JP4360168B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition suitable for forming a light-shielding separator or a black matrix of an organic electroluminescent display device or a liquid crystal display device which is a flat panel display, wherein an ultraviolet-exposed portion is dissolved in an alkaline aqueous solution. .

  Non-luminous liquid crystal displays (LCDs) are widely used as flat panel displays, but organic electroluminescence display devices as self-luminous displays are highly researched and developed due to their high brightness and full color display. is there.

  This organic electroluminescent element operates by applying a voltage between the opposed first electrode and second electrode, or by passing a current. At this time, since the electric field tends to concentrate on the edge portion of the electrode having a small radius of curvature, undesirable phenomena such as dielectric breakdown and generation of leakage current are likely to occur in the edge portion.

To suppress these phenomena, the edge portion of the first electrode is known to cover with an insulating layer (also referred to as separator) (for example, see Patent Document 1). Thereby, it is possible to alleviate electric field concentration at the edge portion of the electrode. Furthermore, the thickness of the insulating layer at the boundary where the insulating layer exposes the first electrode is separated from the boundary so that the organic insulating layer and the second electrode deposited after forming the insulating layer are smoothly deposited. Accordingly, the electric field concentration at the edge portion of the electrode can be suppressed. Recently, for the purpose of increasing contrast in organic light emitting display devices, attempts have been made to add light shielding properties to insulating films and / or element isolation structures by adding carbon black to a non-photosensitive polyimide resin (for example, Patent Document 2).

  In general, polyimide, novolac, acrylic resin, or the like is used as the insulating layer. These resins are known to be non-photosensitive, negative-type photosensitive, and positive-type photosensitive. However, in order to suppress electric field concentration at the edge portion of the electrode, the insulating layer is preferably a positive photosensitive resin.

  When a non-photosensitive resin is used for the insulating layer, the patterning of the insulating layer includes application of the non-photosensitive resin on the substrate, pre-baking (also referred to as drying or semi-cure) of the non-photosensitive resin, and onto the non-photosensitive resin. Photoresist coating, photoresist baking (also called drying or pre-baking), photoresist exposure, photoresist development, non-photosensitive resin etching, photoresist removal, non-photosensitive resin curing (also post-baking) Many photolithographic processes are required. As a result, the process becomes complicated and the yield is poor. Furthermore, in order to make the cross section of the insulating layer into a forward tapered shape, it is necessary to optimize many parameters such as photoresist development conditions and non-photosensitive resin etching conditions, and there is a problem that the condition setting is complicated. there were.

When a photosensitive resin is used for the insulating layer, the insulating layer can be patterned without using a photoresist, so that the complexity of the process and the poor yield can be eliminated. However, with the negative photosensitive resin, the curing reaction inside the coating film in the exposed portion tends to become insufficient gradually from the surface toward the bottom. Since the cross-sectional shape of the negative photosensitive resin after patterning tends to be a reverse taper shape or a rectangle, electric field concentration is likely to occur at the edge portion, and adhesion to the substrate becomes insufficient, resulting in peeling and defects. . Further, the negative photosensitive resist, and the pattern shape forward tapered shape, and developed bake to increase the adhesion, control of line width and shape of the pattern tends to be rather difficult.

  On the other hand, if a positive photosensitive resin is used for the insulating layer, the exposed area dissolves even if the effective radiation intensity into the coated area of the exposed area gradually decreases from the surface of the coated film toward the bottom. In addition, the cross section of the pattern that occurs in the negative photosensitive resin tends to be a reverse taper shape or a rectangle, or the adhesion to the substrate is lowered and the developed pattern is peeled off, resulting in missing, missing, etc. The problem is less likely to occur.

  As the positive photosensitive resin composition for black matrix, a method of adding a quinonediazide compound and a black pigment to an alkali-soluble resin made of a novolak resin and / or a vinyl polymer (see, for example, Patent Document 3), a diazoquinone-novolak resin type A method of adding a color former and a developer to a positive resist has been proposed (for example, see Patent Document 4). As a light-shielding insulating film of an organic EL device, a method of adding a quinonediazide compound and a colorant to an alkali-soluble resin composed of a polymer of a novolak resin and / or a radical polymerizable monomer has been proposed (see, for example, Patent Document 5). Yes.

  However, when an insulating layer is formed using a light-shielding positive photosensitive resin prepared by adding a colorant to the positive resists described above, an organic electroluminescence display device is produced, and an emission durability test is performed. There is a problem that the non-light emitting portion (dark area) gradually proceeds from the outer periphery (boundary portion with the insulating layer) of the light emitting region. Alkali-soluble resins such as novolak resins generally used for positive resists tend to be rectangular in most cases after patterning, making it difficult to obtain the desired forward taper shape, so when laminating organic materials and metal materials by vapor deposition, It becomes difficult to obtain a sufficient layer thickness. Therefore, there is a problem that sufficient light emission luminance cannot be obtained compared to the thick part of the organic layer, and the metal electrode layer is thin near the edge of the insulating layer, so that moisture can easily enter compared to other parts. The dark area is easy to progress. In addition, alkali-soluble resins such as novolak resins generally used for positive resists have a problem in heat resistance at a temperature of 200 ° C. or higher in a heat treatment step performed after patterning, and the resin is likely to deteriorate. As a result, the colorant component, the resin deterioration component, and other organic substances, which are additives, are diffused from the insulating film to the light emitting area and the dark area is easily expanded. In addition, when a coloring material is used as the colorant, the coloring material itself is unstable at high temperature, and thus the deteriorated material diffuses from the insulating film to the light emitting area, and the dark area is likely to expand.

In a positive photosensitive resin composition using a heat-resistant resin as an alkali-soluble resin, the idea of blackening the insulating layer (for example, see Patent Document 6) has been disclosed, but specific methods and means for blackening are disclosed. Is not described.
JP-A-11-97182 (page 1-3) JP-A-11-273870 (page 1-3) Japanese Patent Laid-Open No. 6-230215 (page 1-2) JP-A-10-170715 (page 2-4) JP 2002-116536 A (page 1-3) International Publication No. 02/001922 pamphlet (5-6 pages)

  In view of the above-described problems, an object of the present invention is to provide a positive photosensitive resin composition suitable for forming a light-shielding separator or a black matrix of an organic electroluminescence display device or a liquid crystal display device.

That is, the present invention is, (a) an alkali-soluble heat-resistant resins composed mainly of structure selected from the general formulas (1) to (4), and a quinonediazide compound (b) esterification, (c) (c2 A positive photosensitive resin composition comprising as essential components :) an inorganic pigment comprising an insulating metal compound ; and (c3) at least one colorant selected from carbon black and / or two or more organic pigments. It is a thing.

  According to the present invention, a positive photosensitive resin composition in which a portion exposed to ultraviolet rays is suitable for forming a light-shielding separator or a black matrix of an organic electroluminescence display device or a liquid crystal display device and is dissolved in an alkaline aqueous solution is provided. Can do. Further, when the photosensitive resin composition of the present invention is used, a high-quality organic electroluminescence display device or liquid crystal display device can be supplied.

(A) component in the present invention, Ru necessary der to be soluble in an alkaline aqueous solution used as a developing solution. Specifically, the alkali-soluble heat-resistant resin is a polymer selected from a polyimide precursor, a polyimide, and a polybenzoxazole precursor. Therefore, it is desirable that the polymer has an alkali-soluble group in the molecule. The type of polymer in the present invention is excellent in heat resistance and exhibits excellent characteristics as a separator of an organic electroluminescent device. Therefore, a polymer having a small degassing amount at a high temperature of 230 ° C. or higher after heat treatment is preferable. , polyhydroxy amides, a polyimide precursor or a polybenzoxazole precursor der and polyamide acid or polyamide acid ester is, as a main component the structure selected from the following formulas (1) to (4).

  Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.

式中Ｒ^１は少なくとも２個以上の炭素原子を有する２価から８価の有機基、Ｒ^２は、少なくとも２個以上の炭素原子を有する２価から６価の有機基、Ｒ^３は水素、または炭素数１から２０までの有機基、Ｒ^４は２価の有機基、Ｘはカルボキシル基、フェノール性水酸基、スルホン酸基、チオール基、不飽和炭化水素基を少なくとも１つ以上含有する炭素数１から１０までの炭化水素基、ニトロ基、メチロール基、エステル基、ヒドロキシアルキニル基より少なくとも一つ選ばれる基を有する１価の有機基を示す。ｎは１０から１０００００までの整数、ｍは０から１０までの整数、ｐ、ｑは０から４までの整数、ｒは０から２までの整数を示す。ｐ＋ｑ＞０である。

In which R ¹ is a divalent to octavalent organic group having at least 2 carbon atoms, R ² is a divalent to hexavalent organic group having at least 2 carbon atoms, R ³ is hydrogen, Or an organic group having 1 to 20 carbon atoms, R ⁴ is a divalent organic group, X is a carbon number containing at least one carboxyl group, phenolic hydroxyl group, sulfonic acid group, thiol group, or unsaturated hydrocarbon group. hydrocarbon group having from 1 to 10, a nitro group, a methylol group, an ester group, a monovalent organic group having at least one chosen group from hydroxyalkynyl group shown. n is an integer from 10 to 100,000, m is an integer from 0 to 10, p, q is an integer from 0 to 4, and r is an integer from 0 to 2. p + q> 0.

式中Ｒ^１は少なくとも２個以上の炭素原子を有する２価から８価の有機基、Ｒ^２は、少なくとも２個以上の炭素原子を有する２価から６価の有機基、Ｒ^３は水素、または炭素数１から２０までの有機基、Ｒ^４は２価の有機基、Ｙはカルボキシル基、フェノール性水酸基、スルホン酸基、チオール基、不飽和炭化水素基を少なくとも１つ以上含有する炭素数１から１０までの炭化水素基、ニトロ基、メチロール基、エステル基、ヒドロキシアルキニル基より少なくとも一つ選ばれる基を有する１価の有機基を示す。ｎは１０から１０００００までの整数、ｍは０から１０までの整数、ｐ、ｑは０から４までの整数、ｒは０から２までの整数を示す。ｐ＋ｑ＞０である。

In which R ¹ is a divalent to octavalent organic group having at least 2 carbon atoms, R ² is a divalent to hexavalent organic group having at least 2 carbon atoms, R ³ is hydrogen, Or an organic group having 1 to 20 carbon atoms, R ⁴ is a divalent organic group, Y is a carbon number containing at least one or more carboxyl group, phenolic hydroxyl group, sulfonic acid group, thiol group, or unsaturated hydrocarbon group. hydrocarbon group having from 1 to 10, a nitro group, a methylol group, an ester group, a monovalent organic group having at least one chosen group from hydroxyalkynyl group shown. n is an integer from 10 to 100,000, m is an integer from 0 to 10, p, q is an integer from 0 to 4, and r is an integer from 0 to 2. p + q> 0.

  The above general formulas (1) to (4) represent a polyamic acid having a hydroxyl group, and due to the presence of this hydroxyl group, the solubility in an alkaline aqueous solution is better than that of a polyamic acid having no hydroxyl group. In particular, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than solubility in an aqueous alkali solution. In addition, when each of the general formulas (1) to (4) has a fluorine atom of 10% by weight or more, when developing with an alkaline aqueous solution, water repellency appears moderately at the interface of the film. Etc. are suppressed. However, if the fluorine atom content exceeds 20% by weight, the solubility in an alkaline aqueous solution is reduced, the organic solvent resistance of the polymer having a cyclic structure by heat treatment is reduced, and the solubility in fuming nitric acid is reduced. It is not preferable. Thus, the fluorine atom is preferably contained in an amount of 10% by weight to 20% by weight.

R ¹ contained in the dicarboxylic acid units of the above general formulas (1) to (4) represents a structural component of an acid dianhydride, and represents a divalent to octavalent organic group having at least two carbon atoms. The acid dianhydride is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms, which contains an aromatic ring or an aliphatic ring, and has 0 to 2 hydroxyl groups. .

  When a specific acid dianhydride has no hydroxyl group, 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, 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 anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane anhydride, bis (3,4-dicarboxyphenyl) methane anhydride, bis ( 2,3- Carboxyphenyl) methane anhydride, bis (3,4-dicarboxyphenyl) sulfone anhydride, bis (3,4-dicarboxyphenyl) ether anhydride, 2,2-bis (4- (4-aminophenoxy) phenyl ) Propane, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4 -Dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoro Aromatic tetracarboxylic dianhydrides such as lopan dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylicsan anhydride and aliphatic tetracarboxylics such as “TDA100, Rica Resin TMEG” (trade name, manufactured by Shin Nippon Rika Co., Ltd.) An acid dianhydride etc. can be mentioned. Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 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 anhydride, 1-bis (2,3-dicarboxyphenyl) ethane anhydride, bis (3,4-dicarboxyphenyl) methane anhydride, bis (2,3-dicarboxyphenyl) methane anhydride, bis (3,4- The Ruboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3,4 Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl)- 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride is preferred.

  In the case of having a hydroxyl group, examples of preferred compounds include those shown below, but are not limited thereto.

これらは単独で又は２種以上を組み合わせて使用される。

These are used alone or in combination of two or more.

R ² contained in the diamine units of the above general formulas (1) to (4) represents a divalent to hexavalent organic group having at least 2 carbon atoms. As a preferred example, the heat resistance of the resulting polymer What has more aromaticity is preferable. Specific examples of the diamine having no hydroxyl group 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-aminophenoxy) benzene, benzine, m- Phenylenediamine, P-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, Bis (4-aminophenoxy) biphenyl, bis {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′-tetramethyl-4,4′-diamino Biphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, or aromatic rings thereof Examples include, but are not limited to, compounds substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and the like. The above compound may be a single species or a mixture of two or more species.

2,2-bis [4- (amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl having a fluorine atom when having a hydroxyl group ] Hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine and "ABCH", "ABPS" (trade name, Nippon Kayaku Co., Ltd.) And those having a structure such that R ² (OH) _{q in the} general formulas (1) to (4) is shown below, but are not limited thereto.

これらは単独で又は２種以上を組み合わせて使用される。

These are used alone or in combination of two or more.

  The heat resistant resin precursors represented by the general formulas (1) to (4) of the present invention are synthesized using a known method. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, a diester obtained by tetracarboxylic dianhydride and an alcohol, and then adding a diamine, and then reacting by adding a condensing agent, A diester can be obtained from tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid can be converted to an acid chloride, and a diamine can be added and reacted to make a synthesis.

R ^{3 in the} general formulas (1) to (4) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of the stability of the resulting positive photosensitive resin solution, R ³ is preferably an organic group, but hydrogen is preferred from the viewpoint of the solubility in an aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amount of R ³ hydrogen and the organic group, the dissolution rate in the aqueous alkali solution changes, so that a positive photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. A preferable range is that 10% to 90% of R ³ is a hydrogen atom. If the carbon number of R ³ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ³ preferably contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are preferably hydrogen atoms.

—NH— (R ⁴ ) _m —X, which is a structural component in the general formula (1) and the general formula (2), is represented by the following general formula (5), and these are the first class which is a terminal blocking agent. It is a component derived from monoamine.

また、一般式（３）及び一般式（４）内の構造成分である−ＣＯ−（Ｒ⁴）_m−Ｙは、下記一般式（６）および／または下記一般式（７）で示され、これらは、末端封止剤である酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物から選ばれるものに由来する成分である。

In addition, —CO— (R ⁴ ) _m —Y, which is a structural component in the general formula (3) and the general formula (4), is represented by the following general formula (6) and / or the following general formula (7). These are components derived from those selected from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound, which are end-capping agents.

一般式（５）〜（７）にあるＲ⁴は、−ＣＲ⁸Ｒ⁹−、−ＣＨ₂Ｏ−、−ＣＨ₂ＳＯ₂−より選ばれる２価の基を示し、Ｒ⁸、Ｒ⁹は水素原子、水酸基、カルボキシル基、炭素数１から１０までの炭化水素基より選ばれる１価の基を示す。Ｒ⁷は水素原子、炭素数１から１０までの炭化水素基より選ばれる１価の基を示す。なかでも水素原子、炭素数１から４の炭化水素基が好ましく、特に好ましくは水素原子、メチル基、ｔ−ブチル基である。Ｒ⁸、Ｒ⁹は、水素原子、炭素数１から４までの炭化水素基より選ばれる１価の基あるいは、Ｒ⁸とＲ⁹が直接結合することを示す０価の基を示す。また、Ｒ⁵、Ｒ⁶は水素原子、水酸基、カルボキシル基、スルホン酸基、チオール基、不飽和炭化水素基を少なくとも１つ以上含有する炭素数１から１０までの炭化水素基、ニトロ基、メチロール基、エステル基、ヒドロキシアルキニル基、炭素数１から１０までの炭化水素基より選ばれる。Ａ、Ｂ、Ｇは炭素原子または、窒素原子である。ｍは０から１０までの整数であり、好ましくは０から４の整数である。ｌは０または１であり、好ましくは０である。ｉは０または１であり、好ましくは０である。ｊは１〜３までの整数であり、好ましくは１及び２である。ｋ、ｔ、ｕは０または１である。

R ⁴ in the general formulas (5) to (7) represents a divalent group selected from —CR ⁸ R ⁹ —, —CH ₂ O—, and —CH ₂ SO ₂ —, and R ⁸ and R ⁹ are A monovalent group selected from a hydrogen atom, a hydroxyl group, a carboxyl group, and a hydrocarbon group having 1 to 10 carbon atoms is shown. R ⁷ represents a monovalent group selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. Of these, a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group, and a t-butyl group are particularly preferable. R ⁸ and R ^{9 each} represent a hydrogen atom, a monovalent group selected from hydrocarbon groups having 1 to 4 carbon atoms, or a zero-valent group indicating that R ⁸ and R ⁹ are directly bonded. R ⁵ and R ⁶ are a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a hydrocarbon group having 1 to 10 carbon atoms containing at least one unsaturated hydrocarbon group, a nitro group, and methylol. Selected from a group, an ester group, a hydroxyalkynyl group, and a hydrocarbon group having 1 to 10 carbon atoms. A, B, and G are a carbon atom or a nitrogen atom. m is an integer from 0 to 10, preferably an integer from 0 to 4. l is 0 or 1, preferably 0. i is 0 or 1, preferably 0. j is an integer from 1 to 3, preferably 1 and 2. k, t, and u are 0 or 1.

  Specific examples of the primary monoamine related to the general formula (5) include 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, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-amino Naphthalene, 1-amino-2-hydroxynaphthalene, 1-carbo Ci-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-amino Naphthalene, 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-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalic Tyric acid, 3-amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto -8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene 1-mercapto-2-aminonaphthalene, 1-amino-7-me Lucaptonaphthalene, 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, 2-ethynylaniline, 3-ethynylaniline, 4- Ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-amino Naphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4- Minonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2- Ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-amino Naphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7- Diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, , 8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-amino-naphthalene, and the like, but is not limited thereto.

  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, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like are preferable.

  Specific examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound related to the general formula (6) and the general formula (7) include phthalic anhydride, maleic anhydride, nadic Acids, acid anhydrides such as cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid 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-carboxy Phthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto -4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl Benzoic acid, 2-ethini -1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid Acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl Monocarboxylic acids such as 2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid and the like, and monoacid chloride compounds in which these carboxyl groups are acid chloride, terephthalic acid, phthalic acid, Maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3- Dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxy Monoacid chloride compounds in which only monocarboxyl groups of dicarboxylic acids such as naphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene are acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy And active ester compounds obtained by reaction with -5-norbornene-2,3-dicarboximide.

  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 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid Acid etc. Nocarboxylic acids and monoacid chloride compounds in which these carboxyl groups are converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2 An active ester compound obtained by reaction with 1,3-dicarboximide is preferred.

  The introduction ratio of the component represented by the general formula (5) is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol% with respect to the total amine component.

  The introduction ratio of the components represented by the general formula (6) and the general formula (7) is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol% with respect to the diamine component.

  In the general formulas (1) to (4), n represents the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 10 to 100,000.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ and R ² as long as the heat resistance is not lowered. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  In the alkali-soluble heat-resistant resin precursor represented by the general formulas (1) to (4) of the present invention, a part of the diamine is replaced with a terminal blocking agent that is a monoamine, or an acid dianhydride is replaced with a monocarboxylic acid. It is synthesized using a known method in place of an end capping agent which is an acid, an acid anhydride, a monoacid chloride compound or a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at a low temperature, a tetracarboxylic dianhydride (a part of an acid anhydride or A method of reacting a monoacid chloride compound or a monoactive ester compound with an end-capping agent) and a diamine compound, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine) A method of reacting in the presence of a condensing agent and substitution with a sealant, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is converted to an acid chloride to form a diamine (a part of which is a monoamine) It can be synthesized using a method such as a method of reacting with a sealant.

  Moreover, the terminal blocker used for this invention introduce | transduced in the polymer can be easily detected with 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 used in the present invention can be easily detected. Apart from this, the polymer component into which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum and C13 NMR spectrum measurement.

  The positive photosensitive resin composition of the present invention may be composed of only the respective structural units represented by the general formulas (1) to (4), or represented by the general formulas (1) to (4). It may be a copolymer or blend of each structural unit and other structural units. In that case, it is preferable to contain 50 mol% or more of each structural unit represented by General Formula (1)-(4). The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

  The esterified quinonediazide compound (b) added to the present invention is preferably a compound in which a sulfonic acid of naphthoquinonediazide is bonded with an ester to a compound having a phenolic hydroxyl group. The compounds having a phenolic hydroxyl group used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP. -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-p-CR, Methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade names) , Manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahydroxybenzofe 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced with an ester bond to compounds such as methyl, gallic acid methyl ester, bisphenol A, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) However, other compounds can also be used.

  Further, when the molecular weight of the naphthoquinone diazide compound used in the present invention is 1000 or more, the naphthoquinone diazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, and the adhesion is reduced. There is a possibility that problems such as a decrease in performance may occur. From this point of view, the molecular weight of the preferred naphthoquinonediazide compound is 300 to 1000. More preferably, it is 350 to 800. The addition amount of such a naphthoquinonediazide compound is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polymer.

  If necessary, the compound having a phenolic hydroxyl group may be used as it is without being esterified with naphthoquinone diazide for the purpose of supplementing the alkali developability of the photosensitive heat-resistant precursor composition. By adding this phenolic hydroxyl group-containing compound, the resulting resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Development is easy in a short time. In this case, the addition amount of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

As a colorant component (c) to be added to the present invention, (c2) no machine pigments, the use of at least one or more colorants selected from (c3) organic pigment preferred. Since the colorant exhibits a function as a light-shielding separator or a black matrix of an organic electroluminescence display device or a liquid crystal display device, it is necessary to stably exhibit a wide range of absorption from infrared to ultraviolet. As a coloring method, a method using one or more black dyes or black pigments, a method using a combination of two or more dyes or pigments other than black, one or more black dyes or black pigments and one or more types other than black Examples thereof include a method using a combination of a dye or a pigment.

  The dye (c1) is preferably a dye that is soluble in an organic solvent that dissolves the alkali-soluble heat-resistant resin (a) and is compatible with the resin. Examples of these dyes include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, and direct dyes. As the skeleton structure of the dye, anthraquinone series, azo series, phthalocyanine series, methine series, oxazine series, and metal complex complexes of these dyes can be used. Among them, phthalocyanine series and metal complex complexes are available. Excellent in heat resistance and light resistance, and more preferable. Specifically, Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals) Zapon, Neozapon, Neptune, Acidol dye (BASF Co., Ltd.) Kayaset, Kayakalan dye (Nippon Kayaku Co., Ltd.), Valifast colors dye (Orient Chemical Co., Ltd.) Savinyl, Sandoplast, Polysynthren, Lanasyn dye (Clariant Japan Co., Ltd.), Aizen Spilon dye Tsuchiya Chemical Industry Co., Ltd.). These dyes are used alone or in combination.

As the organic pigment (c 3 ), a pigment having high heat resistance is preferable, and a combination of carbon black and / or two or more organic pigments is particularly preferable. Examples of the carbon black include furnace black such as HCF, MCF, LFF, RCF, SAF, ISAF, HAF, XCF, FEF, GPF, and SRF, thermal black such as FT and MT, channel black, and acetylene black. Can be mentioned. These carbon blacks can be used alone or in admixture of two or more.

  As the organic pigment used in the present invention, a pigment excellent in heat resistance is preferable. Specific examples of typical pigments are indicated by color index (CI) numbers. Examples of yellow pigments include Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 55, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148. , 150, 153, 154, 155, 166, 168, 173, 180, 185 and the like. Examples of the orange pigment include Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and the like. Examples of red pigments include Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, and the like. . Examples of purple pigments include pigment violet 19, 23, 29, 32, 33, 36, 37, 38, and the like. Examples of blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like. Examples of the green pigment include Pigment Green 7, 10, 36, 47, and the like.

As the inorganic pigment (c 2 ), an insulating metal compound is preferable. When an inorganic pigment having poor electrical insulation is used, the function as an insulating layer of the organic electroluminescence display device becomes insufficient, and when a light emitting element is produced, an electrical short circuit or the like is caused and a serious problem occurs. Examples of the insulating metal compound include manganese oxide, titanium oxide, titanium oxynitride, chromium oxide, vanadium oxide, iron oxide, cobalt oxide, and niobium oxide. In particular, manganese oxide and titanium oxynitride are preferably used in the present invention. The manganese oxide generally has a composition of Mn _x O _y (1 <y <x ≦ 2). Specifically gamma-MnO _2, and the like _{β-MnO 2, α-MnO} 2, Mn 2 O 3, Mn 3 O 4, further, noncrystalline _{Mn x O y (1 <y} <x ≦ 2) is also used. The temporary particle diameter of the manganese oxide powder is preferably 100 nm or less, more preferably 60 nm or less. The primary particle diameter can be determined by arithmetic average using an electron microscope.

  The titanium oxynitride suitably used in the present invention generally has a composition of TiNαOβ (0 <α <2.0, 0.1 <β <2.0). The primary particle diameter of the titanium oxynitride is preferably 100 nm or less, more preferably 60 nm or less, like the manganese oxide.

  The amount of the colorant (c) used in the present invention is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of the (a) alkali-soluble heat-resistant resin precursor. (A) When the amount of (c) the colorant used is greater than 300 parts by weight relative to 100 parts by weight of the alkali-soluble heat-resistant resin, the resin ratio is too small, so that the adhesion strength between the photosensitive resin film and the substrate decreases. is there.

  In the present invention, the organic pigment and the inorganic pigment may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic group treatment and the like, if necessary. Moreover, it can be used together with a dispersing agent. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used.

  If necessary, for the purpose of improving the wettability between the positive photosensitive resin composition and the substrate, a surfactant, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3 -Mix esters such as methyl-3-methoxybutyl acetate, alcohols such as 3-methyl-2-butanol and 3-methyl-3-methoxybutanol, ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane. May be used. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder can be added.

Furthermore a silicon wafer or ITO substrate, in order to enhance the adhesion to the underlying substrate, such as SiO _2, a silane coupling agent, may be added from 0.005 to 10 wt% varnish, such as a photosensitive resin composition of titanium chelating agent The base substrate can be pretreated with such a chemical solution.

  When added to the varnish, 0.5 to 10% by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, titanium chelating agent, or aluminum chelating agent is added to the polymer in the varnish. To do.

  When processing a substrate, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, and the like in an amount of 0.5 to 20. Surface treatment is performed by spin coating, slit die coating, bar coating, dip coating, spray coating, steam processing, and the like for the solution in which the weight% is dissolved. In some cases, the reaction between the substrate and the coupling agent is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C.

  Next, a method for forming a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described.

  A photosensitive resin composition is applied onto a substrate. As the substrate, silicon wafers, ceramics, gallium arsenide, soda glass, quartz glass, and the like are used, but are not limited thereto. The coating method includes a slit die coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and the like, and these methods may be applied in combination, but the positive photosensitive resin of the present invention may be used. The slit die coating method is most effective for the composition. 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 100 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. For drying, a hot plate, an oven, an infrared ray, a vacuum chamber or the like is used.

When a hot plate is used, the object to be heated is heated by holding it directly on the plate or on a jig such as a proxy pin installed on the plate. As a material of the proxy pin, there is a metal material such as aluminum or stellenless, or a synthetic resin such as polyimide resin or Teflon (registered trademark), and any proxy pin may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, etc. For example, a resin layer applied on a glass substrate of 300 × 350 × 0.7 mm ³ Is heated, the height of the proxy pin is preferably about 2 to 12 mm.

  The heating temperature varies depending on the type and purpose of the object to be heated, and it is preferably performed in the range of room temperature to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive resin 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 and the like. In the present invention, it is preferable to use i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. .

  Formation of the heat-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 some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 130 ° C. to 400 ° C. is applied to convert to a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. 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 heat-resistant black resin film formed by the positive photosensitive precursor composition according to the present invention is a light-shielding separator or black matrix of an organic electroluminescence display device or a liquid crystal display device, a semiconductor passivation film, a surface protection film of a semiconductor element, Used for applications such as interlayer insulation films.

  In the positive photosensitive resin composition of the present invention, an optical density (OD value) at a thickness of 1.0 μm is preferably 0.1 or more, more preferably a heat-resistant black resin film obtained by heat-treating the positive photosensitive resin composition. Is preferably 0.5 or more. If the optical density is less than 0.1, it is difficult to obtain a function as a light-shielding separator or a black matrix of an organic electroluminescence display device or a liquid crystal display device.

In the present invention, as shown in FIG. 1, it is preferable insulating layer is cross-section of the insulating layer that put the boundary allowed to expose the first electrode is a forward tapered shape. Here, the taper shape corresponds to the angle θ in the figure being less than 90 °. The cross-sectional shape of the insulating layer is preferably 60 ° or less, more preferably 45 ° or less, and further preferably 30 ° or less. When the cross-sectional shape is larger than 60 °, the thin film layer and the second electrode layer tend to be thin at the boundary portion of the insulating layer, and luminance unevenness is likely to occur in the light emitting region. In addition, electric field concentration is likely to occur at the edge portion of the electrode, and undesirable phenomena such as dielectric breakdown and generation of leakage current are likely to occur.

  Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples. In the examples, evaluation of optical density, cross-sectional shape, and durability evaluation of light emission were performed by the following methods.

(1) Evaluation of optical density The optical density (OD) was measured using a microspectroscope (“MCPD2000” manufactured by Otsuka Electronics Co., Ltd.), the incident light intensity in the visible region of wavelength 430 to 640 nm, I ₀ , and transmitted light. The strength was determined by the following formula as I.

O. D = log ₁₀ (I ₀ / I).

(2) Evaluation of cross-sectional shape About the 20 μm pattern line of the heat-resistant black resin film obtained by the heat treatment, the cross-sectional shape is observed using a scanning electron microscope (Hitachi, Ltd., “S-2300 type”). The θ value in FIG. 1 was measured.

(3) the durability of the light emitting evaluated to produce a passive matrix type organic electrolytic light-emitting display device, the effective light-emitting region area to the S _1, and the light-emitting region area of 250 hours held durability after the test at 85 ° C. and S _2, durable The effective light emission area ratio after the property test was determined as S by the following formula.

S (%) = (S ₂ / S ₁ ) × 100.

Synthesis Example 1 Synthesis of hydroxyl-containing acid anhydride (a) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl 34.2 g (0.3 mol) of glycidyl ether was dissolved in 100 g of gamma butyrolactone and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone 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 concentrated by a rotary evaporator and charged into 1 l of toluene to obtain an acid anhydride (a).

合成例２ 水酸基含有ジアミン化合物（ｂ）の合成
２−アミノ−４−ニトロフェノール１５．４ｇ（０．１モル）をアセトン５０ｍｌ、プロピレンオキシド３０ｇ（０．３４モル）に溶解させ、−１５℃に冷却した。ここに２，２ビス−（４−ベンゾイルクロリド）プロパン１７．８ｇ（０．０５５モル）をアセトン６０ｍｌに溶解させた溶液を徐々に滴下した。滴下終了後、−１５℃で４時間反応させた。その後、室温に戻して生成している沈殿をろ過で集めた。

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 ml) and propylene oxide (30 g, 0.34 mol). Cooled down. A solution prepared by dissolving 17.8 g (0.055 mol) of 2,2bis- (4-benzoyl chloride) propane in 60 ml of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 ml of γ-butyrolactone, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain crystals of the target compound.

合成例３ 水酸基含有ジアミン化合物（ｃ）の合成
ＢＡＨＦ１８．３ｇ（０．０５モル）をアセトン１００ｍｌ、プロピレンオキシド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。析出した白色固体をろ別し、５０℃で真空乾燥した。

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (c) 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride 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 precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons were not deflated any more. After completion of the reaction, filtration was performed to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (c). The obtained solid was used for the reaction as it was.

合成例４ 水酸基含有ジアミン化合物（ｄ）の合成
２−アミノ−４−ニトロフェノール１５．４ｇ（０．１モル）をアセトン１００ｍｌ、プロピレンオキシド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２０．４ｇ（０．１１モル）をアセトン１００ｍｌに溶解させた溶液を徐々に滴下した。滴下終了後、−１５℃で４時間反応させた。その後、室温に戻して生成している沈殿をろ過で集めた。この後、合成例２と同様にして目的の化合物の結晶を得た。

Synthesis Example 4 Synthesis of Hydroxyl-Containing Diamine Compound (d) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (100 ml) and propylene oxide (17.4 g, 0.3 mol). Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration. Thereafter, the target compound crystal was obtained in the same manner as in Synthesis Example 2.

合成例５ ３，３’，４，４’−ジフェニルエーテルテトラカルボン酸ジｎ−ブチルエステルジクロリド溶液（ｅ）の合成
乾燥窒素気流下、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物２４．８２ｇ（０．０８モル）、ｎ−ブチルアルコール５９．３ｇ（０．８モル）を９５℃で６時間攪拌反応させた。余剰のｎ−ブチルアルコールを減圧下、留去して、ピロメリット酸ジエチルエステルを得た。ついで塩化チオニルを９５．１７ｇ（０．８モル）、テトラヒドロフラン（ＴＨＦ）７０ｇを仕込み４０℃で３時間反応させた。つづいて、Ｎ−メチルピロリドン２００ｇを添加し、減圧により、余剰の塩化チオニル及びＴＨＦを除去し、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸ジｎ−ブチルエステルジクロリド溶液（ｅ）２３９．６ｇ（０．０８モル）を得た。

Synthesis Example 5 Synthesis of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di n-butyl ester dichloride solution (e) 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride under a dry nitrogen stream 24.82 g (0.08 mol) of the product and 59.3 g (0.8 mol) of n-butyl alcohol were stirred and reacted at 95 ° C. for 6 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain pyromellitic acid diethyl ester. Next, 95.17 g (0.8 mol) of thionyl chloride and 70 g of tetrahydrofuran (THF) were added and reacted at 40 ° C. for 3 hours. Subsequently, 200 g of N-methylpyrrolidone was added, excess thionyl chloride and THF were removed under reduced pressure, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di n-butyl ester dichloride solution (e) 239 0.6 g (0.08 mol) was obtained.

Synthesis Example 6 Synthesis of quinonediazide compound (f) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.23 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 33.58 g (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (f).

合成例７ キノンジアジド化合物（ｇ）の合成
乾燥窒素気流下、４−イソプロピルフェノール６．８１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド１３．４３ｇ（０．０５モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン５．０６ｇを用い、合成例６と同様にして、キノンジアジド化合物（ｇ）を得た。

Synthesis Example 7 Synthesis of quinonediazide compound (g) In a dry nitrogen stream, 6.81 g (0.05 mol) of 4-isopropylphenol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 1,4- Dissolved in 450 g of dioxane and brought to room temperature. Here, 1,4-dioxane 50g and using the mixed triethylamine 5.06g was, in the same manner as in Synthesis Example 6 to obtain a quinonediazide compound (g).

合成例８ キノンジアジド化合物（ｈ）の合成
乾燥窒素気流下、ビスフェノールＡ １１．４１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド２６．８６ｇ（０．１モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１０．１２ｇを用い、合成例６と同様にしてキノンジアジド化合物（ｈ）を得た。

Synthesis Example 8 Synthesis of quinonediazide compound (h) In a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 450 g of 1,4-dioxane. And brought to room temperature. A quinonediazide compound (h) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

合成例９ 活性エステル化合物（ｉ）の合成
乾燥窒素気流下、４−カルボキシ安息香酸クロリド１８．５ｇ（０．１モル）とヒドロキシベンゾトリアゾール１３．５ｇ（０．１モル）をテトラヒドロフラン（ＴＨＦ）１００ｇに溶解させ、−１５℃に冷却した。ここにＴＨＦ５０ｇに溶解させたトリエチルアミン１０．０ｇ（０．１モル）を反応液の温度が０℃を越えないように滴下した。滴下終了後、２５℃で４時間反応させた。この溶液をロータリーエバポレーターで濃縮して、活性エステル化合物（ｉ）を得た。

Synthesis Example 9 Synthesis of active ester compound (i) Under a dry nitrogen stream, 18.5 g (0.1 mol) of 4-carboxybenzoic acid chloride and 13.5 g (0.1 mol) of hydroxybenzotriazole were added to 100 g of tetrahydrofuran (THF). And cooled to -15 ° C. To this, 10.0 g (0.1 mol) of triethylamine dissolved in 50 g of THF was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the mixture was reacted at 25 ° C. for 4 hours. This solution was concentrated by a rotary evaporator to obtain an active ester compound (i).

合成例１０ アルカリ可溶性ポリマー（Ａ）の合成
乾燥窒素気流下、合成例１で得られた水酸基含有酸無水物（ａ）１２．０１ｇ（０．０２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）１００ｇに溶解させた。ここに合成例２で得られた水酸基含有ジアミン（ｂ）９．６ｇ（０．０１６モル）をＮＭＰ２５ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。次に４−アミノフェノール０．８７ｇ（０．００８モル）を加え５０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール７．１５ｇ（０．０６モル）をＮＭＰ１０ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を８０℃の真空乾燥機で４０時間乾燥した。こうしてアルカリ可溶性ポリマー（Ａ）を得た。

Synthesis Example 10 Synthesis of Alkali-Soluble Polymer (A) Under a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was converted to N-methyl-2-pyrrolidone (NMP). ) Dissolved in 100 g. To this was added 9.6 g (0.016 mol) of the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 together with 25 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.87 g (0.008 mol) of 4-aminophenol was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 40 hours. In this way, alkali-soluble polymer (A) was obtained.

Synthesis Example 11 Synthesis of Alkali-Soluble Polymer (B) Under a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was converted to N-methyl-2-pyrrolidone (NMP). ) Dissolved in 100 g. Here, 4.84 g (0.008 mol) of the hydroxyl group-containing diamine (c) obtained in Synthesis Example 3 and 1.94 g (0.008 mol) of the hydroxyl group-containing diamine (d) obtained in Synthesis Example 4 together with 25 g of NMP. In addition, it was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.94 g (0.008 mol) of 4-ethynylaniline was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 40 hours. Thus, an alkali-soluble polymer (B) was obtained.

Synthesis Example 12 Synthesis of Alkali-Soluble Polymer (C) 10.89 g (0.054 mol) of 4,4′-diaminodiphenyl ether, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 86 g (0.0075 mol) was dissolved in 20 g of N-methyl-2-pyrrolidone (NMP). Here, 30.02 g (0.05 mol) of the hydroxyl group-containing acid dianhydride (a) obtained in Synthesis Example 1 was added together with 15 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. . After the reaction, 2.25 g (0.023 mol) of maleic anhydride was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 15.19 g (0.127 mol) of N, N-dimethylformamide dimethylacetal with 4 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 70 ° C. for 60 hours. Thus, an alkali-soluble polymer (C) was obtained.

Synthesis Example 13 Synthesis of alkali-soluble polymer (D) Hydroxyl-containing diamine compound (c) 9.67 (0.016 mol), 1,3-bis (3-aminopropyl) obtained in Synthesis Example 3 under a dry nitrogen stream ) 1.86 g (0.0075 mol) of tetramethyldisiloxane and 0.87 g (0.008 mol) of 3-aminophenol as an end-capping agent were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 70 ° C. for 60 hours. Thus, an alkali-soluble polymer (D) was obtained.

Synthesis Example 14 Synthesis of Alkali-Soluble Polymer (E) Hydroxyl-containing diamine compound (c) 9.67 (0.016 mol), 1,3-bis (3-aminopropyl) obtained in Synthesis Example 3 under a dry nitrogen stream ) 1.86 g (0.0075 mol) of tetramethyldisiloxane was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.94 g (0.008 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 4.77 g (0.04 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 70 ° C. for 60 hours. Thus, an alkali-soluble polymer (E) was obtained.

Synthesis Example 15 Synthesis of alkali-soluble polymer (F) 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added to N-methyl-2-pyrrolidone (NMP) under a dry nitrogen stream. Dissolved in 50 g. 3-aminophenol 1.09g (0.01 mol) was added here as terminal blocker, and it was made to react at 40 degreeC for 1 hour. Next, 3.02 g (0.005 mol) of the hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 1 g (0.005 mol) of 4,4′-diaminodiphenyl ether were added to 10 g of NMP, and further at 40 ° C. for 2 hours. Reacted. Thereafter, a solution obtained by diluting 5.96 g (0.05 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 70 ° C. for 60 hours. Thus, an alkali-soluble polymer (F) was obtained.

Synthesis Example 16 Synthesis of Alkali-Soluble Polymer (G) 18.68 g (0.051 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1,3-bis ( 3-aminopropyl) tetramethyldisiloxane 1.86 g (0.0075 mol), 9.62 g (0.034 mol) active ester compound (i) as a terminal blocking agent 11.93 g (0.151 mol) pyridine It was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride solution (e) was added dropwise so that the temperature in the system would not exceed 10 ° C. . After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours. Thus, an alkali-soluble polymer (G) was obtained.

Synthesis Example 17 Synthesis of alkali-soluble polymer (H) Under a dry nitrogen stream, 7.75 g (0.051 mol) of 3,5-diaminobenzoic acid, 4 g (0.02 mol) of 4,4′-diaminodiphenyl ether, end-capped As stopping agents, 1.96 g (0.018 mol) of 3-aminophenol and 12.66 g (0.16 mol) of pyridine were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride solution (e) was added dropwise so that the temperature in the system would not exceed 10 ° C. . After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours. Thus, an alkali-soluble polymer (H) was obtained.

Example 1
Pigment Red 177 (anthraquinone red) 1.8 g, Pigment Green 7 (phthalocyanine green) 1.8 g, Pigment Blue 15 (phthalocyanine blue) 1.4 g, together with 40 g of γ-butyrolactone, 5 g of butyl cellosolve, and 100 g of glass beads. After dispersing for 30 minutes at 7000 rpm using a homogenizer, the glass beads were removed by filtration to obtain a dispersion having an organic pigment concentration of 10% by weight. A positive photosensitive resin obtained by adding a mixed solution of 5 g of the alkali-soluble polymer (A) obtained in Synthesis Example 10, 2 g of the quinonediazide compound (h) obtained in Synthesis Example 8 and 11 g of ethyl lactate to 32 g of the organic pigment dispersion A varnish A of the composition was obtained.

A 300 mm × 350 mm glass substrate having a 130 nm thick ITO transparent electrode film formed on the surface of a 300 × 350 × 0.7 mm ³ non-alkali glass (Corning Japan Co., Ltd., # 1737) by sputtering vapor deposition is prepared. did. A photoresist was applied onto the ITO substrate by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of the ITO by etching, the ITO film was patterned into a stripe shape having a length of 90 mm and a width of 80 μm by removing the photoresist. The striped first electrodes have a pitch of 100 μm.

Varnish A was applied onto a glass substrate patterned with ITO using a slit die coating method so that the film thickness after soft baking was 1.5 μm. The coating speed was 3 m / min. When the spin coating method was used, the coating was performed by adjusting the rotation speed so that the film thickness after soft baking was 1.5 μm. Then, using a hot plate (EA-4331 manufactured by Chuo Riken Co., Ltd.), the glass substrate is held at a height of 5.0 mm from the hot plate with a proxy pin, and heated at 120 ° C. for 10 minutes, thereby positive-type photosensitive. An adhesive resin coating film was obtained. This coating film of varnish A was exposed to UV light (800 mJ / cm ² ) through a photomask, then developed by dissolving only the exposed portion with a 2.38% TMAH aqueous solution for 90 seconds, and rinsed with pure water. The obtained polyimide precursor resin pattern was cured by heating at 250 ° C. for 60 minutes in a nitrogen atmosphere in a clean oven to form an insulating layer so as to cover the edge of the first electrode. The thickness of the insulating layer was about 1 μm. In this way, a light-shielding insulating layer made of a photosensitive polyimide resin having a shape in which an opening having a width of 70 μm and a length of 250 μm exposes the center of the first electrode and covers the end of the first electrode. Formed. O. of the insulating layer. D was 2.6. The cross section of the boundary portion of the insulating layer has a forward taper shape as shown in FIG. 1, and the taper angle θ is about 45 °.

  Next, an organic electroluminescent display device was manufactured using a substrate on which an insulating layer was formed. The thin film layer including the light emitting layer was formed by a vacuum evaporation method using a resistance wire heating method. A hole transport layer was formed by vapor deposition over the entire substrate effective area, and a light emitting layer and aluminum for the second electrode were formed using a shadow mask.

  The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together a board | substrate and the glass plate for sealing using the ultraviolet curing epoxy resin. In this way, a simple matrix type color organic light emitting display device in which a patterned light emitting layer is formed on the ITO striped first electrode and the striped second electrode is arranged so as to be orthogonal to the first electrode is manufactured. did. When this display device was line-sequentially driven, good display characteristics could be obtained. The thin film layer and the second electrode at the boundary of the insulating layer were formed smoothly without any thinning or disconnection, so there was no uneven brightness in the light emitting region and stable light emission. was gotten. The effective light emission area ratio S after the durability test was 100%, indicating high reliability.

Example 2
10 g of carbon black “MA100” (manufactured by Mitsubishi Chemical Corporation) as a colorant, 10 g of the alkali-soluble polymer (A) obtained in Synthesis Example 10, 114.5 g of γ-butyrolactone, 3-methyl-3-methoxybutyl acetate 60 g of glass beads were dispersed together with 100 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration. To this, 5 g of the quinonediazide compound (h) obtained in Synthesis Example 8 and 0.5 g of vinylmethoxysilane were added to obtain varnish B of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish B was used.

Comparative Example 1
10 g of the alkali-soluble polymer (B) obtained in Synthesis Example 11, 1.7 g of the quinonediazide compound (g) obtained in Synthesis Example 7, 1 g of TrisP-PA, 0.3 g of vinylmethoxysilane, 20 g of γ-butyrolactone and 12 g of ethyl lactate In addition, 5 g of an azo dye Neptun Black X60 (Solvent Black 3, manufactured by BASF Corp.) was added as a colorant to obtain a varnish C of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish C was used and the curing condition was heated at 230 ° C. for 30 minutes in a clean oven under a nitrogen atmosphere.

Example 3
10 g of the alkali-soluble polymer (B) obtained in Synthesis Example 11 and 15 g of manganese oxide powder (electrolytic manganese dioxide: γ-MnO ₂ manufactured by Tosoh Corporation) as a colorant, 100 g of N-methyl-2-pyrrolidone, 3 -67.5 g of methyl-3-methoxybutyl acetate was dispersed with a homogenizer together with 100 g of glass beads at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration. To this, 7.5 g of the quinonediazide compound (h) obtained in Synthesis Example 8 was added to obtain a varnish D of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish D was used and the curing condition was continued to be heated at 170 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven and then heated at 320 ° C. for 30 minutes.

Example 4
As a colorant, Orasol Blue GN (solvent blue 67, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.4 g, Pigment Red 177 (Anthraquinone Red) 1.8 g, Pigment Green 7 (Phthalocyanine Green) 1.8 g the γ- butyrolactone 40 g, butyl cellosolve 5g, using a homogenizer with glass beads 100 g, after 30 minutes dispersion treatment at 7000 rpm, the glass beads were removed by filtration to obtain a dye-organic Pigment concentration 10 wt% of the dispersion. A mixed solution of 5 g of the alkali-soluble polymer (C) obtained in Synthesis Example 12, 2 g of the quinonediazide compound (h) obtained in Synthesis Example 8, 13 g of TrisP-PA and 13 g of γ-butyrolactone was added to 29 g of the dye / pigment dispersion. As a result, varnish E of the positive photosensitive resin composition was obtained. A display device was prepared in the same manner as in Example 1 except that varnish E was used and the curing condition was heated at 200 ° C. for 60 minutes in an air atmosphere in a clean oven.

Example 5
10 g of the alkali-soluble polymer (D) obtained in Synthesis Example 13 and 10 g of the quinonediazide compound obtained in Synthesis Example 7 (10 g of electrolytic manganese dioxide: γ-MnO ₂ manufactured by Tosoh Corporation) which is a colorant g) 6.5 g, 100 g of γ-butyrolactone, and 73.5 g of 3-methyl-3-methoxybutyl acetate were dispersed together with 100 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration. In this way, the varnish F of the positive photosensitive resin composition was obtained. A display device was prepared in the same manner as in Example 1 except that the varnish F was used and the curing condition was continuously heated at 170 ° C. for 30 minutes in a clean oven under a nitrogen atmosphere and then heated at 320 ° C. for 30 minutes.

Example 6
Carbon black “MA100” (Mitsubishi Chemical Corporation) 1.8 g, Pigment Red 177 (Anthraquinone Red) 1.8 g, Pigment Blue 15 (phthalocyanine blue) 1.4 g, γ-butyrolactone 40 g, and butyl cellosolve 5 g of glass beads and 100 g of glass beads were used for dispersion treatment at 7000 rpm for 30 minutes using a homogenizer, and then the glass beads were removed by filtration to obtain a dispersion having an organic pigment concentration of 10% by weight. Positive type photosensitivity by adding a mixed solution of 7 g of the alkali-soluble polymer (D) obtained in Synthesis Example 13, 4 g of the quinonediazide compound (g) obtained in Synthesis Example 7 and 9 g of propylene glycol monomethyl ether to 30 g of the organic pigment dispersion. Varnish G was obtained. A display device was prepared in the same manner as in Example 1 except that the varnish G was used and the curing condition was heated at 280 ° C. for 60 minutes in an air atmosphere in a clean oven.

Comparative Example 2
10 g of the alkali-soluble polymer (E) obtained in Synthesis Example 14, 2.8 g of the quinonediazide compound (f) obtained in Synthesis Example 6, 2.2 g of TrisP-PA, 0.1 g of vinylmethoxysilane, 15 g of γ-butyrolactone and lactic acid In addition to a mixed solvent of 15 g of ethyl, 2.8 g of azochrome complex-based dye Valifast Black 1807 and 2.1 g of phthalocyanine-based Valifast Blue 2620 (produced by Orient Chemical Co., Ltd., described in the catalog of the 2.22.2 version) as a coloring agent Addition to obtain a varnish H of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish H was used and the curing condition was heated at 230 ° C. for 30 minutes in an air atmosphere in a clean oven.

Example 7
Manganese oxide powder (electrolytic manganese dioxide: γ-MnO ₂ manufactured by Tosoh Corporation) as a colorant, 2.5 g of phthalocyanine dye Valifast Blue 2620 (produced by Orient Chemical Co., Ltd., described in the catalog of 2.22.2 version) Was dispersed for 30 minutes at 7000 rpm using a homogenizer together with 42.5 g of γ-butyrolactone and 100 g of glass beads, and then the glass beads were removed by filtration to obtain a dispersion having a dye / inorganic pigment concentration of 10% by weight. Mixing 4 g of the alkali-soluble polymer (E) obtained in Synthesis Example 14, 2 g of the quinonediazide compound (f) obtained in Synthesis Example 6, 1.2 g of TrisP-PA, and 15.8 g of ethyl lactate in 27 g of the dye / pigment dispersion The solution was added to obtain a varnish I of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that the varnish I was used and the curing condition was heated at 250 ° C. for 30 minutes in an air atmosphere in a clean oven.

Example 8
The alkali-soluble polymer obtained in Synthesis Example 15 was obtained by using ₃ g of carbon black “MA100” (Mitsubishi Chemical Corporation) and 2.5 g of manganese oxide powder Mn ₂ O ₃ (Aldrich Chemical Co., Ltd.) as colorants. (F) The glass beads were removed by filtration after dispersion treatment at 7000 rpm for 30 minutes using 10 g, γ-butyrolactone 60 g, and glass beads 100 g using a homogenizer. Thereto was added a mixed solution of 3.3 g of the quinonediazide compound (h) obtained in Synthesis Example 8 and 31.2 g of γ-butyrolactone to obtain a varnish J of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish J was used and the curing condition was heated at 280 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven.

Example 9
Carbon black “MA100” (manufactured by Mitsubishi Chemical Corporation) as a coloring agent was added to 18 g of the alkali-soluble polymer (G) obtained in Synthesis Example 16; 117.5 g of N-methyl-2-pyrrolidone; 3-methyl-3 -After 50 g of methoxybutyl acetate was dispersed together with 100 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, the glass beads were removed by filtration. To this, 4.5 g of the quinonediazide compound (h) obtained in Synthesis Example 8 was added to obtain a varnish K of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish K was used and the curing condition was continued to be heated at 170 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven and then heated at 320 ° C. for 60 minutes.

Example 10
Pigment Red 122 (quinacridone red magenta) which is a coloring agent, 3.2 g of Pigment Blue 15: 6 (phthalocyanine blue E) at 7000 rpm using a homogenizer together with 30 g of γ-butyrolactone, 15 g of butyl cellosolve and 100 g of glass beads. After the dispersion treatment for 30 minutes, the glass beads were removed by filtration to obtain a dispersion having an organic pigment concentration of 10% by weight. To 26 g of the organic pigment dispersion, 5 g of the alkali-soluble polymer (G) obtained in Synthesis Example 16, 1.3 g of the quinonediazide compound (h) obtained in Synthesis Example 8, TrisP-PA 0.7 g, N-methyl-2- A mixed solution of 17 g of pyrrolidone was added to obtain a varnish L of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that the varnish L was used and the curing condition was heated at 280 ° C. for 30 minutes in an air atmosphere in a clean oven.

Example 11
Manganese oxide powder Mn ₃ O ₄ 4.2 g (manufactured by Aldrich Chemical Co., Ltd.) as a colorant, 10 g of alkali-soluble polymer (G) obtained in Synthesis Example 16, 60 g of N-methyl-2-pyrrolidone, glass Using a homogenizer together with 100 g of beads, the glass beads were removed by filtration after a dispersion treatment at 7000 rpm for 30 minutes. To this was added a mixed solution of 2.6 g of the quinonediazide compound (g) obtained in Synthesis Example 7, 1.7 g of TrisP-PA, 0.4 g of vinylsilane, and 21.1 g of N-methyl-2-pyrrolidone. The varnish M of the functional resin composition was obtained. A display device was prepared in the same manner as in Example 1 except that the varnish M was used and the curing condition was continued to be heated at 200 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven and then heated at 350 ° C. for 30 minutes.

Comparative Example 3
10 g of the alkali-soluble polymer (H) obtained in Synthesis Example 17, 3.4 g of the quinonediazide compound (f) obtained in Synthesis Example 6, 1.9 g of TrisP-PA, and 0.2 g of vinylmethoxysilane were added to N-methyl-2- In addition to 30 g of pyrrolidone, 4.5 g of an azo dye Neptun Black X60 (Solvent Black 3, manufactured by BASF Corp.) was added as a colorant to obtain a varnish O of a positive photosensitive resin composition. A display device was prepared in the same manner as in Example 1 except that varnish O was used and the curing condition was heated at 200 ° C. for 30 minutes in a clean oven under a nitrogen atmosphere.

Comparative Example 4
A negative type photosensitive polyimide precursor varnish (UR-3100 manufactured by Toray Industries, Inc., UR-3100) is added with 10 g of azo dye Neptun Black X60 (solvent black 3, manufactured by BASF Corporation) as a colorant. The varnish P of the photosensitive resin composition was obtained. Using this varnish P, it was applied onto a substrate on which the first electrode was formed by spin coating, and prebaked on a hot plate at 80 ° C. for 1 hour. This coating film was exposed to 150 mJ / cm ² UV through a photomask, then developed by dissolving only the non-exposed portion for 40 seconds with a developer (Toray Industries, Inc., DV-505), and rinsed purely . Thereafter, an insulating layer was formed by heating at 180 ° C. for 30 minutes and further at 220 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven. O. of the obtained light-shielding insulating layer. D was 0.4. The cross section of the boundary portion of the insulating layer was rectangular, and the taper angle θ was about 90 °.

  Thereafter, in the same manner as in Example 1, a simple matrix organic electroluminescence display device was produced. When this display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thin at the boundary portion of the insulating layer, and luminance unevenness was observed in the light emitting region. The effective light emission area ratio S after the durability test was 70%.

Comparative Example 5
Under a dry nitrogen stream, 10.7 g (0.049 mol) of pyromellitic dianhydride, 16.1 g (0.05 mol) of benzophenonetetracarboxylic dianhydride, 3, γ-butyrolactone (274 g), 6.2 g (0.025 mol) of 3′-diaminodiphenylsulfone, 14 g (0.07 mol) of 4,4′-diaminodiphenyl ether, 1.2 g (0.005 mol) of bis-3- (aminopropyl) tetramethylsiloxane ) At 60 ° C. for 3 hours, and then 0.2 g (0.002 mol) of maleic anhydride is added and further reacted at 60 ° C. for 1 hour, whereby the precursor polyamic acid solution B (polymer concentration 15 % By weight).

11.2 g of manganese oxide powder (electrolytic manganese dioxide: γ-MnO ₂ manufactured by Tosoh Corp.), polyamic acid solution B8.7 g, N-methyl-2-pyrrolidone 57.2 g, 3-methyl- Using a homogenizer together with 12.9 g of 3-methoxyacetate and 100 g of glass beads, the glass beads were removed by filtration at 7000 rpm for 30 minutes to obtain a pigment dispersion having a pigment concentration of 14% by weight. To 27.5 g of the pigment dispersion, 3.7 g of the polyamic acid solution B, 1 g of γ-butyrolactone, 6 g of N-methyl-2-pyrrolidone, and 1.8 g of solfit acetate are added and mixed, and the varnish Q of the non-photosensitive resin composition is added. Obtained.

  After applying onto the substrate using varnish Q, pre-baking was performed at 145 ° C. to form a polyimide precursor film. A positive type photoresist was applied on the coating film and dried by heating at 90 ° C. to form a photoresist film. The film was exposed to ultraviolet light through a photomask, then immersed in alkali development, and the photoresist film was developed and the polyimide precursor film was etched simultaneously to form openings. After etching, the photoresist film that became unnecessary was peeled off with methyl cellosolve acetate. The etched polyimide precursor film was heated at 290 ° C. for 60 minutes to form a polyimide insulating layer. O. of the obtained light-shielding insulating layer. D was 2.8. The cross section of the boundary portion of the insulating layer was a forward taper shape, and the taper angle θ was about 70 °.

  Thereafter, in the same manner as in Example 1, a simple matrix organic electroluminescence display device was produced. When this display device is driven line-sequentially, the thin film layer and the second electrode layer tend to become thin at the boundary portion of the insulating layer because the cross section of the insulating layer has a forward taper shape with a taper angle of about 70 °. Brightness unevenness was observed in the area. The effective light emission area ratio S after the durability test was 80%.

Comparative Example 6
176 g (0.1 mol) of t-butoxystyrene and 5.8 g (0.04 mol) of azobisisobutyronitrile were dissolved in 250 ml of propylene glycol monomethyl ether, and reacted at 75 ° C. for 4 hours. The poly t-butoxystyrene solution thus obtained was mixed with 50 g of a 5 wt% aqueous sulfuric acid solution, and subjected to a hydrolysis reaction at 100 ° C. for 3 hours. The reaction product was washed 3 times with 1000 ml of deionized water, 500 ml of propylene glycol monomethyl ether acetate was added, and the solvent was replaced to obtain an alkali-soluble resin (polyhydroxystyrene) solution.

  This alkali-soluble resin solution (corresponding to 100 parts by weight of polyhydroxystyrene (solid content)) and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene ] 30 parts by weight of a condensate of bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol), 10 parts by weight of carbon black, and a urethane-based dispersant (trade name Disperbyk-182) 2 parts by weight, 5 parts by weight of γ-methacryloxypropyltrimethoxysilane, and 30 parts by weight of Cymel 300 (manufactured by Mitsui Cyanamid Co., Ltd.) are mixed and mixed with propylene glycol monomethyl ether acetate so that the solid content concentration is 25% by weight. It was dissolved to obtain a varnish R of a positive radiation sensitive resin composition.

The varnish R was applied onto the substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film having a thickness of 5 μm. This coating film was exposed to 300 mJ / cm ² UV through a photomask, developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 90 seconds, and rinsed with pure water. Thereafter, heating was performed at 220 ° C. for 60 minutes in an air atmosphere in a clean oven to form an insulating layer having a thickness of 4.5 μm. O. of the obtained light-shielding insulating layer. D was 1.1. The cross section of the boundary portion of the insulating layer was rectangular, and the taper angle θ was about 90 °.

  Thereafter, in the same manner as in Example 1, a simple matrix organic electroluminescence display device was produced. When this display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thin at the boundary portion of the insulating layer, and luminance unevenness was observed in the light emitting region. The effective light emission area ratio S after the durability test was 70%.

Comparative Example 7
Metacresol 57 g (0.6 mol), paracresol 38 g (0.4 mol), 37 wt% aqueous formaldehyde solution 75.5 g (formaldehyde 0.93 mol), Shusan dihydrate 0.63 g (0.005 mol) Was dissolved in 264 g of methyl isobutyl ketone, and polycondensation was performed for 4 hours with stirring while the reaction solution was refluxed. Subsequently, the temperature was raised over 3 hours, and then the pressure in the flask was reduced to 30 to 50 mmHg to remove volatile components, and the molten resin was cooled to room temperature and recovered. This resin was dissolved in ethyl acetate so that the resin component would be 30%, then 1.3 times the amount of methanol and 0.9 times the amount of water were added and left stirring. Subsequently, the lower layer separated into two layers was taken out, concentrated and dried to obtain a novolak resin having Mw 8000.

  To 100 parts by weight of this novolak resin, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide- 30 parts by weight of a condensate with 5-sulfonic acid chloride (2 mol), 10 parts by weight of carbon black, 2 parts by weight of a urethane dispersant (trade name Disperbyk-182), 5 parts by weight of γ-methacryloxypropyltrimethoxysilane And 30 parts by weight of Cymel 300 (manufactured by Mitsui Cyanamid Co., Ltd.) are mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 25% by weight, and the varnish S of the positive radiation sensitive resin composition Got.

Using this varnish S, an insulating layer was formed in the same manner as in Comparative Example 6 . O. of the obtained light-shielding insulating layer. D was 1.0. The cross section of the boundary portion of the insulating layer was rectangular, and the taper angle θ was about 90 °.

  Thereafter, in the same manner as in Example 1, a simple matrix organic electroluminescence display device was produced. When this display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thin at the boundary portion of the insulating layer, and luminance unevenness was observed in the light emitting region. The effective light emitting area ratio S after the durability test was 50%.

Comparative Example 8
2,2'-azobis (2,4-dimethylvaleronitrile) 7 parts by weight solution in 200 parts by weight of propylene glycol monomethyl ether acetate, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, main methacrylic acid glycidyl 45 weight And 25 parts by weight of dicyclopentanyl methacrylate were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was maintained for 5 hours to obtain an acrylic resin solution.

  This acrylic resin solution (corresponding to 100 parts by weight (solid content) of acrylic resin) and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol), 30 parts by weight, 10 parts by weight of carbon black, and 2 parts by weight of a urethane-based dispersant (trade name Disperbyk-182) Parts, 5 parts by weight of γ-methacryloxypropyltrimethoxysilane and 30 parts by weight of Cymel 300 (manufactured by Mitsui Cyanamid Co., Ltd.) are mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 25% by weight. A varnish T of a positive radiation sensitive resin composition was obtained.

Using this varnish T, an insulating layer was formed in the same manner as in Comparative Example 6 . O. of the obtained light-shielding insulating layer. D was 1.0. The cross section of the boundary portion of the insulating layer was a forward tapered shape, and the taper angle θ was about 85 °.

  Thereafter, in the same manner as in Example 1, a simple matrix organic electroluminescence display device was produced. When this display device is driven line-sequentially, since the cross section of the insulating layer has a forward taper shape with a taper angle of about 85 °, the thin film layer and the second electrode layer become thin at the boundary portion of the insulating layer, and within the light emitting region. Uneven brightness was observed. The effective light emission area ratio S after the durability test was 70%.

Comparative Example 9
In place of 5 g of the azo dye Neptun Black X60 (solvent black 3, manufactured by BASF Corporation), which is the colorant of Comparative Example 1 , 5 g of crystal violet lactone, which is a coloring material, is added to form a positive photosensitive resin composition The product varnish U was obtained.

  Using this varnish U, an insulating layer was formed in the same manner as in Example 1. O. of the obtained light-shielding insulating layer. D was 0.7. The cross section of the boundary portion of the insulating layer was a forward tapered shape, and the taper angle θ was about 60 °.

  Thereafter, in the same manner as in Example 1, a simple matrix organic electroluminescence display device was produced. When this display device was driven line-sequentially, the thin film layer and the second electrode were formed smoothly without causing thinning or disconnection at the boundary portion of the insulating layer, thereby obtaining good display characteristics. I was able to. The effective light emission area ratio S after the durability test was 70%.

The evaluation results of Examples 1 to 11 and Comparative Examples 1 to 9 are shown in Table 1.

Diagram showing the boundary of the insulating layer

Explanation of symbols

1 Substrate 2 First electrode 3 Insulating layer

Claims (3)

(A) From an alkali-soluble heat-resistant resin whose main component is a structure selected from the following general formulas (1) to (4), (b) an esterified quinonediazide compound, and (c ) ( c2) an insulating metal compound And a positive photosensitive resin composition comprising as an essential component an inorganic pigment (c3) and at least one colorant selected from (c3) carbon black and / or two or more organic pigments.

Wherein R ¹ is a divalent to octavalent organic group having at least 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having at least 2 or more carbon atoms, and R ³ is hydrogen or An organic group having 1 to 20 carbon atoms, R ⁴ represents a divalent organic group, and X and Y each contain at least one or more of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and an unsaturated hydrocarbon group; hydrocarbon group having from 1 to 10 carbon atoms which, nitro group, methylol group, an integer of ester groups, .n showing a monovalent organic group having at least one chosen group from hydroxyalkynyl groups from 10 to 100,000, m is an integer from 0 to 10, p and q are integers from 0 to 4, and r is an integer from 0 to 2. p + q> 0. A method for producing a pattern, comprising a step of applying the positive photosensitive resin composition according to claim 1 to a support substrate and drying, a step of exposing, a step of developing using an alkali developer, and a step of heat treatment. An organic light emitting display having a pattern obtained by the manufacturing method according to claim 2.

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