JP2017090619A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition capable of improving adhesiveness to ITO (indium tin oxide) and inhibiting decrease in light emission efficiency when an EL element is fabricated.SOLUTION: The positive photosensitive resin composition comprises: (a) a polymer having at least one of a polyimide precursor, a polybenzoxazole precursor and polyimide and having a weight average molecular weight of 2,000 or more and 100,000 or less; (b) at least one of a triazole compound and a N-hydroxysuccinimide compound having a molecular weight of 300 or less and a hydroxyl group; and (c) a quinone diazide compound.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition. Specifically, a positive photosensitive resin composition in which an ultraviolet-exposed portion is dissolved in an alkali developer, which is suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., and an electron using the same Regarding parts.

  Resins such as polyimide and polybenzoxazole have been used for surface protection films and interlayer insulation films of semiconductor elements such as LSI (Large Scale Integration) because they have excellent heat resistance and electrical insulation. Recently, it is also used for an insulating film of an organic EL element and a flattening film of a TFT substrate (Patent Document 1).

  In these applications, when the adhesiveness between the insulating film or the planarizing film and the substrate is insufficient, the portion peels off, and does not serve as the insulating film or the planarizing film, which causes a problem.

  It is known that when the adhesion between the insulating film or planarization film and the substrate is improved, when the substrate is silicon, a nitride film or the like, it can be improved by using an organosilicon compound.

  However, in the above method, it has been difficult to obtain high adhesiveness with metals such as copper used for rewiring and indium tin oxide (hereinafter referred to as ITO) used as an organic EL element as a transparent electrode.

  For this reason, studies are being made to improve the adhesion to metal by adding a heterocycle-containing compound (Patent Document 2 or 3).

  However, when an organic EL element is produced using a photosensitive resin composition containing a heterocyclic ring-containing compound, when the organic EL element emits light for a long time, the heterocyclic organic compound is decomposed and gas is generated. And there existed a problem that the luminous efficiency of an organic EL element fell with the gas.

JP 2004-54254 A JP 2007-17959 A JP 2006-184660 A

  In view of the above problems, the present invention provides a photosensitive resin composition capable of suppressing adhesiveness with ITO, which is a metal often used in organic EL elements, and a decrease in luminous efficiency when an EL element is produced. To do.

In order to solve the above problems, the present invention has the following configuration.

  That is, (a) a polymer having a weight average molecular weight of 2,000 to 100,000 having at least one of the structures represented by the general formula (1) or (2), (b) the general formula (3) or ( 4) A positive photosensitive resin composition containing at least one of compounds having a molecular weight of 300 or less and (c) a quinonediazide compound.

(In the general formula (1), R ¹ is a 2 to 8 valent organic group having 2 or more carbon atoms, R ² is a 2 to 6 valent organic group having 2 or more carbon atoms, and R ³ is hydrogen or 1 to 20 carbon atoms. M represents an integer of 0 to 4. p and q represent an integer of 0 to 4, and p + q> 0.)

(In General Formula (2), R ⁴ represents a 4 to 8 valent organic group having 2 or more carbon atoms. R ⁵ represents a 2 to 6 valent organic group having 2 or more carbon atoms. R and s are each 0. Represents an integer of ~ 4.)

(In General Formula (3), R ⁶ and R ⁷ each independently represents a 1 to 4 valent organic group.)

(In General Formula (4), R ⁸ and R ⁹ each independently represents a monovalent to tetravalent organic group.)

  According to the present invention, it is possible to obtain a positive photosensitive resin composition capable of suppressing adhesion with ITO (indium tin oxide) and a decrease in luminous efficiency when an EL element is produced.

  The polymer of the present invention has (a) at least one of the structural units represented by the general formula (1) or the general formula (2). The content of the structural unit (a) relative to the whole polymer is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more because heat resistance is improved.

  (A) The structural unit may be composed of either the structural unit of general formula (1) or (2) alone, or may be composed of both structural units of general formulas (1) and (2). It doesn't matter.

  The structural unit represented by the general formula (1) can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. The structural unit represented by the general formula (1) is preferably a polyamic acid or polyamic acid ester of a polyimide precursor, or polyhydroxyamide of a polybenzoxazole precursor. This is because heat resistance and solvent resistance are drastically improved by forming an annular structure after heating.

R ¹ in the general formula (1) represents an acid structural component and represents a divalent to octavalent organic group having 2 or more carbon atoms. Specifically, the following acid components are preferably used, but are not limited thereto.

  Examples of the divalent acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. be able to.

  Examples of the trivalent acid include tricarboxylic acids such as trimellitic acid and trimesic acid.

  Tetravalent acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, naphthalenetetracarboxylic acid, pyridinetetracarboxylic acid, perylenetetracarboxylic acid Carboxylic acids, diester compounds in which two carboxyl groups are methyl or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and two carboxyl groups are methyl or ethyl groups And diester compounds.

  Moreover, the acid which has hydroxyl groups, such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. These acid components may be used alone or in combination of two or more, but preferably contain 1 to 40 mol% of tetracarboxylic acid. Further, from the viewpoint of solubility in an alkali developer and photosensitivity, it is preferable to use 50 mol% or more of an acid component having a hydroxyl group, and 70 mol% or more is more preferable.

  The structural unit represented by the general formula (2) has an imide ring.

R ⁴ in the general formula (2) represents a structural component of an acid, and represents a 4 to 8 valent organic group having 2 or more carbon atoms. Specifically, it is preferable to use the following tetravalent or higher acid component, but it is not limited thereto.

Tetravalent acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, naphthalenetetracarboxylic acid, pyridinetetracarboxylic acid, perylenetetracarboxylic acid Carboxylic acids, diester compounds in which two carboxyl groups are methyl or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and two carboxyl groups are methyl or ethyl groups And diester compounds. These acid components may be used alone or in combination of two or more, but preferably contain 1 to 40 mol% of tetracarboxylic acid. Further, from the viewpoint of solubility in alkali developer and photosensitivity, it is preferable to use 50 mol% or more of an acid component having a hydroxyl group, and more preferably 70 mol% or more. R ¹ in the general formula (1) is heat resistant. It is preferable that it is a trivalent or tetravalent organic group containing an aromatic ring and having 6 to 30 carbon atoms.

Specifically, R ¹ (COOR ³ ) _m (OH) _p in the general formula (1) is preferably represented by the general formula (6).

(In General Formula (5), R ¹⁰ and R ¹² may be the same or different and each represents a divalent to tetravalent organic group having 2 to 20 carbon atoms. R ¹¹ is 3 having 3 to 20 carbon atoms. R ¹³ and R ¹⁴ may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and t and v are integers of 0 to 2. , U represents an integer of 1 to 4, provided that t + v ≦ 2.
From the viewpoint of the heat resistance of the resulting polymer, R ¹⁰ and R ¹² preferably contain an aromatic ring, and particularly preferred structures include residues such as trimellitic acid, trimesic acid and naphthalene tricarboxylic acid.

R ¹¹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Furthermore, it is preferable that the u hydroxyl groups are located adjacent to the amide bond from the viewpoint of facilitating thermal ring closure. As such an example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, bis ( 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4 ′ Examples include diaminobiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.

Further, R ¹³ and R ¹⁴ in the general formula (5) may be the same or different, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and hydrogen or carbon atoms having 1 to 20 carbon atoms. A hydrogen group is preferred. By setting the number of carbon atoms to 20 or less, moderate solubility in an alkali developer can be obtained. t and v each represent an integer of 0 to 2, preferably 1 or 2. However, t + v ≦ 2. U represents an integer of 1 to 4. Within this range, good pattern processability can be obtained.

  Among the structures represented by the general formula (5), examples of preferred structures include the following structures, but are not limited thereto.

R ² in the general formula (1) and R ⁵ in the general formula (2) each represent a divalent to tetravalent organic group having 2 or more carbon atoms, and represent a residue of a diamine structure. The diamines may be used alone or in combination of two or more. Specific examples of diamines are listed below, but are not limited thereto.

Polyethylene oxide, such as Jeffermin KH-511, Jeffermin ED-600, Jeffermin ED-900, Jeffermin ED-2003, Jeffermin EDR-148, Jeffermin EDR-176 Diamine containing a group, D-200, D-400, D-2000, D-4000 (above trade name, manufactured by HUNTSMAN Co., Ltd.), polyoxypropylene diamine, bis (amino-hydroxy-phenyl) hexafluoropropane, Diamine having fluorine atom such as bis (trifluoromethyl) benzidine, phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyf) Nyl) propane, bis (aminophenoxyphenyl) sulfone and other diamines having no fluorine atom, or compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino- Compounds such as pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, aliphatic diamines such as cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, R ² (OH) in general formula (1) _{and q} ⁵ and R ⁵ (OH) _s in the general formula (2) may have a structure represented by any one of the general formulas (6) to (8).
Among these, it is preferable to use 60 mol% or more of a diamine component having a hydroxyl group from the viewpoint of solubility in an alkali developer and photosensitivity.

In the general formula (6), R ¹⁵ and R ¹⁷ represent a trivalent or tetravalent organic group having 2 to 20 carbon atoms, and R ¹⁶ represents a divalent organic group having 2 to 30 carbon atoms. w and x represent 1 or 2. R ¹⁸ and R ^{20 in} the general formula (7) represent a divalent organic group having 2 to ²⁰ carbon atoms, and R ¹⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. y shows the integer of 1-4. In formula (8), R ²¹ represents a divalent organic group having 2 to 20 carbon atoms, and R ²² represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. z shows the integer of 1-4.

In the general formula (6), R ¹⁵ and R ¹⁷ represent a trivalent or tetravalent organic group having 2 to 20 carbon atoms, and those having an aromatic ring are preferred from the viewpoint of heat resistance of the resulting polymer. Examples of -R ¹⁵ (OH) w- and ^-R 17 (OH) x-, specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxy biphenyl group, dihydroxybiphenyl group, a bis (Hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like can be mentioned. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹⁶ represents a divalent organic group having 2 to 30 carbon atoms. What has an aromatic ring from the heat resistant point of the polymer obtained is preferable. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group or the like can also be used.

In the general formula (7), R ¹⁸ and R ²⁰ represent a divalent organic group having 2 to ²⁰ carbon atoms. What has an aromatic ring from the heat resistance of the polymer obtained is preferable. Examples of such a group include the groups shown as examples of R ¹⁶ described above. R ¹⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Examples of -R ¹⁹ (OH) y-, include groups shown as examples of the aforementioned ^-R 15 (OH) w- and ^-R 17 (OH) x-.

In the general formula (8), R ²¹ represents a divalent organic group having 2 to 20 carbon atoms. Those having an aromatic ring are preferred from the heat resistance of the resulting polymer. Examples of such a group include the groups shown as examples of R ¹⁶ described above. R ²² represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Examples of -R ²² (OH) z-, include groups shown as examples of the aforementioned ^-R 15 (OH) w- and ^-R 17 (OH) x-.

  Of the structures represented by the general formula (6), examples of preferable structures include the following structures, but are not limited thereto.

  Further, among the structures represented by the general formula (7), examples of preferable structures include the following structures, but are not limited thereto.

  Further, among the structures represented by the general formula (8), examples of preferable structures include the following structures, but are not limited thereto.

R ³ in the general formula (1) represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solution stability of the resulting photosensitive resin composition solution, R ³ is preferably a monovalent organic group having 1 to 20 carbon atoms, but hydrogen is preferable from the viewpoint of solubility in an alkaline aqueous solution. In the present invention, hydrogen and a monovalent organic group having 1 to 20 carbon atoms can be mixed. By adjusting the amount of R ³ hydrogen and the monovalent organic group having 1 to 20 carbon atoms, the dissolution rate with respect to the aqueous alkali solution is changed. Therefore, the photosensitive resin composition having an appropriate dissolution rate by this adjustment. Can be obtained. A preferred range is from 10 mol% to 90 mol% hydrogen atoms. Further, from the viewpoint of solubility in an alkali developer, the organic group has 20 or less carbon atoms. From the above, R ³ preferably contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are preferably hydrogen atoms.

Moreover, m of General formula (1) has shown the number of the carboxyl group or ester, and is an integer of 0-4. Preferably it is 1 or 2. In the general formula (1), p and q each represent an integer of 0 to 4, and p + q> 0. The polymer having the structure represented by the general formula (1) or (2) as a main component is, for example, the following method Thus, a polymerization solution can be obtained.

  In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound and a monoamino compound used for terminal blocking at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, Thereafter, a method of reacting a diamine compound, a monoamino compound and a condensing agent, a method of obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then converting the remaining dicarboxylic acid to an acid chloride and reacting with the diamine compound or the monoamino compound. and so on.

  In the case of polyhydroxyamide, it can be obtained by a method of reacting a bisaminophenol compound with dicarboxylic acid dichloride.

  In the case of polyimide, after obtaining the polyamic acid or polyamic acid ester, it can be obtained by dehydration and ring closure by heating or chemical treatment such as acid or base.

  Solvents for obtaining the polymerization solution include N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane, dimethyl-2-piperidone, dimethylsulfoxide, and diglyme. However, it is not limited to this.

  The weight average molecular weight (Mw) in the polymer having the structure represented by (a) general formula (1) or (2) as the main component of the present invention is a value measured by gel permeation chromatography (GPC) in terms of polystyrene. Is preferably 2000 to 100,000, more preferably 5000 to 50,000, and even more preferably in the range of 10,000 to 30,000. When the molecular weight represented by the general formula (1) or (2) is within the range of 2,000 to 100,000, the solubility of the polymer in an alkaline developer can be obtained, and the exposed and unexposed areas can be obtained. Since contrast is obtained, it is preferable.

  In addition, the present invention contains (b) at least one of compounds having a molecular weight of 300 or less represented by the general formula (3) or (4).

  In the structures of the general formulas (3) and (4), it is important to contain an N—OH group in order to obtain adhesion and storage stability. Storage stability is lowered with an N—H group, and adhesion cannot be obtained with a hydrocarbon.

  A preferred compound represented by the general formula (3) is 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole, and a preferred compound represented by the general formula (4) is N-hydroxysuccinimide. One or more of these can be used.

  About content of the (b) compound of this invention, it is preferable to contain 0.01-10 mass parts with respect to 100 mass parts of (a) component. The compound (b) is more preferably contained in an amount of 0.01 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the component (a). Adhesiveness with a metal substrate can be improved because the addition amount is 0.01 parts by mass or more. When the addition amount is 10 parts by mass or less, the storage stability can be improved, and when the addition amount is 0.1 parts by mass or less, the storage stability can be further improved. By adjusting the addition amount within the above range, the sensitivity can be maintained, and in the process of filtering with a filter diameter of 0.05 μm or less, the original foreign matter amount can be reduced to improve the process passability. .

  Moreover, the positive photosensitive resin composition of the present invention contains (c) a quinonediazide compound. (C) You may contain 2 or more types of quinonediazide compounds.

  (C) Examples of quinonediazide compounds include quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, quinonediazide sulfonic acid bonded to a polyamino compound with a sulfonamide bond, and a quinonediazide sulfonic acid ester to a polyhydroxypolyamino compound. Examples thereof include a bond and / or a sulfonamide bond.

  (C) The quinonediazide compound can be obtained, for example, by reacting 5-naphthoquinonediazidesulfonyl chloride with a polyhydroxy compound in the presence of triethylamine.

  The polyhydroxy compound, polyamino compound, and polyhydroxypolyamino compound can be added without reacting.

  Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, from the viewpoint of the contrast between the exposed part and the unexposed part, 50 mol% or more of the whole functional group is substituted with quinonediazide. It is preferable. 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.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, 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 (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 2,6-dimethoxy Methyl-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, manufactured by Honshu Chemical Industry Co., Ltd.) Including 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. Although sulfide etc. are mentioned, it is not limited to these.

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

  As the quinonediazide of the present invention, both a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group are preferably used. 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, the number average molecular weight of the (c) quinonediazide compound is preferably 2,500 or less, more preferably 1,500 or less, and even more preferably 1,200 or less. When the number average molecular weight is 2,500 or less, the (c) quinonediazide compound is sufficiently thermally decomposed in the heat treatment after pattern formation, and a cured film having excellent heat resistance, mechanical properties, and adhesiveness can be obtained. On the other hand, in order to suppress volatilization during pre-baking, the molecular weight is preferably 300 or more, more preferably 350 or more.

  Moreover, the positive photosensitive resin composition of this invention contains (d) thermal crosslinking agent represented by General formula (9).

(In the formula, R ²³ represents a direct bond or a monovalent to tetravalent linking group. R ²⁴ represents a monovalent organic group having 1 to 20 carbon atoms, Cl, Br, I, or F. R ²⁵ and R ²⁶ represents CH ₂ OR ²⁸ (R ²⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) R ²⁷ represents a hydrogen atom, a methyl group, or an ethyl group, and h represents 0 to 2 , I represents an integer of 1 to 4. When i is 2 to 4, a plurality of R ^{24 to} R ²⁷ may be the same or different, but the same benzene ring has two R ^{23 ,} in examples 1 to 4 divalent linking group represents a ^{.R 23 R 23} are the ^same, R 29 ^{to R 51} is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, Cl, Br, I Or F.)
In the present invention, if the thermal cross-linking agent represented by the general formula (9) is mixed with an unsubstituted one or a large amount thereof, the cross-linking reaction of the resin composition may not sufficiently proceed. For this reason, the purity of the compound represented by the general formula (9) is preferably 80% or more, and more preferably 95% or more. If the purity is 80% or more, the crosslinking reaction of the resin composition can be sufficiently performed to reduce the number of unreacted groups that become water-absorbing groups, so that the water absorption of the resin composition can be reduced. In order to obtain a high-purity thermal crosslinking agent, there are methods such as recrystallization and distillation to collect only the desired product. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.

  5 mass parts or more are preferable with respect to 100 mass parts of (a) component, and, as for content of (d) thermal crosslinking agent of this invention, 10 mass parts or more are more preferable. If it is 5 parts by mass or more, the crosslink density of the cured film is increased and the chemical resistance is improved, which is preferable. Further, when it is 10 parts by mass or more, higher mechanical properties can be obtained. On the other hand, from the viewpoint of storage stability and mechanical strength of the composition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.

  The positive photosensitive resin composition of the present invention can further contain a silane compound. By containing the silane compound, the adhesiveness with a base substrate such as SIN is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltri Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the following silane compounds are used: Door can be, but are not limited to these.

  The content of the silane compound of the present invention is preferably 0.5 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the component (a) because the adhesion to the base substrate such as SIN is improved. More preferred. On the other hand, from the viewpoint of storage stability and sensitivity of the composition, the content of the silane compound is preferably 50 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of the component (a).

  As the solvent of the present invention, polar aprotic solvents such as γ-butyrolactone, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, Examples include propylene glycol monomethyl ether acetate, esters such as ethyl lactate, and aromatic hydrocarbons such as toluene and xylene, and these solvents may be contained in two or more.

  In the present invention, the viscosity of the positive photosensitive resin composition is preferably adjusted to 1 mPa · s or more, and preferably adjusted to 5 mPa · s or more, because the uniformity of the coating film is improved. Is more preferable. On the other hand, from the viewpoint of storage stability of the positive photosensitive resin composition and ease of liquid feeding at the time of application, it is preferable to adjust the viscosity of the positive photosensitive composition to be 1000 mPa · s or less, and 100 mPa · s. -It is more preferable to adjust so that it may become s or less.

  Next, the manufacturing method of the positive photosensitive resin composition of this invention is illustrated.

  (A) to (d) Ingredients, solvents, and other components as required in glass flasks or stainless steel containers and stirred and dissolved with a mechanical stirrer, etc., ultrasonically dissolved, planetary stirring deaerator And the like.

  At this time, the viscosity of the positive photosensitive resin composition is preferably 1 to 10000 mPa · s from the applicability. Moreover, you may filter with a filter with a pore size of 0.001 micrometer-5 micrometers in order to remove a foreign material. If the pore size is too large, foreign matter cannot be completely removed, and defects or defects will occur after the device is manufactured. If the pore size is too small, filtration takes time.

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

  A photosensitive resin composition is applied onto a substrate. Examples of the substrate include a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, and ITO used for an organic EL element as a transparent electrode, but are not limited thereto.

  Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. 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 150 μm depending on the design of the device.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like within a range of 50 ° C. to 150 ° C. for 1 minute to several hours. If the temperature is too low for a short time, the solvent will not evaporate and a photosensitive film cannot be obtained. If the temperature is too high for a long time, the photosensitizer may be decomposed.

  Next, the photosensitive resin 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. . This is because the naphthoquinone compound easily reacts with this actinic radiation.

  In order to form a pattern of a heat resistant resin from the photosensitive resin film, the exposed portion may be removed using a developer after exposure. 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, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 200 ° C. to 500 ° C. is applied to convert it to a heat resistant resin film. 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, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 320 ° C. over 2 hours can be mentioned.

  The heat-resistant resin film formed by the positive photosensitive resin composition of the present invention can be suitably used for electronic components, and includes surface protection films, interlayer insulating films, and organic EL elements of semiconductor elements such as LSI (Large Scale Integration). It can be used for an insulating film of an element, a planarizing film of a TFT substrate, and the like.

<Sensitivity evaluation method>
(I) Production of photosensitive resin film On a 6-inch silicon wafer, the varnishes obtained in the examples and comparative examples were applied so that the film thickness T1 after pre-baking was 1.5 μm, and then hot plate (Tokyo) A photosensitive resin film was obtained by pre-baking at 120 ° C. for 2 minutes using a coating and developing apparatus Mark-7 manufactured by Electron Co., Ltd. The film thickness was measured at a refractive index of 1.629 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg.

(Ii) Exposure Using the obtained photosensitive resin film, a plurality of patterned reticles were produced. Next, one of the above reticles was set in an exposure machine (i-line stepper DSW-8570i manufactured by GCA), and the photosensitive resin film was exposed with i-line at an intensity of 365 nm for a predetermined exposure time.

(Iii) Development Immediately after the exposure of the photosensitive resin film after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide in 10 revolutions at 50 revolutions using a Mark-7 development device manufactured by Tokyo Electron Ltd. Sprayed for 2 seconds. Thereafter, the plate was allowed to stand for 20 seconds at 0 rotation, rinsed with water at 400 rotation, and then shaken and dried for 10 seconds at 3000 rotation.

(Iv) Evaluation of sensitivity When the film thickness of the exposed portion of the obtained photosensitive resin film is 0 μm, the exposure time is longer under the condition that the exposure time is shorter, and when the film thickness is thicker than 0 μm. Under the conditions, the above measurement was repeated, and the minimum exposure among the exposure doses at which the film thickness of the exposed area became 0 μm after development was evaluated as sensitivity.

Good order to compare the sensitivity, 60 mJ / cm ² or less ◎, 100mJ / cm ² or less ○, 200mJ / cm ² or less △, was evaluated as × in excess of 200 mJ / cm ^2.

<Adhesion evaluation method>
(I) Preparation of Cure Film After a 130 nm thick ITO transparent electrode film was formed on the surface by sputtering deposition on a glass substrate corning 1737 (manufactured by Corning), each varnish was used and T1 = 1.5 μm A pre-baked film was prepared so that the heat treatment was performed in an atmosphere of nitrogen at 230 ° C. for 30 minutes using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd.

(Ii) PCT treatment 10 rows and 10 columns (100 squares) of grid-like cuts are made in the cured film at intervals of 2 mm, and saturated at 121 ° C. and 2 atm using a hast chamber EHS-212MD (manufactured by ESPEC Corporation). A pressure cooker test (PCT) treatment was performed under the conditions. The PCT processing time in which one square or more out of 100 squares by peeling with cellophane tape (registered trademark) was measured.

(Iii) Evaluation of adhesion (base tape test result (peeling time))
The PCT treatment times were compared, and in order of goodness, those that had not been peeled for 100 hours or more were evaluated as “◎”, those that had not peeled for 50 hours or more were evaluated as “、”, and those that had peeled in less than 50 hours were evaluated as “x”.

<Durability evaluation method (luminescence efficiency measurement method)>
(I) Preparation of organic EL element After a 130 nm thick ITO transparent electrode film was formed on the surface of glass substrate corning 1737 (manufactured by Corning) by sputtering vapor deposition, the ITO film was 90 mm long and wide. Patterned into a stripe shape of 80 μm. The stripe-shaped first electrode has a pitch of 100 μm.

  A prebaked film using each varnish is prepared on a glass substrate patterned with ITO so that T1 = 1.5 μm, and an opening with a width of 70 μm and a length of 250 μm is opened by processing such as exposure and development curing. Moreover, an insulating layer having a thickness of about 1 μm made of a resin that covers the end of the first electrode was formed.

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

The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together a board | substrate and the glass plate for sealing using the ultraviolet curing epoxy resin. In this way, a simple matrix type color organic light emitting display device in which a patterned light emitting layer is formed on the ITO striped first electrode and the striped second electrode is arranged so as to be orthogonal to the first electrode is manufactured. Then, the effective light emitting area before the durability test was measured and designated S1.

(Ii) Durability Evaluation With respect to this organic electroluminescence display device, a durability test was performed by holding at 85 ° C. for 250 hours. The area of the light emitting region after the durability test was set to S2, and the effective light emitting area ratio S (%) was obtained by the following formula, which was used as the durability evaluation.
S (%) = (S2 / S1) × 100
In order of good comparison of the durability evaluation results, 99% or more was evaluated as ◎, 90% or more as ◯, 80% or more as Δ, and less than 80% as ×.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) Under a dry nitrogen stream, 183 g (0.5 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl glycidyl 342 g (3 mol) of ether was dissolved in 1000 g of gamma butyrolactone (GBL) and cooled to −15 ° C. 221 g (1.1 mol) of trimellitic anhydride chloride dissolved in 500 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 10 L 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) 183 g (0.5 mol) of BAHF was dissolved in 1 L of acetone and 174 g (3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 204 g (1.1 mol) of 3-nitrobenzoyl chloride in 1 L 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.

  300 g of the obtained solid was put in a 3 L stainless steel autoclave, dispersed in 2.5 L of methyl cellosolve, and 20 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 154 g (1 mol) of 2-amino-4-nitrophenol was dissolved in 500 mL of acetone and 300 g (3.4 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 112 g (0.55 mol) of isophthalic acid chloride in 600 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 GBL2L, and 30 g of 5% palladium-carbon was added and stirred vigorously. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto for recrystallization to obtain a hydroxyl group-containing diamine (c) crystal represented by the following formula.

Synthesis Example 4 Synthesis of quinonediazide compound (d) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40. 28 g (0.15 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 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 (d) represented by the following formula.

Synthesis Example 5 Synthesis of quinonediazide compound (e) TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 4-naphthoquinonediazidesulfonyl acid chloride 32. 23 g (0.12 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, instead of 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was used. The quinonediazide compound (e) represented by these was obtained.

Synthesis Example 6 Synthesis of Polyimide Precursor A 4,4′-Diaminophenyl ether (DAE) 50.1 g (0.25 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane in a dry nitrogen stream (SiDA) 12.4 g (0.05 mol) was dissolved in N-methyl-2-pyrrolidone (NMP) 500 g. To this, 214 g (0.30 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added together with 140 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution obtained by diluting 71.4 g (0.6 mol) of N, N-dimethylformamide dimethylacetal with 50 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours to obtain a polymerization solution. This polymerization solution was added to 5 L of water to form a slurry. This slurry was filtered under reduced pressure and dehydrated, 5 L of water was added, the mixture was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydration was repeated twice. Then, it dried with the 80 degreeC vacuum dryer for 20 hours, and the polyimide precursor A was obtained.

Synthesis Example 7 Synthesis of Polyimide Precursor B Under dry nitrogen stream, 136 g (0.225 mol) of hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 was dissolved in 500 g of NMP. 77.6 g (0.25 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride (ODPA) obtained in Synthesis Example 1 was added together with 300 g of pyridine, and the reaction was performed at 40 ° C. for 2 hours. I let you. Thereafter, 5.8 g (0.05 mol) of 3-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 73.5 g (0.5 mol) of N, N-dimethylformamide diethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours to obtain a polymerization solution. This polymerization solution was added to 5 L of water to form a slurry. This slurry was filtered under reduced pressure and dehydrated, 5 L of water was added, the mixture was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydration was repeated twice. Then, it dried for 72 hours with the 80 degreeC vacuum dryer, and the polyimide precursor B was obtained.

Synthesis Example 8 Synthesis of Polyimide Precursor C Under a dry nitrogen stream, 151 g (0.40 mol) of hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 12.4 g (0.05 mol) of SiDA were dissolved in 500 g of NMP. I let you. ODPA155g (0.5 mol) was added here with NMP210g, and it was made to react at 20 degreeC for 1 hour, and then was made to react at 50 degreeC for 1 hour. Thereafter, 9.5 g (0.08 mol) of 4-allylaniline was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 1 hour. Thereafter, a solution obtained by diluting 132 g (0.9 mol) of N, N-dimethylformamide diethyl acetal with 150 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours to obtain a polymerization solution. This polymerization solution was added to 5 L of water to form a slurry. This slurry was filtered under reduced pressure and dehydrated, 5 L of water was added, the mixture was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydration was repeated twice. Then, it dried with the 80 degreeC vacuum dryer for 20 hours, and the polyimide precursor C was obtained.

Synthesis Example 9 Synthesis of Polybenzoxazole Precursor D Dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid dichloride (DEDC) with 2 mol of 1-hydroxybenzotriazole in a dry nitrogen stream 197 g (0.40 mol) and BAHF 183 g (0.50 mol) were dissolved in NMP 500 g and stirred at 75 ° C. for 12 hours. Next, 37.6 g (0.20 mol) of 3-allylbenzenedicarboxylic anhydride dissolved in 300 g of NMP was added as a terminal blocking agent, and the mixture was further stirred at 75 ° C. for 12 hours to obtain a polymerization solution. This polymerization solution was added to 5 L of water to form a slurry. This slurry was filtered under reduced pressure and dehydrated, 5 L of water was added, the mixture was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydration was repeated twice. Then, it dried for 36 hours with the 80 degreeC vacuum dryer, and the polybenzoxazole precursor D was obtained.

Synthesis Example 10 Synthesis of Polyimide E Under a dry nitrogen stream, 49.6 g (0.135 mol) of BAHF and 3.7 g (0.015 mol) of SiDA were dissolved in 200 g of NMP, and 46.7 g (0.15 mol) of ODPA was added and stirred. And allowed to react at room temperature for 5 hours. Then, it heated to 200 degreeC and made it imidize for 2 hours, and obtained the polymerization liquid.

  The polymerization solution was added to 2 L of water to make a slurry. This slurry was filtered under reduced pressure and dehydrated, 5 L of water was added, the mixture was stirred with a mechanical stirrer, filtered under reduced pressure, dehydrated twice, and dried in an 80 ° C. vacuum dryer for 72 hours to obtain polyimide E.

[Example 1]
10 g of polymer A, quinonediazide compound (d) obtained in Synthesis Example 4 2.0 g 1-hydroxybenzotriazole 1 mg MX-280 2.0 g was dissolved in 60 g of γ-butyllactone and 40 g of ethyl lactate to obtain a varnish.

[Examples 2 to 10 and Comparative Examples 1 to 3]
A varnish was obtained in the same manner as in Example 1 except that the polymer, the quinonediazide compound, the nitrogen-containing compound and the crosslinking material were as shown in Table 1.

  The structure of the used crosslinking agent is shown below.

  The structure of the heterocyclic compound used is shown below.

  Table 1 shows the composition and evaluation results of each component used.

Claims (6)

(A) a polymer having a weight average molecular weight of 2,000 to 1,000,000 having at least one of the structures represented by the general formula (1) or (2), (b) the general formula (3) or (4) A positive photosensitive resin composition comprising at least one of compounds represented by the formula (I) and a quinonediazide compound.

(In the general formula (1), R ¹ is a 2 to 8 valent organic group having 2 or more carbon atoms, R ² is a 2 to 6 valent organic group having 2 or more carbon atoms, and R ³ is hydrogen or 1 to 20 carbon atoms. M is an integer of 0 to 4, p and q are integers of 0 to 4, provided that p + q> 0.)

(In General Formula (2), R ⁴ represents a 4 to 8 valent organic group having 2 or more carbon atoms. R ⁵ represents a 2 to 6 valent organic group having 2 or more carbon atoms. R and s are each 0. Represents an integer of ~ 4.)

(In the general formula (3), R ⁶ and R ⁷ represent 1 to 4 valent organic groups.)

(In the general formula (4), R ⁸ and R ⁹ represent 1 to 4 valent organic groups.) The positive photosensitive resin composition according to claim 1, wherein the compound (b) contains at least one of 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, and N-hydroxysuccinimide. The positive photosensitive resin composition according to claim 1 or 2, wherein the content of the compound (b) is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer (a). The positive photosensitive resin composition according to claim 1, wherein the content of the compound (b) is 0.01 part by mass or more and 0.1 part by mass or less with respect to 100 parts by mass of the polymer (a). Furthermore, the positive photosensitive resin composition in any one of Claims 1-4 containing (d) thermal crosslinking agent represented by General formula (9).

(In the formula, R ²³ represents a direct bond or a monovalent to tetravalent linking group. R ²⁴ represents a monovalent organic group having 1 to 20 carbon atoms, Cl, Br, I, or F. R ²⁵ and R ²⁶ represents CH ₂ OR ²⁸ (R ²⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) R ²⁷ represents a hydrogen atom, a methyl group, or an ethyl group, and h represents 0 to 2 , I represents an integer of 1 to 4. When i is 2 to 4, a plurality of R ^{24 to} R ²⁷ may be the same or different, but the same benzene ring has two R ^{23 ,} in examples 1 to 4 divalent linking group represents a ^{.R 23 R 23} are the ^same, R 29 ^{to R 51} is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, Cl, Br, I Or F.)   The electronic component using the positive photosensitive resin composition in any one of Claims 1-5.