JP2005139433A - Light resistant resin composition and organic electroluminescent device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light resistant resin composition having excellent retention characteristics of voltage resistance property for a long time to inevitable illumination in daily application. <P>SOLUTION: The light resistant resin composition contains a light stabilizer and a cured resin film of the resin composition having 0.05-20μm film thickness satisfies ≥150kV/mm dielectric breakdown voltage after 500 hours treatment by irradiation with a xenon arc lamp. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is suitable for a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescent element, etc., and has a light-resistant resin composition having excellent withstand voltage resistance even under long-time light irradiation, and uses thereof. The present invention relates to an organic electroluminescent device.

  An inorganic film such as a silicon oxide film or an organic resin such as polyimide, novolac resin, or acrylic resin has been used for a surface protective film and an interlayer insulating film of a semiconductor element, and an insulating film of an organic electroluminescent element. Since the silicon oxide film is an inorganic film, there is a problem in that a high process load is required, such as high temperature required for formation and etching using a photoresist as a mask for patterning. Further, an organic resin can be spin-coated, and then a film can be obtained by a process of patterning and heat treatment. Films obtained in this way are subject to light irradiation with ultraviolet rays for a long time due to the characteristics of their use, and the problem is that the insulation of the film is destroyed by such light irradiation and short-circuited. Therefore, there is a need for improved stability during light irradiation.

  For example, when the dielectric strength of an insulating layer provided in an organic electroluminescent element is reduced by light irradiation, current short-circuiting due to loss of the insulating layer or the like, or dielectric breakdown or current leakage occurs when the electric field is concentrated. The light resistance of the insulating layer is important because there is a problem that the phenomenon easily occurs.

Up to now, there is an example in which the light resistance of a hard coat film is improved by using an ultraviolet-absorbing acrylic resin for a hard coat film used for a touch panel such as a membrane switch of an electric product or a cash dispenser (for example, (See Patent Document 1). However, there are no examples of light resistance in organic insulating film applications such as surface protective films and interlayer insulating films of semiconductor elements and insulating layers of organic electroluminescent elements, and the effect on the voltage resistance by the addition of light stabilizers Not sure.
JP 2002-166502 A (Claims 1 to 5)

  An object of this invention is to provide the light-resistant resin composition which has the long-term holding property of the outstanding voltage resistance with respect to the light irradiation which cannot be avoided as a daily use.

  That is, the present invention is a resin composition containing a light stabilizer, and the resin composition is a cured resin film having a thickness of 0.05 to 20 μm, and after irradiation treatment with a xenon arc lamp for 500 hours. A light-resistant resin composition having a dielectric breakdown voltage of 150 kV / mm or more.

  The light-resistant resin composition of the present invention can reduce and suppress the voltage resistance due to sunlight irradiation, and the dielectric breakdown voltage is hardly lowered even when used for a long time under sunlight.

  As a result of intensive studies, the present inventors have found that the use of a resin composition containing a light stabilizer can easily suppress a decrease in voltage resistance against light irradiation. Furthermore, by forming a composition containing photosensitive components such as a photoacid generator and a photopolymerization initiator in these, a necessary pattern can be obtained by photolithography, and an insulating film having necessary voltage resistance can be easily obtained. The present invention has been found. This composition is suitable for an in-vehicle organic EL device particularly requiring light resistance.

  The composition of the present invention has a light stabilizer, and the composition is made into a cured resin film having a film thickness of 0.05 to 20 μm, and irradiation using a xenon arc lamp that is irradiated with ultraviolet rays and visible rays. The composition is characterized in that the dielectric breakdown voltage after the treatment for 500 hours satisfies 150 kV / mm or more, more preferably 200 kV / mm or more. If the dielectric breakdown voltage is not satisfied, the insulation resistance is lowered by the voltage applied to the organic EL light emitting element, and a reliable element cannot be obtained. The dielectric breakdown voltage in the present invention may be any film thickness in the range of 0.05 to 20 μm and satisfy the specified dielectric breakdown voltage value. It is necessary to satisfy the dielectric breakdown voltage in all of the ranges. Absent.

  The polyimide resin having the structure of the following general formula (1) used in the present invention can be generally obtained by heat-treating a polyimide precursor obtained by reacting a tetracarboxylic acid anhydride and a diamine.

式中、Ｒ^１は少なくとも２個以上の炭素原子を有する４価の有機基、Ｒ^２は２価の有機基を示す。さらに、Ｒ^１、Ｒ^２の少なくともどちらか一方にケイ素原子を有する基をＲ^１もしくはＲ^２成分の１〜３０モル％含む。

In the formula, R ¹ represents a tetravalent organic group having at least two carbon atoms, and R ² represents a divalent organic group. ^Further, a group having R 1, at least one or the other to a silicon atom of ^{R 2} containing 1 to 30 mol% of ^{R 1} or ^{R 2} component.

  Examples of the precursor for obtaining the polyimide resin having the structure of the general formula (1) include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.

As the polyimide resin used in the present invention, a polyimide precursor obtained by reacting a tetracarboxylic acid and a diamine can be preferably used, in which case R ¹ in the general formula (1) is tetracarboxylic. The acid residue R ² represents a diamine residue.

  Specific examples of the acid dianhydride that can be used as a raw material for the polyimide of the general formula (1) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Anhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3 , 4-Dicarboxypheny ) Methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3 , 4,9,10-perylenetetracarboxylic dianhydride, aromatic tetracarboxylic dianhydrides such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic Examples thereof include aliphatic tetracarboxylic dianhydrides such as acid dianhydrides and 1,2,3,4-cyclopentanetetracarboxylic dianhydrides. These acid dianhydrides can be used alone or in combination of two or more.

  Specific examples of the diamine that can be used as a raw material for the polyimide of the general formula (1) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-amino Phenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, Bis (4-aminophenoxy) Phenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetra Methyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl Or compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like.

  Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene and the like are preferable. Particularly preferably, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diamino Diphenylsulfone, 1,4-bis (4-aminophenoxy) benzene. These diamines can be used alone or in combination of two or more.

The polyimide used in the present invention preferably has a hydroxyl group from the viewpoint of alkali solubility. More preferably, it has a phenolic hydroxyl group. If having a phenolic hydroxyl group, R ¹ component represented by the following general formula of general formula (1) (3) preferably has one or more kinds of structure (4).

式中、Ｒ^５、Ｒ^７は炭素数２〜２０の有機基、Ｒ^６は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基である。

In the formula, R ⁵ and R ⁷ are organic groups having 2 to 20 carbon atoms, and R ⁶ is an organic group having 6 to 30 carbon atoms having at least one aromatic ring.

式中、Ｒ^８、Ｒ^１０は炭素数２〜２０の有機基、Ｒ^９は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、ｐは１〜４までの整数である。

In the formula, R ⁸ and R ¹⁰ are organic groups having 2 to 20 carbon atoms, R ⁹ is an organic group having 6 to 30 carbon atoms having at least one aromatic ring, and p is an integer of 1 to 4.

As the R ² component having a phenolic hydroxyl group in the general formula (1), the structures of the following general formulas (5) to (10) can be given and are preferably used.

式中、Ｒ^１１、Ｒ^１３は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、Ｒ^１２は炭素数２〜２０の有機基である。

In the formula, R ¹¹ and R ¹³ are organic groups having 6 to 30 carbon atoms having at least one aromatic ring, and R ¹² is an organic group having 2 to 20 carbon atoms.

式中、Ｒ^１４、Ｒ^１６は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、Ｒ^１５は炭素数２〜２０の有機基、ｔ、ｕは１または２である。

In the formula, R ¹⁴ and R ¹⁶ are organic groups having 6 to 30 carbon atoms having at least one aromatic ring, R ¹⁵ is an organic group having 2 to 20 carbon atoms, and t and u are 1 or 2.

式中、Ｒ^１８は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、Ｒ^１７、Ｒ^１９は炭素数２〜２０の有機基である。

In the formula, R ¹⁸ is an organic group having 6 to 30 carbon atoms having at least one aromatic ring, and R ¹⁷ and R ¹⁹ are organic groups having 2 to 20 carbon atoms.

式中、Ｒ^２１は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、Ｒ^２０、Ｒ^２２は炭素数２〜２０の有機基、ｖは１〜４の整数である。

In the formula, R ²¹ is an organic group having 6 to 30 carbon atoms having at least one aromatic ring, R ²⁰ and R ²² are organic groups having 2 to 20 carbon atoms, and v is an integer of 1 to 4.

式中、Ｒ^２４は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、Ｒ^２３は炭素数２〜２０の有機基である。

In the formula, R ²⁴ is an organic group having 6 to 30 carbon atoms having at least one aromatic ring, and R ²³ is an organic group having 2 to 20 carbon atoms.

式中、Ｒ^２６は少なくとも１つの芳香族環を有する炭素数６〜３０の有機基、Ｒ^２５は炭素数２〜２０の有機基、ｗは１または２を表す。

In the formula, R ²⁶ represents an organic group having 6 to 30 carbon atoms having at least one aromatic ring, R ²⁵ represents an organic group having 2 to 20 carbon atoms, and w represents 1 or 2.

  Of the structures represented by the general formula (3), preferred structures are as follows.

一般式（４）で表される構造のうち、好ましい構造は下記のとおりである。

Of the structures represented by the general formula (4), preferred structures are as follows.

一般式（５）、（７）、（９）で表される構造のうち、好ましい構造は下記のとおりである。

Of the structures represented by the general formulas (5), (7) and (9), preferred structures are as follows.

一般式（６）、（８）、（１０）で表される構造のうち、好ましい構造は下記のとおりである。

Of the structures represented by the general formulas (6), (8) and (10), preferred structures are as follows.

本発明に使用するポリイミドは、一般式（１）の繰り返し構造のみを持つものであってもよく、上記した構造を適宜含むものであっても良い。

The polyimide used in the present invention may have only the repeating structure of the general formula (1) or may appropriately include the above-described structure.

  The end of the polyimide having the structure of the general formula (1) can be sealed with monoamine. Examples of such monoamines include 3-amino-4,6-dihydroxypyrimidine having a phenolic hydroxyl group, such as aniline, naphthylamine, aminopyridine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5 -Amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5 Aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2- Hydroxy-6-aminonaphthalene 1-carboxy-8-amino having a carboxyl group, such as 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene Naphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy 2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene 2-carboxy-3-aminona Talen, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, etc. , 5-amino-8-mercaptoquinoline having a thiol group, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminona Phthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto -5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol , 3-aminothiophenol, 4-aminothiophenol and the like.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferably used. These monoamines can be used alone or in combination of two or more.

  The terminal of the polyimide having the structure of the general formula (1) can be sealed with an acid anhydride, acid chloride, or monocarboxylic acid. Examples of such are phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4- Carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1- Hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto- -Carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2 -Monocarboxylic acids such as carboxybenzene sulfonic acid, 3-carboxybenzene sulfonic acid, 4-carboxybenzene sulfonic acid and the like, mono acid chloride compounds in which these carboxyl groups are acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexane Dicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarbo Sinaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene Mono-acid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as diacids is acid chloride, obtained by reaction of mono-acid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide Active ester compounds that can be used.

  Among these, phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, Only monocarboxylic groups of dicarboxylic acids such as phosphoric acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Is preferably a monoacid chloride compound obtained by acid chloride, an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. . These are used individually or in combination of 2 or more types.

  The amount of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid described above is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol% of the whole polyimide resin. is there.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer, and this is measured by gas chromatography (GC) or NMR measurement. The end capping agent can be easily detected. Apart from this, the resin into which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum and C ₁₃ NMR spectrum measurement.

  The polyimide resin used in the present invention can be dissolved in this state or in the form of a precursor in, for example, N-methylpyrrolidone, gamma-butyrolactone, or a solution obtained by mixing ethyl lactate or propylene glycol monomethyl ether acetate, etc. A naphthoquinone diazide sulfonate ester, triphenylsulfonium salt, diphenylsulfuronium salt, etc., which are generators, can be mixed to form a positive photosensitive resin composition precursor solution in which an exposed portion is dissolved in an alkaline developer. .

  Further, bisazides were added, and a photopolymerization initiator such as 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and Michlerketone and / or a sensitizer such as thioxanthone were combined and exposed. It can also be set as the negative photosensitive resin composition precursor solution in which a part remains. However, in terms of the shape of the pattern cross section to be obtained, it is preferable to give positive photosensitivity.

In addition to the polyimide resin used in the present invention, as a silicon component, a silane coupling agent such as trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, or R of the general formula (1) as ^one component, dimethylsilane di phthalate, 1,3-bis (phthalic acid) tetramethyl silicon atom-containing tetracarboxylic acid such as disiloxane or blended copolymer or 1 to 30 mol% of R ¹ component, R ² as component, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-anilino) silicon atom-containing diamine such as tetramethyldisiloxane and 1 to 30 mol% of ^{R 2} component Increase adhesion to substrates by copolymerization or blending At the same time, it is possible to increase resistance to cleaning treatments such as oxygen plasma and UV ozone.

  A cured film obtained by heat-treating a conventional photosensitive resin composition precursor solution may be colored, discolored, or decomposed by ultraviolet rays contained in natural light. In the present invention, the film obtained by heating and curing the photosensitive resin composition precursor solution containing the light stabilizer absorbs ultraviolet rays irradiated with the light stabilizer dispersed therein and reacts with radicals. This suppresses coloring, discoloration, and decomposition of the film. Then, the influence of the ultraviolet rays received by the photosensitive resin composition can be reduced, and the light resistance of the coating after curing can be drastically improved. The dielectric breakdown voltage after the irradiation for 500 hours using a xenon arc lamp is 150 kV / mm or more can be achieved.

  Examples of the light stabilizer added to the photosensitive resin composition precursor solution include a compound that absorbs ultraviolet rays and a compound that acts as a radical trapping agent that reacts with radical species generated when irradiated with ultraviolet rays. However, it is not particularly limited to these. Specifically, the former is, for example, a benzotriazole skeleton (for example, trade name: “ADK ARKLS DN-13” (manufactured by Asahi Denka Kogyo Co., Ltd.)) that exhibits an action of absorbing ultraviolet rays and suppressing the decomposition of the photosensitive resin. , And benzophenone skeleton ("CHIMASSORB 81FL" (Ciba Chemicalty Specials)), triazine skeleton ("TINUVIN400" (Ciba Chemicalty Specials)), and the latter, for example, hindered amine skeleton ( "TINUVIN123", "TINUVIN292" (manufactured by Ciba Chemicalty Specials)). Other examples include commercially available compounds such as “TINUVIN99-2”, “TINUVIN171”, “TINUVIN400”, “TINUVIN1130” (Ciba Chemicalty Specials).

  The addition amount of the light stabilizer mentioned here is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin component. More preferably, it is 0.5-15 weight part. When the amount is less than 0.1 part by weight, it is difficult to obtain sufficient sunlight irradiation resistance. On the other hand, when the amount is more than 30 parts by weight, the light stabilizer may be precipitated during pre-baking, or the obtained light-resistant composition may become brittle and cracks may occur.

The resin having an oxazole structure represented by the general formula (2) used in the present invention is, for example, a product obtained by reacting a bisaminophenol compound with a dicarboxylic acid. In this case, R in the general formula (2) is used. ³ component is a bis-aminophenol residue, R ⁴ component is a dicarboxylic acid residue.

式中、Ｒ^３は炭素数２以上の４価の有機基、Ｒ^４は炭素数２以上の２価の有機基を示す。
ここで、ビスアミノフェノール化合物としては、ジヒドロキシジアミノベンゼン、ジヒドロキシジアミノビフェニル、ビス（アミノヒドロキシフェニル）スルホンビス（アミノヒドロキシフェニル）プロパン、ビス（アミノヒドロキシフェニル）ヘキサフルオロプロパン、ビス（ヒドロキシアミノフェニル）シクロヘキサンなどが挙げられる。

In the formula, R ³ represents a tetravalent organic group having 2 or more carbon atoms, and R ⁴ represents a divalent organic group having 2 or more carbon atoms.
Here, examples of the bisaminophenol compound include dihydroxydiaminobenzene, dihydroxydiaminobiphenyl, bis (aminohydroxyphenyl) sulfone bis (aminohydroxyphenyl) propane, bis (aminohydroxyphenyl) hexafluoropropane, and bis (hydroxyaminophenyl) cyclohexane. Is mentioned.

  Dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, biphenyl dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, diphenylmethane dicarboxylic acid, bis (carboxyl) phenylpropane, and terphenyl dicarboxylic acid. An aromatic dicarboxylic acid such as adipic acid, adipic acid, sebacic acid, dodecanoic acid, diethyl glutaric acid, cyclohexane dicarboxylic acid, norbornene dicarboxylic acid and the like can be used.

  Resins having an oxazole structure used in the present invention can also be capped at the ends with monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids, as with polyimide resins.

Furthermore, silane coupling agents such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, R ³ component of the general formula (2), bis (amino-hydroxyphenyl) dimethylsilane, etc. silicon atom-containing bis-aminophenol, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-anilino) a diamine compound such as tetramethyldisiloxane ^{R 3} ingredients 1-30 By copolymerizing mol% or adding a polyimide resin or polyimide precursor containing a silicon atom, the adhesion to the substrate can be improved, and the oxygen plasma resistance and UV ozone resistance can be increased.

  The novolak resin used in the present invention refers to a product obtained by subjecting phenols to an addition condensation reaction with formaldehyde in the presence of an acid catalyst such as toluenesulfonic acid, oxalic acid or hydrochloric acid. The reaction to obtain this polymer is known as a routine method.

  Specific examples of phenols include phenol, cresol, resorcinol, xylenol, ethylphenol, trimethylphenol, propylphenol, butylphenol, dihydroxybenzene, and naphthols. These phenols can be used alone or in admixture of two or more. Examples of formaldehyde to be subjected to addition condensation reaction with phenols include formaldehyde aqueous solution (formalin) and paraformaldehyde.

  The addition condensation reaction of phenols and formaldehyde is usually performed at 60 to 120 ° C. for 2 to 30 hours. In this reaction, usually, an organic acid, an inorganic acid, a divalent metal salt, or the like is used as a catalyst. Specific examples of the catalyst include oxalic acid, hydrochloric acid, sulfuric acid, perchloric acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, formic acid, zinc acetate, magnesium acetate and the like. This addition condensation reaction may be carried out in the absence of a solvent or in a suitable solvent. The polymer thus obtained is precipitated by adding it to methanol or water to remove monomers and catalysts. This polymer is dried to obtain a polymer powder made of a novolac resin.

  By adding a photoacid generator such as naphthoquinone diazide and a polyphenol compound for adjusting solubility to such a novolak resin, for example, a positive photosensitive resin in which an exposed portion is dissolved can be obtained.

  Also, by adding a benzylamine compound to the novolak resin and combining a crosslinking agent that crosslinks by the action of an acid and a photoacid generator, or by combining a crosslinking agent that crosslinks by the action of an amine and a photoamine generator. A negative photosensitive resin in which the exposed part is insolubilized can be obtained. However, when used for an insulating film of an organic electroluminescent element, it is preferable from the negative type that a positive type in which an exposed portion is dissolved is preferred from the aspect of the tapered shape of the pattern cross section.

  Adding a silane coupling agent such as trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, and a silane coupling agent such as hydroxyphenyltrimethoxysilane to the novolac resin; By blending 5-200 parts by weight of polyimide resin containing silicon atoms, polyimide precursor, polybenzoxazole resin, polybenzoxazole precursor, etc., the adhesion to the substrate is enhanced and the oxygen plasma resistance and UV ozone resistance are enhanced. be able to.

  As the acrylic resin used in the present invention, a monomer containing an acrylic monomer is a radical initiator such as benzoyl peroxide or azoisobutyl nitrile, an anionic polymerization initiator such as sodium methoxide, sodium or butyl lithium, sulfuric acid, phosphoric acid or the like. A polymer polymerized using a cationic polymerization initiator or the like. Such a polymer can be polymerized by a known method.

  Examples of acrylic monomers include acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, or the like. Methacrylic acid cycloalkyl ester, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, hydroxyalkyl methacrylate such as aminomethyl methacrylate, aminomethyl methacrylate, N-methylaminomethyl methacrylate, N, N-diethylaminoethyl methacrylate, etc. Examples include acid aminoalkyl and methacrylamide. The copolymerizable components include vinyl monomers such as styrene monomers such as styrene, vinyl toluene, and α-methylstyrene, vinyl derivatives such as vinyl chloride, vinylidene chloride, vinyl acetate, and isopropenyl acetate, and maleic acid. And unsaturated dibasic acids such as fumaric acid, acid anhydrides thereof, monoesters such as monomethyl esters and monoethyl esters, or diesters such as dimethyl esters and diethyl esters. Further, a photocrosslinking component can be introduced by adding glycidyl methacrylate or the like to the acrylic resin. Moreover, an elastomer component such as acrylic rubber can be further added to the acrylic resin to improve impact resistance.

  In order to give photosensitivity to the acrylic resin, bisazides are added, and photopolymerization initiators such as 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and Michlerketone and / or thioxanthone are added. Positive photosensitivity in which the exposed part dissolves by adding a photoacid generator such as a negative photosensitive light-resistant resin composition precursor or a naphthoquinone diazide sulfonic acid ester, in which a photosensitive agent is combined and the exposed part remains. Light-resistant resin composition. Here, from the cross-sectional shape of the pattern to be obtained, it is preferable to use positive photosensitivity.

  Add a silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, trimethoxy hydroxyphenyl silane to the acrylic resin, polyimide resin containing polyimide, polyimide By blending a precursor, a polybenzoxazole resin, a polybenzoxazole precursor, and the like, it is possible to enhance the adhesion to the substrate and the resistance to cleaning treatments such as plasma and UV ozone.

  As the silica-based resin containing an organic substance used in the present invention, a hydrolysis or condensation product of alkoxysilane is preferably used. Means for forming a silica film by applying these silica-based resins to a substrate and baking them are generally known and preferably used.

  Specific examples of alkoxysilane include tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, butoxysilane, ethylbutoxysilane, phenoxysilane, methyltrimethoxysilane, dimethylmethoxysilane, trimethylmethoxysilane, methyl Examples thereof include triethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, tetra (methoxyethoxy) silane, tetra (ethoxyethoxy) silane, dimethyldi (methoxyethoxy) silane, and the like. These alkoxysilanes may be used alone or in combination. It is also possible to cocondense a metal alkoxide typified by tetraalkoxytitanium and tetraalkoxyzirconium, or a metal alkoxide derivative such as metal acetylacetone.

  Here, the hydrolysis and condensation reaction of alkoxysilane is usually performed in an organic solvent. Accordingly, as the solvent for the alkoxysilane solution, a known organic solvent can be used as appropriate, but a liquid having at least one hydroxyl group and ether bond in the molecule is preferable, and a liquid having a boiling point of 100 to 300 ° C. is preferable. . Examples of such organic solvents include 3-methyl-3-methoxybutanol, 3-methyl-3-ethoxybutyl acetate, propylene glycol mono-methyl ether, propylene glycol mono-methyl ether acetate, dipropylene glycol Mono-methyl ether, tripropylene glycol-mono-methyl ether, propylene glycol-mono-tertiary-butyl ether, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, methyl carbitol acetate , Ethyl carbitol, ethyl carbitol acetate, and the like. The amount of these organic solvents used can be arbitrarily selected, but it is preferably used in the range of 0.5 to 3.0 parts by weight with respect to 1 part by weight of alkoxysilane.

Usually, water is added to an alkoxysilane solution and, if necessary, a hydrolysis catalyst to hydrolyze a part or all of the alkoxy group, and then condensation is performed while causing by-produced alcohol and water to flow out. Here, the alcohol by-produced by the condensation reaction is an alcohol R′OH generated by the decomposition of alkoxysilane [R _X Si (OR ′) _{4 -X} ]. Further, the solution contains water added excessively for hydrolysis and water newly generated by a condensation reaction. The distillation of alcohol and water may be performed by a normal distillation method, that is, by heating an alkoxysilane solution.

  The water used for the hydrolysis condensation reaction is preferably ion-exchanged water, and the amount thereof is preferably used in the range of 1 to 4 times mol for 1 mol of alkoxysilane. Moreover, as a hydrolysis catalyst used as needed, an acid catalyst is preferable, and hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, boric acid, paratoluenesulfonic acid, etc. are preferably used.

  During the polymerization reaction, tetracarboxylic dianhydride, dicarboxylic acid active ester, diamine, or one or more of bisaminophenol may be added and partially modified with polyimide or polybenzoxazole. . Furthermore, you may add the acid component and diamine component which contain the silicon atom here.

  These reaction conditions are determined according to the structure of the reaction system and are not particularly limited. However, hydrolysis is 0 to 70 ° C. for 1 to 5 hours, and condensation is 70 to 150 ° C. for 1 to 10 hours. It is preferable to proceed.

  A photoacid generator such as triphenylsulfonium salt, diphenyliodonium salt, imidosulfonium salt, o-nitrobenzyl ester, cobalt-amine complex, carbamate, By adding a photoamine generator such as acyloximes, a negative photosensitive light-resistant resin composition in which an exposed portion remains can be obtained. In addition, some or all of them are protected with t-butoxycarbonyl group, benzyl group, trimethylsilyl group, etc., which are protecting groups that remove alkali-soluble groups such as carboxyl groups and phenolic hydroxyl groups in the polymer with acid. The dissolution rate can also be adjusted.

  In the present invention, a cross-linking agent may be added in order to enhance resistance such as heat treatment, UV ozone treatment, and plasma treatment.

  Examples of the photoacid generator used in the present invention include diazonium salts, diazoquinonesulfonic acid amides, diazoquinonesulfonic acid esters, diazoquinonesulfonic acid salts, nitrobenzyl esters, onium salts, halides, halogenated isocyanates, halogenated triazines, Examples include bisarylsulfonyldiazomethane, disulfone, and the like compounds that decompose by light irradiation to generate an acid.

  In particular, the o-quinonediazide compound is desirable because it has an effect of suppressing water solubility in the unexposed area. Such compounds include 1,2-benzoquinone-2-azido-4-sulfonic acid ester or sulfonic acid amide, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or sulfonic acid amide, 1,2 -Naphthoquinone-2-diazide-4-sulfonic acid ester or sulfonic acid amide. These include, for example, 1,2-benzoquinone-2-azido-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and the like. The o-quinonediazide sulfonyl chloride and polyhydroxy compound or polyamino compound can be obtained by condensation reaction in the presence of a dehydrochlorination catalyst.

  Examples of polyhydroxy compounds include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2 , 3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 4-phenylmethyl-1,2,3-benzenetriol, 4-ethyl- 1,3-benzenediol, 4-phenylmethyl-1,3-benze Diol, 4- (1-methyl-1-phenylethyl) -1,3-benzenediol, (2,4-dihydroxyphenyl) phenylmethanone, 4-diphenylmethyl-1,2,3-benzenetriol, 2, 4 ′, 4 ″ -trihydroxytriphenylmethane, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 4,6-bis [(4-hydroxyphenyl) methyl] -1, 3-benzenediol, 4,4 ′, 4 ″, 4 ′ ″-(1,2-ethanediylidene) tetrakisphenol, 2,6-bis [(4-hydroxyphenyl Methyl] -4-methylphenol, 4,4 ′-[4- (4-hydroxyphenyl) cyclohexylidene] bisphenol, 2,4-bis [(4-hydroxyphenyl) methyl] -6-cyclohexylphenol, 2,2′-methylenebis [6-[(2 / 4-hydroxyphenyl) methyl] -4-methylphenol], 2,2′-biphenol, 4,4′-cyclohexylidenebisphenol, 4,4′-cyclo Pentylidene bisphenol, 2,2′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bis [benzene-1,2-diol], 5,5 ′-[1,4-phenylenebis (1-methylethylidene)] bis [benzene-1,2,3-tri 4- [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-benzenediol, 4- [1- (4-hydroxyphenyl) cyclohexyl] -1,2-benzenediol, 4 -[1- (4-hydroxyphenyl) cyclohexyl] -1,3-benzenediol, 4-[(4-hydroxyphenyl) cyclohexylidene] -1,2,3-benzenetriol methyl gallate, ethyl gallate, etc. Is mentioned.

  Examples of polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino. And diphenyl sulfide.

  Examples of the polyhydroxyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine.

  Specific examples of the photoacid generator used in the present invention include methyl 3,4,5-trihydroxybenzoate, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1- Methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidenetrisphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4,4 ′, 4′-tetrakis [(1-methylethylidene) bis (1,4-cyclohexylidene)] phenol, 4,4 ′-[4- (4-hydroxyphenyl) cyclohexylidene] bisphenol, And o-quinonediazide compounds in which at least one hydroxyl group is 1,2-naphthoquinonediazide-4-sulfonyl group or 1,2-naphthoquinonediazide-5-sulfonyl group. .

  The addition amount of the photoacid generator is not particularly limited. For example, the o-quinonediazide compound is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the resin having an oxazole structure represented by the general formula (2). More preferably, it is blended in the range of 5 to 40 parts by weight. When the blending amount is less than 5 parts by weight, it is difficult to obtain sufficient sensitivity, and when it exceeds 100 parts by weight, it is difficult to form a pattern by light irradiation and subsequent development, and the heat resistance of the resin composition may be lowered. is there.

  Examples of other photoacid generators that can be used in the present invention include onium salts, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds.

  Specific examples of the onium salt include diazonium salt, ammonium salt, iodonium salt, sulfonium salt, phosnium salt, oxonium salt and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluene Examples thereof include sulfonates.

  Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4, Examples thereof include 6-bis (trichloromethyl) -s-triazine.

  Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Preferred diazoketone compounds are esters of 1,2-naphthoquinonediazido-4-sulfonic acid and 2,2,3,4,4′-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1 , Ester with 1-tris (4-hydroxyphenyl) ethane, and the like.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylyl). Sulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl ( And benzoyl) diazomethane.

  Specific examples of the sulfone compound include β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Here, specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like.

  Specific examples of the sulfonimide compound as a photoacid generator include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy). Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2 2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyl Imido, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxyl N- (camphorsulfonyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- ( 4-Methylphenylsulfonyloxy) phthalimi N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4 -Methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2- Trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylpheny Rusulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenyl) Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane -5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluoro Phenylsulfonyloxy) phthalimide, N- (4-fluorophenylsulfoni) Oxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7- Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide and the like.

  In the light-resistant resin composition of the present invention, a dissolution regulator can be used for the purpose of adjusting the dissolution rate ratio between the unexposed area and the exposed area.

  As the dissolution regulator, any compound such as a polyhydroxy compound, a sulfonamide compound, and a urea compound can be preferably used. In particular, a polyhydroxy compound which is a raw material for synthesizing a quinonediazide compound is preferably used. Specifically, methyl 3,4,5-trihydroxybenzoate, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4 , 4 ', 4 "-ethylidenetrisphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4,4', 4'-tetrakis [(1-methylethylidene ) Bis (1,4-cyclohexylidene)] phenol and the like.

  The dissolution regulator is preferably blended in the range of 1 to 100 parts by weight, more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the resin. If the amount is less than 1 part by weight, a sufficient effect cannot be obtained, and if it exceeds 100 parts by weight, the heat resistance of the resin composition may be lowered.

  Further, for the purpose of improving the wettability between the light-resistant resin composition of the present invention and the substrate as required, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone , Ketones such as methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, or the like can be added.

  Furthermore, in order to improve the adhesiveness with a base substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent or the like is added to the varnish of the resin precursor composition in an amount of 0.5 to 10% by weight, It can also be pretreated with such a chemical.

  When added to the varnish, 0.5 to 10% by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent, or an aluminum chelating agent is added to the resin component in the varnish. It is preferable to do this.

  When the base substrate is pretreated with a chemical solution, the coupling agent described above is a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. The substrate surface is pretreated by spin coating, dipping, spray coating, vapor treatment or the like with a solution in which 0.5 to 20% by weight is dissolved. Moreover, reaction of a board | substrate and the said coupling agent can also be advanced by applying temperature from 50 degreeC to 300 degreeC after that.

  Next, although the method to form a light-resistant resin pattern using the light-resistant resin composition of this invention is demonstrated, this invention is not limited to this.

  A light-resistant precursor composition having a photosensitive function is applied on a substrate. As the substrate, silicon wafers, ceramics, gallium arsenide, soda glass, quartz glass, and the like are used, but are not limited thereto. As a coating method, spin coating using a spinner, spray coating, roll coating, or the like can be used. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 10 μm.

  Next, the substrate coated with the light-resistant precursor composition is dried to obtain a photosensitive light-resistant precursor composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature of 50 ° C. to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive light-resistant precursor composition film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are used. preferable.

  Formation of the light-resistant resin pattern is achieved by removing the exposed portion using a developer after exposure. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In order to improve developability, polar solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide are added to these aqueous alkali solutions. , Alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, or a combination of several May be added.

  After development, rinse with water. For the purpose of rinsing effectively, an alcohol such as ethanol or isopropyl alcohol, or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to water for the rinsing treatment.

  After development, a temperature of 120 ° C. to 500 ° C. is applied to convert the resin precursor into a light-resistant resin film. This heat treatment is preferably carried out for 1 minute to 5 hours while selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. The optimum temperature for the heat treatment is selected depending on the application.

  In the case of an organic electroluminescent device used as an insulating film, the treatment is preferably performed in the range of 120 ° C. to 280 ° C. for 1 minute to 2 hours. If it is less than 120 ° C., it is difficult to imidize sufficiently, and if it exceeds 280 ° C., for example, when the entire organic electroluminescence device is exposed to heat, the device may be adversely affected. A more preferable range is 180 ° C to 250 ° C. In addition, if the heat treatment time is less than 1 minute, the imidization reaction does not proceed sufficiently, and it is difficult to obtain a sufficiently reliable film. When the heat treatment time exceeds 2 hours, the organic electroluminescence device may be adversely affected, and the productivity tends to decrease. A more preferable range is 3 minutes to 1 hour.

  In the case of the use of a surface protective film and an interlayer insulating film of a semiconductor element, it is preferable to perform a heat treatment at a temperature higher than the temperature applied in the process after forming the insulating film. Specifically, the treatment is preferably performed in the range of 200 ° C. to 450 ° C. for 5 minutes to 3 hours. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method of increasing the temperature linearly from room temperature to 250 ° C. over 2 hours or from 400 ° C. over 2 hours may be used.

  The light-resistant resin composition of the present invention is suitably used for applications such as a semiconductor passivation film, a protective film for a semiconductor element, and an insulating layer in a display element equipped with an organic electroluminescent element.

  When the light-resistant resin composition of the present invention is used for an insulating layer of an organic electroluminescent element, it is preferable to form a charge transfer layer, a light emitting layer, and the like by vapor deposition after forming the insulating layer. At that time, if the pattern of the insulating layer is formed at an angle of 90 degrees or more, the entire surface may not be covered well by vapor deposition, and electrical conduction failure may occur and light emission may not occur. Therefore, in order to eliminate electrical connection failure, it is preferable that the insulating layer has a positive taper. The taper angle is 10 to 90 °, more preferably 20 to 70 °, and more preferably 20 to 60 °. From this point of view, the photosensitive material is preferably a positive photosensitive material that is easy to give a positive taper and dissolves the exposed portion.

  The thickness of the insulating layer of the organic electroluminescent element of the present invention is not particularly limited, but it is preferably in the range of 0.05 to 20 μm, more preferably, considering the ease of film formation and patterning. The range is preferably 0.5 to 20 μm, more preferably 0.5 to 15 μm, and particularly preferably 0.8 to 5 μm. If the insulating layer is thinned to a thickness less than the above range, high-accuracy patterning is possible, but the dielectric breakdown voltage may be reduced. Further, when the insulating layer is made thicker than the above range, for example, when the light emitting layer and the second electrode are patterned by a mask vapor deposition method in manufacturing an organic electroluminescent element, the shadow mask damages the layer already formed on the substrate. Although a role as a spacer to prevent this (mask scratches) can be added, pattern processing accuracy may be reduced.

Since the insulating layer of the organic electroluminescent element is often formed so as to straddle adjacent wirings and electrodes, good electrical insulation is required. The volume resistivity of the insulating layer is preferably 5 × 10 ⁶ Ωcm or more, and more preferably 5 × 10 ⁷ Ωcm or more.

  In consideration of long-term reliability, it is preferable that the dielectric breakdown voltage of the insulating film forming the insulating layer after being left at a high temperature of 85 ° C. for one week is 150 kV / mm or more. If it is less than this, the dielectric breakdown voltage decreases during use, and problems such as display defects may occur.

  The organic electroluminescent element of the present invention is suitably used as a display device. Specifically, for example, LCDs, ECDs, ELDs, display devices using organic electroluminescent elements (organic electroluminescent devices), and the like are applicable. The organic electroluminescent device includes a first electrode formed on a substrate, a thin film layer including a light emitting layer made of at least an organic compound formed on the first electrode, and a second electrode formed on the thin film layer. It is a display apparatus which consists of an organic electroluminescent element containing.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these. In addition, preparation and evaluation of the light-resistant resin composition in an Example were performed with the following method.

Preparation of Light Resistant Resin Composition Film A light resistant resin precursor composition was applied by spin coating on a 5 cm × 5 cm non-alkali glass substrate having a thickness of 1.1 mm, and then a hot plate (Dainippon Screen Manufacturing ( SCW-636) manufactured at 110 ° C. for 2 minutes to prepare a light-resistant resin precursor film. This was heated at 100 ° C. for 30 minutes under an air atmosphere in an oven (DT-42) manufactured by Yamato Scientific Co., Ltd., and then heated at 230 ° C. for 1 hour to obtain a light-resistant resin composition film.

Method for Measuring Film Thickness Using a METRICON prism coupler MODEL 2010, a laser light source wavelength of 632.8 nm, a measurement mode TE-TM waveguide conversion, a glass substrate refractive index N = The film thickness was measured in a range of 1.4696 and a measurement refractive index range of 1.48 to 1.64.

Measurement Method of Dielectric Breakdown Voltage Using an withstand voltage / insulation resistance tester TOS9201 manufactured by Kikusui Electronics Co., Ltd., the aluminum substrate on which the light-resistant resin composition film was produced was boosted at a boosting rate of 0.1 kV / sec with DCW. The voltage when dielectric breakdown occurred was divided by the film thickness.

Xenon arc lamp irradiation treatment method for light-resistant resin composition A glass substrate and an Al substrate on which a light-resistant resin composition film was produced were subjected to a xenon long life fade meter FAL-25AX manufactured by Suga Test Instruments Co., Ltd. at a test tank temperature of 46.2 ° C. A xenon arc lamp irradiation treatment was performed at a temperature of 46.2 ° C. and a black panel surface temperature of 63 ° C. for 500 hours.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (1) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter abbreviated as BAHF) under a dry nitrogen stream 18.3 g (0.05 mol) and 34.2 g (0.3 mol) of allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 100 g of gamma butyrolactone (manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as GBL). , Cooled to -15 ° C. Here, 22.1 g (0.11 mol) of trimellitic anhydride chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours.

  This solution was put into 1 L of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a hydroxyl group-containing acid anhydride (1). The structure is shown below.

合成例２ ヒドロキシル基含有ジアミン（１）の合成
ＢＡＨＦ１８．３ｇ（０．０５モル）をアセトン（佐々木化学薬品（株）製、特級）１００ｍｌ、プロピレンオキシド（東京化成（株）製）１７．４ｇ（０．３モル）に溶解させ、−１５℃に冷却した。ここに、４−ニトロベンゾイルクロリド（東京化成（株）製）２０．４ｇ（０．１１モル）をアセトン１００ｍｌに溶解させた溶液を滴下した。滴下終了後、−１５℃で４時間反応させ、その後、室温に戻した。溶液をロータリーエバポレーターで濃縮し、得られた固体を水とアセトンで洗浄し、８０℃の真空乾燥機で乾燥した。

Synthesis Example 2 Synthesis of Hydroxyl Group-Containing Diamine (1) 18.3 g (0.05 mol) of BAHF with acetone (manufactured by Sasaki Chemical Co., Ltd., special grade), 17.4 g of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The solution was concentrated with a rotary evaporator, and the obtained solid was washed with water and acetone and dried with a vacuum dryer at 80 ° C.

  25 g of dried solid and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a 500 ml autoclave together with 300 ml of methyl cellosolve (manufactured by Wako Pure Chemical Industries, Ltd.). Here, hydrogen was pressurized at a pressure of 78.4 MPa, the temperature was raised to 60 ° C., and stirring was continued until no more hydrogen was absorbed. After absorbing hydrogen, the mixture was stirred for 10 minutes, and then the heating was stopped. When the temperature became 30 ° C. or lower, the pressure in the vessel was released to stop the reaction. After completion of the reaction, the solution was filtered, and the filtrate was poured into 1 L of water to obtain a target precipitate. This was dried with a vacuum dryer at 50 ° C. for 20 hours to obtain a hydroxyl group-containing diamine (1). The structure is shown below.

また、以下の実施例で用いたナフトキノンジアジド化合物（１）の構造を下記に示す。

The structure of the naphthoquinonediazide compound (1) used in the following examples is shown below.

式中、３つのＱのうち、平均２．３個は５−ナフトキノンジアジドスルホニル基、残りは水素原子である。

In the formula, an average of 2.3 of the three Qs is a 5-naphthoquinonediazidosulfonyl group, and the rest are hydrogen atoms.

Example 1
To a three-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirring blade, 9.01 g (0.045 mol) of 1,4'-diaminodiphenyl ether (manufactured by Wakayama Chemical Co., Ltd., hereinafter abbreviated as DAE) and 1 , 3-bis (tetramethyldisiloxane) (Toray Dow Corning Silicone Co., Ltd., hereinafter abbreviated as APDS) 1.24 g (0.005 mol) N-methylpyrrolidone (Mitsubishi Chemical Co., Ltd., hereinafter NMP) It was dissolved in 180 g and brought to 30 ° C. The acid anhydride 35.7g (0.05 mol) synthesize | combined in the synthesis example 1 was added here, and it stirred at 30 degreeC for 2 hours, Then, it stirred at 50 degreeC for 1 hour.

  To 100 g of this solution, 4 g of naphthoquinone diazide compound (1) and 0.2 g of CHIMASSORB 81FL (manufactured by Ciba Chemicalty Specials) as a light stabilizer were added and stirred, and the membrane made of polytetrafluoroethylene having a diameter of 0.22 μm It filtered with the filter and obtained the photosensitive polyimide precursor solution. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 403 kV / mm. there were. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 301 kV / mm.

Example 2
27.2 g (0.045 mol) of the diamine synthesized in Synthesis Example 2 and 1.24 g (0.005) mol of APDS were dissolved in 100 g of NMP in a three-necked flask equipped with a nitrogen introduction tube, a thermometer, and a stirring blade, C. To this was added 17.6 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as BPDA) (0.06 mol), and 2 at 30 ° C. Then, 2.18 g of 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd., 0.02 mol) was stirred at 50 ° C. for 1 hour as a terminal blocking agent. Thereafter, 11.9 g of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd., 0.1 mol) was added together with 30 g of NMP, and stirring was continued at 30 ° C. for 3 hours. After completion of the reaction, 4 ml of acetic acid was added to decompose the remaining dimethylformamide dimethyl acetal.

  This solution was poured into 1 L of water to obtain a polymer precipitate. This precipitate was washed twice with water and dried in a vacuum dryer at 50 ° C. for 48 hours. 2 g of polymer powder, 0.4 g of naphthoquinone diazide compound (1), 0.06 g of DN-13 (Asahi Denka Kogyo Co., Ltd.) as a light stabilizer are weighed, and gamma-butyrolactone (manufactured by Mitsubishi Chemical Corporation) (Hereinafter abbreviated as GBL) was dissolved in 15 g. This solution was filtered with a membrane filter made of polytetrafluoroethylene having a diameter of 0.22 μm to obtain a photosensitive polyimide precursor solution. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 424 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 344 kV / mm.

Example 3
DAE 8.01 g (0.04 mol), APDS 1.24 g (0.005 mol), 3-aminophenol 2.18 g (0.02 mol) in a three-necked flask equipped with a nitrogen inlet tube, thermometer and stirring blade Was dissolved in 30 g of NMP and brought to 30 ° C. To this was added 15.5 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (manufactured by Daicel Chemical Industries, Ltd., hereinafter abbreviated as ODPA) (0.05 mol), and 2 at 30 ° C. The mixture was stirred at 50 ° C. for 1 hour. Thereafter, 9.5 g (0.08 mol) of dimethylformamide dimethyl acetal was added together with 10 g of NMP, and stirring was continued at 30 ° C. for 3 hours. After completion of the reaction, 2 ml of acetic acid was added to decompose the remaining dimethylformamide dimethyl acetal. This solution was poured into 1 L of water to obtain a polymer precipitate. This precipitate was washed twice with water and dried in a vacuum dryer at 50 ° C. for 48 hours.

  2 g of polymer powder, 0.12 g of naphthoquinonediazide compound (1), and 0.12 g of TINUVIN292 (manufactured by Ciba Chemicalty Specials Co., Ltd.) as a light stabilizer were weighed and dissolved in 15 g of GBL. This solution was filtered with a membrane filter made of polytetrafluoroethylene having a diameter of 0.22 μm to obtain a photosensitive polyimide precursor solution. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 440 kV / mm. It was. Next, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 419 kV / mm.

Example 4
In a 1 L three-necked flask equipped with a stirrer and a thermometer, 10.9 g of pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd., 0.05 mol) and 16.1 g of benzophenone tetracarboxylic acid (manufactured by Daicel Chemical Industries, Ltd.) 0.05 mol) was dispersed in 250 mL of GBL. To this, 26 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.2 mol) was added 21 g of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd., 0.2 mol), and the mixture was stirred and reacted at 30 ° C. for 5 hours. . The solution was cooled to −10 ° C., and a solution prepared by dissolving 41.3 g of dicyclohexylcarbodiimide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.2 mol) in 50 g of GBL and 30 g of acetone was added dropwise so that the internal temperature did not exceed 0 ° C. did. After completion of dropping, 12.2 g of 3,5-diaminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 0.08 mol) and 4 g of 4-DAE (0.02 mol) were dispersed in 50 g of GBL and added. Stirring was performed at −10 ° C. for 30 minutes, and then the temperature of the solution was gradually increased, and stirring was continued at 30 ° C. for 3 hours. After completion of the reaction, the solution was filtered, and the filtrate was poured into 4 L of water to obtain a polymer precipitate. The polymer precipitate was collected by filtration, washed again with 2 L of water and filtered. This operation was repeated three times and then dried for 48 hours with a vacuum dryer at 50 ° C. to obtain a polymer powder.

  10 g of polymer powder, 0.2 g of N-phenyldiethanolamine, 0.4 g of N-phenylglycine, 2 g of ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., 1G), TINUVIN400 (Ciba Chemicalty Special as light stabilizer) 2 g of NMP) was dissolved in 50 g of NMP, and 0.5 g of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was further added. This solution was filtered with a 0.22 μm membrane filter to obtain a photosensitive polyimide precursor solution. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement. The dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 480 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 420 kV / mm.

Example 5
36.6 g (0.1 mol) of BAHF was dissolved in a mixed solvent of 150 g of NMP and 30 g of acetone, and the solution temperature was cooled to 3 ° C. 88 g of glycidyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., 1.0 mol) was added thereto. To this solution, 32.5 g of diphenyl ether dicarboxylic acid chloride (0.11 mol, manufactured by Nippon Agricultural Chemicals Co., Ltd.) dissolved in 100 g of acetone was added dropwise so that the internal temperature of the solution did not exceed 10 ° C. After completion of dropping, the mixture was returned to room temperature for 2 hours, then returned to room temperature, and 3.32 g of norbornene dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., 0.02 mol) was added as an end-capping agent. Stir.

After stirring, the mixture was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration. Again, a white precipitate was dispersed in 2 L of water, and after stirring, collected by filtration. This operation was repeated three times and dried for 48 hours in a vacuum dryer at 50 ° C. to obtain a white polymer precipitate.
10 g of this polymer powder, 2 g of naphthoquinonediazide compound (1), 1 g of tris (hydroxyphenyl) methane (Honshu Chemical Co., Ltd.), 1 g of TINUVIN400 (manufactured by Ciba Chemicalty Specials Co., Ltd.) as a light stabilizer And was filtered through a 0.22 μm membrane filter to obtain a photosensitive benzoxazole precursor solution. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement. The dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 382 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 278 kV / mm.

Example 6
To a 500 mL three-necked separable flask equipped with a stirrer and a thermometer, 75 g (0.69 mol) of m-cresol and 25 g (0.23 mol) of p-cresol were charged. To this, 70 g of a 37 wt% aqueous formaldehyde solution and 0.04 g of oxalic acid were added. While stirring, the mixture was placed in an oil bath and heated to 100 ° C., and stirring was continued for 10 hours. Thereafter, the thermometer was removed, the internal pressure was reduced to 30 mmHg to remove water, and then heated to 180 ° C. to remove unreacted substances for 1 hour. Then, it cooled to room temperature and obtained novolak resin.

  20 g of this novolak resin, 5 g of naphthoquinonediazide compound (1), and 1.2 g of TINUVIN400 (manufactured by Ciba Chemicalty Specials) as a light stabilizer are dissolved in 75 g of propylene glycol monomethyl ether (manufactured by Kuraray Co., Ltd.) And filtered through a membrane filter made of polytetrafluoroethylene having a diameter of 0.22 μm. This solution was spin-coated and pre-baked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement. The dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 199 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 163 kV / mm.

Example 7
300 mL of propylene glycol monomethyl ether was placed in a 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a dropping funnel, and the temperature of the solution was 85 ° C. Here, 30 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd., 0.29 mol), 30 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 0.35 mol), 40 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.4 Mol) was diluted with 100 g of propylene glycol monomethyl ether dropwise over 2 hours. After completion of the dropwise addition, the temperature of the solution was raised to 95 ° C., and 0.5 g of azoisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions every 30 minutes. Thereafter, the solution temperature was set to 95 ° C. and the mixture was stirred for 1 hour and 30 minutes, and the solution was lowered to room temperature to obtain an acrylic resin solution.

  100 g of this solution was mixed with 2 g of naphthoquinone diazide compound (1) and 1.2 g of TINUVIN 400 (manufactured by Ciba Chemicalty Specials) as a light stabilizer, and filtered through a 0.22 μm membrane filter. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 233 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 152 kV / mm.

Example 8
68 g (0.5 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-13), 19.8 g (0.1 mol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-103) It was dissolved in 171.6 g of propylene glycol monomethyl ether. Acetic acid 0.88 g and water 32.4 g were added thereto with stirring. Stirring was continued at 30 ° C. for 5 minutes, and then the bath temperature was set to 105 ° C. and stirred for 3 hours. As a result, 49 g of distillate was observed centering on methanol as a by-product. Next, the bath temperature was 125 ° C., the internal temperature was 113 ° C., and 27 g of mainly acetic acid, water, and propylene glycol monomethyl ether were distilled. Then, it cooled to room temperature and obtained the alkali-soluble siloxane polymer.

  To 20 g of this solution, 0.1 g of benzoin tosylate as a photoacid generator and 0.2 g of TINUVIN 292 (manufactured by Ciba Chemicalty Specials Co., Ltd.) as a light stabilizer were added. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 201 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 153 kV / mm.

Comparative Example 1
The same composition as in Example 1 was used except that no light stabilizer was added. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement. The dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 416 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 143 kV / mm.

Comparative Example 2
The same composition as in Example 5 was used except that no light stabilizer was added. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 362 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 134 kV / mm.

Comparative Example 3
The composition was the same as in Example 6 except that no light stabilizer was added. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 182 kV / mm. It was. Next, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 101 kV / mm.

Comparative Example 4
The composition was the same as in Example 7 except that no light stabilizer was added. This solution was spin coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement, and the dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 228 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 120 kV / mm.

Comparative Example 5
The composition was the same as in Example 8 except that no light stabilizer was added. This solution was spin-coated and prebaked on a glass substrate for film thickness measurement and an aluminum substrate for dielectric breakdown voltage measurement. The dielectric breakdown voltage after heat treatment at 100 ° C. for 30 minutes and then at 230 ° C. for 1 hour was 162 kV / mm. It was. Subsequently, when the xenon arc lamp irradiation treatment was performed for 500 hours, the dielectric breakdown voltage was 84 kV / mm.

Claims (6)

A resin composition containing a light stabilizer, wherein the resin composition is a cured resin film having a thickness of 0.05 to 20 μm, and a dielectric breakdown voltage after irradiation with a xenon arc lamp for 500 hours is 150 kV / A light-resistant resin composition characterized by satisfying mm or more. The light-resistant resin composition according to claim 1, comprising a resin composition having an imide structure represented by the following general formula (1) or a precursor resin composition thereof, and a photoacid generator.

(R ¹ represents a tetravalent organic group having at least 2 carbon atoms, R ² represents a divalent organic group having at least 2 carbon atoms. Further, at least ^one of R ¹ and R ² One side contains a silicon atom-containing group in an amount of 1 to 30 mol% of the R ¹ or R ² component.) The light-resistant resin composition according to claim 1, comprising a resin composition having an oxazole structure represented by the following general formula (2) or a precursor resin composition thereof and a photoacid generator.

(R ³ represents a tetravalent organic group having 2 or more carbon atoms, and R ⁴ represents a divalent organic group having 2 or more carbon atoms.) The light-resistant resin composition according to claim 1, comprising a novolac resin and a photoacid generator. The light-resistant resin composition according to claim 1, comprising at least one of an acrylic resin or a silica-based resin containing an organic substance. An organic electroluminescent device comprising the light-resistant resin composition according to claim 1 as an insulating layer.