JP6808928B2 - Photosensitive resin composition - Google Patents

Description

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

Resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulating properties, and have been used as surface protective films and interlayer insulating films for semiconductor devices such as LSI (Large Scale Integration). Recently, it has also been used as an insulating film for organic EL elements and a flattening film for TFT substrates (Patent Document 1).

In these applications, if the adhesiveness between the insulating film or the flattening film and the substrate is insufficient, the portion is peeled off and does not play the role of the insulating film or the flattening film, which causes a problem.

It is known that when the adhesiveness between the insulating film or the flattening film and the substrate is improved, if the substrate is silicon, a chipped film or the like, it can be improved by using an organosilicon compound.

However, with the above method, it was difficult to obtain high adhesiveness to copper used for rewiring and metals such as indium tin oxide (hereinafter referred to as ITO) used for organic EL devices as transparent electrodes.

Therefore, studies are underway to improve the adhesiveness with a metal by adding a heterocyclic compound (Patent Document 2 or 3).

However, when an organic EL element is produced using a photosensitive resin composition containing a heterocyclic compound, the heterocyclic organic compound is decomposed and gas is generated when the organic EL element is made to emit light for a long time. Then, there is a problem that the luminous efficiency of the organic EL element is lowered by the gas.

Japanese Unexamined Patent Publication No. 2004-54254 Japanese Unexamined Patent Publication No. 2007-17959 Japanese Unexamined Patent Publication No. 2006-184660

In view of the above problems, the present invention provides a photosensitive resin composition capable of suppressing adhesion to ITO, which is a metal often used for organic EL devices, and reduction in luminous efficiency when the EL device is manufactured. To do.

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

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

(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. Indicates an organic group up to. M indicates an integer of 0 to 4. p and q indicate an integer of 0 to 4, and p + q> 0.)

(In the 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 0, respectively. Indicates an integer of ~ 4.

(In the general formula (3), R ⁶ and R ⁷ each independently represent a 1- to 4-valent organic group.)

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

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) with respect to the entire polymer is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more because the heat resistance is improved.

(A) The structural unit may be composed of either the structural unit of the general formula (1) or (2) alone, or may be composed of both the structural units of the 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 another cyclic structure by heating or a suitable catalyst. The structural unit represented by the general formula (1) is preferably a polyamic acid or polyamic acid ester of the polyimide precursor, or a polyhydroxyamide of the polybenzoxazole precursor. This is because the cyclic structure after heating dramatically improves heat resistance and solvent resistance.

R ¹ in the general formula (1) represents a structural component of an acid, and represents a 2- to 8-valent organic group having 2 or more carbon atoms. Specifically, it is preferable, but not limited to, the following acid components are used.

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.

Tetras having a tetravalent or higher valence include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfonetetracarboxylic acid, naphthalenetetracarboxylic acid, pyridinetetracarboxylic acid, perylenetetracarboxylic acid and the like. Carboxylic acid, diester compounds with two carboxyl groups as methyl or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and two carboxyl groups thereof as methyl and ethyl groups. The above-mentioned diester compound can be mentioned.

Further, an acid having a hydroxyl group such as hydroxyphthalic acid and hydroxytrimellitic 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 alkaline developer and photosensitivity, it is preferable to use 50 mol% or more of the acid component having a hydroxyl group, and more preferably 70 mol% or more.

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 acid components having a tetravalent value or higher, but the present invention is not limited to this.

Tetras having a tetravalent or higher valence include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfonetetracarboxylic acid, naphthalenetetracarboxylic acid, pyridinetetracarboxylic acid, perylenetetracarboxylic acid and the like. Carboxylic acid, diester compounds with two carboxyl groups as methyl or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and two carboxyl groups thereof as methyl and ethyl groups. The above-mentioned diester compound can 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 alkaline developer and photosensitivity, it is preferable to use 50 mol% or more of the acid component having a hydroxyl group, more preferably 70 mol% or more. R ¹ in the general formula (1) has heat resistance. In terms of the above, it is preferably 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 the general formula (5), R ¹⁰ and R ¹² may be the same or different, respectively, and represent divalent to tetravalent organic groups having 2 to 20 carbon atoms. R ¹¹ is 3 having 3 to 20 carbon atoms. Indicates a valent to hexavalent organic group. R ¹³ and R ¹⁴ may be the same or different, respectively, and indicate hydrogen or a monovalent organic group having 1 to 20 carbon atoms. T and v are integers of 0 to 2. , U represent an integer of 1 to 4. However, t + v ≦ 2).
From the viewpoint of heat resistance of the obtained polymer, R ¹⁰ and R ¹² preferably contain an aromatic ring, and particularly preferable structures include residues such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid.

Further, R ¹¹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Further, it is preferable that the u hydroxyl groups are located adjacent to the amide bond in order to facilitate the progress of thermal ring closure. Examples of such are bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing a fluorine atom, bis (3-hydroxy-4-aminophenyl) hexafluoropropane, and bis (3-amino-4-aminophenyl) containing no fluorine atom. 3-Amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4' Examples thereof include those in which the amino groups of −diaminobiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene are bonded.

Further, R ¹³ and R ¹⁴ of the general formula (5) may be the same or different, respectively, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and hydrocarbon or carbonic acid having 1 to 20 carbon atoms. Hydrogen groups are preferred. By setting the number of carbon atoms to 20 or less, appropriate solubility in an alkaline developer can be obtained. Although t and v indicate integers from 0 to 2, they are preferably 1 or 2. However, t + v ≦ 2. Further, u represents an integer of 1 to 4. Within this range, good pattern workability can be obtained.

Among the structures represented by the general formula (5), examples of preferable structures include, but are not limited to, the structures shown below.

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

Polyethylene oxides such as Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176 (trade name, manufactured by HUNTSMAN Co., Ltd.) Group-containing diamines, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), polyoxypropylene diamine, bis (amino-hydroxy-phenyl) hexafluoropropane, Diamines having fluorine atoms such as bis (trifluoromethyl) benzidine, phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone and other fluorine Atomic-free diamines, or compounds in which these aromatic rings are substituted with alkyl groups or halogen atoms, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diamino Compounds such as terephthalic acid, aliphatic diamines such as cyclohexylamine, methylenebiscyclohexylamine, hexamethylenediamine, R ² (OH) _{q in the} general formula (1) and R ⁵ (OH) in the general formula (2). _{Examples of s} have a structure represented by any of the general formulas (6) to (8).
Among these, it is preferable to use 60 mol% or more of the diamine component having a hydroxyl group from the viewpoint of solubility in an alkaline developer and photosensitivity.

R ¹⁵ and R ¹⁷ of the general formula (6) 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 of the general formula (7) represent divalent organic groups having 2 to ²⁰ carbon atoms, and R ¹⁹ represents trivalent to hexavalent organic groups having 3 to 20 carbon atoms. y represents an integer of 1 to 4. R ²¹ of the general formula (8) 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 represents an integer of 1 to 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 preferable from the viewpoint of heat resistance of the obtained polymer. As examples of −R ¹⁵ (OH) w− and −R ¹⁷ (OH) x−, specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis. Examples thereof include (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. Further, an aliphatic group such as a hydroxycyclohexyl group or a dihydroxycyclohexyl group can also be used. R ¹⁶ represents a divalent organic group having 2 to 30 carbon atoms. From the viewpoint of heat resistance of the obtained polymer, those having an aromatic ring are preferable. Examples of such include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, a diphenylsulfone group and the like. In addition to this, an aliphatic cyclohexyl group or the like can also be used.

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

In the general formula (8), R ²¹ represents a divalent organic group having 2 to 20 carbon atoms. From the heat resistance of the obtained polymer, those having an aromatic ring are preferable. An example of such is the group shown as an example of R ¹⁶ described above. R ²² represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and one having an aromatic ring is preferable from the heat resistance of the obtained polymer. Examples of −R ²² (OH) z− include the groups shown as examples of −R ¹⁵ (OH) w− and −R ¹⁷ (OH) x− described above.

Among the structures represented by the general formula (6), examples of preferable structures include, but are not limited to, the structures shown below.

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

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

Further, R ³ of 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, from the viewpoint of solubility in an alkali aqueous solution, preferably hydrogen. In the present invention, hydrogen and a monovalent organic group having 1 to 20 carbon atoms can be mixed. By adjusting the amount of the monovalent organic group of the R ³ hydrogen and having 1 to 20 carbon atoms, since dissolution rate into the alkaline aqueous solution is changed, the photosensitive resin composition having an appropriate dissolution rate by the adjustment Can be obtained. The preferred range is 10 mol% to 90 mol% hydrogen atoms. Further, from the viewpoint of solubility in an alkaline developer, the organic group has 20 or less carbon atoms. From the above, it is preferable that R ³ contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

Further, m in the general formula (1) indicates the number of carboxyl groups or esters, and is an integer of 0 to 4. It is preferably 1 or 2. P and q in the general formula (1) each represent an integer of 0 to 4, and the polymer containing the structure represented by the general formula (1) or (2) in which p + q> 0 is used as a main component is, for example, the following method. Can obtain a polymer solution.

In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound and a monoamino compound used for terminal encapsulation at a low temperature, a diester is obtained with the tetracarboxylic acid dianhydride and an alcohol. Then, a method of reacting with a diamine compound or a monoamino compound in the presence of a condensing agent, a method of obtaining a diester with tetracarboxylic acid dianhydride and an alcohol, and then acid chlorideizing the remaining dicarboxylic acid 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 a dicarboxylic acid dichloride.

In the case of polyimide, it can be obtained by obtaining the above polyamic acid or polyamic acid ester and then dehydrating and closing the ring by heating or chemical treatment with an acid or a base.

Examples of the solvent for obtaining the polymer solution include N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane, dimethyl-2-piperidone, dimethyl sulfoxide, and digrim. It can be mentioned, but it is not limited to this.

The weight average molecular weight (Mw) of the polymer having the structure represented by the general formula (1) or (2) of the present invention as a main component is a value measured by gel permeation chromatography (GPC) in terms of polystyrene. Is preferably 2000-100,000, more preferably 5000-50,000, and even more preferably in the range of 10,000-30,000. When the molecular weight represented by the general formula (1) or (2) is in 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. This is preferable because it provides contrast.

In addition, the present invention contains at least one of (b) a compound 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 adhesiveness and storage stability. Storage stability is reduced with the NH group, and adhesiveness cannot be obtained with the hydrocarbon.

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

The content of the compound (b) of the present invention is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (a). Further, it is more preferable that the compound (b) is contained in an amount of 0.01 part by mass or more and 0.1 part by mass or less with respect to 100 parts by mass of the component (a). When the amount added is 0.01 parts by mass or more, the adhesiveness with the metal substrate can be improved. 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 keeping the addition amount within the above range, the sensitivity can be maintained, and in the process of performing filtration with a filter diameter of 0.05 um or less, the process passability can be improved by reducing the original amount of foreign matter. ..

Further, the positive photosensitive resin composition of the present invention contains (c) a quinone diazide compound. (C) Two or more kinds of quinone diazide compounds may be contained.

(C) Examples of the quinone diazide compound include a polyhydroxy compound in which the sulfonic acid of quinone diazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinone diazide is conjugated with a sulfonamide bond, and a polyhydroxypolyamino compound in which the sulfonic acid of quinone diazide is an ester. Examples thereof include those having a bond and / or a sulfonamide bond.

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

Further, the above-mentioned polyhydroxy compound, polyamino compound and polyhydroxypolyamino compound can be added without reacting.

All the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, but from the viewpoint of contrast between the exposed and unexposed areas, 50 mol% or more of all the functional groups are substituted with quinonediazide. Is preferable. By using such a quinone diazide 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 which 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 (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR- PCHP, BIPC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMEEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2, 6 -Dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, asbestosic acid methyl ester, bisphenol A, bisphenol E, Examples thereof include, but are not limited to, methylene bisphenol and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

The polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl. Examples include, but are not limited to, sulfides and the like.

Further, 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.

As the quinone diazide of the present invention, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has 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 diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound in which a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group are used in combination in the same molecule can also be obtained, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound can be obtained. Can also be mixed and used.

Further, (c) the number average molecular weight of the quinone diazide compound is preferably 2,500 or less, more preferably 1,500 or less, still 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, the molecular weight is preferably 300 or more, more preferably 350 or more, in order to suppress volatilization during prebaking.

Further, the positive photosensitive resin composition of the present invention contains (d) a thermal cross-linking agent represented by the general formula (9).

(In the formula, R ²³ represents a direct bond or a 1- 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 is 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. H is 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 when the same benzene ring has two R ^23. R ²³ is the same. In the example of the 1- to tetravalent linking group representing R ²³ , R ^{29 to} R ⁵¹ are hydrogen atoms, monovalent organic groups having 1 to 20 carbon atoms, Cl, Br, I. , Or F.)
In the present invention, the cross-linking reaction of the resin composition may not proceed sufficiently when the thermally cross-linking agent represented by the general formula (9) is mixed with an unchanged product or an increased amount. Therefore, the purity of the compound represented by the general formula (9) is preferably 80% or more, and more preferably 95% or more. When the purity is 80% or more, the cross-linking reaction of the resin composition can be sufficiently carried out and the number of unreacted groups serving as water-absorbing groups can be reduced, so that the water absorption of the resin composition can be reduced. In order to obtain a high-purity thermal cross-linking agent, there is a method of recrystallization, distillation, etc. to collect only the target product. The purity of the thermal cross-linking agent can be determined by a liquid chromatography method.

The content of the (d) thermal cross-linking agent of the present invention is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the component (a). When it is 5 parts by mass or more, the crosslink density of the cured film becomes high 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, 50 parts by mass or less is preferable, 40 parts by mass or less is more preferable, and 30 parts by mass or less is further preferable.

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

The content of the silane compound of the present invention is preferably 0.5 parts by mass or more, preferably 1.0 part by mass or more with respect to 100 parts by mass of the component (a), because the adhesiveness 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, more preferably 10 parts by mass or less with respect to 100 parts by mass of the component (a).

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

In the present invention, the viscosity of the positive photosensitive resin composition is preferably adjusted to 1 mPa · s or more in order to improve the uniformity of the coating film, and is adjusted to 5 mPa · s or more. 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 so as to be 1000 mPa · s or less, preferably 100 mPa. -It is more preferable to adjust so that it is s or less.

Next, a method for producing the positive photosensitive resin composition of the present invention will be illustrated.

A method of putting the components (a) to (d), a solvent and other components if necessary in a glass flask or a stainless steel container and stirring and dissolving them with a mechanical stirrer, a method of dissolving by ultrasonic waves, a planetary stirring and defoaming device. Examples thereof include a method of stirring and dissolving with.

At this time, the viscosity of the positive photosensitive resin composition is preferably 1 to 10000 mPa · s from the viewpoint of coatability. Further, in order to remove foreign matter, it may be filtered with a filter having a pore size of 0.001 μm to 5 μm. If the pore size is too large, foreign matter cannot be completely removed, resulting in defects or defects after the device is manufactured. If the pore size is too small, it will take time to filter.

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

The photosensitive resin composition is applied onto the substrate. Examples of the substrate include silicon wafers, ceramics, gallium arsenide, metals, glass, metallic oxide insulating films, silicon nitride, and ITO used for organic EL devices as transparent electrodes, but the substrate is not limited thereto.

Examples of the coating method include rotary coating using a spinner, spray coating, roll coating, and slit die coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 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 carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like. If the temperature is too low and the time is too long, the solvent does not volatilize and a photosensitive film cannot be obtained.

Next, the photosensitive resin film is irradiated with chemical rays through a mask having a desired pattern and exposed. The chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. .. This is because the naphthoquinone compound easily reacts with this chemical beam.

In order to form a heat-resistant resin pattern from the photosensitive resin film, the exposed portion may be removed with a developing solution after exposure. The developing solution 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 an alkaline compound such as ethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable. In some cases, these alkaline aqueous solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several types. Good. After development, rinse with water. Here, too, 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 into a heat-resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours while selecting a temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method 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 can be used as a surface protective film, an interlayer insulating film, an organic EL of a semiconductor element such as an LSI (Large Scale Integration). It can be used as an insulating film for an element, a flattening film for a TFT substrate, and the like.

<Sensitivity evaluation method>
(I) Preparation of Photosensitive Resin Film The varnishes obtained in each Example and Comparative Example were applied onto a 6-inch silicon wafer so that the film thickness T1 after prebaking was 1.5 μm, and then a hot plate (Tokyo). A photosensitive resin film was obtained by prebaking at 120 ° C. for 2 minutes using a coating / developing device Mark-7) manufactured by Electron Limited. The film thickness was measured with a refractive index of 1.629 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.

(Ii) Exposure A plurality of reticles with cut patterns were prepared using the obtained photosensitive resin film. Next, one of the above reticles was set in an exposure machine (GCA i-line stepper DSW-8570i), and the photosensitive resin film was exposed with i-rays at an intensity of 365 nm for a predetermined exposure time.

(Iii) Development Immediately after exposing the photosensitive resin film after the above exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide was added at 50 rpm using a Mark-7 developing device manufactured by Tokyo Electron Limited. Sprayed for seconds. After that, the mixture was allowed to stand at 0 rpm for 20 seconds, rinsed with water at 400 rpm, and shaken off at 3000 rpm for 10 seconds to dry.

(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 shorter, and when the film thickness is thicker than 0 μm, the exposure time is longer. Under the conditions, the above measurement was repeated, and the smallest exposure amount at which the film thickness of the exposed portion became 0 μm after development was evaluated as the 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 forming an ITO transparent electrode film with a thickness of 130 nm on the surface of a glass substrate corning 1737 (manufactured by Corning Inc.) by a sputtering vapor deposition method, T1 = 1.5 μm using each varnish. A pre-baked film was prepared so as to be, and heat-treated in a nitrogen atmosphere at 230 ° C. for 30 minutes using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd.

(Ii) PCT treatment Make 10 rows and 10 columns (100 squares) of grid-shaped cuts in the cure film at 2 mm intervals, and saturate at 121 ° C and 2 atm using the Hust Chamber EHS-211MD (manufactured by Espec Co., Ltd.). A pressure cooker test (PCT) process was performed under the conditions. The PCT processing time at which one or more of 100 squares were peeled off by peeling with cellophane tape (registered trademark) was measured.

(Iii) Evaluation of adhesiveness (base mesh tape test result (peeling time))
The PCT treatment times were compared, and in good order, those without peeling for 100 hours or more were evaluated as ⊚, those without peeling for 50 hours or more were evaluated as ◯, and those peeled in less than 50 hours were evaluated as x.

<Durability evaluation method (luminous efficiency measurement method)>
(I) Fabrication of Organic EL Element After forming an ITO transparent electrode film with a thickness of 130 nm on the surface of a glass substrate corning 1737 (manufactured by Corning Inc.) by a sputtering vapor deposition method, the ITO film is 90 mm long and 90 mm wide. It was patterned into a stripe shape of 80 μm. The striped first electrode had a pitch of 100 μm.

A pre-baked film using each varnish is prepared on a glass substrate on which the ITO is patterned so that T1 = 1.5 μm, and an opening having a width of 70 μm and a length of 250 μm is opened by processing such as exposure development cure. Moreover, an insulating layer having a thickness of about 1 μm made of a resin having a shape covering 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 vapor deposition method using a resistance wire heating method. A hole transport layer was formed by vapor deposition on the entire surface of the effective area of the substrate, and a light emitting layer and aluminum of the second electrode were formed using a shadow mask.

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

(Ii) Durability Evaluation This organic electroluminescent display device was subjected to a durability test in which it was held at 85 ° C. for 250 hours. The light emitting area area after the durability test was defined as 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
The durability evaluation results were evaluated in good order, with 99% or more as ⊚, 90% or more as ◯, 80% or more as Δ, and less than 80% as x.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) 183 g (0.5 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl glycidyl under a dry nitrogen stream. 342 g (3 mol) of ether was dissolved in 1000 g of gamma butyrolactone (GBL) and cooled to −15 ° C. To this, 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 the dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated on a rotary evaporator and poured 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 the dropping, the reaction was carried out at −15 ° C. for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

300 g of the obtained solid was placed in a 3 L stainless autoclave, dispersed in 2.5 L of methyl cell solve, and 20 g of 5% palladium-carbon was added. Hydrogen was introduced into this with a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and the mixture was concentrated on 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 the dropping, the reaction was carried out at −15 ° C. for 4 hours. Then, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

This precipitate was dissolved in GBL2L, 30 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon containing hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not shrink any more at room temperature, and further stirred with the balloon of hydrogen gas attached for 2 hours. After stirring was completed, the palladium compound was removed by filtration, and the solution was concentrated on a rotary evaporator to half the volume. Ethanol was added thereto and recrystallization was carried out to obtain crystals of a hydroxyl group-containing diamine (c) represented by the following formula.

Synthesis Example 4 Synthesis of quinonediazide compound (d) Under a dry nitrogen stream, 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. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not rise above 35 ° C. After the dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (d) represented by the following formula.

Synthesis Example 5 Synthesis of quinonediazide compound (e) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 4-naphthoquinonediazide sulfonyl acid chloride 32. 23 g (0.12 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, the following formula was used in the same manner as in Synthesis Example 4, except that 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was used instead of 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane. The quinonediazide compound (e) represented by is obtained.

Synthesis Example 6 Synthesis of Polyimide Precursor A 50.1 g (0.25 mol) of 4,4'-diaminophenyl ether (DAE), 1,3-bis (3-aminopropyl) tetramethyldisiloxane under a dry nitrogen stream. 12.4 g (0.05 mol) of (SiDA) was dissolved in 500 g of N-methyl-2-pyrrolidone (NMP). 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 the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Then, a solution of 71.4 g (0.6 mol) of N, N-dimethylformamide dimethylacetal diluted with 50 g of NMP was added dropwise over 10 minutes. After the 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 slurry was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydrated was repeated twice. After that, it was dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a polyimide precursor A.

Synthesis Example 7 Synthesis of Polyimide Precursor B 136 g (0.225 mol) of the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 was dissolved in 500 g of NMP under a dry nitrogen stream. 77.6 g (0.25 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic acid anhydride (ODPA) obtained in Synthesis Example 1 was added thereto together with 300 g of pyridine, and the reaction was carried out at 40 ° C. for 2 hours. I let you. Then, 5.8 g (0.05 mol) of 3-ethynylaniline was added as an end-capping agent, and the mixture was further reacted at 40 ° C. for 1 hour. Then, a solution of 73.5 g (0.5 mol) of N, N-dimethylformamide diethyl acetal diluted with 50 g of NMP was added dropwise over 10 minutes. After the 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 slurry was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydrated was repeated twice. Then, it was dried in a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor B.

Synthesis Example 8 Synthesis of Polyimide Precursor C 151 g (0.40 mol) of the hydroxyl group-containing diamine compound (c) and 12.4 g (0.05 mol) of SiDA obtained in Synthesis Example 3 were dissolved in 500 g of NMP under a dry nitrogen stream. I let you. To this, 155 g (0.5 mol) of ODPA was added together with 210 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 1 hour. Then, 9.5 g (0.08 mol) of 4-allylaniline was added as an end-capping agent, and the mixture was further reacted at 50 ° C. for 1 hour. Then, a solution of 132 g (0.9 mol) of N, N-dimethylformamide diethyl acetal diluted with 150 g of NMP was added dropwise over 10 minutes. After the 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 slurry was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydrated was repeated twice. After that, it was dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a polyimide precursor C.

Synthesis Example 9 Synthesis of polybenzoxazole precursor D A dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4'-dicarboxylic acid dichloride (DEDC) with 2 mol of 1-hydroxybenzotriazole under a dry nitrogen stream. 197 g (0.40 mol) and 183 g (0.50 mol) of BAHF were dissolved in 500 g of NMP and stirred at 75 ° C. for 12 hours. Next, 37.6 g (0.20 mol) of 3-allylbenzenedicarboxylic acid anhydride dissolved in 300 g of NMP was added as an end-capping agent, and the mixture was further stirred at 75 ° C. for 12 hours to obtain a polymer 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 slurry was stirred with a mechanical stirrer, filtered under reduced pressure, and dehydrated was repeated twice. After that, it was dried in a vacuum dryer at 80 ° C. for 36 hours to obtain a polybenzoxazole precursor D.

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 are dissolved in 200 g of NMP, 46.7 g (0.15 mol) of ODPA is added, and the mixture is stirred. Then, the reaction was carried out at room temperature for 5 hours. Then, it was heated to 200 degreeC and imidized for 2 hours to obtain a polymerization solution.

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

[Example 1]
A varnish was obtained by dissolving 10 g of polymer A and 2.0 g of the quinonediazide compound (d) obtained in Synthesis Example 4 1 mg of 1 mg MX-280 2.0 g of MX-280 in 60 g of γ-butyl lactone and 40 g of ethyl lactate.

[Examples 2 to 11 and Comparative Examples 1 to 3]
A varnish was obtained in the same manner as in Example 1 except that the polymer, quinonediazide compound, nitrogen-containing compound and cross-linking material were as shown in Table 1. Here, Examples 3, 4 , 5, and 7 shall be read as Reference Examples 1 to 4 .

The structure of the cross-linking agent used 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 (3)

(A) A polymer having at least one of the structures represented by the general formula (1) or (2) and having a weight average molecular weight of 2,000 or more and 100,000 or less , and (b) 1-hydroxybenzotriazole and 1-hydroxy. Containing at least one of -7-azabenzotriazole and (c) quinonediazide compound,
A positive photosensitive resin composition, 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).

(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. However, p + q> 0.)

(In the 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 0, respectively. Indicates an integer of ~ 4. ) The positive photosensitive resin composition according to claim 1, further comprising a (d) thermal cross-linking agent represented by the general formula (9).

(In the formula, R ²³ represents a direct bond or a 1- 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 is 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. H is 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 when the same benzene ring has two R ^23. R ²³ is the same. In the example of the 1- to tetravalent linking group representing R ²³ , R ^{29 to} R ⁵¹ are hydrogen atoms, monovalent organic groups having 1 to 20 carbon atoms, Cl, Br, I. , Or F.) An electronic component using the positive photosensitive resin composition according to claim 1 or 2 .