JP2017078799A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition characterized in low out-gassing property and having good sensitivity and resolution and characteristics equal to those of a general-purpose photosensitive resin composition.SOLUTION: The positive photosensitive resin composition comprises (a) a polyalkenyl phenol resin represented by formula (1), (b) an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and (c) a quinonediazide compound. In the formula (1), R, Rand Rrepresent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the like.SELECTED DRAWING: None

Description

  The present invention is a positive photosensitive resin composition characterized by low outgas, having good sensitivity and resolution, and other characteristics that are not different from general-purpose ones.

Photosensitive resin compositions are widely used for forming fine structures by radiation lithography in the production of semiconductors, liquid crystal panel substrates, and the like.
Important characteristics of the photosensitive resin composition in practical use include sensitivity of the formed resist film, developability, resolution, adhesion to the substrate, remaining film ratio, and heat resistance.
Conventionally, as a photosensitive resin composition, a novolak resin-based resin composition has been widely used in semiconductor manufacturing or the like (see, for example, Patent Documents 1 and 2), but these novolak resin-based photosensitive resin compositions. The product has a large amount of outgas from the resist film after heating and baking, and contamination of the light emitting element or the like becomes a problem.

  The photosensitive resin composition is used not only for semiconductor production but also as a component of a light emitting device. For example, the organic electroluminescent element is highly visible due to self-emission and is a complete solid element, and therefore has features such as excellent impact resistance. It includes structures such as insulating films. In the organic electroluminescent device insulating film and fine structure forming applications, the photosensitive resin film has (1) a cross-sectional shape of a forward taper, and (2) a small amount of outgas from the resin film after heating and baking. Is required. From the viewpoint of production, (3) high sensitivity and (4) high resolution are also required.

  In order to improve outgas from the resin film after heating and baking, a photosensitive resin composition (for example, Patent Document 3) in which a novolak resin and a benzoxazine compound, a carbodiimide compound, a triazine thiol compound, or a bismaleimide compound are combined is exemplified. Yes. However, this technology is mainly composed of novolak resin having low heat resistance, and is not sufficient in terms of reducing outgas.

  In addition, photosensitive resin compositions containing polyimide, polybenzoxazole, or a precursor thereof, a novolak resin, a crosslinking agent, and a naphthoquinonediazide compound have been proposed as resins having high heat resistance (Patent Documents 4 to 6). However, even in these techniques, the outgas reduction is insufficient due to the decrease in heat resistance caused by the novolac resin.

On the other hand, improvement of the sensitivity of the positive photosensitive resin composition can generally be achieved by using a low molecular weight novolak resin as a raw material, but this method uses a difference in solubility between the exposed and unexposed areas. , Resulting in a decrease in the remaining film rate and resolution, and an increase in outgas and a decrease in heat resistance due to low molecular weight components.
On the other hand, if a novolak resin having a large molecular weight is used, the heat resistance and resolution are improved, but the sensitivity is lowered. That is, there is a problem that when one is improved, the other is deteriorated.
Although various improvements have been attempted so far, it is still a positive photosensitive resin composition such as sensitivity, developability, resolution, adhesion to the substrate, residual film ratio, heat resistance, outgas resistance, etc. A balance of favorable properties has not been developed and the demand for this continues.

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

  In view of the above-mentioned present situation, the present invention provides a positive photosensitive resin composition characterized by low outgas, having good sensitivity and resolution, and having other characteristics that are not different from general-purpose ones. Objective.

As a result of intensive studies, the inventors of the present invention have good heat resistance of a positive photosensitive resin composition containing a polyalkenylphenol resin, and a polyalkenylphenol resin, a compound having at least two epoxy groups in the molecule. A composition comprising a reaction product of benzoic acid with hydroxybenzoic acid and a quinonediazide compound can form a pattern by a photolithography method with high sensitivity. At the same time, after firing the pattern, low outgas can be realized, and a good resolution and residual can be achieved. It has been found that the film has a film ratio and the like, and the characteristics are balanced.
The present invention is a positive photosensitive resin composition containing a polyalkenylphenol resin, an aqueous alkali 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) Formula (1)

(In Formula (1), R < ¹ >, R < ² > and R < ³ > are respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (2)

(In 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 ˜12. * In formula (2) represents a bond with a carbon atom constituting an aromatic ring.)
And 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, or a divalent organic group having an alicyclic condensed ring. R ⁴ or R ⁵ is 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 the structure:
(B) A positive photosensitive resin composition containing an aqueous alkali-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 formula (3), R ¹ , R ² and R ³ are the same as in formula (1).)
The positive photosensitive resin composition according to [1].
[3] 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 a positive photosensitive resin composition according to [1] or [2], wherein the content 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 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 and hydroxybenzoic acids, which has the formula (10)

The positive photosensitive resin composition according to any one of [1] to [4], which is a compound having the structure:
[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 acid is a dihydroxybenzoic acid.
[8] (d) Formula (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 alkali-soluble resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, the quinonediazide compound (c) The positive photosensitive resin composition according to [8], wherein the content of 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 process in which the positive photosensitive resin composition according to any one of [1] to [11] is dissolved in a solvent and applied to a substrate.
(2) a drying step for removing the solvent in the applied positive photosensitive resin composition;
(3) an exposure step of irradiating radiation through a photomask;
(4) A method for producing a radiation lithographic structure comprising 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.
[13] A method for producing an interlayer insulating film of an organic EL element, comprising the method according to [12].
[14] A method for producing an organic EL device comprising the method according to [12].

  According to the present invention, it is possible to provide a positive photosensitive resin composition characterized by low outgas, having good sensitivity and resolution, and having other characteristics that are not different from general-purpose ones.

  The present invention is described in detail below.

(A) (Polyalkenylphenol resin)
Polyalkenyl phenol resins are phenol novolak resins, cresol novolac resins, triphenylmethane type phenol resins, phenol aralkyl resins, biphenyl aralkyl phenol resins, phenol-dicyclopentadiene copolymer resins, and the like. And further obtained by a Claisen rearrangement of an alkenyl ether group.
The polyalkenyl phenol resin used in the photosensitive resin composition of the present invention has a structure represented by the formula (1). By containing such a resin, it is possible to improve the development characteristics of the resulting photosensitive resin composition and to contribute to the reduction of outgas. In particular, it can be suitably used as an alternative to phenol novolac resins, cresol novolac resins, and polyvinyl phenol resins.

(In Formula (1), R < ¹ >, R < ² > and R < ³ > are respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (2)

(In 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 ˜12. * In formula (2) represents a bond with a carbon atom constituting an aromatic ring.)
Represents an alkenyl group represented by formula (1), 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, or a divalent organic group having an alicyclic condensed ring. R ⁴ or R ⁵ is 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 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, etc. can be mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an 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. Can do. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a 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. Preferable alkenyl groups represented by formula (2) include an allyl group and a methallyl group from the viewpoint of reactivity, and more preferably an allyl group. Most preferably, 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. And a divalent organic group having a combination thereof. 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 a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a 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 ⁴ and R ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom.
Here, specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4-methylenediphenyl group, and a formula (4). And the like.

  Specific examples of the divalent organic group having an alicyclic fused ring include a dicyclopentadienylene group.

Among the polyalkenylphenol resins used in the photosensitive resin composition of the present invention, as a particularly preferred polyalkenylphenol resin from the viewpoint of alkali developability and outgas, when Q in formula (1) is —CH ₂ —, What has a structure represented by Formula (3) is mentioned.

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

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

(In Formula (5), R < ¹ >, R < ² > and R < ³ > are respectively independently a hydrogen atom, a C1-C5 alkyl group, an alkenyl group represented by Formula (2), and a C1-C2 alkoxy group. Or a hydroxyl group and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by 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.)

  Moreover, the number average molecular weight of the polyalkenyl phenol resin used by this invention becomes like this. Preferably it is 500-5000, More preferably, it is 800-3000. If 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 and unexposed areas becomes small, the pattern resolution decreases, and if it exceeds 5000, the alkali developability may deteriorate.

(Production method of polyalkenylphenol resin)
The polyalkenyl phenol resin having the structure of the formula (1) used in the present invention is obtained by alkenyl etherifying a hydroxyl group of a phenol resin used as a raw material, and then alkenyl at the ortho or para position of the original hydroxyl group by a Claisen rearrangement reaction. It is a resin obtained by rearranging groups.
As the raw material phenol resin of the polyalkenyl phenol resin having the structure of the formula (1), a known phenol resin having the structure of the formula (6) can be used.

(In 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 bonded to the hydroxyl group. At least one of the substituents bonded to the carbon atom in the ortho or para position with respect to the carbon atom of the benzene ring is a hydrogen atom, and Q is independently an alkylene represented by the formula —CR ⁴ R ⁵ —. R ⁴ and R ⁵ are a 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 combination thereof. Each independently represents 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.)

In X ¹ , X ² and X ³ of formula (6), 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, etc. can be mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an 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 a phenol novolak resin, a cresol novolak resin, a triphenylmethane type phenol resin, a phenol aralkyl resin, a biphenyl aralkyl phenol resin, a phenol-dicyclopentadiene copolymer resin, and the like. From the viewpoint of alkali developability, a phenol novolak resin or a cresol novolak resin in which Q is an alkylene group represented by -CR ⁴ R ^5- and R ⁴ and R ⁵ are hydrogen atoms is preferably used. Can do.

(Alkenyl etherification reaction of phenol resin)
The alkenyl etherification reaction of a phenol resin includes (i) a known method of reacting a phenol resin with a halogenated alkenyl compound such as allyl chloride, methallyl chloride, allyl bromide, and (ii) a carboxylic acid alkenyl compound such as allyl acetate Two methods of publicly 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. Moreover, the method as described in Unexamined-Japanese-Patent No. 2011-26253 can be used for the method of making a carboxylic acid alkenyl compound and a phenol resin react, for example. 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 a halogenated alkenyl compound that may adversely affect long-term insulation performance is not mixed is preferable. .
The addition amount of the alkenyl halide compound or alkenyl carboxylate to the phenolic hydroxyl group is preferably 0.5 to 1.0 equivalent, more preferably 0.65 to 0.9 equivalent. If the addition amount is less than 0.5 equivalent, the outgas generation amount after heat curing increases.

(Claisen rearrangement reaction of polyalkenyl ether resin)
The target polyalkenyl phenol resin can be obtained by performing a Claisen rearrangement reaction on the polyalkenyl ether resin produced by the method described in the above-mentioned “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 high-boiling solvent or may be solvent-free. In order to accelerate the rearrangement reaction, an inorganic salt such as sodium thiosulfate or sodium carbonate may be added. Details are described in JP-A-2-91113.
An example of a reaction formula of phenol novolac resin → alkenyl ether resin → (Claisen rearrangement reaction) → polyalkenyl phenol resin is shown in the following reaction formula 1.

(Polyalkenylphenol resin content)
The content of the polyalkenylphenol resin in the photosensitive resin composition is (a) a polyalkenylphenol resin, (b) an aqueous alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and a total amount of other solids of 100 parts by mass. 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 for reducing the outgas during heating, and if it is 35 parts by mass or less, the pattern formability during alkali development is good.

(B) (Alkaline 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 acid. Can be obtained.
In the positive photosensitive resin composition of the present invention, since the alkali-soluble resin has an epoxy group, there is an advantage that chemical resistance, heat resistance, etc. are improved by reacting with a phenolic hydroxyl group during heating and crosslinking. Moreover, there exists an advantage that it becomes soluble in alkaline aqueous solution by having a phenolic hydroxyl group.
The following reaction formula 2 shows an example of a reaction in which one of the epoxy groups of the epoxy compound reacts with a carboxyl group of hydroxybenzoic acid to synthesize a compound having a phenolic hydroxyl group.

  Examples of the compound having at least two epoxy groups in one molecule include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, biphenol type epoxy resins, naphthalene skeleton-containing epoxy resins, and alicyclic epoxy resins. And heterocyclic epoxy resins. These epoxy compounds can be used alone or in combination of two or more. In addition, since these compounds are a thermosetting type, it cannot be uniquely described from the difference in the presence or absence of an epoxy group, the kind of functional group, a polymerization degree, etc. as common knowledge of those skilled in the art. An example of the structure of the novolac type epoxy resin is shown in Formula (11).

Examples of the phenol novolac type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation), jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the cresol novolac type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation), EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Co., Ltd.), and the like.
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), and YD-128 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). Bisphenol F type epoxy resin such as JER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation), 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, jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by DIC Corporation), and the like.
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, and TEPIC (registered trademark) -S (manufactured by Nissan Chemical Industries, Ltd.).

  “Hydroxybenzoic acid” refers to a compound in which at least one of positions 2 to 6 of benzoic acid is substituted with a hydroxyl group. 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 Examples include -4-nitrobenzoic acid and 4-hydroxy-3-nitrobenzoic acid, and dihydroxybenzoic acids are preferable in terms of enhancing alkali developability. These hydroxybenzoic acids can 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 epoxy compound and hydroxybenzoic acid is 0.2 to 1.0 equivalent, preferably 0, of hydroxybenzoic acid with respect to 1 equivalent of epoxy group of the epoxy compound. .4 to 0.7 equivalents are used. When the amount of hydroxybenzoic acid is less than 0.2 equivalent, sufficient alkali solubility is not exhibited, and when it is more than 1.0 equivalent, the molecular weight tends to increase due to side reactions.

  A catalyst may be used to accelerate the reaction. The usage-amount of a catalyst is 0.1-10 mass% with respect to the reaction raw material mixture which consists of an epoxy compound and 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 octoate, and zirconium octoate.

  The number average molecular weight of the aqueous alkali-soluble resin having an epoxy group and a phenolic hydroxyl group is preferably in the range of 500 to 8000, and more preferably in the range of 1500 to 5000. When the molecular weight is smaller than 500, the alkali solubility is too high, which is not suitable as a resin for the photosensitive material. When the molecular weight is larger than 8000, there may be a problem in applicability and developability.

  The content of the aqueous alkali-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, 15-60 mass parts is preferable on the basis of 100 mass parts of total amount of solid content, More preferably, it is 25-45 mass parts. If it is 15 parts by mass or more, it is effective to improve alkali developability and pattern formability, and if it is 60 parts by mass or less, the heat resistance is good.

(D) (Copolymer of 4-hydroxyphenyl methacrylate)
Since the positive photosensitive resin composition of the present invention improves the pattern shape maintaining characteristic during heating, the formula (9)

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

  Monomers that can be polymerized with the methacryloyl group include acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and 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) Examples include acrylate, glycidyl (meth) acrylate, styrene, maleic anhydride, N-phenylmaleimide, N-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, and maleimide compounds are preferable from the viewpoint of improving heat resistance. 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 monomer polymerizable with a methacryloyl group 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. These may be used individually by 1 type and may be used in combination of 2 or more type.
At this time, α-methylstyrene dimer, thiol compound, RAFT agent and the like may be used to adjust the molecular weight of the obtained copolymer.

  The number average molecular weight of the 4-hydroxyphenyl methacrylate copolymer is preferably in the range of 5000 to 30000, and more preferably in the range of 8000 to 15000. If the molecular weight is less than 5000, the pattern shape may not be maintained during heating, and if the molecular weight is greater than 30000, there may be a problem in developability.

  The content of the 4-hydroxyphenyl methacrylate copolymer in the photosensitive resin composition is (a) a polyalkenylphenol resin, (b) an aqueous alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d) 4- 5-30 mass parts is preferable on the basis of 100 mass parts of the total amount of the copolymer of hydroxyphenyl methacrylate and other solids, and more preferably 10-20 mass parts. If it is 5 parts by mass or more, it is effective for maintaining the pattern shape during heating, and if it is 30 parts by mass or less, the heat resistance is 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 bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone. Examples 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 compound and polyamino compound are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, 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 , Bisphenol E, methylene bisphenol, BisP-AP (quotient Name, but include the Honshu Chemical Industry Co., Ltd.), and the like, but is not limited to these.

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

  When exposed to ultraviolet light or the like, the quinonediazide compound generates a carboxyl group through the reaction shown in the following reaction formula 3. Generation | occurrence | production of a carboxyl group enables it to melt | dissolve the exposed part (film | membrane) with respect to an alkaline solution, and alkali developability expresses.

  The content of the quinonediazide compound in the photosensitive resin composition varies depending on the quinonediazide compound used, but (a) a polyalkenylphenol resin, (b) an alkaline aqueous resin having an epoxy group and a phenolic hydroxyl group, (d) a quinonediazide. 10-40 mass parts is preferable on the basis of 100 mass parts of total amount of a compound and other solid content, More preferably, it is 15-30 mass parts. Alkali developability is favorable in it being 10 mass parts or more. In addition, when the amount is 30 parts by mass or less, the rate of decrease in heating is difficult 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, a polyalkenylphenol resin, an aqueous alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and optionally, a copolymer of 4-hydroxyphenyl methacrylate and a hydroxypolystyrene resin derivative are dissolved in a solvent. If necessary, a photosensitive resin composition in a solution state can be prepared by mixing a thermosetting agent, a surfactant, or a colorant such as a dye or pigment at a certain ratio.

  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, phenol group are used as long as heat resistance is not impaired. An alkali-soluble resin such as a containing silicone resin, a phenol group-containing epoxy resin, a polybenzoxazole precursor, a polyimide precursor, a phenol group-containing polyimide may be added.

  Here, a commercially available novolak resin generally contains low molecular weight components such as a binuclear product in which two phenol units are condensed and a trinuclear product 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 which is removed by an appropriate operation to reduce the content of the dinuclear body or trinuclear body may be used.

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

  In addition, the positive photosensitive resin composition of the present invention can improve the development characteristics of the resulting photosensitive resin composition and contribute to the reduction of outgas. It is also possible to use a resin (hereinafter also referred to as “hydroxypolystyrene resin derivative”).

(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 a hydrogen atom, a methyl group, an ethyl group and a 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 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 aromatic vinyl compounds having a hydroxyl group, a polymer or a copolymer obtained by polymerizing a single compound or two or more types by a known method may be reacted with formaldehyde by a known method, It is obtained by reacting.

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

  Examples of the solvent for dissolving the positive photosensitive resin composition of the present invention include, for example, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether, methyl cellosolve acetate, Ethylene glycol alkyl ether acetates 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 glycols such as diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene Propylene glycol alkyl ether acetates such as recall ethyl ether acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and cyclohexanone, Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3-methoxy Such as methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc. Examples of the esters include amides such as N-methyl-2-pyrrolidone, 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 thermal radical generator can be used as a thermosetting agent as an optional component. Preferable thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl. Organic peroxides such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. having a 10-hour half-life temperature of 100 to 170 ° C. Can be mentioned.

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

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

Furthermore, the positive photosensitive resin composition of the present invention can contain a colorant as an optional component. Examples of such a colorant include dyes, organic pigments, and inorganic pigments, and they can be used according to 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 And dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

  Examples of pigments 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. And CI pigment brown 23, 25, 26.

(Preparation method)
The positive photosensitive resin composition of the present invention comprises (a) a polyalkenylphenol resin, (b) an alkaline aqueous solution resin having an epoxy group and a phenolic hydroxyl group, (c) a quinonediazide compound and other components as required. It is prepared by dissolving or dispersing the components in the above solvent and mixing, and depending on the intended use, an appropriate solid content concentration can be adopted. For example, the solid content concentration may be 10 to 60% by mass. it can. Moreover, the composition liquid prepared as mentioned above is usually filtered before use. Examples of the filtering means include a Millipore filter having a pore diameter of 0.05 to 1.0 μm.
The positive photosensitive resin composition of the present invention thus prepared is also 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 obtained by dissolving the positive photosensitive resin composition of the present invention in a solvent is applied to the substrate surface, and the solvent is removed by means such as heating. Can be removed by drying or the like to form a coating film. The method for applying the positive photosensitive resin composition to the substrate surface 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 employed.

  After applying the positive photosensitive resin composition of the present invention to the substrate surface, the solvent is usually dried by heating (pre-baking) to form a coating film. Although the heating conditions vary depending on the type of each component, the blending ratio, etc., it is 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 pre-baked coating film is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a mask having a predetermined pattern (exposure process), It develops with a developing solution, an unnecessary part is removed, and a predetermined pattern-like coating film is formed (development process). The preferable radiation for the positive photosensitive resin composition of the present invention is ultraviolet to visible light having a wavelength of 250 to 450 nm because naphthoquinone diazide sulfonic acid ester 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; 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, cyclic amines such as 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane Using an aqueous solution of an alkali such as Kill. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant to the alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds, and the development method may be any of a liquid filling method, a shower method, a dipping method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, unnecessary portions are removed, and the pattern is formed by air drying with compressed air or compressed nitrogen. Thereafter, the coating film can be obtained by heating the pattern at a predetermined temperature of, for example, 100 to 350 ° C. with a heating device such as a hot plate or oven, for 20 to 200 minutes. It does not matter (heat treatment step).

  The radiation lithography structure using the positive photosensitive resin composition of the present invention produced by the above method is further baked under conditions of 350 to 450 ° C. to remove volatile components, and the temperature when the mass decreases by 5%. High radiation lithography structures may be used. When the firing temperature is 450 ° C. or lower, the radiation lithography structure is not easily thermally deteriorated. The firing atmosphere may be either air or an inert gas atmosphere such as nitrogen. The firing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, although it depends 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 process in which the positive photosensitive resin composition is dissolved in a solvent and applied to a substrate, and (2) the solvent in the applied positive photosensitive resin composition is removed. Radiation lithography including: (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 manufacturing method of a structure. By this method, a radiation lithographic structure can be produced.
The present invention is also a method for producing an interlayer insulating film of an organic EL element including 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 producing an organic EL device including the method. That is, the positive photosensitive resin composition of the present invention can be used for producing an organic EL device.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example.

(1) Resin synthesis [Production Example 1] Production of polyallylphenol resin A solution in which 201 g (1.45 mol) of potassium carbonate (made by Nippon Soda Co., Ltd.) was dissolved in 100 g of pure water in a 1000 mL three-necked flask, phenol 100.0 g of novolak resin “Shonol (registered trademark) BRN-5835Y” (manufactured by Showa Denko KK) and 16 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and the reactor was purged with nitrogen and heated to 85 ° C. . Under a nitrogen stream, allyl acetate (made by Showa Denko KK) 84 g (0.84 mol), 50% water content 5% -Pd / C-STD type (metal palladium is dispersed in activated carbon at a content of 5% by mass, and 0.40 g (palladium: 0.188 mmol) of triallylation reaction catalyst, manufactured by NP Chemcat Co., Ltd., which is stabilized by blending water so that the activated carbon in which the metallic palladium is dispersed is 50% by mass, and triphenyl 2.45 g (9.4 mmol) of phosphine (activator of the above-mentioned palladium-containing allylation reaction catalyst, manufactured by Hokuko Chemical Co., Ltd.) was added, and the temperature was raised to 105 ° C. in a nitrogen atmosphere and reacted for 4 hours. Thereafter, 14 g (0.14 mol) of allyl acetate was added, and heating was continued for 10 hours while confirming the formation of allyl ether groups by ¹ H-NMR. Thereafter, the stirring was stopped, and the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After adding pure water (200 g) until the precipitated salt is dissolved, 200 g of toluene is added, and the temperature is kept at 80 ° C. or higher, and it is confirmed that no white precipitate is deposited. Then, Pd / C Was recovered by filtration (pressure (0.3 MPa) using a 1 μm membrane filter (KST-142-JA manufactured by Advantech Co., Ltd.). The filter cake was washed with 100 g of toluene and the aqueous layer was separated. 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.). While stirring at 300 rpm, the temperature was raised to 170 ° C., and the Claisen rearrangement reaction was carried out for 30 hours while confirming the reduction of allyl ether groups 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% by 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 1100, and a weight average molecular weight of 9,900.
In this formula (5), one of R ¹ , R ² and R ³ is an allyl group, the other is a hydrogen atom, R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are hydrogen atoms, and x is 0.85 and y is 0.15.

[Production Example 2] Production of alkaline aqueous solution-soluble resin having epoxy group and phenolic hydroxyl group 60 g of propylene glycol monomethyl ether acetate (manufactured by Daicel Co., Ltd.) as a solvent in a 300 mL three-necked flask, at least two in one molecule As a compound having an epoxy group, 42 g (0.2 (0.2 equivalent)) of EPICLON (registered trademark) N-695 (a cresol novolak epoxy resin manufactured by DIC Corporation) was charged and dissolved at 60 ° C. in a nitrogen atmosphere. 15.5 g (0.10 mol) of 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as the hydroxybenzoic acid and 0.2 g of triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.) as the reaction catalyst. (0.76 mmol) was added and reacted at 110 ° C. for 12 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to recover 260 g (resin liquid B), having a number average molecular weight of 2400 and a weight average molecular weight of 5,600.

[Production Example 3] Production of 4-hydroxyphenyl methacrylate copolymer In a 100 mL three-necked flask, 12.8 g (0.075 mol) of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko KK), N- 6 g (0.035 mol) of phenylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), 6 g (0.034 mol) of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and 50 g of dimethylformamide as a solvent are completely dissolved in 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 (RAFT agent) 0.43 g (manufactured by Sigma-Aldrich) was added, and the mixture was heated to 85 ° C. and reacted for 3 hours, and the reaction solution cooled to room temperature was dropped into 3000 g of toluene to precipitate a polymer. Then, 19 g of milky white powder was recovered by vacuum drying 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). The weight average molecular weight was 24,000.

[Production Example 4] Production of hydroxypolystyrene resin derivative 10.8 g (0.27 mol) of sodium hydroxide was dissolved in 100 g of pure water in a 500 mL eggplant-shaped flask. Next, 17.8 g of Marcalinker H-2P (manufactured by Maruzen Petroleum Co., Ltd.) which is polyvinyl phenol was added and completely dissolved. Then, 92 g of 36-38 mass% formaldehyde aqueous solution (made by Wako Pure Chemical Industries Ltd.) was dripped at 20-25 degreeC over 2 hours. Then, it stirred at 20-25 degreeC 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 and neutralized to 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% by mass (resin liquid D). The number average molecular weight was 5600, and the weight average molecular weight was 36000.
This resin has a structure in which R ¹¹ and R ¹² are hydrogen, m is 1, and n is 1 in Formula (7).

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

Example 2
The 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 12.5 parts by mass, and the resin liquid C 2.5 obtained by Production Example 3. did.

Example 3
The 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 12.5 parts by mass, and the resin liquid D 2.5 obtained in Production Example 4 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, resin liquid B 10 parts by mass, resin liquid C 3.75 parts by mass, and resin liquid E 1.25 parts by mass.

Example 5
Positive photosensitivity 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 10 parts by mass, the resin liquid C 2.5 parts by mass, the resin liquid D 1.25 parts by mass, and the resin liquid E 1.25 parts by mass. A resin composition was prepared.

Example 6
Except for changing to 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, the same as in Example 1. 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 10 parts by mass, the resin liquid C 2.5 parts by mass, and the resin liquid D 2.5 parts by mass.

Comparative Example 1
In place of Resin Liquid A, positive type photosensitivity was obtained in the same manner as in Example 1 except that Resin Liquid F of cresol novolac resin TRR5030G (manufactured by Asahi Organic Materials Co., Ltd.) adjusted to 20% solid content with γ-butyrolactone was used. A functional resin composition was prepared.

Comparative Example 2
Example 1 was used except that the resin liquid B was not used and 7.5 parts by mass of the resin liquid A, 7.5 parts by mass of the resin liquid C, 3.75 parts by mass of the resin liquid D, and 1.25 parts by mass of the resin liquid E were used. 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 E5 parts by mass, resin liquid F12.5 parts by mass, resin liquid G2.5 parts by weight of Marcalinker H-2P (polyparavinylphenol manufactured by Maruzen Petroleum Corporation) adjusted to 20% solid content with γ-butyrolactone A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that was used.

  About the positive photosensitive resin composition prepared in each Example and each comparative example, alkali developability, pattern formation property, pattern linearity, shape maintenance property, and outgas were evaluated. The results are shown in Table 1. The evaluation method is as follows.

[Alkali developability, pattern formability, pattern linearity]
The positive photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were spin-coated on a glass substrate (size 100 mm × 100 mm × 1 mm) so that the dry film thickness was about 2 μm, and 80 ° C. at 80 ° C. Second solvent was dried. Further, exposure was performed at 100 mJ / cm 2 through a quartz photomask using an exposure apparatus (trade name: Multilight ML-251A / B, manufactured by USHIO INC.) Incorporating an ultrahigh pressure mercury lamp. The exposure amount was measured using an ultraviolet integrated light meter (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.), and evaluated for alkali developability. In the observation using an optical microscope (VH-Z250, manufactured by Keyence Corporation), the case where there was no residue after alkali development was judged as ◯, and the case where there was a residue was judged as x.
The pattern forming property was evaluated by measuring the line width of the pattern after alkali development. Using an optical microscope (VH-Z250, manufactured by Keyence Co., Ltd.), this was performed by confirming the locations where the line width of the photomask line & space pattern was 10 μm. Evaluation of pattern formability when the line width of the line and space pattern after alkali development is 1: 1, △ when the line width is within ± 10%, and x otherwise. Went.
In the evaluation of the linearity of the pattern, the case where the pattern is almost linear is indicated by ◯, the case where the pattern is slightly waved is indicated by △, and the other cases are indicated by ×.

[Shape maintenance]
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, change the pattern shape and the line width with a stylus type step gauge (SURFCOM130A, Tokyo Seimitsu Co., Ltd.) Evaluated. The case where neither changed by heating was evaluated as ◯, the case where the pattern shape was rounded was determined as Δ, and the other cases were determined as ×.

[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 obtain a coating film having a thickness of 10 to 20 μm. Furthermore, after drying at 130 ° C. for 30 minutes in the air, curing was performed at 250 ° C. for 60 minutes under nitrogen. Using the coating film, using a differential thermogravimetric simultaneous measurement device TG / DTA7000 (manufactured by Hitachi High-Tech Science Co., Ltd.), in a nitrogen atmosphere, the temperature was increased from room temperature to 10 ° C / min and heated at 300 ° C for 30 minutes. The amount of heating reduction was measured as outgas. The case where the mass decrease from before the temperature increase was less than 4% was evaluated as ◯, 4% or more and less than 8% was evaluated as △, and 8% or more was determined as ×.

  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 such as an organic electroluminescent element.

Claims (14)

(A) Formula (1)

(In Formula (1), R < ¹ >, R < ² > and R < ³ > are respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (2)

(In 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 ˜12. * In formula (2) represents a bond with a carbon atom constituting an aromatic ring.)
And 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, or a divalent organic group having an alicyclic condensed ring. R ⁴ or R ⁵ is 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 the structure:
(B) A positive photosensitive resin composition containing an aqueous alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and (c) a quinonediazide compound. In the polyalkenylphenol resin (a), Q in the formula (1) is “—CH ₂ —”, that is, the formula (3)

(In formula (3), R ¹ , R ² and R ³ are the same as in 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 aqueous alkali-soluble resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, and the content of the quinonediazide compound (c) The positive photosensitive resin composition of Claim 1 or 2 whose rate is 10-40 mass%.   The positive photosensitive resin composition of any one of Claims 1-3 whose alkenyl group represented by Formula (2) is an allyl group. The aqueous alkaline 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 and hydroxybenzoic acids, which has the formula (10)

The positive photosensitive resin composition of any one of Claims 1-4 which is a compound which has the structure of these.   6. The positive photosensitive resin composition according to claim 5, 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 5 or 6, wherein the hydroxybenzoic acid is a dihydroxybenzoic acid. (D) Formula (9)

The positive photosensitive resin composition of any one of Claims 1-7 which further contains the copolymer containing the repeating unit represented by these.   The content of the polyalkenylphenol resin (a) is 10 to 35% by mass, the content of the aqueous alkali-soluble resin (b) having an epoxy group and a phenolic hydroxyl group is 15 to 60% by mass, the content of the quinonediazide compound (c) The positive photosensitive resin composition according to claim 8, wherein 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 8 or 9, wherein the copolymer (d) is a copolymer of 4-hydroxyphenyl methacrylate and a maleimide compound.   The positive photosensitive resin composition according to claim 10, wherein the maleimide compound is at least one selected from the group consisting of N-phenylmaleimide and N-cyclohexylmaleimide. (1) A coating process in which the positive photosensitive resin composition according to any one of claims 1 to 9 is dissolved in a solvent and applied to a substrate.
(2) a drying step for removing the solvent in the applied positive photosensitive resin composition;
(3) an exposure step of irradiating radiation through a photomask;
(4) A method for producing a radiation lithographic structure comprising 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.   The manufacturing method of the interlayer insulation film of the organic EL element containing the method of Claim 12.   The manufacturing method of the organic EL element containing the method of Claim 12.