JPWO2015129092A1 - Display or lighting device and method for forming insulating film - Google Patents

Abstract

[PROBLEMS] To provide a display or lighting device having, as a driving element, a thin film transistor including a semiconductor layer made of a material having a high light deterioration, in which the light deterioration of the material accompanying use of these devices is suppressed. . [Solution] A TFT substrate, a first electrode provided on the TFT substrate and connected to the TFT, and a total light transmission formed on the first electrode so as to partially expose the first electrode. A display or illumination device having an insulating film having a rate of 0 to 15% in a wavelength range of 300 to 400 nm and a second electrode provided to face the first electrode, wherein the insulating film is radiation sensitive. An insulating film formed of a material, wherein the radiation-sensitive material contains (A) a polymer, (B) a photosensitizer, and (C) a resin such as a novolak resin. The display or lighting device whose content of resin (C) is 2-200 mass parts with respect to 100 mass parts of polymers (A).

Description

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

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

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

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

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

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

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

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

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

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention. The present invention relates to the following [1] to [19], for example.

  [1] A TFT substrate including an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn, and a semiconductor layer constituting the TFT provided on the TFT substrate And a first electrode connected to the TFT and formed on the first electrode so as to partially expose the first electrode, the total light transmittance is in the range of 0 to 15% at a wavelength of 300 to 400 nm. And a second electrode provided opposite to the first electrode, wherein the insulating film is an insulating film formed of a radiation sensitive material, and the radiation sensitive The conductive material is (A) a polymer other than the following resin (C), (B) a photosensitive agent, and (C) at least one resin selected from a novolak resin, a resole resin, and a condensate of a resole resin. Containing said radiation sensitive The content of the resin (C) in the fee is 2 to 200 parts by weight per 100 parts by weight polymer (A), display or lighting device.

  [2] Polymer (A) is polyimide (A1), polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5-1), and polybenzoxazole. The display or lighting device according to [1], which is at least one selected from the precursor (A5-2), the polyolefin (A6), and the cardo resin (A7).

  [3] The polymer (A) is composed of polysiloxane (A4), polybenzoxazole (A5-1), the precursor of polybenzoxazole (A5-2), polyolefin (A6), and cardo resin (A7). The display or illumination device according to [1], which is at least one selected.

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

[In Formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. ]
[5] The display or illumination device according to [2] or [3], wherein the polysiloxane (A4) is a polysiloxane obtained by reacting an organosilane represented by the formula (a4).

[In the formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group-containing group having 6 to 15 carbon atoms, or an epoxy ring having 2 to 15 carbon atoms. Or a group formed by replacing one or more hydrogen atoms contained in the alkyl group with a substituent, and when there are a plurality of R ^{1 s} , they may be the same or different; R ² is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when there are a plurality of R ^{2 s} , they may be the same or different; It is an integer of 3. ]
[6] The display or lighting device according to [2] or [3], wherein the polybenzoxazole (A5-1) has a structural unit represented by the formula (a5-1).

[In Formula (a5-1), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group. ]
[7] The display or illumination device according to [2] or [3], wherein the polybenzoxazole precursor (A5-2) has a structural unit represented by the formula (a5-2).

[In Formula (a5-2), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group. ]
[8] The display or illumination device according to any one of [1] to [7], wherein the photosensitive agent (B) is a photoacid generator or a photoradical polymerization initiator.

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

  [10] The display or illumination device according to any one of [1] to [9], wherein the insulating film exposes the first electrode, and a cross-sectional shape at a boundary portion of the insulating film is a forward tapered shape. .

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

  [12] Any one of [1] to [11], wherein the insulating film is formed so as to cover at least an edge portion of the first electrode, and a cross-sectional shape at a boundary portion of the insulating film is a forward tapered shape. The display or illumination device described in 1.

  [13] Any one of the above [1] to [12], wherein the insulating film is a partition partitioning the surface of the TFT substrate into a plurality of regions, and each has pixels formed in the plurality of regions. The display or illumination device described in 1.

  [14] A first electrode provided on the TFT substrate and connected to the TFT, an organic light emitting layer formed on the first electrode in a region partitioned by the partition, and provided on the organic light emitting layer The display or illumination device according to [13], further including an organic EL element including the second electrode.

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

  [16] The first electrode is formed on the planarization layer, and the first electrode is connected to the TFT via a wiring formed in a through hole penetrating the planarization layer. 15].

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

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

  [19] The method for forming an insulating film according to [18], wherein the heating temperature in step 1 is 60 to 130 ° C., and the heating temperature in step 4 is higher than 130 ° C. and not higher than 300 ° C.

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

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

  In the display or lighting device of the present invention, 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. 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 as to partially expose the first electrode; and a first electrode And a second electrode provided to face each other. Here, the total light transmittance of the insulating film is 0 to 15% at a wavelength of 300 to 400 nm.

  Hereinafter, the display or lighting device is also collectively referred to as “device”.

  Examples of the display device of the present invention include a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescent display (ELD), and particularly an organic EL display. As an illuminating device of this invention, organic EL illumination is mentioned, for example.

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

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

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

  The cross-sectional shape of the insulating film is preferably a forward taper at the boundary portion where the first electrode is exposed. Here, the “forward taper shape” means that an angle θ formed by the slope 121 of the boundary portion where the first electrode 110 is exposed in the insulating film 120 and the first electrode surface 113, for example, the angle θ in FIG. 2 is less than 90 °. Corresponds to Hereinafter, the angle θ is also referred to as “taper angle θ”. The taper angle θ is preferably 80 ° or less, more preferably 5 to 60 °, and more preferably 10 to 45 °.

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

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

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

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

  The insulating film is, for example, a partition that partitions the surface of the TFT substrate into a plurality of regions, and pixels are formed in the plurality of regions. The insulating film (partition wall) is preferably formed on the TFT substrate so as to be disposed at least above the semiconductor layer, from the viewpoint of light shielding with respect to the semiconductor layer included in the TFT. Here, “upward” is a direction from the TFT substrate toward the second electrode. As an example, when projected from the top of the TFT substrate, an aspect in which 50% or more of the area of the semiconductor layer overlaps with the insulating film (partition wall), particularly 80% or more of the area of the semiconductor layer, Further, an embodiment in which 90% or more, particularly 100%, overlaps with the insulating film (partition wall) can be mentioned.

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

  For example, the semiconductor layer included in the TFT is a layer containing an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof.

  As an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn, for example, a quaternary system such as an In—Sn—Ga—Zn—O-based oxide semiconductor Metal oxide: In—Ga—Zn—O-based oxide semiconductor, In—Sn—Zn—O-based oxide semiconductor, In—Al—Zn—O-based oxide semiconductor, Sn—Ga—Zn—O-based oxide Ternary metal oxides such as semiconductor, Al—Ga—Zn—O-based oxide semiconductor, Sn—Al—Zn—O-based oxide semiconductor; In—Zn—O-based oxide semiconductor, Sn—Zn—O-based Oxide semiconductor, Al-Zn-O-based oxide semiconductor, Zn-Mg-O-based oxide semiconductor, Sn-Mg-O-based oxide semiconductor, In-Mg-O-based oxide semiconductor, In-Ga-O Binary metal oxides such as In-based materials; In-O-based oxide semiconductors, Sn-O-based materials Compound semiconductor, 1-component metal oxide such as Zn-O-based oxide semiconductor can be mentioned.

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

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

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

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

[Radiosensitive materials]
The radiation-sensitive material can be used for forming the insulating film in the display or lighting device of the present invention. The radiation sensitive material preferably comprises a polymer (A), a photosensitizer (B), and at least one resin (C) selected from a novolac resin, a resole resin, and a condensate of a resole resin. contains.

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

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

  Hereinafter, each component will be described in detail.

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

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

  The weight average molecular weight (Mw) in terms of polystyrene of the polymer (A) is preferably 2,000 to 500,000, preferably 3,000 to 100,000, as measured by gel permeation chromatography (GPC). More preferred is 4,000 to 50,000. When Mw is not less than the lower limit of the above range, an insulating film having sufficient mechanical properties tends to be obtained. When the Mw is not more than the upper limit of the above range, the solubility of the polymer (A) in the solvent or developer tends to be excellent.

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

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

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

Examples of R ¹ include a divalent group represented by the formula (a1).

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

In R ³ , examples of the acyl group include groups having 2 to 20 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group; examples of the alkyl group include a methyl group, an ethyl group, and n- C1-C20 groups, such as a propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, are mentioned.

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

Examples of the tetravalent organic group represented by X include a tetravalent aliphatic hydrocarbon group, a tetravalent aromatic hydrocarbon group, and a group represented by the following formula (1). X is preferably a tetravalent organic group derived from tetracarboxylic dianhydride. Among these, a group represented by the following formula (1) is preferable.

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

  Carbon number of a tetravalent aliphatic hydrocarbon group is 4-30 normally, Preferably it is 8-24. Carbon number of a tetravalent aromatic hydrocarbon group and the trivalent aromatic hydrocarbon group in said formula (1) is 6-30 normally, Preferably it is 6-24.

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

  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. Can be mentioned.

Examples of the tetravalent alicyclic hydrocarbon group include monocyclic hydrocarbons such as cyclobutane, cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, cyclohexene, and cyclooctane; bicyclo [2.2.1] heptane, bicyclo Bicycles such as [3.1.1] heptane, bicyclo [3.1.1] hept-2-ene, bicyclo [2.2.2] octane, bicyclo [2.2.2] oct-5-ene formula hydrocarbons; tricyclo [5.2.1.0 ^2,6] decane, tricyclo [5.2.1.0 ^{2, 6]} deca-4-ene, adamantane, tetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] tetravalent groups derived from tricyclic or higher hydrocarbons such as dodecane.

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

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

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

Examples of the tetravalent aromatic hydrocarbon group and the group represented by the above formula (1) include a tetravalent group represented by the following formula. In the following formula, four “-” extending from the aromatic ring indicate a bond.

A polyimide (A1) can be obtained by imidation of the polyimide precursor (A2) demonstrated below. The imidization here may proceed completely or partially. In other words, the imidation ratio may not be 100%. Therefore, the polyimide (A1) further has at least one selected from the structural unit represented by the formula (A2-1) and the structural unit represented by the formula (A2-2), which will be described below. May be.

  In the polyimide (A1), the imidation ratio is preferably 5% or more, more preferably 7.5% or more, and further preferably 10% or more. The upper limit value of the imidization rate is preferably 50%, more preferably 30%. When the imidation ratio is in the above range, it is preferable from the viewpoint of heat resistance and solubility of the exposed portion in the developer.

The imidation rate can be measured, for example, as follows. First, measuring the infrared absorption spectrum of the polyimide, the absorption peak of the imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, after heat-treating the polyimide at 350 ° C. for 1 hour, the infrared absorption spectrum is measured again. The peak intensity around 1377 cm ⁻¹ before and after heat treatment is compared. The imidation ratio of polyimide after heat treatment is taken as 100%, and the imidization ratio of polyimide before heat treatment = {peak intensity around 1377 cm ⁻¹ before heat treatment / peak intensity around 1377 cm ⁻¹ after heat treatment} × 100 (%) Ask for. For the measurement of the infrared absorption spectrum, for example, “NICOLET6700FT-IR” (manufactured by Thermo Electron) is used.

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

<< Polyimide precursor (A2) >>
The polyimide precursor (A2) is a compound that can generate a polyimide (A1), preferably a polyimide (A1) having a structural unit represented by the formula (A1), by dehydration and cyclization (imidization). . Examples of the polyimide precursor (A2) include polyamic acid and polyamic acid derivatives.

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

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

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

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

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

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

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

<< Synthesis Method of Polyimide (A1) and Polyimide Precursor (A2) >>
The polyamic acid which is a polyimide precursor (A2) can be obtained, for example, by polymerizing a tetracarboxylic dianhydride, a diamine having a hydroxyl group and a diamine containing another diamine as required. The proportion of these used is, for example, 0.3 to 4 mol, preferably approximately equimolar, with respect to 1 mol of the tetracarboxylic dianhydride. In the polymerization, the mixed solution of the tetracarboxylic dianhydride and the total diamine is preferably heated at 50 ° C. to 200 ° C. for 1 hour to 24 hours.

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

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

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

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

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

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

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

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

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

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

  In addition to the diamine (A1-2), another diamine (A1-2 ') other than the (A1-2) may be used. Examples of the other diamine (A1-2 ′) include at least one diamine selected from an aromatic diamine and an aliphatic diamine having no hydroxyl group.

The polyimide (A1) further has a structural unit in which R ¹ in the formulas (A1), (A2-1) and (A2-2) is replaced with the residue of the other diamine (A1-2 ′). It may be. Similarly, the polyimide precursor (A2) further has a structural unit in which R ¹ in the formulas (A2-1) and (A2-2) is changed to the residue of the other diamine (A1-2 ′). You may do it.

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

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

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

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

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

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

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

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

  Examples of the hydroxyalkyl ester of (meth) acrylic acid include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and examples of the epoxy group-containing ester of (meth) acrylic acid include glycidyl (meth) acrylate. , Glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxy Heptyl, α-ethylacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexylmethyl (meth) acrylate; oxetanyl group-containing esters of (meth) acrylic acid include, for example, 3-methyl-3 -(Meth) acryloyloxymethyloxetane 3-ethyl-3- (meth) acryloyloxy methyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane and the like.

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

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

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

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

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

<< Polysiloxane (A4) >>
Examples of the polysiloxane (A4) include polysiloxane obtained by reacting an organosilane represented by the formula (a4).

In formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group-containing group having 6 to 15 carbon atoms, or an epoxy ring having 2 to 15 carbon atoms. group, or the alkyl group formed by substituting a substituent one or more hydrogen atoms contained in the group (substituents) may be the same or different each when R ¹ is more; R ² is A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when there are a plurality of R ^{2 s} , they may be the same or different; n Is an integer from 0 to 3.

  Examples of the substituent include 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 the substituted product thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, 3- (meth) acryloyloxypropyl group Can be mentioned.

  Examples of alkenyl groups include vinyl groups.

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

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

  Examples of the acyl group include an acetyl group.

  Examples of the aryl group include a phenyl group.

  N in the formula (a4) is an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

  Examples of the organosilane include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltrin-butoxysilane. , Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane , N-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltri Toxisilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3, 3 , 3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Trifunctional silanes such as cyclopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di Bifunctional silanes such as n-butyldimethoxysilane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane. Among these organosilanes, trifunctional silanes are preferable from the viewpoint of crack resistance and hardness of the insulating film.

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

From the viewpoint of achieving both crack resistance and hardness of the insulating film, the content of the phenyl group contained in the polysiloxane (A4) is preferably 20 to 70 mol, more preferably 35 to 100 mol of Si atoms. 55 moles. When the phenyl group content is less than or equal to the above upper limit value, an insulating film having a high hardness tends to be obtained, and when the phenyl group content is greater than or equal to the lower limit value, an insulating film having a high crack resistance tends to be obtained. It is in. The content of the phenyl group is measured, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of polysiloxane (A4), and the peak area of Si to which the phenyl group is bonded and the peak area of Si to which the phenyl group is not bonded. It can be obtained from the ratio.

  The polysiloxane (A4) can be obtained, for example, by hydrolyzing and partially condensing the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to organosilane, and the mixture is heated and stirred. During the stirring, hydrolysis by-products such as alcohol and condensation by-products such as water may be distilled off as necessary. Although reaction temperature is not specifically limited, Usually, it is the range of 0 to 150 degreeC. Although reaction time is not specifically limited, Usually, it is the range of 1 to 10 hours.

  Examples of the solvent include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2- Hydroxyl group-containing ketones such as pentanone (diacetone alcohol); ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t- Examples include butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol. Of these, diacetone alcohol is particularly preferably used. A solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

  The addition amount of the solvent is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the organosilane. Moreover, the addition amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.

  Examples of the catalyst include an acid catalyst and a base catalyst. 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 anhydride thereof, and ion exchange resin. Base catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino groups Examples include alkoxysilanes and ion exchange resins. The addition amount of the catalyst is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the organosilane.

<< Polybenzoxazole (A5-1) >>
The polybenzoxazole (A5-1) preferably has a structural unit represented by the formula (a5-1). Hereinafter, the structural unit represented by the formula (a5-1) is also referred to as “structural unit (a5-1)”.

In 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), X ¹ is preferably a tetravalent group containing at least one aromatic ring, more preferably a group having a linear structure, and 1 to 4 aromatic rings. And a group having two aromatic rings is particularly preferable. Polybenzoxazole (A5-1) having such a structure is excellent in rigidity.

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

When X ¹ contains two or more aromatic rings, the plurality of aromatic rings may form any structure of a linked polycyclic system and a condensed polycyclic system, but form a linked polycyclic structure. It is preferable. Polybenzoxazole (A5-1) having such a structure is excellent in both light shielding properties and rigidity.

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

Examples of the structure of X ¹ include 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, the group represented by the formula (g1) is preferable.

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

Specific examples of the structure of X ¹ include, for example, a tetravalent group represented by the following formula. In the following formula, four “-” extending from the aromatic ring represent a bond.

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

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

When Y ¹ contains two or more of the above rings, the plurality of rings may form any structure of a linked polycyclic system and a condensed polycyclic system, but form a linked polycyclic system structure. Preferably it is. Polybenzoxazole (A5-1) having such a structure is excellent in both light shielding properties and rigidity.

Y ¹ has preferably 4 to 24 carbon atoms, more preferably 4 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms. Thereby, the said effect can be exhibited more notably.

Examples of the structure of Y ¹ include aromatic structures such as 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 (g2). An alicyclic structure exemplified below; Among these, the group represented by the formula (g2) is preferable.

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

Specific examples of the structure of Y ¹ include a divalent group represented by the following formula. In the following formula, two “-” extending from the aromatic ring and the alicyclic ring represent a bond.

Polybenzoxazole (A5-1) can be obtained by a cyclization reaction of a polybenzoxazole precursor (A5-2) described below. The cyclization reaction here may proceed completely or partially. That is, the cyclization rate may not be 100%. For this reason, polybenzoxazole (A5-1) may further have a structural unit represented by the formula (a5-2) described below. Hereinafter, the structural unit represented by the formula (a5-2) is also referred to as “structural unit (a5-2)”.

  In polybenzoxazole (A5-1), the cyclization rate is preferably 5% or more, more preferably 7.5% or more, and further 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 the developer.

The cyclization rate can be measured, for example, as follows. First, the infrared absorption spectrum of polybenzoxazole is measured to confirm the presence of an absorption peak (near 1557 cm ⁻¹ , 1574 cm ⁻¹ ) of the benzoxazole ring. Next, after heat-treating the polybenzoxazole at 350 ° C. for 1 hour, an infrared absorption spectrum is measured again. The peak intensity around 1554 cm ⁻¹ before and after heat treatment is compared. The cyclization rate of polybenzoxazole after heat treatment is 100%, and the cyclization rate of polybenzoxazole before heat treatment = {peak intensity around 1554 cm ⁻¹ before heat treatment / peak intensity around 1554 cm ⁻¹ after heat treatment} × 100 (%) is obtained. For the measurement of the infrared absorption spectrum, for example, “NICOLET6700FT-IR” (manufactured by Thermo Electron) is used.

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

<< Polybenzoxazole precursor (A5-2) >>
The polybenzoxazole precursor (A5-2) is dehydrated and cyclized to produce polybenzoxazole (A5-1), preferably polybenzoxazole (A5-1) having a structural unit (a5-1). It is a compound that can be A precursor (A5-2) has a structural unit represented, for example by a formula (a5-2).

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

In 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 divalent organic group represented by tetravalent organic group and Y ¹ represented by X ^1, include the same groups as the groups exemplified as X ¹ and Y ¹ in each formula (a5-1) It is done.

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

<< Synthesis Method of Polybenzoxazole (A5-1) and its Precursor (A5-2) >>
The polybenzoxazole precursor (A5-1) can be obtained, for example, by polymerizing at least one selected from dicarboxylic acids, diesters thereof and dihalides and diamines having two hydroxyl groups. In order to increase the reaction yield, an active ester dicarboxylic acid derivative obtained by reacting dicarboxylic acid with 1-hydroxybenzotriazole or the like in advance may be used as the diester.

  The said use ratio is 0.5-4 mol with respect to the sum total of 1 mol of the said dicarboxylic acid, a diester body, and a dihalide body, for example, Preferably it is 1-2 mol. In the polymerization, the mixed solution is preferably heated at 50 to 200 ° C. for 1 to 72 hours.

  Polybenzoxazole (A5-1) is synthesized, for example, by synthesizing polybenzoxazole precursor (A5-2) by the above method and then dehydrating and cyclizing this polybenzoxazole precursor (A5-2). can do.

  A known method can be applied as the cyclization reaction of the polybenzoxazole precursor (A5-2). In the case of the thermal 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, it may be carried out while removing water in the system using an azeotropic solvent such as toluene, xylene, mesitylene and the like.

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

<< Polyolefin (A6) >>
Examples of the polyolefin (A6) include a cyclic olefin polymer having a protic polar group. The 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 Group 15 or 16 of the periodic table is preferably an atom belonging to the second or third period of Group 15 or 16 of the periodic table, and more preferably an oxygen atom, nitrogen atom or sulfur An atom, particularly preferably an oxygen atom.

  Examples of the protic polar group include polar groups having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a primary amino group, a secondary amino group, and a primary group Examples include polar groups having nitrogen atoms such as amide groups and secondary amide groups (imide groups); polar groups having sulfur atoms such as thiol groups. Among these, a polar group having an oxygen atom is preferable, more preferably a hydroxyl group or a carboxyl group, still more preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group.

  In the following description, examples of 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) Examples include an acryloyl group, a carbonyl group, a sulfonyl group, an N-substituted imide group, an epoxy group, and a carbonyloxycarbonyl group (dicarboxylic acid anhydride structure). Among these, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an N-substituted imide group, a halogen atom and a cyano group are preferable, and an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group and an N-substituted imide group are more preferable. N-substituted imide groups are particularly preferred.

  The cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin having a cyclic structure such as an alicyclic ring or an aromatic ring and a carbon-carbon double bond. The cyclic olefin polymer may have a structural unit derived from a monomer other than the cyclic olefin.

  Hereinafter, the structural unit derived from the monomer A is also referred to as “monomer A unit”.

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

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

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

  Examples of the monomer that forms the cyclic olefin polymer having a protic polar group include, for example, a cyclic olefin (a) having a protic polar group, a cyclic olefin (b) having a polar group other than the protic polar group, and polar Examples thereof include a cyclic olefin having no group (c) and a monomer (d) other than the cyclic olefin. The monomer (d) may have a protic polar group or other polar group, and may not have a polar group at all. The cyclic olefins (a) to (c) are also referred to as “monomers (a) to (c)”, respectively.

  The cyclic olefin polymer having a protic polar group includes a monomer (a), at least one selected from the monomer (b) and the monomer (c), and a monomer (if necessary) d), and more preferably, the monomer (a), the monomer (b) and, if necessary, the monomer (d).

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

In formula (a6-1), R ^{a1 to} R ^a4 each independently represent 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 above-described 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 to 2, preferably 0 or 1. Examples of the divalent organic group in X include an alkylene group having 1 to 18 carbon atoms such as a methylene group and an ethylene group, and an arylene group having 6 to 24 carbon atoms such as a phenylene group.

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

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

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

  A monomer (a) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the monomer (b) include cyclic olefins represented by the following formula.

In the formula (b6-1), R ^b1 is a polar group other than the above-mentioned protic polar group, preferably an acyloxy group having 2 to 12 carbon atoms such as an acetoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, n- C2-C12 alkoxycarbonyl groups such as propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, and aryl groups having 7-24 carbon atoms such as phenoxycarbonyl group A roxycarbonyl group, a cyano group, or a halogen atom such as a chlorine atom; R ^b2 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms such as a methyl group. R ^b3 and R ^b4 are hydrogen atoms. m is an integer of 0 to 2, preferably 0 or 1.

R ^{b1 to} R ^b4 , in any combination, form a 3- to 5-membered heterocyclic structure containing an oxygen atom or a nitrogen atom as a ring atom together with the two carbon atoms to which they are bonded. Also good.

Examples of the 3-membered heterocyclic structure include an epoxy structure. The 5-membered heterocyclic structure includes a dicarboxylic anhydride structure [—C (═O) —O—C (═O) —], a dicarboximide structure [—C (═O) —NR ^b5 —C (═O )-] And the like. R ^b5 is an aryl group having 6 to 24 carbon atoms such as a phenyl group, a naphthyl group, and an anthracenyl group. Among these, a dicarboximide structure is preferable.

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

  A monomer (b) may be used individually by 1 type, and may be used in combination of 2 or more type.

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-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2 -Ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo [8.4.0.1 ^11,14. 0 ^3,7 ] pentadeca-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 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo [9.2.1.0 ^2,10. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-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 ] pentadeca-5,12-diene.

  A monomer (c) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the monomer (d) other than the cyclic olefin include a chain olefin. Examples of the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, C2-C20 α-olefins such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, and the like.

  A monomer (d) may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 monomers (b) to (d) as desired. it can. The polymer obtained by polymerization may be further hydrogenated. Hydrogenated polymers are also included in cyclic olefin polymers having a protic polar group.

  The polymerization method for polymerizing the monomer (a) with at least one monomer selected from the monomers (b) to (d) as desired may be in accordance with a conventional method. Examples include a ring polymerization method and an addition polymerization method.

  As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the polymerization catalyst is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1: 1,000,000, more preferably in the molar ratio of metal compound to cyclic olefin in the polymerization catalyst. Is in the range of 1: 1,000 to 1: 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 for hydrogenation of olefin compounds can be used. Specific examples include Ziegler type homogeneous catalysts, noble metal complex catalysts, and supported noble metal catalysts.

  Among these hydrogenation catalysts, side reactions such as functional group modification do not occur, and noble metal complex catalysts such as rhodium and ruthenium can be used because carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. A nitrogen-containing heterocyclic carbene compound having a high electron donating property or a ruthenium catalyst coordinated with a phosphine is particularly preferable.

  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 hydrogenating the polymer if desired. Can be obtained. Hydrogenation may be performed on the polymer before introduction of the protic polar group. Moreover, the cyclic olefin polymer having a protic polar group may be further modified to introduce a protic polar group.

  The cyclic olefin polymer having no protic polar group is obtained by polymerizing, for example, at least one monomer selected from monomers (b) to (c) and, if necessary, the monomer (d). Can be obtained.

  As a modifier for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used. Examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and atropic acid. Unsaturated carboxylic acids such as cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl 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, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. Alcohol and the like.

  The modification reaction of the cyclic olefin polymer using the above modifier may be performed according to a conventional method, and is usually performed in the presence of a radical generator.

  As the cyclic olefin polymer having a protic polar group, for example, a polymer having a structural unit represented by the formula (A6-1) is preferred, and the structural unit represented by the formula (A6-1) and the formula (A6) -2) is more preferable.

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 skeletal structure in which two cyclic structures are bonded to ring carbon atoms constituting the cyclic structure. As a general structure of the cardo structure, a structure in which two aromatic rings (eg, benzene ring) are bonded to the 9th-position carbon atom of the fluorene ring can be mentioned.

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

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

  The cardo resin is formed by polymerizing a skeleton having the cardo structure by a reaction between functional groups bonded thereto. A cardo resin has, for example, a structure in which a main chain and a cyclic structure that is a bulky side chain are connected by 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, but may be a copolymer with other copolymerizable monomers. The polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.

  Examples of the cardo resin include a polymer of a monomer having a cardo structure.

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

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

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

  A commercially available product can also be used as the cardo resin. For example, polyester compounds having a cardo structure such as Ogzol CR-TR1, Ogzol CR-TR2, Ogzol CR-TR3, Ogzol CR-TR4, Ogzol CR-TR5, Ogzol CR-TR6 manufactured by Osaka Gas Chemical Co., Ltd. It is done.

[Photosensitive agent (B)]
Examples of the photosensitive agent (B) include a photo acid generator and a photo radical polymerization initiator. A radiation sensitive material can exhibit a radiation sensitive characteristic by containing a photosensitive agent (B), and can have favorable radiation sensitivity.

  A photosensitive agent (B) may be used individually by 1 type, or may use 2 or more types together.

  Content of the photosensitive agent (B) in a radiation sensitive material is 5-100 mass parts normally with respect to 100 mass parts of polymers (A), Preferably it is 10-65 mass parts, More preferably, it is 15-60. Part by mass. By setting the content of the photosensitive agent (B) in the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to an alkaline aqueous solution or the like serving as a developer can be increased, and the patterning performance can be improved.

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

  Examples of the photoacid generator include quinonediazide compounds, oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylic acid ester compounds. By using these compounds, a material exhibiting positive radiation sensitive characteristics can be obtained.

  As a photo-acid generator, a quinone diazide compound, an oxime sulfonate compound, an onium salt, and a sulfonate compound are preferable, a quinone diazide compound and an oxime sulfonate compound are more preferable, and a quinone diazide compound is particularly preferable.

<Quinonediazide compound>
The quinonediazide compound generates carboxylic acid by processing including irradiation with radiation and development using an aqueous alkali solution. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “host nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide.

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

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

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

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

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

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

  Examples of other mother nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [ 4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl)- 4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

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

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

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

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

<Other examples>
Specific examples of the oxime sulfonate compound include compounds described in JP 2011-227106 A, JP 2012-234148 A, JP 2013-054125 A, and the like. Specific examples of the onium salt include, for example, Japanese Patent No. 5208573, Japanese Patent No. 5397152, Japanese Patent No. 5413124, Japanese Patent Application Laid-Open No. 2004-210525, Japanese Patent Application Laid-Open No. 2008-129623, Japanese Patent Application Laid-Open No. 2010-215616, and Japanese Patent Application Laid-Open No. 2013-2013. And compounds described in publications such as No. 228526.

  Specific examples of other acid generators are described in, for example, Japanese Patent No. 49242256, Japanese Patent Application Laid-Open No. 2011-064770, Japanese Patent Application Laid-Open No. 2011-232648, Japanese Patent Application Laid-Open No. 2012-185430, Japanese Patent Application Laid-Open No. 2013-242540, and the like. Compound.

<< Photo radical polymerization initiator >>
A material that exhibits negative radiation-sensitive properties by using a radical photopolymerization initiator as the photosensitizer (B) and a cross-linking agent (D) such as a polymerizable carbon-carbon double bond-containing compound described later. Can be obtained.

  As a radical photopolymerization initiator, for example, 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′- Biimidazole compounds such as tetraphenyl-1,2'-biimidazole; diethoxyacetophenone, 2- (di Alkylphenone compounds such as tilamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like Acylphosphine oxide compound; 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) ) 1,3,5-triazine and the like; and benzoin such as benzoin; and benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate and 4-phenylbenzophenone.

[Resin (C)]
The resin (C) is at least one selected from a novolak resin, a resole resin, and a condensate of a resole resin. Among these, a novolak resin is preferable because it has good alkali solubility (developability).

  The resin (C) is a substance that develops color when heated. In the insulating film forming method described later, the coating film itself formed from the radiation-sensitive material containing the resin (C) does not have a light-shielding property at a wavelength of 300 to 400 nm before exposure, but by heating after exposure and development. It is presumed that the resin (C) is ketoized and the obtained insulating film has a light shielding property at the wavelength. By using such a resin (C), it is possible to achieve both light shielding properties and alkali developability in a radiation sensitive material.

  For example, the light shielding property is not imparted at about 60 to 130 ° C., which is a heating temperature at the time of pre-baking, and the light shielding property can be imparted at about 300 ° C. or less exceeding the heating temperature at the time of post baking. .

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

In formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, or a divalent alicyclic group having 4 to 30 carbon atoms. A hydrocarbon group, an aralkylene group having 7 to 30 carbon atoms 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 carbon number; 2 to 20 alkylene groups). 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 having a nitrogen atom, a sulfur atom, an oxygen atom, or the like. Good.

Examples of the alkylene group having 2 to 30 carbon atoms in R ¹ include ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene. Group, octadecylene group, nonadecylene group, icosylene group, henicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacosylene group, octacosylene group, nonacosylene group, triaconylene group.

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

Examples of the aralkylene group having 7 to 30 carbon atoms in R ¹ include a benzylene group, a phenethylene group, a benzylpropylene group, and a naphthylene methylene group.

Examples of the group represented by —R ² —Ar—R ² — in R ¹ include a group represented by —CH ₂ —Ph—CH ₂ — (Ph is a phenylene group).

  Examples of the divalent aromatic group having a phenolic hydroxyl group in A include a benzene ring having a phenolic hydroxyl group and a condensed polycyclic aromatic group having a phenolic hydroxyl group. The condensed polycyclic aromatic group having a phenolic hydroxyl group is, for example, a group in which part or all of the hydrogen atoms bonded to the aromatic ring carbon contained in the condensed polycyclic aromatic hydrocarbon group are substituted with hydroxyl groups. is there. Examples of the condensed polycyclic aromatic hydrocarbon group include a naphthalene ring, an anthracene ring, and a phenanthrene ring.

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

The meaning of each symbol in the formulas (c1-1) to (c1-4) is as follows.

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

  However, a2 + a3 is an integer from 1 to 6, b2 + b3 is an integer from 0 to 5, a2 + a3 + b2 + b3 is an integer from 1 to 6, a4 + a5 + a6 is an integer from 1 to 8, and b4 + b5 + b6 is 0 or more It is an integer of 7 or less, and a4 + a5 + a6 + b4 + b5 + b6 is an integer of 1 or more and 8 or less. Further, 1 ≦ a1 + b1 ≦ 4, a2 + b2 ≦ 4, a3 + b3 ≦ 4, a4 + b4 ≦ 4, a5 + b5 ≦ 4, and a6 + b6 ≦ 2.

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

  R is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. May be different. Examples of the hydrocarbon group include alkyl groups such as a methyl group, a propyl group, an isopropyl group, and a t-butyl group. Examples of the alkoxy group include a methoxy group.

In formula (c1-1) to formula (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. 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 nuclei (for example, the following formula (2)). In the formula, * is a bond. The following formulas (1) and (2) are specific examples of the formula (c1-2), but the same applies to the formulas (c1-3) and (c1-4). For convenience, substituents on the benzene nucleus are omitted.

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

  The group A is preferably a group represented by the formula (c1-2), the formula (c1-3) or the formula (c1-4) from the viewpoints of providing light shielding properties and heat resistance and alkali developability. The group represented by c1-2) or formula (c1-3) is more preferable.

  The resin (C) is preferably a novolak resin because it has good alkali solubility (developability). By containing an alkali-soluble novolak resin in the radiation-sensitive material, a radiation-sensitive material with good resolution can be obtained.

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

The resole resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a base catalyst and distilling off unreacted components as necessary. As reaction conditions, phenols and aldehydes are usually reacted at 40 to 120 ° C. for about 1 to 20 hours in a solvent. Thus, for example, an aromatic ring in the phenol, aldehyde groups derived from: resol (Example -R ¹ -OH, R ¹ has the same meaning as R ¹ in the formula (C1)) is bonded A resin can be obtained. The condensate of the resole resin can be obtained by advancing the dehydration condensation reaction by adding heat or acid to the resole resin. This reaction proceeds by dehydration condensation of groups derived from aldehydes contained in the resole resin. When the reaction proceeds by heating, the resol resin or a solution thereof is usually reacted at 60 to 200 ° C. for about 1 to 20 hours. The resole resin and its condensate can be synthesized by the methods described in, for example, Japanese Patent No. 3889274, Japanese Patent No. 4013111, Japanese Patent Application Laid-Open No. 2010-1111013, and the like.

Examples of phenols include:
Compounds having 1 to 4 hydroxyl groups, preferably 1 to 3 and 1 benzene nucleus, specifically phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2, 5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol , 2-propylphenol, 3-propylphenol, 4 Propyl phenol, 2-isopropyl phenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 5-isopropyl-2-methylphenol;
A compound having 1 to 6 hydroxyl groups, preferably 1 to 3 and 2 benzene nuclei (naphthalene type compound), specifically monohydroxynaphthalene such as 1-naphthol and 2-naphthol, 2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3 -Dihydroxynaphthalene such as dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene;
Compounds having 1 to 8 hydroxyl groups, preferably 1 to 3 and 3 benzene nuclei (anthracene type compound or phenanthrene type compound), specifically 1-hydroxyanthracene, 2-hydroxyanthracene, 9 -Monohydroxyanthracene such as hydroxyanthracene, 1,4-dihydroxyanthracene, dihydroxyanthracene such as 9,10-dihydroxyanthracene, 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, 1,2 , 7-trihydroxyanthracene and the like, and hydroxyphenanthrene such as 1-hydroxyphenanthrene;
Is mentioned.

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

  In the synthesis of the resin (C), the amount of aldehydes to be used is usually 0.3 mol or more, preferably 0.4 to 3 mol, more preferably 0.5 to 2 mol, relative to 1 mol of phenols. It is.

  Examples of the acid catalyst in the synthesis of the novolak resin include hydrochloric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. As a base catalyst in the synthesis | combination of a resole resin, ammonia water and a tertiary amine are mentioned, for example.

  The weight average molecular weight (Mw) in terms of polystyrene of the resin (C) is usually 100 to 50,000, preferably 150 to 10,000, more preferably as measured by gel permeation chromatography (GPC). Is 500 to 6,000. Resin (C) having Mw in the above range is preferable in terms of light shielding properties 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.

  Resin (C) may be used individually by 1 type, or may use 2 or more types together.

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

[Crosslinking agent (D)]
The crosslinking agent (D) is a compound having a crosslinkable functional group. As a crosslinking agent (D), the compound which has a 2 or more crosslinkable functional group in 1 molecule is mentioned, for example.

  When an insulating film made of a radiation-sensitive material is used as a component of an organic EL element, the organic EL element deteriorates when the organic light emitting layer comes into contact with moisture. Is preferably reduced. Moreover, a negative radiation sensitive material can be obtained by using a radical photopolymerization initiator as the photosensitive agent (B) and using a polymerizable carbon-carbon double bond-containing compound as the crosslinking agent (D).

  Examples of crosslinkable functional groups include isocyanate groups and blocked isocyanate groups, oxetanyl groups, glycidyl ether groups, glycidyl ester groups, glycidyl amino groups, methoxymethyl groups, ethoxymethyl groups, benzyloxymethyl groups, acetoxymethyl groups, benzoic groups. Roxymethyl group, formyl group, acetyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; polymerizability such as vinyl group, vinylidene group, (meth) acryloyl group Examples thereof include a group having a carbon-carbon double bond.

  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, novolac resin-based epoxy compounds, resole resin-based epoxy compounds, and poly (hydroxystyrene). Epoxy compound, methoxymethyl group-containing phenol compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxy Alkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzo Anamin resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxymethyl group-containing phenol compound, polymerizable carbon-carbon A double bond containing compound is mentioned.

  Examples of the oxetanyl group-containing compound include 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl, 3,7-bis (3-oxetanyl) -5-oxanonane, and 3,3 ′-[1. , 3- (2-Methylenyl) propanediylbis (oxymethylene)] bis (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,2-bis [ (3-Ethyl-3-oxetanyl) methoxymethyl] ethane, 1,3-bis [(3-ethyl-3-oxetanyl) methoxymethyl] propane, ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether Dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether, triethylene glycol bis [(3-ethyl -3-Oxetanyl) methyl] ether, tetraethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclodecanediyldimethylenebis [(3-ethyl-3-oxetanyl) methyl] ether, trimethylol Propane 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, dipentae Thritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol tetrakis [(3-ethyl-3-oxetanyl) ) Methyl] ether.

  Examples of the oxetanyl group-containing compound further include a reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) Reaction product of methyl] ether and caprolactone, ditrimethylolpropanetetrakis [(3-ethyl-3-oxetanyl) methyl] ether, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide Reaction product, reaction product of bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide When Reaction product, reaction product of hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, bisphenol F bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide And the reaction product.

  As a crosslinking agent (D), the compound which has the group by which the isocyanate group was blocked by the protective group can also be mentioned, for example. The said compound is also called "block isocyanate compound." A group in which an isocyanate group is blocked with a protective group is also referred to as a “blocked isocyanate group”.

  Examples of the blocked isocyanate compound include JP2013-225031, JP51332096, JP5071686, JP2013-223859, JP51999752, JP200341185, Examples thereof include compounds described in Japanese Patent No. 4879557 and Japanese Patent Application Laid-Open No. 2006-119441.

  Examples of the polymerizable carbon-carbon double bond-containing compound include polyfunctional (meth) acrylic acid esters, specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol diester. (Meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F Alkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide added trimethylolpropane tri (meth) acrylate, ethylene oxide added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide added Pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra ( (Meth) acrylate, propylene oxide addition di Entaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone added Dipentaerythritol hexa (meth) acrylate is mentioned.

  A crosslinking agent (D) may be used individually by 1 type, or may use 2 or more types together.

  In a radiation sensitive material, content of a crosslinking agent (D) is 1-210 mass parts normally with respect to 100 mass parts of polymers (A), Preferably it is 4-160 mass parts, More preferably, it is 10-10 mass parts. 150 parts by mass, more preferably 15 to 100 parts by mass. When the content of the crosslinking agent (D) is not less than the lower limit of the above range, the low water absorption of the insulating film tends to be improved. When the content of the crosslinking agent (D) is not more than the upper limit of the above range, the heat resistance of the insulating film tends to be improved.

[Solvent (E)]
The solvent (E) can be used to make the radiation sensitive material liquid.

  As the solvent (E), diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol Monoalkyl ether propionates, triethylene glycol dialkyl ethers, hydroxy group-containing ketones, cyclic ethers or cyclic esters are preferred.

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the solvent (E) include propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), propylene glycol monomethyl ether (hereinafter also referred to as “PGME”), diethylene glycol ethyl methyl ether (hereinafter also referred to as “EDM”), diacetone alcohol. (Hereinafter also referred to as “DAA”) and γ-butyrolactone (hereinafter also referred to as “BL”) are particularly preferred.

  Moreover, in one embodiment, it is preferable to use (gamma) -butyrolactone as a solvent (E), and the mixed solvent containing BL is preferable. As content of BL, 70 mass% or less is preferable in the total amount of 100 mass% of a solvent (E), and 20-60 mass% is more preferable. BL is preferably used in combination with at least one selected from PGMEA, PGME, EDM and DAA. By setting the BL content within the above range, the dissolved state of the polymer (A) in the radiation-sensitive material tends to be favorably maintained.

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

  The solvent exemplified above as the solvent (E) has a low water absorption compared to NMP. Therefore, the above material can be prepared using a low water absorption solvent without using NMP having high water absorption. As a result, the material can exhibit low water absorption. Since the solvent exemplified as the solvent (E) has high safety, the safety of the material can be improved.

  When using the solvent illustrated above as a solvent (E), the insulating film formed from the said material can be made into low water absorption. Therefore, the above material can be suitably used for forming an insulating film included in the organic EL element.

  A solvent (E) may be used individually by 1 type, or may use 2 or more types together.

  In the radiation-sensitive material, the content of the solvent (E) is an amount such that the solid content concentration of the material is usually 5 to 60% by mass, preferably 10 to 50% by mass, more preferably 15 to 40% by mass. . Here, solid content means all components other than a 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 contains other optional components such as an adhesion assistant (F) and a surfactant (G) as necessary within the range not impairing the effects of the present invention in addition to the above essential components and suitable components. May be. Other optional components may be used alone or in combination of two or more.

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

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

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

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

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

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

  The content of the surfactant (G) in the radiation-sensitive material is preferably 20 parts by mass or less, more preferably 0.01 to 15 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the polymer (A). .05 to 10 parts by mass. By making content of surfactant (G) into the said range, the film thickness uniformity of the coating film formed can be improved more.

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

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

  According to the method for forming an insulating film, an insulating film having excellent light shielding properties and a forward tapered shape at the boundary can be formed on the TFT substrate. In addition, since the material is excellent in radiation sensitivity, an insulating film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development, and heating using the characteristics.

<< Process 1 >>
In step 1, a radiation-sensitive material is applied to the substrate surface, and the coating film is formed by removing the solvent (E), preferably by pre-baking. The film thickness of the coating film is preferably 0.3 to 15.0 μm, more preferably 0.5 to 10.0 μm, and still more preferably 1.0 to 5.0 μm as a value after pre-baking. it can.

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

  Examples of the method for applying the radiation sensitive material include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an ink jet method. Among these coating methods, spin coating and slit die coating are preferable.

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

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

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

<< Process 3 >>
In step 3, the coating film irradiated with radiation in step 2 is developed. Thus, for example, when a positive type radiation sensitive material is used, a radiation irradiated part is removed, and when a negative type radiation sensitive material is used, a non-irradiated part is removed, and a desired pattern is formed. Can be formed. As the developer used for the development treatment, an alkaline aqueous solution is preferable.

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

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

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

<< Process 4 >>
In Step 4, after Step 3, an insulating film is obtained by performing a heat treatment (post-bake treatment) on the coating film 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 not more than 300 ° C., and the heating time is, for example, 5 minutes to 90 minutes, although it varies depending on the type of heating equipment. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used. For example, a hot plate or an oven can be used for the heat treatment.

  By the heat treatment in the above temperature range, the insulating film is provided with a light shielding property such that the total light transmittance at a wavelength of 300 to 400 nm is 15% or less, preferably 10% or less, particularly preferably 6% or less. In this manner, an insulating film having a target pattern can be formed on the substrate.

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

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

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

  The organic EL device 1 of FIG. 3 is an active matrix organic EL device having a plurality of pixels formed in a matrix. The organic EL device 1 may be either a top emission type or a bottom emission type. The property of the material constituting each member, such as transparency, is appropriately selected according to the top emission type and the bottom emission type.

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

  The support substrate 2 is made of an insulating material. When the organic EL device 1 is a bottom emission type, the support substrate 2 is required to have high transparency. Therefore, as the insulating material, for example, transparent resins such as highly transparent polyethylene terephthalate, polyethylene naphthalate, and polyimide, and glass materials such as alkali-free glass are preferable. On the other hand, when the organic EL device 1 is a top emission type, any insulator can be used as the insulating material, and the above-described transparent resin and glass material can be used.

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

  The semiconductor layer can be formed using the above-described oxide semiconductor including one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn. In the organic EL device 1, since the second insulating film 7 (partition wall) has a light shielding property, light generated from the organic light emitting layer 8 can be prevented or reduced from reaching the semiconductor layer. Therefore, it is possible to use a semiconductor layer made of IGZO or the like that is easily photodegraded.

  The first insulating film 4 is a flattening film that plays a role of flattening surface irregularities due to the TFT 3. The first insulating film 4 is formed so as to cover the entire TFT 3. The first insulating film 4 may be formed using the radiation-sensitive material described above, or may be formed using a conventionally known radiation-sensitive material. The film thickness of the first insulating film 4 is preferably increased so as 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 in the above-described insulating film forming method.

  The anode 5 forms a pixel electrode. The anode 5 is formed on the first insulating film 4 with 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 highly transparent ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or tin oxide. When the organic EL device 1 is a top emission type, the anode 5 is required to have light reflectivity. Therefore, as the material of the anode 5, APC alloy (silver, palladium, copper alloy), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium alloy), NiCr (nickel and nickel) having high light reflectivity are used. Chromium alloys) are preferred.

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

  The second insulating film 7 serves as a partition (bank) having a recess 70 that defines the arrangement region of the organic light emitting layer 8. The second insulating film 7 is formed so as to cover a part of the anode 5 and to expose a part of the anode 5. The second insulating film 7 has a forward tapered shape in cross section at the boundary portion where the anode 5 is exposed. The second insulating film 7 can be formed using the above-described radiation-sensitive material by the method described in the insulating film forming method.

  The second insulating film 7 can be formed by patterning the coating film by exposure / development so that a plurality of recesses 70 in which the organic light emitting layer 8 is formed are arranged in a matrix in a plan view. .

  The second insulating film 7 is preferably formed so as to fill the through hole 6. By adopting such a configuration, the insulating film formed on the first insulating film 4 and the insulating film formed in the through-hole 6 allow light generated from the organic light emitting layer 8 to enter the semiconductor layer of the TFT 3. It becomes a defensive wall that prevents or reduces reaching. Further, when there are two or more through holes 6 corresponding to one TFT 3, it is possible to further prevent or reduce the light generated from 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 of the TFT 3. Here, “upward” is a direction from the support substrate 2 toward the sealing substrate 11. Since the second insulating film 7 has a light shielding property, light generated from the organic light emitting layer 8 can be prevented or reduced from reaching the semiconductor layer.

  The 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 to 15.0 μm, and preferably 0.5 to 10. 0 μm is more preferable, and 1.0 to 5.0 μm is more preferable.

  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 emits electroluminescence. The organic light emitting layer 8 is formed on the anode 5 in a region defined by the second insulating film 7, that is, a recess 70. In this way, by forming the organic light emitting layer 8 in the recess 70, the periphery of the organic light emitting layer 8 is surrounded by the second insulating film 7, and adjacent pixels can be partitioned.

  The organic light emitting layer 8 is formed in contact with the anode 5 at 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 means the distance from the bottom surface of the organic light emitting layer 8 on the anode 5 to the top surface of the organic light emitting layer 8 on the anode 5.

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

  The cathode 9 is formed so as to cover a plurality of pixels in common and serves as a common electrode of the organic EL device 1. The cathode 9 is made of 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 and an IZO electrode. When the organic EL device 1 is a bottom emission type, the cathode 9 does not need to be a visible light transmissive electrode. In that case, examples of the constituent material of the cathode 9 include barium (Ba), barium oxide (BaO), aluminum (Al), and an alloy containing Al.

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

  The sealing substrate 11 seals the main surface (surface opposite to the support substrate 2 in the TFT substrate) on which the organic light emitting layer 8 is disposed. Examples of the sealing substrate 11 include glass substrates such as non-alkali glass substrates. The main surface on which the organic light emitting layer 8 is disposed is preferably sealed with the sealing substrate 11 through the sealing layer 12 using a sealing agent applied in the vicinity of the outer peripheral edge of the TFT substrate. The sealing layer 12 can be, for example, a layer of an inert gas such as dried nitrogen gas or a layer of a filling material such as an adhesive.

  In the organic EL device 1 of the present embodiment, since the second insulating film 7 has a light shielding property with respect to light having a wavelength of 300 to 400 nm, it is possible to suppress light deterioration of the semiconductor layer due to use of the device or the like. it can. Further, the first insulating film 4 and the second insulating film 7 can be formed using a radiation-sensitive material having low water absorption, and in the process of forming these insulating films 4 and 7, low water absorption It is possible to perform a treatment such as cleaning using a sexual material. Therefore, a slight amount of water contained in the insulating film forming material in the form of adsorbed water or the like can be prevented from gradually entering the organic light emitting layer 8, and deterioration of the organic light emitting layer 8 and deterioration of the light emitting state can be reduced. .

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” means “part by mass” unless otherwise specified.

[GPC analysis]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer (A) and the resin (C) were measured under the following conditions by gel permeation chromatography (GPC).
-Standard material: Polystyrene conversion-Equipment: Tosoh Corporation, trade name: HLC-8020
Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected Solvent: Tetrahydrofuran Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1mL / min
[NMR analysis]
The content of the phenyl group in the polysiloxane (A1) is determined by measuring the ²⁹ Si-nuclear magnetic resonance spectrum using “JNM-ECS400” (manufactured by JEOL Ltd.), and the peak of Si bonded to the phenyl group. It calculated | required from ratio of the area and the peak area of Si which the phenyl group has not couple | 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 a 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 the diamine compound was dissolved in the polymerization solvent, 71 g of 4,4′-oxydiphthalic dianhydride as an acid dianhydride was added. Then, after making it react at 60 degreeC for 1 hour, 19 g of maleic anhydride as a terminal blocker was added, and it was made to react at 60 degreeC for further 1 hour, Then, it heated up and made it react at 180 degreeC for 4 hours. About 600 g of a polyimide solution having a solid content concentration of about 35% by mass including the polymer (A-1) was obtained. Mw of the obtained polymer (A-1) was 8000.

[Synthesis Example A2] Synthesis of Polymer (A-2) (Acrylic Polymer)
After the atmosphere in the flask was replaced 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 charged. Subsequently, 20.0 g of methacrylic acid, 45.0 g of dicyclopentanyl methacrylate, and 30.0 g of 3-ethyl-3-methacryloyloxymethyloxetane were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 100 ° C. for 1 hour to complete the polymerization. Thereafter, the reaction product solution was dropped into a large amount of methanol to solidify the reaction product. The coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of methanol.

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

[Synthesis Example A3] Synthesis of Polymer (A-3) (Acrylic Polymer)
The procedure was the same as in Synthesis Example A2, except that 20.0 g of 2-methacryloyloxyethyl succinic acid, 45.0 g of dicyclopentanyl methacrylate, and 30.0 g of 3,4-epoxycyclohexylmethyl methacrylate were used as monomers. The 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 mol) of a dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid with 2 mol of 1-hydroxybenzotriazole, hexafluoro-2,2-bis ( 3-Amino-4-hydroxyphenyl) propane (366.3 parts, 1.00 mol) was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. -3000 parts of methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath.

  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 the mixture was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (mass ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain a polybenzoxazole precursor. (A-4) was obtained. Γ-Butyrolactone was added so that the concentration of the polymer (A-4) was 35% by mass to obtain a γ-butyrolactone solution of the polymer (A-4). The weight average molecular weight (Mw) of the obtained polymer (A-4) was 15000.

[Synthesis Example A5] Synthesis of Polymer (A-5) (Polysiloxane)
In a 500 mL three-necked flask, 63.39 parts (0.55 mol) of methyltrimethoxysilane, 69.41 parts (0.35 mol) of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 24.64 parts (0.1 mol) and diacetone alcohol 150.36 parts, while stirring at room temperature, 55.8 parts of water was charged with 0.338 parts of phosphoric acid (0.2% by mass relative to the charged monomers). ) Was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 115 parts of methanol and water as by-products were distilled off. Diacetone alcohol is added to the diacetone alcohol solution of the obtained polymer (A-5) so that the concentration of the polymer (A-5) is 35% by mass, and the diacetone of the polymer (A-5) is added. An alcohol solution was obtained. The weight average molecular weight (Mw) of the obtained polymer (A-5) was 5000, and the phenyl group content with respect to 100 mol of Si atoms was 35 mol.

[Synthesis Example A6] Synthesis of Polymer (A-6) (Polyolefin)
Into a nitrogen-substituted 1000 mL autoclave, 8-carboxytetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene 60 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 40 parts, 1,5-hexadiene 2.8 parts, (1,3-dimesi Tilimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and 400 parts of diethylene glycol ethyl methyl ether were charged, and the polymerization reaction was carried out at 80 ° C. for 2 hours with stirring to obtain a polymer (A-6). A polymer solution containing ') was obtained. To this polymer solution, 0.1 part of bis (tricyclohexylphosphine) ethoxymethyleneruthenium dichloride as a hydrogenation catalyst was added, and hydrogen was dissolved at a pressure of 4 MPa for 5 hours to proceed the hydrogenation reaction. 1 part was added, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring. Next, the solution is taken out, filtered through a fluororesin filter having a pore size of 0.2 μm to separate activated carbon, and hydrogen containing a polymer (A-6) that is a hydride of the polymer (A-6 ′) 490 parts of an additional reaction solution was obtained. The hydrogenation reaction solution containing the polymer (A-6) obtained here had a solid content concentration of 21% by mass, and the yield of the polymer (A-6) was 102 parts. The obtained hydrogenation reaction solution of the polymer (A-6) was concentrated with 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)
CR-TR5 (Osaka Gas Chemical Co., Ltd.) which is a propylene glycol monomethyl ether solution of a cardo resin is a product having a solid content of 52.7% by mass and a solid content acid value of 135 KOHmg / g. 100 parts of CR-TR5 was weighed, 50.57 parts of propylene glycol monomethyl ether was added and stirred. Thus, a cardo resin solution (A-7) having a solid concentration of 35% by mass was obtained.

<Synthesis of Resin (C)>
[Synthesis Example C1] Synthesis of Novolak Resin (C-1) In a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92 mass% paraformaldehyde (1.0 mol in terms of formaldehyde) were charged. Subsequently, 3.4 g of paratoluenesulfonic acid was added with stirring. Then, it was made to react at 100 degreeC for 8 hours. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separating funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water became neutral, the solvent was removed from the organic layer under heating and reduced pressure to obtain 140 g of a novolak resin (C-1) composed of a structural unit represented by the following formula. The obtained novolak resin (C-1) had a weight average molecular weight (Mw) of 2000.

From the measurement chart using a Fourier transform infrared spectrophotometer (FT-IR), absorption (2800 to 3000 cm ⁻¹ ) derived from expansion and contraction due to a methylene bond can be confirmed as compared with the raw material, and further, absorption derived from aromatic ether (1000 ˜1200 cm ⁻¹ ) could not be found. Based on these results, it was identified that no dehydration etherification reaction between hydroxyl groups (hydroxyl disappearance) occurred in this synthesis example, and a novolak resin having a methylene bond was obtained. These identifications are the same in the following synthesis examples C2 to C5.

[Synthesis Example C2] Synthesis of Novolak Resin (C-2) In a flask equipped with a thermometer, a condenser tube, a fractionating tube and a stirrer, 144.2 g (1.0 mol) of 1-naphthol and 134.1 g of terephthalaldehyde (1.0 mol) and 3.0 g of trifluoromethanesulfonic acid were charged and reacted at 150 to 160 ° C. for 4 hours while stirring. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separating funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 220 g of a novolak resin (C-2) comprising a structural unit represented by the following formula. The obtained novolak resin (C-2) had a weight average molecular weight (Mw) of 1500.

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

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

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

<Preparation of radiation sensitive material>
The polymers (A) used for the preparation of the radiation-sensitive material are the synthesis examples A1 to A6 and the polymers (A-1) to (A-7) of the preparation example A7, and the resin (C) is the synthesis example C1 to C1. C5 novolak resins (C-1) to (C-5), the photosensitive agent (B), the crosslinking agent (D), the solvent (E), the adhesion assistant (F) and the surfactant (G), It is as follows.

Photosensitizer (B)
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (2.0 mol) (Toyo Gosei Co., Ltd.)
B-2: 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“IRG-379EG” manufactured by BASF)
Cross-linking agent (D)
D-1: 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl ("OXBP" from Ube Industries)
D-2: “C-357” from Gunei Chemical Industry Co., Ltd.
D-3: “M-405” from Toagosei Co., Ltd.
Solvent (E)
E-1: Mixed solvent of 30:20:50 by mass ratio of γ-butyrolactone (BL), propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) 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 surfactant
("SH8400" manufactured by Toray Dow Corning)
[Preparation Example 1]
In a polymer solution containing the polymer (A-1) of Synthesis Example A1 (an amount corresponding to 25 parts (solid content) of the polymer (A-1)), (B-1) 10 parts, (C-1) 40 parts, (D-1) 15 parts, (D-2) 5 parts, (F-1) 4 parts, (G-1) 1 part, and (E-1) were mixed, and the solid content concentration was 25. The positive type material 1 was prepared by adjusting the mass% and filtering through a membrane filter having a diameter of 0.2 μm.

[Preparation Examples 2-33]
Positive materials 2 to 23 and 30 to 31 and negative materials 24 to 29 and 32 to 33 were prepared in the same manner as in Preparation Example 1, except that the components of the types and blending amounts shown in Table 1 were used.

[Examples and Comparative Examples]
Using the radiation-sensitive materials 1 to 33 of Preparation Examples 1 to 33, an insulating film and an organic EL element were produced by the method described below. The patterning property, LWR (Line Width Roughness), light shielding property, taper angle, water absorption and heat resistance of the obtained insulating film, and device characteristics of the obtained organic EL device were evaluated by the following methods.

<Patternability>
Using a clean track (manufactured by Tokyo Electron Co., Ltd .: Mark VZ), the positive type materials obtained in Preparation Examples 1 to 23 and 30 to 31 were applied on a silicon substrate, and then on a hot plate at 120 ° C. for 2 minutes. Pre-baked to form a coating film. This coating film was exposed using an exposure machine (Nikon i-line stepper “NSR-2005i10D”) through a pattern mask having a predetermined pattern at an exposure amount of 100 mJ / cm ² at a wavelength of 365 nm. Thereafter, development was performed by using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washed with running ultrapure water for 1 minute, dried, and 5 μm square on a silicon substrate. A coating film having a pattern in which a plurality of through holes were arranged in a line was formed. This coating film was post-baked on a hot plate at 250 ° C. for 60 minutes to form an insulating film having the pattern and the film thickness described in Table 2.

Moreover, after apply | coating the negative material obtained by the preparation examples 24-29 and 32-33 on a silicon substrate using the clean track (Tokyo Electron make: Mark VZ), on a hotplate at 120 degreeC. Pre-baked for 2 minutes to form a coating film. This coating film was exposed using an exposure machine (Nikon i-line stepper “NSR-2005i10D”) through a pattern mask having a predetermined pattern at an exposure amount of 300 mJ / cm ² at a wavelength of 365 nm. Thereafter, development was carried out using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 120 seconds, washed with running ultrapure water for 1 minute, dried, and dried on a silicon substrate at 5 μm square. A coating film having a pattern in which a plurality of through holes were arranged in a line was formed. This coating film was post-baked on a hot plate at 250 ° C. for 60 minutes to form an insulating film having the pattern and the film thickness described in Table 2.

  At this time, it was confirmed in the coating film whether the exposed portion after development was completely dissolved in the case of a positive type material or whether the non-exposed portion after development was completely dissolved in the case of a negative type material. When a 5 μm square pattern is formed and the insulating film is formed without peeling off or developing residue “excellent”, when a 5 μm square pattern is formed and the insulating film is not peeled off, but there is some developed residue Was determined as “bad” when a 5 μm square pattern could not be formed or when the insulating film peeled off.

<LWR>
Using a scanning electron microscope (SEM; "SU3500" from Hitachi High-Technology Corp.), the line pattern of the coating film before post-baking formed in the above <patterning property> was observed from the top of the pattern. The line width was measured at 10 arbitrary points. The 3 sigma value (variation) of the measured line width was defined as LWR (μm). When the value of this LWR is 0.4 μm or less, it is “good”, when it exceeds 0.4 μm and 0.8 μm or less, it is “good”, and when it exceeds 0.8 μm, it is “bad”. .

<Light shielding>
Using a clean track (manufactured by Tokyo Electron Co., Ltd .: Mark VZ), the radiation-sensitive material obtained in the above preparation example was applied on a glass substrate (Corning “Corning 7059”), and then heated on a hot plate at 120 ° C. After pre-baking for 2 minutes at 250 ° C., it was post-baked on a hot plate at 250 ° C. for 60 minutes to form an insulating film having a film thickness shown in Table 2.

  For the glass substrate having this insulating film, the total light transmittance was measured in the wavelength range of 300 nm to 780 nm using a spectrophotometer (“150-20 type double beam” manufactured by Hitachi, Ltd.). The total light transmittance at 400 nm was determined. The light shielding property is “excellent” when the maximum total light transmittance at a wavelength of 300 to 400 nm is 6% or less, “good” when it exceeds 6% and 10% or less, and exceeds 10% and exceeds 15%. In the following cases, it was set as “slightly good”, and when it exceeded 15%, it was set as “bad”.

<Taper angle and film thickness>
In the <patterning> insulating film, the vertical cross-sectional shape in the direction perpendicular to the plurality of through-hole lines was observed with SEM (Hitachi High-Technology “SU3500”). The taper 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>
Using a clean track (Tokyo Electron Co., Ltd .: Mark VZ), the radiation-sensitive material obtained in the above preparation example was applied onto a silicon substrate, prebaked at 120 ° C. for 2 minutes on a hot plate, and then hot plate The film was post-baked at 250 ° C. for 60 minutes to form an insulating film having a thickness of 3.0 μm.

This insulating film was heated from normal temperature to 200 ° C. at a temperature rising rate of 30 ° C./min using Thermal Desorption Spectroscopy (“TDS1200” manufactured by ESCO) at a vacuum degree of 1.0 × 10 ⁻⁹ Pa. At that time, the sample surface and the gas desorbed from the sample were measured as a detected value of the peak of water (M / z = 18) with a mass spectrometer (“5973N” manufactured by Agilent Technologies). The integrated value [A · sec] of the total peak intensity from 60 ° C. to 200 ° C. was taken to evaluate the water absorption. The water absorption is “excellent” when the integrated value [A · sec] of the total peak intensity from 60 ° C. to 200 ° C. is 3.0 × 10 ⁻⁸ or less, exceeding 3.0 × 10 ⁻⁸ . When it was 0 × 10 ⁻⁸ or less, “good”, and when it exceeded 5.0 × 10 ⁻⁸ , it was determined as “bad”.

<Heat resistance>
In the same manner as in the evaluation of <Water Absorption>, an insulating film is formed using a radiation-sensitive material, and this insulating film is measured from 100 ° C. using a thermogravimetric apparatus (“TGA2950” manufactured by TA Instruments). The TGA measurement was performed at 500 ° C. (in the air, the heating rate was 10 ° C./min) to obtain the 5% weight loss temperature. The heat resistance was defined as “excellent” when the 5% weight loss temperature exceeded 350 ° C., “good” when 350 ° C. to 330 ° C., and “bad” when 330 ° C. or lower.

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

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

  Using a clean track (manufactured by Tokyo Electron: Mark VZ), the radiation-sensitive material obtained in the above preparation example was applied on the TFT substrate, then pre-baked at 120 ° C. for 2 minutes on the hot plate, and then hot plate The insulating film having the film thickness shown in Table 2 was formed by post-baking at 250 ° C. for 60 minutes.

<Switching response characteristics>
The device characteristics were evaluated as switching response characteristics. The switching response characteristic was evaluated by measuring the ON / OFF ratio. The ON / OFF ratio was calculated by measuring the current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode using a prober and a semiconductor parameter analyzer. Specifically, the drain electrode is set to +10 V under the condition that the semiconductor layer is irradiated with white light having an illuminance of 30000 lux centered at a wavelength of 450 nm or 500 nm from above the insulating film formed of the radiation-sensitive material. The ratio of the current value when the voltage applied to the gate electrode is +10 V and −10 V when the source electrode is 0 V is defined as the ON / OFF ratio. The switching response characteristics, that is, the element characteristics, were “good” when the ON / OFF ratio was 1.0 × 10 ⁵ or more, and “bad” when the ON / OFF ratio was less than 1.0 × 10 ⁵ .

<TFT reliability>
TFT reliability refers to changes in Id-Vg characteristics (amount of change in threshold voltage Vth) when an electrical stress is applied between the gate electrode and the source electrode, when the evaluation element is irradiated with light and when light is not irradiated. It was evaluated by comparing with.

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

(Measurement of change in threshold voltage Vth)
Electrical stress was applied by applying a positive voltage of +20 V and a negative voltage of −20 V for 12 hours between the gate electrode and the source electrode. Such electrical stress is a condition in which the semiconductor layer of the evaluation element is irradiated with white light having an illuminance of 30000 lux centered at a wavelength of 450 nm or 500 nm from above the insulating film formed of the radiation-sensitive material. The test was performed under the condition where no light was irradiated to the semiconductor layer. The amount of change in the threshold voltage Vth was calculated from the Id-Vg characteristic for each of the light irradiation condition and the light non-irradiation condition. When the change amount of the threshold voltage Vth at the time of light irradiation is suppressed to less than 1.3 times the change amount of the threshold voltage Vth at the time of no light irradiation, the TFT reliability is assumed to be “excellent”. TFT reliability is “good” when it is suppressed to 3 times or more and less than 1.6 times, and TFT reliability is “slightly good” when it is suppressed to 1.6 times or more and less than 2 times. The TFT reliability is determined to be “bad” when it is twice or more.

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. Moreover, the insulating film formed in Examples 1 to 37 has a light-shielding property and has a forward tapered shape. An element using the insulating film and a semiconductor layer that is easily deteriorated by light has element characteristics (even in a light irradiation environment). Excellent switching response characteristics and TFT reliability). On the other hand, the insulating film formed in Comparative Example 1 is inferior in light shielding property, and the insulating film formed in Comparative Examples 2 and 4 is inferior in patterning property, pattern shape, light shielding property, low water absorption and heat resistance. The insulating films formed in 3 and 5 are inferior in patternability, pattern shape, and low water absorption, and elements using these insulating films and light-degradable semiconductor layers have element characteristics (switching response characteristics) in a light irradiation environment. , TFT reliability).

  DESCRIPTION OF SYMBOLS 1 ... Organic EL apparatus, 2 ... Support substrate, 3 ... TFT, 4 ... 1st insulating film (planarization film), 5 ... Anode, 6 ... Through hole, 7 ... 2nd insulating film (partition), 70 ... Recessed portion, 8 ... organic light emitting layer, 9 ... cathode, 10 ... passivation film, 11 ... sealing substrate, 12 ... sealing layer, 100 ... TFT substrate, 110 ... first electrode, 111 ... opening of insulating film, 112 ... Edge portion of the first electrode, 113 ... first electrode surface, 120 ... insulating film, 121 ... slope of the insulating film

Claims (19)

A TFT substrate in which the semiconductor layer constituting the TFT contains an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb and Zn;
A first electrode provided on the TFT substrate and connected to the TFT;
An insulating film formed on the first electrode so as to partially expose the first electrode and having a total light transmittance in a range of 0 to 15% at a wavelength of 300 to 400 nm;
A display or lighting device having a second electrode provided opposite to the first electrode,
The insulating film is an insulating film formed of a radiation sensitive material;
The radiation sensitive material is
(A) a polymer other than the following resin (C);
(B) a photosensitive agent;
(C) containing at least one resin selected from a novolak resin, a resole resin, and a condensate of a resole resin,
The content of the resin (C) in the radiation sensitive material is 2 to 200 parts by mass with respect to 100 parts by mass of the polymer (A).
Display or lighting device.   Polymer (A) is polyimide (A1), polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5-1), precursor of polybenzoxazole ( The display or lighting device according to claim 1, which is at least one selected from A5-2), polyolefin (A6), and cardo resin (A7).   The polymer (A) is selected from polysiloxane (A4), polybenzoxazole (A5-1), the precursor of polybenzoxazole (A5-2), polyolefin (A6), and cardo resin (A7). The display or illumination device according to claim 1, wherein the display or illumination device is at least one kind. The display or lighting device according to claim 2, wherein the polyimide (A1) has a structural unit represented by the formula (A1).
[In Formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. ] The display or lighting device according to claim 2 or 3, wherein the polysiloxane (A4) is a polysiloxane obtained by reacting an organosilane represented by the formula (a4).
[In the formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group-containing group having 6 to 15 carbon atoms, or an epoxy ring having 2 to 15 carbon atoms. Or a group formed by replacing one or more hydrogen atoms contained in the alkyl group with a substituent, and when there are a plurality of R ^{1 s} , they may be the same or different; R ² is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when there are a plurality of R ^{2 s} , they may be the same or different; It is an integer of 3. ] The display or illumination device according to claim 2 or 3, wherein the polybenzoxazole (A5-1) has a structural unit represented by the formula (a5-1).
[In Formula (a5-1), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group. ] The display or illumination device according to claim 2 or 3, wherein the polybenzoxazole precursor (A5-2) has a structural unit represented by the formula (a5-2).
[In Formula (a5-2), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group. ]   The display or illumination device according to claim 1, wherein the photosensitive agent (B) is a photoacid generator or a photoradical polymerization initiator.   The display or lighting device according to any one of claims 1 to 8, wherein the resin (C) is a novolac resin.   The display or lighting device according to claim 1, wherein a cross-sectional shape at a boundary portion of the insulating film, at which the insulating film exposes the first electrode, is a forward tapered shape.   The display or illumination device according to claim 1, wherein the insulating film has a thickness of 0.3 to 15.0 μm.   The display or illumination according to any one of claims 1 to 11, wherein the insulating film is formed so as to cover at least an edge portion of the first electrode, and a cross-sectional shape at a boundary portion of the insulating film is a forward tapered shape. apparatus. The insulating film is a partition partitioning the surface of the TFT substrate into a plurality of regions,
The display or illumination device according to claim 1, further comprising pixels formed in the plurality of regions.   A first electrode provided on the TFT substrate and connected to the TFT; an organic light emitting layer formed on the first electrode in a region defined by the partition; and a first electrode provided on the organic light emitting layer. The display or illumination device according to claim 13, comprising an organic EL element including two electrodes. The TFT substrate is a TFT substrate having a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a planarization layer covering the TFT,
The partition is formed on the planarization layer so as to cover at least the edge portion of the first electrode, and the partition is disposed at least above the semiconductor layer of the TFT. 15. A display or illumination device according to claim 14, characterized in that   The said 1st electrode is formed on the said planarization layer, The said 1st electrode is connected with the said TFT via the wiring formed in the through hole which penetrates the said planarization layer. Display or lighting device.   The insulating film is formed on the TFT substrate so as to be disposed at least above the semiconductor layer, and 50% or more of the area of the semiconductor layer when projected from above the TFT substrate The display or lighting device according to any one of claims 1 to 16, which overlaps with the insulating film.   The process 1 which forms a coating film on a TFT substrate using the radiation sensitive material according to claim 1, the process 2 which irradiates radiation to at least a part of the coating film, and develops the coating film irradiated with the radiation. The display according to claim 1, further comprising a step 3 of heating and a step 4 of heating the developed coating film to form an insulating film having a total light transmittance in the range of 0 to 15% at a wavelength of 300 to 400 nm. Alternatively, a method for forming an insulating film included in the lighting device.   The method for forming an insulating film according to claim 18, wherein the heating temperature in step 1 is 60 to 130 ° C, and the heating temperature in step 4 is higher than 130 ° C and not higher than 300 ° C.