KR101852050B1 - Organic el device, and method for forming insulating film - Google Patents

Abstract

Disclosed is an organic EL device having an element for driving a thin-film transistor including a semiconductor layer made of a substance having a large photo-deterioration, and an organic EL device in which photo deterioration of the substance is suppressed during use of the device.
A first electrode formed on the TFT substrate and connected to the TFT; and a second electrode formed on the first electrode so as to partially expose the first electrode and having a total light transmittance of 300 to 400 nm Wherein the insulating film is an insulating film formed of a radiation-sensitive material, and the radiation-sensitive material is an insulating film formed of a radiation-sensitive material, (A), (B) a photosensitive agent, and (C) a novolak resin, wherein the content of the resin (C) in the radiation- And 2 to 200 parts by mass.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic EL device and a method for forming an insulating film,

The present invention relates to an organic EL display or a lighting apparatus and a method of forming an insulating film. More specifically, the present invention relates to a plasma display panel comprising a substrate, a first electrode formed on the substrate, an insulating film formed on the first electrode so as to partially expose the first electrode, and a second electrode formed opposite to the first electrode And a method of forming the insulating film.

As a flat panel display, a non-light emitting type liquid crystal display (LCD) is becoming popular. Recently, an electroluminescent display (ELD), which is a self-luminous display, is known. In particular, an organic electroluminescent (EL) device using electroluminescence by an organic compound is expected as a light emitting device to be formed in a next-generation lighting device in addition to a light emitting device formed on a display.

For example, an organic EL display or an illumination device has an insulating film such as a planarizing film and a partition for partitioning a pixel (light emitting element). 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 or flowing a current between the first and second electrodes facing each other. However, at this time, since an electric field is likely to concentrate on the edge portion of the electrode having a small radius of curvature, an undesirable phenomenon such as an insulation breakdown or generation of a leak current tends to occur at the edge portion.

In order to solve this problem, it is necessary to gradually increase the thickness of the insulating film at the boundary portion where the insulating film exposes the first electrode from the center portion of the first electrode toward the edge portion, that is, (For example, refer to Patent Document 3).

Further, in recent years, researches on thin film transistors (TFTs) using oxide semiconductor layers have been actively conducted. Patent Document 4 proposes an example of using a polycrystalline thin film of an oxide made of In, Ga and Zn (hereinafter also referred to as "IGZO") as a semiconductor layer of a TFT. In Patent Documents 4 and 5, an amorphous thin film of IGZO is used as a TFT An example using a semiconductor layer has been proposed.

However, in IGZO, photo deterioration (light deterioration) is known by natural light, lighting, manufacturing process or the like. Therefore, when a TFT including a semiconductor layer made of a material having a large photo-deterioration such as IGZO is used as a driving element of a display or illumination apparatus, particularly, as an element for driving an organic EL element, in view of prevention of light deterioration of IGZO , It is required to impart a light shielding property from ultraviolet to visible light as the above-mentioned characteristic of the insulating film. However, currently used insulating films are transparent in a wavelength range of, for example, 300 to 400 nm, and thus the function of shielding light is required.

Japanese Laid-Open Patent Publication No. 2011-107476 Japanese Patent Application Laid-Open No. 2010-237310 Japanese Patent No. 4982927 Japanese Patent Application Laid-Open No. 2004-103957 International Publication No. 2005/088726 pamphlet

The present invention relates to an organic EL display or illumination device having a thin film transistor including a semiconductor layer made of a material having a large photo deterioration such as IGZO as a driving element, There is provided a display or illumination device in which deterioration is suppressed.

Means for Solving the Problems The present inventors have made extensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by employing the following constitution, and the present invention has been accomplished. The present invention relates to, for example, the following [1] to [19].

 [1] A method of manufacturing a TFT, comprising: forming a TFT substrate on a TFT substrate, the TFT substrate including a semiconductor layer constituting a TFT, the TFT substrate including an oxide semiconductor containing at least one element selected from In, Ga, Sn, Ti, Nb, Sb and Zn; 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; Wherein the insulating film is an insulating film formed of a radiation-sensitive material, and the radiation-sensitive material comprises (A) a polymer other than the resin (C) described below, and a second electrode formed opposite to the first electrode, (B) a photosensitive agent, and (C) a condensate of a novolak resin, a resol resin and a resol resin, wherein the content of the resin (C) in the radiation- Is 2 to 200 parts by mass based on 100 parts by mass of the component (A).

[2] The resin composition according to any one of [1] to [3], wherein the polymer (A) is at least one selected from the group consisting of polyimide (A1), the polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole Is at least one selected from the group consisting of a precursor (A5-2), a polyolefin (A6) and a cado resin (A7).

[3] The polymer according to [1], wherein the polymer (A) is at least one selected from the group consisting of polysiloxane (A4), polybenzoxazole (A5-1), precursor of polybenzoxazole (A5-2), polyolefin (A6) The organic EL device according to the above [1], wherein the organic EL device is at least one type.

[4] Organic EL device according to [2], wherein the polyimide (A1) has a structural unit represented by the formula (A1):

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

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

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an epoxy ring-containing group having 2 to 15 carbon atoms, a group formed by substituting the hydrogen atom or one of two or more of the substituents contained in the alkyl group, in the case of R ^1, a plurality may be the same or different; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms An aryl group having 6 to 15 carbon atoms, and when R ² is plural, they may be the same or different, and n is an integer of 0 to 3).

[6] Organic EL device according to [2] or [3], wherein the polybenzoxazole (A5-1) has a structural unit represented by the formula (a5-1)

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

[7] Organic EL device according to [2] or [3], wherein the precursor (A5-2) of polybenzoxazole has a structural unit represented by formula (a5-2)

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

[8] The organic EL device according to any one of [1] to [7], wherein the photosensitizer (B) is a photo acid generator or a photo radical polymerization initiator.

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

[10] The organic EL device according to any one of [1] to [9], wherein a cross-sectional shape at a boundary portion of the insulating film, in which the insulating film exposes the first electrode, .

[11] The organic EL device described in any one of [1] to [10], wherein the insulating film has a film thickness of 0.3 to 15.0 μm.

[12] The organic EL device according to 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 the cross- .

[13] The organic EL device according to any one of [1] to [12], wherein the insulating film is a partition for partitioning the surface of the TFT substrate into a plurality of regions, .

A first electrode formed on the TFT substrate and connected to the TFT; an organic light emitting layer formed on the first electrode in the region partitioned by the partition; and a second electrode formed on the organic light emitting layer, The organic EL device according to the above [13], wherein the organic EL device includes the organic EL device.

[15] The TFT substrate is a TFT substrate having a support substrate, a TFT formed on the support substrate in correspondence with the organic EL element, and a planarization layer covering the TFT, The organic EL device according to the above-mentioned 14, wherein at least the edge portion is covered, and the partition wall is formed on the planarization layer so as to be disposed at least above the semiconductor layer of the TFT.

[16] The organic EL device according to [15], wherein the first electrode is formed on the planarization layer and the first electrode is connected to the TFT through a wiring formed in a through hole passing through the planarization layer .

The insulating film is formed on the TFT substrate so as to be disposed at least above the semiconductor layer. When projected from above the TFT substrate, at least 50% of the area of the semiconductor layer overlaps with the insulating film And the organic EL device according to any one of the above [1] to [16].

[18] A method of manufacturing a thin film transistor, comprising the steps of: forming a coating film on a TFT substrate using the radiation sensitive material according to the above-mentioned [1]; step 2 of irradiating at least a part of the coating film with radiation; 3; and the step of heating the developed coating film to form an insulating film having a total light transmittance in a range of 0 to 15% at a wavelength of 300 to 400 nm. The organic EL device according to [1] / RTI >

[19] The method for forming an insulating film according to the above [18], wherein the heating temperature in Step 1 is 60 to 130 캜 and the heating temperature in Step 4 is more than 130 캜 and not more than 300 캜.

According to the present invention, in an organic EL display or illumination device having a thin film transistor including a semiconductor layer made of a material having a large photo deterioration such as IGZO as a driving element, It is possible to provide a display or illumination device with suppressed photo deterioration.

1 is a plan view showing an example of the shape of an insulating film.
2 is a cross-sectional view for explaining a net taper shape as a sectional shape of the insulating film.
3 is a cross-sectional view schematically showing the structure of the main part of the organic EL device.

(Mode for carrying out the invention)

The display or illumination device of the present invention is a display or lighting device comprising a TFT substrate in which a semiconductor layer constituting a TFT is a layer containing an oxide semiconductor containing at least one element selected from In, Ga, Sn, Ti, Nb, Sb and Zn, A first electrode formed on the substrate and connected to the TFT, an insulating film formed on the first electrode to partially expose the first electrode, and a second electrode formed opposite to the first electrode. Here, the total light transmittance of the insulating film is 0 to 15% at a wavelength of 300 to 400 nm.

Hereinafter, the display or illumination device is collectively referred to as simply " device ".

Examples of the display device of the present invention include a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescence display (ELD), and an organic EL display in particular. As the illumination device of the present invention, for example, organic EL illumination can be cited.

As the TFT substrate, the first electrode, and the second electrode in the device of the present invention, for example, a specific example (a supporting substrate and a TFT, a positive electrode , And a cathode), respectively.

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

An example of the shape of the insulating film is shown in Fig. A first electrode 110 formed in a stripe shape is formed on a TFT substrate 100. 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, And 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.

It is preferable that the cross-sectional shape of the insulating film has a net taper shape at a boundary portion where the first electrode is exposed. Here, the "net taper shape" refers to an angle (?) Formed by the slope 121 at the boundary portion where the first electrode 110 is exposed in the insulating film 120 and the first electrode surface 113, for example, Corresponds to that the angle of the doublet? Is less than 90 degrees. Hereinafter, the angle [theta] is also referred to as " taper angle [theta] ". The taper angle? Is preferably 80 ° or less, more preferably 5 to 60 °, and still more preferably 10 to 45 °.

For example, in the case of an organic EL device, if the sectional shape of the insulating film at the boundary portion is a net taper shape, even when the organic light emitting layer and the second electrode are formed after the insulating film is formed, It is possible to reduce a film thickness unevenness or the like caused by a step, 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 mu m, more preferably 0.5 to 10.0 mu m, and still more preferably 1.0 to 5.0 mu m in consideration of light shielding property and easiness of film formation and patterning .

The insulating film is formed, for example, over the first electrodes adjacent to each other. For this reason, good insulating property is required for the insulating film. The volume resistivity of the insulating film is preferably 10 ¹⁰ · · cm or more, and more preferably 10 ¹² · · cm or more.

The insulating film has a total light transmittance of 0 to 15%, preferably 0 to 10%, and particularly preferably 0 to 6% at a wavelength of 300 to 400 nm. 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, 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 for partitioning the surface of the TFT substrate into a plurality of regions, and pixels are formed in the plurality of regions. It is preferable that the insulating film (partition wall) is formed on the TFT substrate so as to be disposed at least above the semiconductor layer from the viewpoint of the light shielding property with respect to the semiconductor layer included in the TFT. Here, "upward" refers to the direction from the TFT substrate to the second electrode. As an example, an embodiment in which at least 50% of the area of the semiconductor layer is overlapped with the insulating film (partition wall) when viewed projectively from above the TFT substrate can be cited. In particular, 80% Furthermore, an embodiment in which 90% or more, particularly 100%, is overlapped with the insulating film (partition wall) can be cited.

As described above, in the device of the present invention, the insulating film for exposing the first electrode has a light-shielding property at the above wavelength. By forming such an insulating film, the insulating film functions as a light-shielding film even in an apparatus having a thin film transistor including a semiconductor layer made of a material having a large photo deterioration such as IGZO as a driving element, The photodegradation of the semiconductor layer can be suppressed.

For example, the semiconductor layer constituting the TFT is a layer containing an oxide semiconductor containing at least one element 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.

Examples of the oxide semiconductor containing at least one element selected from In, Ga, Sn, Ti, Nb, Sb and Zn include quaternary metal oxides such as In-Sn-Ga-Zn-O-based oxide semiconductors; In-Zn-O-based oxide semiconductor, In-Sn-Zn-O-based oxide semiconductor, In-Sn-Zn- O-based oxide semiconductors, and Sn-Al-Zn-O-based oxide semiconductors; Zn-O based oxide semiconductor, Sn-Zn-O based oxide semiconductor, Al-Zn-O based oxide semiconductor, Zn-Mg-O based oxide semiconductor, Binary metal oxides such as a system oxide semiconductor and an In-Ga-O system material; Based oxide semiconductors such as In-O-based oxide semiconductors, Sn-O-based oxide semiconductors, and Zn-O-based oxide semiconductors.

In the present invention, even when the semiconductor layer constituting the TFT is the oxide semiconductor layer, particularly in the case of an oxide semiconductor layer made of an In-Ga-Zn-O-based oxide semiconductor (IGZO semiconductor) have.

An apparatus of the present invention includes: a first electrode formed on the TFT substrate and connected to the TFT; an organic light emitting layer formed on the first electrode in the region partitioned by the partition; It is preferable to be an organic EL device having an organic EL element including two electrodes.

The TFT substrate has, for example, a support substrate, a TFT formed on the support substrate in correspondence with the organic EL element, and a planarization layer covering the TFT. For example, the first electrode is formed on the planarization layer, and is connected to the TFT through a wiring formed in a through hole passing through the planarization layer. Further, it is preferable that the insulating film (partition wall) having light shielding property is formed on the first electrode and the planarization layer so as to partially expose the first electrode.

The insulating film for 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 to remove the exposed portion, and a negative type in which unexposed portions are removed by curing by exposure. When a coating film formed of a radiation sensitive material is exposed, light is strongly absorbed from 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 becomes larger than the solubility in the inside, and the opposite tendency is observed in the negative type. In the present invention, since it is preferable that the cross-sectional shape of the boundary portion of the insulating film be a net taper shape, it is preferable to form the pattern using a positive radiation-sensitive material.

[ Sensitizing radiation property  material〕

The radiation sensitive material can be used for forming the insulating film in the display or illumination device of the present invention. The radiation-sensitive material preferably contains at least one resin (C) selected from a polymer (A), a photosensitizer (B), and condensates of a novolac resin, a resol resin and a resol resin.

The radiation-sensitive material may contain a cross-linking agent (D) as a suitable component, and may also contain a solvent (E). The radiation-sensitive material may contain other optional components as long as the effect of the present invention is not impaired.

The radiation-sensitive material can form an insulating film having a high radiation sensitivity and an excellent pattern shape by using the above-described material, and can cope with the demand for narrow pitch of the pattern. Further, an insulating film having low water absorption can be formed by using the above-mentioned material.

Each component will be described in detail below.

[Polymer (A)]

The polymer (A) is preferably an alkali-soluble polymer other than the resin (C). The alkali solubility in the polymer (A) means that the polymer (A) is soluble in an alkali solution, for example, an aqueous solution of 2.38 mass% tetramethylammonium hydroxide.

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

The weight average molecular weight (Mw) of the polymer (A) in terms of polystyrene is preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and more preferably 4,000 to 50,000, as measured by a gel permeation chromatography (GPC) Is more preferable. If the Mw is not lower 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) tends to be superior to the solvent or developer.

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

&Quot; Polyimide (A1) "

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

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

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

In formula (a1), R ² represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group or a bis (trifluoromethyl) methylene group; R ³ are each independently a hydrogen atom, a formyl group, an acyl group or an alkyl group; Provided that at least one of R < ³ > is a hydrogen atom; n1 and n2 are each independently an integer of 0 to 2; Provided that at least one of n1 and n2 is 1 or 2; When the sum of n1 and n2 is 2 or more, a 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, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Lt; / RTI > of 1 to 20 carbon atoms.

The divalent group represented by formula (a1) is preferably a divalent group having 1 to 4 hydroxyl groups, and more preferably a divalent group having two hydroxyl groups. Examples of the divalent group having 1 to 4 hydroxyl groups represented by the formula (a1) include divalent groups represented by the following formulas. Further, in the following formulas, two " - " extending from the aromatic ring represent a bonding hand.

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 them, a group represented by the following formula (1) is preferable.

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

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

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

Examples of the tetravalent alicyclic hydrocarbon group include monocyclic hydrocarbons such as cyclobutane, cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, cyclohexene, and cyclooctane; Bicyclo [2.2.1] heptane, bicyclo [3.1.1] heptane, bicyclo [3.1.1] hept-2-ene, bicyclo [2.2.2] octane, bicyclo [2.2.2] - bicyclic hydrocarbons such as ene; Tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [5.2.1.0 ^2,6 ] dec-4-ene, adamantane, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane And a tetravalent group derived from hydrocarbons having three or more cyclic rings.

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 particularly preferably 1. More specifically, examples thereof include quaternary groups derived from 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene and the like.

In the above description, the above-mentioned hydrocarbon-derived tetravalent group is a tetravalent group formed by removing four hydrogen atoms from the above-mentioned hydrocarbon. The exclusion of the four hydrogen atoms is a site capable of forming a tetracarboxylic acid dianhydride structure when the four hydrogen atoms are substituted with four carboxyl groups.

As the tetravalent aliphatic hydrocarbon group, a tetravalent group represented by the following formula is preferable. In the following formulas, the chain hydrocarbon group and the four "-" extending from the alicyclic ring represent bonding hands.

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

The polyimide (A1) is obtained by imidization of the polyimide precursor (A2) described below. The imidization here may proceed completely or partially. That is, the imidization rate may not be 100%. Therefore, the polyimide (A1) may further comprise at least one selected from structural units represented by the formula (A2-1) and structural units represented by the formula (A2-2) which will be described below.

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

The imidization rate can be measured, for example, as follows. First, the infrared absorption spectrum of the polyimide is measured to confirm the presence of the absorption peak (around 1780 cm ^-1, near 1377 cm ^-1 ) of the imide structure attributable to polyimide. Next, the polyimide is subjected to heat treatment at 350 占 폚 for 1 hour, and the infrared absorption spectrum is again measured. The peak intensity before and after the heat treatment is compared at 1377 cm ^-1 . Imidization rate of polyimide before heat treatment = {peak intensity around 1377 cm ^-1 before heat treatment / peak intensity around 1377 cm ^-1 after heat treatment} × 100 (%). For the measurement of the infrared absorption spectrum, for example, "NICOLET 6700FT-IR" (manufactured by Thermo Electron Limited) is used.

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

&Quot; Polyimide precursor (A2) "

The polyimide precursor A2 is a compound capable of producing a polyimide A1, preferably a polyimide A1 having a structural unit represented by the formula (A1), by dehydration and cyclization (imidization). The polyimide precursor (A2) includes, for example, polyamic acid and polyamic acid derivative.

( Polyamic acid )

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

In the formula (A2-1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. 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 formula (A1).

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

( Polyamic acid  derivative)

The polyamic acid derivative is a derivative synthesized by esterification or the like of polyamic acid. Examples of the polyamic acid derivative include a polymer in which the hydrogen atom of the carboxyl group in the structural unit represented by the formula (A2-1) of the polyamic acid is replaced with another group, and a polyamic acid ester is preferable.

The polyamic acid ester is a polymer in which at least a part of the carboxyl groups of the polyamic acid is esterified. Examples of the polyamic acid ester include polymers having a structural unit represented by the formula (A2-2) capable of producing a polyimide (A1) having a 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 each 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 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, particularly preferably 80% Or more.

&Quot; Method for synthesizing polyimide (A1) and polyimide precursor (A2) "

The polyamic acid which is the polyimide precursor (A2) can be obtained, for example, by polymerizing a tetracarboxylic acid dianhydride, a diamine having a hydroxyl group and, if necessary, a diamine containing other diamine. These use ratios are, for example, 0.3 to 4 moles, preferably about moles, of the total diamine relative to 1 mole of the tetracarboxylic acid dianhydride. In the above polymerization, it is preferable to heat the mixed solution of the tetracarboxylic acid dianhydride and the whole diamine at 50 ° C to 200 ° C for 1 to 24 hours.

Hereinafter, the tetracarboxylic acid dianhydride and the hydroxyl group-containing diamine are also referred to as "acid dianhydride (A1-1)" and "diamine (A1-2)", and the other diamine is referred to as "diamine (A1-2 ' "He says.

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

The polyamic acid derivative as the polyimide precursor (A2) can be synthesized by esterifying the carboxyl group of the polyamic acid. As the esterification method, there is no particular limitation, and a known method can be applied.

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; It is also possible to synthesize a polyamic acid derivative by the above method and then imidize the polyamic acid derivative.

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

When a diamine is excessively used for the tetracarboxylic acid dianhydride, as the endcapping agent for sealing the terminal groups of polyimide, polyamic acid and polyamic acid derivative, for example, a dicarboxylic anhydride such as maleic anhydride may be used It may be used.

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

In 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 the formula (A1).

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

In formula (a3), R ¹ is a divalent group having a hydroxyl group. As the divalent group having a hydroxyl group represented by R ^1, equation (A1) may include the same one exemplified as the groups of R ^1.

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

The polyimide (A1) may further have a structural unit in which R ¹ in the formulas (A1), (A2-1) and (A2-2) is replaced with the residue of the other diamine (A1-2 '). Similarly, the polyamic acid (A2), the formula (A2-1) and (A2-2) may have a in R ^1, the additional structural units replaced by residues of the other diamine (A1-2 ').

As the polymerization solvent used for synthesis of the polyimide (A1) and the polyimide precursor (A2), a raw material for synthesis thereof and a solvent which can dissolve the above (A1) and (A2) and is low in water absorption are preferable. As the polymerization solvent, the same solvent as the solvent exemplified below as the solvent (E) may be used.

(A) or the polyimide precursor (A2) and then isolating the polymer, and a step of redissolving the other solvent after isolation is unnecessary by using the same solvent as the solvent (E) as the polymerization solvent . Thus, the productivity of the device of the present invention can be improved.

The polyimide (A1) and the polyimide precursor (A2) preferably have the above-mentioned specific structure having a hydroxyl group, and thus have excellent solubility to the solvent (E) described later. For this reason, these polymers are also dissolved in a low-absorptive solvent other than N-methylpyrrolidone (NMP), for example, a solvent (E) described later. As a result, for example, by using a solvent other than NMP as the polymerization solvent for obtaining the polymer (A), the insulating film formed of the radiation sensitive material can be lowered in absorption.

&Quot; Acrylic resin (A3) "

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

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

Examples of the monomer constituting the component (A3) include at least one functional group-containing compound selected from a hydroxyalkyl ester of (meth) acrylic acid, an ester group-containing ester of (meth) acrylic acid and an oxetanyl group- Monomer C may also be mentioned.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec- (Meth) acrylate, and t-butyl (meth) acrylate; 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, dicycloheptanyl (meth) , Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like; Examples of the ester group-containing ester of (meth) acrylic acid include phenyl (meth) acrylate and benzyl (meth) acrylate.

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

Examples of the hydroxyalkyl ester of (meth) acrylic acid include, for example, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; Examples of the ester containing an epoxy group of (meth) acrylic acid include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α- (Meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxyheptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexylmethyl Can be heard; Examples of the oxetanyl group-containing esters of (meth) acrylic acid include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

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

In particular, in the acrylic resin (A3), the total content of the structural units derived from the epoxy group-containing ester of (meth) acrylic acid and the oxetanyl group-containing ester of (meth) acrylic acid is preferably from 10 to 70 mass% And more preferably from 20 to 50 mass%. When the structural unit is in the above range, the curing reaction proceeds sufficiently at the time of heating the coating film formed of the radiation-sensitive material, the heat resistance and surface hardness of the resulting pattern tends to be sufficient, There is also an excellent tendency.

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

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

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

&Quot; Polysiloxane (A4) "

Examples of the polysiloxane (A4) include a polysiloxane obtained by reacting an organosilane represented by the formula (a4), for example.

In formula (a4), R ¹ represents 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, an epoxy ring-containing group having 2 to 15 carbon atoms, (Substituent) in which one or more hydrogen atoms contained in R < ¹ > are substituted with substituents, and when R < ¹ > is plural, 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 R ² is plural, they may be the same or different; n is an integer of 0 to 3;

The substituent is at least one selected from, for example, 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 substituent thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, (Meth) acryloyloxypropyl group, a 2-methylpropyl group, a 2-methylpropyl group, a 2-methylpropyl group, .

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

Examples of the aryl group-containing group include an aryl group such as a phenyl group, a tolyl group and a naphthyl group; a hydroxyaryl group such as a p-hydroxyphenyl group; Aralkyl groups such as a benzyl group and a phenethyl group; Hydroxyaryl groups such as a 1- (p-hydroxyphenyl) ethyl group and a 2- (p-hydroxyphenyl) ethyl group; And a 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.

The acyl group includes, for example, an acetyl group.

As the aryl group, for example, a phenyl group can be mentioned.

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

Examples of the organosilane include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane and tetraphenoxysilane; Methyltrimethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, N-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxy Silane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxy (P-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, Methoxy silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, triple Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. Trifunctional silane; Bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane and diphenyldimethoxysilane; And monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane. Of these organosilanes, trifunctional silanes are preferable from the viewpoint of resistance to cracking and hardness of the insulating film.

The organosilane may be used singly or in combination of two or more kinds.

The content of the phenyl group contained in the polysiloxane (A4) is preferably 20 to 70 mol, more preferably 35 to 55 mol, per 100 mol of the Si atom in view of ensuring both crack resistance and hardness of the insulating film. If the content of the phenyl group is less than the upper limit, an insulating film having a high hardness tends to be obtained. If the phenyl group content is lower than the lower limit value, an insulating film having high crack resistance tends to be obtained. The content of the phenyl group can be determined, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of the polysiloxane (A4) and determining the ratio of the peak area of the Si bonded to the phenyl group to the peak area of the Si bonded to the phenyl group .

The polysiloxane (A4) is obtained, for example, by hydrolysis and partial condensation of the above organosilane. General methods can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the 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 by distillation if necessary. The reaction temperature is not particularly limited, but is usually in the range of 0 占 폚 to 150 占 폚. The reaction time is not particularly limited, but is usually in the range of 1 to 10 hours.

Examples of the solvent include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- Hydroxy group-containing ketones such as hydroxy-4-methyl-2-pentanone (diacetone alcohol); Propyleneglycol monoethyl ether, propyleneglycol monoethylether, propyleneglycol mono-n-butylether, propyleneglycol mono-t-butylether, 3-methoxy-1-butanol , 3-methyl-3-methoxy-1-butanol. Of these, diacetone alcohol is particularly preferably used. The solvents may be used alone or in combination of two or more.

The amount of the solvent to be added is preferably 10 to 1000 parts by mass based on 100 parts by mass of the organosilane. The amount of water to be used for the hydrolysis reaction is preferably 0.5 to 2 moles per 1 mole 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 acids or anhydrides thereof, and ion exchange resins. Examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, An ion exchange resin, and the like. The amount of the catalyst to be added is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the organosilane.

&Quot; Polybenzoxazole (A5-1) "

The polybenzoxazole (A5-1) preferably has a structural unit represented by the formula (a5-1). Hereinafter, the structural unit represented by 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 quadrivalent group containing at least one aromatic ring, more preferably a group having a linear structure, more preferably a group having 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 included in X ¹ may be any of substituted or unsubstituted rings. 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, for example, bonded to adjacent carbon atoms on an aromatic ring in X ¹ to form a benzoxazole ring.

When two or more aromatic rings are contained in X ¹ , a plurality of aromatic rings may form any of a connected polycyclic system and a condensed polycyclic system, but preferably form a connected polycyclic system. The polybenzoxazole (A5-1) having such a structure is excellent in both light shielding property and rigidity.

The total carbon number of X ¹ is preferably 6 to 24, more preferably 6 to 20, and further preferably 6 to 18. Thus, the above effect can be more remarkably exerted.

Examples of the structure of X ¹ include a polycyclic structure such as a monocyclic structure such as a benzene ring, a condensed polycyclic structure such as a naphthalene ring, and a group represented by a formula (g1). Among them, the group represented by the formula (g1) is preferable.

In formula (g1), Ar ¹ is independently a trivalent aromatic hydrocarbon group, and R ¹ is a direct bond or a divalent group. The trivalent aromatic hydrocarbon group includes, for example, a benzene ring, and may have a substituent such as an alkyl group, an alkoxy group, an alicyclic hydrocarbon group, etc., two substituents in Ar ¹ are bonded to each other, two Ar ¹ may be bridged to form a divalent group such as a carbonyl group. Examples of the bivalent 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 a tetravalent group represented by the following formula. Further, in the following formula, four "-" extending from the aromatic ring represent a bonding hand.

In the formula (a5-1), Y ¹ is preferably a divalent group containing at least one ring selected from an alicyclic ring and an aromatic ring, more preferably a group having from 1 to 4 aromatic rings, Groups having two aromatic rings are particularly preferable. 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 any of 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 two or more of said rings are included in Y ¹ , a plurality of said rings may form any of a connecting polycyclic system and a condensed polycyclic system, but preferably forms a connected polycyclic structure. The polybenzoxazole (A5-1) having such a structure is excellent in both light shielding property and rigidity.

The total carbon number of Y ¹ is preferably from 4 to 24, more preferably from 4 to 15, and even more preferably from 6 to 12. Thus, the above effect can be more remarkably exerted.

Examples of the structure of Y ¹ include an aromatic structure 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); And an alicyclic structure of the latter example. Among them, a group represented by the formula (g2) is preferable.

In the formula (g2), Ar ² is independently a bivalent aromatic hydrocarbon group, and R ² is a direct bond or a divalent group. Examples of the bivalent aromatic hydrocarbon group include a benzene ring and may have a substituent such as an alkyl group, an alkoxy group and an alicyclic hydrocarbon group. Two substituents in Ar ² may be bonded to each other and two Ar ² or a carbonyl group which may be crosslinked. Examples of the bivalent 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.

As a specific example of the structure of Y ¹ , for example, a divalent group represented by the following formula can be mentioned. Further, in the following formulas, the two "-" extending from the aromatic ring and the alicyclic ring represent bonding hands.

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

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

The conversion rate can be measured, for example, as follows. First, the infrared absorption spectrum of the polybenzoxazole was measured to confirm the presence of the absorption peak (around 1554 cm ^-1, near 1574 cm ^-1 ) of the benzoxazole ring. Next, the polybenzoxazole is subjected to heat treatment at 350 占 폚 for 1 hour, and the infrared absorption spectrum is again measured. The peak intensity before and after the heat treatment at around 1554 cm ^-1 is compared. The rate of conversion of the polybenzoxazole before the heat treatment = {the peak intensity at around 1554 cm ^-1 before the heat treatment / the peak intensity at around 1554 cm ^-1 after the heat treatment}, assuming that the conversion rate of the polybenzoxazole after the heat treatment is 100% × 100 (%) is obtained. For the measurement of the infrared absorption spectrum, for example, "NICOLET 6700FT-IR" (manufactured by Thermo Electron Limited) is used.

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

" Polybenzoxazole  Precursor (A5-2) "

The polybenzoxazole precursor (A5-2) is obtained by dehydrating and cyclizing polybenzoxazole (A5-1), preferably polybenzoxazole (A5-1) having a structural unit (a5-1) Lt; / RTI > The precursor (A5-2) has, for example, a structural unit represented by the formula (a5-2).

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

Tetravalent represented by X ¹ As the divalent organic group represented by the organic group, and Y ^1, a group illustrated as X ¹ and Y ¹ in each of formula (a5-1) can be cited the same groups.

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, Is at least 80% by mass.

" Polybenzoxazole (A5-1) and its precursor (A5-2)

The polybenzoxazole precursor (A5-2) can be obtained by, for example, polymerizing at least one member selected from dicarboxylic acid, a diester thereof and a dihalide thereof and a diamine having two hydroxyl groups. In order to increase the yield of the reaction, an active ester-type dicarboxylic acid derivative in which dicarboxylic acid and 1-hydroxybenzotriazole are previously reacted as the diester may be used.

The usage ratio is, for example, 0.5 to 4 mol, preferably 1 to 2 mol, of the diamine relative to 1 mol of the total amount of the above-mentioned dicarboxylic acid, diester compound and dihalide compound. In the above polymerization, the mixed solution is preferably heated at 50 to 200 캜 for 1 to 72 hours.

The polybenzoxazole (A5-1) can be produced, for example, by synthesizing a polybenzoxazole precursor (A5-2) by the above-mentioned method, and then dehydrating and cyclizing the polybenzoxazole precursor (A5-2) can do.

As the cyclization reaction of the polybenzoxazole precursor (A5-2), a known method can be applied. In the case of the heating and cyclization reaction, it is preferable to heat the solution containing the polybenzoxazole precursor (A5-2) at 150 DEG C to 400 DEG C for 1 to 16 hours. If necessary, an azeotropic solvent such as toluene, xylene or mesitylene may be used to remove water in the system.

From the viewpoint of storage stability, it is preferable to encapsulate the terminal groups of the polybenzoxazole and the precursor thereof. Examples of the terminal endblocker include dicarboxylic anhydrides such as maleic anhydride and 5-norbornene-2,3-dicarboxylic anhydride. For example, it is preferable to synthesize a polybenzoxazole precursor having a structural unit represented by the formula (a5-2) and then encapsulate the terminal amino group contained in the precursor as an amide using a terminal blocking agent.

&Quot; Polyolefin (A6) "

As the polyolefin (A6), for example, a cyclic olefin polymer having a protonic polar group may be mentioned. The protonic polar group is 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 group 16 of the periodic table is preferably an atom belonging to the second or third period of Group 15 or Group 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, Particularly preferably an oxygen atom.

Examples of the protonic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, or a phosphoric acid group; A polar group having a nitrogen atom such as a primary amino group, a secondary amino group, a primary amide group or a secondary amide group (imide group); A thiol group and the like. Among them, 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 the polar group other than the protonic polar group include an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a cyano group, an alkoxy group, a tertiary amino group, a (meth) 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). Of 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 More preferably, an N-substituted imide group is particularly preferable.

The cyclic olefin polymer is a homopolymer or a copolymer of a cyclic olefin having a cyclic structure such as alicyclic or 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 monomer A is also referred to as " monomer A unit ".

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

In the cyclic olefin polymer having a protonic polar group, the ratio of the monomer unit having a protonic polar group to the other monomer unit (monomer unit having a protonic polar group / other monomer unit) is usually from 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 protonic polar group, the protonic polar group may be bonded to a cyclic olefin unit or may be bonded to a monomer unit other than a cyclic olefin, but is preferably bonded to a cyclic olefin unit.

Examples of the monomer forming the cyclic olefin polymer having a protonic polar group include cyclic olefin (a) having a protonic polar group, cyclic olefin (b) having a polar group other than the protonic polar group, cyclic olefin having no polar group c), and a monomer (d) other than the cyclic olefin. The monomer (d) may have a protonic polar group or a polar group other than this, and may not have any 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 protonic polar group is preferably composed of the monomer (a), at least one member selected from the monomers (b) and (c), and optionally the monomer (d) (a), the monomer (b) and, if necessary, the monomer (d).

Examples of the monomer (a) include cyclic olefins represented by the following formulas.

In the 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-mentioned protonic 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 group -X _n -R ^a5 _wherein R ^a5 is a protonic 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 allylene 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, ethyl group, n-propyl group and isopropyl group. The aromatic group in R ^a5 is, for example, an aromatic group having 6 to 24 carbon atoms, and specific examples thereof include an aryl group such as phenyl group, and an aralkyl group such as benzyl group.

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

The monomers (a) may be used singly or in combination of two or more.

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

In formula (b6-1), R ^b1 is a polar group other than the above-mentioned protonic polar group, preferably an acyloxy group having 2 to 12 carbon atoms such as an acetoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, n An alkoxycarbonyl group having 2 to 12 carbon atoms such as a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a 2,2,2-trifluoroethoxycarbonyl group, a phenoxycarbonyl group, etc., An aryloxycarbonyl group having 7 to 24 carbon atoms, 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 may form a 3- to 5-membered heterocyclic ring structure containing an oxygen atom or a nitrogen atom as a ring-constituting atom together with the two carbon atoms to which they are bonded in any combination good.

As the three-membered heterocyclic structure, an epoxy structure and the like can be given. As the 5-membered heterocyclic structure, a dicarboxylic anhydride structure [-C (═O) -OC (═O) -], a dicarboxyimide structure [-C (═O) -NR ^b5 -C (═O) -] . 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 them, a dicarboxyimide structure is preferable.

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

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

Examples of the monomer (c) include monomers such as bicyclo [2.2.1] hept-2-ene (norbornene), 5-ethyl-bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5] deca-3,7-diene (trivial name: dicyclopentadiene), tetracyclo [8.4.0.1 ^{11 , 14} .0 ^3,7] deca-penta -3,5,7,12,11- penta ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] deca-3-ene (trivial name: tetracyclo dodecyl Line), 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca Ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^{2,5 . 10]} dodeca-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8 page Pro -Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, penta-cyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] deca-penta -3,10- Diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10-hexahydroanthracene, 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 (1,4- 9a- tetrahydro -9H- fluorene also known), penta-cyclo [7.4.0.1 ^3,6 .1 ^10,13 .0 ^2,7] deca-penta -4,11- diene, penta-cyclo [9.2.1.1 ^{4, 7.0 2,10} .0 ^3,8] deca-penta can be given -5,12- diene.

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

As the monomer (d) other than the cyclic olefin, for example, chain olefins can be mentioned. The chain olefins include, for example, ethylene; Propene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, Alpha -olefins having 2 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; Nonconjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,5-hexadiene and 1,7- have.

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

The cyclic olefin polymer having a protonic polar group can be obtained by polymerizing the monomer (a) together with at least one kind of monomer selected from the monomers (b) to (d). The polymer obtained by the polymerization may be further hydrogenated. The hydrogenated polymer is also included in the cyclic olefin polymer having a protonic polar group.

The polymerization method for polymerizing the monomer (a) together with at least one kind of monomer selected from the monomers (b) to (d) may be carried out by a conventional method. For example, a ring-opening polymerization method and an addition polymerization method .

As the polymerization catalyst, metal complexes such as molybdenum, ruthenium, and osmium are suitably used. These polymerization catalysts may be used alone, or two or more of them may be used in combination.

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

The hydrogenation of the polymer obtained by polymerizing the monomer is usually carried out using a hydrogenation catalyst. As the hydrogenation catalyst, for example, those generally used when hydrogenating an olefin compound can be used. Specifically, a chisel type homogeneous catalyst, a noble metal complex catalyst, and a supported noble metal catalyst can be given.

Among these hydrogenation catalysts, noble metal complex catalysts such as rhodium and ruthenium are preferable in that side reactions such as denaturation of functional groups do not occur, and carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. These highly nitrogen-containing heterocyclic carbin compounds or ruthenium catalysts for phosphines are particularly preferred.

The cyclic olefin polymer having a protonic polar group can also be obtained by introducing a protonic polar group into a cyclic olefin polymer having no protonic polar group by using a known modifier and conducting hydrogenation as desired. The hydrogenation may be performed on the polymer before the introduction of the protonic polar group. Further, the cyclic olefin polymer having a protonic polar group may be further modified to introduce a protonic polar group.

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

As a modifier for introducing a protonic polar group, a compound having a carbon-carbon unsaturated bond reactive with a protonic polar group in one molecule is generally used. Such compounds include, for example, acrylic acid, methacrylic acid, angelic acid, tribic acid, oleic acid, elaidic acid, erucic acid, brassidic acid, maleic acid, fumaric acid, citraconic acid, Unsaturated carboxylic acids such as rosin acid and cinnamic acid; Allyl alcohol, methylvinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-buten- 3-butene-1-ol, 2-methyl-3-butene-1-ol, 2- 1-ol, 4-methyl-4-en-1-ol and 2-hexene-1-ol.

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

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

In the formula (A6-1), R ^a1 to R ^a4 and m have the same meanings as those of the formula (a6-1). Formula (A6-2) of, R ^{b1 b4} ~R and m have the same meaning and the same symbol in the formula (b6-1).

" Cado  Resin (A7) "

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

As the cadmium resin, it is preferable to use a cado resin having at least one kind of 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 cyclic structures are bonded to the ring carbon atoms constituting the cyclic structure include 9,9-bis (phenyl) fluorene skeleton, 9,9-bis (hydroxyphenyl) fluorene skeleton, 9,9-bis (phenyl) fluorene skeleton having a 9-bis (cyanophenyl or aminoalkylphenyl) fluorene skeleton, a 9,9-bis (phenyl) fluorene skeleton having an epoxy group, .

The cadmium resin is formed by polymerizing a skeleton having a cado structure by a reaction between functional groups bonded thereto. The cadmium resin has, for example, a structure (card structure) in which a main chain and a cyclic structure, which is a bulky side chain, are linked by one element, and has a cyclic structure in a substantially vertical direction with respect to the main chain.

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

As the cardo resin, for example, a polymer of a monomer having a cardo structure can be mentioned.

Examples of the monomer having a cardo structure include 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) Epoxy compounds containing a cadose structure; A (meth) acrylic compound containing a cardo structure such as a compound represented by the following formula: Bisphenol-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3-methylphenyl) 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, and 2-hydroxy-1,3-propanediyl group, R is a hydrogen atom or a methyl group, and p and q are an integer of 1 to 30;

From the viewpoint of alkali solubility, the monomer having the above-exemplified cado structure has at least one group selected from a carboxyl group and a phenolic hydroxyl group on an aromatic ring bonded to a carbon atom at the 9-position of a fluorene ring or fluorene ring There may be.

Commercially available products may also be used as the cadmium resin. Examples thereof include OGSOL CR-TR1, Ogol CR-TR2, Ogol CR-TR3, Ogol CR-TR4, Ogol CR-TR5, Ogol CR-TR6 , And the like.

[Photosensitive Agent (B)]

Examples of the photosensitizer (B) include photo acid generators and photo radical polymerization initiators. By containing the photosensitizer (B), the radiation-sensitive material can exert the radiation-sensitive properties and have a good radiation sensitivity.

The photosensitive agent (B) may be used singly or in combination of two or more kinds.

The content of the photosensitizer (B) in the radiation-sensitive material is usually 5 to 100 parts by mass, preferably 10 to 65 parts by mass, more preferably 15 to 60 parts by mass with respect to 100 parts by mass of the polymer (A) Wealth. By setting the content of the photosensitizer (B) within the above range, it is possible to increase the difference in solubility between the irradiated portion irradiated with the radiation and the unexposed portion with respect to the aqueous alkaline solution or the like serving as the developer, thereby improving the patterning performance.

"mine Generator "

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

Examples of photoacid generators include quinonediazide compounds, oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, Ester compounds. By using these compounds, a material exhibiting positive radiation sensitivity characteristics can be obtained.

As the photoacid generator, a quinone diazide compound, an oxime sulfonate compound, an onium salt, and a sulfonic acid ester compound are preferable, a quinone diazide compound and an oxime sulfonate compound are more preferable, and a quinone diazide compound is particularly preferable .

< Quinone diazide  compound>

The quinone diazide compound generates carbonic acid by treatment including irradiation with radiation and development using an aqueous alkali solution. Examples of the quinone diazide compound include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as &quot; mother nucleus &quot;) and 1,2-naphthoquinonediazide sulfonic acid halide.

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

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

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

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

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

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

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

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

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

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

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

<Other examples>

Specific examples of the oxime sulfonate compound include the compounds described in publications such as Japanese Patent Laid-Open Publication No. 2011-227106, Japanese Laid-Open Patent Publication No. 2012-234148, and Japanese Laid-Open Patent Publication No. 2013-054125. Concrete 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. 2004-2110525, Japanese Patent Application Laid-Open No. 2008-129423, Japanese Patent Application Laid- -215616, and JP-A-2013-228526.

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

"Photo radical polymerization Initiator "

By using a photo-radical polymerization initiator as the photosensitizer (B) and using a cross-linking agent (D) such as a polymerizable carbon-carbon double bond-containing compound to be described later, a material exhibiting negative radiation sensitivity characteristics can be obtained.

Examples of the photoradical polymerization initiator include 2,2'-bis (2,4-dichlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'- '-Bis (2-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4- , 4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-methylphenyl) -4,5,4' Imidazole compounds such as imidazole, 2,2'-diphenyl-4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole; Alkylphenone compounds such as diethoxyacetophenone and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; (Trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) ) -1,3,5-triazine; And benzoin compounds such as benzoin; Benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, and 4-phenylbenzophenone.

[Resin (C)]

The resin (C) is at least one selected from condensates of a novolac resin, a resol resin and a resol resin. Of these, novolac resins are preferred because they have good alkali solubility (developability).

Resin (C) is a substance that develops color by applying heat. In the method of forming an insulating film described later, the coating film itself formed of the radiation-sensitive material containing the resin (C) before exposure does not have light shielding property at a wavelength of 300 to 400 nm. However, ), And the obtained insulating film is presumed to have a light shielding property at the above wavelength. By using such a resin (C), both the impartation of light shielding property and the alkali developing property can be achieved in the radiation-sensitive material.

For example, the light shielding property can be given at a heating temperature of 60 to 130 占 폚, which is a heating temperature at the time of prebaking, and at a heating temperature of more than 130 占 폚 and 300 占 폚 or less, which is a post baking temperature.

As the novolak resin, there may be mentioned, for example, a novolac resin having a structural unit represented by the formula (C1).

In the formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, (Ar is a bivalent aromatic group, and each R ² is independently a methylene group or an alkylene group having 2 to 20 carbon atoms), and the group represented by -R ² -Ar-R ² - One hydrogen atom may be substituted with a heterocyclic ring having a cyclopentadienyl group, an aromatic ring, a group containing an aromatic ring, or a nitrogen atom, a sulfur atom, an oxygen atom or the like.

Examples of the alkylene group having 2 to 30 carbon atoms in R ¹ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, , A tetradecylene group, a hexadecylene group, an octadecylene group, a nonadecylene group, an eicosylene group, a hemexocylene group, a docosylene group, a tricoxylene group, a tetracosylene group, a pentacosylene group, A silylene group, a heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene 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 phenetylene group, a benzylpropylene group and a naphthylene methylene group.

The group represented by -R ² -Ar-R ² - in R ¹ includes, for example, a group represented by -CH ₂ -Ph-CH ₂ - (Ph is 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 contained in a condensed polycyclic aromatic hydrocarbon group in which a part or all of the hydrogen atoms bonded to the aromatic ring carbon are substituted with a hydroxyl group. Examples of the condensed polycyclic aromatic hydrocarbon group include a naphthalene ring, an anthracene ring and a phenanthrene ring.

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

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

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

A2 + a3 is an integer of 1 or more and 6 or less; b2 + b3 is an integer of 0 or more and 5 or less; a2 + a3 + b2 + b3 is an integer of 1 or more and 6 or less; a4 + a5 + a6 is an integer of 1 or more and 8 or less, b4 + b5 + b6 is an integer of 0 or more and 7 or less, and a4 + a5 + a6 + b4 + b5 + b6 is an integer of 1 or more and 8 or less. B4? 4, a4 + b4? 4, a5 + b5? 4, and a6 + b6? 2.

a1, a2 + a3, and a4 + a5 + a6 are each an integer of preferably 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, and when R is plural, they may be the same or 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. As the alkoxy group, for example, a methoxy group can be mentioned.

Formula (c1-1) in the formula ~ (c1-4), the bonding position of the -OH and -R, is not particularly limited, and the two -R ¹ - is not also particularly limited as long as the binding position. For example, two -R ¹ - may be bonded to another benzene nucleus (for example, the following formula (1)) and may be bonded to the same benzene nucleus (for example, the following formula (2)). In the formula, * is a binding hand. 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, the substituent on the benzene nucleus is omitted.

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

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 imparting shielding property and heat resistance and alkali developing property, The group represented by formula (c1-3) is more preferable.

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

The novolak resin can be obtained, for example, by condensation of phenols and aldehydes in the presence of an acid catalyst, and, if necessary, distilling off unreacted components. As the reaction conditions, the phenols and aldehydes are usually reacted in a solvent at 60 to 200 캜 for about 1 to 20 hours. For example, it can be synthesized by the method described in Japanese Patent Publication No. 47-15111, Japanese Patent Application Laid-Open No. 63-238129, and the like.

The resol resin can be obtained, for example, by condensation of phenols and aldehydes in the presence of a base catalyst and, if necessary, distilling off unreacted components. As the reaction conditions, the phenols and aldehydes are usually reacted in a solvent at 40 to 120 DEG C for about 1 to 20 hours. In this way, for example, the aromatic ring contained in a phenol, an aldehyde derived from group of: a combination of resol resin (such as -R ¹ -OH, R ¹ is a formula (C1) in the same as defined as R ¹⁾ Can be obtained. The condensate of the resol resin can be obtained by conducting heat dehydration condensation reaction by adding heat or an acid to the resol resin. This reaction proceeds by dehydration condensation of an aldehyde-derived group contained in the resol resin. When the reaction is carried out by heating, the resol resin or its solution is reacted at 60 to 200 DEG C for about 1 to 20 hours. Resol resins and condensates thereof can be synthesized by, for example, the methods described in Japanese Patent No. 3889274, Japanese Patent No. 4013111, Japanese Patent Application Laid-Open No. 2010-111013, and the like.

Examples of the phenol include compounds having a hydroxyl number of 1 to 4, preferably 1 to 3, and a benzene number of 1, specifically phenol, orthocresol, methacresol, 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 Butylphenol, 4-t-butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-t- 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2- Butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 5-isopropyl-2-methylphenol;

(Naphthalene type compound) having 1 to 6 hydroxyl groups, preferably 1 to 3, and a benzene nucleus number of 2, specifically, monohydroxynaphthalene such as 1-naphthol and 2-naphthol, Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, , Dihydroxynaphthalene such as 8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

(Anthracene compound or phenanthrene compound) having a hydroxyl number of 1 to 8, preferably 1 to 3, and a benzene nucleus number of 3, specifically 1-hydroxyanthracene, 2-hydroxyanthracene, 9- Monohydroxyanthracene such as hydroxyanthracene, 1,4-dihydroxyanthracene, and 9,10-dihydroxyanthracene, 1,2,10-trihydroxyanthracene, 1,8,9 Trihydroxyanthracene such as trihydroxyanthracene and 1,2,7-trihydroxyanthracene, hydroxyphenanthrene such as 1-hydroxyphenanthrene and the like; .

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

In the synthesis of the resin (C), the amount of the aldehyde to be used is usually 0.3 mol or more, preferably 0.4 to 3 mol, and more preferably 0.5 to 2 mol, per 1 mol of the phenol.

Examples of the acid catalyst in the synthesis of the novolak resin include hydrochloric acid, para-toluenesulfonic acid, and trifluoromethanesulfonic acid. The base catalyst in the synthesis of the resol resin includes, for example, ammonia water and tertiary amines.

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

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

The content of the resin (C) in the radiation-sensitive material is usually 2 to 200 parts by mass, preferably 3 to 160 parts by mass, more preferably 4 to 140 parts by mass, per 100 parts by mass of the polymer (A) Particularly preferably 10 to 100 parts by mass. If the content of the resin (C) is lower than the lower limit of the above range, the effect of imparting light shielding property and developability based on the resin (C) tends to be exhibited. If the content of the resin (C) is not more than the upper limit of the above range, there is little possibility that the low absorbability of the insulating film will deteriorate and the heat resistance will deteriorate.

[Crosslinking agent (D)]

The crosslinking agent (D) is a compound having a crosslinkable functional group. Examples of the crosslinking agent (D) include compounds having two or more crosslinkable functional groups in one molecule.

When an insulating film made of a radiation sensitive material is used as a constituent element of an organic EL element, in view of the fact that the organic luminescent layer is deteriorated when it comes into contact with moisture, it is preferable to make the absorbency of the insulating film small by using the crosslinking agent (D) Do. Further, a negative-type radiation-sensitive material can be obtained by using a photo-radical polymerization initiator as the photosensitizer (B) and a polymerizable carbon-carbon double bond-containing compound as the crosslinking agent (D).

Examples of the crosslinkable functional group include an isocyanate group and a block isocyanate group, an oxetanyl group, a glycidyl ether group, a glycidyl ester group, a glycidylamino group, a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, A benzyloxymethyl group, a formyl group, an acetyl group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylolaminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group; A vinyl group, a vinylidene group, and a (meth) acryloyl group.

Examples of the cross-linking agent (D) include oxetanyl group-containing compounds, bisphenol A series epoxy compounds, bisphenol F series epoxy compounds, bisphenol S series epoxy compounds, novolac resin series epoxy compounds, resole resin series epoxy compounds, poly ) Epoxy compounds, methoxymethyl group-containing phenol compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, Containing compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compound, Guanamine Water, carboxymethyl group-containing urea compound, carboxymethyl group-containing phenol compound, a polymerizable carbon-to-carbon double bond-containing compound.

Examples of the oxetanyl group-containing compound include 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl, 3,7-bis (3-oxetanyl) , 3,3'- [1,3- (2-methylenyl) propanediylbis (oxymethylene)] bis (3-ethyloxetane), 1,4-bis [ ) Methoxymethyl] benzene, 1,2-bis [(3-ethyl-3-oxetanyl) methoxymethyl] ethane, 1,3-bis [ ] Propane, ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentenylbis Ethyl-3-oxetanyl) methyl] ether, tetraethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclodecanediyldimethylenebis [ (3-ethyl-3-oxetanyl) methyl] ether, trimethylolpropane tris [ 6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane, Pentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, polyethylene glycol bis [(3-ethyl- 3-oxetanyl) methyl] ether, dipentaerythritol pentaquis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol hexacis [ Methyl] ether, and dipentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether.

Examples of the oxetanyl group-containing compound further include reaction products of dipentaerythritol hexacis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone, dipentaerythritol pentaquis [ -Oxetanyl) methyl] ether and caprolactone, ditrimethylolpropane tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, bisphenol A bis [ (3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, a reaction product of bisphenol A [ (3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, a reaction product of hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, bisphenol F bis [ 3-oxetanyl) methyl] ether and ethylene oxide.

As the crosslinking agent (D), for example, there may be mentioned a compound having a group in which an isocyanate group is blocked by a protecting group. These compounds are also referred to as &quot; block isocyanate compounds &quot;. The group in which the isocyanate group is blocked by the protecting group is also referred to as a &quot; block isocyanate group &quot;.

As the block isocyanate compound, there can be mentioned, for example, JP-A-2013-225031, JP-A-5132096, JP-A-5071686, JP-A-2013-223859, JP-A- 5199752, JP- -41185, Japanese Patent No. 4879557, and Japanese Patent Laid-Open Publication No. 2006-119441.

Examples of the polymerizable carbon-carbon double bond-containing compound include polyfunctional (meth) acrylic acid esters. Specific examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylates such as polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (Meth) acrylates such as alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, (Meth) acrylate, ethylene oxide addition ditrimethylolpropane tetra (meth) acrylate, ethylene oxide addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipentaerythritol hexa Acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) (Meth) acrylate, ε-caprolactone added trimethylolpropane tri (meth) acrylate, ε-caprolactone added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone added pentaerythritol tetra ) &Lt; / RTI &gt; acrylate, epsilon -caprolactone &lt; And dipentaerythritol hexa (meth) acrylate.

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

The content of the crosslinking agent (D) in the radiation-sensitive material is usually 1 to 210 parts by mass, preferably 4 to 160 parts by mass, more preferably 10 to 150 parts by mass, per 100 parts by mass of the polymer (A) More preferably 15 to 100 parts by mass. If the content of the crosslinking agent (D) is not lower than the lower limit of the above range, the low absorptivity 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, heat resistance of the insulating film tends to be improved.

[Solvent (E)]

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

Examples of the solvent (E) include 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 ethers, propylene glycol monoalkyl ether propionates, triethylene glycol dialkyl ethers, hydroxyl 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 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, propylene glycol monobutyl ether propionate, .

As the triethylene glycol dialkyl ether, for example, triethylene glycol dimethyl ether can be mentioned.

Examples of the hydroxyl group-containing ketone include ketones such as acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol).

Examples of cyclic ethers or cyclic esters include? -Butyrolactone, tetrahydrofuran and dioxane.

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

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

In one embodiment, it is preferable to use? -Butyrolactone as the solvent (E), and a mixed solvent containing BL is preferable. The content of BL is preferably 70 mass% or less, and more preferably 20 to 60 mass%, based on 100 mass% of the total amount of the solvent (E). BL is preferably used in combination with at least one member selected from PGMEA, PGME, EDM and DAA. When the content of BL is within the above range, the dissolution state of the polymer (A) in the radiation-sensitive material tends to be suitably maintained.

As the solvent (E), an alcohol solvent such as methanol, ethanol, propanol, and butanol may be added, if necessary, in addition to the solvent exemplified above. Aromatic hydrocarbon solvents such as toluene and xylene may be used in combination.

The solvent exemplified above as the solvent (E) is low in absorbability as compared with NMP. Therefore, the above-described materials can be prepared using a low-absorbency solvent without using NMP having high water absorption. As a result, the material may exhibit low water absorption. The above-mentioned solvent exemplified as the solvent (E) has a high safety, so that the safety of the material can be enhanced.

When the solvent exemplified above as the solvent (E) is used, the insulating film formed of the above-described material can be made low in absorbency. Therefore, the above material can be suitably used for forming an insulating film of the organic EL device.

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

In the radiation sensitive material, the content of the solvent (E) is such that the solid content concentration of the material is usually 5 to 60 mass%, preferably 10 to 50 mass%, and more preferably 15 to 40 mass% . Here, the solid content refers to all components other than the solvent (E). When the content of the solvent (E) is within the above range, low absorptivity of the insulating film formed of the above-mentioned material tends to be improved without deteriorating developability.

[Other optional ingredients]

The radiation-sensitive material may contain other optional components such as the adhesion aid (F) and the surfactant (G), if necessary, in addition to the essential components and the suitable components, as long as the effect of the present invention is not impaired . The other optional components may be used alone or in combination of two or more.

<Adhesion Adjuster (F)>

The adhesion auxiliary agent (F) is a component for improving adhesion between a film formation object such as a substrate and an insulating film. The adhesion auxiliary agent (F) is particularly useful for improving adhesion between an inorganic substrate and an insulating film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride; Gold, copper, and aluminum.

As the adhesion auxiliary agent (F), a functional silane coupling agent is preferred. Examples of the functional silane coupling agent include silane coupling agents having a reactive substituent such as a carboxyl group, a halogen atom, a vinyl group, a methacryloyl group, an isocyanate group, an epoxy group, an oxetanyl group, an amino group, have.

Examples of the functional silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane, , and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Of these, N-phenyl-3-aminopropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, and? -Methacryloxypropyltrimethoxysilane are preferable.

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

&Lt; Surfactant (G) &gt;

The surfactant (G) is a component that enhances the film formability of the radiation-sensitive material. The surface-active property of the coating film can be improved by containing the surfactant (G), and as a result, the film thickness uniformity of the insulating film can be further improved. Examples of the surfactant (G) include a fluorine surfactant and a silicone surfactant.

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

The content of the surfactant (G) in the radiation-sensitive material is preferably 20 parts by mass or less, more preferably 0.01 to 15 parts by mass, and still more preferably 0.05 to 5 parts by mass based on 100 parts by mass of the polymer (A) 10 parts by mass. When the content of the surfactant (G) is within the above range, uniformity of film thickness of the formed coating film can be further improved.

[ Sensitizing radiation property  Method of preparing the material]

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

[ Sensitizing radiation property  Method of forming insulating film using material]

The method for forming an insulating film of the display or illumination device of the present invention includes the steps of forming a coating film on a substrate using the above radiation sensitive material, a step 2 of irradiating at least a part of the coating film with radiation, A step 3 for developing the applied coating film, and a step 4 for heating the developed coating film.

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

&Quot; Process 1 &quot;

In Step 1, a coating film is formed by applying the radiation-sensitive material to the surface of the substrate, and preferably by carrying out prebaking to remove the solvent (E). The film thickness of the coating film is preferably 0.3 to 15.0 mu m, more preferably 0.5 to 10.0 mu m, and still more preferably 1.0 to 5.0 mu m as a value after prebaking.

Examples of the substrate include a resin substrate, a glass substrate, and a silicon wafer. As the substrate, for example, a TFT substrate on which TFTs or wirings are formed can be cited as an organic EL element in the course of manufacture. When the device of the present invention is manufactured, the coating film is formed on the TFT substrate in particular.

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

The conditions for the prebaking are different depending on the composition of the radiation sensitive material and the like. For example, the heating temperature is 60 to 130 캜 and the heating time is 30 to 15 minutes. The prebaking is preferably performed at a temperature at which the light-shielding property based on the resin (C) is not imparted to the coating film.

&Quot; Process 2 &quot;

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

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

&Quot; Process 3 &quot;

In Step 3, the coating film irradiated with the radiation is developed in Step 2. Thus, for example, when a positive radiation-sensitive material is used, the irradiated portion of the radiation is removed, and when a negative radiation-sensitive material is used, the non-irradiated portion of the radiation is removed, . As the developing solution used in the developing treatment, an aqueous alkaline solution is preferable.

Examples of the alkaline compound contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Diethylammonium hydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5, &lt; RTI ID = 0.0 & 4,0] -7-undecene, and 1,5-diazabicyclo [4.3.0] -5-nonane. The concentration of the alkaline compound in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining suitable developing properties.

As the developer, an aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant, or an aqueous solution containing a small amount of various organic solvents dissolving the radiation-sensitive material in an aqueous alkali solution may be used. As the organic solvent in the latter aqueous solution, the same solvent as the polymer (A) or the solvent (E) for obtaining the radiation-sensitive material can be used.

Examples of the developing method include a puddle method, a dipping method, a swing dipping method, and a shower method. The developing time varies depending on the composition of the radiation sensitive material, but is usually about 10 seconds to 180 seconds. In this developing treatment, for example, water washing is carried out for 30 seconds to 90 seconds, and then air is blown with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

&Quot; Process 4 &quot;

In step 4, after step 3, a heating process (post-baking process) is performed on the coating film using a heating device such as a hot plate or an oven to obtain an insulating film. The heating temperature in this heating treatment is, for example, more than 130 DEG C but not more than 300 DEG C, and the heating time varies depending on the type of the heating apparatus, but is, for example, 5 minutes to 90 minutes. At this time, a step baking method in which two or more heating steps are performed may be used. For the heat treatment, for example, a hot plate or an oven can be used.

By the heat treatment in the above temperature range, a light shielding property is given to the insulating film so 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 way, an insulating film of a desired pattern can be formed on the substrate.

In step 4, the patterned coating film may be subjected to rinsing treatment or decomposition treatment before heating the coating film. In the rinsing treatment, it is preferable to clean the coating film using a low-absorptive solvent such as a solvent (E). In the decomposition treatment, the photoresist (B) remaining in the coating film can be decomposed by irradiating the entire surface (post exposure) with radiation by a high-pressure mercury lamp or the like. The exposure amount in the subsequent exposure is preferably about 1000 to 5000 mJ / cm &lt; 2 &gt;.

The insulating film obtained in this manner has light shielding property against light with a wavelength of 300 to 400 nm and is low in absorbability because the constituent material has a low absorbing structure and the treatment using a low absorbing compound It is possible. The insulating film exhibits good characteristics in terms of heat resistance, patterning property, radiation sensitivity, resolution and the like. Therefore, the insulating film can be suitably used as a protective film or an insulating film as a planarizing film, in addition to an insulating film as a barrier rib, for example, of an organic EL element or the like.

[Organic EL display device and organic EL lighting device]

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

The organic EL device 1 of Fig. 3 is an active matrix type organic EL device having a plurality of pixels formed in a matrix shape. The organic EL device 1 may be a top emission type or a bottom emission type. Properties of the materials constituting each member, for example, transparency are appropriately selected in accordance with the top emission type and the bottom emission type.

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

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

The TFT 3 is an active element of each pixel portion and is formed on the supporting substrate 2. [ The TFT 3 has 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 provided on the gate electrode in this order, but a top gate type in which a gate insulating film and a gate electrode are sequentially provided on the semiconductor layer may be used.

The semiconductor layer can be formed using an oxide semiconductor containing at least one element selected from the group consisting of In, Ga, Sn, Ti, Nb, Sb, and Zn. In the organic EL device 1, since the second insulating film 7 (partition wall) has a light shielding effect, it is possible to prevent or reduce the light emitted from the organic light emitting layer 8 from reaching the semiconductor layer. Therefore, a semiconductor layer made of IGZO or the like which is easily photodegradable can be used.

The first insulating film 4 is a flattening film that fulfills the role of flattening the surface unevenness by 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 above-described radiation-sensitive material, or may be formed using a conventionally known radiation-sensitive material. It is preferable that the film thickness of the first insulating film 4 is made large so as to perform an excellent function as a flattening film. The film thickness of the first insulating film 4 is preferably 1 m to 5 m. The first insulating film 4 can be formed by the method described in the above-described method of forming the insulating film.

The anode 5 is a pixel electrode. The anode 5 is formed on the first insulating film 4 by a conductive material. When the organic EL device 1 is of the bottom emission type, the anode 5 is required to be transparent. Therefore, as the material of the anode 5, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and tin oxide, which have high transparency, are preferable. When the organic EL device 1 is a top emission type, light reflectivity is required for the anode 5. As the material of the anode 5, a high reflectivity APC alloy (an alloy of silver, palladium and copper), an ARA (an alloy of silver, rubidium and gold), MoCr (an alloy of molybdenum and chromium), a NiCr And an alloy of chromium).

The through hole 6 is formed for connecting 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 the wiring formed in the through hole 6.

The second insulating film 7 fulfills a role as a partition (bank) having a recess 70 defining an arrangement region of the organic light emitting layer 8. The second insulating film 7 covers a part of the anode 5 and is formed so as to expose a part of the anode 5. The sectional shape of the second insulating film 7 at the boundary portion for exposing the anode 5 has a net taper shape. The second insulating film 7 can be formed by the method described in the insulating film forming method using the above-described radiation sensitive material.

The second insulating film 7 can be formed by patterning by exposure and development of a coating film so that a plurality of recessed portions 70 in which the organic light emitting layer 8 is formed are arranged in a matrix form at the time of planarization.

It is preferable that the second insulating film 7 is formed so as to fill the through hole 6. [ The insulating film formed on the first insulating film 4 and the insulating film formed in the through hole 6 can prevent or prevent light emitted from the organic light emitting layer 8 from reaching the semiconductor layer of the TFT 3, . Further, when two or more through-holes 6 are provided corresponding to one TFT 3, the light emitted from the organic light-emitting layer 8 can be further prevented or reduced 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, &quot; upward &quot; refers to a direction from the support substrate 2 to the encapsulation substrate 11. The second insulating film 7 can prevent or reduce light reaching the semiconductor layer from the light emitted from the organic light emitting layer 8 because the second insulating film 7 has light shielding properties.

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 m, more preferably 0.5 to 10.0 m, To 5.0 m is more preferable.

The organic light-emitting layer 8 emits light by applying an electric field. The organic luminescent layer 8 is a layer containing an electroluminescent material for electroluminescence. The organic light emitting layer 8 is formed on the anode 5 in the region defined by the second insulating film 7, that is, in the recessed portion 70. By forming the organic luminescent layer 8 in the concave portion 70 as described above, the periphery of the organic luminescent layer 8 is surrounded by the second insulating film 7, and a plurality of adjacent pixels can be partitioned.

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

A hole injecting layer and / or a hole transporting layer may be disposed between the anode 5 and the organic light emitting layer 8, and an electron transporting layer and / or an electron injecting layer may be interposed between the organic light emitting layer 8 and the cathode 9. [ May be disposed.

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

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

The encapsulation substrate 11 encapsulates a main surface (a surface opposite to the supporting substrate 2 on the TFT substrate) on which the organic light emitting layer 8 is disposed. As the sealing substrate 11, a glass substrate such as a non-alkali glass substrate can be mentioned. The main surface on which the organic light emitting layer 8 is disposed is preferably sealed with the sealing substrate 11 via the sealing layer 12 using a sealant applied near the outer peripheral end of the TFT substrate Do. The encapsulation layer 12 may be a layer of inert gas such as, for example, dried nitrogen gas, or a layer of a filling material such as an adhesive.

The organic EL device 1 of the present embodiment can suppress the deterioration of the semiconductor layer due to the use of the device in view of the fact that the second insulating film 7 has a light shielding property against light with a wavelength of 300 to 400 nm have. In addition, the first insulating film 4 and the second insulating film 7 can be formed using a radiation-sensitive material having a low water-absorbing property, and in the step of forming these insulating films 4 and 7, Such as washing with a cleaning liquid. Therefore, it is possible to reduce the penetration of a small amount of moisture contained in the insulating film forming material into the organic light emitting layer 8 in the form of adsorbed material or the like, and deterioration of the organic light emitting layer 8 and deterioration of the light emitting state can be reduced.

(Example)

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of examples and the like, &quot; part &quot; means &quot; part by mass &quot; unless otherwise stated.

[ GPC  analysis]

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

· Standard substance: Polystyrene equivalent

Device: manufactured by Toso Co., Ltd., trade name: HLC-802

Column: A column of the guide columns H _XL -H, TSK gel G7000H _XL , TSK gel gel GMH _XL , and TSK gel G2000H _XL ,

Solvent: tetrahydrofuran

Sample concentration: 0.7 mass%

· Injection amount: 70 μL

· Flow rate: 1 mL / min

[NMR analysis]

The content of phenyl group in Synthesis Example A5 was measured by ²⁹ Si-nuclear magnetic resonance spectrum using "JNM-ECS400" (manufactured by Nippon Denshoku Co., Ltd.), and the peak area of Si bonded with the phenyl group and the phenyl group Was determined from the ratio of the peak areas of Si not bonded.

&Lt; Synthesis of Polymer (A) &gt;

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

390 g of? -Butyrolactone as a polymerization solvent was added to a three-necked flask, and 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 a polymerization solvent, 71 g of 4,4'-oxydiphthalic dianhydride as an acid dianhydride was added. Thereafter, the reaction was allowed to proceed at 60 占 폚 for 1 hour, and then 19 g of maleic anhydride as an end-capping agent was added thereto. The reaction was further allowed to proceed at 60 占 폚 for 1 hour, followed by heating to 180 占 폚 for 4 hours. About 600 g of a polyimide solution containing a polymer (A-1) at a solid concentration of about 35% by mass was obtained. The Mw of the obtained polymer (A-1) was 8000.

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

After the inside of the flask was purged with nitrogen, 250.0 g of a propylene glycol monomethyl ether acetate solution containing 5.0 g of 2,2'-azobisisobutyronitrile was added. Subsequently, 20.0 g of methacrylic acid, 45.0 g of dicyclopentanyl methacrylate and 30.0 g of 3-ethyl-3-methacryloyloxymethyloxetane were added, and stirring was started slowly. The temperature of the solution was raised to 80 占 폚, the temperature was maintained for 5 hours, and the polymerization was terminated by heating at 100 占 폚 for 1 hour. Thereafter, the reaction product solution was added dropwise to a large amount of methanol to solidify the reaction product. The coagulated material was washed with water, then redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of methanol.

This redissolution-coagulation operation was carried out three times in total, and the obtained coagulum was vacuum-dried at 60 DEG C for 48 hours to obtain a desired copolymer. Thereafter, propylene glycol monomethyl ether acetate was used to prepare a copolymer solution so that the solid content concentration became about 35 mass%. The polymer (A-2) thus obtained had a weight average molecular weight (Mw) of 10,000.

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

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 polymer (A-3) thus obtained had a weight average molecular weight (Mw) of 20,000.

[Synthesis Example A4] Synthesis of polymer (A-4) (polybenzoxazole precursor)

443.2 g (0.90 mole) of the dicarboxylic acid derivative obtained by reacting 1 mole of diphenyl ether-4,4'-dicarboxylic acid with 2 moles of 1-hydroxybenzotriazole, and 443.2 g (0.90 mole) of hexafluoro-2,2- 366.3 parts (1.00 mols) of amino-4-hydroxyphenyl) propane was placed in a four-necked separable flask equipped with a thermometer, a stirrer, a feed inlet and a dry nitrogen gas introducing tube, and 3,000 parts of N-methyl- And dissolved. Thereafter, the reaction was carried out at 75 DEG 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 reaction was further terminated by stirring for 3 hours. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (by mass ratio), the precipitate was collected by filtration, sufficiently washed with water and then dried under vacuum to obtain polybenzoxazole precursor A-4). ? -Butyrolactone was added so that the concentration of the polymer (A-4) was 35% by mass to obtain a? -Butyrolactone solution of the polymer (A-4). The polymer (A-4) thus obtained had a weight average molecular weight (Mw) of 15,000.

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

63.39 parts (0.55 mol) of methyltrimethoxysilane, 69.41 parts (0.35 mol) of phenyltrimethoxysilane, and 2 (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added to a 500 mL three- (0.1 mol) of diacetone alcohol and 150.36 parts of diacetone alcohol, and while stirring at room temperature, an aqueous solution of phosphoric acid in which 0.338 parts of phosphoric acid (0.2 mass% based on the input monomer) was dissolved in 55.8 parts of water was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 DEG C and stirred for 1 hour, and then the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of raising the temperature, the inner temperature of the solution reached 100 캜, and from there, the mixture was heated and stirred for 2 hours (the inner temperature was 100 to 110 캜). During the reaction, a total of 115 parts of methanol and water as a by-product were spilled out. Diacetone alcohol was added to the diacetone alcohol solution of the obtained polymer (A-5) so that the concentration of the polymer (A-5) was 35% by mass to obtain a diacetone alcohol solution of the polymer (A-5). The polymer (A-5) thus obtained had a weight average molecular weight (Mw) of 5,000 and a phenyl group content of 100 mol of Si atoms was 35 mol.

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

60 parts of 8-carboxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene and 10 parts of N-phenyl- (5-norbornene- Dicarboxyimide) 40 parts, 1,5-hexadiene 2.8 parts, (1,3-dimethylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and diethylene glycol And 400 parts of ethyl methyl ether, and the polymerization reaction was carried out at 80 ° C for 2 hours under stirring to obtain a polymer solution containing the polymer (A-6 '). To this polymer solution, 0.1 part of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst was added and hydrogen was dissolved at a pressure of 4 MPa for 5 hours to carry out the hydrogenation reaction. Thereafter, 1 part of activated carbon powder And hydrogen was dissolved at 150 DEG C under a pressure of 4 MPa for 3 hours while stirring. Subsequently, the solution was taken out and filtered with a filter made of a fluorine resin having a pore size of 0.2 탆 to separate activated carbon to obtain 490 parts of a hydrogenation reaction solution containing a polymer (A-6) as a hydride of the polymer (A-6 '). The hydrogenation reaction solution containing the polymer (A-6) thus obtained had a solid concentration of 21 mass% and a polymer (A-6) in an amount of 102 parts. The hydrogenation reaction solution of the obtained polymer (A-6) was concentrated with a rotary evaporator to adjust the solid concentration to 35 mass% to obtain a solution of the polymer (A-6). The polymer (A-6) thus obtained had a weight average molecular weight (Mw) of 4000.

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

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

&Lt; Synthesis of Resin (C) &gt;

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

(1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92% by mass of paraformaldehyde (1.0 mol in terms of formaldehyde) were placed in a flask equipped with a stirrer, a thermometer, Respectively. Then, 3.4 g of paratoluenesulfonic acid was added while stirring. Thereafter, the reaction was carried out at 100 DEG C for 8 hours. After completion of the reaction, 200 g of pure water was added, and the solution in the system was transferred to a separatory funnel to separate and remove the aqueous layer from the organic layer. Next, water was washed until the washing water exhibited neutrality, and the solvent was removed from the organic layer under heating and reduced pressure to obtain 140 g of a novolak resin (C-1) having the structural unit represented by the following formula. The novolak resin (C-1) thus obtained had a weight average molecular weight (Mw) of 2000.

From the measurement chart by the Fourier transform infrared spectrophotometer (FT-IR), it is possible to confirm the absorption (2,800 to 3,000 cm ^-1 ) derived from expansion and contraction due to methylene bonding as compared with the raw material, 1200 cm ^-1 ) could not be found. Based on these results, it was identified that the novolak resin having a methylene bond could be obtained without generating a dehydration etherification reaction (disappearance of a hydroxyl group) between the hydroxyl groups in this synthesis example. These identifications are also the same in the following Synthesis Examples C2 to C5.

[Synthesis Example C2] Synthesis of novolac resin (C-2)

144.2 g (1.0 mole) of 1-naphthol, 134.1 g (1.0 mole) of terephthalaldehyde and 3.0 g of trifluoromethanesulfonic acid were placed in a flask equipped with a thermometer, a cooling tube, a classification tube and a stirrer, And the reaction was carried out at 160 ° C for 4 hours. After completion of the reaction, 200 g of pure water was added, and the solution in the system was transferred to a separatory funnel to separate and remove the aqueous layer from the organic layer. Next, water was washed until the washing water exhibited neutrality, and then the solvent was removed from the organic layer under reduced pressure to obtain 220 g of a novolak resin (C-2) having the structural unit represented by the following formula. The weight average molecular weight (Mw) of the resulting novolac resin (C-2) was 1500.

[Synthesis Example C3] Synthesis of novolak resin (C-3)

Except that 134.1 g (1.0 mol) of terephthalaldehyde, 160.2 g (1.0 mol) of 1,6-dihydroxynaphthalene, and 3.0 g of trifluoromethanesulfonic acid were used as the raw material component and the acid catalyst. 230 g of a novolak resin (C-3) composed of the structural unit represented by the following formula was obtained. The novolak resin (C-3) thus obtained had a weight average molecular weight (Mw) of 1000.

[Synthesis Example C4] Synthesis of novolac resin (C-4)

As in the case of Synthesis Example C1, except that 194.2 g (1.0 mole) of 1-hydroxyanthracene, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92% by mass of paraformaldehyde (1.0 mol in terms of formaldehyde) . 180 g of a novolac resin (C-4) composed of the structural unit represented by the following formula was obtained. The novolak resin (C-4) thus obtained had a weight average molecular weight (Mw) of 2000.

[Synthesis Example C5] Synthesis of novolak resin (C-5)

Except that 210.2 g (1.0 mole) of 1,4-dihydroxyanthracene as a raw material component, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92% by mass of paraformaldehyde (1.0 mol in terms of formaldehyde) . 190 g of a novolak resin (C-5) composed of the structural unit represented by the following formula was obtained. The weight average molecular weight (Mw) of the obtained novolak resin (C-5) was 3000.

< Sensitizing radiation property  Preparation of materials>

Polymers (A) used in the preparation of the radiation-sensitive material were polymers (A-1) to (A-7) in Synthesis Examples A1 to A6 and Preparation Example A7, (B), the crosslinking agent (D), the solvent (E), the adhesion auxiliary agent (F) and the surfactant (G) are as follows.

Photosensitizer (B)

B-1: Synthesis of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediamine (Condensation product of zid-5-sulfonic acid chloride (2.0 mol)) (Doago Kosan Co., Ltd.)

B-2: IRG-379 (trade name, manufactured by BASF) was used in place of 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] EG ")

Cross-linking agent (D)

D-1: 4,4-Bis [(3-ethyl-3-oxetanyl) methyl] biphenyl ("OXBP"

D-2: C-357 of Igagaku Kogyo K.K.

D-3: "M-405" manufactured by Toagosei Co., Ltd.

Solvent (E)

E-1: A mixed solvent of 30:20:50 by mass ratio of? -Butyrolactone (BL), propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME)

DAA: diacetone alcohol

EDM: diethylene glycol ethyl methyl ether

Adhesion Adjuster (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 Dow Corning Toray Silicone Co., Ltd.)

[ Preparation example  One]

10 parts of (B-1), 40 parts of (C-1), and 10 parts of (B-1) were added to a polymer solution (Polymer (A- (D-1) 15 parts, (D-2) 5 parts, (F-1) 4 parts, (G-1) 1 part and (E-1) were mixed to obtain a solid content concentration of 25 mass% And filtered through a membrane filter having a pore size of 0.2 탆 to prepare a positive-type material 1.

[ Preparation example  2 to 33]

Positive materials 2 to 23 and 30 to 31, and negative type materials 24 to 29 and 32 to 33 were prepared in the same manner as in Preparation Example 1, except that each of the components shown in Table 1 and the respective amounts were used.

[ Example  And Comparative Example ]

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

< Patterning property >

The positive type materials obtained in Preparation Examples 1 to 23 and 30 to 31 were applied onto a silicon substrate using a clean track (Mark VZ, manufactured by Tokyo Electron Co., Ltd.), and then prebaked on a hot plate at 120 캜 for 2 minutes Baked to form a coating film. This coating film was exposed to light at an exposure amount of 100 mJ / cm 2 at a wavelength of 365 nm via a pattern mask having a predetermined pattern using an exposure machine (i-line stepper "NSR-2005i10D" manufactured by Nikon). Thereafter, development was carried out by a puddle method at 25 DEG C for 80 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, followed by water washing with ultrapure water for 1 minute, followed by drying to obtain a plurality of 5 mu m square through- Thereby forming a coating film having a pattern in which holes are arranged in parallel. This coating film was post-baked on a hot plate at 250 DEG C for 60 minutes to form an insulating film having the above-described pattern and the film thickness shown in Table 2. [

The negative type materials obtained in Preparative Examples 24 to 29 and 32 to 33 were applied on a silicon substrate using a clean track (Mark VZ, manufactured by Tokyo Electron Co., Ltd.) Baked for minute to form a coating film. This coating film was exposed to light at an exposure amount of 300 mJ / cm 2 at a wavelength of 365 nm via a pattern mask having a predetermined pattern using an exposure machine (i-line stepper "NSR-2005i10D" manufactured by Nikon). Thereafter, the resist film was developed in a puddle method at 25 DEG C for 120 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with ultra-pure water for 1 minute, and dried to form a plurality of through- Thereby forming a coating film having a pattern in which holes are arranged in parallel. This coating film was post-baked on a hot plate at 250 DEG C for 60 minutes to form an insulating film having the above-described pattern and the film thickness shown in Table 2. [

At this time, in the case of the above-mentioned coating film, it was confirmed whether the exposed portion after development was completely dissolved in the case of the positive type material or whether the unexposed portion after development was completely dissolved in the case of the negative type material. A case of forming a pattern of 5 mu m square and a case of forming an insulating film without an insulating film peeling or development residue is referred to as &quot; good &quot;, a pattern of 5 mu m square is formed, and a case where there is no peeling of the insulating film, , A case where a pattern of 5 mu m square could not be formed or an insulating film was peeled off was defined as &quot; defective &quot;.

< LWR >

A square pattern having a line width of 5 占 퐉 of the coating film formed in the above <patterning property> was observed from above the pattern using a scanning electron microscope (SEM; "SU3500" manufactured by Hitachi High-Technologies Corporation) The line width was measured. The 3-sigma value (gap) of the measured line width was defined as LWR (탆). When the value of the LWR is 0.4 탆 or less, it is determined as &quot; good &quot;, and when it is more than 0.4 탆 and 0.8 탆 or less, &quot; good &quot;

<Shading property>

The radiation sensitive material obtained in the preparation example was coated on a glass substrate ("Corning 7059" manufactured by Corning Inc.) using a clean track (Mark VZ manufactured by Tokyo Electron Co., Ltd.) After pre-baking for 2 minutes, post-baking was performed on a hot plate at 250 DEG C for 60 minutes to form an insulating film having the film thickness shown in Table 2.

For the glass substrate having this insulating film, the total light transmittance was measured in a wavelength range of 300 nm to 780 nm using a spectrophotometer (&quot; 150-20 type double beam &quot; manufactured by Hitachi Seisakusho Co., Ltd.) Was determined. The light shielding property is "good" when the maximum total light transmittance is 6% or less at a wavelength of 300 to 400 nm, "good" when it is more than 6% and less than 10%, and "good" when it is more than 10% Slightly poor &quot;, and &quot; poor &quot; when it exceeds 15%.

< Taper  Angle and Film thickness >

In the above <patterning property> insulating film, the vertical cross-sectional shape in a direction orthogonal to the lines of the plurality of through holes was observed with an SEM ("SU3500" manufactured by Hitachi High-Technologies Corporation). From this SEM image, the taper angle of the insulating film was determined. In each evaluation, the film thickness of the insulating film was determined from the same SEM image.

<Absorbency>

The radiation sensitive material obtained in the above preparation example was coated on a silicon substrate using a clean track (Mark VZ, manufactured by Tokyo Electron Co., Ltd.), prebaked on a hot plate at 120 캜 for 2 minutes, Lt; RTI ID = 0.0 &gt; 250 C &lt; / RTI &gt; for 60 minutes to form an insulating film having a film thickness of 3.0 m.

The insulating film, Thermal Desorption Spectroscopy, and the mixture was heated in a vacuum of 1.0 × 10 ^-9 Pa using (ESCO's "TDS1200"), the speed to 200 ℃ 30 ℃ / min temperature rise from room temperature. The sample surface at that time and the gas desorbed from the sample were measured as the value of the peak of water (M / z = 18) with a mass spectrometer ("5973N" manufactured by Agilent Technologies). The integrated value [A 占 퐏] of the total peak intensity at 60 占 폚 to 200 占 폚 was taken and the water absorbency was evaluated. The absorbent is, "good" in the case where [A · sec] values of the total peak intensity of 60 ℃ ~200 ℃ integral 3.0 × 10 ^-8 or lower case "excellent", more than 3.0 × 10 ^-8 5.0 × 10 ^-8 or less , And when it exceeded 5.0 x 10 &lt; ^-8 &gt;

<Heat resistance>

An insulating film was formed using a radiation-sensitive material in the same manner as in the evaluation of &lt; absorptivity &gt;. The TGA measurement was performed on the insulating film at 100 ° C to 500 ° C using a thermogravimetric analyzer ("TGA2950" (Under air, a temperature raising rate of 10 캜 / min) to obtain a 5% weight reduction temperature. The heat resistance was "good" when the 5% weight reduction temperature exceeded 350 ° C, "good" when the temperature was 350 to 330 ° C, and "poor" when the weight reduction temperature was less than 330 ° C.

&Quot; Evaluation of device characteristics &

A TFT substrate on which a TFT was formed on a glass substrate ("Corning 7059" by Corning Inc.) was fabricated, and an insulating film was formed on the TFT substrate to form an evaluation device. The evaluation device was evaluated for the evaluation device.

The TFT substrate was formed in the following order. First, a molybdenum film was formed on a glass substrate by sputtering, and a gate electrode was formed by photolithography and etching using a resistor. Next, a silicon oxide film was formed on the entire surface of the glass substrate and the upper layer of the gate electrode by sputtering to form a gate insulating film. An InGaZnO 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 resistor. A molybdenum film was formed on the semiconductor layer by sputtering, and the source electrode and the drain electrode were formed by photolithography and etching using a resistor. Finally, a silicon oxide film was formed by sputtering over the entire surface of the substrate, the source electrode, and the drain electrode, and a passivation film was obtained to obtain a TFT substrate.

After applying the radiation-sensitive material obtained in the preparation example on the TFT substrate using a clean track (Mark VZ manufactured by Tokyo Electron Co., Ltd.), the substrate was prebaked on a hot plate at 120 캜 for 2 minutes, And post baked at 250 DEG C for 60 minutes to form an insulating film having the film thickness shown in Table 2. [

<Switching Response Characteristics>

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

<TFT Reliability>

The TFT reliability is obtained by changing the change of the Id-Vg characteristic (change amount of the threshold voltage (Vth)) when the electrical stress is applied between the gate electrode and the source electrode, .

(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 and the potential of the drain electrode at +10 V and the potential Vg of the gate electrode at - 20V to + 20V. The Id-Vg characteristic was obtained by plotting the current Id flowing between the drain electrode and the source electrode when the potential Vg of the gate electrode was changed as described above. In this Id-Vg characteristic, the voltage at which the current value is turned ON is set to the threshold voltage (Vth).

( Threshold  Voltage( Vth ) &Lt; / RTI &gt;

Electrical stress was given by applying a positive voltage of + 20V and a negative voltage of -20V for 12 hours between the gate electrode and the source electrode. This electrical stress is caused by the fact that under the condition that 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, And under the condition not irradiated. The variation amount of 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 variation amount of the threshold voltage Vth at the time of light irradiation is suppressed to less than 1.3 times the variation amount of the threshold voltage Vth at the time of light irradiation, the TFT reliability is considered to be &quot; good & TFT reliability is &quot; good &quot; when the TFT reliability is suppressed to less than 1.6 times, and the TFT reliability is &quot; slightly better &quot; when the TFT reliability is suppressed to 1.6 times or more and less than 2 times. Poor ".

As shown in Table 2, the radiation sensitive materials of Preparation Examples 1 to 29 were excellent in patterning property, pattern shape, low water absorption property and heat resistance. The insulating films formed in Examples 1 to 37 are excellent in light shielding property and in a net taper shape and the device using the insulating film and the semiconductor layer susceptible to light deterioration can exhibit device characteristics (switching response characteristics, TFT reliability). On the contrary, the insulating films formed in Comparative Example 1 were inferior in light shielding property, and the insulating films formed in Comparative Examples 2 and 4 had inferior patterning properties, pattern shape, light shielding property, low water absorbability and heat resistance, The formed insulating film is inferior in patterning property, pattern shape and low absorptivity, and the device using these insulating films and the semiconductor layer which is easily photodegraded has poor device characteristics (switching response characteristics, TFT reliability) under a light irradiation environment.

1: Organic EL device
2: Support substrate
3: TFT
4: A first insulating film (planarization film)
5: anode
6: Through hole
7: Second insulating film (barrier rib)
70:
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 the insulating film
112: edge portion of the first electrode
113: first electrode surface
120: insulating film
121: slope of insulating film

Claims (19)

A TFT substrate in which a semiconductor layer constituting a TFT contains an oxide semiconductor containing at least one element selected from In, Ga, Sn, Ti, Nb, Sb and Zn;
A first electrode formed 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 second electrode formed opposite to the first electrode
The organic EL device comprising:
Wherein the insulating film is an insulating film formed of a radiation-
Wherein the radiation-
(A) a polyimide precursor (A2), a polysiloxane (A4), a polybenzoxazole (A5-1), a precursor of the polybenzoxazole (A5-2), a polyolefin (A6) And the cadoprene resin (A7) (except for the following resin (C)),
(B) a photosensitive agent,
(C) at least one resin selected from novolak resins, resole resins and condensates of resole resins,
(D) a crosslinking agent which is a compound having two or more crosslinkable functional groups in one molecule
&Lt; / RTI &gt;
Wherein the content of the resin (C) in the radiation-sensitive material is 2 to 200 parts by mass relative to 100 parts by mass of the polymer (A)
Organic EL device. delete The method according to claim 1,
Wherein the polymer (A) is at least one selected from the group consisting of polysiloxane (A4), polybenzoxazole (A5-1), precursor of polybenzoxazole (A5-2), polyolefin (A6) , Organic EL device. The method according to claim 1,
Wherein the polymer (A) comprises at least the polyimide (A1)
An organic EL device wherein the polyimide (A1) has a structural unit represented by the formula (A1):

(In the formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group). The method according to claim 1,
Wherein the polymer (A) comprises at least a polysiloxane (A4)
An organic EL device wherein the polysiloxane (A4) is a polysiloxane obtained by reacting an organosilane represented by the formula (a4)

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an epoxy ring-containing group having 2 to 15 carbon atoms, a group formed by substituting the hydrogen atom or one of two or more of the substituents contained in the alkyl group, in the case of R ^1, a plurality may be the same or different; R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms An aryl group having 6 to 15 carbon atoms, and when R ² is plural, they may be the same or different, and n is an integer of 0 to 3). The method according to claim 1,
Wherein the polymer (A) comprises at least polybenzoxazole (A5-1)
Polybenzoxazole (A5-1) is an organic EL device having a structural unit represented by the formula (a5-1):

(In the formula (a5-1), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group). The method according to claim 1,
Wherein the polymer (A) comprises at least a polybenzoxazole precursor (A5-2)
An organic EL device in which the precursor (A5-2) of polybenzoxazole has a structural unit represented by the formula (a5-2):

(In the formula (a5-2), X ¹ is a tetravalent organic group having an aromatic ring, and Y ¹ is a divalent organic group). The method according to claim 1,
Wherein the photosensitizer (B) is a photo acid generator or photo radical polymerization initiator. The method according to claim 1,
Wherein the resin (C) is a novolac resin. 10. The method according to any one of claims 1 to 9,
Wherein a cross-sectional shape of a boundary portion of the insulating film, in which the insulating film exposes the first electrode, is in a forward tapered shape. 10. The method according to any one of claims 1 to 9,
Wherein the insulating film has a film thickness of 0.3 to 15.0 mu m. 10. The method according to any one of claims 1 to 9,
Wherein the insulating film is formed so as to cover at least an edge portion of the first electrode, and a cross-sectional shape at a boundary portion of the insulating film has a net taper shape. 10. The method according to any one of claims 1 to 9,
Wherein the insulating film is a partition for partitioning the surface of the TFT substrate into a plurality of regions,
And a plurality of pixels formed in the plurality of regions. 14. The method of claim 13,
A first electrode formed on the TFT substrate and connected to the TFT, an organic light emitting layer formed on the first electrode in the region partitioned by the partition, and a second electrode formed on the organic light emitting layer, An organic EL device having an EL element. 15. The method of claim 14,
Wherein the TFT substrate is a TFT substrate having a support substrate, a TFT formed on the support substrate in correspondence with the organic EL element, and a planarization layer covering the TFT,
Wherein the partition wall covers at least an edge portion of the first electrode and the partition wall is formed on the planarization layer so as to be disposed at least above the semiconductor layer of the TFT. 16. The method of claim 15,
Wherein the first electrode is formed on the planarization layer and the first electrode is connected to the TFT through a wiring formed in a through hole passing through the planarization layer. 10. The method according to any one of claims 1 to 9,
Wherein the insulating film is formed on the TFT substrate so as to be disposed at least above the semiconductor layer, and when projected from the top of the TFT substrate, 50% or more of the area of the semiconductor layer is overlapped with the insulating film EL device. A step (1) of forming a coating film on the TFT substrate using the radiation sensitive material according to claim 1, a step (2) of irradiating at least a part of the coating film with radiation, a step (3) of developing the coating film irradiated with the radiation, And a step (4) of heating the applied coating film to form an insulating film having a total light transmittance in a range of 0 to 15% at a wavelength of 300 to 400 nm. The method of claim 18, wherein
Wherein the heating temperature in Step 1 is 60 to 130 占 폚 and the heating temperature in Step 4 is 130 占 폚 to 300 占 폚.

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