JP5212103B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, it is suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer or spacer layer of an organic electroluminescence element (organic EL element), a planarization layer of a thin film transistor substrate (TFT substrate), an insulating layer of an organic transistor, etc. The present invention relates to a positive photosensitive resin composition in which an exposed part is dissolved in an alkaline aqueous solution.

  Conventionally, as a positive photosensitive resin composition, a polyamic acid ester which is a polyimide precursor and / or a photosensitive polyimide precursor composition containing a polyamic acid and a quinonediazide compound, or a polybenzoxazole precursor and a quinonediazide compound are contained. A photosensitive polybenzoxazole precursor composition and the like have been known. Films obtained by subjecting these photosensitive resin compositions to a heat treatment after patterning have been suitably used as an insulating layer for organic EL elements and a planarizing layer for TFT substrates. In particular, in a low molecular light emission type organic EL element, a pattern shape with a low taper angle is suitable as the insulating layer pattern from the viewpoint of preventing disconnection of the upper electrode. In addition, a pattern shape with a low taper angle is also suitable for the planarization layer of the TFT substrate from the viewpoint of preventing disconnection of the electrodes of the display element. For this reason, these positive photosensitive resin compositions have been preferably used rather than the negative type in which the pattern tends to be rectangular.

  When manufacturing an organic EL element, the substrate may be divided in accordance with the size of the vapor deposition machine before the light emitting layer is vapor deposited with the recent increase in size of the substrate. In this case, since the resist is applied after the insulating layer is formed and the resist is peeled off after dicing, the insulating layer has been required to have chemical resistance against the stripping solution. Also, the planarization layer of the TFT substrate may be etched using a photoresist as a mask in order to pattern the electrodes of the display element. In this case, since the resist is peeled off after etching, the flattening layer of the TFT substrate is also required to have chemical resistance against the stripping solution.

As a method for improving the chemical resistance of a positive photosensitive resin composition, a method in which a positive photosensitive polyimide precursor composition contains a thermally crosslinkable compound having a methylol group substituted with an organic group (for example, patent document) 1) or a method of containing an epoxy compound (for example, see Patent Document 2). These compositions can improve the chemical resistance of the thermosetting film by the reaction of a thermally crosslinkable compound or an epoxy compound. However, there is a problem that a low taper angle pattern shape required for an insulating layer of an organic EL element or a planarization layer of a TFT substrate cannot be obtained. Also, a positive photosensitive resin composition containing a polyimide precursor, a diazonaphthoquinone photosensitizer, and a component that causes a crosslinking reaction or self-thermal polymerization reaction with the polyimide precursor, such as an epoxy compound or a monofunctional acrylate (for example, a patent Document 3) has been proposed. This technique also has a problem that a low taper angle pattern shape required for an insulating layer of an organic EL element or a planarization layer of a TFT substrate cannot be obtained. Furthermore, when the content of the monofunctional acrylate is increased, there is a problem that the acrylate polymer is easily phase-separated during the heat treatment. In addition, a positive photosensitive resin composition containing a hydroxy polyamide, an acrylate compound, and a photosensitive diazoquinone compound (for example, see Patent Documents 4 and 5) has been proposed. In these compositions, a pattern shape with a low taper angle required for an insulating layer of an organic EL element or a flattening layer of a TFT substrate cannot be obtained, and further, high temperature treatment at 280 ° C. or higher is required. It was difficult to use as an insulating layer of an EL element or a flattening layer of a TFT substrate.
U.S. Patent No. 6933087 JP 2000-39714 A (Claims 1 to 4) JP 2000-221677 A (Claims 1 to 4) JP 2006-47377 A (Claim 1) JP 2007-193322 A (Claim 1)

  In view of the above problems, an object of the present invention is to provide a positive photosensitive resin composition that is excellent in chemical resistance after heat treatment and can form a pattern with a low taper angle.

The present invention comprises (a) a polyamic acid and / or a polyamic acid ester having a structural unit represented by the general formula (1), (b) a quinonediazide compound, (c) a polyfunctional acrylate compound and (d) a component ( It is a positive photosensitive resin composition containing a compound having a plurality of allyl groups and / or vinyl groups other than c) .

(In the general formula (1), R ¹ represents a 3 to 8 valent organic group having 2 or more carbon atoms, and R ² represents a 2 to 8 valent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same. May be different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, p and q are integers of 0 to 4, r is 1 or 2, and s is an integer of 0 to 2, provided that p + q> 0.)

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which is excellent in the chemical resistance after heat processing and can form a low taper angle pattern can be obtained. By using the positive photosensitive resin composition of the present invention, a heat resistant resin pattern having a low taper angle and excellent chemical resistance can be obtained.

Schematic showing the boundary of the insulating layer Cross-sectional view of a TFT substrate with a planarization layer and insulating layer formed

Explanation of symbols

1 Substrate 2 First electrode 3 Insulating layer 4 TFT
5 Insulating film 6 Wiring 7 Flattening layer 8 Contact hole θ Taper angle

  The positive photosensitive resin composition of the present invention contains (a) a polyamic acid and / or a polyamic acid ester having a structural unit represented by the general formula (1).

In the general formula (1), R ¹ represents a 3 to 8 valent organic group having 2 or more carbon atoms, and R ² represents a 2 to 8 valent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. p and q are integers of 0 to 4, r is 1 or 2, and s is an integer of 0 to 2. However, p + q> 0.

  The general formula (1) represents a structural unit of a polyamic acid or a polyamic acid ester having a hydroxyl group. By having a hydroxyl group, solubility in an alkaline aqueous solution is improved. Of the hydroxyl groups, phenolic hydroxyl groups are more preferred. In addition, polyamic acid or polyamic acid ester has an advantage that low-temperature curing is possible because the dehydration ring-closing reaction proceeds by 90% or more even by heat treatment at 250 ° C. or lower to become a polyimide resin. On the other hand, polyhydroxyamide having a hydroxyl group at the ortho position of the amide group similarly requires heat treatment at 280 ° C. or higher in order for 90% or more of the dehydration ring-closing reaction to progress to polybenzoxazole resin. Therefore, a pattern excellent in chemical resistance cannot be obtained by low-temperature curing at 250 ° C. or lower.

  Moreover, it is preferable to have 10 weight% or more of fluorine atoms in the structural unit represented by the general formula (1). By containing 10% by weight or more of fluorine atoms, water repellency is appropriately imparted to the interface of the film, and soaking of the interface can be suppressed when developing with an alkaline aqueous solution. The fluorine atom content is preferably 20% by weight or less in the structural unit represented by the general formula (1). By setting the fluorine atom content to 20% by weight or less, high solubility in an alkaline aqueous solution can be maintained. Moreover, the chemical resistance of the polyimide obtained after heat treatment, particularly the resistance to organic solvents can be further improved. Furthermore, the solubility with respect to fuming nitric acid of the polyimide obtained after heat processing can be maintained.

R ¹ in the general formula (1) represents a structural component of an acid, and represents a 3 to 8 valent organic group having 2 or more carbon atoms. R ¹ is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms containing an aromatic ring or an aliphatic ring, and more preferably a tetravalent organic group. It may be combined with ^{R 1} 2 or more.

Examples of the acid constituting R ¹ (OH) _p (COOR ³ ) _r include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride when p = 0. 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-Dicarboxyphenyl) methane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2- Bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3 5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2 , 2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl ) Hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, “Licacid®” TMEG-100 Aromatic tetracarboxylic dianhydrides such as (trade name, manufactured by Shin Nippon Rika Co., Ltd.), cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2 , 3,5,6-cyclohexanetetracarboxylic dianhydride, “Epiclon (registered trademark)” B-4400 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) and “Licacid” TDA-100, BT-100 Aliphatic tetracarboxylic dianhydrides such as (trade name, manufactured by Shin Nippon Rika Co., Ltd.) can be mentioned. Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyfe Nyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3,4 Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl)- 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride is preferred. These are used alone or in combination of two or more.

In the case of p ≧ 1, examples of R ¹ (OH) _p (COOR ³ ) _r include the following structures, but are not limited thereto. In the following formula, R ³ may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

R ² in the general formula (1) represents a structural component of diamine and represents a divalent to octavalent organic group having 2 or more carbon atoms. R ² is preferably a C 6-30 divalent to tetravalent organic group containing an aromatic ring or an aliphatic ring. From the viewpoint of the heat resistance of the resulting polymer, those having an aromatic ring are more preferred. It may be combined with ^{R 2} 2 or more.

Examples of the diamine constituting R ² (OH) _q (COOR ⁴ ) _s include, when q = 0, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4- Bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) ) Sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenyl) Noxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2 ′ -Diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-Tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'- Examples include diaminobiphenyl or compounds in which the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic cyclohexyl diamine, methylene bis cyclohexyl amine, and the like. Not.

When q ≧ 1, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis [ 4- (4-amino-3-hydroxyphenoxy) phenyl] hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, 2,2-bis (3-amino-4 -Hydroxyphenyl) cyclohexane, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone and the like. In addition to these, examples of R ² (OH) _q (COOR ⁴ ) _s include, but are not limited to, the structures shown below.

R ³ and R ^{4 in} the general formula (1) represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of the stability of the obtained positive photosensitive resin composition, R ³ and R ⁴ are preferably hydrocarbon groups. On the other hand, a hydrogen atom is preferable from the viewpoint of solubility in an alkaline aqueous solution. In the present invention, hydrogen atoms and hydrocarbon groups can be mixed. By adjusting the amounts of the hydrogen atoms and hydrocarbon groups of R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a positive photosensitive resin composition having an appropriate dissolution rate is obtained by this adjustment. be able to. A preferred range is that 10 mol% to 90 mol% of R ³ and R ⁴ are hydrogen atoms. When the number of carbon atoms in R ³ and R ⁴ exceeds 20, the alkali solubility is lowered. From the above, R ³ and R ⁴ contains one or more hydrocarbon group having 1 to 16 carbon atoms, it is preferred that the others are hydrogen atoms.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ or R ² in the general formula (1) as long as the heat resistance is not lowered. The content is preferably 1 to 10 mol% in R ¹ or R ² . Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylpentasiloxane.

  (A) The weight average molecular weight of the polyamic acid or polyamic acid ester having the structural unit represented by the general formula (1) is preferably 2,000 or more, more preferably 3,000 or more, and further preferably 5,000 or more. Preferably, it is 100,000 or less, More preferably, it is 50,000 or less, More preferably, it is 30,000 or less. When the weight average molecular weight is 2,000 or more, resolution and developability are improved, and chemical resistance is further improved. On the other hand, when it is 100,000 or less, developability and sensitivity are improved, and a pattern having a lower taper shape is obtained. In addition, the weight average molecular weight in this invention points out the molecular weight calculated | required by polystyrene conversion using the gel permeation chromatography.

  In the present invention, the polyamic acid or polyamic acid ester of component (a) may be composed only of the structural unit represented by the general formula (1), or the structural unit represented by the general formula (1). And other structural units. In the present invention, the structural unit represented by the general formula (1) is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, and more preferably 90 mol% or more. More preferred. The type and amount of the structural unit used for copolymerization are preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the heat treatment. Examples of other structural units include phenol novolak, cresol novolak, and a structural unit of a radical polymerizable polymer having an alkali-soluble group.

  Further, in the present invention, in addition to the polyamic acid or polyamic acid ester of component (a), phenol novolak, cresol novolak, polyhydroxystyrene, alkali-soluble group, as long as the heat resistance of the cured film obtained by heat treatment is not impaired. You may contain resin, such as a radically polymerizable polymer which has. When these resins are contained, the content thereof is preferably 100 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of component (a). More preferably, it is 10 parts by weight.

  Further, (a) the polyamic acid or polyamic acid ester having the structural unit represented by the general formula (1) may be obtained by reacting a terminal blocking agent at the terminal. As the terminal capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used. By reacting the end-capping agent, the molecular weight can be easily adjusted to a preferred range. Moreover, various organic groups can be introduce | transduced as a terminal group by making terminal blocker react.

  Preferred examples of monoamines used as end-capping agents include 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 Acid, 4-aminobenzoic acid, 4-aminosalicyl 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3- Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynyl And aniline.

  Preferable examples of the acid anhydride used as the end-capping agent include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and the like. Preferred examples of the monocarboxylic acid include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3 -Ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid and the like can be mentioned. Preferable examples of the monoacid chloride compound include a compound obtained by acidifying the carboxyl group of the monocarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6- Examples thereof include compounds obtained by acidifying one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene and 2,6-dicarboxynaphthalene. Preferable examples of the monoactive ester compound include compounds obtained by reacting the monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. .

  The introduction ratio of the monoamine used as the end-capping agent is preferably in the range of 0.1 to 60 mol%, more preferably 5 to 5%, based on all amine components in the polyamic acid or polyamic acid ester of component (a). 50 mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent is 0 with respect to the total diamine component in the polyamic acid or polyamic acid ester of component (a). The range of 0.1-100 mol% is preferable, More preferably, it is 5-90 mol%. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

The end-capping agent introduced into the polyamic acid or the polyamic acid ester can be easily detected by the following method. For example, by dissolving a polymer having an end-capping agent introduced into an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the polymer, and measuring this by gas chromatography (GC) or NMR, The end capping agent can be easily detected. In addition, it can be easily detected by directly measuring a polymer into which a terminal blocking agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C-NMR spectrum.

  The polyamic acid or polyamic acid ester having the structural unit represented by the general formula (1) used in the present invention is synthesized by the following method. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and the resulting diester is reacted with a diamine compound in the presence of a condensing agent Examples thereof include a method, a method in which a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with a diamine compound. Examples of the reaction solvent used in these known methods include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and γ-butyrolactone.

  The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound. 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. The thing etc. which couple | bonded are mentioned. 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. By using the quinonediazide compound substituted by 50 mol% or more, the affinity of the quinonediazide compound with respect to the alkaline aqueous solution can be lowered, and the solubility of the resin composition in the unexposed area in the alkaline aqueous solution can be greatly reduced. On the other hand, since the quinonediazidosulfonyl group is changed to indenecarboxylic acid by exposure, the dissolution rate of the resin composition in the exposed portion in the alkaline aqueous solution is increased. As a result, it is possible to obtain a pattern with high resolution by increasing the dissolution rate ratio between the exposed area and the unexposed area of the composition. 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. Moreover, you may contain a 2 or more types of quinonediazide compound.

  Polyhydroxy compounds include 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-TPHAP (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, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, Asahi Organic Materials Co., Ltd.) Manufactured), 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 Chemical Industry Co., Ltd.), but is not limited thereto.

  Examples of polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino. Examples thereof include, but are not limited to, diphenyl sulfide.

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

  In the present invention, the sulfonic acid ester of quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl 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-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure and full-wavelength 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. Also, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group or a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound are used in combination. You can also

  The molecular weight of the quinonediazide compound is preferably 300 or more, more preferably 350 or more, preferably 3,000 or less, more preferably 1,500, from the viewpoint of heat resistance, mechanical properties and adhesiveness of the film obtained by heat treatment. It is as follows.

  The content of the (b) quinonediazide compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, preferably 50 parts by weight with respect to 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of the component (a). It is 40 parts by weight or less, more preferably 40 parts by weight or less.

  The quinonediazide compound is synthesized by, for example, a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a polyhydroxy compound such as a phenol compound in the presence of triethylamine. 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.

  Moreover, you may further contain a polyhydroxy compound for the purpose of supplementing the alkali developability of the photosensitive resin composition as needed. The photosensitive resin composition containing a polyhydroxy compound hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. For this reason, film loss due to development is small, and development in a short time becomes easy. In this case, the content of the polyhydroxy compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of component (a), preferably 50 parts by weight or less, more preferably 40 parts by weight or less. If it is 1 to 50 parts by weight, the sensitivity can be increased while suppressing the film loss of the unexposed part.

  The positive photosensitive resin composition of the present invention contains (c) a polyfunctional acrylate compound. The positive photosensitive resin composition of the present invention is subjected to a heat treatment after pattern processing. At this time, the polyfunctional acrylate compound is thermally polymerized, thereby improving the chemical resistance of the cured film and reducing the taper shape. A pattern can be formed. In the present invention, it is important that the component (c) is an acrylate compound and is multifunctional. Compared with the conventional reaction start temperature of a thermal crosslinking agent having a methylol group or an epoxy group being 120 ° C to 180 ° C, the thermal polymerization reaction of an acrylate compound has a high reaction start temperature of 200 ° C or higher. Therefore, the shrinkage of the film due to heating and the progress of reflow are not inhibited. Therefore, since the acrylate compound is thermally polymerized in a state where reflow by heating is advanced, a low taper pattern can be obtained. However, the monofunctional acrylate-based compound is poorly compatible with the polyamic acid and the polyamic acid ester resin as the component (a) and often easily causes phase separation. For this reason, the content of the monofunctional acrylate compound is limited to a small amount, and it is difficult to obtain the effect of reducing the taper angle. Furthermore, in the case of a monofunctional acrylate-based compound, the curing of the film by thermal polymerization does not proceed sufficiently, and the effect of improving chemical resistance and insulation cannot be obtained.

  In the present invention, the acrylate compound means a compound having an acryloyl group or a methacryloyl group. For example, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, etc. can be mentioned. In addition, the polyfunctional acrylate compound refers to a compound having two or more acryloyl groups and / or methacryloyl groups.

  Preferable examples of the polyfunctional acrylate compound include NK ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, and BPE-100 manufactured by Shin-Nakamura Chemical Co., Ltd. , BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT, A-9300, ATM-4E, ATM-35E, ATM-4P, AD-TMP, AD-TMP-L , A-DPH and the like. In addition, Kyoeisha Chemical Co., Ltd. light ester series P-1M, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, 1.10DC, G -101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM, TMP, etc. are mentioned. Moreover, Kyoeisha Chemical Co., Ltd. light acrylate series 3EG-A, 4EG-A, 9EG-A, 14EG-A, TMGA-250, NP-A, MPD-A, 1.6HX-A, BEPG-A, 1 .9ND-A, MOD-A, DCP-A, BP-4EA, BP-4PA, BA-134, BP-10EA, HPP-A, TMP-A, TMP-3EO-A, TMP-6EO-3A, PE -3A, PE-4A, DPE-6A and the like. Moreover, Kyoeisha Chemical Co., Ltd. epoxy ester series 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, 3000M, 3000A etc. are mentioned. In addition, "Aronix (registered trademark)" series M-203, M-208, M-210, M-211B, M-215, M-220, M-225, M-240, M- manufactured by Toa Gosei Co., Ltd. 243, M-245, M-260, M-270, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-350, M-360, M-402, M-408, M-450 etc. are mentioned. In addition, “KAYARAD (registered trademark)” series manufactured by Nippon Kayaku Co., Ltd. R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712, R-604 , R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), RP-1040, and the like. In addition, “Blemmer (registered trademark)” series GMR-H, GAM, PDE-50, PDE-100, PDE-150, PDE-200, PDE-400, PDE-600, PDE-1000, manufactured by NOF Corporation ADE-200, ADE-400, PDP-400, ADP-200, ADP-400, PDT-650, ADT-250, PDBE-200, PDBE-250, PDBE-450, PDBE-1300, ADBE-200, ADBE- 250, ADBE-450 and the like. Further, MBAA manufactured by MRC Unitech Co., Ltd. can be mentioned. You may contain 2 or more types of these compounds.

  Of these polyfunctional acrylate compounds, compounds having three or more acryloyl groups and / or methacryloyl groups are preferred. Even if it has 3 or more of either acryloyl group or methacryloyl group, it may have both acryloyl group and methacryloyl group, and the total of these may be 3 or more. By having three or more acryloyl groups and / or methacryloyl groups, the polymer film is thermally polymerized during heat treatment after pattern processing to form a network structure, and the chemical resistance and insulation of the cured film are further improved. More preferably, it is 4 or more, more preferably 5 or more, and still more preferably 6 or more.

  In addition, (c) the polyfunctional acrylate compound may have a thermally polymerizable group or a thermally crosslinkable group other than acryloyl group and methacryloyl group. Examples of the thermally polymerizable group other than acryloyl group and acryloyl group include vinyl group, ethynyl group, allyl group, oxetane group, and epoxy group. Examples of the thermally crosslinkable group include a methylol group and an alkoxymethylol group. In order to effectively advance the reflow during heating, the number of these thermally polymerizable groups or thermally crosslinkable groups is preferably 1 or less in the compound. In the present invention, the polyfunctional acrylate compound is classified as (c) even if it has a plurality of allyl groups and / vinyl groups.

  Examples of the acrylate compound having a thermally polymerizable group include 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate, and the like. Examples of the acrylate compound having a thermally crosslinkable group include NMAA, NMMA, NBMA, IBMA, NMMM, NEMM, NBMM, IBMM, NEMA (and above, trade names) manufactured by MRC Unitech Co., Ltd.

  (C) The content of the polyfunctional acrylate compound is preferably 1 part by weight or more, more preferably 5 parts by weight or more, with respect to 100 parts by weight of the total amount of the polyamic acid and the polyamic acid ester of component (a). The amount is preferably 100 parts by weight or less, more preferably 30 parts by weight or less. If content of an acrylate type compound is 1 weight part or more, chemical-resistance will improve more. If it is 100 parts by weight or less, the storage stability of the resulting composition is improved. Furthermore, if it is 30 parts by weight or less, stable sensitivity can be obtained regardless of the standing time from exposure to development.

The positive photosensitive resin composition of the present invention further contains a compound having a plurality of allyl groups and / or vinyl groups other than (d) component (c) . (D) When a compound having a plurality of allyl groups and / or vinyl groups other than component (c) is contained, chemical resistance is further improved by copolymerization with an acrylate compound as well as self-polymerization upon heating. . Examples of such compounds include allyl compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, triallyl isocyanurate, diallyl benzene tricarboxylate, bisallyl nadiimide compound, and divinyl compounds such as divinylbenzene. Can be mentioned. Of these, triallyl isocyanurate, bisallyl nadiimide, divinylbenzene and the like are preferable from the viewpoint of chemical resistance and heat resistance. More preferred is a bisallyl nadiimide compound. Specific examples include BANI-M and BANI-X (trade names) manufactured by Maruzen Petrochemical Co., Ltd., which are preferable in terms of chemical resistance, heat resistance, and low taper. You may contain 2 or more types of these compounds.

(D) The content of the compound having a plurality of allyl groups and / or vinyl groups other than component (c) is preferably 1 part by weight or more with respect to 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of component (a). More preferably, it is 5 parts by weight or more, preferably 30 parts by weight or less, more preferably 10 parts by weight or less. If the content of the compound having a plurality of allyl groups and / or vinyl groups is 1 part by weight or more, high chemical resistance is obtained by the film after thermosetting, and if it is 30 parts by weight or less, the sensitivity stability of the composition and Storage stability is further improved.

  The positive photosensitive resin composition of the present invention preferably contains (e) a thermally crosslinkable compound having a group represented by the general formula (2).

In general formula (2), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Examples of such a heat-crosslinking compound include (e1) a compound having a phenolic hydroxyl group, wherein the ortho atom of the phenolic hydroxyl group and / or the hydrogen atom at the para position is substituted with a group represented by the general formula (2) (E2) The compound etc. which have a urea bond represented by General formula (3) are mentioned.

In general formula (3), R ⁵ may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Specifically, as having one group represented by the general formula (2), ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML -MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC -Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTr sPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), “Nicalak (registered trademark)” MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.) , 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like, TriML-P, TriML- TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, etc., having 35 XL, TriML-TrisCR-HAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) , TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), “Nicarac” MX HML-TPPHBA, HML-TPHAP, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) such as 280, MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) ), “Nicarac” MW-30HM, MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like. You may contain 2 or more types of these compounds.

  Among these, what contains at least 2 group represented by General formula (2) in this invention is preferable. More preferably, as having two groups represented by the general formula (2), 46DMOC, 46DMOEP, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML -34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, "Nicalac" MX-290, 2,6-dimethoxymethyl-4-t-butylphenol, 2 , 6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc., having three, TriML-P, TriML-35XL, etc., having four, TM-BIP-A, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA TMOM-BP, "NIKALAC" MX-280, MX-270, etc., HML-TPPHBA as having one 6, HML-TPHAP, HMOM-TPHAP, "NIKALAC" MW-30HM, etc. MW-100LM and the like.

Furthermore, it is preferable that R ⁵ in the general formula (2) is a hydrocarbon. When R ⁵ is a hydrocarbon, the thermal crosslinking proceeds more slowly than hydrogen atoms, and a pattern with a low taper angle is more likely to be obtained after curing.

  The content of the thermally crosslinkable compound as the component (e) is preferably 1 part by weight or more, more preferably 5 parts by weight or more with respect to 100 parts by weight of the total amount of the polyamic acid or the polyamic acid ester as the component (a). Further, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and preferably equal to or less than the content of the component (c). (E) If the content of the heat crosslinkable compound is 1 part by weight or more with respect to the component (a), the chemical resistance of the thermosetting film is further improved. Moreover, if it is 50 parts by weight or less and equal to or less than the content of the component (c), the reflow during heating proceeds effectively, and a pattern with a lower taper angle can be formed.

  The positive photosensitive resin composition of the present invention can contain a polymerization inhibitor, a thermal radical generator, a surfactant, an adhesion improver and the like as required.

  Examples of the polymerization inhibitor include hydroquinone polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and parabenzoquinone, 2,2-diphenyl-1-picrylhydrazyl, nitrobenzene, and the like. Two or more of these may be contained. By containing the polymerization inhibitor, the storage stability of the positive photosensitive resin composition can be obtained, and the sensitivity is stabilized regardless of the standing time from exposure to development.

The content of the polymerization inhibitor is 0.001 with respect to 100 parts by weight of the total amount of (c) the polyfunctional acrylate compound and (d) the compound having a plurality of allyl groups and / or vinyl groups other than component (c). -1 part by weight is preferred.

Examples of the thermal radical generator include organic peroxides such as hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, diacyl peroxides, peroxydicarbonates, peroxyesters, and azo compounds. Two or more of these may be contained. By containing a thermal radical generator, radicals are generated during heating, and (c) polymerization of a compound having a plurality of allyl groups and / or vinyl groups other than the polyfunctional acrylate compound and (d) component (c). The chemical resistance of the cured film can be further improved.

The content of the thermal radical generator is 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the compound having a plurality of allyl groups and / or vinyl groups other than (c) the polyfunctional acrylate compound and (d) component (c) . 50 parts by weight is preferred.

Adhesion improvers include silane coupling agents such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, titanium chelating agent, aluminum chelating agent, aromatic amine compound and alkoxy group-containing silicon. Examples include compounds obtained by reacting compounds. Two or more of these may be contained. By containing these compounds, it is possible to further improve the adhesion to an underlying substrate such as a silicon wafer, ITO, SiO ₂ , SiN _x , and to improve resistance to oxygen plasma and UV ozone treatment used for cleaning and the like. .

  The content of the adhesion improving agent is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of component (a).

  Surfactants (trade name, manufactured by Sumitomo 3M Co., Ltd.), “Megafac (registered trademark)” (manufactured by Dainippon Ink & Chemicals, Inc.), Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.) Fluorosurfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (BIC) -Acrylic polymer surfactants such as organosiloxane surfactants such as Chemi Corporation and Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Two or more of these may be contained. When the surfactant is contained, paintability with the substrate can be improved.

  The content of the surfactant is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of component (a).

  In general, the positive photosensitive resin composition of the present invention contains a solvent in addition to these components. As the solvent, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, Ethers such as propylene 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-methoxy Examples thereof include esters such as butyl acetate, methyl lactate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

  The content of the solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, preferably 2,000 parts by weight, based on 100 parts by weight of the total amount of the polyamic acid or polyamic acid ester of component (a). Hereinafter, it is more preferably 1,500 parts by weight or less. If it is the range of 50-2,000 weight part, it will become a viscosity suitable for application | coating and the film thickness after application | coating can be adjusted easily.

  The viscosity of the positive photosensitive resin composition of the present invention is preferably 3 to 500 mPa · s. By setting the viscosity to 3 mPa · s or more, a film having a desired thickness can be easily formed. On the other hand, when the viscosity is 500 mPa · s or less, a coating film having a uniform film thickness can be easily formed. The viscosity of the positive photosensitive resin composition can be adjusted to a desired range by adjusting the solid content concentration.

  The resin composition obtained by the present invention has positive photosensitivity in which the exposed part is dissolved in an alkaline aqueous solution.

  Next, a method for producing a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described. In the present invention, a heat-resistant resin pattern can be formed by (1) a patterning process of the positive photosensitive resin composition of the present invention and (2) a heat treatment process. The step of (1) pattern processing is preferably (1-1) a step of applying the positive photosensitive resin composition of the present invention to a substrate to obtain a photosensitive resin composition film, (1-2) A step of exposing the photosensitive resin composition film with actinic radiation, and (1-3) a step of developing the exposed photosensitive resin composition film with a developer. Hereinafter, each step will be described.

  First, the positive photosensitive resin composition of the present invention is applied on a substrate. As the substrate, for example, a silicon wafer, ceramics, gallium arsenide, soda glass, quartz glass, or the like is used, but is not limited thereto. Examples of the coating method include a slit die coating method, a spin coating method, a spray coating method, a roll coating method, and a bar coating method, and these methods may be used in combination.

  In addition, before applying the positive photosensitive resin composition, the substrate may be pretreated with a chemical solution containing the above-described adhesion improver. Specifically, the adhesion improver was dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like in an amount of 0.5 to 20% by weight. It is preferable to perform surface treatment by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment using a solution. If necessary, a heat treatment at 50 ° C. to 300 ° C. can then be performed to advance the reaction between the substrate and the adhesion improver.

  Next, the substrate coated with the positive photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying can be performed using a hot plate, an oven, infrared rays, a vacuum chamber, or the like. 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. The material of the proxy pin includes a metal material such as aluminum or stainless steel, 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 photosensitive resin composition coated on a glass substrate of 300 mm × 350 mm × 0.7 mm When heating an object, 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. Examples of the actinic radiation used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, it is preferable to use ultraviolet rays. In particular, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

  In order to form the pattern of the photosensitive resin, the exposed portion may be removed using a developer after exposure. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound exhibiting alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be used alone or in combination. 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, it is converted into a heat resistant resin film by heat treatment. The heat treatment temperature is generally from 180 ° C. to 400 ° C., but in the present invention, it is preferably from 180 ° C. to 300 ° C. When heat treatment is performed at a temperature of 180 ° C. or higher, (a) the imidization reaction of the polyamic acid and / or the polyamic acid ester having the structural unit represented by the general formula (1) proceeds to reduce the taper angle, Insulation performance is improved. Furthermore, the taper angle is reduced by melting the acrylate compound of component (c), and the thermal polymerization reaction proceeds to further improve chemical resistance and insulation performance. Moreover, by heat-processing at the temperature of 300 degrees C or less, the thermal decomposition of (c) acrylate type compound can be suppressed, and chemical resistance and insulation can be improved more. When the positive photosensitive resin composition of the present invention is used as an insulating layer and / or a planarizing film of an organic EL device, considering the operation stability including the TFT design temperature and the ITO resistance value, It is desirable to perform heat treatment in the range of 180 ° C. or higher and 250 ° C. or lower.

  The taper angle of the heat-resistant resin pattern formed from the positive photosensitive resin composition of the present invention is preferably 45 ° or less at a film thickness of 1 μm when used as an insulating layer of an organic EL element. More preferably, it is 40 ° or less, and further preferably 30 ° or less. By setting the taper angle to 45 ° or less, when the organic light emitting layer or the first electrode is formed, the organic light emitting layer or the second electrode is locally thinned or disconnected at the boundary between the insulating layer and the first electrode. Therefore, a stable light emission without luminance unevenness can be obtained. When used as a planarization layer of a TFT substrate, the taper angle of the heat resistant resin pattern is preferably 45 ° or less at a film thickness of 2 μm. More preferably, it is 40 ° or less. By setting the taper angle to 45 ° or less, the first electrode formed on the planarizing layer can be smoothly formed without locally thinning. In the present invention, the taper angle refers to an angle formed between the side surface of the pattern and the surface of the substrate, and refers to an angle indicated by θ in FIG. The taper angle is measured by observing the cross section of the pattern with an electron microscope.

  The insulation resistance of the heat-resistant resin pattern formed from the positive photosensitive resin composition of the present invention preferably has a dielectric breakdown voltage value of 250 V / μm or more. More preferably, it is 300 V / μm, more preferably 350 V / μm or more. When the heat resistant resin pattern obtained by the present invention is used as an insulating layer of an organic EL element, the film thickness between both electrodes of the light emitting layer is about 200 nm, and a voltage of about 10 V at maximum may be applied. The insulating layer needs to insulate this 200 nm with sufficient reliability. The insulation performance of 250 V / μm is 50 V insulation at 200 nm, and is expected to be 5 times more reliable than the practical voltage. Within this range, long-term stable insulation reliability can be maintained.

  The organic EL element of the present invention has a first electrode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a second electrode in this order, and on the surface of the first electrode, the heat resistant resin pattern of the present invention. It has an insulating layer formed. An insulating layer is located around the organic light emitting layer to define a light emitting region. Since the heat-resistant resin pattern of the present invention has a small taper angle, it is suitably used for an insulating layer of an organic EL element. That is, when the organic light emitting layer and the first electrode are formed, the organic EL element that can emit light stably without luminance unevenness can be formed smoothly at the boundary portion between the insulating layer and the first electrode. Can be obtained.

  The display device of the present invention has a planarization layer and a display element formed in this order on the substrate on which the TFT is formed, with the heat resistant resin pattern of the present invention. For example, a liquid crystal display device, an organic EL display device, etc. are mentioned. Taking an active matrix display device as an example, a TFT and a wiring for driving a display element and a planarization layer covering the TFT are provided on a substrate, and the display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer. Since the taper angle of the resin pattern of the present invention is small, an electrode can be smoothly formed on the planarization layer. For this reason, the resin pattern of this invention is used suitably as a planarization layer of a TFT substrate.

  FIG. 2 shows a cross-sectional view of a TFT substrate on which a planarizing layer and an insulating layer are formed. On the substrate 1, bottom-gate or top-gate TFTs 4 are provided in a matrix, and an insulating film 5 made of an inorganic material is formed so as to cover the TFTs 4. In addition, a wiring 6 connected to the TFT 4 is provided on the insulating film 5. Further, a planarizing layer 7 is provided on the insulating film 5 so as to bury the wiring 6. A contact hole 8 reaching the wiring 6 is provided in the planarizing layer 7. A display element (for example, an organic EL element) is provided on the planarization layer 7 in a state where it is connected to the wiring 6 through the contact hole 8. In the organic EL element, the first electrode 2 is formed so as to be connected to the wiring 6, and the insulating layer 3 is formed so as to cover the contact hole 8 and the end face of the first electrode 2. A hole transport layer, a light emitting layer, an electron transport layer, and a second electrode (not shown) are sequentially formed on the first electrode opening. The organic EL element may be a top emission type that emits light from the side opposite to the substrate 1 or a bottom emission type that extracts light from the substrate 1 side. In this manner, an active matrix organic EL display device in which the TFT 4 for driving the organic EL element is connected to each organic EL element is obtained.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the positive photosensitive resin composition was performed with the following method.

(1) Measurement of weight average molecular weight of polymer The weight average molecular weight was calculated in terms of polystyrene using gel permeation chromatography (Waters 2690, manufactured by Nippon Waters Co., Ltd.). As the column, TOSOH TXK-GEL α-2500 and α-4000 manufactured by Tosoh Corporation were used in series, and N-methyl-2-pyrrolidone was used for the moving layer.

(2) Preparation of heat-resistant resin pattern for evaluation Preparation of pre-baked film A positive photosensitive resin composition (hereinafter referred to as varnish) was applied on a 4-inch silicon wafer. Subsequently, using a hot plate D-SPIN (manufactured by Dainippon Screen Mfg. Co., Ltd.), a prebaked film was obtained by prebaking at 110 ° C. for 2 minutes. The film thickness was adjusted to 1 μm after curing.

Measurement of film thickness Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used. The refractive index was 1.629.

Exposure Using an exposure machine (PLA-501F, manufactured by Canon Inc.), a gray scale mask with a line-and-space pattern cut was set, and the pre-baked film was irradiated with a gh mixed line of a mercury lamp. The exposure dose was irradiated so as to 50~200mJ / cm ² at 5 mJ / cm ² increments through a gray scale mask.

Development Within 5 minutes after exposure, the pre-baked film was dip-developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water for 30 seconds.

Calculation of sensitivity The minimum exposure amount at which the film thickness of the exposed area after development was 0 μm was determined.

Preparation of cured film The developed film was subjected to 40 minutes at 220 ° C. under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd. (Comparative Example 7 was 40 minutes at 300 ° C.) Heat treatment was performed to produce a cured film (heat resistant resin film).

(3) Evaluation of taper angle Using a field emission type operation electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation, a cross section of a 30 μm line after curing was observed. In this cross section, the angle formed by the pattern side surface of the line and the substrate surface was determined as the taper angle. If the taper angle is 10 to 40 °, it can be determined that the taper angle is suitable for the insulating layer of the organic EL element and the planarization layer of the TFT substrate.

(4) Evaluation of chemical resistance The cured film produced by the method described in (2) above was immersed in a peeling solution N-300 manufactured by Nagase ChemteX Corporation for 1 minute at 60 ° C. The film thickness before and after the treatment was measured, and the amount of film reduction by the immersion treatment was determined. If the amount of film loss is 0.3 μm or less, it can be judged that the chemical resistance is good. If it is 0.1 micrometer or less, it can be judged that it is very favorable.

(5) Evaluation of sensitivity stability Among the methods described in (2) above, the sensitivity (sensitivity after 1 hour) is obtained when the time until development after exposure is changed to 1 hour, and the method described in (2) above. The sensitivity obtained by the method (sensitivity within 5 minutes) was compared. If the change in sensitivity (((sensitivity after 1 hour−sensitivity within 5 minutes) / sensitivity within 5 minutes) × 100) is within 5%, it can be determined to be stable.

(6) Evaluation of insulation A heat-resistant resin film having a film thickness of about 1 μm was produced on a highly doped silicon wafer in the same manner as in the above (2) except that exposure was not performed. The heat-resistant resin film was boosted with DCW at a boosting rate of 0.1 kV / 4 seconds using a withstand voltage / insulation resistance tester TOS9201 manufactured by Kikusui Electronics Co., Ltd., and the voltage at which dielectric breakdown occurred was measured. The dielectric breakdown voltage per unit film thickness was determined by dividing the obtained voltage by the film thickness. If it is 300 V / micrometer or more, it can be judged that insulation is favorable. If it is 350 V / micrometer or more, it can be judged that it is very favorable.

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

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.). Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The 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, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (b) crystal represented by the following formula.

Synthesis Example 3 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, 9.21 g (0.05 mol) of gallic acid methyl ester and 40.30 g (0.15 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were 1,4- Dissolved in 450 g of dioxane and brought to room temperature. Here, 12.65 g (0.15 mol) 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. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (c) represented by the following formula.

Synthesis Example 4 Synthesis of Polyamic Acid Ester (A) Under a dry nitrogen stream, 5.01 g (0.025 mol) of 4,4′-diaminophenyl ether, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1 .24 g (0.005 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). To this, 21.4 g (0.03 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added together with 14 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. 4-Ethynylaniline 0.703g (0.006mol) was added here as terminal blocker, and also it was made to react at 60 degreeC for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polyamic acid ester (A). The polyamic acid ester had a weight average molecular weight of 24,000. The fluorine content in the structural unit represented by the general formula (1) was 12% by weight.

Synthesis Example 5 Synthesis of Polyamic Acid Ester (B) 12.1 g (0.02 mol) of hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 and 1,3-bis (3-aminopropyl) in a dry nitrogen stream 1.24 g (0.005 mol) of tetramethyldisiloxane was dissolved in 50 g of NMP. To this, 7.76 g (0.025 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. 3-aminophenol 1.36g (0.0125mol) was added here as terminal blocker, and also it was made to react at 60 degreeC for 2 hours. Thereafter, a solution obtained by diluting 5.96 g (0.05 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polyamic acid ester (B). The weight average molecular weight of this polyamic acid ester was 26,000. The fluorine content in the structural unit represented by the general formula (1) was 10% by weight.

Synthesis Example 6 Synthesis of polyhydroxyamide (C) In a separable flask having a volume of 2 L, 197.8 g (0.54 mol) of BAHF, 75.9 g (0.96 mol) of pyridine, and 692 g of dimethylacetamide were mixed at room temperature (25 ° C.). Stir to dissolve. Separately, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of dimethyl glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.

  Next, this was cooled to 8 ° C. with a water bath, and a solution prepared by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise from the dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropping, the above reaction solution was dropped into 12 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water as appropriate, dehydrated and then vacuum dried to obtain polyhydroxyamide (C). Obtained. The weight average molecular weight of this polyhydroxyamide was 14,000.

Comparative Example 1
Polyamide acid ester (A) 10 g (100 parts by weight), quinonediazide compound (c) 2.5 g (25 parts by weight), light acrylate TMP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 3.5 g (35 parts by weight) -It was dissolved in 20 g (200 parts by weight) of butyrolactone and 20 g (200 parts by weight) of ethyl lactate to obtain a varnish. Using this varnish, the taper angle, chemical resistance, sensitivity stability, and insulation were evaluated.

Examples 1-5 , Comparative Examples 2-14
Varnishes were prepared with the compositions described in Tables 1 and 2, and the taper angle, chemical resistance, sensitivity stability, and insulation were evaluated in the same manner as in Comparative Example 1 .

  Light acrylates TMP-A, MTG-A, PE-4A, DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), triallyl isocyanurate (manufactured by Aldrich Co., Ltd.) BANI- used in Examples and Comparative Examples M (manufactured by Maruzen Petrochemical Co., Ltd.), “Nicarak (registered trademark)” MX-270 (manufactured by Sanwa Chemical Co., Ltd.), HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), NC-6000 (Nihon Kasei) The structure of Yakuhin Co., Ltd. is shown below.

Tables 1 and 2 summarize the evaluation results of the taper angles, chemical resistance, and sensitivity stability of Examples 1 to 5 and Comparative Examples 1 to 14 .

Comparative Example 15
A glass substrate having an ITO transparent electrode film with a thickness of 130 nm formed on the surface of non-alkali glass (Corning Japan Co., Ltd., # 1737) of 730 mm × 920 mm × 0.5 mm was prepared. A photoresist was applied onto the glass substrate by a spinner and patterned by exposure / development by a normal photolithography method. After removing unnecessary portions of the ITO by etching, the ITO film was patterned into a stripe shape having a length of 90 mm and a width of 80 μm by removing the photoresist. This striped first electrode had a pitch of 100 μm.

On the glass substrate on which this ITO was patterned, the varnish produced in Comparative Example 6 was applied by spin coating so that the film thickness after soft baking was 1.5 μm. Thereafter, the glass substrate was held at a height of 5 mm from the hot plate using a hot plate and heated at 120 ° C. for 3 minutes to obtain a positive photosensitive resin coating film. The coating film was exposed to UV through a photomask, developed with a 2.38% tetramethylammonium aqueous solution, and rinsed with pure water. The obtained resin pattern was heated at 250 ° C. for 60 minutes in an air atmosphere in a clean oven to form an insulating layer. The thickness of the insulating layer was about 1 μm. The opening of the insulating layer had a width of 70 μm and a length of 250 μm, and the first electrode was exposed at the center from the insulating layer and covered at the end by the insulating layer. The cross section of the boundary portion of the insulating layer had a forward taper shape as shown in FIG. 1, and the taper angle θ was 28 °.

  On this electrode substrate with an insulating layer, a photoresist was spin-coated so as to have a film thickness of about 2 μm, and heated at 100 ° C. for 3 minutes to form a protective film. The substrate with a protective film was diced into four parts to obtain a substrate with a protective film of 365 mm × 460 mm × 0.5 mm. Next, the protective film was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and dehydrated by heating at 200 ° C. for 30 minutes to obtain an electrode substrate with an insulating film. The change in film thickness dimension of the insulating layer was less than 15% both after the protective film was peeled off and after the heat dehydration, compared to before the protective film was produced.

  Next, an organic electroluminescent device was produced using the electrode substrate with an insulating layer. The thin film layer including the light emitting layer was formed by a vacuum evaporation method using a resistance wire heating method. A hole transport layer was formed on the entire surface of the substrate by vapor deposition, and a light emitting layer, an electron transport layer, and aluminum for the second electrode were formed using a shadow mask. At the boundary portion of the insulating layer, the thin film layer and the second electrode were formed smoothly without being thinned or disconnected.

  The obtained said board | substrate was taken out from the vapor deposition machine, the board | substrate and the glass plate for sealing were bonded together using the ultraviolet curing epoxy resin, and it sealed. A simple matrix type color organic EL display device in which a patterned light emitting layer was formed on the ITO stripe-shaped first electrode and the stripe-shaped second electrode was arranged so as to be orthogonal to the first electrode was produced. When this display device was line-sequentially driven, good display characteristics could be obtained. No luminance unevenness was observed in the light emitting region, and stable light emission was obtained.

Example 6
An organic EL display device using the TFT shown in FIG. 2 was produced by the following method.

A bottom gate type TFT 4 was formed on the glass substrate 1, and an insulating film 5 made of Si ₃ N ₄ was formed so as to cover the TFT 4. Next, a contact hole (not shown) is formed in the insulating film 5, and then a wiring 6 (height 1.0 μm) connected to the TFT 4 through the contact hole is formed on the insulating film 5. . The wiring 6 is for connecting the TFT 4 with an organic EL element formed between TFTs 4 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 6, the flattening layer 7 was formed on the insulating film 5 in a state where the unevenness due to the wiring 6 was embedded. The planarization layer 7 is formed by spin-coating the varnish obtained in Example 4 on a substrate, pre-baking (120 ° C. × 3 minutes) on a hot plate, and then exposing and developing through a mask having a desired pattern. The heat treatment was performed at 230 ° C. for 60 minutes under an air flow. The applicability when applying the varnish was good, and wrinkles and cracks were not observed in the cured film obtained after exposure, development and heat treatment. Furthermore, the average step of the wiring 6 was 500 nm, and a contact hole of 5 μm square was formed in the produced planarization layer, and the film thickness was about 2 μm.

  Next, a top emission type organic EL element was formed on the planarized layer 7 obtained. First, the first electrode 2 made of ITO was formed on the planarizing layer 7 by being connected to the wiring 6 through the contact hole 8. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, patterning of the first electrode 2 was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and dehydrated by heating at 200 ° C. for 30 minutes to obtain an electrode substrate with a planarizing layer. The film thickness dimensional change of the flattening layer was less than 1% after heat dehydration with respect to the treatment before the stripping solution treatment. The first electrode thus obtained corresponds to the anode of the organic EL element.

  Next, the insulating layer 3 having a shape covering the end portion of the first electrode was formed. Similarly, the varnish obtained in Example 11 was used for the insulating layer. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al / Mg was formed on the entire surface above the substrate. Further, a SiON sealing film was formed by CVD film formation. 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.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 4 for driving the organic EL element was obtained. When voltage was applied through the drive circuit, good light emission was exhibited.

  With the positive photosensitive resin composition of the present invention, a heat-resistant resin pattern having a low taper angle and excellent chemical resistance can be obtained. The positive photosensitive resin composition of the present invention is a surface protective film for semiconductor elements such as LSI (Large Scale Integration), interlayer insulating films, insulating layers and spacer layers for organic EL elements, and flat TFT substrates. For applications such as insulating layers for organic transistors, interlayer insulating films for multilayer wiring for high-density mounting, wiring protective films for circuit boards, on-chip microlenses and various displays for solid-state image sensors, and flattening layers for solid-state image sensors It can be preferably used.

Claims (9)

(A ) Other than the polyamic acid and / or polyamic acid ester having the structural unit represented by the general formula (1), (b) quinonediazide compound, (c) polyfunctional acrylate compound and (d) component (c) A positive photosensitive resin composition containing a compound having a plurality of allyl groups and / or vinyl groups.

(In the general formula (1), R ¹ represents a 3 to 8 valent organic group having 2 or more carbon atoms, and R ² represents a 2 to 8 valent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same. May be different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, p and q are integers of 0 to 4, r is 1 or 2, and s is an integer of 0 to 2, provided that p + q> 0.) The positive photosensitive resin composition according to claim 1, wherein the component (c) is a trifunctional or higher functional acrylate compound. Wherein component (d) is positive photosensitive resin composition of claim 1 wherein the bis-allyl-nadi-imide compound. The positive photosensitive resin composition according to any one of claims 1 to 3, further comprising (e) a thermally crosslinkable compound having a group represented by the general formula (2).

(In General Formula (2), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) A heat-resistant resin pattern comprising at least (1) a step of patterning the positive photosensitive resin composition according to any one of claims 1 to 4 , and (2) a step of heat-treating at a temperature of 180 ° C to 250 ° C in this order. Production method. A heat resistant resin pattern having a taper angle of 10 ° to 40 ° obtained by the method according to claim 5 . It has a 1st electrode, a positive hole transport layer, an organic light emitting layer, an electron carrying layer, and a 2nd electrode in this order, The insulating layer formed with the heat resistant resin pattern of Claim 6 on said 1st electrode surface An organic electroluminescence device having the same. The display apparatus which has the planarization layer and display element which were formed with the heat resistant resin pattern of Claim 6 on the board | substrate with which the thin-film transistor was formed in this order. The display device according to claim 8 , wherein the display element is an organic electroluminescence element.

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