JP2007183388A - Photosensitive resin composition, method for producing heat resistant resin pattern, and organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which has superior suitability to coating, without impairing the storage stability of the solution, and which has chemical resistance and can be baked at a low temperature. <P>SOLUTION: The photosensitive resin composition comprises (a) a polyimide resin, represented by a specific formula and having a terminal group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group and (b) a photoacid generator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. More specifically, for surface protective films of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements and flexible organic EL elements, planarizing films of TFT substrates for display devices, overcoat films of color filter substrates for display devices, etc. The present invention relates to a suitable positive photosensitive resin composition in which a portion exposed to ultraviolet rays is dissolved in an alkali developer.

  In recent years, in applications such as surface protection films for semiconductor elements, interlayer insulation films, insulation layers for organic electroluminescent elements, TFT substrates for display devices, planarization films for color filters, and overcoat films, (1) The cross-sectional shape is a forward taper shape, and (2) heat-firing at 230 ° C. or at a lower temperature is required. Although the negative photosensitive resin composition has heat resistance by heating and baking at 230 ° C. or lower, it is inappropriate because the cross-sectional shape is rectangular or inversely tapered. On the other hand, in the positive photosensitive resin composition in which quinonediazide is added to polyamic acid, the heat treatment at 230 ° C. or lower does not sufficiently progress the cyclic structure of the polymer, and heat resistance and solvent resistance sufficient for the film after heat treatment Since performance could not be imparted, practical application was difficult.

  On the other hand, a photosensitive resin composition made of an alkali-soluble polyimide in which the resin itself is already imidized can be fired at a low temperature and is suitable for semiconductor applications and display element applications. As alkali-soluble polyimide resin, what contains alkali-soluble groups, such as a phenolic hydroxyl group and a carboxyl group, is disclosed in the amine component in a principal chain (for example, refer patent documents 1-3). These polyimide resins are excellent in alkali solubility, and have a basic solubility in organic solvents because they use fluorine-containing aromatic groups or aliphatic groups in the acid component and diamine component to obtain transparency. The chemical resistance of the resulting polyimide resin film is not sufficient. Moreover, although an alkali-soluble polyamide-imide resin using an acid component containing a hydroxyl group has been disclosed (see, for example, Patent Document 4), an amide group was introduced to obtain heat resistance and transparency, but a fat was added to the amine component. The chemical resistance was still insufficient.

Furthermore, these disclosed alkali-soluble polyimide resins and alkali-soluble polyamideimide resins have a large molecular weight, and the resulting resin itself has a reduced viscosity or logarithmic viscosity as high as 0.5 dl / g. The viscosity of the photosensitive resin composition obtained using such a high molecular weight resin is higher than that of a normal photoresist typified by a novolak resin, and often has a problem in the coating process. Usually, a photosensitive resin composition is applied to a substrate by a spin coating method or a slit coating method. However, with the recent increase in size of a substrate, a highly viscous resin composition is imparted with good film thickness uniformity. It has become difficult to apply. As a specific problem when applying a resin composition having a high viscosity, for example, in the spin coating method, in order to obtain a uniform coating film, the substrate must be rotated at a high speed. It was. Further, in the slit coating method, when the viscosity is high, smooth ejection from the nozzle is hindered, often causing liquid breakage, and there is a problem that it cannot be applied to the entire surface of the substrate. As a countermeasure, it is conceivable to lower the solid content concentration of the resin composition to lower the viscosity, but the problem is that the coating film becomes thin because the concentration is low in any coating method, and the desired film thickness cannot be obtained. Could not be avoided.
Japanese Patent No. 2935994 Japanese Patent No. 2990637 JP-A-2005-196130 JP 2002-88154 A

  An object of the present invention is to provide a positive-type photosensitive resin composition that has excellent coating properties and has chemical resistance, without impairing the storage stability of a solution, and can be fired at low temperature.

  That is, the present invention is a photosensitive resin composition comprising (a) a resin having a structural unit represented by any one of the general formulas (1) to (4) and (b) a photoacid generator. is there.

(In the formula, R ¹ represents a 4- to 14-valent organic group, R ² represents a ^2- to 12-valent organic group. R ³ and R ⁵ represent a hydrogen atom, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or carbon. R ⁴ represents a divalent organic group, and X and Y are a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. A monovalent organic group having at least one group selected from the above, n is in the range of 3 to 200, and m, r, and s are integers of 0 to 10.)

  ADVANTAGE OF THE INVENTION According to this invention, the positive type photosensitive polyimide resin composition which is excellent in storage stability and application | coating property, and has high chemical resistance under low-temperature baking can be provided.

  The photosensitive resin composition of the present invention contains (a) a resin having a structural unit represented by any one of the general formulas (1) to (4) and (b) a photoacid generator.

R ^{1 in the} above general formulas (1) to (4) is a 4- to 14-valent organic group, and preferably has an aromatic ring. Furthermore, it is preferable that it is a C4-C40 organic group. R ³ may be the same or different, and represents a hydrogen atom or a group selected from a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and an organic group having 1 to 20 carbon atoms. R ^1- (R ³ ) _r represents a structural component of acid dianhydride. R ² is a divalent to divalent organic group and preferably has an aromatic ring. Furthermore, it is preferable that it is a C4-C40 organic group. R ⁵ may be the same or different, and represents a hydrogen atom or a group selected from a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and an organic group having 1 to 20 carbon atoms. R ² — (R ⁵ ) _s represents a structural component of diamine. At least one of R ¹ and R ² has at least one group selected from 1,1,1,3,3,3-hexafluoropropyl group, ether group, thioether group, SO ₂ group, and cyclobutane residue. Is preferred. More preferably, both R ¹ and R ² have at least one group selected from a 1,1,1,3,3,3-hexafluoropropyl group, an ether group, a thioether group, an SO ₂ group, and a cyclobutane residue. .

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyl Nyl) methane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic Aromatic tetracarboxylic dianhydrides such as acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3 , 4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, and Aromatic dianhydrides such as acid dianhydrides having an amide group shown below can be mentioned. These are used alone or in combination of two or more.

In the above formula, R ⁷ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ⁸ and R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.

  By using these acid dianhydrides having an alkali-soluble group and an amide group as raw materials, alkali solubility and chemical resistance can be improved.

  In addition to the above acid dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3- Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5,6-tetraca Aliphatic tetracarboxylic dianhydrides such as boronic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.

  Of these, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoro Propane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydrides, aliphatic tetracarboxylic dianhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and acid dianhydrides having an amide group shown below Any aromatic or aliphatic dianhydride is particularly preferred. These are used alone or in combination of two or more.

In the above formula, R ⁷ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ⁸ and R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.

In addition, it is preferable that R ¹ is an organic group having an aromatic ring and / or a heterocyclic ring at both ends and an amide group, since chemical resistance is improved. The proportion of the amide group of the organic group relative to the total amount of R ¹ is preferably 10 to 200 mol%. More preferably, it is 40-200 mol%.

  Specific examples of diamines include 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, and 2,6-naphthalenediamine. 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'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'- Diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or these aromatic rings substituted with alkyl groups or halogen atoms Compounds, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Scan and (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds substituted with alkyl group or halogen atom in the aromatic ring, and a diamine having an amide group shown below. These are used alone or in combination of two or more.

In the above formula, R ⁷ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ⁸ and R ⁹ each independently represent a hydrogen atom, a hydroxyl group or a thiol group.

  By using these diamines having an alkali-soluble group and an amide group as raw materials, alkali solubility and chemical resistance can be improved.

  Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Scan (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds substituted with alkyl group or halogen atom in the aromatic ring, and the like diamines having an amide group shown in the following may be mentioned as preferred. These are used alone or in combination of two or more.

In the above formula, R ⁷ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ⁸ and R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group. These are used alone or in combination of two or more.

In addition, it is preferable that R ² is an organic group having an aromatic ring and / or a heterocyclic ring at both ends and an amide group, since chemical resistance is improved. The ratio of the amide group of the organic group to the total amount of R ² is preferably 10 to 200 mol%. More preferably, it is 40-200 mol%. Also, the amide group contained in ^{R 1} and ^{R 2,} the proportion with respect to ^{R 1} and ^{R 2} total is preferably 10 to 200 mol%.

R ³ and R ^{5 in the} general formulas (1) to (4) may be the same or different and are selected from a hydrogen atom, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or an organic group having 1 to 20 carbon atoms. Represents a group. In order to dissolve and remove the unfired film obtained by applying and drying the photosensitive resin composition solution on a substrate with an alkaline aqueous solution, phenolic hydroxyl groups and sulfonic acids in which R ³ and R ⁵ are alkali-soluble groups It is preferably a group or a thiol group. In the present invention, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group can be mixed with a hydrogen atom or an organic group having 1 to 20 carbon atoms.

By adjusting the amount of the alkali-soluble group of R ³ and R ⁵ and the amount of hydrogen atom or organic group having 1 to 20 carbon atoms, the dissolution rate in the alkaline aqueous solution changes. A photosensitive resin composition can be obtained. A preferable range is that 5% to 100% of the total amount of R ³ and R ⁵ is an alkali-soluble group. If the number of carbon atoms in R ³ and R ⁵ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ³ and R ⁵ preferably contain one or more hydrogen atoms or hydrocarbon groups having 1 to 16 carbon atoms, and the others are more preferably alkali-soluble groups.

X- (R ⁴ ) _m-, which is a structural component of the general formula (1) and the general formula (2), is preferably represented by the following general formula (6), which is a primary which is a terminal blocking agent. It is a component derived from monoamine.

In general formula (3), the general formula is a structural component of ^{(4) Y- (R 4)} m - is preferably represented by the general formula (7) or the general formula (8), these, end It is a component derived from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound that are sealing agents.

In general formulas (6) to (8), R ¹⁰ may be the same or different and represents a divalent group selected from —CR ¹⁷ R ¹⁸ —, —CH ₂ O—, and —CH ₂ SO ₂ —. It is preferable that the end-capping agents represented by the general formulas (6) to (8) are excellent in solubility in an alkaline aqueous solution. R ¹⁷ and R ¹⁸ represent a hydrogen atom, a hydroxyl group or a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ¹⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. Of these, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a methyl group and a t-butyl group are particularly preferable. R ¹⁵ and R ¹⁶ represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a ring structure in which R ¹⁵ and R ¹⁶ are directly bonded. (For example, nadiimide ring). From the viewpoint of solubility in an aqueous alkali solution, at least one is preferably a carboxyl group, a sulfonic acid group or a thiol group. R ¹² and R ¹³ represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a hydrocarbon group having 1 to 10 carbon atoms. From the viewpoint of solubility in an alkaline aqueous solution, at least one is preferably a hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group. A ¹ , A ² and A ³ are carbon atoms, nitrogen atoms or sulfur atoms, and may be the same or different. m is an integer of 0 to 10, preferably an integer of 0 to 4. l is 0 or 1, preferably 0. i is 0 or 1, preferably 0. j is an integer of 1 to 3, preferably 1 or 2. k, t and u are 0 or 1.

  Specific examples of the primary monoamine constituting the structure represented by the general formula (6) include aniline, 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-amino Naphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydro Sinaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1- Carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-amino Nicotinic acid, 4-aminosalicylic acid, 5-amino Salicylic acid, 6-aminosalicylic acid, 3-amino-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 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-aminonaphth Talene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto -3-Aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like.

  Among these, from the viewpoint of solubility in an aqueous alkali solution, 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, -Aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. These are used alone or in combination of two or more.

  Specific examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound which are end-capping agents constituting the structure represented by the general formula (7) or (8) include phthalic anhydride, Maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxy Thiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4 -Carboxynaphthalene, 1-hydroxy-3 Carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1- Monocarboxylic acids such as mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid And monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-di Rubonic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene and other monocarboxylic acid compounds in which only the monocarboxyl group of dicarboxylic acids is acid chloride And an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

  Among these, from the ease of introduction into the polymer, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 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- Monocarboxylic acids excellent in alkali solubility such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid are preferably used. . These are used alone or in combination of two or more.

The introduction ratio of the component represented by the general formula (6) (the-(R ⁴ ) _m -X component of the general formulas (1) and (2)) is the primary monoamine component of the end-capping agent which is the original component. In terms of the total amine component, the range is preferably from 1 to 70 mol%, more preferably from 5 to 70 mol%, still more preferably from 20 to 60 mol%. The introduction ratio of the component represented by the general formula (7) or the general formula (8) (general formula (3),-(R ⁴ ) _m -Y component of ( ⁴ )) is the end component which is the original component. In terms of the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound component of the agent, the range of 1 to 70 mol% is preferable with respect to the diamine component, more preferably 5 to 70 mol%, Preferably it is 20-60 mol%. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

  In the general formulas (1) to (4), n represents the number of repeating structural units of the resin and is in the range of 3 to 200. Preferably, it is 8-150. When it says with a weight average molecular weight, 3000-80000 are preferable in polystyrene conversion by gel permeation chromatography, More preferably, it is 8000-50000. When n is smaller than 3, the molecular weight becomes too low, and it becomes difficult to obtain a good coating film.

  In the present invention, (a) the resin having the structural unit represented by any one of the general formulas (1) to (4) has an end group represented by X or Y as an essential component, and seals the end group. The effect can suppress an increase in polymer molecular weight. Therefore, the photosensitive resin composition which suppressed gelation and was excellent in storage stability can be obtained. Furthermore, the photosensitive resin composition of the present invention exhibits excellent applicability when applied by spin coating or slit coating. That is, by using a resin having a structural unit represented by any one of the general formulas (1) to (4), the resulting photosensitive resin composition is compared to the case where a polyimide resin that is not end-capped is used, The solid content concentration is high, but the viscosity is low. Therefore, in the spin coating method, in order to obtain a coating film having a uniform film thickness, it can be achieved by a small amount of coating and not by high-speed rotation coating with danger but by safe low-speed rotation coating. Moreover, it is the slit coat method that the coating property with especially low viscosity and high density | concentration obtained using resin of this invention exhibits the outstanding coating property. Specifically, a coating film having a uniform film thickness can be formed on the entire surface of the substrate without causing liquid breakage. In addition, with the recent increase in size of the coated substrate, a uniform coated film is formed on the entire surface of the substrate without causing liquid breakage even when the slit nozzle is scanned (swept) at high speed from the viewpoint of productivity. be able to. In addition, since the solid content concentration is high, it can be formed without lowering the target film thickness.

  In the present invention, (a) a resin having a structural unit represented by any one of the general formulas (1) to (4) whose end is capped has a logarithmic viscosity in dimethylacetamide at 25 ° C. of 0.05 to 0.45 dl. / G is preferable. More preferably, it is 0.1-0.35 dl / g. In order to obtain a resin having such a logarithmic viscosity, for example, the polymerization ratio of the terminal blocking agent may be 1 to 70 mol% with respect to 100 mol of acid dianhydride and / or diamine. More preferably, it is 5-70 mol%, More preferably, it is 20-60 mol%.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ and / or R ² as long as the heat resistance is not lowered. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-anilino) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, acid Examples of the dianhydride component include 1 to 10 mol% copolymerized 3,4-dicarboxyphenyltetramethyldisiloxane dianhydride.

  In the present invention, the resin of the component (a) may be composed only of the structural unit represented by any one of the general formulas (1) to (4), or may be a copolymer with other structural units or A mixture may be sufficient. In that case, it is preferable to contain 50 mol% or more of the structural units represented by any one of the general formulas (1) to (4). The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.

  In the resin of component (a) used in 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, an acid anhydride, a monoacid chloride compound, a monoamine It replaces with the terminal blocker which is an active ester compound, and is synthesize | combined using a well-known method. 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 diamine compound with a monoacid chloride compound or a mono-active ester compound, and a diamine compound, a diester is obtained by reaction of tetracarboxylic dianhydride and alcohol, and then a diamine (partially with a monoamine) A method of reacting with a certain end-capping agent and the presence of a condensing agent, a diester is obtained by reaction of tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is acid chlorided to obtain a diamine (partially Using a method such as a method of reacting with a monoamine end-capping agent), a polyimide precursor is obtained. It can be synthesized by utilizing a method of amidation reaction.

Moreover, the terminal blocker introduced in the resin can be easily detected by the following method. For example, by dissolving the resin into which the end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component that are the structural units of the resin, this is measured by gas chromatography (GC) or NMR measurement, The end capping agent can be easily detected. Apart from this, the resin component into which the end-capping agent is introduced can be easily detected by directly measuring by pyrolysis gas chromatography (PGC), infrared spectrum or C ¹³ NMR spectrum.

  The photosensitive resin composition of the present invention may contain other alkali-soluble resins in addition to the resin that is component (a). Specifically, there are alkali-soluble polybenzoxazole resin, polyamic acid that is a polyimide precursor, polyhydroxyamide that is a polybenzoxazole precursor, acrylic polymer copolymerized with acrylic acid, novolak resin, siloxane resin, and the like. Such a resin is soluble in an aqueous solution of alkali such as choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate in addition to tetramethylammonium hydroxide. . In addition to polyamic acid, polyamic acid ester, polyisoimide, polyamic acid sulfonamide, polyamic acid with 5 to 50% imide, and the like can also be used. These resins may be used singly or may be used as a mixture, and the proportion of the resin including the component (a) in the whole resin is preferably 60% by weight or less.

  Examples of the photoacid generator as component (b) of the present invention include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

  The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a sulfonic acid of quinonediazide is bonded to a polyamino compound in a sulfonamide, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound in an ester bond and / or sulfonamide. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. If it is less than 50 mol%, the solubility in an alkali developer becomes too high, and a contrast with an unexposed portion cannot be obtained, and a desired pattern may not be obtained. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can. Such compounds may be used alone or in combination of two or more. Moreover, by using two types of photo-acid generators, the ratio of the dissolution rate of an exposed part and an unexposed part can be taken larger, As a result, a highly sensitive photosensitive resin composition can be obtained.

  Polyhydroxy compounds are Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Manufactured by Manabu Kogyo Co.) and the like, but not limited to.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Examples thereof include, but are not limited to, sulfhydrides.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  In addition, when the molecular weight of the quinonediazide compound is greater than 5000, the quinonediazide 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, the adhesiveness is lowered, and the like. Problems can arise. From such a viewpoint, the molecular weight of the preferred quinonediazide compound is 300 to 3000. More preferably, it is 350-1500.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  Among the photoacid generators used as the component (b) of the present invention, the photoacid generator that appropriately stabilizes the acid component generated by exposure is preferably a sulfonium salt, a phosphonium salt, or a diazonium salt. Since the resin composition obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is environmentally undesirable for phosphorus or the like to remain, and it is necessary to consider the color tone of the film. In this case, a sulfonium salt is preferably used. Of the sulfonium salts, structures represented by the general formulas (9) to (11) are preferably used.

R < ¹⁹ > -R < ²¹ > of General formula (9)-(11) may be same or different, respectively, and shows a C1-C20 organic group. R ²² represents a single bond or an organic group having 1 to 20 carbon atoms. Z ⁻ represents an anion moiety selected from R ²³ SO ₃ ⁻ , R ²³ COO ⁻ and SbF ₆ ^— . ^{Wherein, R 23} represents an organic group having 1 to 20 carbon atoms. Specific examples of the sulfonium salt represented by the general formula (9) are shown below, but are not limited thereto.

  Although the specific example of the sulfonium salt represented by General formula (10) is shown below, it is not limited to these.

  Although the specific example of the sulfonium salt represented by General formula (11) is shown below, it is not limited to these.

  Particularly preferred is a triarylsulfonium salt represented by the general formula (12).

In the formula, each R ²⁴ may be the same or different, and represents hydrogen or an organic group having 1 to 20 carbon atoms. R ²⁵ represents an organic group having 1 to 20 carbon atoms. α, β and γ each represent an integer of 0 to 5.

  Specific examples of the triarylsulfonium salt represented by the general formula (12) are shown below, but are not limited thereto.

  Since the photosensitive resin composition of the present invention contains (b) a photoacid generator, an acid is generated in the light irradiation part, and the solubility of the light irradiation part in the alkaline aqueous solution is increased. A positive relief pattern that dissolves can be obtained.

  The content of the photoacid generator used as the component (b) in the present invention is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin of the component (a). Of these, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight. Further, the compound selected from sulfonium salt, phosphonium salt and diazonium salt is preferably in the range of 0.05 to 40 parts by weight, more preferably in the range of 0.1 to 30 parts by weight. (B) By making content of a photo-acid generator into this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  Moreover, you may contain the compound which has a phenolic hydroxyl group in the range which does not reduce the shrinkage | contraction rate after hardening for the purpose of improving the sensitivity of the said photosensitive resin composition as needed.

  Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ. Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26 -OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR -PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Among these, preferred compounds having a phenolic hydroxyl group used in the present invention include, for example, 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-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F etc. are mentioned. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR- BIPC-F. By containing the compound having a phenolic hydroxyl group, the obtained resin composition is hardly dissolved in an alkali developer before exposure, and easily dissolved in an alkali developer upon exposure. Development is easy in a short time.

  The content of such a 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 resin (a).

The photosensitive resin composition of the present invention preferably contains (c) a thermally crosslinkable compound. (C) It is preferable that a thermally crosslinkable compound has an organic group represented by General formula (5). In General Formula (5), R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cyclic aliphatic group having 4 to 20 carbon atoms.

  The compound having the structure represented by the general formula (5) preferably has a phenolic hydroxyl group or a urea organic group represented by the general formula (13).

R ²⁶ represents a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms.

  Examples of the thermally crosslinkable compound (c) preferably used in the present invention include, but are not limited to, the following compounds.

  Specific examples of the thermally crosslinkable compound containing the urea organic group represented by the general formula (13) are shown below, but are not limited thereto.

  Furthermore, the thermally crosslinkable compound which has the following melamine resin type structures is also mentioned.

  By containing the compound exhibiting these thermal crosslinkability, the resulting photosensitive resin composition dramatically improves the chemical resistance of the fired film. Further, it hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer when exposed to light, so that film loss due to development is small and development can be performed in a short time.

  In particular, the alkoxymethyl group-containing thermally crosslinkable compound containing a urea-based organic group represented by the general formula (13) has a film after firing compared to an aromatic thermally crosslinkable compound having a phenolic hydroxyl group. Since a film having a high transmittance at 400 nm is obtained, it is more preferable. Further, since the absorption with respect to light of the exposure wavelength is extremely small, the exposure energy is efficiently transmitted to the photosensitizer, so that there are advantages of high sensitivity and excellent heat resistance.

  In the present invention, the content of the (c) thermally crosslinkable compound is preferably 0.5 to 100 parts by weight, more preferably 3 to 80 parts by weight with respect to 100 parts by weight of the resin of the component (a). It is a range.

  The photosensitive resin composition of the present invention preferably contains (d) a compound containing a secondary aromatic amine and a silicon atom having an alkoxy group. By containing 0.01 to 100 parts by weight of such a compound with respect to 100 parts by weight of the resin of component (a), without adversely affecting the photoacid generator that is a photosensitive component, a silicon substrate, a ceramic, Adhesiveness with a base material such as metal can be enhanced, and as a result, there is an effect of improving the adhesiveness of the photosensitive resin composition after development with the base material. Examples of such a compound include a compound obtained by reacting an aromatic amine compound and an alkoxy group-containing silicon compound, or a compound obtained by reacting an aromatic amine compound and an alkoxy group-containing silicon compound by adding other components. is there. Any compound may be used as long as it is obtained in this manner, and more preferable examples include compounds represented by any one of the following general formulas (14) to (16). The compound represented by any one of the general formulas (14) to (16) is obtained by reacting an alkoxysilane compound having an epoxy group, a chloromethyl group, or the like, which is a group that reacts with an amino group of an aromatic amine, A compound having adhesiveness to the substrate can be obtained without reducing the activity of the aromatic amine and promoting the decomposition of the naphthoquinonediazide compound. The silanol group on the surface of the silicon substrate and the secondary amino group in the compound represented by any one of the general formulas (14) to (16) act even at a low temperature of 50 to 200 ° C. The alkoxy group in the compound represented by any of (16) to (16) can form a siloxane bond with a silanol group on the surface of the silicon substrate, but the bond is promoted by the catalytic action of the secondary amino group. With the above configuration, the adhesive force with the silicon substrate is further increased. In addition, since silicon nitride, silicon oxide, ceramics and the like similarly act on the surface silanol groups as the silicon-based substrate surface, the same effect can be obtained. Further, even on a metal surface such as iron, nickel, copper, ITO, etc., it acts with OH groups (hydroxyl groups) formed in a thin layer of metal oxide formed on the surface, so that good adhesion can be obtained. Further, in the compound represented by any one of the general formulas (14) to (16), since a large substituent is bonded to the secondary amino group, naphthoquinone diazide sulfone which is a photosensitive component weak to the amino group. Does not adversely affect the acid ester. Therefore, excellent storage stability can be exhibited.

In the above formula, R ²⁷ , R ³³ and R ³⁷ each independently represents a group selected from an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group and a carboxyl group. R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , R ³⁵ , R ³⁶ , R ⁴³ , R ⁴⁴ and R ⁴⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, a substituent Represents a group selected from phenyl groups. R ³¹ , R ³² , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴⁶ are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, or an alkoxy group having 1 to 6 carbon atoms. It represents a selected organic group, and at least one of R ³¹ , R ³² , R ⁴⁶ and at least one of R ⁴⁰ , R ⁴¹ , R ⁴² is an alkoxy group having 1 to 6 carbon atoms. E ¹ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a nitro group, a hydroxyl group, an alkoxy group, a carboxyl group, an ester group having 2 to 10 carbon atoms, or an amide group having 2 to 10 carbon atoms.

E ² E ² , E ³ E ³ is a single bond, the following formula

Represents a group selected from R ⁴⁷ and R ⁴⁸ each independently represent hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group or an alkoxy group. p, q, f, h and v are integers of 1 to 4, b is an integer of 1 to 3, d is an integer of 0 to 2, a, c, y and w are integers of 0 to 10; An integer of 4, o is 0 or 1, g and h are integers of 1 to 100. x represents an integer of 1 to 3.

The compound represented by the general formula (14) is obtained by reacting an aromatic amino compound having one amino group with a silane coupling agent having a group that reacts with the amino group of the aromatic amino compound. Obtainable. R ²⁷ and R ³³ are alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, fluorinated alkyl groups such as trifluoromethyl group, pentafluoroethyl group, perfluoropropyl group, and perfluorobutyl group, and hydroxyl groups. , A nitro group, a carboxyl group, an amino group, an ester group having 2 to 10 carbon atoms, an amide group having 2 to 10 carbon atoms, and the like. Among these, an alkyl group, a fluorinated alkyl group, and a hydroxyl group are preferable.

R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , R ³⁵ and R ³⁶ are preferably a methyl group, an ethyl group, a propyl group, a phenyl group or the like. R ³¹ , R ³² and R ⁴⁶ are preferably a methyl group, an ethyl group, a propyl group, a phenyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group, and one of them is necessarily a methoxy group, an ethoxy group, a propoxy group or a butoxy group. An alkoxy group such as a group. E ¹ is preferably a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, or a nitro group.

  The aromatic amine preferably used in the present invention has a pKa (dissociation constant in an aqueous solution) of 3 to 9. When the pKa is 3 or more, the adhesion to the substrate is improved, and when the pKa is 9 or less, the stability of the photosensitive component is improved. More preferably, the pKa is in the range of 4-8. Aromatic amines with pKa in the range of 3-9 include aniline, cyanoaniline, hydroxylaniline, nitroaniline, chloroaniline, ethyl aminobenzoate, trifluoromethylaniline, methylaniline, dimethylaniline, methylhydroxylaniline, amino Aromatic amines such as pyridine, methylaminopyridine, dihydroxyaniline and hydroxyaminopyridine, or aromatic polyamines such as diaminobenzene, triaminobenzene, diaminopyridine, triaminopyridine, hydroxydiaminobenzene and dihydroxydiaminobenzene Mention may be made of polyvalent amines.

  By reacting these aromatic amines with an alkoxysilane compound having a group that reacts with an amino group, a compound of component (d) can be obtained. Preferred examples of the group that reacts with these amino groups include an epoxy group and a chloromethyl group. Examples of such alkoxysilane compounds include trimethoxy-1-dimethylene chloride, trimethoxyepoxysilane, triethoxyepoxysilane, carboxylpropyltrimethoxysilane, bis (epoxy) tetramethoxydisiloxane, tris (epoxy) trimethoxy. Examples thereof include silane compounds having a group that reacts with an amino group such as an epoxy group such as disiloxane and tris (epoxy) penta (methoxy) trisiloxane, and a chloromethyl group.

  The compound represented by the general formula (15) is obtained by reacting an aromatic amino compound having two or more amino groups with an alkoxysilane compound having a group that reacts with the amino group of the aromatic amino compound. Obtainable.

  The aromatic amino compound having two or more amino groups includes an aromatic diamine compound having two amino groups, an aromatic triamino compound having three amino groups, and an aromatic tetra compound having four amino groups. Examples include amino compounds. The pKa is preferably in the range of 3-9. Examples of such aromatic diamine compounds include phenylenediamine, methylphenylenediamine, cyanophenylenediamine, hydroxyphenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminobiphenyl, dimethyldiaminobiphenyl, dimethoxydiaminobiphenyl, bis (trifluoromethyl). ) Diaminobiphenyl, bis (aminophenoxy) benzene, bis (aminohydroxyphenyl) propane, bis (aminophenyl) dipropylbenzene, bis (aminophenoxy) diphenyl ether, bis (aminophenoxy) diphenylsulfone, bis (aminophenoxy) diphenylpropane Bis (aminohydroxyphenyl) hexafluoropropane, bis (aminohydroxypheny ) Propane, bis (amino-hydroxyphenyl) sulfone, bis (such aminophenoxy phenyl) ether, and substituted or unsubstituted aromatic diamine. In particular, it is preferable to use a diamine having a phenolic hydroxyl group.

  Moreover, as an aromatic amino compound having three or more amino groups, tri (aminophenyl) methane, tri (aminophenyl) ethane, tri (aminophenyl) propane, tetra (aminophenyl) methane, tri (aminophenyl) Examples thereof include trifluoroethane, triamino compounds having a substituent such as a nitro group, an ester group, and an alkyl group attached thereto, and tetraamino compounds such as tetra (aminophenyl) methane.

  The compound represented by the general formula (16) is obtained by reacting an aromatic diamine, a triamine, or a triamine or higher polyamine with a silane coupling agent having a group that reacts with an amino group having these amine compounds. Obtainable.

  As the alkoxysilane compound that can be used to obtain the compound represented by the general formula (15) or (16), the same compounds as those used in the general formula (14) can be preferably used.

  Preferable specific examples of the compound represented by any one of the general formulas (14) to (16) include, but are not limited to, compounds represented by the following.

  Compound (d) (hereinafter referred to as adhesion improver) is an aromatic amine and an alkoxysilane compound as they are or mixed in a solvent and reacted in the range of -20 ° C to 150 ° C for 1 minute to 1 week. Can be obtained. At this time, the compounding ratio of the aromatic amine and the alkoxysilane compound is preferably in the range of 10 to 400 mol%, more preferably 50 to 200 mol% with respect to the total amino group amount of 100 mol%. is there. More preferably, it is the range of 60-150 mol%. When the amount of the alkoxysilane compound is 10 mol% to 400 mol% with respect to 100 mol% of the aromatic amine, the adhesion improving effect can be stably obtained without adversely affecting the storage stability. Moreover, it is preferable to make it react as a 1-90% solution by adding a solvent.

  Also, organic acids having 1 to 10 carbon atoms such as formic acid, acetic acid and oxalic acid, acid compounds such as sulfuric acid, hydrochloric acid and phosphoric acid, or amines having 1 to 10 carbon atoms such as triethylamine and pyridine, sodium hydroxide, hydroxylated Bases such as potassium and sodium carbonate may be added as a catalyst. These catalysts are preferably 0.0001 to 10 parts by weight with respect to 100 parts by weight as the total weight of the aromatic amine and the silane compound.

  From the solubility and stability of the obtained adhesion improver, alcohols having 1 to 7 carbon atoms, esters having 2 to 20 carbon atoms, ketones having 3 to 20 carbon atoms, amides having 3 to 20 carbon atoms, It is preferable to dilute using at least one selected from sulfur-containing solvents having 3 to 20 carbon atoms. By diluting with these solvents, the stability of the solution can be enhanced. The content of such a solvent is preferably 1 to 10,000 parts by weight with respect to 100 parts by weight of the adhesion improver. More preferably, it is 10 to 1000 parts by weight. When the content of the solvent is 1 to 10,000 parts by weight, the storage stability of the adhesion improver alone is good, and the adhesion improvement effect is stably obtained without adversely affecting the storage stability of the composition. It is done. Specific examples of the solvent include alcohols such as ethanol, propanol, butanol and methoxymethylbutanol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate and propylene carbonate, ethers such as propylene glycol monomethyl ether and tetrahydrofuran. And N-methyl-2-pyrrolidone, dimethylacetamide, dimethylimidazoline, dimethyl sulfoxide and the like.

  Moreover, the photosensitive resin composition of this invention may contain the compound or vinylsilane compound which are represented by the following general formula (17) or (18) for the purpose of raising adhesiveness with a board | substrate after baking.

Ar ¹ and Ar ^{2 in the} general formulas (17) to (18) represent an aromatic ring having 6 or more carbon atoms or an aromatic heterocyclic structure having 2 or more carbon atoms. Specific examples include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, a triazine group, and a pyridine group.

R ⁴⁹ , R ⁵⁰ , R ⁵⁷ , R ⁵⁸ , R ⁶⁵ and R ⁶⁶ in the general formulas (17) to (18) may be the same or different and each represents hydrogen or an organic group having 1 to 4 carbon atoms. Specific examples of the organic group having 1 to 4 carbon atoms include hydrocarbon such as methyl group, ethyl group and propyl group, and carbonyl group such as acetyl group. If the number of carbon atoms is 5 or more, the film shrinkage during curing becomes large, so care must be taken. R ⁵¹ , R ⁵⁹ and R ⁶⁴ may be the same or different and each represents an organic group having 1 to 6 carbon atoms; R ^{52 to} R ⁵⁶ and R ^{60 to} R ⁶³ may be the same or different; A hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group is represented. However, at least one of R ^{52 to} R ⁵⁶ and R ^{60 to} R ⁶³ is an alkoxy group having 1 to 6 carbon atoms. Specific examples of the hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, and a propyl group. Specific examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group. If the hydrocarbon group or alkoxy group has 7 or more carbon atoms, the film shrinkage at the time of curing will increase, so care must be taken. Preferable specific examples of the compounds represented by the general formulas (17) to (18) include the following structures, but are not limited thereto.

  Among them, the structure shown below is more preferable.

  Examples of the vinyl silane compound include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl tris (β-methoxy ethoxy) silane, etc. In addition to this, 3-methacryloxypropyl trimethoxy silane, 3- Carbon-carbon unsaturated bond-containing silane compounds such as acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane can also be used. Vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  The compounds represented by the above general formulas (17) to (18) and the vinylsilane compound may be used alone or in combination, and in any case, good adhesion is exhibited after firing on various substrates. .

  The content of the compounds represented by the general formulas (17) to (18) and the vinylsilane compound is preferably 0.001 to 30 parts by weight with respect to 100 parts by weight of the component (a) resin. More preferably, it is 0.005-20 weight part, More preferably, it is 0.01-15 weight part. When it is in the range of 0.001 to 30 parts by weight, the adhesion improving effect can be stably obtained while maintaining the heat resistance of the composition.

  Further, in the present invention, from the viewpoint of improving the adhesion and the stability of the solution, the composition after the polymerization of the resin of the component (a) is represented by the above components (d) and general formulas (17) to (18). It is preferable to add a compound to be prepared or a vinylsilane compound. A preferred method of addition is to add the reprecipitated polymer at the time of re-dissolving in the solvent or after re-dissolution.

  In addition, the photosensitive resin composition of the present invention includes surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and alcohols such as ethanol, if necessary, for the purpose of improving the wettability with the substrate. Further, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be contained. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  In addition, the photosensitive resin composition of the present invention may further contain a silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane as a silicon component, and the storage stability is impaired. You may contain in the range which is not. A preferable content is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin of component (a).

  Furthermore, in order to improve adhesiveness with a base material such as a silicon wafer, the base material can be pretreated with the above-described adhesion improver. In this case, a solution obtained by dissolving 0.5-20% by weight of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment, etc. In some cases, the reaction between the substrate and the adhesion improving agent is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C. thereafter.

  The photosensitive resin composition of the present invention preferably contains a solvent. Solvents are polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl Esters such as acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, etc. Aromatic hydrocarbons and the like can be used alone or in combination. The content of the solvent is preferably 50 to 2000 parts by weight and more preferably 100 to 1500 parts by weight with respect to 100 parts by weight of the resin of component (a).

  The viscosity of the photosensitive resin composition obtained in the present invention is preferably 2 to 100 m · Pas. If the solid content concentration is adjusted so that the viscosity is lower than 2 m · Pas, the solid content concentration becomes too low, and it becomes difficult to obtain a desired film thickness. On the other hand, when the viscosity is greater than 100 m · Pas, it is difficult to obtain a highly uniform coating film. The photosensitive resin composition having such a viscosity can be easily obtained by using, for example, the resin of the component (a) and setting the solid content concentration in the entire photosensitive resin composition to 5 to 60%.

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

The photosensitive resin composition of this invention is apply | coated on a base material. Examples of the material of the base material include all materials that can provide a metal for an electrode on the surface, such as metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and polymer film. Preferably glass is used. The material of the glass is not particularly limited, but alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, molten Quartz glass, synthetic quartz glass, and the like are used, and soda-lime glass with a barrier coating such as non-alkali glass or SiO ₂ that usually has few ions eluted from the glass is used. As the material of the polymer film, polyethylene terephthalate, polyethersulfone, and materials having a similar chemical structure can be used. Also, since the thickness should be sufficient to maintain the mechanical strength, if the material is inorganic, it is 0.1 mm or more, preferably 0.5 mm or more, and if the material is organic, 0.05 mm or more, Preferably it is 0.1 mm or more. The size of the substrate is not particularly limited, but a rectangular or square rectangular substrate having a side of 150 mm or more and a round substrate can provide a good coating film on a substrate having a diameter of 6 inches or more. The coating method includes a slit 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 used in combination. Further, 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 becomes 0.1 to 100 μm. If the material is a polymer film and one side is 300 mm or more and it is difficult to maintain the mechanical strength even if the thickness is adjusted, the polymer film is attached to a glass substrate or the like to maintain the mechanical strength and It can apply | coat by the apply | coating method.

  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 coated on a 400 × 500 × 0.7 mm ³ glass substrate is used. When heating, 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 rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form the pattern of the heat resistant resin from the photosensitive resin composition film, after the exposure, development is performed to remove the exposed portion using a developer. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl 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, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Contains 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 alone or in combination of several kinds Good. After development, it is preferable to 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, heat treatment at 130 ° C. to 400 ° C. is performed to convert to a heat resistant resin pattern. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing the temperature. As an example, a method of performing heat treatment at 130 ° C., 150 ° C., 200 ° C., 350 ° C. for 30 minutes or 60 minutes, or raising the temperature linearly from room temperature to 230 ° C. over 1 hour may be mentioned.

  The heat-resistant resin pattern formed from the photosensitive resin composition according to the present invention is used for applications such as a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, and an insulating layer for an organic electroluminescent element. Preferably used.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. First, an evaluation method in each example will be described.

(1) Production of photosensitive resin composition film 400 × 500 × 0.7 mm ³ and 200 × 214 × 0.7 mm ³ non-alkali glass (Corning Japan Co., Ltd., # 1737) surface is thickened by sputtering deposition 400 × 500 mm and 200 × 214 mm glass substrates on which an ITO transparent electrode film having a thickness of 125 nm was formed were prepared. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm. This striped ITO film becomes the first electrode when an organic electroluminescent device is formed.

  A photosensitive resin composition (hereinafter referred to as varnish) was applied onto a glass substrate patterned with ITO so that the film thickness after drying was 1.5 μm. Application onto a 200 × 214 mm substrate was performed by spin coating, the amount of varnish dropped onto the center of the substrate was 20 g, and the rotation speed was 800 rpm for 10 seconds. Coating on a 400 × 500 mm substrate was performed using a slit coating method, the nozzle scanning speed was 4 m / min, and the gap between the nozzle and the substrate was 150 μm. Thereafter, 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, heated at 120 ° C. for 10 minutes, and dried. A photosensitive resin composition film was obtained.

(2) Viscosity measurement Using an Ubbelohde viscometer, logarithmic viscosity measurement was performed at 25 ° C. of a 0.5 dl / g polyimide resin dilute solution in dimethylacetamide. Moreover, the viscosity measurement of the varnish was performed using the E-type rotational viscometer (made by Toki Sangyo Co., Ltd.). Furthermore, the varnish was allowed to stand at 23 ° C. for 2 weeks, and the viscosity was measured at 25 ° C. to evaluate the storage stability of the viscosity. When the rate of change in viscosity after 2 weeks was within ± 10%, it was evaluated as stable. The gelled product could not be measured for viscosity.

(3) Evaluation of coating property About the photosensitive resin composition film formed by the spin coating method described in the above (1), the coating property to the edge of the substrate under irradiation with a sodium lamp, and the photosensitive film formed by the slit coating method. The surface of the conductive resin composition film was visually observed for the presence of running out of liquid and vertical stripes under sodium lamp irradiation. Good coverage was evaluated as “good”, and poor coverage was determined as “bad”. In addition, a sample in which no liquid breakage or vertical stripe was generated was determined to be good--, and one that was any one of liquid breakage or vertical stripe was determined to be defective-x.

(4) Film thickness measurement Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film after pre-baking and after development is measured with a refractive index of 1.63, and the cured film has a refractive index of 1.65. It was measured.

(5) Evaluation of photosensitive properties For Examples 1 to 3 and 10 to 12 and Comparative Examples 1 to 6, a varnish was spin-coated on a 6-inch silicon wafer, and then a hot plate at 120 ° C. (Tokyo Electron Limited) A pre-baked film having a thickness of 2 μm was finally prepared by pre-baking for 2 minutes using a coating and developing apparatus Mark-7). The prebaked film sets cut reticle having patterns, using an i-line stepper (GCA Corp. DSW-8000), were exposed in 10 mJ / cm ² steps by the exposure amount 0~400mJ / cm ² at 365 nm. After exposure, the film was developed with a 2.38% tetramethylammonium (TMAH) aqueous solution (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 60 seconds, and then rinsed with pure water.

For Examples 4 and 5, varnish was spin-coated on a 6-inch silicon wafer, then pre-baked for 1 minute 30 seconds on a hot plate (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) at 100 ° C., and finally A pre-baked film having a thickness of 1.5 μm was produced. A reticle having a pattern cut was set on the pre-baked film, and exposed using an i-line stepper (DSC-8000 manufactured by GCA) at an exposure amount of 0 to 200 mJ / cm ² at 365 nm in 5 mJ / cm ² steps. After the exposure, development was performed with a 2.38% TMAH aqueous solution (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 60 seconds, followed by rinsing with pure water.

In Examples 6 to 9, varnish was spin-coated on a 6-inch silicon wafer, then pre-baked for 2 minutes on a 110 ° C. hot plate (Tokyo Electron Co., Ltd., Mark-7), and finally 1 A 5 μm pre-baked film was prepared. A reticle having a pattern cut was set on the pre-baked film, and exposed using an i-line stepper (DSC-8000 manufactured by GCA) at an exposure amount of 0 to 200 mJ / cm ² at 365 nm in 5 cm ² steps. After the exposure, the film was developed with a 0.4% aqueous potassium hydroxide solution for 60 seconds and rinsed with pure water.

  The obtained pattern was observed with a microscope, and it was observed how many μm of the pattern in which the line and space of the developed wafer was 1: 1 remained. It is preferable that fine numbers remain, and those that remain only 30 μm or more were judged to be defective. The pattern used for the exposure is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, 100 μm, and a pattern in which a pattern of 20 μm or less remains is preferable. More preferably, a pattern of 5 μm or less remains.

(6) Evaluation of chemical resistance (5) A prebaked film formed according to the preparation method in the evaluation of photosensitive characteristics is heated at 200 ° C. for 60 minutes to form a heat-resistant resin film having a thickness of 2 μm on the silicon wafer. did. This heat-resistant resin film was immersed in a release agent “TOK106” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute at 40 ° C., and the amount of film thickness reduction was measured before and after the treatment. The case where all were dissolved was regarded as defective.

Synthesis Example 1 Synthesis of amide group-containing acid anhydride (a) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF, manufactured by Central Glass Co., Ltd.) 18.3 g under a dry nitrogen stream (0.05 mol) and 34.2 g of allyl glycidyl ether (0.3 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 g of gamma butyrolactone (GBL, manufactured by Mitsubishi Chemical Corporation) and cooled to -15 ° C. . Here, 22.1 g of trimellitic anhydride chloride (0.11 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 L of toluene to obtain an amide group-containing acid anhydride (a) represented by the following formula.

Synthesis Example 2 Synthesis of Amide Group-Containing Diamine Compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g of propylene oxide (0.3 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and −15 Cooled to ° C. A solution prepared by dissolving 20.4 g of 3-nitrobenzoyl chloride (0.11 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The 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 (manufactured by Wako Pure Chemical Industries, Ltd.) 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 did not squeeze 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 an amide group-containing diamine compound (b) represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of Amide Group-Containing Diamine Compound (c) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 mL) and propylene oxide (30 g, 0.34 mol) at −15 ° C. Cooled to. A solution prepared by dissolving 11.2 g of isophthalic acid chloride (0.055 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) 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 GBL, 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 here and recrystallization was performed to obtain crystals of an amide group-containing diamine compound (c) represented by the following formula.

Synthesis Example 4 Synthesis of quinonediazide compound (d) Under a dry nitrogen stream, BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 16.10 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.1 mol, NAC-5, manufactured by Toyo Gosei Co., Ltd.) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in 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 and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (d) represented by the following formula.

Synthesis Example 5 Synthesis of quinonediazide compound (e) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and NAC-5 26.86 g (0. 10 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and in the same manner as in Synthesis Example 5, an average of 2 of Q was converted to 5-naphthoquinonediazide sulfonate by the following formula. The quinonediazide compound (e) represented was obtained.

Synthesis Example 6 Synthesis of quinonediazide compound (f) TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol), and NAC-5 13.43 g (0. 05 mol), 13.43 g (0.05 mol, NAC-4, manufactured by Toyo Gosei Co., Ltd.) of 4-naphthoquinone diazide sulfonyl chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and in the same manner as in Synthesis Example 5, one of Q on average became 5-naphthoquinonediazide sulfonic acid ester, and one on average A quinonediazide compound (f) represented by the following formula, which was 4-naphthoquinonediazidesulfonic acid ester, was obtained.

  The thermally crosslinkable compounds used in each example and comparative example are shown below.

Synthesis Example 7 (Synthesis of adhesion improver A1)
To a 200 mL four-necked flask, 10.9 g of 3-aminophenol (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was taken, and 100 g of ethyl lactate (EL, manufactured by Musashino Chemical Co., Ltd.) was added thereto. Next, 23.6 g of 3-glycidoxypropyltrimethoxysilane (0.1 mol, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this solution and stirred at 60 ° C. for 3 hours to obtain an adhesion improver A1. Obtained.

Synthesis Example 8 (Synthesis of adhesion improver B1)
36.6 g (0.1 mol) of BAHF was dissolved in 100 g of EL. Next, 55.6 g (0.2 mol, KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) of 3-glycidoxypropyltriethoxysilane was added to this solution, and the mixture was stirred at 50 ° C. for 6 hours to obtain an adhesion improver B1. It was.

Synthesis Example 9 (Synthesis of adhesion improver B2)
28 g of bis (3-amino-4-hydroxyphenyl) sulfone (0.1 mol, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 30 g of N-methyl-2-pyrrolidone (NMP, manufactured by Mitsubishi Chemical Corporation), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (36.9 g, 0.15 mol, KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred at 70 ° C. for 4 hours. Obtained.

Synthesis Example 10 (Synthesis of adhesion improver C1)
As an aromatic polyamine, 9.5 g of M-1540 (manufactured by Daito Sangyo Co., Ltd., active H equivalent 95 g / eq) was dissolved in 30 g of N-methyl-2-pyrrolidone, and cyclohexylepoxysilane (0.33 mol, KBM- 600, manufactured by Shin-Etsu Chemical Co., Ltd.) and stirred at 40 ° C. for 8 hours to obtain an adhesion improver C1.

Synthesis Example 11 (Synthesis of adhesion improver D1)
3.58 g (0.02 mol) of KBM-903 was dissolved in 20 g of NMP. 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 3.22 g (manufactured by Daicel Chemical Industries, Ltd., 0.01 mol) was added as a solid. The solution was stirred at 30 ° C. for 6 hours. As a result, a silane compound (D1) in which the amino group of the aminosilane compound was amide-bonded with an aromatic carboxylic acid was obtained.

Example 1
Under a dry nitrogen stream, 29.30 g (0.08 mol) of BAHF, 1.24 g (0.005 mol, SiDA) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 3.27 g (0.03 mol) of aminophenol (Tokyo Kasei Kogyo Co., Ltd., 3-APh) was dissolved in 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Here, 31.2 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (manac Co., Ltd., 0.1 mol, ODPA) was added together with 20 g of NMP and reacted at 20 ° C. for 1 hour. Subsequently, it was made to react at 50 degreeC for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After completion of stirring, the solution was poured into 3 l of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution of this polyimide polymer adjusted to a concentration of 0.5 g / dl in dimethylacetamide was 0.15 dl / g.

  Varnish A of the photosensitive polyimide resin composition was obtained by adding 1.76 g of the quinonediazide compound (e) obtained in Synthesis Example 5 to NMP66.5 g to 11.74 g of the polyimide polymer A thus obtained. The viscosity of varnish A was 24 mPa · s. Using the obtained varnish A, the applicability, photosensitivity and chemical resistance were evaluated as described above. The evaluation results are shown in Table 2.

Example 2
Under a dry nitrogen stream, amide group-containing diamine (b) obtained in Synthesis Example 2 (24.18 g, 0.04 mol), BAHF (10.99 g, 0.03 mol), SiDA (1.24 g, 0.005 mol), terminal As a sealant, 5.46 g (0.05 mol) of 3-APh was dissolved in 200 g of NMP. ODPA 31.02g (0.1mol) was added here, and it stirred at 40 degreeC for 4 hours. Then, it stirred at 180 degreeC for 5 hours.

After completion of the stirring, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer B. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution of this polyimide polymer adjusted to a concentration of 0.5 g / dl in dimethylacetamide was 0.12 dl / g.

  10.4 g of the polymer B solid thus obtained was weighed, and 10.4 g of the quinonediazide compound (f) obtained in Synthesis Example 6 was combined with 29.6 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) and NMP 29. It was made to melt | dissolve in 6g of mixed solvents, and the varnish B of the photosensitive polyimide resin composition was obtained. The viscosity of varnish B was 50 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 3
Under a dry nitrogen stream, 26.46 g (0.07 mol) of the amide group-containing diamine (c) obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of SiDA, 4-aminothiophenol 6 as a terminal blocking agent .26 g (0.05 mol, 4-ASPh) was dissolved in 200 g of NMP. 71.4 g (0.1 mol) of the amide group-containing acid dianhydride (a) obtained in Synthesis Example 1 was added thereto and reacted at 60 ° C. for 6 hours. 15 g of xylene was added and stirred at 150 ° C. for 5 hours while azeotropically reacting with xylene. After completion of stirring, the solution was poured into 2 l of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution of this polyimide polymer adjusted to a concentration of 0.5 g / dl in dimethylacetamide was 0.15 dl / g.

  9.1 g of the polymer C solid thus obtained was weighed, and 4.1 g of the quinonediazide compound (d) obtained in Synthesis Example 4 was dissolved in a mixed solvent of PGME 33.4 g and GBL 33.4 g to obtain a photosensitive polyimide. A varnish C of the resin composition was obtained. The viscosity of varnish C was 10 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish C as described above.

Example 4
Under a dry nitrogen stream, 8.01 g (0.04 mol, 3,4'-DAE) of 3,4'-diaminodiphenyl ether, 16.48 g (0.045 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, terminal As a sealant, 2.18 g (0.02 mol) of 3-APh was dissolved in 200 g of NMP. Here, 35.7 g (0.05 mol) of the amide group-containing acid dianhydride (a) obtained in Synthesis Example 1 and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 22 .21 g (6FDA, 0.05 mol) was added and stirred at 50 ° C. for 6 hours. Then, it stirred at 180 degreeC for 5 hours.

After completion of the stirring, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. Further, it was washed 3 times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer D. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.25 dl / g.

  9.1 g of the polymer D thus obtained was weighed, and 2.1 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and 2 g of the quinonediazide compound (f) obtained in Synthesis Example 6 were combined with PGME66. Varnish D of the photosensitive polyimide resin composition was obtained by dissolving in 8 g. The viscosity of varnish D was 35 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 5
Under a dry nitrogen stream, 15.68 g (0.08 mol, CBDA) of cyclobutanetetracarboxylic dianhydride and 5.93 g (0.04 mol) of phthalic anhydride as an end-capping agent were dissolved in 200 g of NMP. To this were added 57.43 g (0.095 mol) of the amide group-containing diamine (b) obtained in Synthesis Example 2 and 1.24 g (0.005 mol) of SiDA, and the mixture was stirred at 40 ° C. for 3 hours. Then, it stirred at 180 degreeC for 5 hours.

After completion of the stirring, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. Furthermore, it was washed 3 times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain polymer E. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.13 dl / g.

  11.56 g of the polymer E thus obtained was weighed, and 2.89 g of the quinonediazide compound (e) obtained in Synthesis Example 5 was dissolved in 65.5 g of PGME to obtain a varnish E of a photosensitive polyimide resin composition. Got. The viscosity of varnish E was 19 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 6
11.25 g of the polyimide polymer A obtained in Example 1 was weighed, and 1.12 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and 1.12 g of Nicalac MX270 as a thermally crosslinkable compound were dissolved in 66.5 g of NMP. The varnish F of the conductive polyimide resin composition was obtained. The viscosity of varnish F was 15 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 7
10.91 g of polyimide polymer B obtained in Example 2 was weighed, and 0.65 g of the quinonediazide compound (f) obtained in Synthesis Example 6 and 0.65 g of Nicalac 100LM as a thermally crosslinkable compound were dissolved in 68.0 g of PGME. 0.01 g of a silicon surfactant was added to obtain a varnish G of a photosensitive polyimide resin composition. The viscosity of varnish G was 8 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 8
9.3 g of the polyimide polymer A obtained in Example 1 was weighed, 1.86 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and 1.86 g of Nicalac MX270 as a thermally crosslinkable compound, the adhesion obtained in Synthesis Example 8 0.4 g of improver B1 was dissolved in 33.2 g of EL and 33.4 g of NMP to obtain varnish H of a photosensitive polyimide resin composition. The viscosity of varnish H was 10 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 9
9.26 g of the polyimide polymer B obtained in Example 2 was weighed, 1.85 g of the quinonediazide compound (f) obtained in Synthesis Example 6 and 1.85 g of Nicalac 100LM as a thermally crosslinkable compound, the adhesion obtained in Synthesis Example 7 0.9 g of improver A1 was dissolved in 19.8 g of GBL and 46.2 g of PGME to obtain varnish I of a photosensitive polyimide resin composition. The viscosity of varnish I was 7 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish I as described above.

Example 10
11.4 g of the polyimide polymer C obtained in Example 3 was measured, and 2.85 g of the quinonediazide compound (d) obtained in Synthesis Example 4 and 0.8 of the adhesion improver B2 obtained in Synthesis Example 9 were added to 64.9 g of PGME. It was made to melt | dissolve and the varnish J of the photosensitive polyimide resin composition was obtained. The viscosity of varnish J was 17 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish J as described above.

Example 11
12.26 g of the polyimide polymer D obtained in Example 4 was weighed, and 1.23 g of the quinonediazide compounds (e) and (f) obtained in Synthesis Examples 5 and 6 and 1.84 g of HMOM-TPHAP as a thermally crosslinkable compound, respectively. Then, 1.0 g of the adhesion improver C1 obtained in Synthesis Example 10 was dissolved in 14.0 g of GBL, 30.0 g of PGME, and 20.0 g of NMP to obtain a varnish K of a photosensitive polyimide resin composition. The viscosity of varnish K was 25 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish K as described above.

Example 12
9.51 g of the polyimide polymer E obtained in Example 5 was measured, 1.9 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and 2.85 g of Nicalac MX270 as a thermally crosslinkable compound, and the adhesion obtained in Synthesis Example 11 0.8 g of improver D1 was dissolved in 65.2 g of PGME to obtain varnish L of a photosensitive polyimide resin composition. The viscosity of the varnish L was 10 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish L as described above.

Example 13
Varnish A obtained in Example 1 was subjected to UV exposure through a photomask having a shape covering the edge of the first electrode. After the exposure, development was performed by dissolving only the exposed portion with a 2.38% TMAH aqueous solution, followed by rinsing with pure water. Subsequently, the photosensitive polyimide resin film was cured by heating at 230 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven to obtain a polyimide insulating layer. The thickness of the insulating layer was about 1 μm. The insulating layer is formed so as to cover the edge of the first electrode, and an opening having a width of 70 μm and a length of 250 μm is provided in the central portion so that the first electrode is exposed. The insulating layer had a gentle forward taper as shown in FIG. The taper angle θ was 20 °.

  Next, a hole transport layer, a light emitting layer, and an aluminum layer serving as a second electrode were sequentially formed on the substrate on which the insulating layer was formed by a vacuum vapor deposition method using a resistance wire heating method. The hole transport layer was deposited on the entire substrate effective area. The light emitting layer was formed by patterning on the stripe-shaped first electrode using a shadow mask. The second electrode was formed by patterning in a stripe shape so as to be orthogonal to the first electrode.

  The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin. In this way, a simple matrix type color organic electroluminescent device was produced. 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.

Example 14
A thin film (thickness: 0.2 μm) of oxynitride composite chromium was formed on an alkali-free glass substrate by sputtering. A photosensitive resist is coated on the composite chrome thin film, mask exposure, development, and etching of the composite chrome thin film are sequentially performed, so that a rectangular opening of 80 μm × 280 μm has a pitch of 100 μm in the short side direction and a long side. A black matrix arranged on the matrix at a pitch of 300 μm in the direction was formed.

  Next, a photosensitive coating composition for forming color filter layers of red, green, and blue was prepared. As a red colorant, a condensed azo pigment (Ciba Geigy, Chromophthalred BRN), as a green colorant, a phthalocyanine-based green pigment (Toyo Ink Manufacturing Co., Ltd., Lionol Green 2Y-301), and as a blue colorant Each anthraquinone pigment (Ciba Geigy Co., Chromophthal Blue A3R) was used, polyvinyl alcohol (10% aqueous solution) was used as the binder resin, and one part of each colorant was added to 10 parts of the polyvinyl alcohol aqueous solution. Is also mixed and dispersed at a ratio of mass basis), and 100 parts of the resulting solution is mixed with 1 part of ammonium dichromate as a crosslinking agent to form a color coating layer for each color filter layer. A composition was obtained.

  The color filter layer of each color was formed using the above-mentioned photosensitive coating composition for forming each color filter layer in sequence. That is, a photosensitive coating composition for forming a red color filter layer was applied by spin coating on the transparent substrate on which the black matrix was formed, and prebaked at 100 degrees for 5 minutes. Then, it exposed using the photomask and developed with the developing solution (0.05% KOH aqueous solution). Next, post-baking is performed at a temperature of 230 ° C. for 60 minutes, the black matrix pattern is tuned to the opening, a band-like red pattern having a width of 85 μm, a thickness of 1.5 μm, and the width direction of the black matrix opening. It was formed to be in the short side direction. Thereafter, a green color filter layer forming photosensitive coating composition and a blue color filter layer forming photosensitive coating composition are sequentially used to form a green pattern and a blue pattern. A color filter layer in which patterns were repeatedly arranged in the width direction was formed.

  On this color filter, the photosensitive polyimide varnish H obtained in Example 8 was applied by spin coating, and prebaked at 120 ° C. for 2 minutes. Next, an area of 10 mm from the edge of the color filter substrate was exposed using a photomask and developed with a developer (0.5% KOH aqueous solution). Next, a transparent overcoat layer covering the entire color filter substrate was formed by baking at 230 ° C. for 30 minutes.

  Further, a 300 nm thick SiON thin film was formed on the formed protective layer by sputtering to form a transparent barrier layer. Subsequently, an ITO transparent electrode film having a thickness of 125 nm was formed on the transparent barrier layer by a sputtering vapor deposition method. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm.

  A hole transport layer, a white light emitting layer, and an aluminum layer serving as a second electrode were sequentially formed by a vacuum vapor deposition method using a resistance wire heating method. The hole transport layer and the white light emitting layer were deposited on the entire surface of the substrate effective area. The second electrode was formed by patterning in a stripe shape so as to be orthogonal to the first electrode.

  The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin. In this way, a simple matrix white color filter type organic electroluminescent device was produced. 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.

Example 15
On a 0.2 mm thick polymer film substrate made of polyethersulfone resin, a 0.1 μm thick barrier layer made of SiON was formed by a reactive sputtering apparatus. Subsequently, a transparent electrode made of ITO having a thickness of 0.1 mm was formed as a first electrode on the barrier layer by a sputtering method. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm.

  The varnish G obtained in Example 7 was spin-coated on the substrate, and UV exposure was performed through a photomask having a shape covering the edge of the first electrode. After the exposure, development was performed by dissolving only the exposed portion with a 2.38% TMAH aqueous solution, followed by rinsing with pure water. Subsequently, the photosensitive polyimide resin film was cured by heating at 150 ° C. for 60 minutes under a nitrogen atmosphere in an oven to obtain a polyimide insulating layer. The thickness of the insulating layer was about 1 μm. The insulating layer is formed so as to cover the edge of the first electrode, and an opening having a width of 70 μm and a length of 250 μm is provided in the central portion so that the first electrode is exposed. The cross section of the insulating layer had a gentle forward taper as shown in FIG. The taper angle θ was 30 °.

  An EL layer having a thickness of 1.5 μm made of a hole transport material and an organic light emitting material was formed on the first electrode on which the insulating pattern was formed by a printing method. After forming the EL layer, a metal electrode made of silver and having a thickness of 0.5 μm was formed as a second electrode by a vapor deposition method. On the second electrode, a sealant made of a two-component curable epoxy adhesive was formed by screen printing so as to have a thickness of about 50 μm. On the sealing agent, a sealing substrate provided with a barrier layer was provided. In addition, the sealing base material provided with the barrier layer is a barrier layer having a thickness of 0.1 μm made of SiON by a continuous vapor deposition apparatus on a sealing base material having a thickness of 100 μm obtained by extruding a polyethersulfone resin in advance. What formed was used.

  Thus, a simple matrix type flexible organic electroluminescent device was produced. 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.

Comparative Example 1
To a 500 ml four-necked flask equipped with a thermometer, a condenser, a Dean-Stark trap, a mechanical stirrer, and a nitrogen introduction tube, 7.32 g (0.02 mol) of BAHF was added to a monochlorobenzene under a nitrogen atmosphere. (MCB) Charged with 128 ml and NMP 32.0 ml. The mixture was stirred until a clear solution was obtained, and 6.2 g (0,5′-oxy-bis-1,3-isobenzofurandione [= 4,4′-oxydiphthalic dianhydride, ODPA) was obtained. 0.02 mol) was added. The contents of the flask were heated to 90 ° C. and 0.04 g of p-toluenesulfonic acid (PTSA) was added. The contents were then heated at reflux temperature (about 142 ° C.). In the first hour, about 100 ml of water-chlorobenzene azeotrope was separated into the Dean-Stark trap. 100 ml of chlorobenzene was newly added to the flask, and the contents were heated to reflux at 142-145 ° C. for 10 hours.

  100 ml of NMP was then added to the flask. Excess monochlorobenzene was distilled off at 160-165 ° C. The reaction mixture was cooled and a precipitate was slowly deposited in an ice-water-methanol mixture. The precipitated white precipitate was thoroughly washed with hot water, and the resulting polymer was dried overnight in a vacuum dryer at 125 ° C. The logarithmic viscosity of this polymer was 0.50 dl / g at a concentration of 0.5 g / dl in dimethylacetamide at 25 ° C.

  13 parts by weight of this hydroxypolyimide and 13 parts by weight of trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid mixed ester (Z-2000 photosensitizer) are mixed with 74 parts by weight of a mixed solvent comprising the same weight of PGME and NMP. Dissolve in varnish M of photosensitive polyimide resin composition. The viscosity of Varnish M was 500 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 2
As diamine, 3,5-diaminobenzoic acid (DBA) 2.28 g (0.015 mol), bis [4- (3-aminophenoxy) phenyl] sulfone (BAPS) 6.49 (0.015 mol), acid As dianhydride, 13.3 g (0.03 mol) of 6FDA and 125 g of NMP were used and reacted at room temperature for 8 hours. After dilution with NMP to a solid content of 7% by weight, 24.7 g of acetic anhydride and 28.7 g of pyridine were added and reacted at 40 ° C. for 30 minutes. This solution was poured into ethanol, filtered and dried to obtain about 22 g of a light brownish powder. As a result of measuring the infrared absorption spectrum of this powder, peaks of imide groups were confirmed near 1780 cm ⁻¹ and 800 cm ⁻¹ . As a result of NMR spectrum measurement of this powder, no peak of acetyl group was confirmed. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.55 dl / g.

  A 3-mol substituted compound of 1,2-naphthoquinonediazide-5-sulfonic acid of 2,3,4,4′-tetrahydroxybenzophenone with respect to 100 parts by weight of resin in an NMP solution of the organic solvent-soluble polyimide resin thus obtained (4NT-300) 50 parts by weight was added to obtain a varnish N of a photosensitive polyimide resin composition. The viscosity of varnish N was 180 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 3
To the reaction vessel was added trimellitic anhydride 134 g (0.70 mol), 5-hydroxyisophthalic acid 55 g (0.30 mol), isophorone diisocyanate 229 g (1.03 mol), potassium fluoride 1.2 g, and NMP 375 g. The mixture was reacted at 130 ° C. for 1 hour, heated to 190 ° C., and further reacted at 190 ° C. for 5 hours to obtain a polyamideimide resin. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyamideimide resin was 0.47 dl / g.

  Varnish adjustment was carried out in the same manner as in Example 1 using the polyamideimide polymer H thus obtained, to obtain a varnish O of a photosensitive polyimide resin composition. The viscosity of varnish O was 170 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 4
In a container with a ball condenser equipped with a trap with a silicon cock attached to a 300 ml separable three-necked flask equipped with a stirrer, 17.77 g of 6FDA and 6.05 g of 3,3′-dihydroxybenzidine (HOAB), 3 , 5-diaminobenzoic acid (DAB) 1.82 g, γ-caprolactone 0.45 g, pyridine 0.63 g, NMP 96.8 g and toluene 19.4 g were added, and the mixture was heated to 180 ° C. and reacted for 2 hours. The number of rotations was 250 rpm, and was appropriately reduced as the reaction decreased. The water produced during the reaction was removed from the silicon cock to obtain a reaction liquid (varnish). Thereafter, the reaction solution was put into methanol and stirred at a high speed, followed by filtration with a glass filter to obtain 16.0 g of a white polyimide resin powder.
The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide resin was 0.50 dl / g. 16.0 g of the present polyimide resin was made into a 12% solution of propylene glycol-1-monomethyl ether, 3.6 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and the quinonediazide compound (f) obtained in Synthesis Example 6. 6 was added as a photosensitive agent to obtain a photosensitive polyimide varnish P. The viscosity of varnish P was 80 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 5
Under a dry nitrogen stream, 29.30 g (0.08 mol) of BAHF and 1.24 g (0.005 mol) of SiDA were dissolved in 80 g of NMP. 31.2 g of ODPA was added thereto together with 20 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 liters of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.48 dl / g.

  Varnish Q of the photosensitive polyimide resin composition was obtained by adding 1.76 g of the quinonediazide compound (e) obtained in Synthesis Example 5 to NMP66.5 g to 11.74 g of the polyimide polymer J thus obtained. The viscosity of varnish Q was 170 mPa · s. Table 2 shows the results of various evaluations as described above using the obtained varnish Q.

Diagram showing the boundary of the insulating layer

Explanation of symbols

1 Substrate 2 First electrode 3 Insulating layer

Claims (7)

(A) A photosensitive resin composition comprising a resin having a structural unit represented by any one of the general formulas (1) to (4) and (b) a photoacid generator.

(In the formula, R ¹ represents a 4- to 14-valent organic group, R ² represents a ^2- to 12-valent organic group. R ³ and R ⁵ represent a hydrogen atom, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or carbon. R ⁴ represents a divalent organic group, and X and Y are a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. A monovalent organic group having at least one group selected from the above, n is in the range of 3 to 200, and m, r, and s are integers of 0 to 10.) In the general formulas (1) to (4), all or part of R ¹ and / or R ² is an organic group having an aromatic ring and / or a heterocyclic ring at both ends, and an amide group, and ^2. The photosensitive resin composition according to claim 1, wherein the ratio of the amide group to the total amount of R ¹ and R ² is 10 to 200 mol%. The photosensitive resin composition according to claim 1, further comprising (c) a thermally crosslinkable compound. The photosensitive resin composition according to claim 3, wherein the thermally crosslinkable compound (c) has an organic group represented by the general formula (5).

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cyclic aliphatic group having 4 to 20 carbon atoms.) The photosensitive resin composition according to claim 1, further comprising (d) a compound containing a secondary aromatic amino group and a silicon atom having an alkoxy group. At least (1) a step of applying a photosensitive resin composition according to any one of claims 1 to 5 to a substrate to obtain a photosensitive resin composition coating; and (2) a step of exposing the photosensitive resin composition coating with ultraviolet rays. (3) A method for producing a heat-resistant resin pattern, comprising: a step of developing the exposed photosensitive resin composition film using an alkaline aqueous solution; and (4) a step of heat-treating the developed photosensitive resin composition film. The organic electroluminescent element which has a heat resistant resin pattern obtained by the method of Claim 6.

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