film exhibits good characteristics in terms of heat resistance, patternability, radiation sensitivity, resolution, and the like. Therefore, the insulating film can be preferably used as an insulating film as a protective film or a planarizing film, for example, in addition to an insulating film as a partition wall included in an organic EL element or the like.

[Organic EL display device and organic EL lighting device]

Hereinafter, an organic EL display or lighting device as a specific example of the display or lighting device of the present invention will be described with reference to FIG. 3 . 3 is a cross-sectional view schematically showing the structure of the main part of the organic EL display or lighting device (hereinafter also simply referred to as "organic EL device") of 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 of a top emission type or a bottom emission type. Properties of materials constituting each member, such as transparency, are appropriately selected according to the top-emission type and the bottom-emission type.

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

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

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

The semiconductor layer can be formed using the oxide semiconductor containing one or more elements selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn. In the organic EL device 1, the second insulating film 7 (partition wall) has light-shielding properties, so that light generated in the organic light-emitting layer 8 can be prevented or reduced from reaching the semiconductor layer. Therefore, a semiconductor layer including IGZO or the like which is easily photodegraded can be used.

The first insulating film 4 is a planarizing film that functions to planarize surface irregularities caused by the TFT 3 . The first insulating film 4 is formed to cover the entire TFT 3 . The first insulating film 4 may be formed using the aforementioned radiation sensitive material, or may be formed using a conventionally known radiation sensitive material. The film thickness of the first insulating film 4 is preferably increased in order to exhibit an excellent function as a planarizing film. The film thickness of the first insulating film 4 is preferably 1 μm to 5 μm. The first insulating film 4 can be formed by the method described above in the method of forming the insulating film.

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

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

The second insulating film 7 functions as a partition wall (bank) having a concave portion 70 defining an arrangement region of the organic light emitting layer 8 . The second insulating film 7 is formed to cover a part of the anode 5 while exposing a part of the anode 5 . In addition, the cross-sectional shape of the boundary portion of the second insulating film 7 where the anode 5 is exposed is a right conical shape. The second insulating film 7 can be formed by the method described in the method of forming an insulating film using the above-mentioned radiation-sensitive material.

The second insulating film 7 is patterned by exposure and development of the coating film, thereby forming a plurality of recesses 70 in which the organic light-emitting layer 8 is formed in a matrix in plan view.

In addition, the second insulating film 7 is preferably formed so as to fill the via hole 6 . With such a configuration, the insulating film formed on the first insulating film 4 and the insulating film formed in the via hole 6 serve as defense walls that prevent or reduce light generated from the organic light emitting layer 8 from reaching the semiconductor layer of the TFT 3 . In addition, if there are two or more via holes 6 corresponding to one TFT 3 , it is possible to further prevent or reduce the light generated in the organic light emitting layer 8 from reaching the semiconductor layer of the TFT 3 .

The second insulating film 7 is preferably formed on the first insulating film 4 so as to be disposed at least above the semiconductor layer included in the TFT 3 . The term “upward” here refers to the direction from the supporting substrate 2 toward the sealing substrate 11 . The second insulating film 7 has light-shielding properties, so that light generated in the organic light-emitting layer 8 can be prevented or reduced from reaching the semiconductor layer.

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

The organic light emitting layer 8 emits light when an electric field is applied. The organic light-emitting layer 8 is a layer containing an organic light-emitting material that performs electroluminescence. The organic light emitting layer 8 is formed on the anode 5 in the region defined by the second insulating film 7 , that is, in the concave portion 70 . Thus, by forming the organic light emitting layer 8 in the concave portion 70, the periphery of the organic light emitting layer 8 is surrounded by the second insulating film 7, and a plurality of adjacent pixels can be separated from each other.

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

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

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

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

The sealing substrate 11 seals the main surface (the surface of the TFT substrate opposite to the support substrate 2 ) on which the organic light emitting layer 8 is disposed. As the sealing substrate 11, glass substrates, such as an alkali-free glass substrate, are mentioned. The main surface on which the organic light-emitting layer 8 is disposed is preferably sealed by the sealing substrate 11 via the sealing layer 12 using a sealant applied near the outer peripheral end of the TFT substrate. The sealing layer 12 can be set, for example, as a layer of an inert gas such as dried nitrogen or a layer of a filler such as an adhesive.

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

[Example]

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples. In descriptions such as the following examples, "parts" are "parts by mass" unless otherwise mentioned.

[GPC Analysis]

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

・Standard material: polystyrene conversion

・Device: manufactured by Tosoh Co., Ltd., trade name: HLC-8020

·Tube column: Two pieces of guard column (guard column) H _XL -H, TSK gelG7000H _XL , TSK gel GMH _XL and TSK gel G2000H _XL manufactured by Tosoh Co., Ltd. are sequentially connected

Solvent: Tetrahydrofuran

・Sample concentration: 0.7% by mass

·Injection volume: 70μL

·Flow rate: 1mL/min

[NMR analysis]

The phenyl group content in polysiloxane (A1) was measured using "JNM-ECS400" (manufactured by Japan Electronics Co., Ltd.) to measure ²⁹ Si-NMR spectrum, based on the peak area of Si to which the phenyl group is bonded and Calculated from the ratio of the peak area of Si to which no phenyl group is bonded.

<Synthesis of polymer (A)>

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

After adding 390 g of γ-butyrolactone as a polymerization solvent to the three-necked flask, 120 g of 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a diamine compound was added to the polymerization solvent. After dissolving the diamine compound in the polymerization solvent, 71 g of 4,4'-oxydiphthalic dianhydride was added as an acid dianhydride. Then, after reacting at 60 degreeC for 1 hour, 19 g of maleic anhydrides were added as a terminal blocking agent, and after reacting further at 60 degreeC for 1 hour, it heated up and reacted at 180 degreeC for 4 hours. About 600 g of the polyimide solution whose solid content concentration containing a polymer (A-1) was about 35 mass % was obtained. The Mw of the obtained polymer (A-1) was 8000.

[Synthesis example A2] Synthesis of polymer (A-2) (acrylic polymer)

After replacing the inside of the flask with nitrogen, 250.0 g of a propylene glycol monomethyl ether acetate solution in which 5.0 g of 2,2'-azobisisobutyronitrile was dissolved was added. Next, after adding 20.0 g of methacrylic acid, 45.0 g of dicyclopentyl methacrylate, and 30.0 g of 3-ethyl-3-methacryloyloxymethyloxetane, stirring was started gradually. After raising the temperature of the solution to 80° C. and maintaining the temperature for 5 hours, the solution was 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 reactant. After washing this coagulation with water, it was redissolved in 200 g of tetrahydrofuran, and it coagulated again with a large amount of methanol.

After performing this redissolution-coagulation operation a total of three times, the obtained solidified product was vacuum-dried at 60° C. for 48 hours to obtain the target copolymer. Thereafter, a copolymer solution was prepared using propylene glycol monomethyl ether acetate so that the solid content concentration would be about 35% by mass. The weight average molecular weight (Mw) of the obtained polymer (A-2) was 10000.

[Synthesis example A3] Synthesis of polymer (A-3) (acrylic polymer)

In addition to using 20.0g of 2-methacryloxyethylsuccinic acid, 45.0g of dicyclopentyl methacrylate and 30.0g of 3,4-epoxycyclohexylmethyl methacrylate as monomers, the synthesis Example A2 is operated in the same way. The weight average molecular weight (Mw) of the obtained polymer (A-3) was 20000.

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

443.2 g (0.90 moles) of dicarboxylic acid derivatives obtained by reacting 1 mole of diphenyl ether-4,4'-dicarboxylic acid with 2 moles of 1-hydroxybenzotriazole, hexafluoro-2,2-bis Add 366.3 parts (1.00 moles) of (3-amino-4-hydroxyphenyl) propane to a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen inlet tube, and add N-methyl-2- 3000 parts of pyrrolidone and make it dissolve. Then, it was made to react at 75 degreeC using an oil bath for 16 hours.

Next, 32.8 parts (0.20 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 100 parts of N-methyl-2-pyrrolidone was added, and it stirred for 3 hours more, and the reaction was terminated. After the reaction mixture is filtered, the reaction mixture is put into a solution of water/isopropanol=3/1 (mass ratio), the precipitate is collected by filtration and fully washed with water, and dried under vacuum to obtain polybenzoxane Azole precursor (A-4). γ-butyrolactone was added so that the concentration of the polymer (A-4) would be 35% by mass to obtain a γ-butyrolactone solution of the polymer (A-4). The weight average molecular weight (Mw) of the obtained polymer (A-4) was 15000.

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

Add 63.39 parts (0.55mol) of methyltrimethoxysilane, 69.41 parts (0.35mol) of phenyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy 24.64 parts (0.1 mol) of silane and 150.36 parts of diacetone alcohol were added over 10 minutes while stirring at room temperature. Phosphoric acid aqueous solution in which 0.338 parts of phosphoric acid (0.2% by mass relative to the added monomer) was dissolved in 55.8 parts of water . Then, after immersing the flask in a 70 degreeC oil bath and stirring for 1 hour, the oil bath was heated up to 115 degreeC over 30 minutes. The internal temperature of the solution reached 100°C 1 hour after the start of the temperature increase, and then heated and stirred for 2 hours (the internal temperature was 100°C to 110°C). During the reaction, a total of 115 parts of methanol and water as by-products were distilled off. To the obtained diacetone alcohol solution of the polymer (A-5), diacetone alcohol was added so that the concentration of the polymer (A-5) became 35% by mass to obtain a diacetone alcohol solution of the polymer (A-5) . The obtained polymer (A-5) had a weight average molecular weight (Mw) of 5000 and a phenyl group content of 35 mol with respect to 100 mol of Si atoms.

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

In a 1000mL autoclave replaced with nitrogen, 60 parts of 8-carboxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene, N-phenyl-(5-norbornene -2,3-dicarboxyimide) 40 parts, 1,5-hexadiene 2.8 parts, dichloride (1,3-di-s-trimethylphenylimidazolidine-2-ylidene) (tricyclohexylphosphine ) 0.05 parts of benzylidene ruthenium and 400 parts of diethylene glycol ethyl methyl ether were polymerized under stirring at 80° C. for 2 hours to obtain a polymer solution containing the polymer (A-6′). Add 0.1 part of dichlorobis(tricyclohexylphosphine)ethoxymethylene ruthenium as a hydrogenation catalyst to the polymer solution, dissolve hydrogen at a pressure of 4 MPa for 5 hours, and perform hydrogenation reaction, then add 1 part of activated carbon powder , while stirring, hydrogen was dissolved at 150° C. for 3 hours at a pressure of 4 MPa. Then, the solution was taken out, and the active carbon was separated by filtration through a filter made of fluororesin with a pore size of 0.2 μm to obtain 490 parts of a hydrogenation reaction solution containing the polymer (A-6) as a hydrogenated product of the polymer (A-6′). . The solid content concentration of the hydrogenation reaction solution containing the polymer (A-6) obtained here was 21 mass %, and the yield of the polymer (A-6) was 102 parts. The obtained hydrogenation reaction solution of the polymer (A-6) was concentrated by a rotary evaporator, and the solid content concentration was adjusted to 35% by mass to obtain a solution of the polymer (A-6). The weight average molecular weight (Mw) of the obtained polymer (A-6) was 4000.

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

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

<Synthesis of resin (C)>

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

In the flask that thermometer, condensing tube, fractionating tube, stirrer are installed, add 1-naphthol 144.2g (1.0 mole), methyl isobutyl ketone 400g, water 96g and 92 mass % paraformaldehyde 32.6g (with Formaldehyde conversion is 1.0 mol). Then, 3.4 g of p-toluenesulfonic acid was added, stirring. Then, it reacted at 100 degreeC for 8 hours. After the reaction was completed, 200 g of pure water was added, the solution in the system was moved to a separatory funnel, and the water 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 reduced pressure under heating to obtain 140 g of novolac resin (C-1) including a structural unit represented by the following formula. The weight average molecular weight (Mw) of the obtained novolac resin (C-1) was 2000.

[chem 33]

According to the measurement spectrum of Fourier Transform Infrared Spectrophotometer (Fourier Transform Infrared, FT-IR), compared with the raw material, it can be confirmed that the absorption originating from the expansion and contraction of the methylene bond (2800cm ^-1 ~ 3000cm ^-1 ), and then No absorption derived from aromatic ethers (1000 cm ^-1 to 1200 cm ^-1 ) was found. From these results, it was confirmed that the dehydration etherification reaction of hydroxyl groups did not occur (the hydroxyl group disappeared) in this synthesis example, and a novolac resin having a methylene bond was obtained. These identifications are also the same in Synthesis Example C2 to Synthesis Example C5 below.

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

In a flask equipped with a thermometer, a condenser tube, a fractionation tube, and an agitator, 144.2 g (1.0 moles) of 1-naphthol, 134.1 g (1.0 moles) of terephthalaldehyde, and 3.0 g of trifluoromethanesulfonic acid were charged on one side. Reaction was performed at 150° C. to 160° C. for 4 hours while stirring. After the reaction was completed, 200 g of pure water was added, the solution in the system was moved to a separatory funnel, and the water layer was separated and removed from the organic layer. Then, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under reduced pressure under heating to obtain 220 g of a novolac resin (C-2) containing a structural unit represented by the following formula. The weight average molecular weight (Mw) of the obtained novolak resin (C-2) was 1500.

[chem 34]

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

The same procedure as in Synthesis Example C2 except that 134.1 g (1.0 mol) of terephthalaldehyde, 160.2 g (1.0 mol) of 1,6-dihydroxynaphthalene, and 3.0 g of trifluoromethanesulfonic acid were used as raw material components and an acid catalyst. synthetically. 230 g of novolac resin (C-3) containing the structural unit represented by the following formula was obtained. The weight average molecular weight (Mw) of the obtained novolak resin (C-3) was 1000.

[chem 35]

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

In addition to using 194.2 g (1.0 mol) of 1-hydroxyanthracene as raw material components, 400 g of methyl isobutyl ketone, 96 g of water, and 32.6 g of 92% by mass paraformaldehyde (1.0 mol in terms of formaldehyde), the synthesis Example C1 was synthesized in the same manner. 180 g of novolac resin (C-4) containing the structural unit represented by the following formula was obtained. The weight average molecular weight (Mw) of the obtained novolac resin (C-4) was 2000.

[chem 36]

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

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% by mass paraformaldehyde (1.0 mol in terms of formaldehyde) were used as raw material components. , was synthesized in the same manner as in Synthesis Example C1. 190 g of novolak resin (C-5) containing the structural unit represented by the following formula was obtained. The weight average molecular weight (Mw) of the obtained novolak resin (C-5) was 3000.

[chem 37]

<Preparation of Radiation Sensitive Material>

The polymer (A) used to prepare the radiation-sensitive material is the polymer (A-1) to the polymer (A-7) of Synthesis Example A1 to Synthesis Example A6 and Preparation Example A7, and the resin (C) is Synthesis Example C1 ~Novolac resin (C-1) of Synthesis Example C5~Novolak resin (C-5), photosensitizer (B), crosslinking agent (D), solvent (E), adhesion aid (F) and surface active agent The agent (G) is as follows.

Sensitizer (B)

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

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

Cross-linking agent (D)

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

D-2: "C-357" of Qunying Chemical Industry Co.

D-3: "M-405" of Toa Gosei Co.

Solvent (E)

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

DAA: diacetone alcohol

EDM: Diethylene glycol ethyl methyl ether

Adhesion aid (F)

F-1: N-phenyl-3-aminopropyltrimethoxysilane

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

Surfactant (G)

G-1: Silicone-based surfactant

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

[Preparation Example 1]

10 parts of (B-1), (C- 1) 40 parts, (D-1) 15 parts, (D-2) 5 parts, (F-1) 4 parts, (G-1) 1 part and (E-1), the solid content concentration is 25 mass %, and filtered using a membrane filter with a caliber of 0.2 μm to prepare positive-type material 1.

[Preparation Example 2 to Preparation Example 33]

Positive material 2 to positive material 23, positive material 30 to positive material 31, negative material 24 to negative Material 29 and negative material 32 - negative material 33 .

[Table 1]

[Example and Comparative Example]

Using the radiation-sensitive material 1 to the radiation-sensitive material 33 of Preparation Example 1 to Preparation Example 33, an insulating film and an organic EL element were fabricated by the method described below. The patternability, line width roughness (Line Width Roughtness, LWR), light-shielding property, cone angle, water absorption and heat resistance of the obtained insulating film, and the device characteristics of the obtained organic EL device were respectively carried out by the following methods. evaluate.

<patternability>

The silicon substrate obtained in Preparation Example 1 to Preparation Example 23 and Preparation Example 30 to Preparation Example 31 was coated on a silicon substrate using a leveling developing device (Clean track) (manufactured by Tokyo Electron: Mark VZ). After positive-type materials, pre-bake them on a heating plate at 120°C for 2 minutes to form a coating film. The coating film was exposed at an exposure dose of 100 mJ/cm ² at a wavelength of 365 nm through a pattern mask having a predetermined pattern using an exposure machine (Nikon's i-ray stepper "NSR-2005i10D"). Thereafter, using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 25°C, it was developed for 80 seconds by the flood method, washed with ultrapure water for 1 minute, and dried to form a film with a thickness of 5 μm on the silicon substrate. A coating film with a pattern in which a plurality of square through holes are arranged in a row is baked on a hot plate at 250° C. for 60 minutes to form a film with the pattern and Table 2. thick insulating film.

In addition, using a uniform film development equipment (Clean track) (Tokyo Electron (Tokyo Electron) Co., Ltd.: mark (Mark) VZ), coating in the preparation example 24 to preparation example 29 and preparation example 32 to preparation example 33 on the silicon substrate The obtained negative-type material was pre-baked on a heating plate at 120° C. for 2 minutes to form a coating film. The coating film was exposed at an exposure dose of 300 mJ/em ² at a wavelength of 365 nm through a pattern mask having a predetermined pattern using an exposure machine (Nikon's i-ray stepper "NSR-2005i10D"). Thereafter, using a 2.38% by mass tetramethylammonium hydroxide aqueous solution, develop at 25°C for 120 seconds by the flood method, wash with ultrapure water for 1 minute, and dry it to form a film with a thickness of 5 μm on the silicon substrate. A coating film with a pattern in which a plurality of square through holes are arranged in a row. This coating film was post-baked on a hot plate at 250° C. for 60 minutes to form an insulating film having the above pattern and the film thickness described in Table 2.

At this time, in the coating film, it was confirmed whether the exposed portion after development was completely dissolved in the case of the positive type material, and whether the non-exposed portion after development was completely dissolved in the case of the negative type material. The formation of a 5 μm square pattern without peeling of the insulating film or the formation of an insulating film was evaluated as “excellent”, and the formation of a 5 μm square pattern without peeling of the insulating film but slight development residue was evaluated. The case where a 5 μm square pattern could not be formed or the peeling of the insulating film occurred was evaluated as “favorable” as “good”.

<LWR>

Using a scanning electron microscope (Scanning Electron Microscope, SEM; "SU3500" of Hitachi-High Technology Co., Ltd.), the line width of the coating film before post-baking formed in the above-mentioned <patternability> was 5 μm The square pattern is observed from the top of the pattern, and the line width is measured at any 10 points. Let the 3σ value (deviation) of the measured value of the line width be LWR (μm). When the LWR value was 0.4 μm or less, it was evaluated as “excellent”, when it exceeded 0.4 μm and 0.8 μm or less, it was evaluated as “good”, and when it exceeded 0.8 μm, it was evaluated as “poor”.

<Shading property>

The preparation was coated on a glass substrate ("Corning 7059" by Corning) using a leveling developing device (Clean track) (manufactured by Tokyo Electron: Mark VZ). The radiation-sensitive material obtained in the example was pre-baked on a hot plate at 120°C for 2 minutes, and then post-baked on a hot plate at 250°C for 60 minutes to form a film with the thickness described in Table 2. 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 (Double Beam)" manufactured by Hitachi, Ltd.) on the glass substrate with the insulating film, The total light transmittance at a wavelength of 300 nm to 400 nm was obtained. With regard to light-shielding properties, it was evaluated as "excellent" when the maximum total light transmittance at a wavelength of 300 nm to 400 nm was 6% or less, and "good" when it exceeded 6% and 10% or less, and it was evaluated as "good" when it exceeded 10%. % and 15% or less, it was evaluated as "slightly good", and when it exceeded 15%, it was evaluated as "poor".

<Cone angle and film thickness>

In the insulating film of the above-mentioned <patternability>, the vertical cross-sectional shape in the direction perpendicular to the line of the plurality of via holes was observed by SEM ("SU3500" of Hitachi High Technology Co., Ltd.). The cone angle of the insulating film was determined from this SEM image. In each evaluation, the film thickness of the insulating film was similarly determined from the SEM image.

<Water absorption>

After coating the radiation-sensitive material obtained in the above-mentioned Preparation Example on a silicon substrate using a clean track (Tokyo Electron Co., Ltd.: Mark VZ), it was placed on a heating plate. After pre-baking at 120° C. for 2 minutes, post-baking was performed at 250° C. for 60 minutes on a hot plate to form an insulating film having a film thickness of 3.0 μm.

Using Thermal Desorption Spectroscopy ("TDS1200" of ESCO Corporation) for this insulating film, the temperature was raised from room temperature to 200°C at a rate of 30°C/min at a vacuum degree of 1.0×10 ^-9 Pa. ℃. The gas desorbed from the sample surface and the sample at this time was measured as a detection value of the water peak (M/z=18) using a mass spectrometer ("5973N" of Agilent Technology). The water absorption was evaluated by taking the integrated value [A·sec] of the total peak intensity from 60°C to 200°C. With regard to water absorption, it was evaluated as "excellent" when the integrated value [A·sec] of the total peak intensity from 60°C to 200°C was 3.0×10 ^-8 or less, and it was evaluated as "excellent" when it exceeded 3.0×10 ^-8 and was 5.0×10 When it was ^-8 or less, it was evaluated as "good", and when it exceeded 5.0×10 ^-8 , it was evaluated as "poor".

<Heat resistance>

Similar to the evaluation of <water absorption>, an insulating film was formed using a radiation-sensitive material, and the insulating film was measured at 100°C to 500°C using a thermogravimetric measurement device ("TGA2950" from TA Instruments). Thermogravimetric analysis (Thermogravimetric Analysis, TGA) measurement (under air, temperature increase rate 10°C/min), from which the 5% weight loss temperature was calculated. With regard to heat resistance, when the 5% weight loss temperature exceeds 350°C, it is evaluated as "excellent", when it is 350°C to 330°C, it is evaluated as "good", and when it is 330°C or less, it is evaluated as "poor". .

"Component Characteristic Evaluation"

Using a glass substrate (Corning 7059), a TFT substrate in which TFTs were formed on the glass substrate was fabricated, and an insulating film was formed on the TFT substrate to fabricate an evaluation element. The element characteristics were evaluated for the element for evaluation.

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

After coating the radiation-sensitive material obtained in the above-mentioned preparation example on the TFT substrate using a clean track (Tokyo Electron (Tokyo Electron) Co., Ltd.: Mark VZ), the radiation-sensitive material obtained in the above-mentioned preparation example was coated on a heating plate. After prebaking at 120° C. for 2 minutes, post-baking was performed on a hot plate at 250° C. for 60 minutes to form an insulating film having a film thickness described in Table 2.

<Switch Response Characteristics>

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

<TFT reliability>

TFT reliability was evaluated by comparing the change in Id-Vg characteristics (threshold voltage Vth change) for comparison.

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

Imprinting of electrical stress can be carried out by keeping the potential of the source electrode of the evaluation element at 0V and the potential of the drain electrode at +10V, and imprinting a voltage between the source electrode and the drain electrode. , the potential Vg of the gate electrode changes from -20V to +20V. When the potential Vg of the gate electrode is changed in this way, 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 becomes ON (ON) is set as the threshold voltage Vth.

(Measurement of change amount of threshold voltage Vth)

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

As shown in Table 2, the radiation-sensitive materials of Preparation Examples 1 to 29 were excellent in patternability, pattern shape, low water absorption, and heat resistance. In addition, the insulating films formed in Examples 1 to 37 are excellent in light-shielding properties and have a right conical shape, and the device using this insulating film and a semiconductor layer that is easily degraded by light has excellent device characteristics (switching response characteristics) even in a light irradiation environment. , TFT reliability) are also excellent. In contrast, the insulating film formed in Comparative Example 1 was poor in light-shielding properties, the insulating films formed in Comparative Examples 2 and 4 were poor in patternability, pattern shape, light-shielding properties, low water absorption, and heat resistance, and Comparative Example 3 was poor. The patternability, pattern shape, and low water absorption of the insulating film formed in Comparative Example 5 are poor, and the device characteristics (switching response characteristics, TFT reliability) of the device using these insulating films and semiconductor layers that are easily degraded by light under the light irradiation environment Difference.

[explanation of the symbol]

1: Organic EL device

2: Support substrate

3: TFT

4: 1st insulating film (planarizing film)

5: anode

6: Through hole

7: Second insulating film (partition wall)

70: Concave

8: Organic light-emitting layer

9: Cathode

10: Passivation film

11: Sealed substrate

12: sealing layer

100: TFT substrate

110: 1st electrode

111: opening of insulating film

112: edge portion of the first electrode

113: 1st electrode surface

120: insulating film

121: slope of insulating film

Claims (19)

1. display or an illuminator, has:

Thin film transistor base plate, the semiconductor layer constituting thin film transistor (TFT) contains oxide semiconductor, described oxide semiconductor Containing more than one the element in In, Ga, Sn, Ti, Nb, Sb and Zn；

1st electrode, is arranged on thin film transistor base plate, and is connected with described thin film transistor (TFT)；

Dielectric film, is formed on the 1st electrode in the way of making the 1st electrode expose partly, and full light transmittance is at wavelength 300nm ～under 400nm in the range of 0%～15%；And

2nd electrode, relative with the 1st electrode to and arrange；And

Described dielectric film is the dielectric film formed by radioactivity-sensitive material,

Described radioactivity-sensitive material contains:

(A) polymer beyond following resin (C),

(B) photosensitizer, and

(C) at least one resin in the condensation substance of novolac resin, bakelite and bakelite, and Relative to polymer (A) 100 mass parts, the content of the resin (C) in described radioactivity-sensitive material is 2 mass parts～200 matter Amount part.

Display the most according to claim 1 or illuminator, wherein polymer (A) is selected from polyimides (A1), described The precursor (A2) of polyimides, acrylic resin (A3), polysiloxanes (A4), polybenzoxazoles (A5-1), described polyphenyl are also The precursor (A5-2) of oxazole, polyolefin (A6) and block at least one in many resins (A7).

Display the most according to claim 1 or illuminator, wherein polymer (A) is selected from polysiloxanes (A4), polyphenyl And the precursor (A5-2) of oxazole (A5-1), described polybenzoxazoles, polyolefin (A6) and block at least one in many resins (A7).

Display the most according to claim 2 or illuminator, wherein polyimides (A1) is containing the knot represented by formula (A1) Structure unit,

[changing 1]

[in formula (A1), R¹For having the bilvalent radical of hydroxyl, X is quadrivalent organic radical].

5., according to the display described in Claims 2 or 3 or illuminator, wherein polysiloxanes (A4) is for making represented by formula (a4) The polysiloxanes of organosilan reaction gained,

[changing 2]

[in formula (a4), R¹For hydrogen atom, the alkyl of carbon number 1～10, the thiazolinyl of carbon number 2～10, the base containing aryl of carbon number 6～15 Group, the group containing epoxide ring of carbon number 2～15 or the hydrogen atom by 1 contained by described alkyl or more than 2 are substituted by replacement The group of base, at R¹Can distinguish when there is multiple situations identical also can be different；R²For hydrogen atom, the alkyl of carbon number 1～6, The acyl group of carbon number 1～6 or the aryl of carbon number 6～15, at R²Can distinguish when there is multiple situations identical also can be different；N be 0～ The integer of 3].

6., according to the display described in Claims 2 or 3 or illuminator, wherein polybenzoxazoles (A5-1) contains formula (a5-1) institute The construction unit represented,

[changing 3]

[in formula (a5-1), X¹For having the quadrivalent organic radical of aromatic ring, Y¹For divalent organic base].

7., according to the display described in Claims 2 or 3 or illuminator, wherein the precursor (A5-2) of polybenzoxazoles contains formula (a5-2) construction unit represented by,

[changing 4]

[in formula (a5-2), X¹For having the quadrivalent organic radical of aromatic ring, Y¹For divalent organic base].

Display the most according to any one of claim 1 to 7 or illuminator, wherein photosensitizer (B) is light acid producing agent Or optical free radical polymerization initiator.

Display the most according to any one of claim 1 to 8 or illuminator, wherein resin (C) is novolac resin.

Display the most according to any one of claim 1 to 9 or illuminator, wherein said dielectric film makes the 1st electrode dew The section shape of the boundary member of the described dielectric film gone out is positive round taper.

11. display according to any one of claim 1 to 10 or illuminators, the thickness of wherein said dielectric film is 0.3 μm～15.0 μm.

12. according to the display according to any one of claim 1 to 11 or illuminator, and wherein said dielectric film is with coating the The mode of at least edge part of 1 electrode and formed, the section shape of the boundary member of described dielectric film is positive round taper.

13. according to the display according to any one of claim 1 to 12 or illuminator, and wherein said dielectric film is for by described thin The dividing wall in multiple region it is separated on the face of film transistor substrate,

There is the pixel formed respectively in the plurality of region.

14. display according to claim 13 or illuminators, have organic electroluminescent device, and described organic electroluminescence is sent out Optical element contains: the 1st electrode, is arranged on described thin film transistor base plate and is connected with described thin film transistor (TFT)；Organic light emission Layer, is formed in the region that described dividing wall separates and is formed on the 1st electrode；And the 2nd electrode, it is arranged at organic light emission On layer.

15. display according to claim 14 or illuminators, wherein said thin film transistor base plate is for having a support group Plate, on described support substrate and the thin film transistor (TFT) that arrange and coating institute corresponding with described organic electroluminescent device State the thin film transistor base plate of the planarization layer of thin film transistor (TFT),

Described dividing wall is coated at least edge part of the 1st electrode, and described dividing wall is at least to be configured at described film crystal The mode of the top of the semiconductor layer that pipe is had and be formed on described planarization layer.

16. display according to claim 15 or illuminators, wherein said 1st electrode is formed at described planarization layer On, described 1st electrode is connected with described thin film transistor (TFT) via the distribution formed in the through hole running through described planarization layer.

17. according to the display according to any one of claim 1 to 16 or illuminator, and wherein said dielectric film is at least to join It is placed in the mode of the top of described semiconductor layer and is formed on thin film transistor base plate, above thin film transistor base plate During the situation of viewed in projection, more than the 50% of the area of semiconductor layer repeats with described dielectric film.

The forming method of 18. 1 kinds of dielectric films, forms display according to claim 1 or insulation that illuminator is had Film, and the forming method of described dielectric film comprises the following steps: step 1, uses radiation according to claim 1 Property material forms film on thin film transistor base plate；Step 2, irradiates lonizing radiation at least partially to described film；Step 3, the described film irradiated through lonizing radiation is developed；And step 4, described developed film is heated, is formed Full light transmittance dielectric film in the range of 0%～15% under wavelength 300nm～400nm.

The forming method of 19. dielectric films according to claim 18, the heating-up temperature in wherein said step 1 be 60 DEG C～ 130 DEG C, the heating-up temperature in described step 4 is for more than 130 DEG C and be less than 300 DEG C.