JP5966972B2 - Radiation sensitive resin composition, insulating film and organic EL device - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, an insulating film, and an organic EL (Electro Luminescence) element.

An organic EL element using electroluminescence by an organic compound is expected as a next-generation lighting technology in addition to a display element such as a display, and has been actively developed.
An organic EL display element of a display element using an organic EL element is self-luminous, does not require a backlight, and can display an image at a wide viewing angle and at a high speed. Furthermore, it has low power consumption and has excellent characteristics such as thinness and light weight.

  Such an organic EL display element is manufactured as follows, for example. First, an anode (hole injection electrode) made of ITO (Indium Tin Oxide) or the like and a hole transport layer pattern are formed on a substrate. Next, in the passive organic EL display element, after forming an insulating film pattern and a cathode barrier rib pattern, the organic light emitting layer, the electron transport layer, and the cathode (electron injection electrode) are patterned by, for example, vapor deposition.

In an active organic EL display element, an ITO pattern and an insulating film pattern that also serves as a partition of the organic light emitting layer are formed, and then the organic light emitting layer pattern is formed by a masking method, an ink jet method, or the like. Next, an electron transport layer and a cathode (electron injection electrode) are formed. Here, the insulating film serving as the partition wall can be formed using a resin that can be patterned by a photolithography method (see, for example, Patent Documents 1 and 2). The organic light emitting layer, for example, it is possible to use a material doped with quinacridone or coumarin base matrix such as Alq _3, BeBq _3.

  In recent years, display elements have been required to have high definition, and studies have been made to increase the aperture ratio of organic EL display elements so that the brightness is not reduced by the increase in definition.

For example, in an active organic EL display element, in addition to an insulating film forming a partition wall, an insulation having a flattening function as described in Patent Document 1 and Patent Document 2 can be realized so as to realize a higher aperture ratio. The introduction of membranes is being considered. Patent Document 3 discloses a TFT technique using high-performance IGZO (indium gallium zinc oxide) as a semiconductor layer.
The active organic EL display element having such a structure is manufactured by, for example, the following method.

  First, a thin film transistor (TFT), which is an active element, is formed for each of a plurality of pixels provided in a matrix on a substrate such as glass. A first insulating film that also serves as a planarizing film is formed on the TFT. Next, an anode pattern is formed on the first insulating film. For this pattern formation, a wet etching method is usually used. A hole transport layer pattern is formed on the first insulating film by a masking method. Subsequently, a second insulating film serving as a partition between the anode and the organic light emitting layer is formed by patterning, and the pattern of the organic light emitting layer is formed by a masking method, an ink jet method or the like, and then an electron transport layer and a cathode are sequentially formed. Is done. At this time, in order to connect the anode and the TFT, it is necessary to form a through hole having a size of about 1 μm to 15 μm in the first insulating film.

  Although the organic EL display element has the above structure and manufacturing method, it is preferable to use a resin that can be easily patterned as desired for the insulating film functioning as a partition of the organic light emitting layer and a planarizing film on the TFT. In that case, the resin constituting the insulating film is required to have various characteristics such as heat resistance and mechanical strength. Furthermore, in the formation of the insulating film, a liquid radiation-sensitive resin composition having excellent developability is used so that simple film formation and simple patterning using, for example, a photolithography method are possible. It is preferable to use it.

  From such a viewpoint, Patent Document 4 discloses a technique of using polyimide for an insulating film of an organic EL element. Polyimide has good properties such as heat resistance and mechanical strength, and a liquid resin composition can be used for film formation. Furthermore, it is possible to prepare a resin composition having radiation sensitivity. In that case, as the resin component, polyimide can be used in addition to polyamic acid and polyamic acid ester which are polyimide precursors.

JP 2011-107476 A JP 2010-237310 A JP 2006-165529 A JP 2009-9934 A

  As described above, in the organic EL element, heat resistance and mechanical strength are required for the insulating film constituting the partition walls, the planarizing film, and the like, patterning properties are required, and good developability is required. Yes. Therefore, studies have been made to use, for example, polyimide for the insulating film of the organic EL element.

When polyimide is used for the insulating film, it is usual to first synthesize the polyimide precursor or polyimide.
In the synthesis of polyimide precursors and polyimides, aprotic solvents such as N-methylpyrrolidone (NMP) are frequently used as the polymerization solvent used for the synthesis because of the low solubility of polyamic acids and polyimides. The And after polyamic acid, a polyimide, etc. are synthesize | combined, it is preferable to be used for formation of an insulating film as a resin composition in the state of the NMP solution.

  However, in an organic EL element, when forming an insulating film functioning as a partition of an organic light emitting layer or a planarizing film on a TFT, high hygroscopicity may be a problem with N-methylpyrrolidone (NMP). is there.

  In an organic EL element such as an organic EL display element, even if the organic light emitting layer is a low molecule-organic light emitting layer using a low molecular material, it is a polymer-organic light emitting layer using a polymer material. However, it is known that when it comes into contact with moisture, it quickly deteriorates and its light emission state is inhibited. It is considered that such moisture may enter from the external environment, and a trace amount of moisture contained in the insulating film forming material in the form of adsorbed water may gradually enter the organic light emitting layer. Polyimide itself is a low water-absorbing material compared to other photosensitive polymer materials, and is originally a material with little such concern. Therefore, what is concerned is NMP with high hygroscopicity.

  That is, if NMP remains in the organic EL element, the organic light emitting layer of the organic EL element may be deteriorated due to its high hygroscopicity. As the resin composition for forming the insulating film of the organic EL element, it is preferable to use other than NMP as a solvent or the like so as to suppress the remaining NMP in the organic EL element.

  In that case, when it was going to use a polyimide for an insulating film, the manufacturing process of the organic EL element might become complicated. That is, when using polyimide for the insulating film of the organic EL element, it is necessary to synthesize desired polyamic acid or polyimide using NMP as a polymerization solvent, and then precipitate them to isolate the polyamic acid or polyimide. Then, the isolated polyamic acid or polyimide is purified to remove NMP, then dissolved again in a solvent that does not cause the organic light emitting layer to deteriorate, the components are adjusted, and a resin composition for forming an insulating film is obtained. Need to be prepared. Therefore, when using a polyimide for an insulating film, there exists a possibility that the number of processes in manufacture of an organic EL element will increase, and productivity may fall. Therefore, there has been a demand for a polyimide that can be used without using NMP as a polymerization solvent and is suitable for forming an insulating film.

  Furthermore, in recent organic EL elements, as a function of an insulating film, in addition to a function as a partition for partitioning an organic light emitting layer and a function as a planarizing film, a function as a protective film for protecting a TFT is strongly demanded. It is supposed to be. From such a viewpoint, polyimide having excellent mechanical strength is suitable as an insulating film.

  However, mechanical strength alone is not sufficient to protect the TFT. For example, in the case of a TFT using an oxide semiconductor such as IGZO for the semiconductor layer, there is a problem in light resistance. Specifically, in the case of a semiconductor layer using an oxide semiconductor, the semiconductor layer may have absorption in an ultraviolet region or the like. Therefore, in a TFT using an oxide semiconductor, when it is irradiated with light from the outside, the resistance at the time of OFF decreases, and a sufficient ON / OFF ratio as a switching element cannot be obtained. Therefore, when a TFT using an oxide semiconductor is used for an organic EL element, there is a problem that characteristics deteriorate due to the influence of light from the outside.

  The problem of deterioration of characteristics due to light irradiation is a problem even in TFTs using conventional amorphous silicon or the like as a semiconductor layer, although there is a difference in lightness, and the light shielding characteristics in an insulating film that covers and protects the TFT. Improvement is demanded. In that case, the conventional insulating film made of polyimide has not been sufficiently studied for improving the light shielding property, and from this point of view, it has not been sufficient as a protective film.

  As described above, there is a demand for an insulating film having excellent heat resistance and mechanical strength, excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties. . And the radiation sensitive resin composition suitable for formation of such an insulating film is calculated | required. Furthermore, an organic EL element having such an insulating film is required.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to form an insulating film having excellent resistance to heat, etc., excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties. It is to provide a radiation sensitive resin composition.

  Another object of the present invention is to provide an insulating film having excellent heat resistance and the like, excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties. .

  Furthermore, an object of the present invention is to provide an organic EL device having an insulating film having excellent heat resistance and the like, excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties. It is to provide.

The first aspect of the present invention is:
(A) an acid component containing an acid component having a group represented by the following formula (1-1) (A1) and an amine component containing an amine component (A2) having a group represented by the following formula (1-2); Polyimide obtained by condensing
(B) an acid component containing a (B1) acid component having a group represented by the following formula (1-1), and an amine component containing (B2) an amine component having a group represented by the following formula (1-2): A polyamic acid obtained by condensing
(C) a quinonediazide compound, and
(D) It is related with the radiation sensitive resin composition characterized by including the compound shown by following formula (2).

（式（１−２）中、Ｘは炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基、炭素数１から６のフルオロアルキル基および水酸基のうちのいずれかを示す。）

(In formula (1-2), X represents any one of an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a hydroxyl group.)

（式（２）中、Ｒ^２は水素原子および炭素数１〜６のアルキル基のうちのいずれかを示し、Ｚは単結合、メチレン基および炭素数２から６のアルキレン基のうちのいずれかを示し、Ｒ^３は、水素原子およびフェニル基のうちのいずれかを示す。ｙは０〜２の整数を表し、ａは０〜１２の整数を表す。）

(In the formula (2), R ² represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and Z represents any of a single bond, a methylene group, and an alkylene group having 2 to 6 carbon atoms. R ³ represents any one of a hydrogen atom and a phenyl group, y represents an integer of 0 to 2, and a represents an integer of 0 to 12.)

In the first aspect of the present invention, (A) polyimide is a polyimide obtained by condensing (A1) an acid component and (A2) an amine component,
(B) The polyamic acid is preferably a polyamic acid obtained by condensing (B1) an acid component and (B2) an amine component.

  In the first aspect of the present invention, it is preferable that the compound further comprises (E) a compound having one or more oxetanyl groups.

  In the first aspect of the present invention, the mixing ratio of (A) polyimide and (B) polyamic acid is 100% by mass of (A) polyimide and (B) polyamic acid, and (A) polyimide is 60% by mass. It is preferable that -99 mass% and (B) polyamic acid are the range of 1 mass%-40 mass%.

  1st aspect of this invention WHEREIN: It is preferable that (A) component has at least 1 structural part shown by following formula (3)-following formula (7).

（式（３）〜式（７）中、Ｒ^１１は下記式で示される構成部位の群から選ばれる少なくとも一つの構成部位である。Ｒ^１２〜Ｒ^１４はそれぞれ独立に、炭素数１〜１２のアルキル基およびフェニル基の少なくとも一方を含む２価の基である。）

(In the formulas (3) to (7), R ¹¹ is at least one component selected from the group of components represented by the following formula. R ^{12 to} R ¹⁴ each independently has 1 to 12 carbon atoms. And a divalent group containing at least one of an alkyl group and a phenyl group.)

  In a first aspect of the invention, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, propylene glycol monoalkyl ether and γ- It is preferable to include at least one solvent selected from the group consisting of butyrolactone.

  A second aspect of the present invention relates to an insulating film formed using the radiation-sensitive resin composition of the first aspect of the present invention and used for an organic EL element.

  According to a third aspect of the present invention, there is provided an organic EL element comprising the insulating film according to the second aspect of the present invention.

  According to the first aspect of the present invention, an insulating film having excellent heat resistance and the like, excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties can be formed. A radiation sensitive resin composition is obtained.

  According to the second aspect of the present invention, an insulating film having excellent heat resistance and the like, excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties can be obtained. .

  According to the third aspect of the present invention, an organic material having an insulating film having excellent heat resistance and the like, excellent exposure sensitivity and developability, good patternability, low water absorption, and good light shielding properties. An EL element is obtained.

It is sectional drawing which illustrates typically the structure of the principal part of the organic EL display element of this embodiment.

Hereinafter, embodiments of the present invention will be described.
In the present invention, “radiation” irradiated upon exposure is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present embodiment is a radiation sensitive resin composition used for forming an insulating film of an organic EL device, and includes (A) polyimide, (B) polyamic acid, (C) quinonediazide compound, And (D) a compound is contained. Hereinafter, each component will be described.

[(A) Polyimide]
The polyimide (A) contained in the radiation-sensitive resin composition of the present embodiment is a polyimide obtained by condensing an acid component and an amine component. Tetracarboxylic dianhydride is preferably selected as the acid component, and diamine is preferably selected as the amine component.
(A) A polyimide is a polyimide and has a low water absorption compared with other photosensitive resins, such as an acrylic resin. The (A) polyimide is preferably an alkali-soluble resin. (A) Since polyimide exhibits alkali solubility, the insulating film formed from the radiation-sensitive resin composition of the present embodiment can have developability, and high-precision patterning is possible.

  Furthermore, it is preferable that the polyimide (A) has a property of improving the light shielding property of the insulating film so that the insulating film formed from the radiation sensitive resin composition of the present embodiment has a suitable light shielding property.

  The polyimide (A) contained in the radiation-sensitive resin composition of the present embodiment uses an acid component or a structural site derived from an acid component as an acceptor (electron acceptor), and an amine component or a structural site derived from an amine component. It is configured to allow charge transfer interaction as a donor (electron donor). Accordingly, (A) polyimide has charge transfer (CT) absorption derived from its charge transfer interaction in a wavelength region including the ultraviolet region. Therefore, the insulating film formed from the radiation-sensitive resin composition of the present embodiment can exhibit excellent light shielding properties in a wavelength region including the ultraviolet region.

  (A) As the polyimide exhibits the above properties, in particular, the acid component for obtaining the polyimide (A) has a group represented by the following formula (1-1) so as to exhibit excellent light shielding properties ( A1) It is preferable that an acid component is included. And it is preferable that the amine component for obtaining (A) polyimide contains the (A2) amine component which has group shown by following formula (1-2).

（式（１−２）中、Ｘは炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基、炭素数１から６のフルオロアルキル基および水酸基のうちのいずれかを示す。）

(In formula (1-2), X represents any one of an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a hydroxyl group.)

  (A1) The acid component has a group of the above formula (1-1) containing a carboxyl group and exhibiting electron withdrawing property, and (A2) the amine component contains an amino group and exhibits electron donating property. By having the group of the formula (1-2), the (A) polyimide formed by using the group enables charge transfer type interaction in the molecule or between the molecules.

  Moreover, (A) polyimide can improve the solubility to a solvent and can show low water absorption because (A1) acid component has group of said Formula (1-1). And the (A2) polyimide has improved solubility in a solvent because the (A2) amine component has the group of the above formula (1-2), and (A) the radiation sensitive composition of the present embodiment containing the polyimide. The insulating film formed from the conductive resin composition can exhibit good patterning properties.

  As the (A1) acid component for obtaining the (A) polyimide capable of exhibiting the above-mentioned characteristics, any acid component having a group represented by the above formula (1-1) can be used. Are, for example, compounds represented by the following formulas (1-1-1) to (1-1-5). (A1) By using a compound represented by the following formula (1-1-1) to formula (1-1-5) as an acid component, (A) polyimide has improved solubility in a solvent, , Can exhibit light shielding properties.

（式（１−１−１）〜式（１−１−５）中、Ｒ^１２〜Ｒ^１４はそれぞれ独立に、炭素数１〜１２のアルキル基およびフェニル基の少なくとも一方を含む２価の基である。）

(In Formula (1-1-1) to Formula (1-1-5), R ^{12 to} R ¹⁴ each independently represents a divalent group containing at least one of an alkyl group having 1 to 12 carbon atoms and a phenyl group. .)

  Here, (A) Acid component for obtaining polyimide, (A1) As an acid component that can be used together with the acid component, for example, (A1) aromatic tetracarboxylic dianhydride other than the acid component, etc. Can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  As mentioned above, (A) As an acid component for obtaining a polyimide, it has 1 to 4 aromatic rings, and when it has two or more aromatic rings, a single bond or one atom is formed between the aromatic rings. An aromatic tetracarboxylic dianhydride having a structure bonded via the above can be mentioned.

  Specific examples of the aromatic tetracarboxylic dianhydride having such a structure include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′. , 4,4′-biphenyltetracarboxylic dianhydride, 4,4-oxydiphthalic acid (ODPA), ethylene glycol bistrimellitic dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) Phenyl} propane dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester (TAHQ), 4,4′-hexafluoroisopropylidenediphthalic dianhydride Product (6FDA), a compound represented by the following formula (1-1-a) (hereinafter referred to as HQDA), and a compound represented by the following formula (1-1-b) (hereinafter referred to as “HQDA”). Say PPTA.), Etc. In addition to the like include tetracarboxylic dianhydride described in Japanese Patent Application No. 2010-97188.

  Among these, particularly preferred aromatic tetracarboxylic dianhydrides include 4,4-oxydiphthalic acid (ODPA), 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4. Mention may be made of -phenylene ester (TAHQ), 4,4'-hexafluoroisopropylidene diphthalic dianhydride (6FDA), HQDA and PPTA.

  In addition, as the amine component (A2) for obtaining the polyimide (A) capable of exhibiting the above-described properties, any amine component having a group represented by the above formula (1-2) may be used. Can do. And (A2) As an amine component, the amine compound shown by following formula (1-2a) can be mentioned, for example. The (A) polyimide formed using the amine compound represented by the following formula (1-2a) can exhibit excellent solubility and light shielding properties.

R ⁴ in the above formula (1-2a) is selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. At least one group. Also, ^{R 5} in the formula (1-2a) independently of one another, a hydrogen atom, an acyl group or alkyl group. Preferred acyl groups include, for example, formyl group, acetyl group, propionyl group, butyroyl group, isobutyroyl group and the like, and preferred alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group. , N-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group and the like. Note that at least one of R ⁵ is a hydrogen atom. Moreover, n1 and n2 in said formula (1-2a) are integers of 0-2, and at least one of n1 and n2 is 1 or more.

  And as an amine compound shown by the said Formula (1-2a), the diamine of a following formula can be mentioned, for example.

  Moreover, as an amine compound shown by the said Formula (1-2a), it is preferable that it is diamine which has two hydroxyl groups of a following formula, for example.

  Moreover, as an amine compound shown by the said Formula (1-2a), it is preferable that it is a diamine which has three hydroxyl groups of a following formula, for example.

  Furthermore, as an amine compound shown by the said Formula (1-2a), it is preferable that it is a diamine which has four hydroxyl groups of a following formula, for example.

  And as an amine compound shown by the said Formula (1-2a), it is more preferable that it is diamine which has two hydroxyl groups of the said formula. By being a diamine having two hydroxyl groups of the above formula, the polyimide (A) formed using the diamine can exhibit better solubility.

  Here, (A) It is an amine component for obtaining a polyimide, Comprising: As an amine component which can be used with (A2) amine component, aromatic diamines other than (A2) amine component can be mentioned, for example. Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, and 4,4. '-Diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'- Dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3 , 3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3, '-Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9 -Bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-te Lachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4 , 4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] Hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, etc. Can be mentioned.

As described above, (A) the acid component for obtaining the polyimide preferably contains (A1) an acid component, and the amine component preferably contains (A2) an amine component.
At this time, the amount of the (A1) acid component used is preferably 60% by mass to 100% by mass when the total amount of the acid component for obtaining the (A) polyimide is 100% by mass. In addition, the amount of the (A2) amine component used is preferably 60% by mass to 100% by mass when the total amount of the amine component for obtaining the (A) polyimide is 100% by mass. By making the usage amounts of the (A1) acid component and the (A2) amine component in such a range, the (A) polyimide has improved solubility in a solvent and can exhibit low water absorption. And the insulating film formed from the radiation sensitive resin composition of this embodiment containing (A) polyimide can have both favorable patterning property and light-shielding property.

  In particular, it is preferable that all of the acid components for obtaining (A) polyimide are (A1) acid components having a group represented by the above formula (1-1). And it is preferable that all the amine components for obtaining (A) polyimide are (A2) amine components which have group shown by said Formula (1-2). By carrying out like this, (A) polyimide can show the outstanding solubility to a solvent, and can show more preferred low water absorption. And the insulating film formed from the radiation sensitive resin composition of this embodiment containing (A) polyimide can show more favorable patterning property and more excellent light-shielding property.

  (A) Polyamic acid obtained by synthesizing polyamic acid by reacting (A1) an acid component containing an acid component and (A2) an amine component containing an amine component according to a known method as a method for synthesizing polyimide. A method of obtaining a polyimide by dehydrating and ring-closing is suitable.

  The use ratio of the acid component containing the (A1) acid component and the amine component containing the (A2) amine component used in the polyamic acid synthesis reaction is as follows: The acid anhydride group is preferably 0.2 equivalents to 2 equivalents, more preferably 0.3 equivalents to 1.2 equivalents.

  The synthesis reaction is preferably performed in an organic solvent. The reaction temperature is preferably −20 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C. The reaction time is preferably 0.5 hours to 24 hours, and more preferably 2 hours to 12 hours.

As the polymerization solvent, a solvent capable of dissolving the raw materials and products at the time of synthesis is selected.
First, the polymerization solvent is selected from the group consisting of diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate and propylene glycol monoalkyl ether. It is preferable to use at least one selected from the above. These compounds can be used alone as a solvent for polymerization, and two or more kinds can be mixed and used.

Specific examples of these solvents include diethylene glycol dialkyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and the like.
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, diethylene glycol monobutyl ether acetate, and the like.
Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.
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 and the like.
Examples of propylene glycol monoalkyl ether include propylene glycol monomethyl ether.

  Examples of a preferable solvent as a polymerization solvent include ketones. Specific examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, methyl-3-methoxypropyl. Pionate etc. can be mentioned.

  Among these, propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA), diethylene glycol ethyl methyl ether (hereinafter sometimes abbreviated as EDM) and the like are particularly preferable.

  Furthermore, γ-butyrolactone (hereinafter sometimes abbreviated as BL) may be mentioned as a preferred solvent for the polymerization solvent. γ-Butyrolactone can be used, for example, alone as a polymerization solvent, or can be used by mixing with those mentioned above as the preferred polymerization solvent.

  Furthermore, if necessary, alcohol solvents such as methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol and 2- (2-ethoxyethoxy) ethanol, Ether solvents such as diglyme and triglyme and aromatic hydrocarbon solvents such as toluene and xylene may be added to the polymerization solvent.

  The polyimide (A) of the present embodiment is excellent in solubility and can synthesize polyamic acid as a precursor thereof without using NMP that has been widely used as a polymerization solvent. It is synthesized from the polyamic acid without using it.

  In this way, a reaction solution containing dissolved polyamic acid is obtained. This reaction solution may be used as it is for the imidation reaction to obtain (A) polyimide, or may be used for the imidization reaction after isolating the polyamic acid contained in the reaction solution. Moreover, you may use for the imidation reaction, after refine | purifying the isolated polyamic acid. The isolation and purification of the polyamic acid can be performed according to a known method.

  For the imidization reaction for obtaining (A) polyimide from the polyamic acid, known methods such as a heat imidization reaction and a chemical imidation reaction can be applied. When (A) a polyimide is synthesized by a heating imidization reaction, the synthesis solution of polyamic acid is preferably heated at 120 ° C. to 210 ° C. for 1 hour to 16 hours. If necessary, the reaction may be performed while removing water in the system using an azeotropic solvent such as toluene or xylene.

  The synthesized (A) polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure that the polyamic acid that is a precursor thereof has, and only a part of the amic acid structure is dehydrated and cyclized, It may be a partially imidized product in which an amic acid structure and an imide ring structure coexist in the molecule.

  The polyimide (A) of this embodiment preferably has an imidation ratio of 20% or more, more preferably 40% to 99%, and still more preferably 50% to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of (A) polyimide amic acid structures and the number of imide ring structures in percentage.

  (A) About a polyimide, the polystyrene conversion weight average molecular weight (henceforth "Mw") measured by gel permeation chromatography (GPC) becomes like this. Preferably it is about 2000-500000, More preferably, it is about 3000-300000. It is. If Mw is less than 2000, sufficient mechanical properties as an insulating film tend not to be obtained. On the other hand, when Mw is more than 500,000, the solubility of the radiation-sensitive resin composition obtained using (A) polyimide in a solvent or a developer tends to be poor.

  In addition, when synthesizing a polyamic acid by reacting an acid component containing (A1) an acid component and an amine component containing (A2) an amine component, a terminal-modified type is used with these components together with an appropriate molecular weight regulator. The polymer may be synthesized. By setting it as such a terminal-modified polymer, the applicability | paintability (printability) of the radiation sensitive resin composition of this embodiment can be improved, without impairing the effect of this invention.

  The molecular weight modifier is also referred to as a terminal blocking agent, and for example, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, and the like can be used. In that case, the use ratio of the molecular weight modifier (end-capping agent) is preferably 20% by mass or less and more preferably 10% by mass or less with respect to 100% by mass of the total amount of the acid component and amine component used.

  The (A) polyimide obtained by condensing the acid component and the amine component described above preferably has a constituent site derived from the structures of the (A1) acid component and the (A2) amine component. For example, it is preferable that (A) polyimide has the components of the following formulas (3) to (7). The radiation sensitive resin composition of this embodiment is an insulating film that exhibits good patternability and excellent light-shielding properties by containing (A) polyimide having the components of the following formulas (3) to (7). Can be formed.

（式（３）〜式（７）中、Ｒ^１１は、下記式（１−２ｂ）で示される構成部位である。Ｒ^１２〜Ｒ^１４はそれぞれ独立に、炭素数１〜１２のアルキル基およびフェニル基の少なくとも一方を含む２価の基である。）

(In the formulas (3) to (7), R ¹¹ is a component represented by the following formula (1-2b). R ^{12 to} R ¹⁴ are each independently an alkyl group having 1 to 12 carbon atoms and It is a divalent group containing at least one of the phenyl groups.)

(R ⁴ in Formula (1-2b) is selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. R ⁵ independently of one another represents a hydrogen atom, an acyl group or an alkyl group, and preferred acyl groups include, for example, a formyl group, an acetyl group, a propionyl group, a butyroyl group, An isobutyroyl group etc. can be mentioned, As a preferable alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, for example , n- decyl group, can be mentioned n- dodecyl group. at least one ^{R 5} is hydrogen atom. Further, n1 and n Is an integer from 0 to 2, at least one of n1 and n2 is 1 or more.)

(A) In the constituent parts of the above formulas (3) to (7), which are preferably contained in the polyimide, R ¹¹ is specifically a divalent group having one of the following hydroxyl groups. Is preferred.

Further, preferably containing at (A) the polyimide, the component parts of the above formula (3) to the equation (7), R ¹¹ is to be configured site is a divalent group having two the following hydroxyl preferable.

Further, preferably containing at (A) the polyimide, the component parts of the above formula (3) to the equation (7), R ¹¹ is to be configured site is a divalent group having three following hydroxyl preferable.

Furthermore, in the constituent parts of the above formulas (3) to (7) that are preferably contained in (A) polyimide, R ¹¹ may be a constituent part that is a divalent group having four hydroxyl groups as follows. preferable.

(A) In the constituent parts of the above formulas (3) to (7), which are preferably contained in the polyimide, R ¹¹ is a constituent part that is a divalent group having two hydroxyl groups. Most preferred. The radiation sensitive composition of the present embodiment containing (A) polyimide having the constituent parts of the above formula (3) to the above formula (7) because R ¹¹ is a constituent part that is a divalent group having two hydroxyl groups. The insulating resin composition can form an insulating film that exhibits better developability, patternability, and better light shielding properties.

[(B) Polyamic acid]
The (B) polyamic acid contained in the radiation sensitive resin composition of the present embodiment is a polyamic acid obtained by condensing an acid component and an amine component. Tetracarboxylic dianhydride is preferably selected as the acid component, and diamine is preferably selected as the amine component. (B) The polyamic acid is an alkali-soluble resin. Therefore, the insulating film formed from the radiation-sensitive resin composition of the present embodiment can have developability and has good patternability.

  Furthermore, (B) polyamic acid is a polyimide formed by itself and preferably dehydrating and closing it so that the insulating film formed from the radiation-sensitive resin composition of the present embodiment has suitable light-shielding properties. However, it is preferable to have the characteristic of improving the light shielding property of the insulating film.

  The (B) polyamic acid contained in the radiation-sensitive resin composition of the present embodiment uses an acid component or a structural site derived from an acid component as an acceptor (electron acceptor), and a structural site derived from an amine component or an amine component. Is configured to enable charge transfer interaction using as a donor (electron donor). Accordingly, (B) the polyamic acid and the polyimide formed by dehydration and ring closure thereof can have charge transfer (CT) absorption derived from the charge transfer interaction in a wavelength region including the ultraviolet region. Therefore, the insulating film formed from the radiation-sensitive resin composition of the present embodiment can exhibit excellent light shielding properties in a wavelength region including the ultraviolet region.

  (B) It is preferable that the acid component for obtaining (B) polyamic acid contains (B1) acid component which has group shown by said Formula (1-1) so that a polyamic acid may show the above characteristic. . And it is preferable that the amine component for obtaining (B) polyamic acid contains the (B2) amine component which has group shown by the said Formula (1-2). That is, the (B1) acid component is the same as the (A1) acid component used to form the (A) polyimide of the (A) component described above, and (B2) the amine component is the same as the (A) component described above. (A) It is preferable that it is the same as the (A2) amine component used for formation of a polyimide.

  Here, (B) an acid component for obtaining a polyamic acid, and (B1) an acid component other than the acid component is the above-described acid component for obtaining (A) a polyimide and (A1) an acid. Acid components other than the components can be exemplified. Moreover, (B) It is an amine component for obtaining a polyamic acid, Comprising: As an amine component other than (B2) amine component, it is an amine component for obtaining the above-mentioned (A) polyimide, Comprising: (A2) Amine component Other amine components can be exemplified.

  At this time, the amount of (B1) acid component used to obtain (B) polyamic acid is 60% by mass to 100% by mass, assuming that the total amount of (B) acid component for obtaining polyamic acid is 100% by mass. Is preferred. Moreover, (B) The usage-amount of (B2) amine component for obtaining a polyamic acid is 60 mass%-100 mass% when the whole quantity of the amine component for obtaining (B) polyamic acid is 100 mass%. preferable. By using the amounts of (B1) acid component and (B2) amine component in this way, (B) the insulating film formed from the radiation-sensitive resin composition of this embodiment containing polyamic acid is excellent. Light-shielding properties can be shown.

  In particular, it is preferable that all of the acid components for obtaining (B) polyamic acid are (B1) acid components having a group represented by the above formula (1-1). And it is preferable that all the amine components for obtaining (B) polyamic acid are (B2) amine components which have group shown by said Formula (1-2). By carrying out like this, the insulating film formed from the radiation sensitive resin composition of this embodiment containing (B) polyamic acid can show the more excellent light-shielding property.

  (B) As the polyamic acid exhibits the above properties, (B1) the acid component for obtaining the polyamic acid (B1) is an acid component having a group represented by the above formula (1-1). Anything can be used. And the compound of said Formula (1-1-1)-said Formula (1-1-5) illustrated as an (A1) acid component for obtaining (A) polyimide can be mentioned, for example.

  As (B2) amine component for obtaining (B) polyamic acid, any amine component having a group represented by the above formula (1-2) can be used. And, for example, (A) the amine compound represented by the above formula (1-2a) exemplified as the amine component (A2) for obtaining polyimide, and the above-mentioned diamine shown as a specific example thereof it can.

  (B) The method for synthesizing the polyamic acid can be the same as the method for synthesizing the polymic acid in the above-described method for synthesizing the polyimide (A).

  The (B) polyamic acid obtained by condensing the acid component and the amine component described above preferably has a component part having a structure derived from the (B1) acid component and the (B2) amine component. For example, it is preferable that (B) polyamic acid has a structural site represented by the following formula (8) to the following formula (12). By containing (B) polyamic acid having the components of the following formula (8) to the following formula (12), the radiation-sensitive resin composition of the present embodiment exhibits good patterning properties and excellent light shielding properties. An insulating film can be formed.

（式（８）〜式（１２）中、Ｒ^１１は、上記式（１−２ｂ）で示される構成部位である。Ｒ^１２〜Ｒ^１４はそれぞれ独立に、炭素数１〜１２のアルキル基およびフェニル基の少なくとも一方を含む２価の基である。）

(In the formulas (8) to (12), R ¹¹ is a component represented by the above formula (1-2b). R ^{12 to} R ¹⁴ are each independently an alkyl group having 1 to 12 carbon atoms and It is a divalent group containing at least one of the phenyl groups.)

Then, the component parts of (B) is preferably contained in the polyamic acid, the formula (8) to the equation (12), R ¹¹ is specifically a divalent group having one the following hydroxyl It is preferable.

Also, (B) is preferably contained in the polyamic acid, the component parts of the above formula (8) to the equation (12), it R ¹¹ is a component part is a divalent group having two the following hydroxyl Is preferred.

Also, (B) is preferably contained in the polyamic acid, the component parts of the above formula (8) to the equation (12), it R ¹¹ is a component part is a divalent group having three following hydroxyl Is preferred.

Furthermore, (B) In the constituent parts of the above formula (8) to the above formula (12) that are preferably contained in the polyamic acid, R ¹¹ is a constituent part that is a divalent group having the following four hydroxyl groups. Is preferred.

Then, (B) is preferably contained in the polyamic acid, the component parts of the above formula (8) to the equation (12), it R ¹¹ is a component part is a divalent group having two above-mentioned hydroxyl group Is most preferred. R ¹¹ is a constituent site that is a divalent group having two hydroxyl groups, so that the sensitivity of the present embodiment containing the polyamic acid (B) having the constituent sites of the above formula (8) to the above formula (12). The radiation resin composition can form an insulating film that exhibits better developability, patternability, and better light shielding properties.

  As mentioned above, (B) polyamic acid contained in the radiation sensitive resin composition of this embodiment can be formed using the acid component and amine component similar to the above-mentioned (A) polyimide. However, (A) polyimide and (B) polyamic acid are preferably synthesized separately. And when preparing the radiation sensitive resin composition of this embodiment demonstrated later, it is preferable that they are mixed and used.

  At this time, the mixing ratio of (A) polyimide and (B) polyamic acid contained in the radiation sensitive resin composition of the present embodiment was such that the total amount of (A) polyimide and (B) polyamic acid was 100% by mass. In this case, it is preferable that (A) polyimide is in the range of 60% by mass to 99% by mass, and (B) polyamic acid is in the range of 1% by mass to 40% by mass. By setting it as such a mixing ratio, the insulating film formed using the radiation sensitive resin composition of this embodiment can be compatible with low water absorption and developability, and is used for an organic EL element. Excellent light shielding properties can be exhibited.

[Other resins]
The radiation-sensitive resin composition of the present embodiment may further contain other resins other than the above-mentioned (A) polyimide and (B) polyamic acid, as necessary, within a range not impairing the effects of the present invention. Can do. Other resins that can be contained are not particularly limited, but alkali-soluble ones are preferable. Furthermore, it is more preferable to contain an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as a phenol resin) because the resolution of the insulating film obtained from the radiation-sensitive resin composition is improved.

  Examples of the phenol resin that can be contained include novolak resin, polyhydroxystyrene and its copolymer, phenol-xylylene glycol dimethyl ether condensation resin, cresol-xylylene glycol dimethyl ether condensation resin, phenol-dicyclopentadiene condensation resin, and the like. be able to.

  Specific examples of the novolak resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin.

  The novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols used in this case include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

  Monomers other than hydroxystyrene constituting the copolymer of polyhydroxystyrene are not particularly limited. Specifically, styrene, indene, p-methoxystyrene, p-butoxystyrene, p-acetoxystyrene, p-hydroxy- Styrene derivatives such as α-methylstyrene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec -(Meth) acrylic acid derivatives such as butyl (meth) acrylate and t-butyl (meth) acrylate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether and t-butyl vinyl ether; maleic anhydride, italy anhydride It can be exemplified acid anhydride derivatives such as phosphate.

  The content of the phenol resin is preferably 0% by mass to 90% by mass, preferably 5% by mass to 80% by mass, with the total amount of (A) polyimide, (B) polyamic acid and phenol resin being 100% by mass. More preferably, it is more preferable to set it as 10 mass%-70 mass%. When the content is less than 5% by mass, the effect of containing this phenol resin tends to be hardly exhibited. On the other hand, if it exceeds 90% by mass, the mechanical strength of the film tends to decrease.

  Furthermore, the radiation-sensitive resin composition of the present embodiment can contain a phenolic low molecular compound in addition to the above-described phenol resin. Specific examples of the phenolic low molecular weight compound that can be contained include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) -1-phenylethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4- Hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2- Tiger (4-hydroxyphenyl) ethane and the like.

  The content ratio of the phenolic low molecular weight compound is 100% by mass of the total amount of (A) polyimide and (B) polyamic acid (however, when other resins other than (A) polyimide and (B) polyamic acid are further contained) Is (A) polyimide, (B) polyamic acid and the total amount of other resins are 100% by mass), preferably 0% by mass to 100% by mass, more preferably 1% by mass to 60% by mass. Preferably, it is more preferable to set it as 5 mass%-40 mass%. If it is less than 1% by mass, the effect of containing this phenolic low molecular weight compound tends to be hardly exhibited. On the other hand, if it exceeds 100% by mass, the mechanical strength of the film tends to decrease.

[(C) quinonediazide compound]
The radiation sensitive resin composition of this embodiment contains (C) quinonediazide compound as an essential component with (A) polyimide and (B) polyamic acid which were mentioned above. (A) Polyimide and (B) polyamic acid are alkali-soluble resin components. By containing (C) a quinonediazide compound that controls alkali solubility, the radiation-sensitive resin composition of this embodiment is a positive type. It can be used as a radiation sensitive resin composition.

  (C) A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. (C) As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

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

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

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

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

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

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

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

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

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

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

  These quinonediazide compounds can be used alone or in combination of two or more.

  The use ratio of the (C) quinonediazide compound in the radiation sensitive resin composition of the present embodiment is 100% by mass of the total amount of resin components contained in the radiation sensitive resin composition such as (A) polyimide and (B) polyamic acid. In this case, 5% by mass to 100% by mass is preferable, and 10% by mass to 50% by mass is more preferable. (C) By making the use ratio of a quinonediazide compound into the above-mentioned range, in the coating film of the radiation-sensitive resin composition of the present embodiment, the solubility of the irradiated part and the non-irradiated part with respect to the alkaline aqueous solution serving as the developer. Thus, the patterning performance of the insulating film can be improved. Moreover, the solvent resistance of the insulating film obtained using this radiation sensitive resin composition can also be made favorable.

[(D) Compound]
The radiation sensitive resin composition of this embodiment contains (D) compound as an essential component with (A) polyimide, (B) polyamic acid, etc. which were mentioned above.

  (D) A compound is a compound provided with the performance which improves the adhesiveness with the board | substrate with which it is formed in the insulating film obtained using the radiation sensitive resin composition of this embodiment.

  The compound (D) can be, for example, a compound known as a silane coupling agent.

  And as a preferable (D) compound, the compound shown by following formula (2) can be mentioned.

（式（２）中、Ｒ^２は水素原子および炭素数１〜６のアルキル基のうちのいずれかを示し、Ｚは単結合、メチレン基および炭素数２から６のアルキレン基のうちのいずれかを示し、Ｒ^３は、水素原子およびフェニル基のうちのいずれかを示す。ｙは０〜２の整数を表し、ａは０〜１２の整数を表す。）

(In the formula (2), R ² represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and Z represents any of a single bond, a methylene group, and an alkylene group having 2 to 6 carbon atoms. R ³ represents any one of a hydrogen atom and a phenyl group, y represents an integer of 0 to 2, and a represents an integer of 0 to 12.)

  As a preferable (D) compound represented by the said Formula (2), the compound of a following formula can be mentioned, for example.

  The proportion of the compound (D) used in the radiation-sensitive resin composition of this embodiment is 100% by mass of the total amount of resin components contained in the radiation-sensitive resin composition such as (A) polyimide and (B) polyamic acid. In this case, 0.01% by mass to 20% by mass is preferable, and 0.1% by mass to 15% by mass is more preferable. (D) By making the use ratio of a compound into the above-mentioned range, when the radiation sensitive resin composition of this embodiment forms an insulating film on a board | substrate using it, adhesion of the board | substrate and an insulating film is carried out. Can be improved.

[(E) Oxetanyl group-containing compound]
As described above, the radiation-sensitive resin composition of the present embodiment is configured to contain (A) polyimide, (B) polyamic acid, (C) quinonediazide compound, and (D) compound. Depending on the, other components may be included.

  For example, the radiation sensitive resin composition of the present embodiment can contain (E) an oxetanyl group-containing compound. Here, (E) an oxetanyl group-containing compound is a compound having one or more oxetanyl groups.

  As described above, (B) the radiation-sensitive resin composition of this embodiment containing (C) a quinonediazide compound together with an alkali-soluble resin component such as polyamic acid is used as a positive radiation-sensitive resin composition. can do. Therefore, in the patterning of the insulating film using the same, the exposed portion is removed, and the unexposed portion is left as a patterned insulating film. In that case, the unreacted (C) quinonediazide compound remains in the insulating film.

  The (C) quinonediazide compound left in the insulating film then absorbs light or, when heated and decomposes, forms a carboxyl group in the molecule. Therefore, an undesirable carboxyl group is contained in the insulating film, which may increase the hygroscopicity of the insulating film.

  Then, the radiation sensitive resin composition of this embodiment contains the (E) oxetanyl group containing compound which has 1 or more oxetanyl groups, and makes it react with the generated carboxyl group. And the number of the carboxyl groups which exist in an insulating film is reduced, and it suppresses that the water absorption of an insulating film increases.

  (E) The oxetanyl ring-containing compound is not particularly limited as long as it contains at least one oxetanyl ring in the molecule. For example, it is represented by the following formula (13-1) to the following formula (13-3). And the like.

（式（１３−１）〜式（１３−３）の各々において、Ｒ^２３はメチル基、エチル基、プロピル基等のアルキル基であり、Ｒ^２１はメチレン基、エチレン基、プロピレン基等のアルキレン基であり、Ｒ^２２はメチル基、エチル基、プロピル基、ヘキシル基等のアルキル基；フェニル基、キシリル基等のアリール基；下記式（ｉ）で表されるジメチルシロキサン残基；メチレン基、エチレン基、プロピレン基等のアルキレン基；フェニレン基；又は下記式（ｉｉ）〜（ｖｉ）で表される基を示し、ｂはＲ^２２の価数に等しく、１〜４の整数である。尚、下記式（ｉ）〜（ｖｉ）における「＊」は、結合部位を示す。

(In each of the formulas (13-1) to (13-3), R ²³ is an alkyl group such as a methyl group, an ethyl group or a propyl group, and R ²¹ is an alkylene such as a methylene group, an ethylene group or a propylene group. R ²² represents an alkyl group such as a methyl group, an ethyl group, a propyl group, or a hexyl group; an aryl group such as a phenyl group or a xylyl group; a dimethylsiloxane residue represented by the following formula (i); a methylene group; An alkylene group such as an ethylene group or a propylene group; a phenylene group; or a group represented by the following formulas (ii) to (vi), wherein b is equal to the valence of R ²² and is an integer of 1 to 4. In the following formulas (i) to (vi), “*” represents a binding site.

（式（ｉ）および式（ｉｉ）におけるｃおよびｄは、それぞれ独立に、０〜５０の整数である。また、式（ｉｉｉ）におけるＺは、単結合、または、−ＣＨ２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−若しくは−ＳＯ_２−で表される２価の基である。）

(C and d in formula (i) and formula (ii) are each independently an integer of 0 to 50. Z in formula (iii) is a single bond, or —CH 2 —, —C ( _{CH 3) 2 -, - C} (CF 3) 2 - or -SO ₂ - is a divalent group represented by).

  Specific examples of the compounds represented by the above formula (13-1) to the above formula (13-3) include 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (trade name) “OXT-121” manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name “OXT-221” manufactured by Toa Gosei Co., Ltd.), 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (Ube Industries, trade name “ETERARNACOLL (registered trademark) OXBP”), bis [(3-ethyl-3-oxetanylmethoxy) methyl -Phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl- Enyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3 -Oxetanylmethoxy) methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and compounds represented by the following formula (14-a) to the following formula (14-g). it can.

  In addition, the radiation sensitive resin composition of this embodiment may contain only 1 type (E) oxetanyl group containing compound, and may contain 2 or more types.

  The use ratio of the (E) oxetanyl group-containing compound in the radiation-sensitive resin composition of this embodiment is 100 based on the total amount of resin components contained in the radiation-sensitive resin composition such as (A) polyimide and (B) polyamic acid. In the case of mass%, it is preferably 1% by mass to 100% by mass, more preferably 1% by mass to 70% by mass, and still more preferably 5% by mass to 40% by mass. (E) When the usage-amount of an oxetanyl group containing compound is less than 1 mass%, the effect which reduces the number of the carboxyl groups which exist in the insulating film mentioned above cannot fully be acquired. And when it is 1 mass%-100 mass%, the effect of reducing the number of the carboxyl groups which exist in an insulating film is fully acquired, and it can suppress that the water absorption of an insulating film increases.

[solvent]
As described above, the radiation-sensitive resin composition of the present embodiment is configured to contain (A) polyimide, (B) polyamic acid, (C) quinonediazide compound, and (D) compound. Depending on the solvent, it may contain a solvent. By containing the solvent, the radiation-sensitive resin composition of the present embodiment can be made into a liquid resin composition, and the applicability can be improved when an insulating film is formed on the substrate.

  As a solvent, what was mentioned as a preferable polymerization solvent for obtaining the above-mentioned (A) polyimide can be used. That is, selected from the group consisting of diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether propionate, propylene glycol monoalkyl ether and γ-butyrolactone At least one kind can be used. These solvents can be used alone or in combination of two or more.

  In addition, when using (gamma) -butyrolactone as a solvent, it is preferable that a solvent contains 20 mass%-40 mass% of (gamma) -butyrolactone by making the whole quantity into 100 mass%. By setting the content of γ-butyrolactone in such a range, it is possible to suitably maintain the dissolved state of the resin component such as (A) polyimide in the radiation-sensitive resin composition of the present embodiment, and to improve the coating property. it can.

  Here, when the above-mentioned solvents are used, they are less hygroscopic than NMP. Therefore, the radiation sensitive resin composition of the present embodiment can be prepared using a low hygroscopic solvent without using NMP having a high hygroscopic property. As a result, the radiation sensitive resin composition of the present embodiment can exhibit low hygroscopicity. Moreover, the above-mentioned each solvent is highly safe, and can provide the radiation sensitive resin composition of this embodiment with high safety | security.

  And when using the same thing as polymerization solvents, such as the above-mentioned (A) polyimide, after synthesizing (A) polyimide etc., they are precipitated and (A) this isolation is carried out without isolating polyimide etc. It becomes possible to use it for preparation of the radiation sensitive resin composition of a form. That is, when the above-mentioned solvent is used, it is possible to eliminate the process of (A) synthesizing polyimide and the like and then isolating and re-dissolving in another solvent. As a result, an increase in the number of steps in the production of the organic EL element and a concern about a decrease in productivity associated therewith are reduced.

[Other additives]
The radiation-sensitive resin composition of the present embodiment can contain other additives such as a surfactant, if necessary, as long as the effects of the present invention are not impaired.

(Surfactant)
The radiation sensitive resin composition of the present embodiment may contain a surfactant for the purpose of improving various properties such as coating properties, antifoaming properties, and leveling properties. Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFac (registered trademark) F142D, F172, F173, F173 (manufactured by DIC), and Florad FC. -135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon (registered trademark) S-112, S-113, S-131, S-141, Under the trade names such as S-145 (AGC Seimi Chemical Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (Toray Dow Corning Silicone Co., Ltd.) A commercially available fluorosurfactant can be used.

  The content of the surfactant in the radiation sensitive resin composition of the present embodiment is 100% by mass of the total amount of resin components contained in the radiation sensitive resin composition such as (A) polyimide and (B) polyamic acid. In this case, the content is preferably 5% by mass or less.

[Preparation of radiation-sensitive resin composition]
As described above, the radiation-sensitive resin composition of the present embodiment includes (A) polyimide, (B) polyamic acid, (C) quinonediazide compound, and (D) compound. And as needed, it can contain (E) an oxetanyl group containing compound, a solvent, and other additives.

  At this time, the use ratio of (A) polyimide and (B) polyamic acid, that is, the mixing ratio is determined in consideration of the solubility and water absorption of these resin components. (B) Although polyamic acid is excellent in solubility, it is attributed to an amic acid structure and has higher water absorption than (A) polyimide. Therefore, the radiation-sensitive resin composition of the present embodiment uses (B) polyamic acid and, as a resin component, a mixture of a polyimide having no or little amic acid structure (A) and a polyamic acid content. Control. And in the insulating film which consists of a radiation sensitive resin composition of this embodiment, it is made to make developability and low water absorption compatible.

At this time, in the radiation sensitive resin composition of the present embodiment, the mixing ratio of (A) polyimide and (B) polyamic acid is (A) polyimide and (B) 100% by mass of the total amount of polyamic acid, (A It is preferable that polyimide is in the range of 60% by mass to 99% by mass and (B) polyamic acid is in the range of 1% by mass to 40% by mass.
By using the mixing ratio of (A) polyimide and (B) polyamic acid as described above, in the insulating film made of the radiation-sensitive resin composition of the present embodiment, developability and low water absorption are obtained. Can be compatible.

  Next, when the radiation sensitive resin composition of this embodiment contains a solvent, components other than the solvent, that is, (A) polyimide, (B) polyamic acid, (C) quinonediazide compound and (D) compound, When other additives are added, the total ratio of the additives can be arbitrarily set according to the purpose of use, desired film thickness, and the like. And components other than a solvent become like this. Preferably they are 2 mass%-50 mass%, More preferably, they are 5 mass%-40 mass%, More preferably, they are 10 mass%-35 mass%. The radiation-sensitive resin composition thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm to 0.5 μm.

<Formation of insulating film>
Next, a method for forming the insulating film of the present embodiment using the above-described radiation-sensitive resin composition of the present embodiment will be described. The method for forming an insulating film according to the present embodiment can be constituted by including the following steps as main steps, in the following order.
(1) The process of forming the coating film of the radiation sensitive resin composition of this embodiment on a board | substrate (Hereafter, it may only be called a coating film formation process.),
(2) A step of irradiating at least a part of the coating film formed in step (1) (hereinafter sometimes simply referred to as a radiation irradiation step),
(3) A step of developing the coating film irradiated with radiation in the step (2) (hereinafter, simply referred to as a developing step), and (4) heating the coating film developed in the step (3). (Hereinafter, simply referred to as a heating step).
Hereinafter, the steps (1) to (4) will be described in more detail.

(1) Coating film forming step In the above-mentioned (1) coating film forming step, the radiation-sensitive resin composition of the present embodiment is applied to the substrate surface, and preferably prebaked to remove components used as a solvent. Then, a coating film of the radiation sensitive resin composition is formed. Examples of the types of substrates that can be used include resin substrates, glass substrates, and silicon wafers. Examples of the substrate used for forming the organic EL display element include a substrate on which a TFT and its wiring are formed.

  The application method of the radiation sensitive resin composition of the present embodiment is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method), a slit die coating method, a bar coating method, An appropriate method such as an inkjet method can be employed. Among these coating methods, the spin coating method and the slit die coating method are particularly preferable. The prebaking conditions vary depending on the type of each component, the use ratio, and the like, but for example, the heating temperature can be 60 ° C. to 110 ° C. and the heating time can be about 30 seconds to 15 minutes. The film thickness of the coating film to be formed can be 1 μm to 10 μm as a value after pre-baking.

(2) Radiation irradiation process In the above-mentioned (2) radiation irradiation process, the formed coating film is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable. The exposure amount is ^preferably set to ^{50J / m 2 ~1500J / m 2} .

(3) Development step (3) In the development step, development is performed on the coating film irradiated with radiation in the above-described (2) radiation irradiation step, and the radiation irradiated portion is removed to form a desired pattern. be able to. Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonane can be used. Also, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents that dissolve the radiation-sensitive resin composition of the present embodiment. Can be used as a developer. As the organic solvent, those mentioned as the polymerization solvent for obtaining the above-mentioned (A) polyimide can be used.

  Furthermore, as a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but can be, for example, 30 seconds to 120 seconds.

(4) Heating step (4) In the heating step, after the above-mentioned (3) development step, the patterned coating film can be preferably rinsed with running water. Moreover, it is also possible to perform the rinse process which wash | cleans a coating film using the low hygroscopic solvent mentioned as a polymerization solvent for obtaining the above-mentioned (A) polyimide.

Subsequently, the quinonediazide compound remaining in the coating film is decomposed by irradiating the entire surface with radiation (post-exposure), preferably with a high-pressure mercury lamp or the like. Next, the coating film is subjected to a heat treatment (post-bake treatment) using a heating device such as a hot plate or an oven, whereby the coating film is cured to obtain the insulating film of the present embodiment. Exposure amount in the exposure after the above is preferably 2000J ^{/ m 2} ~5000J ^/ m 2 approximately. Moreover, the heating temperature in this hardening process is 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device. For example, when heat treatment is performed on a hot plate, it may be 5 minutes to 30 minutes, and when heat treatment is performed in an oven, it may be 30 minutes to 90 minutes. it can. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used. In this manner, an insulating film having a target pattern can be formed on the substrate.

  The insulating film formed as described above has a low water absorption component and can be treated with a low hygroscopic solvent or the like in the manufacturing process, and has preferable moisture absorption characteristics (water absorption). Have. In addition, PGMEA cleaning properties that enable cleaning using PGMEA solvents, light shielding properties, heat resistance, patterning properties, patterning shape properties, development margin properties, solvent resistance, radiation sensitivity, resolution, etc. Good properties In addition to the insulating film forming the partition wall of the organic EL element, it can be suitably used as an insulating film having the above-described planarization function.

<Organic EL device>
As an organic EL element of the present embodiment, an example of the organic EL display element of the present embodiment will be used and described with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically illustrating the structure of the main part of the organic EL display element of this embodiment.

  The organic EL display element 1 of this embodiment is an active matrix type organic EL display element having a plurality of pixels formed in a matrix. The organic EL display element 1 may be either a top emission type or a bottom emission type. The organic EL display element 1 includes a thin film transistor (hereinafter also referred to as TFT) 3 that is an active element in each pixel portion on the substrate 2.

  As for the substrate 2 of the organic EL display element 1, when the organic EL display element 1 is a bottom emission type, the substrate 2 is required to be transparent. As an example of the material of the substrate 2, PET (polyethylene terephthalate) or Transparent resins such as PEN (polyethylene naphthalate) and PI (polyimide), and glass such as non-alkali glass are used. On the other hand, when the organic EL display element 1 is a top emission type, the substrate 2 does not need to be transparent, so that an arbitrary insulator can be used as the material of the substrate 2. Similarly to the bottom emission type, a glass material such as alkali-free glass can be used.

  The TFT 3 is disposed on the substrate 2 via a gate electrode 4 that forms part of a scanning signal line (not shown), a gate insulating film 5 that covers the gate electrode 4, and a gate insulating film 5 on the gate electrode 4. A first source-drain electrode 7 connected to the semiconductor layer 6 by forming a part of a video signal line (not shown), and a second source-drain electrode 8 connected to the semiconductor layer 6. And is configured.

  The gate electrode 4 can be formed by forming a metal thin film on the substrate 2 by vapor deposition or sputtering, and performing patterning using an etching process. In addition, a metal oxide conductive film or an organic conductive film can be patterned and used.

  As a material of the metal thin film constituting the gate electrode 4, for example, aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), gold (Au), Mention may be made of metals such as tungsten (W) and silver (Ag), alloys of these metals, and alloys such as Al-Nd and APC alloys (silver, palladium, copper alloys). And as a metal thin film, it is also possible to use the laminated film which consists of a layer of a different material, such as a laminated film of Al and Mo.

As a material of the metal oxide conductive film constituting the gate electrode 4, metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide) and indium zinc oxide (IZO) are used. Can be mentioned.
Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, or a mixture thereof.
The thickness of the gate electrode 4 is preferably 10 nm to 1000 nm.

The gate insulating film 5 disposed so as to cover the gate electrode 4 can be formed by forming an oxide film or a nitride film by sputtering, CVD, vapor deposition or the like. The gate insulating film 5 can be formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN alone or in a stacked manner. It can also be composed of an organic material such as a polymer material. The film thickness of the gate insulating film 5 is preferably 10 nm to 10 μm. In particular, when an inorganic material such as a metal oxide is used, 10 nm to 1000 nm is preferable, and when an organic material is used, 50 nm to 10 μm is preferable.

For the first source-drain electrode 7 and the second source-drain electrode 8 connected to the semiconductor layer 6, a conductive film constituting these electrodes is formed by a sputtering method, a CVD method, an evaporation method in addition to a printing method or a coating method. After forming using a method such as a method, patterning using a photolithography method or the like can be performed. Examples of the constituent material of the first source-drain electrode 7 and the second source-drain electrode 8 include metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W, and Ag, and those metals. Mention may be made of alloys and alloys such as Al-Nd and APC. Also, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum doped zinc oxide) and GZO (gallium doped zinc oxide), polyaniline, polythiophene and polypyro Examples thereof include conductive organic compounds such as As the conductive film constituting these electrodes, a laminated film made of layers of different materials such as a laminated film of Ti and Al can be used.
The thicknesses of the first source-drain electrode 7 and the second source-drain electrode 8 are preferably 10 nm to 1000 nm.

The semiconductor layer 6 is made of, for example, silicon (such as amorphous a-Si (amorphous-silicon)) or p-Si (polysilicon) obtained by crystallizing a-Si by excimer laser or solid phase growth. It can be formed by using Si) material.
When a-Si is used for the semiconductor layer 6, the thickness of the semiconductor layer 6 is preferably 30 nm to 500 nm. In addition, an n + Si layer (not shown) for forming an ohmic contact is formed with a thickness of 10 nm to 150 nm between the semiconductor layer 6 and the first source-drain electrode 7 or the second source-drain electrode 8. It is preferable.

  The semiconductor layer 6 of the TFT 3 can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 6 include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  Examples of the amorphous oxide applicable to the semiconductor layer 6 include an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn).

  Specific examples of amorphous oxides applicable to the semiconductor layer 6 include Sn—In—Zn oxide, In—Ga—Zn oxide (IGZO: indium gallium zinc oxide), and In—Zn—Ga—Mg oxide. Zn-Sn oxide (ZTO: zinc tin oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga An oxide, a Sn—In—Zn oxide, and the like can be given. In the above case, the composition ratio of the constituent materials is not necessarily 1: 1, and a composition ratio that realizes desired characteristics can be selected.

For example, when the semiconductor layer 6 using an amorphous oxide is formed using IGZO or ZTO, a film is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method or the like. Is formed by patterning using a resist process and an etching process. The thickness of the semiconductor layer 6 using an amorphous oxide is preferably 1 nm to 1000 nm.
By using the oxides exemplified above, the semiconductor layer 6 with high mobility can be formed at a low temperature, and the TFT 3 with excellent performance can be provided.

As oxides that are particularly preferable for forming the semiconductor layer 6 of the semiconductor element 1 of the present embodiment, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide ( ZIO).
By using these oxides, the TFT 3 has the semiconductor layer 6 having excellent mobility formed at a lower temperature and can exhibit a high ON / OFF ratio.

In the semiconductor layer 6 of the TFT 3, a SiO 2 having a thickness of, for example, 5 nm to 80 nm is formed in a channel region where the first source-drain electrode 7 and the second source-drain electrode 8 are not formed on the upper surface of the semiconductor layer 6. _A protective layer (not shown) of ₂ can be provided. This protective layer is sometimes referred to as an etching stop layer or a stop layer. Such a protective layer is a particularly preferable component when the above-described oxide is used for the semiconductor layer 6.

An inorganic insulating film 19 can be provided on the TFT 3 so as to cover the TFT 3. The inorganic insulating film 19 can be formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN alone or in a stacked manner. The inorganic insulating film 19 is provided to protect the semiconductor layer 6 and prevent it from being influenced by humidity, for example. In the organic EL display element 1 of the present embodiment, the inorganic insulating film 19 is not provided, and the first insulating film 10 that is an insulating film made of an organic material described later is disposed on the TFT 3. Is possible.

  Next, in the organic EL display element 1, the first insulating film 10 is disposed on the inorganic insulating film 19 so as to cover the TFT 3 on the substrate 2. The first insulating film 10 has a function of flattening unevenness caused by the TFT 3 formed on the substrate 2. The first insulating film 10 is an insulating film formed using the radiation-sensitive resin composition of the present embodiment described above, and is an organic film formed using an organic material. The first insulating film 10 preferably has an excellent function as a planarizing film, and is preferably formed thick from this viewpoint. For example, the first insulating film 10 can be formed with a film thickness of 1 μm to 6 μm. The first insulating film 10 is formed according to the method for forming the insulating film described above.

  On the first insulating film 10, an anode 11 serving as a pixel electrode is disposed. The anode 11 is made of a conductive material. The material of the anode 11 is preferably selected from materials having different characteristics depending on whether the organic EL display element 1 is a bottom emission type or a top emission type. In the case of the bottom emission type, since the anode 11 is required to be transparent, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide, or the like is selected as the material of the anode 11. On the other hand, when the organic EL display element 1 is a top emission type, the anode 11 is required to have light reflectivity. As the material of the anode 11, APC alloy (silver, palladium, copper alloy) or ARA (silver, rubidium) is used. , Gold alloy), MoCr (molybdenum and chromium alloy), NiCr (nickel and chromium alloy), and the like are selected. The thickness of the anode 11 is preferably 100 nm to 500 nm.

  Since the anode 11 disposed on the first insulating film 10 is connected to the second source-drain electrode 8, a through hole 12 that penetrates the first insulating film 10 is formed in the first insulating film 10. Has been. The through hole 12 is formed so as to also penetrate the inorganic insulating film 19 under the first insulating film 10. The 1st insulating film 10 can be formed using the radiation sensitive resin composition of this embodiment mentioned above. Therefore, in accordance with the method for forming an insulating film, the first insulating film 10 having a through hole having a desired shape is formed by irradiating the coating film of the radiation-sensitive resin composition with radiation, and then the first insulating film is formed. By performing dry etching on the inorganic insulating film 19 using the film 10 as a mask, the through hole 12 can be completed. In the case where the inorganic insulating film 19 is not disposed on the TFT 3, a through hole formed by irradiating the first insulating film 10 with radiation constitutes the through hole 12. As a result, the anode 11 covers at least a part of the first insulating film 10 and is applied to the TFT 3 through the through hole 12 provided in the first insulating film 10 so as to penetrate the first insulating film 10. It can be connected to the second source-drain electrode 8 to be connected.

  In the organic EL display element 1, a second insulating film 13 is formed on the anode 11 on the first insulating film 10 and serves as a partition that defines the arrangement region of the organic light emitting layer 14. The second insulating film 13 can be manufactured as a cured film by using the radiation-sensitive resin composition of the present embodiment described above and patterning the coating film according to the method for forming the insulating film described above. The second insulating film 13 can have, for example, a lattice shape in plan view. In an area defined by the second insulating film 13, an organic light emitting layer 14 that emits electroluminescence is disposed. In the organic EL display element 1, the second insulating film 13 serves as a barrier surrounding the periphery of the organic light emitting layer 14 and partitions each of a plurality of adjacent pixels.

  In the organic EL display element 1, the height of the second insulating film 13 (the distance between the upper surface of the second insulating film 13 and the upper surface of the anode 11 in the region where the organic light emitting layer 14 is disposed) is 0.1 μm to 2 μm. It is preferable that it is 0.8 micrometer-1.2 micrometers. When the height of the second insulating film 13 is 2 μm or more, the second insulating film 13 may collide with the sealing substrate 20 above the second insulating film 13. Further, when the height of the second insulating film 13 is 0.1 μm or less, an ink-like luminescent material composition is applied to the region defined by the second insulating film 13 by an ink jet method. Sometimes, the luminescent material composition may leak from the second insulating film 13.

  The second insulating film 13 of the organic EL display element 1 is cured by using the radiation-sensitive resin composition of the present embodiment described above and patterning the coating film according to the method of forming the insulating film described above. It can be formed as a film. That is, the second insulating film 13 can be configured to include a resin. The second insulating film 13 defines a region to which the ink-like luminescent material composition containing an organic luminescent material is applied when the ink-like luminescent material composition is applied by an ink-jet method. Is preferably low. When the wettability of the second insulating film 13 is controlled to be particularly low, the second insulating film 13 can be plasma-treated with fluorine gas, and the second insulating film 13 is formed in this embodiment. You may make the radiation sensitive resin composition of a form contain a liquid repellent. Since the plasma treatment may adversely affect other components of the organic EL display element 1, it is preferable to include a liquid repellent in the radiation sensitive resin composition of the present embodiment for forming the second insulating film 13. There is.

  An organic light emitting layer 14 that emits light by applying an electric field is disposed in a region defined by the second insulating film 13. The organic light emitting layer 14 is a layer containing an organic light emitting material that emits electroluminescence.

The organic light emitting material contained in the organic light emitting layer 14 may be a low molecular weight organic light emitting material or a polymer organic light emitting material. For example, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ or BeBq ₃ can be used. Moreover, when using the coating method of the organic luminescent material by the inkjet method, it is preferable that it is a polymeric organic luminescent material suitable for it. Examples of the polymer organic light emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof, polyparaphenylene ethylene and derivatives thereof, poly 3 -Hexylthiophene (Poly 3-hexyl thiophene (P3HT)) and its derivatives, polyfluorene (Poly fluorene (PF)) and its derivatives, etc. can be selected and used.

  The organic light emitting layer 14 is disposed on the anode 11 in a region defined by the second insulating film 13. The thickness of the organic light emitting layer 14 is preferably 50 nm to 100 nm. Here, the thickness of the organic light emitting layer 14 means the distance from the bottom surface of the organic light emitting layer 14 on the anode 11 to the top surface of the organic light emitting layer 14 on the anode 11.

  A hole injection layer and / or an intermediate layer may be disposed between the anode 11 and the organic light emitting layer 14. When the hole injection layer and the intermediate layer are disposed between the anode 11 and the organic light emitting layer 14, the hole injection layer is disposed on the anode 11, the intermediate layer is disposed on the hole injection layer, and An organic light emitting layer 14 is disposed on the intermediate layer. Further, the hole injection layer and the intermediate layer may be omitted as long as holes can be efficiently transported from the anode 11 to the organic light emitting layer 14.

  In the organic EL display element 1, a cathode 15 is formed so as to cover the organic light emitting layer 14 and the second insulating film 13 for pixel division. The cathode 15 is formed so as to cover a plurality of pixels in common and serves as a common electrode of the organic EL display element 1.

The organic EL display element 1 of this embodiment has a cathode 15 on the organic light emitting layer 14, and the cathode 15 is made of a conductive member. The material used for forming the cathode 15 differs depending on whether the organic EL display element 1 is a bottom emission type or a top emission type. In the case of the top emission type, the cathode 15 is preferably an ITO electrode or an IZO electrode that constitutes a visible light transmissive electrode. On the other hand, when the organic EL display element 1 is a bottom emission type, the cathode 15 does not have to be visible light transmissive. In this case, the constituent material of the cathode 15 is not particularly limited as long as it is conductive. For example, barium (Ba), barium oxide (BaO), aluminum (Al), and an alloy containing Al can be selected. is there.
In addition, between the cathode 15 and the organic light emitting layer 14, the electron injection layer which consists of barium (Ba), lithium fluoride (LiF), etc. may be arrange | positioned, for example.

  A passivation film 16 can be provided on the cathode 15. The passivation film 16 can be formed by using a metal nitride such as SiN or aluminum nitride (AlN) alone or by laminating them. Due to the action of the passivation film 16, the intrusion of moisture and oxygen into the organic EL display element 1 can be suppressed.

  The main surface of the substrate 2 thus configured on which the organic light emitting layer 14 is disposed uses a sealing agent (not shown) applied in the vicinity of the outer peripheral end portion, and the sealing substrate via the sealing layer 17. It is preferable to seal with 20. The sealing layer 17 can be a layer of an inert gas such as dried nitrogen gas or a layer of a filler material such as an adhesive. As the sealing substrate 20, a glass substrate such as non-alkali glass can be used.

  In the organic EL display element 1 of the present embodiment having the above structure, the first insulating film 10 and the second insulating film 13 which are constituent elements have a low hygroscopic property of the radiation-sensitive resin composition of the present embodiment. And has a low water absorption structure. Further, in the forming process, a treatment such as cleaning using a low hygroscopic material is possible. Therefore, a slight amount of moisture contained in the insulating film forming material in the form of adsorbed water or the like can be prevented from gradually entering the organic light emitting layer, and deterioration of the organic light emitting layer and inhibition of the light emitting state can be reduced.

  Further, in the organic EL display element 1, the first insulating film 10 and the second insulating film 13 which are constituent elements have suitable light shielding properties, and the semiconductor layer 6 of the TFT 3 is not irradiated with undesirable light. It also functions as a light shielding film. Therefore, the organic EL display element 1 can reduce deterioration of the characteristics of the TFT 3 due to the influence of light from the outside. Even if the TFT 3 of the organic EL display element 1 has the semiconductor layer 6 formed of an oxide semiconductor such as IGZO, the first insulating film 10 and the second insulating film 13 are suitable as a light shielding film. It is possible to reduce the deterioration of the characteristics of the TFT 3 due to the influence of external terms.

Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.
The solution viscosity of each resin solution and the imidization ratio of polyimide in the synthesis examples were measured by the following methods.

[Solution viscosity of resin body solution]
The solution viscosity (mPa · s) of the resin solution was measured at 25 ° C. using an E-type rotational viscometer for a solution in which a good solvent for the resin was used and the concentration of the resin component was adjusted to 10% by weight.

（数式（１）中、Ａ^１は化学シフト１０ｐｐｍ付近に現れるＮＨ基のプロトン由来のピーク面積であり、Ａ^２はその他のプロトン由来のピーク面積であり、αはポリイミドの前駆体（ポリアミック酸）におけるＮＨ基のプロトン１個に対するその他のプロトンの個数割合である。） [Imidation rate of polyimide]
The polyimide solution was poured into pure water, and the resulting precipitate was sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. . From the obtained ¹ H-NMR spectrum, the imidization ratio was determined by the formula shown by the following formula (1).

(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). The number ratio of other protons to one proton of NH group in

<Synthesis of polyimide>
[Synthesis Example 1]
After adding 64 g of gamma butyrolactone (BL) and 16 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to the reaction vessel, diamine and tetracarboxylic acid are added so that the solid content concentration becomes 20% with respect to a total of 80 g of the polymerization solvent. Acid dianhydride was added into the polymerization solvent.
As the diamine, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was added. After these were dissolved, 4,4-oxydiphthalic acid (ODPA) and 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4 were then used as tetracarboxylic dianhydrides. -Phenylene ester (TAHQ) was added so that the composition ratio of tetracarboxylic dianhydride was ODPA: TAHQ = 80: 20 (molar ratio). At this time, the acid component which is tetracarboxylic dianhydride added 85 mol part with respect to 100 mol part of the whole quantity of a diamine component.

Then, after making them react at 60 degreeC for 1 hour, 30 mol part of phthalic anhydride was added as terminal blocker, and after making it react at 60 degreeC for further 1 hour, it heated up and made it react at 120 degreeC for 4 hours. . During the reaction, the low boiling solvent PGMEA was distilled off using a Dean-Stark tube under N ₂ (nitrogen) flow conditions. As a result, about 84 g of a polyimide (polyimide (A-1)) solution having a solid content concentration of 23.8% was obtained.
The solution viscosity of the obtained polyimide solution was 28 mPa · s, and the imidization ratio of polyimide (A-1) was 25%. The evaluation results of the solution viscosity and the imidization rate are also shown in Table 1 below.

[Synthesis Example 2 to Synthesis Example 7 and Comparative Synthesis Example 1 to Comparative Synthesis Example 2]
For Synthesis Examples 2 to 7, Synthesis Examples except for the polymerization solvents used, the types and blending ratios of the tetracarboxylic dianhydride that is an acid component and the diamine that is an amine component, as shown in Table 1 below. In the same manner as in Example 1, solutions containing polyimide (polyimide (A-2) to polyimide (A-7)) were prepared.
And about the comparative synthesis example 1 and the comparative synthesis example 2, the point which made the kind and compounding ratio of the polymerization solvent to be used, the tetracarboxylic dianhydride which is an acid component, and the diamine which is an amine component as shown in Table 1 below. Except for the same procedure as in Synthesis Example 1, a solution containing polyimide (polyimide (A-8) to polyimide (A-9)) was prepared.
And like the synthesis example 1, the evaluation result of a solution viscosity and imidation rate is put together in following Table 1, and is shown.

In Table 1, a blank indicates that the corresponding component is not contained. Moreover, the unit “mol%” of the concentration shown in the table is the corresponding tetracarboxylic dianhydride with respect to the total amount of tetracarboxylic dianhydride used in the synthesis for tetracarboxylic dianhydride. The content of is shown. Similarly, about diamine, the content of the applicable diamine with respect to the whole quantity of diamine used for the synthesis is shown.
The components indicated by the symbols in Table 1 below are as follows.

[Polymerization solvent]
s-1: Propylene glycol monoethyl ether acetate (PGMEA)
s-2: γ-butyrolactone (γ-BL)
s-3: N-methylpyrrolidone (NMP)

[Tetracarboxylic dianhydride]
t-1: 4,4-oxydiphthalic acid (ODPA)

  t-2: 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester (TAHQ)

  t-3: 6FDA

t-4: PPTA

  t-5: HQDA

  t-6: pyromellitic dianhydride (PMDA)

[Diamine]
d-1: 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF)

  d-2: 4,4-diaminodiphenyl ether

  d-3: TFMB

<Synthesis of polyamic acid>
[Synthesis Example 8]
After adding 80 g of gamma butyrolactone (BL) as a polymerization solvent to the reaction vessel, diamine and tetracarboxylic dianhydride were added to the polymerization solvent so that the solid content concentration was 20% with respect to the total amount of 80 g of the polymerization solvent. .
As the diamine, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was added. After these were dissolved, 4,4-oxydiphthalic acid (ODPA) and 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4 were then used as tetracarboxylic dianhydrides. -Phenylene ester (TAHQ) was added so that the composition ratio of tetracarboxylic dianhydride was ODPA: TAHQ = 80: 20 (molar ratio). At this time, the acid component which is tetracarboxylic dianhydride added 85 mol part with respect to 100 mol part of the whole quantity of a diamine component.

Then, after making them react at 60 degreeC for 1 hour, 30 mol part of phthalic anhydride was added as terminal blocker, and it was made to react at 60 degreeC for further 1 hour, solid content concentration 20% polyamic acid (polyamic acid (B About 100 g of the solution of -1)) was obtained.
The solution viscosity of the obtained polyamic acid solution was 25 mPa · s, and as a result of evaluating the imidization rate, the imidization rate was 0%. The evaluation results of the solution viscosity and the imidization rate are also shown in Table 2 below.

[Synthesis Example 9 to Synthesis Example 14]
For Synthesis Examples 9 to 14, Synthesis Examples, except that the polymerization solvent used, the tetracarboxylic dianhydride that is the acid component, and the type and blending ratio of the diamine that is the amine component are as shown in Table 2 below. In the same manner as in Example 8, a solution containing polyamic acid (polyamic acid (B-2) to (B-8)) was prepared.
And like the synthesis example 8, the evaluation result of a solution viscosity and imidation rate is put together in following Table 2, and is shown.

In Table 2, the blank indicates that the corresponding component is not contained. Moreover, the unit “mol%” of the concentration shown in the table is the corresponding tetracarboxylic dianhydride with respect to the total amount of tetracarboxylic dianhydride used in the synthesis for tetracarboxylic dianhydride. The content of is shown. Similarly, about diamine, content of the applicable diamine with respect to the whole quantity of diamine used for the synthesis | combination is shown.
The components indicated by the symbols in Table 2 below are as described above, as in Table 1.

<Preparation of radiation-sensitive resin composition>
[Example 1]
Using a solution containing the polyimide (A-1) of Synthesis Example 1 as the polyimide of [A] component, and using a solution containing the polyamic acid (B-1) of Synthesis Example 9 as the polyamic acid of [B] component, When the total amount of polyimide (A-1) and polyamic acid (B-1) contained when mixing them is 100 parts by mass (solid content), the proportion of polyimide (A-1) used is 94 parts by mass ( Each solution was prepared so that the use ratio of the polyamic acid (B-1) was 6 parts by mass (solid content). And the total amount (solid content) of the polyimide (A-1) and polyamic acid (B-1) contained in each solution was 100 mass parts, and the use ratio of the other component was as follows.

As the quinonediazide compound of the component [C], 4,4 ′-[1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bisphenol (1.0 mol) and 1,2 -It was set as 20 mass parts using the condensate (C-1) of naphthoquinone diazide-5-sulfonic-acid chloride (2.0 mol).
N-phenyl-3-aminopropyltrimethoxysilane (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) (D-1) was used as the silane coupling agent of the component [D], and the amount was 5 parts by mass.
As the oxetanyl group-containing compound of the component [E], isophthalic acid = bis [(3-ethyloxetane-3-yl) methyl] (E-1) was used, and the amount was 5 parts by mass.
As a surfactant that is another additive, SH8400 manufactured by Toray Dow Corning Silicone Co., Ltd. was used, and the content was 0.01 parts by mass.

Next, each of the above components is mixed and prepared using a solvent so that the solid content concentration is 28% by mass, and then filtered through a membrane filter having a diameter of 0.2 μm to obtain a solution of the radiation sensitive resin composition. (S-1) was prepared.
The use ratio of each component of [A]-[E] of the solution (S-1) of the obtained radiation sensitive resin composition is shown together in Table 3. In Table 3, the type of solvent used and the blending ratio are also shown.

[Examples 2 to 14 and Comparative Examples 1 to 3]
[A]-[E] The radiation sensitive resin composition (S-2) which becomes an Example similarly to Example 1 except having made the kind and usage ratio of each component which were described in Table 3 into- (S-14) was prepared.
And the radiation sensitive resin composition (S-15) used as a comparative example is carried out similarly to Example 1 except having made the kind and usage ratio of each component of [A]-[E] component into Table 3. ) To (S-17) were prepared.

  In Table 3, the blank indicates that the corresponding component is not contained. The components indicated by the symbols in Table 3 below are as follows.

[C] component (quinonediazide compound)
C-1: 4,4 ′-[1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate of sulfonic acid chloride (2.0 mol)

[D] component (silane coupling agent)
D-1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical KBM-573)

  D-2: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu Chemical KBM-603)

[E] component (oxetanyl group-containing compound)
E-1: Isophthalic acid = bis [(3-ethyloxetane-3-yl) methyl]

  E-2: 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene

  Next, using the radiation sensitive resin compositions (S-1) to (S-17) obtained in Examples 1 to 14 and Comparative Examples 1 to 3, an insulating film was formed, Evaluation was performed. The evaluation results are summarized in Table 3.

[Example 15]
(Evaluation of water absorption)
Using each of the radiation-sensitive resin compositions (S-1) to (S-17) and applying onto a silicon substrate using a spinner or a slit die coater, pre-baking on a hot plate at 120 ° C. for 2 minutes. Thereafter, the film was post-baked at 250 ° C. for 45 minutes in a clean oven to form a coating film having a thickness of 3.0 μm. Using TDS (Thermal Desorption Spectroscopy) for each formed film, the film surface and the gas desorbed from the film when the temperature is raised from room temperature to 200 ° C. are detected with a mass spectrometer, and the water peak M / z The detected value of = 18 was measured, and the water absorption was evaluated. Specifically, the integrated value of the total peak intensity from 60 ° C. to 200 ° C. was calculated and evaluated as water absorption. When the integrated value of the total peak intensity at 60 ° C. to 200 ° C. was 1.0 × 10 ⁻⁷ or less, the water absorption was evaluated as “good”.

[Example 16]
(Evaluation of PGMEA detergency)
Each of the radiation sensitive resin compositions (S-1) to (S-17) was applied to a silicon substrate by using a spinner or a slit die coater to form a coating film, and then 80 seconds using a PGMEA solvent. Shower development was performed. Thereafter, the state of the coating film on the silicon substrate was confirmed. When the coating film was completely dissolved and no residue could be visually confirmed, the cleaning property was evaluated as “good”.

[Example 17]
(Evaluation of light shielding properties)
An insulating film was formed on the glass substrate in the same manner as in the evaluation of water absorption in Example 15 except that Corning (registered trademark) 7059 (manufactured by Corning) was used as the glass substrate instead of the silicon substrate. Using a spectrophotometer 150-20 type double beam (manufactured by Hitachi, Ltd.), the total light transmittance of the glass substrate having the insulating film is measured in a wavelength range of 380 nm to 780 nm, and each insulating film has a wavelength of 400 nm. The shading rate (transmittance) at was determined. When the light shielding rate was 50% or more (transmittance was 50% or less), the light shielding property was evaluated as “good”.

[Example 18]
(Evaluation of heat resistance)
In the same manner as in the evaluation of water absorption in Example 15 described above, an insulating film was formed, and for each of the obtained cured films, using a thermogravimetric measuring device (TA Instruments 2950 manufactured by TA Instruments) at 100 ° C to 500 ° C. TGA measurement (in air, temperature rising rate: 10 ° C./min) was performed to obtain a 5% weight loss temperature. When the 5% weight loss temperature was 350 ° C. or higher, the heat resistance was evaluated as “good”.

[Example 19]
(Evaluation of patterning properties)
Using each of the radiation sensitive resin compositions (S-1) to (S-17) and applying onto a silicon substrate using a spinner or a slit die coater, prebaking on a hot plate at 120 ° C. for 2 minutes. A coating film having a thickness of 3.0 μm was formed. 1. After exposing each coating film by changing the exposure time through a pattern mask having a predetermined pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Development was performed with a 38% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 80 seconds by a puddle method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. It was confirmed whether the 20.0 μm line-and-space (10 to 1) space pattern was completely dissolved. “Development” means that the residual film ratio after development is 60% or more and the pattern is formed without peeling off, “Fair” means that the residual film ratio after development is less than 60%, or the pattern is peeled off and is not formed. "

[Example 20]
(Evaluation of pattern shape)
A pattern was formed on the substrate in the same manner as in the patterning evaluation of Example 19 described above, except that a 20 μm line and space pattern (one-to-one) mask was used. The obtained pattern was heated and cured at 250 ° C. for 45 minutes in a clean oven to obtain an insulating film having a thickness of 3 μm. In each insulating film thus obtained, the vertical cross-sectional shape in the direction orthogonal to the line of the 20 μm line pattern is observed with an SEM, and the bottom of the cross-section has the maximum line width, that is, the forward tapered shape. When it was formed, it was evaluated as “good”, otherwise it was evaluated as “bad”. The case where the pattern could not be formed was described as “X” in Table 3.

[Example 21]
(Evaluation of radiation sensitivity)
Using each of the radiation sensitive resin compositions (S-1) to (S-17), applying onto a silicon substrate using a spinner or a slit die coater, prebaking on a hot plate at 120 ° C. for 2 minutes. Thus, a coating film having a thickness of 2.0 μm was formed. For each of the obtained coating films, using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and performing exposure by changing the exposure time through a pattern mask having a predetermined pattern, 2. Development with a 38% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. Then, the exposure amount necessary for completely dissolving the 30.0 μm line-and-space (10 to 1) space pattern was measured. This value was defined as radiation sensitivity (exposure sensitivity). When this radiation sensitivity was 100 mJ / cm ² or less, the sensitivity of the insulating film to radiation was evaluated as “good”.

In Table 3, for convenience, it is described as “sensitivity (mJ / cm ² )”, and is necessary for completely dissolving the 30.0 μm line-and-space (10 to 1) space pattern. The exposure amount is described in the corresponding column. The case where the pattern could not be formed was described as “X” in Table 3.

[Example 22]
(Evaluation of development margin)
Using the radiation-sensitive resin compositions (S-1) to (S-17), each coating film was formed on a silicon substrate in the same manner as in Example 21 (Evaluation of radiation sensitivity). Next, each of the obtained each was obtained through a mask having a 3.0 μm line-and-space (10 to 1) pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The coating film was exposed with an exposure amount corresponding to the radiation sensitivity value measured in (Evaluation of Radiation Sensitivity) of Example 21 described above, and 25 ° C. in a 2.38% tetramethylammonium hydroxide aqueous solution. Then, development was performed by changing the development time and using the liquid piling method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. At this time, the development time necessary for the line width to be 3.0 μm is set as the optimum development time, and the time until the 3.0 μm line pattern is peeled off when the development is further continued from the optimum development time. Measured and evaluated as a development margin (acceptable range of development time). When this time was 30 seconds or more, the development margin was evaluated as “good”.
The case where the pattern could not be formed was described as “X” in Table 3.

[Example 23]
(Evaluation of solvent resistance)
Each of the radiation sensitive resin compositions (S-1) to (S-17) was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 120 ° C. for 2 minutes to obtain a film thickness of 3 A coating film having a thickness of 0.0 μm was formed. The obtained coating film was heated at 220 ° C. for 1 hour in a clean oven to obtain each insulating film. The film thickness (T1) of the obtained insulating film was measured. Then, the silicon substrate on which this insulating film is formed is immersed in dimethyl sulfoxide whose temperature is controlled at 70 ° C. for 20 minutes, and then the film thickness (t1) of the insulating film on the silicon substrate is measured, and the film obtained by immersion is used. The thickness change rate {| t1-T1 | / T1} × 100 [%] was calculated. When the value of the rate of change in film thickness was 4% or less, the solvent resistance was evaluated as “good”. In the evaluation of solvent resistance, patterning of the film to be formed is unnecessary, so the radiation irradiation step and the development step were omitted, and only the coating film forming step and the heating step were performed for evaluation. In Table 3, the value of the film thickness change rate is described in the corresponding column.

[Example 23]
(Resolution evaluation)
Using each of the radiation sensitive resin compositions (S-1) to (S-17) and applying onto a silicon substrate using a spinner or a slit die coater, prebaking on a hot plate at 120 ° C. for 2 minutes. Each coating film having a thickness of 3.0 μm was formed. For each of the obtained coating films, using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and performing exposure by changing the exposure time through a pattern mask having a predetermined pattern, The film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. The lower limit of the formed pattern width was evaluated as the resolution (μm). The case where the pattern could not be formed was described as “X” in Table 3.

  As is apparent from Table 3, the radiation-sensitive resin compositions (S-1) to (S-14) of Examples 1 to 14 of the present invention have good PGMEA cleanability, patternability, sensitivity, and development. Have margin and resolution at the same time. Moreover, the insulating film obtained using the radiation sensitive resin compositions (S-1) to (S-14) of Examples 1 to 14 of the present invention has low water absorption, heat resistance and solvent resistance. It was found to have excellent light shielding properties.

  The organic EL device of the present invention can increase the effective area of the organic light-emitting layer in the pixel and can be manufactured with high productivity. And the performance fall by impurities, such as a water | moisture content, can be reduced. Therefore, the organic EL device of the present invention can be suitably used for a display device of a large flat-screen television or a portable information device that requires excellent display quality and reliability.

1 Organic EL display element 2 Substrate 3 TFT
DESCRIPTION OF SYMBOLS 4 Gate electrode 5 Gate insulating film 6 Semiconductor layer 7 1st source-drain electrode 8 2nd source-drain electrode 10 1st insulating film 11 Anode 12 Through hole 13 2nd insulating film 14 Organic light emitting layer 15 Cathode 16 Passivation film 17 Sealing layer 19 Inorganic insulating film 20 Sealing substrate

Claims (8)

(A) an acid component containing an acid component having a group represented by the following formula (1-1) (A1) and an amine component containing an amine component (A2) having a group represented by the following formula (1-2); Polyimide obtained by condensing
(B) an acid component containing a (B1) acid component having a group represented by the following formula (1-1), and an amine component containing (B2) an amine component having a group represented by the following formula (1-2): A polyamic acid obtained by condensing
(C) a quinonediazide compound, and
(D) The radiation sensitive resin composition characterized by including the compound shown by following formula (2).

(In formula (1-2), X represents any one of an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a hydroxyl group.)

(In the formula (2), R ² represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and Z represents any of a single bond, a methylene group, and an alkylene group having 2 to 6 carbon atoms. R ³ represents any one of a hydrogen atom and a phenyl group, y represents an integer of 0 to 2, and a represents an integer of 0 to 12.) (A) polyimide is a polyimide obtained by condensing (A1) acid component and (A2) amine component,
The radiation-sensitive resin composition according to claim 1, wherein the (B) polyamic acid is a polyamic acid obtained by condensing the (B1) acid component and the (B2) amine component.   The radiation-sensitive resin composition according to claim 1 or 2, further comprising (E) a compound having one or more oxetanyl groups.   The mixing ratio of (A) polyimide and (B) polyamic acid is that the total amount of (A) polyimide and (B) polyamic acid is 100% by mass, (A) polyimide is 60% by mass to 99% by mass, and (B) polyamic acid. The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the acid is in the range of 1% by mass to 40% by mass. The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the component (A) has at least one component represented by the following formula (3) to the following formula (7). object.

(In the formulas (3) to (7), R ¹¹ is at least one component selected from the group of components represented by the following formula. R ^{12 to} R ¹⁴ each independently has 1 to 12 carbon atoms. And a divalent group containing at least one of an alkyl group and a phenyl group.)

  At least one selected from the group consisting of diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, propylene glycol monoalkyl ether and γ-butyrolactone The radiation-sensitive resin composition according to any one of claims 1 to 5, comprising a seed solvent.   An insulating film formed using the radiation-sensitive composition according to claim 1 and used for an organic EL device.   An organic EL element comprising the insulating film according to claim 7.

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