JP7066978B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition .

Thermal acid generators are known to be useful for generating acid catalysts for photosensitive resins. Therefore, various reports have been made so far on the photosensitive resin material containing the thermal acid generator (for example, Patent Document 1).

Patent Document 1 describes an alkali-soluble polyimide, a specific S, as a material useful for obtaining a cured film having excellent adhesion to metal materials such as copper, gold, and titanium-based metals even at low temperature firing at 250 ° C. or lower. A positive photosensitive resin composition containing an S-bond-containing compound, a quinonediazide compound, a heat-crosslinking agent and a heat acid generator is described.

Japanese Unexamined Patent Publication No. 2013-72935

The conventional photosensitive resin composition containing the thermoacid generator described in Patent Document 1 and the like may be used, for example, to form a permanent film constituting an electronic device.
The present inventor has studied an electronic device having a resin film formed of such a photosensitive resin composition, and found that an appearance defect may occur when a pressure cooker test (PCT) is carried out. rice field. Further, according to the study of the present inventor, in the case of an electronic device provided with a resin film formed of a conventional photosensitive resin composition, there are inconveniences that the aluminum wiring is corroded and the connection reliability is lowered due to the corrosion. It also became clear that there was a possibility.

Therefore, the present invention produces an electronic device provided with a resin film that has an excellent balance of corrosion resistance, patterning property, storage property and chemical resistance, and can maintain its appearance even when a pressure cooker test is carried out. To provide a photosensitive resin composition useful for this purpose.

（上記一般式（２）中、Ｒ ¹¹ は、水素またはアセチル基であり、Ｒ ¹² およびＲ ¹³ は、それぞれ独立して、炭素数１以上１１以下の炭化水素基である。Ｘ ^- は、Ｂ ^- （Ｃ ₆ Ｆ ₅ ） ₄ である。） According to the present invention, an alkali-soluble resin and
With a photoacid generator
With a thermoacid generator
Thermal cross-linking agent and
A photosensitive resin composition containing
The thermal acid generator is a compound represented by the following general formula (2) .
Provided is a photosensitive resin composition having a pH measured under the following conditions of 1.3 or more and 3.5 or less.
(Conditions: A cured product obtained by curing the photosensitive resin composition at 230 ° C. for 30 minutes is crushed in a mortar to obtain a pulverized product. After putting it in water, the pH of the hot water extract obtained by heating the ultrapure water at 125 ° C. for 20 hours is measured.)

(In the above general formula (2), R ¹¹ is a hydrogen or acetyl group, and R ¹² and R ¹³ are independently hydrocarbon groups having 1 or more and 11 or less carbon atoms. X ^- is B. ^- (C ₆ F ₅ ) _4. )

Further, according to the present invention, there is provided a resin film obtained by curing the photosensitive resin composition according to the present invention.

According to the present invention, an electronic device having an excellent balance of corrosion resistance, patterning property, storage property and chemical resistance, and having a resin film capable of maintaining the appearance even when a pressure cooker test is carried out is manufactured. It is possible to provide a photosensitive resin composition useful for this purpose.

Hereinafter, embodiments of the present invention will be described with reference to specific examples of each component. In addition, each component can be used alone or in combination of two or more. In addition, "-" represents "greater than or equal to" to "less than or equal to" unless otherwise noted.

In the present embodiment, the photosensitive resin composition contains an alkali-soluble resin, a photoacid generator, a thermoacid generator, and a heat-crosslinking agent.
The thermal acid generator is an aromatic sulfonium salt, and the pH measured under the following conditions is 1.3 or more and 3.5 or less.
(Conditions: A cured product obtained by curing the photosensitive resin composition at 230 ° C. for 30 minutes is crushed in a mortar to obtain a pulverized product. After putting it in water, the pH of the hot water extract obtained by heating the ultrapure water at 125 ° C. for 20 hours is measured.)

As described above, the resin film obtained by using the photosensitive resin composition has a balance of corrosion resistance, patterning property, storage property and chemical resistance in order to make the resin film useful for manufacturing electronic devices. It is required that the resin film is excellent in quality and that the appearance can be maintained even when the pressure cooker test is carried out. Therefore, as a result of the study by the present inventor, it has been found that the above-mentioned problems can be solved by making the photosensitive resin composition contain the above-mentioned components and controlling the above-mentioned pH so as to be in a specific range. I found it.
Hereinafter, each component will be described in more detail.

(Alkali-soluble resin)
In the present embodiment, as the alkali-soluble resin, a resin having a hydroxyl group such as a phenolic hydroxyl group and / or a carboxyl group in the main chain or the side chain can be used, for example, a phenol resin, a hydroxystyrene resin, a methacrylic acid resin, or a methacryl. Examples thereof include acrylic resins such as acid ester resins, cyclic olefin resins, precursors having an amide bond such as polybenzoxazole precursors and polyimide precursors, and resins obtained by dehydrating and ring-closing the precursors. Among these, from the viewpoint of improving the balance of heat resistance, film toughness, mechanical strength, thermal stability, and adhesion to other members, a phenol resin, a hydroxystyrene resin, or a precursor having an amide bond is included. Is preferable, and it is more preferable to contain a precursor having an amide bond from the viewpoint of effectively improving thermal stability and adhesion to other members. The alkali-soluble resin can contain one or more of these.

As the precursor having an amide bond in the alkali-soluble resin, for example, a precursor having a repeating unit represented by the following general formula (1) can be used from the viewpoint of improving heat resistance.

(In the above general formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, —OR ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when a plurality of them are present, they are each. It may be the same or different. R ₂ is a hydroxyl group, a carboxyl group, -OR _{3 or -COO-R 3 ,} and when having a plurality of them, they may be the same or different. R ₃ in R ₁ and R ₂ is an organic group having 1 to 15 carbon atoms. If R ₁ has no hydroxyl group, at least one of R ₂ is a carboxyl group. If R ₂ has no carboxyl group. , At least one of R ₁ is a hydroxyl group. M is an integer of 0 to 8 and n is an integer of 0 to 8.)

In the precursor having an amide bond represented by the general formula (1), X, Y, R ₁ to R ₃ , m and n may be the same for each repeating unit or may be different from each other. good.

In a precursor having an amide bond having a structure represented by the general formula (1), a polyimide resin or a polybenzoxazole resin, or an imide bond and an oxazole ring can be obtained by causing a dehydration reaction using heat dehydration or a catalyst. A copolymer containing it is produced. When a precursor having an amide bond is used as the alkali-soluble resin, the alkali-soluble resin may further contain one or both of the polyimide resin and the polybenzoxazole resin.

When the precursor having an amide bond represented by the general formula (1) is a polybenzoxazole precursor, at least one of R ₁ is a hydroxyl group. In this case, a dehydration ring closure occurs between R ₁ and the amide structure by heat dehydration or a catalyst-based dehydration reaction, and a polybenzoxazole resin having an oxazole ring is produced. At this time, the alkali-soluble resin contains at least one of the polybenzoxazole precursor and the polybenzoxazole resin.
Further, when the precursor having an amide bond represented by the general formula (1) is a polyimide precursor, at least one of R ₂ is a carboxyl group. In this case, a dehydration ring closure (imidization) occurs between R ₂ and the amide structure by heat dehydration or a dehydration reaction using a catalyst, and a polyimide resin is produced. At this time, the alkali-soluble resin contains at least one of the polyimide precursor and the polyimide resin.

In the precursor having an amide bond having a repeating unit represented by the general formula (1), R ₁ and R ₂ are hydroxyl groups or carboxyls in adjusting the solubility of the precursor having an amide bond in an aqueous alkaline solution. The group can include a group protected by the protecting group R ₃ . As such R ₁ , -OR _{3 can be used, and as R 3, -OR 3 or -COO-R 3 can be used} , respectively. Examples of the organic group having 1 to 15 carbon atoms as R ₃ include a formyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a tertiary butoxycarbonyl group, a phenyl group, a benzyl group and a tetrahydrofuranyl. Groups and tetrahydropyranyl groups are mentioned.

The organic group as X of the precursor having an amide bond having the structure represented by the general formula (1) is not limited, but from the viewpoint of improving heat resistance, for example, a benzene ring, a naphthalene ring or a bisphenol. Examples thereof include an aromatic group having a structure such as a structure, a heterocyclic organic group having a structure such as a pyrrole ring or a furan ring, and a siloxane group. More specifically, those represented by the following general formulas are preferable. These can be used alone or in combination of two or more.

(In the above general formula, * indicates that it is bonded to the NH group in the general formula (1). A is an alkylene group, a substituted alkylene group, —O—C ₆ H ₄ −O−, —O−, −. S-, -SO _2- , -C (= O)-, -NHC (= O)-or a single bond. R ₄ is selected from the group consisting of an alkyl group, an alkyl ester group and a halogen atom. It may be the same or different for each repeating unit. R ₅ indicates one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom. S represents 0. It is an integer of ~ 4. Each of R ₆ to R ₉ is an organic group. Here, the substituent R ₁ of X represented by the general formula (1) is omitted.)

Among these, more preferable ones are shown below, for example (general formula (1)).
Includes those with R ₁ shown in. ).

(Here, * indicates that the bond is attached to the NH group in the general formula (1). In the formula, A is an alkylene group, a substituted alkylene group, —O—, —S—, —SO _2- , —C (=). O)-, -NHC (= O)-, -CH _3- , -C (CH ₃ ) H-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or a single bond. R ₁₀ is one selected from the group consisting of an alkyl group, an alkoxy group, an acyloxy group and a cycloalkyl group, and when there are a plurality of R ₁₀ , each R ₁₀ may be the same or different. C is 0. It is an integer of 3 or more.)

Specific examples of the alkylene group as A and the substituted alkylene group include -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) (CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH) ₂ CH ₂ CH ₃ )-,-CH (CH (CH ₃ ) ₂ )-, -C (CH ₃ ) (CH (CH ₃ ) ₂ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH (CH ₂ CH (CH ₃ ) ₂ )-, -C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-and-C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-. Among these, -CH _2- , -CH (CH ₃ )-, and -C (CH ₃ ) ₂ -have sufficient solubility not only in an alkaline aqueous solution but also in a solvent, and have a better balance. It is preferable because a precursor having an amide bond can be obtained.

Y in the precursor having an amide bond having a structure represented by the general formula (1) is an organic group, and examples of such an organic group include those similar to X. The Y in the general formula (1) is, for example, an aromatic group having a structure such as a benzene ring, a naphthalene ring or a bisphenol structure, a heterocyclic organic group having a structure such as a pyrrole ring, a pyridine ring or a furan ring, and a siloxane group. And so on. More specifically, those shown below are preferable. These can be used alone or in combination of two or more.

(Here, * indicates that it is bonded to the C = O group in the general formula (1). J indicates -CH _2- , -C (CH ₃ ) _2- , -O-, -S-,-. SO _2- , -C (= O)-, -NHC (= O)-, -C (CF ₃ ) _2- or a single bond. R ₁₃ is an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl. Indicates one selected from the group consisting of ether groups and halogen atoms, which may be the same or different for each repeating unit. R ₁₄ is selected from the group consisting of hydrogen atoms, alkyl groups, alkyl ester groups and halogen atoms. T is an integer of 0 or more and 2 or less. R ₁₅ to R ₁₈ are organic groups. Here, the substituent R ₂ of Y represented by the general formula (1) is omitted. .)

Among these, those shown below (including those shown by R ₂ represented by the general formula (1)) are preferable, for example.
Regarding the structures derived from tetracarboxylic acid dianhydride among those shown below, those in which the positions bonded to the C = O group in general (1) are both in the meta position and those in which both are in the para position are listed. However, it may be a structure including a meta position and a para position, respectively.

(Here, * indicates that it is bonded to the C = O group in the general formula (1). R ₁₉ is selected from the group consisting of an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group and a halogen atom. It may be the same or different for each repeating unit. R ₂₀ indicates one selected from a hydrogen atom or an organic group having 1 or more and 15 or less carbon atoms, and is partially substituted. It may be. U is an integer of 0 or more and 2 or less.)

In the case of a precursor having an amide bond represented by the general formula (1), the amino group at the terminal of the precursor is set to an alkenyl group, an alkynyl group, to the extent that the mechanical properties and heat resistance of the cured product are not affected. And an acid anhydride or a monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one organic group selected from among the hydroxyl groups can also be end-sealed as an amide.
Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one organic group selected from among alkenyl groups, alkynyl groups, and hydroxyl groups include maleic anhydride and citraconic acid anhydride. , 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornen -2,3-Dicarboxylic acid anhydride, methyl-5-norbornen-2,3-dicarboxylic acid anhydride, itaconic acid anhydride, het acid anhydride, 5-norbornen-2-carboxylic acid, 4-ethynylphthalic acid anhydride Things, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid can be mentioned. These may be used alone or in combination of two or more, and a part of the terminal-sealed amide moiety may be dehydrated and ring-closed.

Further, in the case of a precursor having an amide bond represented by the general formula (1), the carboxylic acid residue at the terminal of the precursor is at least an organic group selected from an alkenyl group, an alkynyl group and a hydroxyl group. It can also be terminally sealed as an amide using an amine derivative containing one aliphatic group or cyclic compound group.

In the case of a precursor having an amide bond represented by the general formula (1), a group end-sealed with a nitrogen-containing cyclic compound at at least one of the ends so as not to affect the mechanical properties and heat resistance of the cured product. May have. This makes it possible to improve the adhesion to metal wiring (for example, copper wiring) and the like. Examples of the nitrogen-containing cyclic compound include a 1- (5-1H-triazoyl) methylamino group, a 3- (1H-pyrazoyl) amino group, a 4- (1H-pyrazoyl) amino group, and a 5- (1H-pyrazoyl) amino group. , 1- (3-1H-pyrazoyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H-tetrazol-5-yl) amino Groups include 1- (1H-tetrazol-5-yl) methyl-amino groups, and 3- (1H-tetrazol-5-yl) benz-amino groups.

The precursor having an amide bond having the structure represented by the general formula (1) is, for example, a compound selected from diamine, bis (aminophenol) containing X in the general formula (1), 2,4-diaminophenol and the like. , Y-containing tetracarboxylic acid dianhydride, trimellitic acid anhydride, dicarboxylic acid, dicarboxylic acid dichloride, dicarboxylic acid derivative and the like can be reacted and synthesized. When a dicarboxylic acid is used, an active ester-type dicarboxylic acid obtained by previously reacting the dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole or the like in order to increase the reaction yield of the precursor having an amide bond. Derivatives may be used.

From the viewpoint of improving low temperature curability, the precursor having an amide bond having a repeating unit represented by the general formula (1) is preferably 4,4'-methylenebis (2-aminophenol) represented by the following formula or It is made by polymerizing one or more monomers containing at least one of 4,4'-methylenebis (2-amino-3,6 dimethylphenol), more preferably 4,4'-methylenebis (2-). It is made by polymerizing two or more kinds of monomers containing aminophenol) and 4,4'-methylenebis (2-amino-3,6 dimethylphenol).
From the same viewpoint, the alkali-soluble resin preferably contains a polyamide resin, and more preferably 4,4'-methylenebis (2-aminophenol) or 4,4'-methylenebis (2-amino-3) represented by the following formula. , 6 Dimethylphenol), including polymers of one or more monomers, more preferably 4,4'-methylenebis (2-aminophenol) and 4,4'-methylenebis (, 6dimethylphenol). 2-Amino-3,6 Dimethylphenol) containing 2 or 3 or more monomer polymers.

As the phenol resin in the alkali-soluble resin, for example, a reaction product of a phenol compound represented by a novolak type phenol resin and an aldehyde compound, or a reaction product of a phenol compound represented by a phenol aralkyl resin and a dimethanol compound is used. Can be done. Among these, it is more preferable to use a phenol resin obtained by reacting a phenol compound with an aldehyde compound from the viewpoint of suppressing film loss in the developing process, improving thermal stability, and manufacturing cost.

Phenolic compounds include, but are not limited to, cresols such as phenol, o-cresol, m-cresol or p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-. Xylenols such as xylenol, 3,4-xylenol or 3,5-xylenol, ethylphenols such as o-ethylphenol, m-ethylphenol or p-ethylphenol, isopropylphenol, butylphenol or p-tert-butylphenol and the like. Alkylphenols or polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol or fluoroglucolcin can be used. These phenol compounds can be used alone or in combination of two or more.

The aldehyde compound is not limited as long as it is an organic group having an aldehyde group, and for example, formalin, paraformaldehyde, acetaldehyde, benzaldehyde, or salicylaldehyde can be used. As the benzaldehyde, one substituted with at least one of an alkyl group, an alkoxy group or a hydroxy group, or an unsubstituted one can be used. These aldehyde compounds can be used alone or in combination of two or more.
In the present embodiment, for example, a phenol resin which is an alkali-soluble resin can be obtained by reacting the phenol compound with the aldehyde compound under an acid catalyst and synthesizing the compound. As the acid catalyst, for example, oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluene sulfonic acid, phenol sulfonic acid, or benzene sulfonic acid can be used.

The dimethanol compound is not limited, for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3,3'-. Dimethanol compounds such as biphenyldimethanol or 2,6-naphthalenedimethanol, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl , 3,4'-Bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl or bis (alkoxymethyl) compounds such as 2,6-naphthalenedicarboxylate methyl, or 1,4-bis (chloro). Methyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 3,4 '-Bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl or 3,3'-bis ( Bis (halgenoalkyl) compounds such as bromomethyl) biphenyl can be used. These dimethanol compounds can be used alone or in combination of two or more.

As the hydroxystyrene resin in the alkali-soluble resin, a polymerization reaction product or a copolymerization reaction product obtained by radical polymerization, cationic polymerization or anionic polymerization of hydroxystyrene, styrene or a derivative thereof can be used.

In the present embodiment, the content of the alkali-soluble resin is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total non-volatile components of the photosensitive resin composition. Is more preferable. By setting the content of the alkali-soluble resin to the above lower limit value or more, the curability of the photosensitive resin composition can be improved. This makes it possible to improve the heat resistance, mechanical strength, and durability of the resin film formed by using the photosensitive resin composition. On the other hand, the content of the alkali-soluble resin is preferably 90% by mass or less, more preferably 80% by mass or less, based on the total non-volatile components of the photosensitive resin composition, for example. By setting the content of the alkali-soluble resin (A) to the above upper limit value or less, the resolution in lithography can be improved.
The proportion (mass%) of the non-volatile component in the photosensitive resin composition can be measured, for example, as follows. First, 1.0 g of a photosensitive resin material is weighed as a sample in an aluminum cup whose mass (w0) has been measured. At this time, the total mass of the sample and the aluminum cup is set to w1. Next, the aluminum cup is held in a hot air dryer adjusted to 210 ° C. under normal pressure for 1 hour, then taken out of the hot air dryer and cooled to room temperature. Next, the total mass (w2) of the cooled sample and the aluminum cup is measured. Then, the ratio (mass%) of the non-volatile component in the photosensitive resin composition is calculated from the following formula.
Non-volatile component (mass%) = (w2-w0) / (w1-w0) × 100

(Photoacid generator)
In the present embodiment, as the photoacid generator, a compound that generates an acid by light can be used, for example, a photosensitive diazoquinone compound, a diallyl iodonium salt, an onium salt such as a triarylsulfonium salt or a sulfonium borate salt, 2- A nitrobenzyl ester compound, an N-iminosulfonate compound, an imidesulfonate compound, a 2,6-bis (trichloromethyl) -1,3,5-triazine compound, or a dihydropyridine compound can be used. Among these, it is more preferable to use a photosensitive diazoquinone compound from the viewpoint of excellent sensitivity and solvent solubility. As the photosensitive diazoquinone compound, for example, those shown below can be used.

(Here, n2 is an integer of 1 or more and 5 or less.)

In each of the above compounds, Q is any of the structures shown in the following (a) to (c) or a hydrogen atom. However, at least one of the Qs of each compound has any of the structures shown in the following (a) to (c).

In the present embodiment, as the photosensitive diazoquinone compound, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Is more preferable to use. When the photosensitive resin material is of the positive type, the photoacid generator remaining in the relief pattern of the unexposed portion is considered to be decomposed by heat during curing to generate acid, and photoacid is also generated as a reaction accelerator. The agent plays an important role. As the photosensitive diazoquinone compound having such a role, it is more preferable to use an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid, which is more easily decomposed by heat.
From the same viewpoint, the photoacid generator is preferably 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-. It comprises one or more selected from the group consisting of sulfonic acid esters and sulfonic acid esters of trisphenol and naphthoquinone diazide, more preferably 1,2-naphthoquinone diazide-4-sulfonic acid ester.

In the present embodiment, the content of the photoacid generator is preferably, for example, 5% by mass or more, more preferably 8% by mass or more, based on the total non-volatile components of the photosensitive resin composition. The content of the photoacid generator is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, based on the total non-volatile components of the photosensitive resin composition. By setting in such a numerical range, it becomes possible to realize a photosensitive resin composition having good patterning performance.

(Thermal acid generator)
The thermal acid generator is preferably aromatic from the viewpoint of excellent balance of corrosion resistance, patterning property, storage property and chemical resistance, and from the viewpoint of obtaining a resin film that can maintain its appearance even when a pressure cooker test is carried out. It is a group sulfonium salt.

From the same viewpoint, specific examples of the aromatic sulfonium salt include a boron compound salt or a phosphorus compound salt of an aromatic compound having a sulfur atom directly bonded to a benzene ring, and a benzenesulfonborate salt is preferable. From the same viewpoint, the thermoacid generator is preferably a compound represented by the following general formula (2).

(In the above general formula (2), R ¹¹ is a hydrogen or acetyl group, and R ¹² and R ¹³ are independently hydrocarbon groups having 1 or more and 11 or less carbon atoms. X ^- is PF. ₆ ^- or B (C ₆ F ₅ ) ₄ )

In the general formula (2), R ¹¹ is one selected from hydrogen and acetyl groups.
In the general formula (2), R ¹² and R ¹³ are each independently a hydrocarbon group having 1 or more and 11 or less carbon atoms. R ¹² and R ¹³ preferably independently consist of an alkyl group having 1 or more and 4 or less carbon atoms, a benzyl group and an α-naphthylmethyl group which may be substituted with an alkyl group having 1 or more and 4 or less carbon atoms. It is one selected from the group consisting of a methyl group, a benzyl group, a methylbenzyl group and an α-naphthylmethyl group, more preferably independently of each other, and more preferably independently of each other. It is one selected from a methyl group and a methylbenzyl group, and is even more preferably a methyl group.
Further, in the general formula (2), X ^- is one selected from PF _6- ^or B (C ₆ F ₅ ) ₄ .

The thermoacid generator is preferably described below from the viewpoint of excellent balance of corrosion resistance, patterning property, storage property and chemical resistance, and from the viewpoint of obtaining a resin film that can maintain its appearance even when a pressure cooker test is carried out. It contains one or two selected from the group consisting of the compounds represented by the formulas (a) and (b), and more preferably contains the compound represented by the following formula (a) or the following formula (b).

The thermal acid generators include SAN-AID SI-B2A, AN-AID SI-B3A, AN-AID SI-B3, AN-AID SI-B5, AN-AID SI-B4, and AN-AID SI-300. , AN-AID SI-360, AN-AID SI-110 (all manufactured by Sanshin Chemical Industry Co., Ltd.) and other aromatic sulfonium salts.

In the present embodiment, the content of the thermoacid generator is, for example, relative to 100 parts by mass of the total weight of the alkali-soluble resin from the viewpoint of improving the chemical resistance of the resin film obtained by curing the photosensitive resin composition. It is 0.1% by mass or more, preferably 0.5% by mass or more. Further, from the viewpoint of improving the patterning characteristics of the resin film obtained by curing the photosensitive resin composition, the content of the thermoacid generator is, for example, 15% by mass or less with respect to 100 parts by mass of the total weight of the alkali-soluble resin. It is preferably 10% by mass or less.

Further, when the content of the photoacid generator in 100 parts by weight of the alkali-soluble resin is A and the content of the thermoacid generator in 100 parts by weight of the alkali-soluble resin is B, (B / C). ) Is preferably 0.5 or more, more preferably 1 or more, from the viewpoint of improving the patterning characteristics of the resin film obtained by curing the photosensitive resin composition. Further, from the viewpoint of improving the chemical resistance of the resin film obtained by curing the photosensitive resin composition, the above (B / C) is preferably 20 or less, more preferably 15 or less.

(Thermal crosslinker)
The thermal cross-linking agent is not limited as long as it is a compound having a group capable of reacting with the alkali-soluble resin by heat, and is, for example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzene. Dimethanol (paraxylylene glycol), 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4 , 4'-Methylbis (2,6-dialkoxymethylphenol) and other compounds having a methylol group; 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4, 4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl, 2,6-naphthalenedicarboxylate methyl, 4,4'-methylenebis ( A compound having an alkoxymethyl group typified by 2,6-dimethoxymethylphenol) or the like; a methylol melamine compound typified by hexamethylol melamine, hexabutanol melamine or the like; an alkoxy melamine compound typified by hexamethoxy melamine or the like; tetramethoxy An alkoxymethylglycol uryl compound represented by methyl glycol uryl or the like; a methylol urea compound represented by methylol benzoguanamine compound, dimethylol ethylene urea or the like; a cyano compound represented by dicyanoaniline, dicyanophenol, cyanophenyl sulfonic acid or the like; 1 , 4-Phenylenediisocyanate, isocyanato compounds typified by 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, Epoxy group-containing compounds typified by bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene-based epoxy resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin, etc .; N, N'-1,3-phenylenedi maleimide , N, N'-maleimide compounds typified by methylenedimaleimide and the like, but are not limited thereto. These heat cross-linking agents can be used alone or in combination of two or more.
The thermal cross-linking agent is preferably 1,4-benzenedimethanol (paraxylylene glycol) from the viewpoint of improving the chemical resistance of the resin film obtained by curing the photosensitive resin composition.

The content of the thermal cross-linking agent in the photosensitive resin composition of the present embodiment is not limited, but is 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total weight of the alkali-soluble resin. It is preferably present, and more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the addition amount is within the above range, a cured film having excellent residual film ratio and heat resistance at the time of curing can be formed.

(Manufacturing method of photosensitive resin composition)
The photosensitive resin composition is prepared by mixing and dissolving each of the above-mentioned components and, if necessary, other components in an organic solvent.
Further, in the present embodiment, the photosensitive resin composition is used in the form of a varnish by dissolving, for example, the above-mentioned components and, if necessary, other components in an organic solvent.

Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene. Glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, and ethyl pyruvate and methyl-3-methoxy Propylene and the like can be mentioned. These may be used alone or in combination of two or more.

(PH)
In the photosensitive resin composition obtained in the present embodiment, the pH measured under the following conditions is 1.3 or more and 3.5 or less.
(Conditions: A cured product obtained by curing the photosensitive resin composition at 230 ° C. for 30 minutes is crushed in a mortar to obtain a pulverized product. After putting it in water, the pH of the hot water extract obtained by heating the ultrapure water at 125 ° C. for 20 hours is measured.)

A resin that has an excellent balance of corrosion resistance, patterning property, storage property and chemical resistance by controlling the pH to be within a specific range, and can maintain its appearance even when a pressure cooker test is carried out. A membrane can be obtained.
Here, in the present embodiment, for example, by appropriately selecting a combination of a photoacid generator and a thermoacid generator, the pH of the photosensitive resin composition can be controlled within a desired range.

In the present embodiment, the pH is 1.3 or more, preferably 1.4 or more, and more preferably 1.5 or more, from the viewpoint of improving the storage stability of the photosensitive resin composition.
Further, from the viewpoint of improving the chemical resistance of the resin film obtained by curing the photosensitive resin composition, the pH is 3.5 or less, preferably 3.3 or less, and more preferably 3.0 or less. Is.
Further, in the present embodiment, the ultrapure water used for pH measurement is specifically ultrapure water manufactured by Kanto Chemical Co., Inc.

Further, in the present embodiment, the photosensitive resin composition may contain components other than the above. As components other than the above, for example, additives such as antioxidants, fillers, terminal encapsulants, sensitizers, adhesion aids, and surfactants may be added.

Of these, as the adhesion aid, for example, a silane cup rig agent can be used. Examples of such a silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and p-styryltrimethoxysilane, 3. -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3 -Examples include, but are not limited to, isocyanate propyltriethoxysilane and silicon compounds obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride.
The silicon compound obtained by reacting the above-mentioned silicon compound having an amino group with an acid dianhydride or an acid anhydride is described in the formula (9) described later or from the viewpoint of improving the storage stability of the photosensitive resin composition. The compound represented by (10) is preferable.

The silicon compound having an amino group is not limited, but for example, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyl. Examples thereof include dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.

The acid dianhydride or acid anhydride is not limited, but for example, maleic anhydride, maleic chloroanhydride, maleic anhydride, cytoconic acid, phthalic anhydride, pyromellitic anhydride, 4 , 4'-biphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-carbonyldiphthalic acid anhydride and the like. In addition, it can be used alone or in combination of two or more.

The amount of the silane coupling agent added is not limited, but is preferably 0.05 to 50 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the cyclic olefin resin. Is more preferable. When the addition amount is within the above range, the adhesion to the substrate and the storage stability of the photosensitive resin composition can be suitably compatible with each other.

Further, as the surfactant, specifically, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton is included. In the present embodiment, from the viewpoint of enhancing the wettability of the photosensitive resin composition to the substrate, it is more preferable to use a surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is more preferable to use a fluorine-based surfactant. It is particularly preferred to use a surfactant. Examples of the fluorine-based surfactant include Megafuck F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, and F- of DIC Corporation. Examples thereof include, but are not limited to, 554, F-556 and F-557, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Ltd.

In the present embodiment, the content of the surfactant is, for example, 10 ppm or more, preferably 50 ppm, with respect to the total amount of the varnish made of the photosensitive resin composition, from the viewpoint of enhancing the wettability of the photosensitive resin composition to the substrate. That is all. Further, from the viewpoint of improving the patterning characteristics of the resin film obtained by curing the photosensitive resin composition, the content of the surfactant is, for example, 5000 ppm or less with respect to the total amount of the varnish made of the photosensitive resin composition. It is preferably 2000 ppm or less.

A resin film can be obtained by curing the photosensitive resin composition in the present embodiment. Further, the resin film in the present embodiment is formed by curing the photosensitive resin composition.
This resin film constitutes, for example, a permanent film of an electronic device. In the present embodiment, for example, a coating film composed of a photosensitive resin composition is patterned into a desired shape by exposure and development, and then the coating film is cured by heat treatment or the like to form a permanent film.

Examples of the permanent film formed by using the photosensitive resin composition include an interlayer film, a surface protective film, and a dam material. The use of the photosensitive resin composition is not limited to this.
The interlayer film refers to an insulating film provided in the multilayer structure, and the type thereof is not particularly limited. Examples of the interlayer film include those used in semiconductor device applications such as an interlayer insulating film constituting a multilayer wiring structure of a semiconductor element, a build-up layer or a core layer constituting a wiring substrate, and the like. Further, as the interlayer film, for example, a flattening film covering a thin film transistor (TFT) in a display device, a liquid crystal alignment film, and protrusions provided on a color filter substrate of an MVA (Multi Domain Vertical Alignment) type liquid crystal display device. Alternatively, those used in display device applications such as partition walls for forming a cathode of an organic EL element can also be mentioned.

The surface protective film refers to an insulating film formed on the surface of an electronic component or an electronic device and for protecting the surface, and the type thereof is not particularly limited. Examples of such a surface protective film include a passivation film or buffer coat layer provided on a semiconductor element, and a cover coat provided on a flexible substrate. Further, as the dam material, for example, a spacer used for forming a hollow portion for arranging an optical element or the like on a substrate can be mentioned.

（上記一般式（２）中、Ｒ ¹¹ は、水素またはアセチル基であり、Ｒ ¹² およびＲ ¹³ は、それぞれ独立して、炭素数１以上１１以下の炭化水素基である。Ｘ ^- は、ＰＦ ₆ ^- またはＢ（Ｃ ₆ Ｆ ₅ ） ₄ である。）
５． 前記熱酸発生剤が下記式（ａ）または下記式（ｂ）で表される化合物を含む、１．乃至４．のいずれか一つに記載の感光性樹脂組成物。

６． 前記光酸発生剤が、１，２－ベンゾキノンジアジド－４－スルホン酸エステル、１，２－ナフトキノンジアジド－４－スルホン酸エステル、１，２－ナフトキノンジアジド－５－スルホン酸エステル、およびトリスフェノールとナフトキノンジアジドのスルホン酸エステルからなる群より選択される１種または２種以上を含む、１．乃至５．のいずれか一つに記載の感光性樹脂組成物。
７． 前記アルカリ可溶性樹脂が、下記一般式（１）により示される繰り返し単位を有する、アミド結合を有する前駆体を含む、１．乃至６．のいずれか一つに記載の感光性樹脂組成物。

（上記一般式（１）中、ＸおよびＹは、有機基である。Ｒ ₁ は、水酸基、－Ｏ－Ｒ ₃ 、アルキル基、アシルオキシ基、またはシクロアルキル基であり、複数有する場合にはそれぞれ同一であっても異なってもよい。Ｒ ₂ は、水酸基、カルボキシル基、－Ｏ－Ｒ ₃ 、または－ＣＯＯ－Ｒ ₃ であり、複数有する場合にはそれぞれ同一であっても異なってもよい。Ｒ ₁ およびＲ ₂ におけるＲ ₃ は、炭素数１～１５の有機基である。Ｒ ₁ として水酸基がない場合、Ｒ ₂ の少なくとも１つはカルボキシル基である。Ｒ ₂ としてカルボキシル基がない場合は、Ｒ ₁ の少なくとも１つは水酸基である。ｍは０～８の整数であり、ｎは０～８の整数である。）
８． 前記アミド結合を有する前駆体が、下記式で示される４，４'－メチレンビス（２－アミノフェノール）または４，４'－メチレンビス（２－アミノ－３，６ジメチルフェノール）の少なくとも一方を含む１種または２種以上の単量体の重合体である、７．に記載の感光性樹脂組成物。

９． １．乃至８．のいずれか一つに記載の感光性樹脂組成物を硬化させてなる、樹脂膜。
１０． 電子装置の永久膜を構成する、９．に記載の樹脂膜。

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1. Alkali-soluble resin and
With a photoacid generator
With a thermoacid generator
Thermal cross-linking agent and
A photosensitive resin composition containing
The thermal acid generator is an aromatic sulfonium salt,
A photosensitive resin composition having a pH measured under the following conditions of 1.3 or more and 3.5 or less.
(Conditions: A cured product obtained by curing the photosensitive resin composition at 230 ° C. for 30 minutes is crushed in a mortar to obtain a pulverized product. After putting it in water, the pH of the hot water extract obtained by heating the ultrapure water at 125 ° C. for 20 hours is measured.)
2. 2. 1. The content of the alkali-soluble resin is 50% by mass or more and 90% by mass or less with respect to the total amount of the non-volatile components of the photosensitive resin composition. The photosensitive resin composition according to.
3. 3. When the content of the photoacid generator in 100 parts by weight of the alkali-soluble resin is B and the content of the thermoacid generator in 100 parts by weight of the alkali-soluble resin is C.
(B / C) is 0.5 or more and 20 or less. Or 2. The photosensitive resin composition according to.
4. 1. The thermoacid generator is a compound represented by the following general formula (2). To 3. The photosensitive resin composition according to any one of the above.

(In the above general formula (2), R ¹¹ is a hydrogen or acetyl group, and R ¹² and R ¹³ are independently hydrocarbon groups having 1 or more and 11 or less carbon atoms. X ^- is PF. ₆ ^- or B (C ₆ F ₅ ) ₄ )
5. 1. The thermal acid generator contains a compound represented by the following formula (a) or the following formula (b). To 4. The photosensitive resin composition according to any one of the above.

6. The photoacid generator comprises 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazido-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, and trisphenol. 1. Containing one or more selected from the group consisting of sulfonic acid esters of naphthoquinone diazide. ~ 5. The photosensitive resin composition according to any one of the above.
7. 1. The alkali-soluble resin contains a precursor having an amide bond having a repeating unit represented by the following general formula (1). ~ 6. The photosensitive resin composition according to any one of the above.

(In the above general formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, —OR ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when a plurality of them are present, they are each. It may be the same or different. R ₂ is a hydroxyl group, a carboxyl group, -OR ₃ or -COO-R ₃ , and when having a plurality of them, they may be the same or different. R ₃ in R ₁ and R ₂ is an organic group having 1 to 15 carbon atoms. If R ₁ has no hydroxyl group , at least one of R 2 is a carboxyl group. _If R ₂ has no carboxyl group. , At least one of R ₁ is a hydroxyl group. M is an integer of 0 to 8 and n is an integer of 0 to 8.)
8. The precursor having an amide bond contains at least one of 4,4'-methylenebis (2-aminophenol) or 4,4'-methylenebis (2-amino-3,6 dimethylphenol) represented by the following formula 1. 7. A polymer of seeds or two or more monomers. The photosensitive resin composition according to.

9. 1. 1. ~ 8. A resin film obtained by curing the photosensitive resin composition according to any one of the above.
10. 2. Consists of the permanent film of the electronic device. The resin film described in.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

First, the alkali-soluble resin (A), the photoacid generator (B) and the adhesion aid (D) used in each Example and each Comparative Example were synthesized by the following methods.

<Synthesis Example 1: Alkali-soluble resin (A-1)>
206.58 g (0.800 mol) of diphenyl ether-4,4'-dicarboxylic acid and 216. in a four-port glass separable flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet. 170.20 g (0.346 mol) and 4.01 g of a mixture of dicarboxylic acid derivatives obtained by reacting 19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazol monohydrate. (0.047 mol) 5-aminotetrazole, 45.22 g (0.196 mol) of 4,4'-methylenebis (2-aminophenol) and 56.24 g (0.196 mol) of 4,4'-methylenebis. (2-Amino-3,6 dimethylphenol) and was added. Then, 578.3 g of N-methyl-2-pyrrolidone was added into the separable flask to dissolve each raw material component. Next, the reaction was carried out at 90 ° C. for 5 hours using an oil bath. Next, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the separable flask, and the reaction was carried out at 90 ° C. for 2 hours with stirring. After that, the reaction was terminated by cooling to 23 ° C.
The filtrate obtained by filtering the reaction mixture in the separable flask was put into a solution of water / isopropanol = 7/4 (volume ratio). Then, the precipitate was separated by filtration, washed thoroughly with water, and then dried under vacuum to obtain the desired alkali-soluble resin (A-1). The weight average molecular weight of the obtained alkali-soluble resin (A-1) was 18,081.

<Synthesis Example 2: Photoacid generator (B-1)>
11.04 g (0.026 mol) of phenol represented by the following formula (P-1) and 1, 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-5-sulfonyl chloride and 170 g of acetone were added and stirred to dissolve.
Then, while cooling the flask in a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting as it was at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further carried out for 30 minutes. Then, after filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 mL / 10 mL). The precipitate was then collected by filtration, washed thoroughly with water and then dried under vacuum. As a result, a photoacid generator (B-1) represented by the structure of the following formula (Q-1) was obtained.

<Synthesis Example 3: Adhesion Aid (D-1)>
Cyclohexene-1,2-dicarboxylic acid anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g) in an appropriately sized reaction vessel equipped with a stirrer and a condenser, and a constant temperature bath was used. Was adjusted to 30 ° C. Then, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into the dropping funnel, and the solution was added dropwise over 60 minutes. After the dropping was completed, the mixture was stirred under the conditions of 30 ° C. for 18 hours to obtain a silane coupling agent represented by the following formula (9) as an adhesion aid (D-1).

<Synthesis Example 4: Adhesion Aid (D-2)>
N-Methyl-2-pyrrolidone (669 g) of 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (32.2 g, 100 mmol) in an appropriately sized reaction vessel equipped with a stirrer and a condenser. ), And the temperature was adjusted to 30 ° C. in a constant temperature bath. Then, 3-aminopropyltriethoxysilane (42.1 g, 190 mmol) was charged into the dropping funnel and added dropwise to the solution over 60 minutes. After the dropping was completed, the mixture was stirred under the conditions of 30 ° C. for 18 hours to obtain a silane coupling agent represented by the following formula (10) as an adhesion aid (D-2).

In addition, other components used in Examples or Comparative Examples are shown below.
<Thermal acid generator (C)>
-Heat acid generator (C-1): Sun-Aid-SIB4 (manufactured by Sanshin Chemical Industry Co., Ltd.), compound represented by the above formula (a) -Heat acid generator (C-2): Sun-Aid-SIB5 (Sanshin) Chemical Industry Co., Ltd.), the compound represented by the above formula (b)

<Thermal crosslinker (E)>
・ (E-1) Paraxylylene glycol (manufactured by Ihara Nikkei Chemical Industry Co., Ltd.)

<Surfactant (F)>
(F-1) Fluorine-based surfactant (manufactured by Sumitomo 3M Ltd., FC4430)
<Acid (G) and (H)>
-(G-1): benzenesulfonic acid- (H-1): oxalic acid

<Solvent>
N-Methylpyrrolidone (NMP) / γ-butyrolactone (GBL) = 6/4 (mass ratio)

(Examples 1 to 4, Comparative Examples 1 and 2)
By blending and blending the components shown in Table 1, the photosensitive resin compositions of each example were obtained.
In Table 1, the composition of the components (A) to (E) is by mass. The solvent composition is 102 parts by mass for NMP and 68 parts by mass for GBL with respect to 100 parts by mass of the resin. The blending amount of the surfactant of the component (F) is the concentration (ppm) with respect to the entire varnish-like resin composition containing the solvent.
The photosensitive resin compositions obtained in each example were measured and evaluated as follows. However, in Comparative Example 2, precipitation occurred at the stage (pH 3.7) in which 5 phr of oxalic acid was added to 100 parts by mass of the resin at the time of preparation, and a resin composition having desired properties could not be obtained. No measurements or evaluations were made.

-PH: First, the obtained varnish-like photosensitive resin composition was applied onto a hot plate and cured at 230 ° C. for 30 minutes to obtain a cured product of the photosensitive resin composition. Next, the cured product was collected and transferred to a mortar, and the cured product was pulverized to obtain a pulverized product. Next, the obtained pulverized product is placed in 5 times the amount of ultrapure water (manufactured by Kanto Chemical Co., Ltd.), and then the ultrapure water is heated at 125 ° C. for 20 hours for pH measurement. A hot water extract was obtained. The pH of the hot water extract thus obtained was measured with a pH meter.

-Patternability: The obtained photosensitive resin composition was applied onto an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120 ° C. for 4 minutes to form a coating film having a film thickness of about 6 μm. Got An i-line stepper (NSR-4425i manufactured by Nikon Corporation) is passed through this coating film through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a punching pattern having a width of 0.88 to 50 μm are drawn). It was used to irradiate with different exposures. Next, under a temperature condition of 23 ° C., a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and the developing time was such that the difference between the film thickness after prebaking and the film thickness after development was 1.5 μm. The exposed part was dissolved and removed by performing paddle development twice, and then rinsed with pure water for 10 seconds. The value of the minimum exposure amount at which a 100 μm square via hole pattern was formed was determined as the patterning sensitivity and evaluated according to the following criteria.
⊚: No residue is observed.
◯: Although a residue was observed, it can be used practically.
X: Residues are observed and it is difficult to withstand practical use.

Appearance of the surface of the cured film after the pressure cooker treatment (after the PCT treatment): First, a 6-inch silicon wafer (Si substrate) was prepared, and the obtained varnish-like photosensitive resin composition was used with a spin coater. After the coating, the solvent was removed by heating at 120 ° C. for 4 minutes. As a result, a resin film formed of the photosensitive resin composition was obtained. Next, the obtained resin film was cured by heat treatment at 230 ° C. for 60 minutes under a nitrogen atmosphere to obtain a cured film. Then, it was treated with a pressure cooker tester (PCT) at 125 ° C. and a relative humidity of 100% for 24 hours. The surface of the cured film thus obtained was observed under a microscope, and its appearance was evaluated according to the following criteria.
○: White turbidity ×: No white turbidity

Preservability: The initial viscosity η ₁ of the obtained photosensitive resin composition was measured using a cone-type viscometer (TVE-22H, manufactured by Toki Sangyo Co., Ltd.). Next, after storing the photosensitive resin composition at 23 ° C. for 7 days, the viscosity η ₂ of the photosensitive resin composition was measured using a cone-type viscometer (TVE-22H, manufactured by Toki Sangyo Co., Ltd.). Was done. The rotation speed was measured at 20 rpm.
Then, the value of the viscosity change rate after storage for 7 days calculated by the following formula (X) was calculated, and the storage stability was evaluated according to the following criteria.
Formula (X): Viscosity change rate after storage for 7 days [%] = (η ₂ -η ₁ ) / η ₁ × 100
◯: Viscosity change less than 5% ×: Viscosity change 5% or more

Corrosion resistance: The obtained photosensitive resin composition is applied onto a silicon wafer (AS8R) in which an aluminum circuit is formed in a comb shape, and dried on a hot plate at 120 ° C. for 4 minutes to form a resin film. Got Next, the obtained resin film was cured by heat treatment in a nitrogen atmosphere at 230 ° C. for 60 minutes to obtain a wafer with a cured film. The obtained wafer was treated with a pressure cooker tester (PCT) at 125 ° C. and 100% relative humidity for 24 hours. The aluminum circuit in the wafer thus obtained was observed with a microscope, and the corrosion resistance was evaluated according to the following criteria.
◎: No corrosion of aluminum wiring ○: 1 corroded part of aluminum wiring ×: 2 or more corroded parts of aluminum wiring

-Chemical resistance (double layer coating): The obtained photosensitive resin composition is coated on an 8-inch silicon wafer using a spin coater, and then prebaked at 120 ° C. for 4 minutes on a hot plate to form a film. A coating film having a thickness of about 6 μm was obtained. Next, the coating film was subjected to a thermosetting treatment at 230 ° C. for 60 minutes to obtain a cured film (first film). Next, the obtained photosensitive resin composition was applied onto the first film using a spin coater, and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a film thickness of about 6 μm. Second film) was obtained. The surface of the cured film composed of the first film and the second film thus obtained was observed with an optical microscope. The evaluation was performed on 5 cured films (N = 5), and the chemical resistance was evaluated according to the number of cracked cured films according to the following criteria, and "Δ" or higher was regarded as acceptable.
◎: 0 pieces ○: 1 piece △: 2 pieces ×: 3 pieces or more

Claims (7)

Alkali-soluble resin and
With a photoacid generator
With a thermoacid generator
Thermal cross-linking agent and
A photosensitive resin composition containing
The thermal acid generator is a compound represented by the following general formula (2).
A photosensitive resin composition having a pH measured under the following conditions of 1.3 or more and 3.5 or less.
(Conditions: A cured product obtained by curing the photosensitive resin composition at 230 ° C. for 30 minutes is crushed in a mortar to obtain a pulverized product. After putting it in water, the pH of the hot water extract obtained by heating the ultrapure water at 125 ° C. for 20 hours is measured.)

(In the above general formula (2), R ¹¹ is a hydrogen or acetyl group, and R ¹² and R ¹³ are independently hydrocarbon groups having 1 or more and 11 or less carbon atoms. X ^- is B. ^- (C ₆ F ₅ ) _4. ) The photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin is 50% by mass or more and 90% by mass or less with respect to the total amount of the non-volatile components of the photosensitive resin composition. When the content of the photoacid generator in 100 parts by weight of the alkali-soluble resin is B and the content of the thermoacid generator in 100 parts by weight of the alkali-soluble resin is C.
The photosensitive resin composition according to claim 1 or 2, wherein (B / C) is 0.5 or more and 20 or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the thermal acid generator contains a compound represented by the following formula (a) or the following formula (b).

The photoacid generator includes 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, and trisphenol. The photosensitive resin composition according to any one of claims 1 to 4, which comprises one or more selected from the group consisting of sulfonic acid esters of naphthoquinone diazide. The photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin contains a precursor having an amide bond, which has a repeating unit represented by the following general formula (1).

(In the above general formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, —OR ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when a plurality of them are present, they are each. It may be the same or different. R ₂ is a hydroxyl group, a carboxyl group, -OR _{3 or -COO-R 3 ,} and when having a plurality of them, they may be the same or different. R ₃ in R ₁ and R ₂ is an organic group having 1 to 15 carbon atoms. If R ₁ has no hydroxyl group, at least one of R ₂ is a carboxyl group. If R ₂ has no carboxyl group. , At least one of R ₁ is a hydroxyl group. M is an integer of 0 to 8 and n is an integer of 0 to 8.) The precursor having an amide bond contains at least one of 4,4'-methylenebis (2-aminophenol) or 4,4'-methylenebis (2-amino-3,6 dimethylphenol) represented by the following formula 1. The photosensitive resin composition according to claim 6, which is a polymer of a seed or two or more kinds of monomers.