JP6700020B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention is a positive-type photosensitive resin composition characterized by low outgassing, good sensitivity and resolution, and other properties not different from those of general-purpose ones.

Photosensitive resin compositions are widely used for forming fine structures by radiation lithography in the production of substrates for semiconductors and liquid crystal panels.
Important properties of the photosensitive resin composition in practical use include sensitivity of the formed resist film, developability, resolution, adhesive force with a substrate, residual film rate, and heat resistance.
Conventionally, as a photosensitive resin composition, a novolac resin-based resin composition has been widely used in semiconductor manufacturing and the like (see, for example, Patent Documents 1 and 2), but these novolac resin-based photosensitive resin compositions are used. Since a large amount of outgas is emitted from the resist film after heating and baking, the contamination of the light emitting element and the like becomes a problem.

  The photosensitive resin composition is used not only for semiconductor production but also as a constituent element of a light emitting device. For example, an organic electroluminescent element has high visibility because it self-luminesces, and since it is a completely solid element, it is noted as a light emitting element in a display device because it has characteristics such as excellent impact resistance. It includes a structure such as an insulating film. In the use of forming an insulating film or a fine structure of an organic electroluminescent device, the photosensitive resin film has (1) a cross-sectional shape of a forward taper shape, and (2) less outgas from the resin film after heating and baking. Is required. Further, from the viewpoint of production, (3) high sensitivity and (4) high resolution are also required.

  In order to improve the outgas from the resin film after heating and baking, a photosensitive resin composition (for example, Patent Document 3) in which a novolac resin and a benzoxazine compound, a carbodiimide compound, a triazinethiol compound or a bismaleimide compound are combined is exemplified. There is. However, in that technique, novolac resin having low heat resistance is the main component, and it is not sufficient from the viewpoint of reducing outgas.

  Further, a photosensitive resin composition containing polyimide or polybenzoxazole or a precursor thereof, a novolac resin, a crosslinking agent, or a naphthoquinonediazide compound as a resin having high heat resistance has been proposed (Patent Documents 4 to 6). However, even in these techniques, the outgas reduction is insufficient because the heat resistance is lowered due to the novolac resin.

On the other hand, the sensitivity of a positive photosensitive resin composition can be generally improved by using a low molecular weight novolak resin as a raw material, but with this method, the difference in solubility between exposed and unexposed areas Is reduced, the residual film rate and the resolution are lowered, and the increase in outgas and the decrease in heat resistance due to the low molecular weight components are also observed.
On the other hand, when a novolak resin having a large molecular weight is used, heat resistance and resolution are improved, but sensitivity is lowered. That is, there is a problem that if one tries to improve, the other deteriorates.
Despite various attempts to improve, it is still used as a positive type photosensitive resin composition such as sensitivity, developability, resolution, adhesion to substrate, residual film rate, heat resistance, outgas resistance, etc. No balance of favorable properties has been developed and the demand for this continues.

JP-A-62-260147 JP-A-5-94013 JP, 2009-222923, A JP, 2005-250160, A JP, 2008-268788, A JP-A-2009-198957

  In view of the above situation, the present invention provides a positive photosensitive resin composition that is characterized by low outgassing, and has good sensitivity and resolution, and other characteristics that are the same as those of general-purpose ones. To aim.

As a result of intensive studies, the present inventors have found that a positive photosensitive resin composition containing a polyalkenylphenol resin has good heat resistance, and further has a polyalkenylphenol resin and a compound having at least two epoxy groups in the molecule. The composition containing a quinonediazide compound with a reaction product of benzoic acid with a hydroxybenzoic acid compound can form a pattern with high sensitivity by a photolithography method, and at the same time, after firing the pattern, low outgas can be realized, and good resolution and residual It has been found that it has a film rate and the like and the properties are balanced.
The present invention is a positive photosensitive resin composition containing a polyalkenylphenol resin, an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and a quinonediazide compound.

That is, the present invention includes the following aspects.
[1] (a) Expression (1)

(In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formula (2)

(In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or 6 carbon atoms. Represents an aryl group of to 12. The * in the formula (2) represents a bond with a carbon atom constituting an aromatic ring.)
Represents an alkenyl group, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2). Q is each independently an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, and a divalent organic group having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. )
A polyalkenylphenol resin having a structure of
A positive photosensitive resin composition containing (b) an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and (c) a quinonediazide compound.
[2] In the polyalkenylphenol resin (a), Q in the formula (1) is “—CH ₂ —”, that is, the formula (3).

(In the formula (3), R ¹ , R ² and R ³ are the same as those in the formula (1).)
The positive photosensitive resin composition as described in [1].
[3] The content of the polyalkenylphenol resin (a) is 10 to 35% by mass, the content of the aqueous alkaline solution-soluble resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, and the quinonediazide compound (c). The positive photosensitive resin composition according to [1] or [2], in which the content of (1) is 10 to 40% by mass.
[4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the alkenyl group represented by the formula (2) is an allyl group.
[5] The alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid, and has the formula (10)

The positive photosensitive resin composition according to any one of [1] to [4], which is a compound having the structure of.
[6] The positive photosensitive resin composition according to [5], wherein the compound having at least two epoxy groups in one molecule is a cresol novolac type epoxy resin.
[7] The positive photosensitive resin composition according to [5] or [6], wherein the hydroxybenzoic acids are dihydroxybenzoic acids.
[8] (d) Expression (9)

The positive photosensitive resin composition according to any one of [1] to [7], further containing a copolymer containing a repeating unit represented by:
[9] The content of the polyalkenylphenol resin (a) is 10 to 35% by mass, the content of the aqueous alkaline solution-soluble resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, and the quinonediazide compound (c) is included. The positive photosensitive resin composition according to [8], wherein the content of the copolymer is 10 to 40% by mass, and the content of the copolymer (d) is 5 to 30% by mass.
[10] The positive photosensitive resin composition according to [8] or [9], wherein the copolymer (d) is a copolymer of 4-hydroxyphenyl methacrylate and a maleimide compound.
[11] The positive photosensitive resin composition according to [10], wherein the maleimide compound is at least one selected from the group consisting of N-phenylmaleimide and N-cyclohexylmaleimide.
[12] (1) A coating step of dissolving the positive photosensitive resin composition according to any one of [1] to [11] in a solvent and coating the solution on a substrate.
(2) A drying step of removing the solvent in the applied positive photosensitive resin composition,
(3) An exposure step of irradiating radiation through a photomask,
A method for producing a radiation lithographic structure, comprising (4) a developing step of forming a pattern by alkali development, and (5) a heat treatment step of heating at a temperature of 100 to 350°C.
[13] A method for manufacturing an interlayer insulating film of an organic EL device, including the method according to [12].
[14] A method for manufacturing an organic EL device, including the method according to [12].

  According to the present invention, it is possible to provide a positive photosensitive resin composition that is characterized by low outgassing, has good sensitivity and resolution, and has other characteristics that are the same as those of general-purpose ones.

  The present invention will be described in detail below.

(A) (polyalkenylphenol resin)
The polyalkenylphenol resin is an alkenyl ether of a hydroxyl group of a known phenol resin such as phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin. And a Claisen rearrangement of the alkenyl ether group.
The polyalkenylphenol resin used in the photosensitive resin composition of the present invention has the structure of formula (1). By containing such a resin, it is possible to improve the developing characteristics of the obtained photosensitive resin composition and contribute to the reduction of outgas. In particular, it can be suitably used as a substitute for a phenol novolac resin, a cresol novolac resin, and a polyvinyl phenol resin.

(In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formula (2)

(In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or 6 carbon atoms. Represents an aryl group of to 12. The * in the formula (2) represents a bond with a carbon atom constituting an aromatic ring.)
Represents an alkenyl group represented by, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (2). Q is each independently an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, and a divalent organic group having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. )

R ¹ , R ² and R ^{3 in} formula (1) represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (2), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group. And at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2).
In R ¹ , R ² and R ³ of the formula (1), specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- A butyl group, a t-butyl group, an n-pentyl group and the like can be mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include methoxy group and ethoxy group.

In the alkenyl group represented by the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group and n-pentyl group. You can Examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group and cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group and a naphthyl group. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkenyl group represented by the formula (2) is preferably an allyl group or a methallyl group from the viewpoint of reactivity, more preferably the allyl group. It is most preferable that any one of R ¹ , R ² and R ³ is an allyl group or a methallyl group and the other two are hydrogen atoms.

Q in formula (1) independently represents an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, and an alicyclic condensed ring. It is a divalent organic group or a divalent group in which these are combined. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group and n-pentyl group. be able to. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group. Examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group and cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include phenyl group, methylphenyl group, ethylphenyl group, biphenyl group and naphthyl group. R ⁴ and R ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably both are hydrogen atoms.
Here, specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group and the like. Specific examples of the divalent organic group having an aromatic ring are represented by a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, 4,4-methylenediphenyl group, and a formula (4). Groups and the like.

  Specific examples of the divalent organic group having an alicyclic condensed ring include a dicyclopentadienylene group and the like.

Among the polyalkenylphenol resins used in the photosensitive resin composition of the present invention, as a particularly preferable polyalkenylphenol resin from the viewpoints of alkali developability and outgas, when Q in the formula (1) is —CH ₂ —, that is, Examples thereof include those having a structure represented by formula (3).

(In the formula (3), R ¹ , R ² and R ³ are the same as those in the formula (1).)
Preferred R ^1, R ² and R ³ are the same as the preferred R ^1, R ² and R ³ in the formula (1).

  The phenolic hydroxyl group in the polyalkenylphenol resin is ionized in the presence of the basic compound and can be dissolved in water. Therefore, from the viewpoint of alkali developability, the phenolic hydroxyl group needs to be present in a certain amount or more. Therefore, the structural unit represented by formula (1) or formula (3) is preferably 50 to 100 mol% in the polyalkenylphenol resin, more preferably 70 to 100 mol%, and further preferably It is 85 to 100 mol %. The polyalkenylphenol resin containing the structure of formula (3) is particularly preferably the polyalkenylphenol resin represented by formula (5).

(In formula (5), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (2), an alkoxy group having 1 to 2 carbon atoms. Alternatively, it represents a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2): R ^1′ , R ^2′ and R ^3′ are each independently a hydrogen atom or Represents an alkyl group having 1 to 5 carbon atoms, x and y represent ratios in the polyalkenylphenol resin, x is 0.5 to 1, y is 0 to 0.5, and x+y=1. z is an integer of 1 to 3000.)

  The number average molecular weight of the polyalkenylphenol resin used in the present invention is preferably 500 to 5000, more preferably 800 to 3000. When the number average molecular weight is less than 500, the alkali developability is too fast, so that the difference in dissolution rate between the exposed area and the unexposed area becomes small and the resolution of the pattern decreases, and when it exceeds 5,000, the alkali developability may deteriorate.

(Method for producing polyalkenylphenol resin)
The polyalkenylphenol resin having the structure of formula (1) used in the present invention is alkenyl etherified at the ortho or para position of the original hydroxyl group by the Claisen rearrangement reaction after alkenyl etherification of the hydroxyl group of the starting phenol resin. It is a resin obtained by transposing a group.
As the raw material phenol resin for the polyalkenylphenol resin having the structure of the formula (1), a known phenol resin having the structure of the formula (6) can be used.

(In the formula (6), X ¹ , X ² and X ³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 2 carbon atoms or a hydroxyl group, and are bonded to the hydroxyl group. At least one of the substituents bonded to the carbon atom in the ortho position or the para position with respect to the carbon atom of the benzene ring is a hydrogen atom, and Q is an alkylene represented by the formula —CR ⁴ R ⁵ —. Group, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group obtained by combining these, R ⁴ and R ⁵ Each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

Specific examples of the alkyl group having 1 to 5 carbon atoms in X ¹ , X ² and X ³ of the formula (6) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec- A butyl group, a t-butyl group, an n-pentyl group and the like can be mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include methoxy group and ethoxy group. Also, Q, ^{R 4} and ^{R 5} are the same as Q, ^{R 4} and ^{R 5,} respectively formula (1).
Specific examples of the phenol resin represented by the formula (6) include phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin. From the viewpoint of alkali developability, it is preferable to use a phenol novolac resin or a cresol novolac resin in which Q is an alkylene group represented by —CR ⁴ R ⁵ — and R ⁴ and R ⁵ are hydrogen atoms. You can

(Phenolic resin alkenyl etherification reaction)
The alkenyl etherification reaction of a phenol resin is carried out by (i) a known method of reacting a halogen resin such as allyl chloride, methallyl chloride or allyl bromide with a phenol resin, and (ii) a carboxylic acid alkenyl compound such as allyl acetate. Two known methods of reacting a phenol resin can be exemplified.
For the alkenyl etherification reaction using a halogenated alkenyl compound, for example, the method described in JP-A-2-91113 can be used. Further, as the method for reacting the alkenyl carboxylic acid compound and the phenol resin, for example, the method described in JP2011-26253A can be used. Since the photosensitive resin composition of the present invention is required to have long-term insulation performance, the method (ii) above in which a halogen compound derived from an alkenyl halide compound that may adversely affect long-term insulation performance is not mixed is preferable. ..
The amount of the alkenyl halide compound or alkenyl carboxylate added to the phenolic hydroxyl group is preferably 0.5 to 1.0 equivalent, more preferably 0.65 to 0.9 equivalent. When the addition amount is less than 0.5 equivalent, the amount of outgas generated after heat curing increases.

(Claisen rearrangement reaction of polyalkenyl ether resin)
The target polyalkenylphenol resin can be obtained by performing the Claisen rearrangement reaction of the polyalkenyl ether resin produced by the method described in the above "alkenyl etherification reaction of phenol resin". The Claisen rearrangement reaction can be obtained by heating to a temperature of 100 to 250° C. and reacting for 1 to 20 hours. The Claisen rearrangement reaction may use a solvent having a high boiling point or may be solventless. Further, an inorganic salt such as sodium thiosulfate or sodium carbonate may be added to accelerate the rearrangement reaction. Details are described in JP-A-2-91113.
An example of the reaction formula of phenol novolac resin→alkenyl ether resin→(Claisen rearrangement reaction)→polyalkenylphenol resin is shown in the following reaction formula 1.

(Content of polyalkenylphenol resin)
The content of the polyalkenylphenol resin in the photosensitive resin composition is (a) the polyalkenylphenol resin, (b) the alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and the total solid content of 100 parts by mass. The amount is preferably 10 to 35 parts by mass, more preferably 15 to 30 parts by mass. If it is 10 parts by mass or more, it is effective in reducing outgas at the time of heating, and if it is 35 parts by mass or less, the pattern formability at the time of alkali development becomes good.

(B) (alkali aqueous solution soluble resin having epoxy group and phenolic hydroxyl group)
The positive photosensitive resin composition of the present invention contains an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group.
The alkaline aqueous solution-soluble resin reacts, for example, an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as “epoxy compound”) with a carboxyl group of hydroxybenzoic acids. Can be obtained.
In the positive photosensitive resin composition of the present invention, the alkali-soluble resin having an epoxy group has an advantage that it reacts with a phenolic hydroxyl group during heating and crosslinks to improve chemical resistance, heat resistance, etc. Further, having a phenolic hydroxyl group has an advantage that it becomes soluble in an alkaline aqueous solution.
An example of a reaction in which one of the epoxy groups of the epoxy compound and a carboxyl group of hydroxybenzoic acid react to synthesize a compound having a phenolic hydroxyl group is shown in the following reaction formula 2.

  Examples of the compound having at least two epoxy groups in one molecule include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin. , Heterocyclic epoxy resins, and the like. These epoxy compounds may be used alone or in combination of two or more. Since these compounds are thermosetting, it is a common knowledge of those skilled in the art that they cannot be unambiguously described because of the presence or absence of an epoxy group, the type of functional group, the degree of polymerization and the like. Formula (11) shows an example of the structure of the novolac type epoxy resin.

Examples of the phenol novolac type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation) and jER (registered trademark)-152 (manufactured by Mitsubishi Chemical Corporation).
Examples of the cresol novolac type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) and EOCN (registered trademark)-102S (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), YD-128 (trade name, manufactured by Nippon Steel & Sumitomo Metal Corporation). , JER (registered trademark) 806 (manufactured by Mitsubishi Chemical Co., Ltd.), YDF-170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like.
Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation).
Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation).
Examples of the alicyclic epoxy resin include EHPE (registered trademark) 3150 (manufactured by Daicel Corporation).
Examples of the heterocyclic epoxy resin include TEPIC (registered trademark)-L, TEPIC (registered trademark)-H, TEPIC (registered trademark)-S (manufactured by Nissan Chemical Industries, Ltd.) and the like.

  "Hydroxybenzoic acid" refers to a compound in which at least one of 2- to 6-positions of benzoic acid is substituted with a hydroxyl group, and for example, salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4 -Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy -4-Nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid and the like can be mentioned, but dihydroxybenzoic acids are preferable from the viewpoint of enhancing alkali developability. These hydroxybenzoic acids may be used alone or in combination of two or more.

  The method for obtaining a compound having a phenol group soluble in an alkaline aqueous solution from the above-mentioned epoxy compound and hydroxybenzoic acid is 0.2 to 1.0 equivalent of hydroxybenzoic acid, preferably 0 equivalent to 1 equivalent of epoxy group of the epoxy compound. Use 4 to 0.7 equivalents. When the hydroxybenzoic acid is less than 0.2 equivalent, sufficient alkali solubility is not expressed, and when it is more than 1.0 equivalent, the molecular weight tends to increase due to a side reaction.

  A catalyst may be used to accelerate the reaction. The amount of the catalyst used is 0.1 to 10 mass% with respect to the reaction raw material mixture composed of the epoxy compound and the hydroxybenzoic acid. The reaction temperature is 60 to 150° C., and the reaction time is 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, zirconium octanoate and the like.

  The number average molecular weight of the alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group is preferably in the range of 500 to 8000, and more preferably 1500 to 5000. When the molecular weight is less than 500, it is unsuitable as a resin for a photosensitive material because the alkali solubility is too high, and when the molecular weight is more than 8,000, problems may occur in coatability and developability.

  The content of the alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group in the photosensitive resin composition is (a) a polyalkenylphenol resin, (b) an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and Based on 100 parts by mass of the total solid content, 15 to 60 parts by mass is preferable, and 25 to 45 parts by mass is more preferable. If it is 15 parts by mass or more, it is effective in improving the alkali developability and pattern formability, and if it is 60 parts by mass or less, the heat resistance becomes good.

(D) (Copolymer of 4-hydroxyphenyl methacrylate)
The positive photosensitive resin composition of the present invention has the following formula (9) in order to improve the pattern shape maintaining property upon heating.

It is preferable to further contain a copolymer containing a repeating unit represented by (hereinafter also referred to as a “copolymer of 4-hydroxyphenyl methacrylate”). The 4-hydroxyphenyl methacrylate copolymer is a copolymer of 4-hydroxyphenyl methacrylate and a methacryloyl group and a polymerizable monomer. The methacryloyl group-polymerizable monomer may be any that can react with 4-hydroxyphenyl methacrylate.

  Examples of the monomer capable of polymerizing with the methacryloyl group include acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth). Acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate , Ethylene glycol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, styrene, maleic anhydride, N- Examples thereof include phenylmaleimide, N-hydroxyphenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of improving heat resistance, maleimide compounds are preferable, and N-phenylmaleimide and N-cyclohexylmaleimide are more preferable.

  The 4-hydroxyphenyl methacrylate copolymer can be obtained by carrying out a polymerization reaction of 4-hydroxyphenyl methacrylate and a methacryloyl group-polymerizable monomer in the presence of a reaction initiator.

As the reaction initiator, benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-benzoate, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionic acid)dimethyl and the like can be mentioned. These may be used alone or in combination of two or more.
At this time, in order to adjust the molecular weight of the obtained copolymer, α-methylstyrene dimer, thiol compound, RAFT agent, etc. may be used.

  The number average molecular weight of the 4-hydroxyphenyl methacrylate copolymer is preferably in the range of 5,000 to 30,000, and more preferably in the range of 8,000 to 15,000. When the molecular weight is less than 5,000, the pattern shape may not be maintained during heating, and when the molecular weight is more than 30,000, developability may be a problem.

  The content of the 4-hydroxyphenyl methacrylate copolymer in the photosensitive resin composition is (a) a polyalkenylphenol resin, (b) an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d) 4-. The amount is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, based on 100 parts by mass of the total amount of the hydroxyphenyl methacrylate copolymer and other solids. When it is 5 parts by mass or more, the pattern shape is maintained during heating, and when it is 30 parts by mass or less, heat resistance becomes good.

(C) (quinonediazide compound)
The positive photosensitive resin composition of the present invention contains a quinonediazide compound as a radiation sensitive compound. The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bound with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bound in a sulfonamide bond, and a polyhydroxypolyamino compound in which a sulfonic acid of a quinonediazide is bound to an ester and/or a sulfone. Examples thereof include amide-bonded ones. From the viewpoint of the contrast between the exposed area and the unexposed area, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive-type photosensitive resin composition that is sensitive to general ultraviolet rays i line (365 nm), h line (405 nm), and g line (436 nm) of a mercury lamp. it can.

  Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and 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 names, manufactured by Asahi Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, Examples thereof include, but are not limited to, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

  Specific examples of the quinonediazide compound include 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the above polyhydroxy compound.

  When exposed to ultraviolet light or the like, the quinonediazide compound forms a carboxyl group through the reaction shown in the following reaction formula 3. By the formation of the carboxyl group, the exposed portion (film) can be dissolved in the alkali solution, and the alkali developability is exhibited.

  Although the content of the quinonediazide compound in the photosensitive resin composition varies depending on the quinonediazide compound used, (a) a polyalkenylphenol resin, (b) an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, (d) a quinonediazide Based on 100 parts by mass of the total amount of the compound and other solids, 10 to 40 parts by mass is preferable, and 15 to 30 parts by mass is more preferable. When the amount is 10 parts by mass or more, the alkali developability is good. If the amount is 30 parts by mass or less, the heating reduction rate is unlikely to increase.

(E) (solvent)
The photosensitive resin composition of the present invention is dissolved in a solvent and used in a solution state. For example, polyalkenylphenol resin, an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, if desired, a copolymer of 4-hydroxyphenylmethacrylate, a hydroxypolystyrene resin derivative is dissolved in a solvent, and in this solution, a quinonediazide compound, A photosensitive resin composition in a solution state can be prepared by mixing a thermosetting agent, a surfactant or a coloring agent such as a dye or a pigment at a constant ratio, if necessary.

  Further, in order to improve sensitivity and resolution, phenol novolac resin, cresol novolac resin, polyvinyl phenol resin, carboxylic acid-containing acrylic polymer, phenol group-containing acrylic polymer, carboxylic acid-containing silicone resin, and phenol group within a range that does not impair heat resistance and the like. Alkali-soluble resins such as silicone resin containing, epoxy resin containing phenol group, polybenzoxazole precursor, polyimide precursor, polyimide containing phenol group and the like may be added.

  The commercially available novolak resin generally contains low molecular weight components such as a binuclear compound in which two phenol units are condensed and a trinuclear compound in which three phenol units are condensed. Such low molecular weight components may cause scum or deteriorate the pattern shape. When the novolak contains a large amount of these low molecular weight components, a resin in which the content of the binuclear body and the trinuclear body is reduced by removing it by an appropriate operation may be used.

The following method can be used as the treatment for removing the low molecular weight component from the novolac resin.
(1) Extraction method The novolak resin is finely pulverized, and an organic solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, a mixed solution of an organic solvent such as methanol and ethanol and water, or a constant temperature with water. Stir at to extract low molecular weight components.
(2) Reprecipitation method The novolak resin is dissolved in an organic solvent such as methanol, ethanol, acetone or ethyl cellosolve. Then, a poor solvent such as water, petroleum ether, hexane or the like is dropped into this novolak solution, or a novolak solution is dropped into the poor solvent to precipitate a novolak resin, which is separated and dried.
(3) Separation method A novolak resin is dissolved in a mixed solvent of water, such as methanol, ethanol, acetone, and ethyl cellosolve, which is miscible with water, and ethylcellosolve acetate, propylene glycol monomethyl ether acetate, and other water immiscible organic solvent. , Water is added dropwise to separate the two layers, and the organic layer is separated and concentrated.

  Further, in the positive photosensitive resin composition of the present invention, since it is possible to improve the developing characteristics of the obtained photosensitive resin composition and contribute to the reduction of outgas, the structural unit of formula (7) is added. You may use the resin (henceforth a "hydroxypolystyrene resin derivative") which it has.

(In the formula (7), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m represents 1 to 4, n represents 1 to 4, and m+n is in the range of 2 to 5. R ¹² Represents an atom or one group selected from the group consisting of hydrogen atom, methyl group, ethyl group and propyl group.)
From the viewpoint of alkali developability and outgassing, a copolymer having a structural unit represented by formula (7) and a structural unit represented by formula (8) is preferable.

(In the formula (8), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p represents 1 to 5.)

  The structural unit represented by the formula (7) is, for example, phenolic such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol. Among the aromatic vinyl compounds having a hydroxyl group, a part of a polymer or a copolymer obtained by polymerizing one or more kinds of aromatic vinyl compounds by a known method is reacted with formaldehyde by a known method or further with an alcohol. Obtained by reacting.

  As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and/or m-hydroxystyrene is preferably used.

  As a solvent for dissolving the positive photosensitive resin composition of the present invention, for example, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, glycol ether such as ethylene glycol monoethyl ether, methyl cellosolve acetate, Ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other diethylene glycols, propylene glycol methyl ether acetate, propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and other ketones, 2-hydroxy Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, esters such as γ-butyrolactone, N-methyl-2-pyrrolidone, Examples thereof include amides such as N,N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

  In the positive photosensitive resin composition of the present invention, a heat radical generator can be used as a heat curing agent as an optional component. Examples of preferable heat radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and tert-butyl. Organic peroxides such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide having a 10-hour half-life temperature of 100 to 170° C. Can be mentioned.

  The preferable content of the thermosetting agent is 0.1 to 5 parts by mass, based on 100 parts by mass of the total amount of polyalkenylphenol resin, an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and other solid content. , And more preferably 0.5 to 3 parts by mass.

The positive photosensitive resin composition of the present invention may further contain a surfactant as an optional component, for example, for improving the coating property or for improving the developability of the coating film.
Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether. Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251 and F-281 , F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558 (these are trade names. , DIC Corporation), Surflon (registered trademark) S-242, S-243, S-420, S-611 (above, trade name, manufactured by ACG Seimi Chemical Co., Ltd.) and the like. And organosiloxane polymers KP323, KP326, KP341 (these are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more. Such a surfactant is a polyalkenylphenol resin, an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and 2 parts by mass or less, preferably 1 part by mass, based on 100 parts by mass of the total solid content. It is blended in the following amounts.

Furthermore, the positive photosensitive resin composition of the present invention may contain a coloring material as an optional component. Examples of such a coloring material include dyes, organic pigments, and inorganic pigments, which can be used depending on the purpose.
Specific examples of dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes. Examples thereof include dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

  Examples of the pigment include black pigments such as carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black and titanium black, and C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240, C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. I. Pigment Green 7, C.I. I. Pigment Brown 23, 25, 26 and the like.

(Preparation method)
The positive photosensitive resin composition of the present invention comprises the above-mentioned (a) polyalkenylphenol resin, (b) an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, (c) a quinonediazide compound and, if necessary, other It is prepared by dissolving or dispersing the components in the solvent and mixing them, and depending on the purpose of use, an appropriate solid content concentration can be adopted. For example, the solid content concentration is 10 to 60% by mass. it can. The composition liquid prepared as described above is usually filtered before use. Examples of filtration means include a Millipore filter having a pore size of 0.05 to 1.0 μm.
The positive photosensitive resin composition of the present invention thus prepared is excellent in long-term storage stability.

(Pattern formation/curing method)
When the positive photosensitive resin composition of the present invention is used for radiation lithography, first, a solution of the positive photosensitive resin composition of the present invention in a solvent is applied to a substrate surface, and the solvent is applied by a means such as heating. Can be removed by drying or the like to form a coating film. The method of applying the positive photosensitive resin composition onto the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method, a slit method, and a spin coating method can be adopted.

  After coating the positive photosensitive resin composition of the present invention on the surface of a substrate, the solvent is usually dried by heating (prebaking) to form a coating film. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but are usually 70 to 130° C., and the predetermined time is, for example, 1 to 20 minutes on a hot plate and 3 to 60 minutes in an oven. A membrane can be obtained.

  Next, the prebaked coating film is irradiated with radiation (eg, visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron rays, gamma rays, synchrotron radiation, etc.) through a mask having a predetermined pattern (exposure step), Development is performed with a developing solution, and unnecessary portions are removed to form a predetermined patterned coating film (developing step). The preferred radiation for the positive photosensitive resin composition of the present invention is ultraviolet rays to visible rays having a wavelength of 250 to 450 nm because naphthoquinone diazide sulfonate is preferably used as the positive photosensitive compound. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, diamine -Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Quaternary ammonium salts such as; pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane and other cyclic amines Aqueous solutions of alkalis such as An aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol to the above alkaline aqueous solution, or a surfactant can also be used as a developer. The developing time is usually 30 to 180 seconds, and the developing method may be any of a liquid puddle method, a shower method, a dipping method and the like. After the development, washing with running water is carried out for 30 to 90 seconds to remove unnecessary portions and air-dry with compressed air or compressed nitrogen to form a pattern. After that, a coating film can be obtained by subjecting this pattern to heat treatment for 20 to 200 minutes at a predetermined temperature of, for example, 100 to 350° C. with a heating device such as a hot plate or an oven, but the temperature is raised stepwise. It does not matter (heat treatment step).

  The radiation lithographic structure using the positive photosensitive resin composition of the present invention prepared by the above method is further baked at 350 to 450° C. to remove volatile components, and the temperature at the time of 5% mass reduction The radiation lithographic structure may have a high reflectivity. If the firing temperature is 450° C. or lower, the radiation lithography structure is less likely to be thermally deteriorated. The firing atmosphere may be either in air or in an atmosphere of an inert gas such as nitrogen. The firing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, depending on the firing temperature. If the firing time is less than 5 minutes, the effect may not be seen, and if it exceeds 60 minutes, the productivity may decrease.

The present invention also includes (1) a coating step of dissolving the positive photosensitive resin composition in a solvent and applying the solution to a substrate, and (2) removing the solvent in the positive photosensitive resin composition applied. Radiation lithography including a drying step of (3), an exposure step of irradiating radiation through a photomask, (4) a development step of forming a pattern by alkali development, and (5) a heat treatment step of heating at a temperature of 100 to 350° C. It is a method of manufacturing a structure. By this method, a radiation lithographic structure can be manufactured.
The present invention is also a method for producing an interlayer insulating film of an organic EL element, which includes the above method. That is, the positive photosensitive resin composition of the present invention can be used for producing an interlayer insulating film of an organic EL device.
The present invention is also a method for manufacturing an organic EL device including the above method. That is, the positive photosensitive resin composition of the present invention can be used for producing an organic EL device.

  Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

(1) Resin Synthesis [Production Example 1] Production of polyallylphenol resin In a 1000 mL three-necked flask, 201 g (1.45 mol) of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) was dissolved in 100 g of pure water, phenol. Novolak resin "SHONOL (registered trademark) BRN-5834Y" (manufactured by Showa Denko KK) (100.0 g) and isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) (16 g) were charged, and the reactor was replaced with nitrogen and heated to 85°C. .. Allyl acetate (manufactured by Showa Denko KK) 84 g (0.84 mol), 50% water content 5%-Pd/C-STD type (metal palladium dispersed in activated carbon at a content of 5% by mass, and 0.40 g (palladium: 0.188 mmol) and triphenyl of a catalyst for an allylation reaction in which activated carbon in which the metal palladium is dispersed is blended with water so as to be 50% by mass and stabilized, manufactured by NE Chemcat Corporation. 2.45 g (9.4 mmol) of phosphine (activator of allylation reaction catalyst containing palladium, manufactured by Hokuko Kagaku Kogyo Co., Ltd.) was added, and the temperature was raised to 105° C. and reacted for 4 hours in a nitrogen atmosphere. After that, 14 g (0.14 mol) of allyl acetate was added, and heating was continued for 10 hours while confirming the formation of allyl ether group by ¹ H-NMR. Then, the stirring was stopped and the mixture was allowed to stand to separate into two layers, an organic layer and an aqueous layer. Pure water (200 g) was added until the precipitated salt was dissolved, 200 g of toluene was added, and the mixture was kept at a temperature of 80° C. or higher to confirm that no white precipitate was deposited, and then Pd/C Was recovered by filtration (1 μm membrane filter (pressurized (0.3 MPa) using KST-142-JA manufactured by Advantech). This filter cake was washed with 100 g of toluene and the aqueous layer was separated. Was washed twice with 200 g of water, and the aqueous layer was confirmed to be neutral.The organic layer was separated and concentrated under reduced pressure to obtain a brown oily phenol novolac type polyallyl ether resin.
Subsequently, 125 g of phenol novolac type polyallyl ether resin was placed in a 500 mL flask equipped with a mechanical stirrer and diluted with 130 g of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.). The temperature was raised to 170° C. with stirring at 300 rpm, and the Claisen rearrangement reaction was carried out for 30 hours while confirming the decrease of the allyl ether group by ¹ H-NMR. After the reaction, the solution was returned to room temperature and diluted with γ-butyrolactone to a solid content of 20 mass% to obtain a phenol novolac type polyallylphenol resin solution (resin solution A). The polyallylphenol resin had a hydroxyl group equivalent of 132, a number average molecular weight of 1,100 and a weight average molecular weight of 9,900.
This resin has the formula (5), wherein, among R ¹ , R ² and R ³ , one is an allyl group and the other is a hydrogen atom, R ^1′ , R ^2′ and R ^3′ are hydrogen atoms, and x is 0.85 and y show 0.15.

[Production Example 2] Production of alkaline aqueous solution-soluble resin having epoxy group and phenolic hydroxyl group Propylene glycol monomethyl ether acetate (manufactured by Daicel Co., Ltd.) 60 g as a solvent in a 300 mL three-necked flask, and at least two per molecule. 42 g (0.2 (0.2 equivalent)) of EPICLON (registered trademark) N-695 (cresol novolac type epoxy resin manufactured by DIC Corporation) was charged as a compound having an epoxy group and dissolved at 60° C. under a nitrogen atmosphere. There, 15.5 g (0.10 mol) of 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as hydroxybenzoic acids, and 0.2 g of triphenylphosphine (manufactured by Kitako Chemical Co., Ltd.) as a reaction catalyst. (0.76 mmol) was added and reacted for 12 hours at 110° C. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20 mass %, and the solution was filtered to recover 260 g (resin solution B). The number average molecular weight was 2,400 and the weight average molecular weight was 5,600.

[Production Example 3] Production of 4-hydroxyphenyl methacrylate copolymer 4-hydroxyphenyl methacrylate (Showa Denko KK "PQMA") 12.8 g (0.075 mol), N- in a 100 mL three-necked flask. Phenylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) 6 g (0.035 mol), N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) 6 g (0.034 mol), and 50 g of dimethylformamide as a solvent were added and completely dissolved under a nitrogen atmosphere. It was Next, 0.26 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and S-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid)trithiocarbonate (as a RAFT agent 0.43 g (manufactured by Sigma-Aldrich) was added, and the reaction was carried out for 3 hours by raising the temperature to 85° C. The reaction solution cooled to room temperature was dropped into 3000 g of toluene to precipitate the polymer, and the precipitated polymer was recovered by filtration. Then, 19 g of a milky white powder was recovered by vacuum drying for 3 hours at 60° C. This was dissolved in γ-butyrolactone to obtain a resin liquid having a solid content of 20% by mass (resin liquid C) having a number average molecular weight of 10,000, The weight average molecular weight was 24,000.

[Production Example 4] Production of hydroxypolystyrene resin derivative In a 500 mL eggplant-shaped flask, 10.8 g (0.27 mol) of sodium hydroxide was dissolved in 100 g of pure water. Next, 17.8 g of Maruka Linker H-2P (manufactured by Maruzen Petroleum Co., Ltd.), which is polyvinylphenol, was added and completely dissolved. Subsequently, 92 g of a 36-38% by mass formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at 20 to 25° C. over 2 hours. Then, the mixture was stirred at 20 to 25°C for 24 hours. To this, 13.3 g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of pure water were added dropwise to neutralize and precipitate a solid. The solid was washed with water, filtered, and vacuum dried at 35° C. for 12 hours to recover 27 g of milky white powder. This was dissolved in γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a resin liquid having a solid content of 20 mass% (resin liquid D). The number average molecular weight was 5,600 and the weight average molecular weight was 36,000.
This resin has a structure in which R ¹¹ and R ¹² are hydrogen, m is 1 and n is 1 in the formula (7).

(2) Preparation and Evaluation of Positive Photosensitive Resin Composition Example 1
6.25 parts by mass of the resin solution A and 13.75 parts by mass of the resin solution B obtained in Production Examples 1 and 2 were mixed and dissolved, and TS-200A as a quinonediazide compound (manufactured by Toyo Gosei Co., Ltd., α, α, 1 part by mass of 1,2-naphthoquinonediazide-5-sulfonic acid ester of α-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene was added and further mixed. After visually confirming dissolution, the mixture was filtered through a Millipore filter having a pore size of 0.45 μm to prepare a positive photosensitive resin composition.

Example 2
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin liquid A was 5 parts by mass, the resin liquid B was 12.5 parts by mass, and the resin liquid C obtained in Production Example 3 was 2.5 parts by mass. did.

Example 3
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin liquid A was 5 parts by mass, the resin liquid B was 12.5 parts by mass, and the resin liquid D obtained in Production Example 4 was 2.5 parts by mass. did.

Example 4
A novolak phenol resin BRM-595M (manufactured by Showa Denko KK) from which low molecular weight components were removed by a reprecipitation method was adjusted to a solid content mass of 20% with γ-butyrolactone (resin liquid E).
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin liquid A was changed to 5 parts by mass, the resin liquid B to 10 parts by mass, the resin liquid C to 3.75 parts by mass, and the resin liquid E to 1.25 parts by mass.

Example 5
Positive type photosensitivity as in Example 1 except that the resin liquid A was 5 parts by mass, the resin liquid B was 10 parts by mass, the resin liquid C was 2.5 parts by mass, the resin liquid D was 1.25 parts by mass, and the resin liquid E was 1.25 parts by mass. A resin composition was prepared.

Example 6
Same as Example 1 except that 6.25 parts by mass of resin liquid A, 3.75 parts by mass of resin liquid B, 3.75 parts by mass of resin liquid C, 3.75 parts by mass of resin liquid D, and 2.5 parts by mass of resin liquid E. A positive photosensitive resin composition was prepared.

Example 7
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin liquid A was changed to 5 parts by mass, the resin liquid B to 10 parts by mass, the resin liquid C to 2.5 parts by mass, and the resin liquid D to 2.5 parts by mass.

Comparative Example 1
Positive-type exposure was performed in the same manner as in Example 1 except that a resin liquid F of cresol novolac resin TRR5030G (manufactured by Asahi Organic Materials Co., Ltd.) adjusted to a solid content of 20% with γ-butyrolactone was used instead of the resin liquid A. A resin composition was prepared.

Comparative example 2
The same as Example 1 except that the resin liquid B was not used, and the resin liquid A was 7.5 parts by mass, the resin liquid C was 7.5 parts by mass, the resin liquid D was 3.75 parts by mass, and the resin liquid E was 1.25 parts by mass. A positive photosensitive resin composition was prepared.

Comparative Example 3
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin liquid F was used instead of the resin liquid B.

Comparative Example 4
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 20 parts by mass of the resin liquid F was used.

Comparative Example 5
Resin liquid E 5 parts by mass, resin liquid F 12.5 parts by mass, resin liquid G 2.5 parts by mass of marca linker H-2P (polyparavinylphenol manufactured by Maruzen Petroleum Co., Ltd.) adjusted to a solid content mass of 20% with γ-butyrolactone. A positive type photosensitive resin composition was prepared in the same manner as in Example 1 except that was used.

  With respect to the positive-type photosensitive resin compositions prepared in each example and each comparative example, alkali developability, pattern formability, pattern linearity, shape retention, and outgas were evaluated. The results are shown in Table 1. The evaluation method is as follows.

[Alkali developability, pattern formability, pattern linearity]
Glass substrates (size 100 mm×100 mm×1 mm) were spin-coated with the positive photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 so that the dry film thickness was about 2 μm, and the temperature was 80° C. at 80° C. Second solvent dried. Further, 100 mJ/cm@2 exposure was performed through a quartz photomask with an exposure device (trade name: Multilight ML-251A/B, manufactured by Ushio Inc.) incorporating an ultra-high pressure mercury lamp. The exposure amount was measured using an ultraviolet integrated photometer (trade name: UIT-150, light receiving unit UVD-S365, manufactured by Ushio Inc.). The exposed coating film was subjected to alkali development with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.) to evaluate alkali developability. In observation using an optical microscope (VH-Z250, manufactured by Keyence Corporation), the case where there was no residue after alkali development was evaluated as ◯, and the case where there was residue was evaluated as x.
The pattern formability was evaluated by measuring the line width of the pattern after alkali development. Using an optical microscope (VH-Z250, manufactured by Keyence Corporation), it was performed by confirming the positions where the line widths of the line and space patterns of the photomask were each 10 μm. If the line width of the pattern & line space of the pattern after alkali development is 1:1, it is ○, the line width of the line part is within ±10% is △, and the other is x, the pattern formability is evaluated. I went.
In the evaluation of the linearity of the pattern, the one having a substantially linear pattern was evaluated as ◯, the one having a slightly wavy pattern was evaluated as Δ, and the other patterns were evaluated as x.

[Shape retention]
After forming the pattern in the same manner as above, after placing the glass substrate on a hot plate heated to 150° C. for 30 minutes, the change of the pattern shape and the line width is measured by a stylus type step meter (SURFCOM130A, Tokyo Seimitsu Co., Ltd.). It evaluated using. Those that did not change by heating were evaluated as ◯, those with a rounded pattern shape were evaluated as Δ, and other cases were evaluated as x.

[Outgas]
The positive photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were applied to an aluminum plate by dropping a dropper and dried at 100° C. for 30 minutes to form a coating film having a thickness of 10 to 20 μm. Further, after drying in air at 130° C. for 30 minutes, it was cured under nitrogen at 250° C. for 60 minutes. Using the coating film, using a differential thermogravimetric simultaneous measurement apparatus TG/DTA7000 (manufactured by Hitachi High-Tech Science Co., Ltd.), under a nitrogen atmosphere, the temperature was raised from room temperature at 10° C./minute and heated at 300° C. for 30 minutes. The amount of decrease in heating was measured as outgas. The case where the mass reduction from before the temperature rise was less than 4% was judged as ◯, the case of 4% or more and less than 8% was judged as Δ, and the case of 8% or more was judged as x.

  The photosensitive resin composition of the present invention can be suitably used for positive radiation lithography. In particular, it can be suitably used for forming an insulating film of an organic electroluminescence device or the like.

Claims (13)

(A) Formula (1)

(In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formula (2)

(In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or 6 carbon atoms. Represents an aryl group of to 12. The * in the formula (2) represents a bond with a carbon atom constituting an aromatic ring.)
Represents an alkenyl group, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2). Q is each independently an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, and a divalent organic group having an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents a group or an aryl group having 6 to 12 carbon atoms. )
A polyalkenylphenol resin having a structure of
(B) an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and (c) a quinonediazide compound ,
The (b) the alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid, and has the formula (10)

A positive photosensitive resin composition , which is a compound having the structure of In the polyalkenylphenol resin (a), Q in the formula (1) is “—CH ₂ —”, that is, the formula (3).

(In the formula (3), R ¹ , R ² and R ³ are the same as those in the formula (1).)
The positive photosensitive resin composition according to claim 1, wherein   The content of the polyalkenylphenol resin (a) is 10 to 35% by mass, the content of the alkaline aqueous solution-soluble resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, and the quinonediazide compound (c) is contained. The positive photosensitive resin composition according to claim 1, wherein the ratio is 10 to 40 mass %.   The positive photosensitive resin composition according to claim 1, wherein the alkenyl group represented by the formula (2) is an allyl group. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having at least two epoxy groups in one molecule is a cresol novolac type epoxy resin. The positive photosensitive resin composition according to claim 1, wherein the hydroxybenzoic acids are dihydroxybenzoic acids. (D) Formula (9)

The positive photosensitive resin composition according to any one of claims 1 to 6 containing a copolymer containing in represented by repeating units further. The content of the polyalkenylphenol resin (a) is 10 to 35% by mass, the content of the aqueous alkaline solution resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, the content of the quinonediazide compound (c). Is 10 to 40% by mass, and the content of the copolymer (d) is 5 to 30% by mass, the positive photosensitive resin composition according to claim 7 . The positive photosensitive resin composition according to claim 7 or 8 , wherein the copolymer (d) is a copolymer of 4-hydroxyphenyl methacrylate and a maleimide compound. The positive photosensitive resin composition according to claim 9 , wherein the maleimide compound is at least one selected from the group consisting of N-phenylmaleimide and N-cyclohexylmaleimide. (1) An application step of dissolving the positive photosensitive resin composition according to any one of claims 1 to 10 in a solvent and applying the solution to a substrate.
(2) A drying step of removing the solvent in the applied positive photosensitive resin composition,
(3) An exposure step of irradiating radiation through a photomask,
A method for producing a radiation lithographic structure, comprising (4) a developing step of forming a pattern by alkali development, and (5) a heat treatment step of heating at a temperature of 100 to 350°C. A method for manufacturing an interlayer insulating film of an organic EL device, comprising the method according to claim 11 . A method for manufacturing an organic EL device, comprising the method according to claim 11 .