JP2021096311A - Photosensitive resin composition, cured film, electronic component, and semiconductor device - Google Patents

Abstract

To provide a high-sensitive photosensitive resin composition capable of obtaining a cured film which has high adhesion to metal at high elongation.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble resin containing one or more selected from the group consisting of a polybenzoxazole precursor, a polyimide precursor, a polyamideimide precursor, polyimide and two or more copolymers selected from them, (B) a phenol resin, (C) a triarylsulfonium salt and (D) a naphthoquinonediazide compound. The (A) alkali-soluble resin has an aliphatic group, a percentage content of the (B) phenol resin is 30% or more and 70% or less with respect to 100% of the total of weights of the (A) alkali-soluble resin and the (B) phenol resin, and a percentage content of the (C) triarylsulfonium salt is 12.5% or more and 56.0% or less with respect to 100% of the total of weights of the (C) triarylsulfonium salt and the (D) naphthoquinonediazide compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive resin composition used as a surface protective film or an interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescent element, a flattening film of a TFT substrate, and the like.

Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance and electrical insulation have been used as surface protective films and interlayer insulating films of semiconductor devices, insulating layers of organic electric field light emitting elements, and flattening films of TFT substrates. Widely used. Further, a photosensitive polyimide having photosensitivity and a photosensitive polybenzoxazole have been studied in order to improve productivity.

A photosensitive resin composition using a resin having an aliphatic group in the diamine of the polybenzoxazole precursor and the polyimide precursor has been proposed in order to increase the elongation, reduce the stress, and adhere to a high metal (Patent Documents). 1)
Further, in order to increase the sensitivity, a photosensitive resin composition (see Patent Document 2) in which a triarylsulfonium salt is added to a polybenzoxazole precursor and a polyimide precursor, and a phenol resin to the polybenzoxazole precursor and the polyimide precursor. (See Patent Document 3) has been proposed. (See Patent Document 3)

International Publication No. 2017/0649484 Japanese Unexamined Patent Publication No. 2004-202743 Japanese Unexamined Patent Publication No. 2004-170821

With the photosensitive resin composition described in the above document, it is difficult to achieve both the sensitivity during pattern processing, the elongation of the cured film when used as a cured film, and the adhesiveness to a metal at a high level, and one of the characteristics is one of them. Was insufficient.

The present invention provides a highly sensitive photosensitive resin composition capable of obtaining a cured film having high elongation and high adhesiveness to a metal.

It is a figure which showed the enlarged cross section of the pad part of the semiconductor device which has a bump. It is a figure which showed the detailed manufacturing method of the semiconductor device which has a bump. It is an enlarged sectional view of the pad part of the semiconductor device which shows the Example of this invention. It is sectional drawing of the coil component of the inductor device which shows the Example of this invention.

(A) An alkali-soluble resin containing at least one selected from the group consisting of a polybenzoxazole precursor, a polyimide precursor, a polyamide-imide precursor, a polyimide, and two or more copolymers selected from them, and ( B) contains a phenol resin, (C) a triarylsulfonium salt, and (D) a naphthoquinonediazide compound.
The alkali-soluble resin (A) has an aliphatic group and has an aliphatic group.
The content ratio of (B) phenol resin is 30% or more and 70% or less with respect to the total weight of (A) alkali-soluble resin and (B) phenol resin 100%.
A photosensitive resin in which the content ratio of the (C) triarylsulfonium salt is 12.5% or more and 56.0% or less with respect to 100% of the total weight of the (C) triarylsulfonium salt and the (D) naphthoquinonediazide compound. Composition.

The photosensitive resin composition contains at least one selected from the group consisting of (A) polybenzoxazole precursor, polyimide precursor, polyamide-imide precursor, polyimide and two or more copolymers selected from them. Contains an alkali-soluble resin (hereinafter, may be referred to as "(A) alkali-soluble resin").

Alkali-soluble in the present invention means that a solution of a resin dissolved in γ-butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a film thickness of 10 μm ± 0.5 μm. The dissolution rate obtained from the film thickness reduction when the membrane is immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ± 1 ° C. for 1 minute and then rinsed with pure water is 50 nm / min or more. Say that.

As the alkali-soluble resin (A), known ones can be contained.

The alkali-soluble resin (A) preferably has an acidic group in the structural unit of the resin and / or at the end of the main chain. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group. Having such an acidic group can impart good alkali solubility.

Further, the alkali-soluble resin (A) has an aliphatic group.
The aliphatic group has at least one organic group of an alkylene group, a cycloalkylene group, an oxyalkylene group and an oxycycloalkylene group.

The alkali-soluble resin (A) preferably has a structural unit represented by the following general formula (1) and / or general formula (2). It may also have other structural units. Examples of other structural units in such a case include, but are not limited to, a cardo structure and a siloxane structure. When further having other structural units, it is preferable to have the structural units represented by the general formula (1) and / or the general formula (2) in an amount of 50 mol% or more of the total number of structural units.

In the general formula (1), X and Y each represent a 2-8 valent organic group having 2 to 3000 carbon atoms independently. R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. r and s represent integers in the range 0-2, p and q represent integers in the range 0-4, and r + q> 0.

In the general formula (2), X ₂ and Y ₂ each represent a 2-8 valent organic group having 2 to 3000 carbon atoms independently. R ³ and R ⁴ independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. t and u represent integers in the range 0-4, and t + u> 0.
Further, the aliphatic group is preferably represented by the general formula (3).

In the general formula (3), R ^{5 to} R ⁸ independently represent an alkylene group having 1 to 6 carbon atoms. R ^{9 to} R ¹⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms. However, the structures shown in parentheses are different. x, y, and z each independently represent an integer of 0 to 35, and x + y + z> 0.

Since the alkali-soluble resin (A) has an aliphatic group, the cured film obtained by curing the resin composition containing the (A) alkali-soluble resin has high elongation.
Further, since the alkali-soluble resin (A) has an aliphatic group, the aliphatic group has low ultraviolet absorption, and its introduction improves i-ray transparency and can realize high sensitivity at the same time.

The alkali-soluble resin (A) preferably has a weight average molecular weight of 10,000 or more and 50,000 or less. When the weight average molecular weight is 10,000 or more, the mechanical properties after curing can be improved, which is preferable, and more preferably 20,000 or more. On the other hand, when the weight average molecular weight is 50,000 or less, the developability with an alkaline aqueous solution can be improved, which is preferable.

The weight average molecular weight (Mw) can be confirmed by using GPC (gel permeation chromatography). It can be obtained by measuring using N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) as a developing solvent and calculating in terms of polystyrene.

The alkali-soluble resin (A) preferably has a structural unit represented by the general formula (1). In the general formula (1), (OH) p-X- (COOR ¹ ) r represents an acid residue. X is a divalent to octavalent organic group having 2 to 3000 carbon atoms, and more preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or an aliphatic group.

Examples of the acid component include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid as examples of dicarboxylic acids, and trimerits as examples of tricarboxylic acids. Examples of tetracarboxylic acids such as acids, trimesic acids, diphenyl ether tricarboxylic acids, biphenyl tricarboxylic acids are pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyl. Tetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2 , 2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1- Bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) Methan, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis (3,4-dicarboxyphenyl) fluorene, 9,9-bis {4 -(3,4-Dicarboxyphenoxy) phenyl} fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetra Carous acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane and aromatic tetracarboxylic acid having the structure shown below, butane tetracarboxylic acid, cyclobutane tetracarboxylic acid, 1, 2, 3, Examples include, but are not limited to, aliphatic tetracarboxylic acids such as 4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

R ¹⁷ represents an oxygen atom, C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ . R ¹⁸ and R ¹⁹ represent a hydrogen atom or a hydroxyl group.
These acids can be used as is or as acid anhydrides, halides and active esters.

Further, (OH) q-Y- (COOR ² ) s in the general formula (1) represents a diamine residue. Y is a divalent to octavalent organic group having 2 to 3000 carbon atoms, and more preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or an aliphatic group.

Specific examples of the amine used in the (A) alkali-soluble resin include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and the like. 1,4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis { 4- (4-Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4 '-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4, 4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 9,9 -Bis (4-aminophenyl) fluorene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane or at least some of the hydrogen atoms in these aromatic rings were substituted with alkyl or halogen atoms. Examples include, but are not limited to, compounds, aliphatic cyclohexyldiamines, methylenebiscyclohexylamines and diamines having the structures shown below. Two or more of these may be used.

R ¹⁷ represents an oxygen atom, C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ . R ^{18 to} R ²¹ independently represent a hydrogen atom or a hydroxyl group, respectively.

These can be used as diamines or as the corresponding diisocyanate compounds, trimethylsilylated diamines.

(A) The alkali-soluble resin has an aliphatic group. Then, it is preferable that X and / or Y in the general formula (1) and / or the general formula (2) have an aliphatic group. Further, it is more preferable that those aliphatic groups are aliphatic groups represented by the general formula (3).

By having the aliphatic group represented by the general formula (3) in X and / or Y in the general formula (1) and / or the general formula (2), the adhesiveness of the substrate to the metal (for example, copper) is improved. Can be made to. Specifically, since an interaction such as a coordination bond can be obtained between the ether group contained in the general formula (3) and the metal, high adhesiveness to the metal of the substrate can be obtained.

Specific examples of the acid having an aliphatic group include cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, and tetrafluorosuccin. Acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2 , 2-Dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimeric acid, 2,2 , 6,6-tetramethylpimelic acid, suberic acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid , Pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid, eikosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosane Examples thereof include aliphatic dicarboxylic acids such as diacid, octacosandioic acid, nonacosanedioic acid, triacanthodiic acid, hentoriacontanedioic acid, dotriacontandioic acid and diglycolic acid.

The aliphatic group is preferably contained in the total acid residue in an amount of 5 to 40 mol%, more preferably 10 to 30 mol%. By including the aliphatic group in this range, the developability when developing with an alkaline aqueous solution is enhanced, and the elongation of the cured film obtained by heating is improved.

Specific examples of the diamine having an aliphatic group include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, and 2-methyl-. 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-Diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1, 4-Bis (Aminomethyl) Cyclohexane, 4,4'-Methylenebis (Cyclohexylamine), 4,4'-Methylenebis (2-Methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP- 409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, and the like (these trade names are manufactured by HUNTSMAN Co., Ltd.) and the like can be mentioned. In addition, -S-, -SO-, -SO _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ )-, -N (CH ₂ CH ₂ CH ₃ )-, -N (CH) (CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, -NHCONH- and the like may be included. Among these, a diamine having an aliphatic group represented by the general formula (2) is preferable, and for example, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D. -200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009 , RT-1000, HE-1000, HT-1100, HT-1700, (the above trade names, manufactured by HUNTSMAN Co., Ltd.) and the like are preferable.

The aliphatic group is preferably contained in the total diamine residue in an amount of 5 to 40 mol%, more preferably 10 to 30 mol%. By including the aliphatic group in this range, the developability when developing with an alkaline aqueous solution is enhanced, and the elongation of the cured film obtained by heating is improved.

Further, the alkali-soluble resin (A) may contain an aliphatic group having a siloxane structure as long as the heat resistance is not lowered, whereby the adhesiveness to the substrate can be improved. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like. .. When it contains 1 mol% or more, it is preferable from the viewpoint of improving the adhesiveness with a substrate such as a silicon wafer, and when it contains 15 mol% or less, it is preferable from the viewpoint that the solubility in an alkaline solution is not lowered.

Further, the alkali-soluble resin (A), which is an alkali-soluble resin, is preferably a resin having an acidic group at the end of the main chain. Such a resin can be obtained by sealing the end of the alkali-soluble resin with a known monoamine having an acidic group, an acid anhydride, an acid chloride, or a monocarboxylic acid.
(A) The alkali-soluble resin can be produced by a known method.
As a method for producing a polybenzoxazole precursor, for example, it can be obtained by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction. Specifically, a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a bisaminophenol compound thereto, or a dicarboxylic acid in a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. For example, a solution of dichloride is dropped. Further, it may have an imide precursor structure or an imide structure. In that case, the content ratio of the imide precursor structure or the imide structure in the polybenzoxazole precursor is 100 parts by weight. Is preferably 101 to 10,000 parts by weight.

As a method for producing a polyimide precursor, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, a diester is obtained with a tetracarboxylic acid dianhydride and an alcohol, and then in the presence of an amine and a condensing agent. It can be synthesized by a method of reacting with, a method of obtaining a diester with a tetracarboxylic acid dianhydride and an alcohol, and then acid chlorideizing the remaining dicarboxylic acid and reacting with an amine. When having a benzoxazole precursor structure, the benzoxazole precursor structure is introduced into the polyimide precursor by using a diamine having a benzoxazole precursor in advance or by applying the method for producing a polybenzoxazole precursor. Can be done. In that case, when the imide precursor structure in the polyimide precursor is 100 parts by weight, the content ratio of the benzoxazole precursor structure is preferably 1 to 99 parts by weight.

As a method for producing a polyamideimide precursor, for example, tricarboxylic acid is first made into an acid anhydride, and the remaining carboxylic acid is reacted with a dehydration condensing agent such as acid chloride or dicyclohexylcarbodiimide (DCC) to react with an amine. Can be synthesized. When having a benzoxazole precursor structure, the benzoxazole precursor structure is introduced into the polyamideimide precursor by using a diamine having a benzoxazole precursor in advance or by applying the method for producing a polybenzoxazole precursor. be able to. In that case, when the imide precursor structure in the polyamide-imide precursor is 100 parts by weight, the content ratio of the benzoxazole precursor structure is preferably 50 to 10,000 parts by weight.

The method for producing polyimide can be obtained by reacting an acid dianhydride with a diamine and dehydrating and ring-closing the polyimide by heating or a chemical treatment such as an acid or a base, but the method is not limited to this.

The photosensitive resin composition may contain other alkali-soluble resin in addition to (A) alkali-soluble resin. Specific examples thereof include polybenzoxazoles, phenol resins, polymers of radically polymerizable monomers having an alkali-soluble group, siloxane polymers, cyclic olefin polymers, and cardo resins. These resins may be used alone or in combination of a plurality of resins. In that case, when the total amount of the alkali-soluble resin (A) and the other alkali-soluble resin is 100 parts by weight, the content ratio of the other alkali-soluble resin is preferably 1 to 50 parts by weight.

From the viewpoint of coatability, the alkali availability resin (A) preferably contains 5 parts by weight to 40 parts by mass with respect to the total amount of the photosensitive resin group organisms.

The photosensitive resin composition contains (B) a phenol resin.
Examples of the phenol resin (B) include novolak phenol resin and resolphenol resin.
From the viewpoint of improving the sensitivity, the content ratio of the (B) phenol resin in the photosensitive resin composition is 30% or more with respect to the total weight of the (A) alkali-soluble resin and the (B) phenol resin of 100%. , 60% or more is preferable. On the other hand, from the viewpoint of improving the elongation, the content ratio of the (B) phenol resin in the photosensitive resin composition is 70% with respect to the total weight of the (A) alkali-soluble resin and the (B) phenol resin of 100%. It is less than or equal to 60% or less.
The phenol resin (B) is obtained by polycondensing various phenols alone or a mixture thereof with an aldehyde such as formalin by a known method.

Examples of the phenols constituting the novolak phenol resin and the resolephenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. , 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2 , 4,5-trimethylphenol, methylenebisphenol, methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol , Α-naphthol, β-naphthol and the like, which can be used alone or as a mixture of multiples.

In addition to formalin, examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, which can be used alone or as a mixture of a plurality of aldehydes.

The preferred weight average molecular weight of the (B) phenol resin is 2,000 to 50,000, preferably 3,000 to 40,000 in terms of polystyrene by GPC (gel permeation chromatography).

The photosensitive resin composition contains (C) a triarylsulfonium salt. By including the triarylsulfonium salt (C), the sensitivity and the stability after exposure can be improved.
From the viewpoint of increasing sensitivity, the compound represented by the general formula (4) is preferable as the triarylsulfonium salt.

In the general formula (4), R ²² to R ²⁴ may be the same or different, respectively, and indicate a monovalent organic machine having 1 to 20 carbon atoms. R ²⁵ represents a monovalent organic machine having 1 to 20 carbon atoms. a, b, and c independently represent integers from 0 to 5, respectively.
Further, from the viewpoint of increasing sensitivity, the compound (C) in which the triarylsulfonium salt is represented by the general formula (5) is more preferable.

In the general formula (5), R ²⁶ represents a monovalent organic machine having 1 to 20 carbon atoms.

Specific examples of the (C) triarylsulfonium salt are shown below, but are not limited thereto.

The content of the (C) triarylsulfonium salt is preferably in the range of 2.5 to 14 parts by weight with respect to 100 parts by weight of the total amount of the (A) alkali-soluble resin and (B) phenol resin.

The photosensitive resin composition contains (D) a naphthoquinone diazide compound. By containing the (D) naphthoquinone diazide compound, the photosensitive resin composition can be imparted with photosensitivity.

As the (D) naphthoquinone diazide compound, a naphthoquinone diazidosulfonyl ester compound in which the sulfonic acid of naphthoquinone diazidosulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is preferable.

Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP. -PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, Asahi Organic Materials Industry (trade name, Asahi Organic Materials Industry) Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate Examples thereof include esters, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.). A naphthoquinone diazide sulfonyl ester compound obtained by introducing 4-naphthoquinone diazido sulfonic acid or 5-naphthoquinone diazido sulfonic acid into these compounds having a phenolic hydroxyl group by an ester bond is exemplified as a preferable compound, but other compounds may be used. You can also.

Further, it is preferable that 50 mol% or more of the total phenolic hydroxyl group of the compound having a phenolic hydroxyl group is naphthoquinonediazidesulfonyl esterified. By using a naphthoquinone diazide compound in which 50 mol% or more of the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group is sulfonyl esterified, the affinity of the naphthoquinone diazide compound with respect to the alkaline aqueous solution is lowered, and the resin in the unexposed portion is used. The solubility of the composition in an alkaline aqueous solution is greatly reduced, and the naphthoquinone diazide structure portion of the naphthoquinone diazidosulfonyl group is changed to indencarboxylic acid by exposure to obtain a large dissolution rate of the resin composition in the exposed portion in the alkaline aqueous solution. As a result, the dissolution rate ratio of the exposed portion and the unexposed portion of the composition can be increased, and a pattern can be obtained with high resolution. By using such a naphthoquinone diazide compound, it is possible to obtain a resin composition having positive photosensitivity that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general mercury lamp. it can. Further, the photosensitive compound may be used alone or in combination of two or more, and a resin composition having high sensitivity can be obtained.

As the group having the naphthoquinone diazide structure, any of 5-naphthoquinone diazidosulfonyl group and 4-naphthoquinone diazidosulfonyl group is preferably used. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure and all-wavelength exposure. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound in which a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group are used in combination in the same molecule can also be used, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound can be used. Can also be used together.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.

The molecular weight of (D) naphthoquinone diazide is preferably 300 or more, more preferably 350 or more, preferably 3,000 or less, more preferably 3,000 or less, from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment. It is 1,500 or less.

The content of the compound (D) is preferably in the range of 11 parts by weight to 26 parts by weight with respect to the total amount of the (A) alkali-soluble resin and (B) phenol resin from the viewpoint of increasing sensitivity. Further, it is more preferably contained in the range of 15 to 20 parts by weight.

The content ratio of the (C) triarylsulfonium salt is preferably 12.5% or more with respect to 100% of the total weight of the (C) triarylsulfonium salt and the (D) naphthoquinonediazide compound. On the other hand, the content ratio of the (C) triarylsulfonium salt is 56.0% or less and 41.0% or less with respect to the total weight of the (C) triarylsulfonium salt and the (D) naphthoquinonediazide compound of 100%. Is preferable, and 35% or less is more preferable. Within this range, high sensitivity can be achieved while maintaining adhesion and elongation with the metal substrate.

Further, in order to improve the adhesiveness with the base substrate such as a silicon wafer, 0.5 to 10 parts by weight of a silane coupling agent, a titanium chelating agent, etc. are added to 100 parts by weight of the photosensitive resin composition, or the base substrate is added. It can also be pretreated with such a chemical solution.

When added to the photosensitive resin composition, 0 silane coupling agents such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, titanium chelating agents, and aluminum chelating agents are added to 100 parts by weight of the photosensitive resin composition. Add 5 to 10 parts by weight.

When treating the substrate, 0.5 to 20 of the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. The dissolved solution is surface-treated by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, the reaction between the substrate and the coupling agent can be allowed to proceed by subsequently applying a temperature of 50 to 300 ° C.

Further, in order to improve the elongation characteristics of the film after curing after the reliability evaluation and the adhesiveness with the metal material, 0.1 to 10 parts by weight of a hindered phenol compound or the like is added to the photosensitive resin composition. You can also do it.

The photosensitive resin composition preferably contains a known cross-linking agent. The cross-linking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group. The amount of the cross-linking agent added is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A).

The photosensitive resin composition preferably contains a solvent. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2. -Polar aprotonic solvents such as imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate. Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

The content of the solvent is preferably 100 parts by weight or more in order to dissolve the composition in 100 parts by weight of the alkali-soluble resin (A), and 1,500 in order to form a coating film having a film thickness of 1 μm or more. It is preferably contained in an amount of parts by weight or less.

Further, the resin composition may contain a dissolution modifier within a range that does not increase the shrinkage rate after curing. As the dissolution modifier, any compound such as a polyhydroxy compound, a sulfonamide compound, and a urea compound, which is generally used as a dissolution modifier in a positive resist, can be preferably used. In particular, a polyhydroxy compound, which is a raw material for synthesizing a quinonediazide compound, is preferably used.

The viscosity of the photosensitive resin composition is preferably 2 to 5,000 mPa · s. The viscosity can be measured using an E-type rotational viscometer. By adjusting the solid content concentration so that the viscosity is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5,000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. A photosensitive resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by weight.

Next, a method of forming a heat-resistant resin pattern as a cured film obtained by curing the photosensitive resin composition will be described.

First, the photosensitive resin composition is applied to the substrate. As substrates, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, composite substrates of silicon wafers and sealing resins such as epoxy resins, and circuit constituent materials were arranged on these substrates. Examples include, but are not limited to these. Examples of organic circuit boards include glass substrate copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass non-woven fabrics and epoxy copper-clad laminates, temporary carrier substrates, and polyetherimides. Examples thereof include heat-resistant and thermoplastic substrates such as resin substrates, polyether ketone resin substrates and polysulfone-based resin substrates, flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates.

Examples of inorganic circuit boards include ceramic substrates such as glass substrates, alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit constituent materials are conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and highs. Examples thereof include a high-dielectric material containing inorganic particles having a dielectric constant, an insulator containing a glass-based material, and the like.

As a coating method, rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater A method such as ter can be mentioned. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm. In the case of a photosensitive uncured sheet, it is then dried and peeled off.

In order to enhance the adhesiveness between a substrate such as a silicon wafer and the photosensitive resin composition, the substrate can also be pretreated with the above-mentioned silane coupling agent. For example, a solution prepared by dissolving 0.5 to 20% by weight of a silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. Surface treatment by spin coating, dipping, spray coating, steam treatment, etc. In some cases, heat treatment is then performed at 50 ° C. to 300 ° C. to allow the reaction between the substrate and the silane coupling agent to proceed.

Next, the substrate on which the photosensitive resin composition is applied is dried to obtain a photosensitive resin composition coating. Drying is preferably carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like.

Next, a chemical line is irradiated and exposed through a mask having a desired pattern on the above-mentioned photosensitive resin composition coating. The chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. ..

To form a pattern, after exposure, a developer is used to remove the exposed area in the case of a positive type. The developing solution includes tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethyl. A solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable.

In some cases, these alkaline solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several types. Good.

Development can be carried out by a method such as spraying the above-mentioned developer on the film surface, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. After development, it is preferable to rinse with water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.

After development, a temperature of 150 ° C. to 500 ° C. is applied to allow the thermal cross-linking reaction to proceed to obtain a cured film. By cross-linking, heat resistance and chemical resistance can be improved. As the method of this heat treatment, a method of selecting a certain temperature and gradually raising the temperature, or a method of selecting a certain temperature range and continuously raising the temperature for 5 minutes to 5 hours can be selected. As an example of the former, there is a method of heat treatment at 130 ° C. and 200 ° C. for 30 minutes each. As an example of the latter, there is a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours. The curing conditions in the present invention are preferably 150 ° C. or higher and 350 ° C. or lower.

The cured film formed by the photosensitive resin composition was arranged as a semiconductor device, more preferably a semiconductor device arranged as an interlayer insulating film between rewiring, or an electronic component, more preferably as an interlayer insulating film between rewiring. It can be used for electronic components. Specifically, it is suitably used for applications such as a passivation film for a semiconductor, a surface protective film for a semiconductor element, an interlayer insulating film, an interlayer insulating film for multilayer wiring for high-density mounting, and an insulating layer for an organic electric field light emitting element. It is not limited to, and can take various structures.

Next, an application example of the photosensitive resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings (Application Example 1). FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump of the present invention. As shown in FIG. 1, in the silicon wafer 1, a passivation film 3 is formed on an aluminum (hereinafter, Al) pad 2 for input / output, and a via hole is formed in the passivation film 3. Further, an insulating film 4 is formed on this as a pattern by the photosensitive resin composition of the present invention, and further, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, electroplating or the like. Metal wiring (Al, Cu, etc.) 6 is formed in the above. The metal film 5 etches the periphery of the solder bump 10 to insulate between the pads. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. The photosensitive resin composition of the insulating film 7 can be thick-filmed on the scribe line 9. When the flexible component is introduced into the photosensitive resin composition, the warp of the wafer is small, so that exposure and transportation of the wafer can be performed with high accuracy. Further, since the resin of the present invention is also excellent in high elongation, the stress from the sealing resin can be relaxed even at the time of mounting by deforming the resin itself, so that bumps, wirings, and low-k layers are damaged. It is possible to provide a highly reliable semiconductor device.

Next, FIG. 2 shows a detailed manufacturing method of the semiconductor device. As shown in 2a of FIG. 2, an Al pad 2 for input / output and a passivation film 3 are formed on the silicon wafer 1, and an insulating film 4 is formed as a pattern by the photosensitive resin composition of the present invention. Subsequently, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and as shown in 2c of FIG. 2, the metal wiring 6 is plated. Form a film. Next, as shown in 2d'of FIG. 2, the photosensitive resin composition of the present invention is applied, and the insulating film 7 is formed as a pattern as shown in 2d of FIG. 2 through a photolithography step. Wiring (so-called rewiring) can be further formed on the insulating film 7. When forming a multi-layer wiring structure having two or more layers, by repeating the above steps, rewiring of two or more layers is separated by an interlayer insulating film obtained from the resin composition of the present invention. The structure can be formed. At this time, the formed insulating film comes into contact with various chemicals a plurality of times, but the insulating film obtained from the resin composition of the present invention has excellent adhesiveness, so that a good multilayer wiring structure can be obtained. Can be formed. There is no upper limit to the number of layers in the multi-layer wiring structure, but those with 10 or less layers are often used.

Next, as shown in 2e and 2f of FIG. 2, the barrier metal 8 and the solder bump 10 are formed. Then, dicing along the last scribe line 9 and cutting into chips.

Next, an application example 2 to a semiconductor device having bumps using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 3 is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film of the present invention, and has a structure called a fan-out wafer level package (fan-out WLP). Similar to the above application example 1, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced, cut into chips, and then sealed with the resin 11. An insulating film 4 is formed as a pattern by the photosensitive resin composition of the present invention over the sealing resin 11 and the chip, and further, a metal (Cr, Ti, etc.) film 5 and a metal wiring 6 are formed. After that, the barrier metal 8 and the solder bump 10 are formed in the opening of the insulating film 7 formed on the sealing resin outside the chip. In the fan-out WLP, an expansion portion is provided around the semiconductor chip using a sealing resin such as epoxy resin, rewiring is performed from the electrode on the semiconductor chip to the expansion portion, and a solder ball is also mounted on the expansion portion. It is a semiconductor package that secures the required number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material made of two or more kinds of materials such as a semiconductor chip with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film.

Further, the fan-out WLP is arranged as an interlayer insulating film between rewiring on the support substrate on which the temporary attachment material is arranged, and after the silicon chip and the sealing resin are arranged on the support substrate, the temporary attachment material is arranged. There is a type of package created in the process of peeling off the board and rewiring. In this type of package, a glass substrate or the like, which is more easily warped than a silicon wafer, is often used as the support substrate, so it is preferable that the insulating film has a low stress.

In addition to this, in a type of semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. .. Also in this embodiment, an interlayer insulating film is formed on a base material made of two or more kinds of materials, and wiring is formed on the interlayer insulating film. The cured film obtained by curing the resin composition of the present invention has high elongation and high adhesive strength to a semiconductor chip provided with metal wiring, and also has high adhesive strength to a sealing resin to an epoxy resin or the like. Therefore, it is suitably used as an interlayer insulating film provided on a base material made of two or more kinds of materials.

Further, in the fan-out WLP, the miniaturization of rewiring is progressing. Since the cured film of the photosensitive resin composition of the present invention has high metal adhesiveness even for wiring in which the width of the metal wiring and the distance between adjacent wirings are 5 μm or less, it is suitably used for fine rewiring.

Next, an application example 3 of the inductor device to a coil component using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 4 is a cross-sectional view of a coil component having an insulating film of the present invention. As shown in FIG. 3, an insulating film 13 is formed on the substrate 12, and an insulating film 14 is formed as a pattern on the insulating film 13. Ferrite or the like is used as the substrate 12. The photosensitive resin composition of the present invention may be used for either the insulating film 13 or the insulating film 14. A metal (Cr, Ti, etc.) film 15 is formed at the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 16 is plated and formed on the metal (Cr, Ti, etc.) film 15. The metal wiring (Ag, Cu, etc.) 16 is formed on a spiral. By repeating the steps of forming 13 to 16 a plurality of times and laminating them, the function as a coil can be provided. Finally, the metal wiring (Ag, Cu, etc.) 16 is connected to the electrode 18 by the metal wiring (Ag, Cu, etc.) 17, and is sealed by the sealing resin 19.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in each Example and Comparative Example will be described. For the evaluation, a photosensitive resin composition (hereinafter referred to as varnish) filtered with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Molecular Weight Measurement, Imidization Rate Measurement The weight average molecular weight (Mw) of the resin was confirmed using a GPC (gel permeation chromatography) apparatus Waters2690-996 (manufactured by Japan Waters Co., Ltd.). The developing solvent was measured as N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and the weight average molecular weight (Mw) and the degree of dispersion (PDI = Mw / Mn) were calculated in terms of polystyrene.

Regarding the imidization ratio of the resin, a solution of the resin dissolved in γ-butyl lactone was spin-coated on a silicon wafer and dried at 120 ° C. for 3 minutes to obtain a coating film having a film thickness of 5 μm, and an infrared absorption spectrum was obtained. It was measured, the absorption peak (1780 cm around ^-1, 1377 cm around ^-1) of an imide structure confirmed the presence of. Next, the coating film was heat-treated at 350 ° C. for 1 hour, the imidization rate was taken as a sample of 100%, the infrared absorption spectrum was measured, and the peak intensities ^{of the resin around 1377 cm -1 before and after the heat treatment were compared.} The content of imide groups in the resin before heat treatment was calculated, and the imidization rate was determined. For the measurement of the infrared absorption spectrum, "FT-720" (trade name, manufactured by HORIBA, Ltd.) was used as a measuring device.

(2) Photosensitivity evaluation A varnish is applied onto a 12-inch silicon wafer by a spin coating method so that the film thickness after prebaking T1 (film thickness after prebaking) = 8.5-9.0 μm, and then a hot plate (Tokyo). A photosensitive resin film was obtained by prebaking at 120 ° C. for 3 minutes using a coating / developing device ACT12) manufactured by Electron Limited. The film thickness was measured using a film thickness measuring device (optical interference type film thickness measuring device VM-1210 manufactured by SCREEN Co., Ltd.). A reticle with a cut pattern was set in an exposure machine (Canon i-line stepper FPA-5500iZ), and the photosensitive resin film was exposed to the i-line at a strength of 365 nm for a predetermined time. Using a developing device of ACT12 manufactured by Tokyo Electron Limited, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 rpm. After that, it was allowed to stand at 0 rotation for 50 seconds. The developer was shaken off, tetramethylammonium hydroxide was sprayed again, and the mixture was allowed to stand for 50 seconds. After that, the mixture was rinsed with water at 400 rpm, shaken off at 3,000 rpm for 10 seconds, and dried. By repeating changing the exposure time in the above exposure and development, the minimum exposure amount (Eth) at which the 50 μm pad pattern after development opens to 50 μm was determined. Eth is very good if 500 mJ / cm ² or less (A), if larger 600 mJ / cm ² or less than 500 good (B), variable if larger 700 mJ / cm ² or less than 600 (C), 700mJ If it is larger than / cm ^2, it is considered as defective (D).

(3) Evaluation of Elongability Apply varnish on an 8-inch silicon wafer by spin coating using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes is 11 μm. Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to 220 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 220 ° C. for 1 hour. I did. When the temperature became 50 ° C. or lower, the wafer was taken out and immersed in 45% by weight of hydrofluoric acid for 5 minutes to peel off the film of the resin composition from the wafer. This film is cut into strips having a width of 1 cm and a length of 9 cm, and using Tencilon RTM-100 (manufactured by Orientec Co., Ltd.), the tensile speed is 50 mm / at room temperature of 23.0 ° C. and humidity of 45.0% RH. It was pulled in minutes and the break point elongation was measured. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was calculated from the results. A breaking point elongation value of 50% or more was regarded as extremely good (A), a breaking point elongation value of 30% or more and less than 50% was regarded as good (B), and a breaking point elongation value of less than 30% was regarded as defective (C).

(4) Evaluation of metal adhesiveness A substrate (copper-plated substrate) having a metal material layer having a copper plating film having a thickness of 2 μm formed by sputtering titanium and copper on a silicon wafer at 100 nm and then electroplating is prepared. did. Varnish was applied onto this substrate by a spin coating method using a spinner (manufactured by Mikasa Co., Ltd.), and then baked at 120 ° C. for 3 minutes using a hot plate (D-SPIN manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a prebake film having a thickness of 8 μm was prepared. Using a clean oven (CLH-21CD-S manufactured by Koyo Thermosystem Co., Ltd.), these films were heated at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less), and then further heated to 220 ° C. It was cured for 1 hour to obtain a photosensitive resin cured film. Using a single-edged blade, 10 rows and 10 columns of grid-shaped cuts were made in the cured film at 2 mm intervals. The number of cells peeled out of 100 cells by peeling with cellophane tape (registered trademark) was counted, and the adhesive properties between the metal material / resin cured film before the PCT treatment were evaluated.
The one with 0 squares before the PCT treatment was regarded as extremely good (A), the one with 1 to 9 squares was regarded as good (B), and the one with 10 or more squares was regarded as defective (C).
Further, when the PCT treatment was performed for 100 hours and 400 hours under a saturation condition of 121 ° C. and 2 atm using a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabyes PICT Co., Ltd.), the above-mentioned A peeling test was performed. Those having 0 squares after the PCT treatment were regarded as extremely good (A), those having 1 to 9 squares were regarded as good (B), and those having 10 or more squares were regarded as defective (C).

Synthesis Example 1 Synthesis of Acid A 27.2 g (0.4 mol) of imidazole was placed in a 250 ml three-necked flask under a nitrogen stream, 100 g of methylene chloride was added, and the mixture was stirred at room temperature. This is cooled to -5 ° C or lower, and the temperature of the reaction solution does not exceed 0 ° C in a liquid in which 29.5 g (0.1 mol) of 4,4'-diphenyl ether dicarboxylic acid dichloride is dispersed in 100 g of methylene chloride. In this way, it was added dropwise over 1 hour. After the dropping, the reaction solution was stirred at room temperature for another 3 hours, and the precipitate formed during the reaction was filtered. The filtered precipitate was washed with pure water several times and dried in a vacuum oven at 50 ° C. for 100 hours to obtain acid A represented by the following formula.

Synthesis Example 2 (A) Synthesis of alkali-soluble resin (I) Under a dry nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) (11.9 g, 0. 033 mol), RT-1000 (15.0 g, 0.015 mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.62 g, 0.0025 mol) were dissolved in 100 g of NMP. Here, acid A (11.26 g, 0.038 mol), 4,4'-oxydiphthalic anhydride (2.33 g, 0.0075 mol), 5-norbornene-2,3-dicarboxylic acid (0.82 g). , 0.005 mol) was added with 25 g of NMP and reacted at 85 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (13.20 g, 0.25 mol) was added together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour. After completion of stirring, the solution was poured into 1.5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a ventilation dryer at 50 ° C. for 3 days to obtain a powder of (A) alkali-soluble resin (I). The imidization rate of the resin thus obtained was 96%. The weight average molecular weight is 36,300, and the PDI is. It was 1.9.

Synthesis Example 3 (A) Synthesis of alkali-soluble resin (II) According to Synthesis Example 3, BAHF (11.9 g, 0.033 mol), hexamethylenediamine (1.7 g, 0.015 mol), 1,3-bis (3-Aminopropyl) Tetramethyldisiloxane (0.62 g, 0.0025 mol), Acid A (11.26 g, 0.038 mol), 4,4'-oxydiphthalic acid anhydride (2.33 g, 0. 0075 mol), 5-norbornene-2,3-dicarboxylic acid (0.82 g, 0.005 mol), acetic acid (13.20 g, 0.25 mol), NMP 150 g, and (A) alkali-soluble. A powder of resin (II) was obtained. The imidization rate of the resin thus obtained was 97%. The weight average molecular weight is 36,100, and the PDI is. It was 1.9.

Synthesis Example 4 Synthesis of Resin (III) According to Synthesis Example 1, BAHF (18.31 g, 0.06 mol), Acid A (7.51 g, 0.025 mol), 4,4'-oxydiphthalic anhydride (7) The same procedure was carried out using .75 g, 0.025 mol) and 150 g of NMP to obtain a resin (XIII) powder. The imidization ratio of the polymer powder thus obtained was 59%. The weight average molecular weight is 35,100, and the PDI is. It was 1.9.

Synthesis Example 5 (B) Synthesis of phenol resin (IV) Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 37 wt% formaldehyde aqueous solution 75 After charging 5.5 g (0.93 mol of formaldehyde), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methylisobutylketone, the mixture was immersed in an oil bath and subjected to polycondensation for 4 hours while refluxing the reaction solution. A condensation reaction was carried out. Then, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is reduced to 40 to 67 hPa to remove volatile components, and the dissolved resin is cooled to room temperature to be alkaline soluble. A polymer solid of novolak resin (XV) was obtained. The Mw from GPC was 3,500. Γ-Butyrolactone (GBL) was added to the obtained novolak resin (XV) to obtain a (B) phenol resin (IV) solution as a novolak resin having a solid content concentration of 43% by weight.

Example 1
4.0 g of resin I as the obtained (A) alkali-soluble resin, 6.0 g of (B) phenol resin (IV) solution as (B) phenol resin, and (C3) (WPAG) as (C) triarylsulfonium salt. -314, trade name, manufactured by Wako Pure Chemical Industries, Ltd. 1.25 g, (D) as a naphthoquinone diazide compound (D1) (TP5-280, trade name, manufactured by Toyo Synthetic Co., Ltd.) 1.00 g, 0.50 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 0.50 g of "NIKALAC" (registered trademark) MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.), γ as a solvent A varnish was prepared by adding 20.0 g of −butyrolactone.

[Examples 2 to 12, Comparative Examples 1 to 9]
Adjusted to the ratios shown in Table 1 of (A) alkali-soluble resin, (B) phenol resin, (C) triarylsulfonium salt and (D) naphthoquinone diazide compound, HMOM-TPHAP, MW-100LM and γ-butyrolactone. I made a varnish.
The structures of (C1), (C2), (C3) and (D1) used in the examples are shown below.

The characteristics of these varnishes were measured by the above evaluation method.
The results obtained are shown in Table 2.

1 Silicon wafer 2 Aluminum pad 3 Passivation film 4 Insulation film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulation film 8 Barrier metal 9 Scribline 10 Solder bump 11 Resin 12 Substrate 13 Insulation film 14 Insulation film 15 Metal (Cr, Ti, etc.) film 16 Metal wiring (Ag, Cu, etc.)
17 Metal wiring (Ag, Cu, etc.)
18 Electrode 19 Encapsulating resin

Claims (10)

(A) An alkali-soluble resin containing at least one selected from the group consisting of a polybenzoxazole precursor, a polyimide precursor, a polyamide-imide precursor, a polyimide, and two or more copolymers selected from them, and ( B) contains a phenol resin, (C) a triarylsulfonium salt, and (D) a naphthoquinonediazide compound.
The alkali-soluble resin (A) has an aliphatic group and has an aliphatic group.
The content ratio of (B) phenol resin is 30% or more and 70% or less with respect to the total weight of (A) alkali-soluble resin and (B) phenol resin 100%.
A photosensitive resin in which the content ratio of the (C) triarylsulfonium salt is 12.5% or more and 56.0% or less with respect to 100% of the total weight of the (C) triarylsulfonium salt and the (D) naphthoquinonediazide compound. Composition. The alkali-soluble resin (A) has a structural unit represented by the general formula (1) and / or the general formula (2), and X and / or Y in the general formula (1) is the general formula (3). The photosensitive resin composition according to claim 1, which has an aliphatic group represented by.

(In the general formula (1), X and Y represent 2 to 8-valent organic groups each independently having 2 to 3000 carbon atoms. R ¹ and R ² are independently hydrogen atoms or carbons, respectively. Represents a monovalent organic group of numbers 1 to 20. R and s represent integers in the range 0-2, p and q represent integers in the range 0-4, and r + q> 0).

(In the general formula (2), X ₂ and Y ₂ each independently represent a 2-8 valent organic group having 2 to 3000 carbon atoms. R ³ and R ⁴ are independent hydrogen atoms, respectively. Alternatively, it represents a monovalent organic group having 1 to 20 carbon atoms. T and u represent integers in the range of 0 to 4, and t + u> 0.)

(In the general formula (3), R ^{5 to} R ⁸ independently represent an alkylene group having 1 to 6 carbon atoms, and R ^{9 to} R ¹⁶ independently represent a hydrogen atom, a fluorine atom, or an alkylene group having 1 to 6 carbon atoms. It represents an alkyl group. However, the structures represented in parentheses are different. X, y, and z each independently represent an integer of 0 to 35, and x + y + z> 0.) The photosensitive property according to claim 1 or 2, wherein the (D) naphthoquinone diazide compound is contained in the range of 11 to 26 parts by weight with respect to 100 parts by weight of the total amount of the (A) alkali-soluble resin and (B) phenol resin. Resin composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the triarylsulfonium salt (C) contains a compound represented by the general formula (4).

(In the general formula (4), R ²² to R ²⁴ may be the same or different, and indicate any of the monovalent organic machines having 1 to 20 ^{carbon atoms. R 25} has 1 carbon atom. Indicates a monovalent organic machine from to 20. A, b, and c each independently indicate an integer from 0 to 5.) The photosensitive resin composition according to claim 4, wherein the triarylsulfonium salt (C) contains a compound represented by the general formula (5).

(In the general formula (5), R ²⁶ represents a monovalent organic machine having 1 to 20 carbon atoms.) A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 5. An electronic component having the cured film according to claim 6. A semiconductor device having the cured film according to claim 6. An electronic component in which the cured film according to claim 6 is arranged as an interlayer insulating film between rewiring. A semiconductor device in which the cured film according to claim 6 is arranged as an interlayer insulating film between rewiring.

Images