KR20130121722A - Radiation-sensitive resin composition, insulating layer, and organic el element - Google Patents

Abstract

The present invention provides a radiation-sensitive resin composition capable of forming an insulating layer of an organic EL device with an excellent property by being prepared without NMP, an insulating layer and an organic EL device. The radiation-sensitive resin composition comprises: at least one kind among a polyimide structure, a polyimide precursor structure and a polyamic acid ester structure; a quinonediazide compound; at least one kind among diethyleneglycoldialkylether, ethyleneglycolmonoalkyletheracetate, diethyleneglycolmonoalkyletheracetate, propyleneglycolmonoalkyletheracetate and propyleneglycolmonoalkyletheracetate as a solvent; and γ-butyrolactone. A first insulating layer (19) on a TFT (3) of an organic EL display device (1) and a second insulating layer (13) which becomes a partition of an organic emission layer (14) are formed with the radiation-sensitive resin composition. .

Description

Radiation-sensitive resin composition, insulating film and organic EL element {RADIATION-SENSITIVE RESIN COMPOSITION, INSULATING LAYER, AND ORGANIC EL ELEMENT}

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

Organic EL devices using electroluminescence by organic compounds are expected as next-generation lighting technologies in addition to display devices such as displays.

The organic EL display element which is a display element using an organic EL element does not require a backlight as a self-luminous type, and can display an image of a high speed response at a wide time. It has low power consumption and has excellent features such as thinness and light weight. Therefore, development of organic electroluminescent display elements is actively progressing in recent years.

Such an organic EL display element is generally manufactured by the following method. First, a pattern of an anode (hole injection electrode) and a hole transport layer made of ITO (Indium Tin Oxide) or the like is formed on a substrate. Subsequently, in the passive organic EL display element, after forming the pattern of an insulating film and the pattern of a cathode partition, the organic light emitting layer, an electron carrying layer, and a cathode (electron injection electrode) are patterned by vapor deposition, for example. In addition, as an active organic EL display element, an ITO pattern and a pattern of an insulating film serving as partitions of the organic light emitting layer are formed, and then the pattern of the organic light emitting layer is formed by a masking method, an inkjet method, or the like, followed by an electron transport layer and a cathode ( Electron injection electrode). Here, the insulating film used as a partition can be comprised using resin which can be patterned by the photolithographic method (for example, refer patent document 1 and 2). And, as the organic light emitting layer, for example, it is possible to use Alq _3, BeBq _3, etc. of the base material (基材) doped with coumarin quinazoline Clichy money or the base material.

In recent years, the display element is required to have a high definition, and studies have been made to increase the aperture ratio even in the organic EL display element.

For example, the introduction of an insulating film having a planarization function, as described in Patent Documents 1 and 2, in addition to the insulating films forming the partition walls, is studied as an active organic EL display element so as to realize a higher aperture ratio. It is becoming. Such an active organic EL display element is manufactured by the following method, for example. First, thin film transistors (Thin-Film-Transistors (TFTs)) which are active elements are formed for a plurality of pixels formed in a matrix on a substrate such as glass. A first insulating film also serving as a planarization film is formed on the TFT. Subsequently, a pattern of an anode is formed thereon. The pattern formation at this time uses the wet etching method normally. Moreover, the pattern of a hole transport layer is formed on it by the masking method. Subsequently, the pattern of the second insulating film serving as a partition between the anode and the organic light emitting layer, and the pattern of the organic light emitting layer are formed by a masking method, an inkjet method, or the like, and then the electron transporting layer and the cathode are sequentially formed. At this time, in order to connect the anode and the TFT, it is necessary to form a through hole of about 1 µm to 15 µm in the first insulating film.

Although the organic electroluminescent display element by the above structure and manufacturing method, it is preferable to use resin which desired patterning is easy for the insulating film which functions as the partition of an organic light emitting layer, or the planarization film on TFT. In that case, the resin which comprises an insulating film is requested | required that various characteristics, such as heat resistance and mechanical strength, are favorable. Moreover, in formation of an insulating film, it is preferable that a liquid radiation sensitive resin composition can be used so that simple film formation and simple patterning using the photolithographic method, for example, are possible. In view of this, Patent Literature 3 discloses a technique of using polyimide for an insulating film of an organic EL device.

Various characteristics, such as heat resistance and mechanical strength, are favorable for a polyimide, and liquid resin composition can be used for the film formation. And formation using the resin composition which has radiation sensitivity is possible. In that case, polyamic acid, polyamic acid ester, polyimide, etc. which are polyimide precursors can be used as the resin component.

When using a polyimide precursor, a polyimide, etc. as a component of the resin composition for polyimide formation, it is common to first synthesize | combine this polyimide precursor, a polyimide, etc. first.

When synthesizing a polyimide precursor, a polyimide, or the like, since the solubility of polyamic acid, polyimide, etc. is low, as a polymerization solvent used for synthesis, non-protons such as N-methylpyrrolidone (NMP) The solvent of the sex will be overused. After polyamic acid, polyimide, and the like are synthesized, the NMP solution is preferably used as a resin composition for forming an insulating film.

Japanese Laid-Open Patent Publication No. 2011-107476 Japanese Laid-Open Patent Publication No. 2010-237310 Japanese Laid-Open Patent Publication No. 2009-9934

However, in the organic EL element, when forming the insulating film which functions as a planarization film on the partition of an organic light emitting layer or TFT, the height of hygroscopicity may become a problem with respect to N-methylpyrrolidone (NMP).

In an organic EL device such as an organic EL display device, even if the organic light emitting layer is a low molecular-organic light emitting layer using a low molecular weight material or a polymer-organic light emitting layer using a high molecular material, it deteriorates quickly when it comes into contact with moisture, It is known to be inhibited. It is thought that such moisture may infiltrate from an external environment, and the trace amount of moisture contained in an insulating film formation material in the form of adsorption water etc. may infiltrate into an organic light emitting layer gradually.

Therefore, with respect to N-methylpyrrolidone (NMP), the organic light emitting layer of an organic EL element may deteriorate by the hygroscopic height even if it is a low molecular weight organic light emitting layer or a high molecular weight organic light emitting layer. As a result, NMP may inhibit the light emission state of an organic EL element, and it is not preferable to use it for formation of the insulating film of an organic EL element. That is, it is not preferable to contain NMP as a solvent etc. of the resin composition which forms the insulating film of organic electroluminescent element. It is preferable that the resin composition which forms the insulating film of organic electroluminescent element contains a solvent other than NMP as a solvent etc ..

Therefore, although polyimide is preferable because various characteristics, such as heat resistance and mechanical strength, are favorable, there existed a case where application to organic electroluminescent element made a manufacturing process complicated. That is, when polyimide is used for the insulating film of organic electroluminescent element, polyamic acid and polyimide are contained as a component in the resin composition for formation. In that case, after synthesize | combining desired polyamic acid and polyimide as NMP as a polymerization solvent, it was necessary to precipitate them and isolate polyamic acid and polyimide. Then, the isolated polyamic acid or polyimide is purified to remove NMP, and then dissolved in a solvent which is not likely to deteriorate the organic light emitting layer again, and then the components are adjusted to prepare a radiation-sensitive resin composition for forming an insulating film. It was.

As mentioned above, in order to make the insulating film of organic electroluminescent element favorable characteristics, such as heat resistance, when polyimide is used, it is isolated after synthesize | combining polyamic acid, a polyimide, etc., and going through the process which re-dissolves in another solvent. It became necessary. Therefore, the number of processes in manufacture of an organic electroluminescent element increased, and it was concerned that the productivity will fall.

Therefore, an insulating film formed from a resin composition without using NMP, desired patterning is possible, and various characteristics such as heat resistance and mechanical strength are required, and a radiation-sensitive resin composition suitable for the formation is desired. And the organic electroluminescent element which has this insulating film is calculated | required.

This invention is made | formed in view of the above problem. That is, an object of the present invention is to provide a radiation-sensitive resin composition which is prepared without using NMP and can be used to form an insulating film of an organic EL device having good characteristics.

Moreover, the objective of this invention is providing the insulating film of the organic electroluminescent element which is formed using the radiation sensitive resin composition prepared without using NMP, and has favorable characteristics.

Moreover, the objective of this invention is providing the organic electroluminescent element which has the insulating film formed by using the radiation sensitive resin composition prepared without using NMP, and has a characteristic.

The first aspect of the present invention,

(A) Resin containing at least 1 sort (s) chosen from the group which consists of a polyimide structure, a polyimide precursor structure, and a polyamic acid ester structure,

(B) quinonediazide compound,

(C) Solvent

And a radiation sensitive resin composition which is used for formation of an insulating film of an organic EL element,

(C) at least a solvent 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 It is related with the radiation sensitive resin composition containing 1 type and (gamma) -butyrolactone.

In the 1st aspect of this invention, it is preferable that the polyimide structure of (A) component contains the repeating unit represented by following formula (1):

(In formula (1), R <_1> is bivalent group containing at least one of a C1-C12 alkyl group and a phenyl group, and R <_2> is a bivalent group which has a hydroxyl group.).

In the 1st aspect of this invention, it is preferable that R <_2> in said Formula (1) is a bivalent group represented by either of the following formulas.

In the first aspect of the present invention, the polyimide structure of component (A) preferably contains a repeating unit represented by the following General Formula (2):

(In formula (2), R <_3> is a bivalent group which has a hydroxyl group, X is a tetravalent group represented by either of following formula.).

In the 1st aspect of this invention, it is preferable that R <_3> in said Formula (2) is a bivalent group represented by either of the following formulas.

In the 1st aspect of this invention, it is preferable that (C) solvent contains 20 mass%-40 mass% of (gamma) -butyrolactone.

The 2nd aspect of this invention is formed using the radiation sensitive resin composition of the 1st aspect of this invention, and relates to the insulating film characterized by the above-mentioned.

The 3rd aspect of this invention is related with the organic electroluminescent element characterized by having the insulating film of the 2nd aspect of this invention.

According to the first aspect of the present invention, a radiation-sensitive resin composition is prepared without using NMP, and can be used to form an insulating film of an organic EL device having good characteristics.

According to the 2nd aspect of this invention, it forms using the radiation sensitive resin composition prepared without using NMP, and the insulating film of the organic electroluminescent element of favorable characteristic is obtained.

According to the 3rd aspect of this invention, the organic electroluminescent element which has an insulating film formed by using the radiation sensitive resin composition prepared without using NMP, and has a favorable characteristic is obtained.

1 is a cross-sectional view schematically illustrating the structure of main parts of the organic EL display element of the present embodiment.

(Mode for carrying out the invention)

Hereinafter, an embodiment of the present invention will be described.

In addition, in this invention, the "radiation radiation" irradiated at the time of exposure is the concept containing visible light, an ultraviolet-ray, an ultraviolet-ray, an X-ray, a charged particle beam, etc.

<Radiation-Resistant Resin Composition>

The radiation sensitive resin composition of this embodiment is a radiation sensitive resin composition used for formation of the insulating film of organic electroluminescent element, and contains (A) resin, (B) quinonediazide compound, and (C) solvent. . Hereinafter, the detail of each component is demonstrated.

[(A) Resin]

(A) resin contained in the radiation sensitive resin composition of this embodiment is a polymer containing at least 1 sort (s) chosen from the group which consists of a polyimide structure, a polyimide precursor structure, and a polyamic acid ester structure in the molecular structure ( Resin) is not particularly limited. Since it contains such a structure, (A) resin contained in the radiation sensitive resin composition of this embodiment can be equipped with the low water absorption structure. And it is preferable that (A) resin is alkali-soluble resin. In addition, polyamic acid is contained in the polyimide precursor here.

It is preferable that the polyimide structure which can be contained in (A) resin contains the repeating unit represented by following formula (1).

R <_1> in said Formula (1) is a bivalent group containing at least one of a C1-C12 alkyl group and a phenyl group, and R <_2> is a bivalent group which has a hydroxyl group.

It is preferable that R <_2> in said Formula (1) is a bivalent group represented by following formula (3).

R ₄ in the formula (3) is at least one 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 It is the flag of. In addition, R <_5> in said Formula (3) represents a hydrogen atom, an acyl group, or an alkyl group independently of each other. Preferred acyl groups include, for example, formyl group, acetyl group, propionyl group, butyroyl group, isobutyroyl group, and the like. As preferable alkyl groups, 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, etc. are mentioned. In addition, at least one of R ₅ is a hydrogen atom. In addition, n1 and n2 in said Formula (3) are integers of 0-2, and at least one of n1 and n2 is 1 or more.

And as for the polyimide structure which can be contained in (A) resin, it is preferable that R <_2> in said Formula (1) has a bivalent group which has one next hydroxyl group specifically ,.

Moreover, it is preferable that the polyimide structure which can be contained in (A) resin has a bivalent group in which R <_2> in said Formula (1) has _two next hydroxyl groups.

Moreover, it is preferable that the polyimide structure which can be contained in (A) resin is a bivalent group in which R <_2> in said Formula (1) has three next hydroxyl groups.

Moreover, it is preferable that the polyimide structure which can be contained in (A) resin is a bivalent group which R <_2> in said Formula (1) has four next hydroxyl groups.

And in the polyimide structure which can be contained in (A) resin, More preferably, R <_2> in said Formula (1) is a divalent group which has two hydroxyl groups mentioned above.

Moreover, it is preferable that the polyimide structure which can be contained in (A) resin contains the repeating unit represented by following formula (2) similarly to the above-mentioned.

In said formula (2), R <_3> is a bivalent group which has a hydroxyl group, X is a tetravalent group represented by either of the following formulas.

And it is preferable that the polyimide structure which can be contained in (A) resin is a divalent group which R <_3> in said Formula (2) has a hydroxyl group, and is group represented by said Formula (3). More specifically, the polyimide structure which can be contained in (A) resin is a bivalent group which has one hydroxyl group of the thing of at least one of R <_1> and R <_2> in above-mentioned Formula (1), and the hydroxyl group mentioned above It is preferable when it is any of the bivalent group which has two, the divalent group which has three hydroxyl groups mentioned above, and the bivalent group which has four hydroxyl groups.

R ₃ in the formula (2) is particularly preferably a divalent group having two hydroxyl groups.

Although the polyimide precursor structure which can be contained in (A) resin is not specifically limited, It is preferable that it is a structure used as the precursor of the polyimide structure containing the repeating unit represented by said Formula (1). And it is equally preferable that it is a structure used as the precursor of the polyimide structure containing the repeating unit represented by said Formula (2).

For example, it is preferable that the polyimide precursor structure which can be contained in (A) resin is a structure containing the repeating unit represented by following formula (1-1).

In said Formula (1-1), R <_1> and R <_2> is synonymous with R <_1> and R <_2> of said Formula (1).

In addition, it is preferable that the polyimide precursor structure which can be contained in (A) resin is a structure containing the repeating unit represented by following formula (2-1), for example.

　

　

In said Formula (2-1), X and R <_3> are synonymous with X and R <_3> of the said Formula (2).

Although the polyamic acid ester structure which can be contained in (A) resin is not specifically limited, In the polyamic acid structure used as the precursor of the polyimide structure containing the repeating unit represented by said Formula (1), the carboxyl group is esterified, It is preferable to show the ester derivative structure of polyamic acid. And in the polyamic acid structure used as the precursor of the polyimide structure containing the repeating unit represented by said Formula (2), it is equally preferable that the carboxyl group is esterified and shows the ester derivative structure of polyamic acid.

For example, it is preferable that the polyamic acid ester structure which can be contained in (A) resin is a structure containing the repeating unit represented by following formula (1-2).

In said Formula (1-2), R <_1> and R <_2> is synonymous with R <_1> and R <_2> of said Formula (1). R <_4> is a C1-C5 alkyl group.

For example, it is preferable that the polyamic acid ester structure which can be contained in (A) resin is a structure containing the repeating unit represented by following formula (2-2).

In said Formula (2-2), X and R <_3> are synonymous with X and R <_3> of the said Formula (2). R <_5> is a C1-C5 alkyl group.

(A) resin containing at least 1 sort (s) chosen from the group which consists of the above polyimide structure, a polyimide precursor structure, and a polyamic acid ester structure has a low water absorption structure, shows low water absorption, and has the outstanding solubility. Therefore, it melt | dissolves also in the low hygroscopic solvent other than NMP. For example, it is melt | dissolved also in the (C) solvent mentioned later. Therefore, solvent (other than NMP) can be used as a polymerization solvent for obtaining (A) resin, and also the radiation-sensitive resin composition of this embodiment which is liquid and low hygroscopic prepared using solvents other than NMP. It becomes a suitable component for.

The resin (A) containing the polyimide structure described above is represented by, for example, a monomer represented by the following formula (4-1) (hereinafter also referred to as monomer (4-1)) and the following formula (5-1). It can obtain by synthesize | combining a polyimide by making it react in a polymerization solvent using a monomer (henceforth a monomer (5-1)), synthesize | combining a polyamic acid, and performing imidation reaction further.

R ₁ and R ₂ in the formulas (4-1) and (5-1) have the same meanings as R ₁ and R ₂ of the formula (1).

At this time, the polyamic acid synthesize | combined in the middle can be made into (A) resin containing the polyimide precursor structure mentioned above. In addition, the polyamic acid ester obtained by esterifying it according to a well-known method can be made into (A) resin containing the polyamic acid ester structure mentioned above.

Similarly, (A) resin containing the above-mentioned polyimide structure is a monomer (henceforth a monomer (4-2) represented by following formula (4-2)) and following formula (5-2), for example. The polyimide can be synthesize | combined by making it react in a superposition | polymerization solvent using the monomer represented by (hereinafter also called monomer (5-2)), and carrying out imidation reaction.

X in said Formula (4-2) and R <_3> in Formula (5-2) are synonymous with X and R <_3> of said Formula (2).

At this time, the polyamic acid synthesize | combined in the middle can be made into (A) resin containing the polyimide precursor structure mentioned above. In addition, the polyamic acid ester obtained by esterifying it according to a well-known method can be made into (A) resin containing the polyamic acid ester structure mentioned above.

In addition, (A) resin containing the above-mentioned polyimide structure is a polymerization solvent using monomer (4-1) and monomer (4-2), and monomer (5-1) or monomer (5-2). It can obtain by synthesize | combining a polyimide by making it react in the inside, synthesize | combining a polyamic acid, and performing an imidation reaction further. And polyamic acid synthesize | combined in the middle can be made into (A) resin containing the polyimide precursor structure mentioned above. In addition, the polyamic acid ester obtained by esterifying it according to a well-known method can be made into (A) resin containing the polyamic acid ester structure mentioned above.

The following two types of methods are applicable, and you may synthesize | combine the synthesis procedure of the polyamic acid for obtaining (A) resin containing a polyimide structure. That is, after dissolving the monomer (5-1) in the polymerization solvent, the method of reacting the monomer (4-1) and the monomer (5-2) in the same manner as the monomer (5-2) are dissolved in the polymerization solvent. The method of reacting -2), (ii) the monomer (4-1) is dissolved in the polymerization solvent, and then the monomer (5-1) is reacted, and the monomer (4-2) is dissolved in the polymerization solvent in the same manner. It is a method of making monomer (5-2) react after making it carry out.

Moreover, when obtaining (A) resin containing a polyimide structure, diamine compounds other than monomer (5-1) and monomer (5-2) as needed in the range which does not impair the effect of this invention. Can be reacted. As a diamine compound which can be made to react, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, 4,4 ', for example. -Diaminodiphenylsulfide, 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'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino Phenoxy) 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) Zen, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4- Aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro -4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneiso Propylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoro Lopropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octa Aromatic diamines such as fluorobiphenyl;

Metaxylylenediamine, paraxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7 Aliphatic and alicyclic diamines such as -methanoindanylenedimethylenediamine, tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, and 4,4'-methylenebis (cyclohexylamine); .

In addition, when obtaining (A) resin containing a polyimide structure, if necessary, tetra, other than a monomer (4-1) and a monomer (4-2) in the range which does not impair the effect of this invention. Tetracarboxylic acid derivatives, such as carboxylic acid dianhydride, can be made to react. As a tetracarboxylic-acid derivative which can be made to react, it is other than a monomer (4-1) and a monomer (4-2), For example, X in the said Formula (4-2) is a tetravalent aromatic hydrocarbon group or tetravalent aliphatic. It is a hydrocarbon group. Specific examples of the tetravalent aromatic hydrocarbon group include tetravalent groups in which four hydrogens of the parent skeleton of the aromatic hydrocarbon are substituted.

Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alkyl alicyclic hydrocarbon group. More specifically, the tetravalent group by which four hydrogens of the backbone of a linear hydrocarbon group, an alicyclic hydrocarbon, or an alkyl alicyclic hydrocarbon are substituted is mentioned. In addition, these tetravalent aliphatic hydrocarbon groups may contain an aromatic ring in at least one part of the structure. Here, as a chain hydrocarbon, ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, n-dodecane, etc. are mentioned. Moreover, as an alicyclic hydrocarbon, a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or more hydrocarbon, etc. are mentioned specifically ,.

The synthesis | combining procedure of the polyamic acid for obtaining (A) resin containing the said polyimide structure in the case of using the above-mentioned diamine compound, the following two types of methods are possible, for example, even if it synthesize | combines by any method good. That is, after dissolving the monomer (5-1) and the above-mentioned diamine compound in a polymerization solvent, the method of making monomer (4-1) react, and the monomer (5-2) and the above-mentioned diamine compound similarly After dissolving in the polymerization solvent, the monomer (4-2) is reacted, (ii) the monomer (4-1) is dissolved in the polymerization solvent, and then the diamine compound and monomer (5-1) described above are reacted. It is a method and similarly, after melt | dissolving monomer (4-2) in a polymerization solvent, it is a method of making the above-mentioned diamine compound and monomer (5-2) react.

In the case of using the above-mentioned tetracarboxylic acid derivative, the synthesis procedure of the polyamic acid for obtaining (A) resin containing the said polyimide structure can be the following two methods, for example, by either method You may synthesize. That is, after dissolving the monomer (5-1) in the polymerization solvent, the method of reacting the above-described tetracarboxylic acid derivative and the monomer (4-1) and the monomer (5-2) in the same manner as the polymerization solvent After dissolving in the above, the method of reacting the above-mentioned tetracarboxylic acid derivative and the monomer (4-2), (ii) the monomer (4-1) and the above-mentioned tetracarboxylic acid derivative are dissolved in a polymerization solvent, and then the monomer (5 -1) and the method of reacting monomer (5-2) after dissolving monomer (4-2) and the above-mentioned tetracarboxylic acid derivative in a polymerization solvent similarly.

The synthesis | combining procedure of the polyamic acid for obtaining (A) resin containing the said polyimide structure in the case of using the above-mentioned diamine compound and the above-mentioned tetracarboxylic acid derivative is possible, for example with the following two types of methods. You may synthesize | combine by any method. That is, after dissolving the monomer (5-1) and the diamine compound described above in a polymerization solvent, the method of reacting the above-mentioned tetracarboxylic acid derivative and the monomer (4-1) and monomer (5- 2) and the above-mentioned diamine compound are dissolved in a polymerization solvent, and then the above-mentioned tetracarboxylic acid derivative and monomer (4-2) are reacted, (ii) monomer (4-1) and the above-mentioned tetracarboxylic acid derivative After dissolving in a polymerization solvent, the method of making the above-mentioned diamine compound and monomer (5-1) react, and the monomer (4-2) and the tetracarboxylic acid derivative mentioned above are dissolved in a polymerization solvent similarly, It is a method of making a diamine compound and monomer (5-2) react.

In addition, when reacting in a polymerization solvent using monomer (4-1) and monomer (4-2), monomer (5-1) or monomer (5-2), monomer (4) -1) and the above-mentioned tetracarboxylic acid derivative added when necessary and monomer (4-2) are first dissolved in the polymerization solvent, and then the monomer (5-1) or monomer (5-2), if necessary The method of making it react using the above-mentioned diamine compound is possible. On the contrary, monomer (5-1) or monomer (5-2) and the above-mentioned diamine compound added when necessary are first dissolved in a polymerization solvent, and then monomer (4-1) and monomer (4- It is possible to react with 2) and the above-mentioned tetracarboxylic acid derivative added when necessary.

As a polymerization solvent, what can melt | dissolve the raw material and a product at the time of the synthesis | combination of (A) resin is selected. That is, the polymerization solvent is at least 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 It is preferable to use 1 type. These compounds can be used alone as a solvent for polymerization, and can also be used by mixing two or more kinds.

As a specific example of these solvents, As diethylene glycol dialkyl ether, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol ethyl methyl ether, etc .; As ethylene glycol monoalkyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; As diethylene glycol monoalkyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; As propylene glycol monoalkyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc .; 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 the ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, methyl-3-methoxypropionate, and the like.

Among these, propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA), diethylene glycol ethylmethyl ether (hereinafter sometimes abbreviated as EDM) are particularly preferable.

Moreover, (gamma) -butyrolactone (henceforth abbreviated as BL) is mentioned as a preferable polymerization solvent. (gamma) -butyrolactone can be used in mixture with what was illustrated as a preferable polymerization solvent mentioned above, for example.

And if necessary, methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and the like Alcohol solvents; Ether solvents such as diglyme and triglyme; You may add aromatic hydrocarbon solvents, such as toluene and xylene, and N-methylpyrrolidone (NMP). However, since NMP has high hygroscopicity and may deteriorate the organic light emitting layer of organic electroluminescent element, it is preferable not to use NMP.

When using NMP as needed, it is preferable to use so that it may become 5 mass% or less with respect to the total amount of (C) solvent.

The imidation reaction for obtaining (A) resin containing a polyimide structure can apply well-known methods, such as a heating imidation reaction and a chemical imidation reaction. When synthesize | combining (A) resin by a heat imidation reaction, Preferably, it carries out by heating the synthesis solution of polyamic acid at 120 degreeC-210 degreeC for 1 hour-16 hours. Moreover, you may react, removing water in a system using azeotropic solvents, such as toluene and xylene, as needed.

(A) Resin WHEREIN: 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 3000- 300,000 or so. If Mw is less than 2000, there is a tendency that sufficient mechanical properties are not obtained as an insulating film. On the other hand, when Mw is more than 500000, there exists a tendency for the solubility to a solvent and a developing solution of the photosensitive resin composition obtained using this (A) resin to run short.

[Other resins]

The radiation sensitive resin composition of this embodiment can further contain other resins other than the above-mentioned (A) resin as needed in the range which does not impair the effect of this invention. Although the "other resin" which can be contained is not specifically limited, It is preferable that it is alkali-soluble, Furthermore, what contains alkali-soluble resin (henceforth a phenol resin) which has a phenolic hydroxyl group is solved. It is more preferable because the viability is improved.

As a phenol resin which can be contained, a novolak resin, polyhydroxy styrene, its copolymer, phenol- xylene glycol dimethyl ether condensation resin, cresol- xylene glycol dimethyl ether condensation resin, phenol- dicyclopentadiene condensation resin, etc. Can be mentioned.

Specific examples of the novolak resins include phenol / formaldehyde condensation novolac resins, cresol / formaldehyde condensation novolac resins, and phenol-naphthol / formaldehyde condensation novolac resins.

Novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols used at this time 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-letter Illenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Although monomers other than hydroxy styrene which comprise the copolymer of polyhydroxy styrene are not specifically limited, Specifically, styrene, indene, p-methoxy styrene, p-butoxy styrene, p-acetoxy styrene, p Styrene derivatives such as hydroxy-α-methylstyrene; (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) (Meth) acrylic acid derivatives such as) 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; And acid anhydride derivatives such as maleic anhydride and itaconic anhydride.

The content ratio of the phenol resin is preferably 0 parts by mass to 90 parts by mass, more preferably 5 parts by mass to 80 parts by mass, and more preferably 10 parts by mass based on 100 parts by mass of the total of (A) resin and the phenol resin. It is more preferable to set it as -70 mass parts. If it is less than 5 mass parts, there exists a tendency for the effect of containing this phenol resin to become difficult to be exhibited. On the other hand, when it is more than 90 mass parts, there exists a tendency for the mechanical strength of a film | membrane to fall.

In addition, the radiation sensitive resin composition of this embodiment can contain a phenolic low molecular weight compound other than the above-mentioned phenol resin. As a specific example of the phenolic low molecular weight compound which can be contained, 4,4'- dihydroxy diphenylmethane, 4,4'- dihydroxy diphenyl ether, tris (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl) -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-tetra (4 -Hydroxyphenyl) ethane, and the like.

The content rate of a phenolic low molecular weight compound is 100 mass parts of (A) resin (however, when it contains another polymer other than (A) resin, 100 mass parts of total of (A) resin and another polymer) It is preferable to set it as 0 mass part-100 mass parts with respect to it, It is more preferable to set it as 1 mass part-60 mass parts, It is still more preferable to set it as 5 mass parts-40 mass parts. If it is less than 1 mass part, there exists a tendency for the effect of containing this phenolic low molecular weight compound to become difficult to be exhibited. On the other hand, when it is more than 100 mass parts, there exists a tendency for the mechanical strength of a film | membrane to fall.

[(B) quinonediazide compound]

The radiation sensitive resin composition of this embodiment contains the (B) quinonediazide compound as an essential component with (A) resin mentioned above. Thereby, the radiation sensitive resin composition of this embodiment can be used as a positive radiation sensitive resin composition.

(B) The quinonediazide compound is a quinonediazide compound which produces | generates a carboxylic acid by irradiation of a radiation. (B) As a quinone diazide compound, the condensate of a phenolic compound or an alcoholic compound (henceforth "mother nucleus"), and 1, 2- naphthoquinone diazide sulfonic-acid halide can be used.

Examples of the above-mentioned mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, other mother nucleus and the like.

As trihydroxy benzophenone, 2, 3, 4- trihydroxy benzophenone, 2, 4, 6- trihydroxy benzophenone etc. are mentioned, for example.

As tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3,4,3'- tetrahydroxy benzophenone, 2,3,4,4', for example. -Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc. are mentioned. Can be.

As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc. are mentioned, for example.

As hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy, for example. Benzophenone etc. are mentioned.

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-phenyl propane, 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'-spirobiindene- 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavane, etc. are mentioned.

As another mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3 -(1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxy Phenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1, 3-dihydroxybenzene, etc. are mentioned.

Of these mother cores, 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. As 1, 2- naphthoquinone diazide sulfonic-acid chloride, a 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride, a 1, 2- naphthoquinone diazide- 5-sulfonic acid chloride, etc. are mentioned, for example. have. Among these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride is more preferable.

In the condensation reaction between the phenolic compound or the alcoholic compound (parent nucleus) and the 1,2-naphthoquinone diazide sulfonic acid halide, the molar ratio of the OH group in the phenolic compound or the alcoholic compound is preferably 30 mol% to 85 mol. %, More preferably, 1, 2- naphthoquinone diazide sulfonic-acid halide corresponding to 50 mol%-70 mol% can be used. Condensation reaction can be performed in accordance with a well-known method.

Moreover, as a quinone diazide compound, the 1,2-naphthoquinone diazide sulfonic-acid amides which changed the ester bond of the mother-nucleus illustrated above to an amide bond, for example, 2, 3, 4- triamino benzophenone- 1,2-naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably.

These quinonediazide compounds can be used individually or in combination of 2 or more types. 5 mass parts-100 mass parts are preferable with respect to 100 mass parts of resin, and, as for the usage ratio of the quinone diazide compound in the radiation sensitive resin composition of this embodiment, 10 mass parts-50 mass parts are more preferable. By making the use ratio of a quinone diazide compound into the above-mentioned range, the difference in the solubility of the irradiation part and the unirradiation part of the radiation with respect to the alkaline aqueous solution used as a developing solution can be enlarged, and patterning performance can be improved. Moreover, the solvent resistance of the protective film obtained using this radiation sensitive resin composition can also be made favorable.

[(C) Solvent]

The radiation sensitive resin composition of this embodiment contains the (C) solvent with the above-mentioned (A) resin and (B) quinonediazide compound. By containing the (C) solvent, the radiation sensitive resin composition of this embodiment can be made into a liquid resin composition.

As (C) solvent, what was illustrated as the polymerization solvent for obtaining above-mentioned (A) resin can be used. That is, 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, and propylene glycol monoalkyl ether propionate can be used. Can be. And (gamma) -butyrolactone can be used. These compounds can be used individually as a solvent (C), and can also mix and use 2 or more types.

When (gamma) -butyrolactone is used as (C) solvent, It is preferable that (C) solvent contains 20 mass%-40 mass% of (gamma) -butyrolactone. By making content of (gamma) -butyrolactone into such a range, the melted state of (A) resin in the radiation sensitive resin composition of this embodiment can be suitably maintained, and coating property can be improved.

Here, when the compound mentioned above is used as a solvent (C), they are low hygroscopic compared with NMP. Therefore, the radiation sensitive resin composition of this embodiment can be prepared using a low hygroscopic solvent without using NMP having high hygroscopicity. As a result, the radiation sensitive resin composition of this embodiment can exhibit low hygroscopicity. Moreover, the above-mentioned (C) solvent is high in safety and can provide the radiation sensitive resin composition of this embodiment with high safety.

And when using for the same (C) solvent as the polymerization solvent mentioned above, after synthesize | combining (A) resin and precipitating them, it isolates (A) resin, and of the radiation sensitive resin composition of this embodiment. It becomes possible to use for preparation. That is, when using said thing as (C) solvent, it can isolate | separate after synthesize | combining (A) resin and can make unnecessary the process of re-dissolving in another solvent. As a result, the concern about the increase in the number of steps in the production of the organic EL element and the accompanying decrease in productivity is reduced.

[Other additives]

The radiation sensitive resin composition of this embodiment can be made to contain other additives, such as an adhesion | attachment adjuvant and surfactant, as needed in the range which does not impair the effect of this invention.

(Adhesive preparation)

In order to improve adhesiveness with a board | substrate, the radiation sensitive resin composition of this embodiment can also be made to contain an adhesion | attachment adjuvant. As the adhesion aid, a functional silane coupling agent is effective. Here, a functional silane coupling agent means the silane coupling agent which has reactive substituents, such as a carbonyl group, a methacryloyl group, an isocyanate group, an epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. It is preferable that content of an adhesion | attachment adjuvant shall be 10 mass parts or less with respect to 100 mass parts of (A) resin.

(Surfactants)

The radiation-sensitive resin composition of the present embodiment may contain a surfactant for the purpose of improving agent properties such as coating property, antifoaming property and leveling property. As the surfactant, for example, BM-1000, BM-1100 (above, manufactured by BM Chemi Corporation), Mega Pack (MEGAFACE) (registered trademark) F142D, copper F172, copper F173, copper F183 (or more, DIC) Company), Fluorad (Fluorad) FC-135, copper FC-170C, copper FC-430, copper FC-431 (above, Sumitomo 3M company make), SURFLON (registered trademark) S-112, copper S-113, copper S-131, copper S-141, copper S-145 (above, AGC Seimi Chemical Co., Ltd.), SH-28PA, copper-190, copper-193, SZ-6032, SF-8428 (more Fluorine-based surfactants such as those manufactured by Toray Dow Corning Silicon Co., Ltd.) can be used. It is preferable to make content of surfactant into 5 mass parts or less with respect to 100 mass parts of (A) resin.

Although the radiation sensitive resin composition of this embodiment contains each above component, the ratio of components other than (C) solvent (that is, the total amount of (A) resin, (B) quinonediazide compound, and other additives) Although silver can be arbitrarily set according to a purpose of use, a desired film thickness, etc., Preferably it is 5 mass%-50 mass%, More preferably, 10 mass%-40 mass%, More preferably, 15 mass%-35 mass% to be. The radiation sensitive resin composition thus prepared may be used for use after being filtered using a Millipore filter or the like having a pore size of about 0.2 μm.

<Formation of Insulation Film>

Next, the method of forming the insulating film of this embodiment is demonstrated using the radiation sensitive resin composition of this embodiment mentioned above. The method of forming the insulating film of this embodiment can be comprised including the following processes as a main process and in the following procedure.

(1) Process of forming the coating film of the radiation sensitive resin composition of this embodiment on a board | substrate (Hereinafter, it may only be called a coating film formation process.),

(2) Process of irradiating at least a part of coating film formed in process (1) (Hereinafter, it may only be called radiation irradiation process),

(3) Process of developing the coating film irradiated with the radiation in process (2) (Hereinafter, it may only be called development process),

(4) A step of heating the coating film developed in step (3) (hereinafter, may be simply referred to as a heating step).

Hereinafter, each process of (1)-(4) is demonstrated in more detail.

(1) Coating film formation process

In the above-mentioned (1) coating film formation process, the radiation sensitive resin composition of this embodiment is apply | coated to the surface of a board | substrate, Preferably the component used as a solvent is removed by prebaking, and the coating film of a radiation sensitive resin composition To form. As a kind of substrate which can be used, a resin substrate, a glass substrate, and a silicon wafer are mentioned, for example. And the board | substrate with which TFT and its wiring was formed is mentioned, for example used for formation of an organic electroluminescent display element.

The coating 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 rotary coating method (also called a spin coating method), a slit die coating method, a bar coating method, An appropriate method such as an inkjet method can be adopted. Among these coating methods, the spin coating method and the slit die coating method are particularly preferable. As conditions of prebaking, although it changes also with the kind, usage ratio, etc. of each component, heating time can be made into about 30 to 15 minutes at 60 degreeC-110 degreeC, for example. As a film thickness of the coating film formed, it can be set to 1 micrometer-10 micrometers as a value after prebaking.

(2) irradiation process

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

Examples of the ultraviolet ray mentioned above include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example. Among these radiations, ultraviolet rays are preferable, and radiation including g rays and / or i rays is particularly preferred among the ultraviolet rays. As an exposure amount, it is preferable to set it as 50J / m <2> -1500J / m <2>.

(3) Development process

(3) In the developing step, the coating film irradiated with the radiation in the above (2) irradiation step can be developed, and the irradiation portion of the radiation can be removed to form a desired pattern. Examples of the developer used for the developing treatment include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n. -Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5, Aqueous solutions of alkali (basic compounds) such as 4,0] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonane can be used. Moreover, the developing solution contains the aqueous solution which added a suitable amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, and various organic solvents which melt | dissolve the radiation sensitive resin composition of this embodiment to the aqueous solution of the above-mentioned alkali, a developing solution. It can be used as. As this organic solvent, what was illustrated as the polymerization solvent for obtaining above-mentioned (A) resin can be used.

As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method, a shower method, or the like can be used. Although image development time changes with compositions of a radiation sensitive resin composition, it can be set as 30 seconds-120 seconds, for example.

(4) Heating process

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

Subsequently, preferably, the whole surface is irradiated (post-exposure) with radiation by a high-pressure mercury lamp or the like, so as to decompose the 1,2-quinonediazide compound remaining in the coating film. Subsequently, this coating film is heat-processed (post-baking process) using heating apparatuses, such as a hotplate and oven, and hardening of a coating film is performed and the insulating film of this embodiment is obtained. The exposure amount in the post-exposure described above is preferably about 2000 J / m 2 to 5000 J / m 2. In addition, the heating temperature in this hardening process is 120 degreeC-250 degreeC, for example. Although heating time changes with kinds of a heating apparatus, it can be set as 5 minutes-30 minutes, when performing heat processing on a hotplate, and 30 minutes-90 minutes when heat processing in an oven. At this time, the step baking method etc. which perform two or more heating processes can also be used. In this way, the insulating film of the target pattern can be formed on a board | substrate.

The insulating film formed as mentioned above has a low water absorption structure as a constituent material, and is low water absorption, can also process using a low hygroscopic compound also in a manufacturing process, and has favorable moisture absorption characteristics (absorbency). In addition, PGMEA cleaning properties, permeability, heat resistance, patterning properties, patterning shape characteristics, development margin characteristics, solvent resistance, radiation sensitivity, resolution, etc., which enable cleaning using a PGMEA solvent, exhibit good characteristics, and are organic EL. Besides the insulating film which forms a partition of an element, it can use suitably as an insulating film with the above-mentioned flattening function.

&Lt; Organic EL device &

As an organic electroluminescent element of this embodiment, the example of the organic electroluminescent display element of this embodiment is demonstrated using drawing.

1 is a cross-sectional view schematically illustrating a structure of main parts of the organic EL display element of the present embodiment.

The organic EL display element 1 of the present embodiment is an active matrix 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 has a thin film transistor (hereinafter also referred to as TFT) 3 as 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, since the substrate 2 is required to be transparent, as an example of the material of the substrate 2, Transparent resins, such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PI (polyimide), glass, such as an alkali free glass, etc. are used. On the other hand, when the organic EL display element 1 is a top emission type, since the substrate 2 does not need to be transparent, any insulator can be used as the material of the substrate 2. It is also possible to use glass materials, such as an alkali free glass, similarly to a bottom emission type.

The TFT 3 includes a gate electrode 4 that forms part of a scanning signal line (not shown) on the substrate 2, a gate insulating film 5 that covers the gate electrode 4, and a gate electrode 4. A semiconductor layer 6 disposed on the semiconductor layer 5 via the gate insulating film 5, a first source-drain electrode 7 forming part of an image signal line (not shown) and connecting to the semiconductor layer 6; It is comprised with the 2nd source-drain electrode 8 connected to the semiconductor layer 6.

The gate electrode 4 can be formed by forming a metal thin film on the substrate 2 by a vapor deposition method, a sputtering method, or the like, and patterning using an etching process. Moreover, it is also possible to pattern and use a metal oxide conductive film or an organic conductive film.

Examples of the material of the metal thin film constituting the gate electrode 4 include aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium Au, tungsten (W) and silver (Ag), alloys of these metals, and alloys such as Al-Nd and APC alloys (silver, palladium and copper alloys). And as a metal thin film, it is also possible to use the laminated film which consists of layers of different materials, such as a laminated film of Al and Mo.

Examples of the material of the metal oxide conductive film constituting the gate electrode 4 include metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, ITO (indium dope tin oxide) and zinc indium oxide (IZO). have.

In addition, examples of the material of 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 to cover the gate electrode 4 can be formed by forming an oxide film or a nitride film by a sputtering method, a CVD method, a vapor deposition method, or the like. The gate insulating film 5 can be formed by using a metal oxide such as SiO ₂ or a metal nitride such as SiN alone or by laminating them. Moreover, it is also possible to comprise with organic materials, such as a polymeric material. As the film thickness of the gate insulating film 5, 10 nm-10 micrometers are preferable, Especially, when using inorganic materials, such as a metal oxide, 10 nm-1000 nm are preferable, When using an organic material, 50 nm-10 Μm is preferred.

The first source-drain electrode 7 and the second source-drain electrode 8 to be connected to the semiconductor layer 6 may be formed by the sputtering method or the CVD method, in addition to the printing method and the coating method. After forming using a method such as a vapor deposition method, it can be formed by performing a patterning using a photolithography method or the like. As the constituent material of the first source-drain electrode 7 and the second source-drain electrode 8, for example, metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, Metal alloys, and alloys such as Al-Nd and APC. In addition, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum dope zinc oxide) and GZO (gallium doped zinc oxide), polyaniline, polythiophene and polypyrrole And the like. And as a conductive film which comprises these electrodes, it is also possible to use the laminated film which consists of layers of materials different from the laminated film of Ti and Al.

The thickness of the first source-drain electrode 7 and the second source-drain electrode 8 is preferably 10 nm to 1000 nm.

The semiconductor layer 6 may be formed of a-Si (amorphous-silicon) in an amorphous state or p-Si (polysilicon) or the like obtained by crystallizing a-Si by an excimer laser or solid- , Or a silicon (Si) material.

In addition, 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 single crystal oxides, polycrystalline oxides, amorphous oxides, and mixtures thereof. As a polycrystal oxide, zinc oxide (ZnO) etc. are mentioned, for example.

Examples of the amorphous oxide applicable to the semiconductor layer 6 include amorphous oxides composed of at least one kind of element selected from indium (In), zinc (Zn) and tin (Sn).

Specific examples of the amorphous oxide applicable to the semiconductor layer 6 include Sn-In-Zn oxide, In-Ga-Zn oxide (IGZO: Indium Gallium Zinc Oxide), In-Zn-Ga-Mg oxide, Zn-Sn oxide ( ZTO: zinc oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga oxide, Sn-In-Zn oxide, etc. have. In addition, in the above case, the composition ratio of the constituent material does not necessarily need to be 1: 1, and the composition ratio can be selected to realize desired characteristics.

For example, when the semiconductor layer 6 using amorphous oxide is formed using IGZO or ZTO, a semiconductor layer is formed by a sputtering method or a vapor deposition method using an IGZO target or a ZTO target, and the photolithography method or the like. It is formed by patterning by a resist process and an etching process by using. The thickness of the semiconductor layer 6 using the amorphous oxide is preferably 1 nm to 1000 nm.

When the above-described oxide is used for the semiconductor layer 6 of the TFT 3, the first source-drain electrode 7 and the second source-drain electrode 8 on the upper surface of the semiconductor layer 6 are not formed. in that region, for example, it is preferable to form a protective layer (not shown) made of SiO ₂ having a thickness of 5㎚~80㎚. This protective layer may be called an etching stop layer, a stop layer, or the like.

By using the oxides exemplified above, the high mobility semiconductor layer 6 can be formed at low temperature, and the TFT 3 having excellent performance can be provided.

And as an especially preferable oxide in forming the semiconductor layer 6 of the organic electroluminescent display element 1 of this embodiment, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and oxidation Indium zinc (ZIO).

By using these oxides, the TFT 3 can form the semiconductor layer 6 which is excellent in mobility at a lower temperature, and can exhibit a high ON / OFF ratio.

The inorganic insulating film 19 can be formed on the TFT 3 so as to cover the TFT 3. The inorganic insulating film 19 can be formed by using a metal oxide such as SiO ₂ or a metal nitride such as SiN alone or by laminating them. The inorganic insulating film 19 is formed to protect the semiconductor layer 6 and to be prevented from being affected by humidity, for example. In the organic EL display element 1 of the present embodiment, the inorganic insulating film 19 is not formed, and the first insulating film 10, which is an insulating film made of an organic material, described later, is disposed on the TFT 3. It is also 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 upper portion of the TFT 3 on the substrate 2. This first insulating film 10 has a function of flattening the unevenness caused by the TFT 3 formed on the substrate 2. The 1st insulating film 10 is an insulating cured film formed using the radiation sensitive resin composition of this embodiment mentioned above, and is an organic insulating film formed using the organic material. The first insulating film 10 preferably has an excellent function as a planarization film, and is preferably formed thick in this respect. For example, the first insulating film 10 can be formed to a thickness of 1 m to 6 m. The first insulating film 10 is formed in accordance with the method of forming the insulating film described above.

The anode 11 constituting the pixel electrode is disposed on the first insulating film 10. The anode 11 is made of a conductive material. It is preferable to select the material of the anode 11 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 TinOxide), IZO (Indium Zinc Oxide), tin oxide, etc. are selected as the material of the anode 11. On the other hand, when the organic EL display element 1 is a top emission type, light reflectivity is required for the anode 11, and the material of the anode 11 is APC alloy (alloy of silver, palladium, copper) or ARA ( Silver, rubidium, gold alloy), MoCr (alloy of molybdenum and chromium), NiCr (alloy of nickel and chromium), etc. 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, the first insulating film 10 is provided with the through holes 12 Is formed. The through hole 12 is also formed so as to 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, according to the method of forming the insulating film described above, after irradiating the coating film of the radiation-sensitive resin composition to form the first insulating film 10 having a through hole of a desired shape, the first insulating film 10 is formed. The through hole 12 can be completed by performing dry etching on the inorganic insulating film 19 using the mask as a mask. In the case where the inorganic insulating film 19 is not disposed on the TFT 3, the 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 portion of the first insulating film 10 and passes through the through hole 12 formed in the first insulating film 10 so as to pass through the first insulating film 10. It can connect with the 2nd source-drain electrode 8 connected to (3).

In the organic EL display element 1, on the anode 11 on the first insulating film 10, a second insulating film 13 serving as a partition wall defining an arrangement area of the organic light emitting layer 14 is formed. The 2nd insulating film 13 can be manufactured as a cured film by patterning a coating film according to the formation method of the insulating film mentioned above using the radiation sensitive resin composition of this embodiment mentioned above, For example, from a plane When viewed, it may have a shape that is lattice-shaped. In the region defined by the second insulating film 13, an organic light emitting layer 14 for electroluminescence is disposed. In the organic EL display element 1, the second insulating film 13 serves as a barrier surrounding 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 arrangement region of the organic light emitting layer 14) is It is preferable that it is 0.1 micrometer-2 micrometers, and it is more preferable that it is 0.8 micrometer-1.2 micrometers. When the height of the second insulating film 13 is 2 μm or more, there is a fear that the sealing substrate 20 is bumped above the second insulating film 13. Moreover, when the height of the 2nd insulating film 13 was 0.1 micrometer or less, when it tries to apply | coat the light emitting material composition of the ink state by the inkjet method in the area | region prescribed | regulated by the 2nd insulating film 13, There is a risk of leakage from the second insulating film 13.

The second insulating film 13 of the organic EL display element 1 is cured by applying a pattern or the like to the coating film according to the method of forming the insulating film described above using the radiation-sensitive resin composition of the present embodiment described above. It can be formed as a film. That is, the second insulating film 13 may be made of resin. When the light emitting material composition in the ink state is applied by the ink jet method, the second insulating film 13 has a low wettability property in that it defines the region to which the light emitting material composition in the ink state including the organic light emitting material is applied desirable. In the case where the wettability of the second insulating film 13 is controlled to be particularly low, it is possible to plasma-treat the second insulating film 13 with fluorine gas, and the radiation-sensitive radiation of the present embodiment to form the second insulating film 13. You may make it contain a liquid repellent in the resin composition. Since the plasma treatment may adversely affect other constituent members of the organic EL display element 1, it is preferable to include the liquid repellent in the radiation-sensitive resin composition of the present embodiment for forming the second insulating film 13. There is.

In the region defined by the second insulating film 13, an organic light emitting layer 14 to which an electric field is applied to emit light is disposed. The organic luminescent layer 14 is a layer containing an electroluminescent material for electroluminescence.

The organic luminescent material contained in the organic luminescent layer 14 may be a low molecular weight organic luminescent material or a high molecular weight organic luminescent material. For example, Alq _3, BeBq the base matrix, such as ₃ can be used quinazoline Clichy money or material doped with the coumarin. Moreover, when using the coating method of the organic light emitting material by the inkjet method, it is preferable that it is a polymeric organic light emitting material suitable for it. As the polymer organic light emitting material, for example, polyphenylene vinylene and its derivatives, poly acetylene and its derivatives, poly phenylene and its derivatives, poly paraphenylene ethylene ) And derivatives thereof, poly 3-hexyl thiophene (P3HT) and derivatives thereof, poly fluorene (PF) and derivatives thereof, and the like.

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

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

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

The organic EL display element 1 of the present 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 a top emission type, it is preferable that the cathode 15 is an ITO electrode, an IZO electrode, etc. which comprise a visible ray permeable electrode. On the other hand, when the organic EL display element 1 is a bottom emission type, the cathode 15 does not need 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, and for example, barium Ba, barium oxide (BaO), aluminum (Al) Do.

An electron injection layer made of barium Ba or lithium fluoride (LiF) may be disposed between the cathode 15 and the organic light emitting layer 14, for example.

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

The main surface of the substrate 2 configured as described above in which the organic light emitting layer 14 is disposed is interposed between the sealing layer 17 using a sealing agent (not shown) applied near the outer peripheral end thereof. It is preferable to seal by the sealing substrate 20. The sealing layer 17 can be a layer of inert gas, such as dried nitrogen gas, or a layer of filling materials, such as an adhesive agent. As the sealing substrate 20, a glass substrate such as alkali-free 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 the constituents, use the radiation-sensitive resin composition of the present embodiment having low hygroscopicity. Formed, and has a low absorption structure. Moreover, in the formation process, processing, such as washing | cleaning using a low hygroscopic material, is possible. Therefore, it is possible to reduce the intrusion of a small amount of moisture contained in the insulating film forming material in the form of adsorption water into the organic light emitting layer gradually, and to reduce the degradation of the organic light emitting layer and the inhibition of the light emission state.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described based on an Example, this invention is not limitedly interpreted by this Example.

The solution viscosity of each resin solution in a synthesis example, and the imidation ratio of polyimide resin were measured by the following method.

[Solution Viscosity of Resin Solution]

The solution viscosity (mPa * s) of the resin solution was measured at 25 degreeC using the E-type rotational viscometer about the solution adjusted to 10 mass% of resin concentration using the positive solvent of this resin.

[Imidization Rate of Polyimide]

The solution of polyimide was put into pure water, and the obtained precipitate was dried under reduced pressure sufficiently at room temperature, 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 rate was determined by the equation shown by the following formula (1).

Imidation ratio (%) = {(1-A ¹ ) / (A ² × α)} × 100 (1)

(In Formula (1), A <^1> is the peak area derived from the proton of the NH group which shows around 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polyimide. It is number ratio of other protons to one proton of NH group of.)

<Synthesis of resin>

(Synthesis Example 1)

The polyimide is synthesized as a resin containing a polyimide structure or the like.

After adding 80 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to a reaction container, it superposes | polymerizes diamine compound and tetracarboxylic acid dianhydride which is tetracarboxylic acid derivative so that solid content concentration may be 20 mass% with respect to 80 g of polymerization solvents in total. More of the solvent. In this example, as the diamine compound, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was used to dissolve it, and then 2,2 as tetracarboxylic dianhydride. 3,5-tricarboxycyclopentylacetic dianhydride (TCA) and 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester (TMHQ) The composition of carboxylic acid dianhydride was added so that TCA: TMHQ = 95: 5 (molar ratio). And 90 mol part of tetracarboxylic dianhydride was added with respect to 100 mol parts of total amounts of a diamine compound. Then, this mixture was made to react at 60 degreeC for 3 hours. This obtained about 100 g of polyamic acid solutions of 20 mass% of solid content concentration and 100 mPa * s of solution viscosity.

Subsequently, for imidization, pyridine and acetic anhydride were added to 900 mol parts of pyridine and 400 mol parts of acetic anhydride with respect to 100 mol parts of total amounts of tetracarboxylic dianhydride and dehydrated and closed for 4 hours at 110 ° C. . After the imidation reaction, the pyridine and acetic anhydride used for the imidation reaction were removed by the evaporator out of the reaction system. This obtained the polyimide (resin (A-1)) of 70% of imidation ratio, and obtained the resin solution of about 100 g of 20 mass% of solid content concentration, and the solution viscosity of 28 mPa * s.

Synthesis Example 2 to Synthesis Example 20 and Comparative Synthesis Example 1

In the synthesis examples 2 to 20, the polyimide (resin ( Solutions containing A-2) to (A-20)) were prepared, respectively.

In Comparative Synthesis Example 1, polyamic acid (resin (A -21)) was prepared a resin solution.

In addition, in Table 1, "molar ratio" with respect to a tetracarboxylic acid derivative shows the content rate (molar ratio) with respect to the total amount of the tetracarboxylic acid derivative used for synthesis.

The compounding component which the symbol of following Table 1 shows is respectively as follows.

[Polymerization Solvent]

PGMEA: propylene glycol monoethyl ether acetate

EDM: diethylene glycol ethyl methyl ether

BL:? -Butyrolactone

NMP: N-methylpyrrolidone

[Diamine]

BAHF: 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

[Tetracarboxylic acid dianhydride]

TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

TMHQ: 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester

BT-100: 1,2,3,4-butanetetracarboxylic anhydride

BTA: Bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride

PMDA-HS:

CB: cyclobutane tetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

<Preparation of radiation sensitive resin composition>

(Example 1)

The amount equivalent to 100 mass parts (solid content) of resin containing the resin solution containing resin (A-1) of the synthesis example 1, and the resin solution containing resin (A-2) of the synthesis example 2 as a component [A]. (Mass ratio of resin (A-1) and resin (A-2) is 80 to 20), and 4,4 '-[1- {4- (1- [4-hydroxyphenyl) which is the [B] component ] -1-methylethyl) phenyl} ethylidene] bisphenol (1.0 mol) 20 parts by mass of a condensate of 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol), trimethylol as the [C] component 5 parts by mass of propanepolyglycidyl ether, 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane as the [D] component, and 0.01 parts by mass of SH8400 manufactured by Toray Dow Corning as the [E] component are mixed, [F] Preparation was carried out using γ-butyrolactone (BL) and propylene glycol monoethyl ether acetate (PGMEA) as components, so that the solid content concentration was 28% by mass, and the mass ratio of BL and PGMEA contained was 30 to 70. As far as possible And, to the mixture was filtered through a milli pore filter having a pore size 0.2㎛, to prepare a radiation-sensitive resin composition (S-1).

(Examples 2 to 10 and Comparative Example 1)

[A] component and [F] component are used in the kind and quantity as shown in Table 2, and [B] component, [C] component, [D] component, and [E] component are shown in Table 2, Using the same quantity, the radiation sensitive resin composition (S-2)-(S-10) was prepared like Example 1.

And as a component [A], the resin solution containing resin (A-21) of the comparative synthesis example 1, and N-methylpyrrolidone (NMP) as an [F] component are used by the quantity shown in Table 2, and [ The radiation sensitive resin composition (S-11) was prepared like Example 1 using the component B], the component [C], the component [D], and the component [E] in the amounts as described in Table 2. .

<Performance evaluation as an insulating film>

(Example 11)

The various characteristics as an insulating film were evaluated as follows using the radiation sensitive resin composition of the Example and comparative example which were prepared as mentioned above.

[Evaluation of Absorbency]

After applying each radiation sensitive resin composition of Table 2 to a silicon substrate using the spinner about the radiation sensitive resin composition of Table 2, it prebaked on a hotplate for 2 minutes at 120 degreeC, and then in a clean oven. It post-baked at 250 degreeC for 45 minutes, and formed the insulating film as a cured film with a film thickness of 3.0 micrometers. A mass spectrometer was used to detect the surface of the insulating film sample and the gas detached from the insulating film sample when the temperature was raised from room temperature to 200 ° C. using TDS (Thermal Desorption Spectroscopy) on the formed insulating film to detect the peak M / z of water. Value was measured and water absorption was evaluated. When total peak intensity was ^7.0x10-9 or less, water absorption was made into "good | favorableness." When the total peak intensity was higher than 7.0 × 10 ⁻⁹ , the absorptivity was defined as “poor”.

[Evaluation of PGMEA Detergency]

Application | coating on the silicon substrate after 80 second shower-development using PGMEA solvent after apply | coating each radiation sensitive resin composition of Table 2 on a silicon substrate using a spinner about the radiation sensitive resin composition of Table 2 using a spinner The liquid state was confirmed. When all the coating film is melt | dissolved and cannot be visually confirmed, PGMEA cleaning property is set to "(circle)", and when a part of coating film is not melt | dissolved, PGMEA cleaning property is set to "(triangle | delta)", × ”.

[Evaluation of permeability]

The above-mentioned [evaluation of absorbency] except having used the glass substrate "Corning 7059 (made by Corning)" instead of a silicon substrate using the radiation sensitive resin composition (except S-11) of Table 2 Similarly, the insulating film was formed on the glass substrate as a cured film. Using the spectrophotometer "150-20 type double beam (made by Hitachi, Ltd.)", the total light transmittance of the glass substrate which has this insulating film was measured in the wavelength of 380 nm-780 nm. The total 400 nm transmittance was measured. The result is shown in following Table 3 as "permeability%."

[Evaluation of heat resistance]

Using the radiation sensitive resin composition (except S-11) shown in Table 2, an insulating film was formed in the same manner as in the above [absorbency evaluation], and a thermogravimetric measuring device (manufactured by TA Instruments Inc.) was obtained. Using TGA 2950, TGA measurement (under air, temperature increase rate of 10 ° C./min) was performed. When the weight reduction in 10 degreeC to 300 degreeC was within 5%, heat resistance was made into "good | favorableness", and when it exceeded, it was set as "defective."

[Patternity Evaluation]

Using a spinner, the radiation-sensitive resin composition (except S-11) shown in Table 2 was applied onto a silicon substrate, and then prebaked at 120 ° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. did. The obtained coating film was exposed to light by changing the exposure time through a pattern mask having a predetermined pattern using a Canon PLA-501F exposure machine (ultra high pressure mercury lamp), followed by 2.38% tetramethylammonium hydroxide. It developed by the puddle method at 25 degreeC and 80 second in aqueous side solution. Subsequently, flowing water was washed for 1 minute with ultrapure water, and dried to form a pattern on the wafer. It was confirmed whether the space pattern of the line and space (10: 1) of 20.0 micrometers melt | dissolved completely. It was judged as "good" that the image development residual film rate was 60% or more, and the pattern was not peeled off, and it was set as "defect" that the image residual film rate after development was less than 60%, or the pattern peeled off and was not formed.

[Pattern shape evaluation (taper angle measurement)]

Using the radiation sensitive resin composition (except S-11) of Table 2, except having used the mask of a 20 micrometer line and space pattern (1 to 1), it carried out similarly to the above [pattern evaluation], A pattern was formed on it. The obtained pattern was heated and hardened at 250 degreeC for 45 minutes in the clean oven, and the insulating film of 3 micrometers of film thicknesses was obtained. In the insulating film thus obtained, the cross-sectional shape of the 20 µm line pattern was observed by SEM. At this time, the angle (taper angle) with respect to the board | substrate of cross-sectional shape was measured. The measurement result of a taper angle is shown in following Table 3 as a "taper angle (degree)."

[Evaluation of Developing Margin]

Using a spinner, the radiation-sensitive resin composition (except S-11) shown in Table 2 was applied onto a silicon substrate, and then prebaked at 120 ° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. did. About the obtained coating film, it uses the Canon-made PLA-501F exposure machine (ultra high pressure mercury lamp), and interposes the mask which has a pattern of a line-and-space (10: 1) of 3.0 micrometers, and mentions below [radiation sensitivity] The exposure was performed at an exposure amount corresponding to the value of the radiation sensitivity measured in [Evaluation], and the development time was changed by changing the developing time at 25 ° C. in a 2.38% aqueous tetramethylammonium hydroxide solution. Subsequently, flowing water was washed with ultrapure water for 1 minute, dried and a pattern was formed on a silicon substrate. At this time, the developing time required for the line line width to be 3.0 µm was evaluated as the optimum developing time. Subsequently, when developing was further continued from the optimum developing time, the time until the 3.0-micrometer line pattern was peeled off was measured and evaluated as developing margin (permissible range of developing time). When this value was 30 seconds or more, the developing margin was made "good".

[Evaluation of solvent resistance]

Using a spinner, the radiation-sensitive resin composition (except S-11) shown in Table 2 was applied onto a silicon substrate, and then prebaked at 120 ° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. did. The obtained coating film was heated at 220 degreeC in clean oven for 1 hour, and the insulating film was obtained as a cured film. The film thickness T1 of the obtained insulating film was measured. After the silicon substrate on which the insulating film is formed is immersed in dimethyl sulfoxide controlled at 70 ° C. for 20 minutes, the film thickness t1 of the insulating film on the silicon substrate is measured, and the film thickness change rate due to the immersion {| t1 − T1 | / T1} x100 [%] was computed. When the value of the film thickness change rate was 4% or less, the solvent resistance was "good". In addition, since the patterning of the film to form is unnecessary in evaluation of solvent resistance, the irradiation process and the image development process were abbreviate | omitted, and only the coating film formation process and the heating process were performed for evaluation.

[Evaluation of Radiation Sensitivity]

Using a spinner, the radiation-sensitive resin composition (except S-11) shown in Table 2 was applied onto a silicon substrate, and then prebaked at 120 ° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. did. The obtained coating film was exposed to light after changing exposure time through a pattern mask having a predetermined pattern using a Canon PLA-501F exposure machine (ultra high pressure mercury lamp), followed by 2.38% tetramethylammonium hydroxide. It developed by the puddle method at 25 degreeC and 80 second in aqueous side solution. Subsequently, flowing water was washed for 1 minute with ultrapure water, and dried to form a pattern on the wafer. The exposure amount required in order for the space pattern of the line and space (10: 1) of 20.0 micrometers to melt | dissolve completely was measured. This value was evaluated as radiation sensitivity (exposure sensitivity), and is shown in following Table 3. When this value was 300 J / m <2> or less, the sensitivity was made "good".

[Evaluation of resolution]

Using a spinner, the radiation-sensitive resin composition (except S-11) shown in Table 2 was applied onto a silicon substrate, and then prebaked at 120 ° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. did. The obtained coating film was exposed to light after changing exposure time through a pattern mask having a predetermined pattern using a Canon PLA-501F exposure machine (ultra high pressure mercury lamp), followed by 2.38% tetramethylammonium hydroxide. It developed by the puddle method at 25 degreeC and 80 second in aqueous side solution. Subsequently, flowing water was washed for 1 minute with ultrapure water, and dried to form a pattern on the wafer. The minimum of the formed pattern width was evaluated, and it showed in Table 3 about this minimum. As shown in the following Table 3, the lower limit showed the outstanding resolution.

The result of the performance evaluation of the insulating film formed using the radiation sensitive resin composition of Table 2 mentioned above was put together in Table 3 below. In addition, in the column which shows an Example in Table 3, each radiation sensitive resin composition of Example 1-Example 10 and Comparative Example 1 was written together as "(composition)."

As shown in said Table 3, the insulating film formed using the radiation sensitive resin composition ((S-1)-(S-10)) of Examples 1-10 has favorable water absorption. In addition, in terms of PGMEA cleaning property, permeability, heat resistance, patterning property, pattern shape property, development margin property, solvent resistance, radiation sensitivity, resolution, and the like, the insulating film and the planarizing film forming the partition of the organic EL device are exhibited. It turned out that it can use suitably as an insulating film with a function.

The organic EL element of this invention can enlarge the effective area of the organic light emitting layer in a pixel, and can manufacture it with high productivity. And performance degradation by impurities, such as moisture, can be reduced. Therefore, the organic electroluminescent element of this invention can be used suitably for the display element of large flat-panel televisions and portable information devices which require the outstanding display quality and reliability.

1: organic EL display element
2: substrate
3: TFT
4: gate electrode
5: gate insulating film
6: semiconductor layer
7: first source-drain electrode
8: second source-drain electrode
10: First insulating film
11: anode
12: Through hole
13: second insulating film
14: organic light emitting layer
15: cathode
16: passivation film
17: sealing layer
19: Inorganic insulating film
20: sealing substrate

Claims (9)

(A) Resin containing at least 1 sort (s) chosen from the group which consists of a polyimide structure, a polyimide precursor structure, and a polyamic acid ester structure,
(B) quinonediazide compound,
(C) solvent
And a radiation sensitive resin composition which is used for formation of an insulating film of an organic EL element,
(C) at least a solvent 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 A radiation sensitive resin composition containing 1 type and (gamma) -butyrolactone. The method of claim 1,
The radiation sensitive resin composition characterized by the polyimide structure of (A) component containing the repeating unit represented by following formula (1):

(In formula (1), R <_1> is bivalent group containing at least one of a C1-C12 alkyl group and a phenyl group, and R <_2> is a bivalent group which has a hydroxyl group.). 3. The method of claim 2,
R <_2> in said Formula (1) is a bivalent group represented by either of the following formulas, The radiation sensitive resin composition characterized by the above-mentioned.

4. The method according to any one of claims 1 to 3,
The radiation sensitive resin composition characterized by the polyimide structure of (A) component containing the repeating unit represented by following General formula (2):

(In formula (2), R <_3> is a bivalent group which has a hydroxyl group, X is a tetravalent group represented by either of following formula.).

5. The method of claim 4,
R <_3> in said Formula (2) is a divalent group represented by either of the following formulas, The radiation sensitive resin composition characterized by the above-mentioned.

4. The method according to any one of claims 1 to 3,
The solvent (C) contains 20 mass%-40 mass% of (gamma) -butyrolactone, The radiation sensitive resin composition characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
Furthermore, content of N-methylpyrrolidone of (C) solvent is 5 mass% or less, The radiation sensitive resin composition characterized by the above-mentioned. It is formed using the radiation sensitive resin composition in any one of Claims 1-3, and is used for organic electroluminescent element, The insulating film characterized by the above-mentioned. The organic electroluminescent element which has the insulating film of Claim 8.

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