JP2019012181A - Photosensitive resin composition, photosensitive sheet, cored film, interlayer dielectric film, semiconductor-protecting film, semiconductor apparatus manufacturing method, semiconductor electronic component, and semiconductor apparatus - Google Patents

Abstract

To provide a photosensitive resin composition capable of forming a cured film excellent in adhesion to copper and corrosion resistance of copper.SOLUTION: The photosensitive resin composition contains (a) an alkali-soluble resin and (b) a photosensitizer. The (a) alkali-soluble resin has a structural unit represented by general formula (1) and/or general formula (2). The organic group represented by Rin general formula (1) and general formula (2) includes at least one of the structures represented by general formulas (3) to (5).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition suitably used for a surface protective film such as a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, a cured film thereof, and a manufacturing method thereof.

  Polyimide resins and polybenzoxazole resins, which are excellent in heat resistance and electrical insulation, are widely used for buffer coats of semiconductor elements, insulating layers of organic electrolytic elements, and planarization films of TFT substrates. In addition, studies have been made on photosensitive polyimide imparted with photosensitivity for improving productivity and photosensitive polybenzoxazole.

  In recent years, with the miniaturization of pattern processing in semiconductor devices, miniaturization and high density of packages, and high speed and large capacity, not only polyimide is used as a buffer coat, but also multiple layers as interlayer insulation films between metal wiring There is an increasing demand for rewiring applications to be used. For this purpose, high reliability is required for adhesion between metal wiring such as copper and an interlayer insulating film, electrical characteristics and film properties when stored for a long time under high temperature and high humidity conditions. In addition, from the viewpoint of reducing the stress of the substrate and the heat resistance of the device, it is necessary to satisfy the above-described requirements for the insulating film with a cured film cured under a low-temperature curing condition of 250 ° C. or lower.

  Until now, as a polyimide for photosensitive insulating film, polyimide precursor resin having a carboxyl group or a partially esterified carboxyl group in the resin (for example, Patent Document 1), or an alkali having a hydroxy group in the resin A soluble polyimide resin (for example, Patent Document 2) has been reported.

Japanese Patent No. 4341293 JP 2007-183388 A

  However, when the polyimide precursor resin composition as in Patent Document 1 is not cured by high-temperature curing at 300 ° C. or higher, the carboxylic acid component remains in the film and is stored for a long time under high temperature and high humidity conditions. There was a risk of causing copper ion migration. Moreover, although the alkali-soluble polyimide as in Patent Document 2 can be cured at a low temperature of 250 ° C. or lower, there is a problem that when it is stored for a long time under a high temperature and high humidity condition, copper is gradually corroded and discoloration or peeling occurs. It was.

  The present inventors have found that the positional relationship between the imide group and the hydroxyl group in the resin is one of the causes of copper corrosion and discoloration observed in many polyimide resins so far, and the imide group in the resin and The inventors have found a photosensitive resin composition that can be cured at low temperature by adjusting the distance of the hydroxy group, and that can provide a cured film having excellent adhesion to copper and corrosion resistance.

  The present invention is a photosensitive sheet, a cured film, an interlayer insulating film, a semiconductor protective film, a method for manufacturing a semiconductor device, a semiconductor electronic component, and a semiconductor device using the photosensitive resin composition and the photosensitive resin composition.

  According to the photosensitive resin composition of the present invention, a cured film having high adhesion to copper and copper corrosion resistance can be obtained.

It is sectional drawing of the pad part of the semiconductor device which shows the Example of this invention. It is sectional drawing of the pad part of the semiconductor device which shows the Example of this invention. It is sectional drawing of the coil components of the inductor apparatus which shows the Example of this invention.

The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin and (b) a photosensitizer, and the (a) alkali-soluble resin is represented by the general formula (1) and / or the general formula (2). The organic group represented by R ² in the general formula (1) and the general formula (2) is selected from the group consisting of the structures represented by the general formulas (3) to (5). Including at least one selected from the group consisting of

(R ¹ in the general formula (1) represents a divalent to tetravalent organic group having 2 to 100 carbon atoms, and R ³ is either hydrogen or an organic group having 1 to 20 carbon atoms. A represents an integer satisfying 0 ≦ a ≦ 2.)

(R ⁴ in the general formula (2) represents a tetravalent organic group having 2 to 100 carbon atoms.)

(R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formulas (3) to (5) represent an organic group having 1 to 80 carbon atoms which does not contain a hydroxy group. X in the general formula (5) is hydrogen. An atom, a halogen element, or an organic group having 1 to 10 carbon atoms is shown.)
The organic group represented by R ² in the general formula (1) and the general formula (2) includes at least one selected from the group consisting of structures represented by the general formulas (3) to (5). Thus, when the cured film is stored for a long period of time under high temperature and high humidity, corrosion of metallic copper as a base can be suppressed. In this mechanism, since the distance between the carbonyl group of the acid dianhydride residue and the hydroxy group of the diamine residue is large, hydrolysis reaction due to the interaction between the carbonyl group and the hydroxy group is less likely to occur. It is assumed that this is because.

  Moreover, it is desirable that the hydroxy group in the (a) alkali-soluble resin is a phenolic hydroxy group, and the resin composition contains a phenolic hydroxyl group as represented by the general formulas (3) to (5). It is possible to improve the alkali solubility and the chemical resistance and heat resistance of the cured film.

In the present invention, alkali-soluble means that the dissolution rate is 50 nm / min or more.
Specifically, a solution in which a resin is dissolved in γ-butyrolactone is applied onto a silicon wafer,
Pre-baking at 120 ° C. for 4 minutes to form a pre-baked film with a film thickness of 10 μm ± 0.5 μm,
After immersing the pre-baked film in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ± 1 ° C. for 1 minute,
It means that the dissolution rate obtained from the decrease in film thickness when rinsed with pure water is 50 nm / min or more.

  The distance between the carbonyl group of the acid dianhydride residue in the (a) alkali-soluble resin and the hydroxy group of the diamine residue may be in the range of 0.3 nm to 5 nm when calculated by the molecular dynamics method. desirable. When the distance between the carbonyl group and the hydroxy group is within this range, a cured film having a high inhibitory effect on copper corrosion can be obtained while the resin composition has appropriate alkali solubility.

  Next, an example of a calculation method for the distance between the carbonyl group of the acid dianhydride residue and the hydroxy group of the diamine residue will be described.

  First, the molecular structure is optimized. The molecular structure is handled as a model molecule of ABA structure, where A is the acid dianhydride in the resin and B is the diamine. Using the molecular dynamics calculation program FORCITE in the molecular modeling and simulation software “Materials Studio” (manufactured by Daikin Industries, Ltd.) (force field: COMPASS II), after adjusting the three-dimensional structure, the quantum mechanical calculation program DMoL3 Used (functional: GGA-BLYP), and the structure is further adjusted. Next, the obtained structure is input to molecular orbital calculation software “Gaussian” (manufactured by Gaussian) (functional: B3LYP, basis function: 6-31G (d)) to optimize the three-dimensional structure.

  The distance between the oxygen atom of the carbonyl group of acid dianhydride A and the oxygen atom of the hydroxy group of diamine B in the structure optimized by the above method is measured. The distance can be measured by inputting the optimized molecular structure into molecular modeling software “Facio” or the like.

In the photosensitive resin composition of the present invention, among the diamine residues contained in (a) the alkali-soluble resin, the structures represented by the general formulas (3) to (5) are represented by the general formula (1) and formula (2) preferably contained 5-90 mole% of all ^{R 2} in preferred since it contained 40 to 90 mol%, the resulting higher corrosion inhibiting effect. When the content ratio of the structures represented by the general formulas (3) to (5) is within this range, the resin composition has a suitable alkali solubility and obtains a cured film having a high inhibitory effect on copper corrosion. be able to.

  In the photosensitive resin composition of the present invention, the (a) alkali-soluble resin contains a diamine having a structure other than those represented by the general formulas (3) to (5) as long as the alkali-soluble and copper corrosion-inhibiting effects are not lowered. It doesn't matter. Specifically, “Jeffamine” (registered trademark) HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D -4000, “Elastamine” (registered trademark) RP-409, RP-2009, RT-1000, HT-1100, HE-1000, HT-1700 (above, manufactured by HUNTSMAN Co., Ltd.) (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) ) Methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) Hydroxyl group-containing diamines such as biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, and thiol group-containing diamines such as dimercaptophenylenediamine 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene Diamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, 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′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, Any aromatic diamine, a compound obtained by substituting a part of hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, or a fatty acid such as cyclohexyldiamine or methylenebiscyclohexylamine. Examples thereof include cyclic diamines. These diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines.

  Among these diamines, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4′-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } Ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-Bis [4- (4-aminophenoxy) phenyl] propane Such diamines having 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds of these aromatic rings substituted with an alkyl group or a halogen atom, and an amide group as preferred. These diamines are used alone or in combination of two or more.

  In addition, an aliphatic diamine having a siloxane structure may be copolymerized within a range in which the heat resistance is not lowered, and the adhesion to the substrate can be improved. Specifically, what copolymerized 1-15 mol% of bis (3-aminopropyl) tetramethyl disiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. are mentioned.

  In the photosensitive resin composition of the present invention, (a) the acid dianhydride used for the alkali-soluble resin is specifically pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyl. Tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2, 2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) Ethane dianhydride, bis (3 4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Sulfone dianhydrides, aromatic tetracarboxylic dianhydrides such as 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, or compounds in which the hydrogen atoms of these compounds are substituted with alkyl groups or halogen atoms, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, , 4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride, 3 , 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, such as alicyclic, semi-alicyclic tetracarboxylic dianhydride and 2,2-bis (3 4-dicarboxyfe E.) Compounds containing fluorine atoms such as hexafluoropropane dianhydride, compounds in which these aromatic rings and hydrogen atoms are substituted with alkyl groups or halogen atoms, and acid dianhydrides having amide groups it can. These may be used alone or in combination of two or more.

Further, instead of the acid dianhydride, a tricarboxylic acid anhydride, a dicarboxylic acid having a structure of R ¹ (COOH) ₂ , or a dicarboxylic acid derivative having a structure of R ¹ (COZ) ₂ may be used. it can. Specific examples of the tricarboxylic acid anhydride include trimellitic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
R ^{1 of the} dicarboxylic acid and the dicarboxylic acid derivative preferably has the same structure as the acid dianhydride residue R ^{1 of the} polymer obtained from the above acid dianhydride. Z of the dicarboxylic acid derivative is a group selected from an organic group having 1 to 12 carbon atoms or a halogen element, and is preferably a group selected from the following structural formula.

(In the formula, B and C include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, and a nitro group. Not limited.)
In the photosensitive resin composition of the present invention, in order to improve the storage stability of the photosensitive resin composition, (a) the alkali-soluble resin is monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound at the main chain end, It is preferable to seal with a terminal blocking agent such as a monoactive ester compound. In addition, by sealing the terminal of the resin with a terminal sealing agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the dissolution rate of the resin in an alkaline solution and the resulting cure The mechanical properties of the membrane can be easily adjusted to a preferred range. The introduction ratio of the end-capping agent is preferably 0.1 mol% in order to prevent the molecular weight of (a) the alkali-soluble resin from being increased and the solubility in the alkali solution from being lowered with respect to the total amine component. Above, particularly preferably 5 mol% or more, (a) In order to suppress a decrease in mechanical properties of the cured film obtained by reducing the molecular weight of the alkali-soluble resin, preferably 60 mol% or less, particularly preferably 50 mol. % Or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  As monoamines, M-600, M-1000, M-2005, M-2070 (above trade names, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5- Amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy -7-aminonaphthalene, 2-carboxy-6-a Nonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  Acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc., as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds Product, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like; Mono-acid chloride compounds in which the carboxyl group is converted to acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene , Monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or imidazole, N-hydroxy-5-norbornene-2 An active ester compound obtained by reaction with 3-dicarboximide is preferred. Two or more of these may be used.

  (A) As for the weight average molecular weight of alkali-soluble resin, 3,000-80,000 are preferable in polystyrene conversion by gel permeation chromatography, More preferably, it is 8,000-50,000. If it is this range, a thick film can be formed easily.

The (a) alkali-soluble resin having the structure represented by the general formula (1) and the general formula (2) should be manufactured according to a known polyimide precursor, polyimide, polybenzoxazole precursor and polyamide manufacturing method. Can do. For example, (I) a tetracarboxylic dianhydride or tricarboxylic anhydride having a R ¹ group or a dicarboxylic acid or dicarboxylic acid derivative, a diamine compound having an R ² group, and a monoamino compound that is a terminal blocking agent are subjected to low temperature conditions. (II) A diester is obtained from a tetracarboxylic dianhydride having an R ¹ group and an alcohol, and then a diamine compound having an R ² group, a monoamino compound as a terminal blocking agent, and a condensing agent. (III) A diester is obtained from a tetracarboxylic dianhydride having an R ¹ group and an alcohol, and then the remaining two carboxyl groups are acid chlorideed to form a diamine compound having an R ² group, end-capping The method of making it react with the monoamino compound which is an agent can be mentioned.

  It is desirable to isolate the alkali-soluble resin (a) polymerized by the above method by adding it to a large amount of water or a methanol / water mixture, causing it to precipitate, filtering, drying and isolating. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved. Moreover, after imidating the polyimide precursor and ring-closing polyimide, after obtaining said polyimide precursor, it can synthesize | combine using the method of making a well-known imidation reaction.

Hereinafter, an example of a method for producing a polyimide precursor will be described as a preferred example of (I). First, a diamine compound having an R ² group is dissolved in a polymerization solvent. To this solution, a tetracarboxylic dianhydride having an R ¹ group in a substantially equimolar amount with the diamine compound is gradually added. Using a mechanical stirrer, the mixture is stirred at -20 to 100 ° C, preferably 10 to 50 ° C for 0.5 to 100 hours, more preferably 2 to 24 hours. When using an end-capping agent, after adding tetracarboxylic dianhydride, stirring at the required temperature and time, the end-capping agent may be added gradually or added all at once to react. You may let them.

  It is also possible to change the alkali-soluble resin from a polyimide precursor to a polyimide by stirring at 180 to 200 ° C. for 2 to 24 hours during the above production. According to the photosensitive resin composition of the present invention, a cured film having a copper corrosion inhibitory effect and high adhesion to copper can be obtained with either a polyimide precursor or polyimide, but an acid component that causes corrosion. Polyimide can obtain a higher corrosion-inhibiting effect in that there are few carbonyl groups.

  The polymerization solvent is not particularly limited as long as it can dissolve tetracarboxylic dianhydrides and diamines which are raw material monomers. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N-methyl-2-pyrrolidone amides, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ -Cyclic esters such as caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, Examples thereof include acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like.

  If the polymerization solvent is 100 parts by mass or more with respect to 100 parts by mass of the obtained (a) alkali-soluble resin, the reaction can be carried out without precipitation of raw materials and resins, and if it is 1900 parts by mass or less, the reaction is promptly performed. Since it advances, 150-950 mass parts is more preferable.

  The photosensitive resin composition of the present invention has positive or negative photosensitivity by containing (b) a photosensitizer. As the photosensitive agent, in the case of a positive type, a photoacid generator is used. In the case of the negative type, a pattern can be formed by using a polymerization initiator that generates radicals by light and reacting with a monomer having a polymerizable unsaturated bond.

  Next, the case where the photosensitive resin composition of the present invention has positive photosensitivity will be described, but the scope of the present invention is not limited thereto.

  The photoacid generator contained in the photosensitive resin composition of the present invention has a characteristic that an acid is generated when irradiated with light, and the solubility of the light-irradiated portion in an alkaline aqueous solution is increased. Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like.

  The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a sulfonic acid of quinonediazide is bonded to a polyamino compound in a sulfonamide, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound in an ester bond and / or sulfonamide. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. When the substitution with quinonediazide is 50 mol% or more, the solubility in an alkali developer is not excessively high, a contrast with an unexposed portion is obtained, and a desired pattern can be obtained. By containing such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray is obtained. Can do. Such compounds may be contained singly or in combination of two or more. Further, by containing two kinds of photoacid generators, the ratio of the dissolution rate between the exposed part and the unexposed part can be increased, and as a result, a highly sensitive photosensitive resin composition can be obtained.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.) and the like, but are not limited thereto.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Examples thereof include, but are not limited to, sulfhydrides.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the photosensitive resin composition of the present invention, the quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.

  In the photosensitive resin composition of this invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound according to the wavelength to expose. In addition, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester. A compound may be mixed and contained.

  As for the molecular weight of the quinonediazide compound which the photosensitive resin composition of this invention contains, 300-3000 are preferable. When the molecular weight of the quinonediazide compound is less than 3000, the quinonediazide compound is sufficiently thermally decomposed in the subsequent heat treatment, and the heat resistance, mechanical properties, and adhesiveness of the resulting film can be suppressed.

  The quinonediazide compound contained in the photosensitive resin composition of the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  Among the photoacid generators contained in the photosensitive resin composition of the present invention, the photoacid generator that appropriately stabilizes the acid component generated by exposure may be a sulfonium salt, a phosphonium salt, or a diazonium salt. preferable. Since the cured film obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is environmentally undesirable for phosphorus and the like to remain, and it is necessary to consider the color tone of the film. A sulfonium salt can be preferably contained. Particularly preferred is a triarylsulfonium salt, which can significantly improve the standing stability after exposure.

  In the photosensitive resin composition of the present invention, the content of the photoacid generator is based on 100 parts by mass of (a) the alkali-soluble resin having a structure represented by the general formula (1) and / or the general formula (2). The amount is preferably 0.01 to 50 parts by mass. Among these, the quinonediazide compound has a preferable range of 3-40 mass parts. Further, the compound selected from sulfonium salt, phosphonium salt and diazonium salt is preferably in the range of 0.05 to 40 parts by mass, more preferably in the range of 0.1 to 30 parts by mass. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  Furthermore, the photosensitive resin composition of the present invention preferably contains (c) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof. By containing these compounds, corrosion of copper under high temperature and high humidity conditions can be further suppressed. This mechanism is based on the fact that (c) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof are used as quenchers for the acid remaining in the cured film that causes copper corrosion. It is thought to work.

  (C) The total content of one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof is 0.005% by mass or more and 5% by mass or less in 100% by mass of the cured film. It is preferable. (C) When the total content of one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof is 0.005% by mass or more, an effect of inhibiting copper corrosion can be obtained. In addition, when the content is 5% by mass or less, swelling and elution of components hardly occur when the cured film is immersed in a chemical solution, and thus a cured film having excellent chemical resistance can be obtained. In the photosensitive resin composition for forming a cured film, the content of one or more compounds selected from the group consisting of (c) cyclic amide, cyclic urea, and derivatives thereof is alkali-soluble resin (a) 100. Preferably it is 0.1 mass part or more with respect to a mass part, More preferably, it is 1 mass part or more, Preferably it is 15 mass parts or less, More preferably, it is 10 mass parts or less. (C) A cured film having a high copper corrosion inhibition effect is obtained by setting the content of one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof to 0.1 parts by mass or more. When the content is 15 parts by mass or less, a cured film having excellent chemical resistance can be obtained.

  (C) One or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof may have a boiling point of 170 ° C. or higher from the viewpoint of easily remaining in the cured film after heat treatment. Preferably, if it is 210 ° C. or higher, it is more preferable because it is more likely to remain in the cured film. Moreover, it is preferable that a boiling point is 400 degrees C or less from a viewpoint of suppressing the nonuniformity at the time of application | coating. When the boiling point cannot be measured at normal pressure, it can be converted to the boiling point at normal pressure using a boiling point conversion table. The boiling point conversion table is shown in Science of Petroleum, Vol. II. p. 1281 (1938) is used.

  (C) One or more kinds of compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof preferably have a structure represented by the following general formula (6). You may contain.

  Specific examples of cyclic amide, cyclic urea and derivatives thereof include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone N-butyl-2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N-pentyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl -2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, N-phenyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N′-dimethylpropylene Urea, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 2-piperidone, ε-caprolacta Or the like. Among these, N-cyclohexyl-2-pyrrolidone (boiling point: 154 ° C./7 mmHg, normal pressure boiling point conversion: 305 ° C.), N- (2-hydroxyethyl) -2-pyrrolidone (boiling point: 175 ° C./10 mmHg, normal (Pressure boiling point conversion: 313 ° C.) is preferable because it has a high boiling point and tends to remain in the film after heat treatment.

  The photosensitive resin composition of the present invention may contain a solvent in addition to (c) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof. As the solvent, polar aprotic solvents such as γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, dimethylsulfoxide, tetrahydrofuran, Ethers such as dioxane, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxymethylpropanate, 3-ethoxy Examples thereof include esters such as ethyl propanate, ethyl acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

  If the content of the solvent is 100 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass of the (a) alkali-soluble resin, a photosensitive resin composition having an appropriate viscosity is obtained.

  Moreover, the photosensitive resin composition of this invention may contain the compound which has a phenolic hydroxyl group for the purpose of improving a sensitivity.

  Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ. Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26 X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Among these, preferred compounds having a phenolic hydroxyl group used in the present invention include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ. , BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F etc. are mentioned. Among these, particularly preferred compounds having a phenolic hydroxyl group are, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC -F. By containing this compound having a phenolic hydroxyl group, the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. There is little decrease, and development is easy in a short time.

  The content of the compound having a phenolic hydroxyl group is preferably 1 to 100 parts by mass of the alkali-soluble resin (a) having a structure represented by the general formula (1) and / or the general formula (2). It is 50 mass parts, More preferably, it is the range of 3-40 mass parts.

  The photosensitive resin composition of the present invention preferably contains a compound having an alkoxymethyl group, a methylol group, or an epoxy group as a thermal crosslinking agent. Since a methylol group and an alkoxymethyl group cause a crosslinking reaction in a temperature range of 100 ° C. or higher, they can be crosslinked by heat treatment to obtain a heat-resistant resin film having excellent mechanical properties.

  Examples having an alkoxymethyl group or a methylol group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMO -BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, NIKACALAC MX -280, NIKACALAC MX-270, NIKACALAC MX-279, NIKACAL MW-100LM, NIKACALAC MX-750LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.). Among these, when HMOM-TPHAP and MW-100LM containing a large number of alkoxymethyl groups are added, crosslinking efficiency is preferable.

  In addition, the epoxy group thermally crosslinks with the polymer at 200 ° C. or lower and does not cause a film shrinkage because a dehydration reaction due to crosslinking does not occur. Therefore, in addition to mechanical properties, it is effective for low temperature curing and low warpage. Examples of the compound having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) siloxane, and the like, silicone However, the present invention is not limited to these. Specifically, Epicron 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514, Epicron EXA-4880, Epicron EXA-4850-150, Epicron EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Recare Resin BEO-60E Product name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (Adeka Co., Ltd.), and the like.

  You may contain 2 or more types of these compounds which have an alkoxymethyl group, a methylol group, or an epoxy group.

  The content of the compound having an alkoxymethyl group, a methylol group, or an epoxy group is based on 100 parts by mass of (a) the alkali-soluble resin having the structure represented by the general formula (1) and / or the general formula (2). 10 to 50 parts by mass, and preferably 10 to 40 parts by mass from the viewpoint of obtaining storage stability and moderate alkali solubility.

  The photosensitive resin composition of the present invention can further contain a silane compound. By containing the silane compound, the adhesion of the heat-resistant resin film is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltri Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples include methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. The content of the silane compound is preferably 0.01 with respect to 100 parts by mass of the (a) alkali-soluble resin having at least one of the structural units represented by the general formula (1) and / or the general formula (2). It is not less than 15 parts by mass.

  In addition, the photosensitive resin composition of the present invention contains a surfactant, alcohols such as ethanol, and ketones such as cyclohexanone and methyl isobutyl ketone for the purpose of improving the wettability with the substrate, if necessary. May be. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder may be contained for the purpose of suppressing the thermal expansion coefficient, increasing the dielectric constant, and reducing the dielectric constant.

  Since the photosensitive resin composition of the present invention has an effect of inhibiting copper corrosion by the above-described copper corrosion inhibition mechanism, it is particularly preferably used as an insulating film in contact with a metal wiring containing a copper element.

  Although the photosensitive resin composition of this invention can also be used with the viscosity of 1-10,000 mPa * s, it can also be used as a photosensitive sheet | seat by removing a solvent using the below-mentioned manufacturing method. By using it as a photosensitive sheet, it is possible to improve flatness when an insulating film is formed on a step.

  Moreover, the photosensitive sheet | seat which removed the solvent from the photosensitive resin composition of this invention and the photosensitive resin composition makes it a cured film by heat-processing using the below-mentioned method. By performing the heat treatment, (a) the ring closure of the imide ring in the alkali-soluble resin, and (a) the reaction of the alkali-soluble resin and the thermal crosslinking agent in the photosensitive resin composition proceeds, insulation, heat resistance, An insulating film having chemical resistance can be obtained.

  Next, the manufacturing method of the photosensitive resin composition of this invention is illustrated. Put each of the above components, and if necessary, other components in a glass flask or stainless steel container, stir and dissolve with a mechanical stirrer, etc., dissolve with ultrasound, stir and dissolve with a planetary stirring and deaerator The method etc. are mentioned. The viscosity of the photosensitive resin composition is preferably 1 to 10,000 mPa · s. Moreover, you may filter the photosensitive resin composition with a 0.1 micrometer-5 micrometers pore size filter in order to remove a foreign material.

  Next, a method for forming a relief pattern of a cured film on a support substrate used in a semiconductor device using the photosensitive resin composition of the present invention will be described.

  The photosensitive resin body composition of this invention can be made into the relief pattern of a polyimide through the process of apply | coating and drying on a support substrate, the process of exposing, the process of developing, and the process of heat-processing.

  First, a photosensitive resin composition is applied on a support substrate. As the support substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but is not limited thereto. When the photosensitive resin composition of the present invention is processed on metallic copper, effects such as particularly high corrosion resistance can be obtained. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. The coating film thickness varies depending on the coating method, the solid content concentration of the photosensitive resin composition, the viscosity, and the like, but is generally applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the support substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, actinic radiation is irradiated on the photosensitive resin film through a mask having a desired pattern. Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are used. preferable.

  In order to form a relief pattern from the photosensitive resin film, the exposed portion may be removed using a developer after exposure. Developer is tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate An aqueous solution of a compound exhibiting alkalinity, such as cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. In some cases, polar aqueous solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol are used in these alkaline aqueous solutions. One or more kinds of alcohols such as ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added. After development, it is common to rinse with water. For the rinsing treatment, one or more alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and 3-methoxymethylpropanoate may be added to water.

  After development, a temperature of 100 ° C. to 400 ° C. is applied to convert to a cured film. This heat treatment is preferably carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. Generally, the higher the heat treatment temperature, the more the acid components and low molecular components in the cured film are volatilized, and the reliability such as heat resistance and copper corrosion resistance is improved. However, in recent years, semiconductor devices are increasingly used to form a rewiring layer on a sealing resin with low heat resistance, on a memory device, or on a chip after soldering using a photosensitive resin composition. The one where the heat processing temperature of a composition is low is preferable. Specifically, it is preferable that a highly reliable cured film can be obtained by heat treatment at 150 to 230 ° C. The photosensitive resin composition of the present invention is a photosensitive resin composition capable of obtaining a copper corrosion resistance effect and high adhesion even at a low temperature treatment of 230 ° C. or lower, and as an example, after being treated at 100 ° C. for 30 minutes. And a method of heat-treating at 200 ° C. for 1 hour, a method of linearly raising the temperature from room temperature to 200 ° C. over 1 hour, and heat-treating at 200 ° C. for 1 hour.

  Next, a method for processing the photosensitive resin composition of the present invention into a photosensitive sheet and a method for forming a relief pattern of a cured film on a support substrate used in a semiconductor device using the photosensitive sheet will be exemplified.

  The photosensitive resin composition produced as described above is applied onto a substrate, the organic solvent is removed, and a photosensitive sheet is produced. A film such as polyethylene terephthalate (PET) can be used as the substrate on which the photosensitive resin composition is applied. When it is necessary to peel and remove the base material when the photosensitive sheet is bonded to a substrate such as a silicon wafer, it is easy to use a base material with a release agent such as silicone resin coated on the surface. It is preferable because the photosensitive sheet and the substrate can be peeled off.

  Screen printing, spray coater, bar coater, blade coater, die coater, spin coater, etc. can be used as a method for applying the photosensitive resin composition onto the substrate. Examples of the method for removing the organic solvent include heating with an oven or a hot plate, vacuum drying, heating with an electromagnetic wave such as infrared rays or microwaves, and the like. Here, when the removal of the organic solvent is insufficient, the cured product obtained by the next curing treatment may be in an uncured state or may have poor thermomechanical properties.

  Although the thickness of a base material is not specifically limited, From a workability viewpoint, it is preferable that it is the range of 30-80 micrometers. Further, in order to protect the surface of the uncured sheet from dust in the atmosphere, a cover film may be bonded to the surface. Moreover, when the solid content concentration of the photosensitive resin composition is low and an uncured sheet having a desired film thickness cannot be produced, two or more photosensitive sheets after removal of the organic solvent may be bonded together.

  When laminating the photosensitive sheet produced by the above method onto another substrate, even if using a laminating device such as a roll laminator or a vacuum laminator, manually using a rubber roller on the substrate heated on the hot plate You may paste together. After bonding to the substrate, the PET film is peeled off after sufficiently cooling.

  Next, similar to the method of forming the relief pattern of the cured film using the photosensitive resin composition described above, the photosensitive sheet bonded to the substrate through a mask having a desired relief pattern is irradiated with actinic radiation and developed. After removing an exposed part using a liquid, the temperature of 100 degreeC-400 degreeC is added and it converts into a cured film.

  The cured film formed with the photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, a semiconductor passivation film, a surface protection film of a semiconductor element, an interlayer insulation film, an interlayer insulation film of a multilayer wiring for high-density mounting, a surface protection film of an inductor device, an interlayer insulation film, and an insulation layer of an organic electroluminescence element And a spacer layer, a planarization layer of a thin film transistor substrate (TFT substrate), an insulating layer of an organic transistor, and the like, but is not limited thereto, and various structures can be taken.

  Next, application example 1 to a semiconductor device having bumps using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film of the present invention. As shown in FIG. 1, a passivation film 3 is formed on an input / output Al pad 2 in a silicon wafer 1, and a via hole is formed in the passivation film 3. On this, an insulating film 4 is formed as a pattern made of the photosensitive resin composition of the present invention, and a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2. A metal wiring (Al, Cu, etc.) 6 is formed thereon. By stacking 4-6, a high-density and high-performance semiconductor device can be manufactured without increasing the chip area. Thereafter, UBM (under bump metal) 8 and solder bumps 10 are formed in the openings of the insulating film 7. The scribe line 9 is opened as a relief pattern in each layer of the insulating film 4. The substrate is diced along the scribe line and divided into one semiconductor element.

  The metal wiring 6 (Al, Cu, etc.) is called a rewiring, and the insulating films 4 and 7 function as an interlayer insulating film. By laminating a plurality of metal wiring layers and interlayer insulating films, a more complicated circuit can be formed, and a high-performance semiconductor device can be obtained.

  Next, application example 2 to the semiconductor device having bumps using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 2 is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film according to the present invention. Similar to the first application example, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced, cut into chips, and sealed with a sealing resin 11. Over the sealing resin 11 and the chip, an insulating film 4 is formed as a pattern made of the photosensitive resin composition of the present invention, and a metal (Cr, Ti, etc.) film 5 and a metal wiring 6 are further formed. Thereafter, UBMs 8 and solder bumps 10 are formed in the openings of the insulating film 7 formed on the sealing resin outside the chip.

  By using the sealing resin 11 as described above, the sealing resin 11 can be a part of the substrate when the rewiring and the interlayer insulating film are formed. Since the rewiring layer can be expanded outside the silicon chip, a more complicated circuit can be formed, and a high-performance semiconductor device can be obtained.

  Next, an application example 3 of the inductor device to the coil component using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 3 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 thereon as a pattern. As the substrate 12, ferrite or the like is used. 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 in the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 16 is formed thereon by plating. The metal wiring 16 (Ag, Cu, etc.) is formed on the spiral. The function as a coil can be given by laminating | stacking 13-16. Finally, the metal wiring 16 (Ag, Cu, etc.) is connected to the electrode 18 by the metal wiring 17 (Ag, Cu, etc.) and sealed with the sealing resin 19.

  It is important from the viewpoint of electrical reliability that the metal wiring 6 and the metal wiring 16 of FIGS. 1 to 3 maintain adhesion with the insulating film even after the high temperature and high humidity test and that no corrosion is observed. For these metal wirings, copper is widely used from the viewpoint of cost and workability, but the adhesion to the insulating film and the degree of corrosion are greatly affected by the material of the insulating film. The photosensitive resin composition of the present invention is useful in an apparatus as shown in FIGS. 1 to 3 because high adhesion and corrosion resistance can be obtained even after a high temperature and high humidity test.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. In addition, preparation and evaluation of the resin and photosensitive resin composition in an Example were performed with the following method.

(1) Production of developing film A A photosensitive resin composition was applied on an 8-inch silicon wafer by spin coating (using a coating and developing apparatus ACT-8 manufactured by Tokyo Electron Co., Ltd.), and then on a hot plate at 120 ° C. After baking for 3 minutes, a pre-baked film having a thickness of 10 μm was produced. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~1000mJ / cm ² using an i-line stepper (NIKON NSR i9). After exposure, ACT-8 is used to develop for 90 seconds with an aqueous tetramethylammonium solution (hereinafter 2.38% TMAH, manufactured by Tama Chemical Industry Co., Ltd.) and then rinsed with pure water to have a line and space pattern. A developed film A was obtained.

(2) Sensitivity evaluation In the development film A, the exposure amount (hereinafter referred to as the minimum exposure amount Eth) at which the exposed portion was not completely eluted after exposure and development was defined as sensitivity. Eth can be judged to be highly sensitive if 700 mJ / cm ² or less, 500 mJ / cm ² or less being more preferred.

(3) Production of cured film by heat treatment The developed film A produced in (1) was subjected to 3.5 ° C./20 ppm or less at an oxygen concentration of 20 ppm or less using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.). The temperature was raised to 200 ° C. or 170 ° C. in minutes, and heat treatment was performed at 200 ° C. or 170 ° C. for 1 hour.

(4) (c) Compound content measurement in cured film Using a coating / developing apparatus ACT-8, a photosensitive resin composition was applied onto an 8-inch silicon wafer by spin coating, and a hot plate at 120 ° C. for 3 minutes. Was baked to prepare a pre-baked film having a thickness of 5.0 μm. Then, after developing with 2.38 TMAH for a time when the film loss during development is 1.0 μm using ACT-8, rinsing with pure water, shaking off and drying, a solid film after development (3 The cured film was obtained by heat treatment in an inert oven under the conditions (1).

  The film thickness of the obtained cured film was measured, and 1 × 5 cm was cut out and was adsorbed and trapped by the purge and trap method. Specifically, the collected cured film was heated at 400 ° C. for 60 minutes using helium as a purge gas, and the desorbed components were collected in an adsorption tube.

  The collected components were thermally desorbed using a thermal desorption apparatus at a primary desorption condition of 260 ° C. for 15 minutes, a secondary adsorption desorption condition of −27 ° C. and 320 ° C. for 5 minutes, and then a GC-MS apparatus 7890 / GC-MS analysis was performed using 5975C (manufactured by Agilent) under the conditions of column temperature: 40 to 300 ° C., carrier gas: helium (1.5 mL / min), scan range: m / Z 29 to 600. (C) The amount of gas generation was calculated by preparing a calibration curve by GC-MS analysis under the same conditions as above for each component of the compound.

The obtained value (μg) was divided by an area of 5 cm ² to obtain μg / cm ² . The value is divided by (a) the density of the alkali-soluble resin (μg / cm ³ ) multiplied by the film thickness (cm) and multiplied by 100 to obtain the total content (% by mass) of the compound (c) in the cured film. Calculated.

(5) Evaluation of chemical resistance The silicon wafer with a cured film obtained in (3) was divided into 1 cm square and immersed in dimethyl sulfoxide at 70 ° C. for 15 minutes. The film thickness of the cured film before and after immersion is measured, and the swelling ratio (%) by the chemical solution is evaluated by calculating (film thickness after immersion−film thickness before immersion) × 100 / (film thickness before immersion). did. The swelling rate is preferably 30% or less, and more preferably 10% or less.

(6) Adhesion evaluation with a copper substrate A photosensitive resin composition was applied on a copper substrate using a spinner so that the film thickness after pre-baking would be 10 μm, and then 3 ° C. at 120 ° C. using a hot plate. A photosensitive resin film was obtained by baking for a minute. The produced photosensitive resin film was heat-treated in an inert oven under the condition (3) to obtain a cured film.

  The cured film was cut with a 1 mm interval in a grid pattern with a cutter, 10 × 10 squares were made, and a peeling test was performed using “Cellotape” (registered trademark). (JIS K 5600-5-6: 1999) In 100 squares, the number of peeled pieces was counted. In the peeling test, the number of peeling is preferably 20/100 or less, and more preferably 0/100. Furthermore, after storing for 200 hours under the conditions of 121 ° C., humidity 100%, and 2 atm using a highly accelerated life test apparatus (saturated pressure cooker test apparatus), the adhesion by the peel test was similarly evaluated.

(7) Discoloration evaluation of copper substrate After the test by the advanced accelerated life test apparatus of (6), the discoloration of the copper substrate was visually evaluated. A sample showing no discoloration was designated as A, a sample showing a slight brown color change as B, a sample showing a clear brown color change as C, and a black color change as D.

The names of the abbreviations of acid dianhydride and diamine shown in the following examples and comparative examples are as follows.
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride ED-600: Jeffamine ED-600 (trade name, manufactured by HUNTSMAN Co., Ltd.)
SiDA: 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane BAHF: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane HFHA: 2, 2′-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoropropane MAP: metaaminophenol KBM-1003: vinyltrimethoxysilane NMP: N-methyl-2-pyrrolidone GBL: γ-Butyrolactone The compounds used in Examples and Comparative Examples are shown below.

[Synthesis Example 1] Synthesis of quinonediazide compound a TrisP-PA (21.2 g (50.0 mmol)), 5-naphthoquinonediazidesulfonyl chloride (26.9 g (100 mmol)), 4-naphthoquinonediazidesulfonyl under a dry nitrogen stream Acid chloride (13.4 g (50.0 mmol)) was dissolved in 1,4-dioxane (50.0 g), and triethylamine (15.2 g) mixed with 1,4-dioxane (50.0 g) was added thereto. The solution was added dropwise so that the temperature in the system did not exceed 35 ° C. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain quinonediazide compound a.

[Synthesis Example 2] Synthesis of diamine A The synthesis of diamine A was performed as follows with reference to Reference Document 1.
(Reference 1) Chinese Patent Application No. 10386867 The specification, 2,7-dinitro-9-fluorenone (20.0 g (74.0 mmol)), phenol (14.1 g (150 mmol)), trifluoro, under a dry nitrogen stream L-methanesulfonic acid (5.50 g (37.0 mmol)) and 3-mercaptopropionic acid (1.20 g (37.0 mmol)) were dissolved in methanol (500 g) and stirred at 70 ° C. for 6 hours. The reaction product was filtered off and washed with ethanol to obtain Precursor 1. The obtained precursor 1 (25.0 g) was dissolved in a mixed solution of tetrahydrofuran (300 g) and methanol (150 g) at 40 ° C., 5% palladium-carbon (0.600 g) was added, and saturated hydrazine (22.22 g) was added. 7 g) was added dropwise over 30 minutes. After stirring at 40 ° C. for 4 hours, the reaction product was filtered to remove palladium-carbon, and poured into water to obtain a product precipitate. The precipitate was washed with water and methanol to obtain diamine A.

[Synthesis Example 3] Synthesis of Diamine B Synthesis of diamine B was performed as follows with reference to Reference Document 2.
(Reference 2) Macromolecules 2004, 37, p. 248-250.
Precursor 2 (20.0 g (68.0 mmol)) was dissolved in a 10% aqueous potassium hydroxide solution (50.0 g) under a dry nitrogen stream, refluxed at 100 ° C. for 2 hours, and then cooled to room temperature (25 ° C.). And neutralized with hydrochloric acid. The precipitate was filtered and washed with water to obtain Precursor 3. A mixture of Precursor 3 (10.0 g (47.0 mmol)), aniline hydrochloride (24.2 g (190 mmol)) and aniline (43.7 g (470 mmol)) was stirred at 180 ° C. for 1 hour. The organic layer was separated using ethyl acetate and aqueous sodium hydrogen carbonate solution, and the resulting solid was recrystallized using methanol and water to obtain diamine B.

[Synthesis Example 4] Synthesis of diamine C In a dry nitrogen stream, 2-fluoro-4-aminophenol (25.0 g (200 mmol)) and lithium chloride (8.33 g (200 mmol)) were dissolved in NMP (200 g) and reacted. While cooling the vessel with ice, a solution of 3,5-dinitrobenzoyl chloride (46.3 g (200 mmol)) dissolved in NMP was added dropwise, stirred at 0 ° C. for 1.5 hours, and then at room temperature (25 ° C.). Stir for 5 hours. The organic layer was separated with ethyl acetate and water, and ethyl acetate was concentrated and recrystallized to obtain precursor 4. The obtained precursor 4 (32.1 g) was dissolved in a mixed solution of tetrahydrofuran (300 g) and methanol (150 g), 5% palladium-carbon (1.00 g) was added, and 30% saturated hydrazine (40.0 g) was added. It was added dropwise over a period of minutes. After stirring at 40 ° C. for 4 hours, the reaction product was filtered to remove palladium-carbon, and poured into water to obtain a product precipitate. The precipitate was washed with water and methanol to obtain diamine C.

[Example 1]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Furthermore, diamine A (12.4 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) were added together with NMP (20.0 g), The mixture was reacted at 50 ° C. for 1 hour and then stirred at 200 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin A powder. Obtained alkali-soluble resin A (3.50 g), quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows the components of the alkali-soluble resin A, and Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 2]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Furthermore, diamine B ((12.4 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) was added together with NMP (20.0 g). The mixture was reacted for 1 hour at 50 ° C. and then stirred for 4 hours at 200 ° C. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate, which was collected by filtration and washed three times with water. Then, it dried for 72 hours with a 50 degreeC vacuum dryer, and obtained the powder of alkali-soluble resin B. The obtained alkali-soluble resin B (3.50g) and the quinonediazide compound a (0. 500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) were added to GBL (5.56 g), and the varnish of the photosensitive resin composition The components of the alkali-soluble resin B are shown in Table 1, and the components of the photosensitive resin composition are shown in Table 2. As described above, the sensitivity, chemical resistance, and adhesion to the copper substrate were obtained using the obtained varnish. The evaluation results are shown in Table 3.

[Example 3]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Furthermore, diamine C (8.49 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) were added together with NMP (20.0 g), The mixture was reacted at 50 ° C. for 1 hour and then stirred at 200 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin C powder. Obtained alkali-soluble resin C (3.50 g), quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows the components of the alkali-soluble resin C, and Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 4]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 , KBM-1003 (50.0 mg) and N-methyl-2-pyrrolidone (0.167 g) were added to GBL (5.39 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 5]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 , KBM-1003 (50.0 mg) and N-methyl-2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 6]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 7]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 , KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (3.34 g) were added to GBL (2.22 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 8]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of a photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. At that time, the temperature during the heat treatment was 170 ° C. The evaluation results are shown in Table 3.

[Example 9]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 , KBM-1003 (50.0 mg) and N-methyl-2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. At that time, the temperature during the heat treatment was 170 ° C. The evaluation results are shown in Table 3.

[Example 10]
Alkali-soluble resin C (3.50 g) obtained in Example 3, quinonediazide compound a (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) obtained in Synthesis Example 1 KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. At that time, the temperature during the heat treatment was 170 ° C. The evaluation results are shown in Table 3.

[Example 11]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Diamine C (7.18 g (27.5 mmol)), BAHF (1.83 g (5.00 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) ) Was added along with NMP (20.0 g) and allowed to react at 50 ° C. for 1 hour and then stirred at 200 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin D powder. Obtained alkali-soluble resin D (3.50 g), quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows components of the alkali-soluble resin D, and Table 2 shows components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 12]
Alkali-soluble resin D (3.50 g) obtained in Example 11, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) , KBM-1003 (50.0 mg) and N-methyl-2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 13]
Alkali-soluble resin D (3.50 g) obtained in Example 11, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 14]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Furthermore, diamine C (4.57 g (17.5 mmol)), BAHF (5.49 g (15.0 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) ) Was added along with NMP (20.0 g) and allowed to react at 50 ° C. for 1 hour and then stirred at 200 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin E powder. Obtained alkali-soluble resin E (3.50 g), quinonediazide compound a obtained in Synthesis Example 1 (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows the components of the alkali-soluble resin E, and Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 15]
Alkali-soluble resin E (3.50 g) obtained in Example 14, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) , KBM-1003 (50.0 mg) and N-methyl-2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 16]
Alkali-soluble resin E (3.50 g) obtained in Example 14, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 17]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Furthermore, diamine C (8.49 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) were added together with NMP (20.0 g), The mixture was reacted at 50 ° C. for 1 hour and then stirred at 85 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin F powder. Obtained alkali-soluble resin F (3.50 g), quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows the components of the alkali-soluble resin F, and Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 18]
Alkali-soluble resin F (3.50 g) obtained in Example 17, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) , KBM-1003 (50.0 mg) and N-methyl-2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Example 19]
Alkali-soluble resin F (3.50 g) obtained in Example 17, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Comparative Example 1]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Furthermore, BAHF (11.9 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) were added together with NMP (20.0 g), and 50 The mixture was reacted at 1 ° C. for 1 hour and then stirred at 200 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin G powder. Obtained alkali-soluble resin G (3.50 g), quinonediazide compound a obtained in Synthesis Example 1 (0.500 g), HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows the components of the alkali-soluble resin G, and Table 2 shows the components of the photosensitive resin composition. Using the obtained varnish, as described above, sensitivity, adhesion with a copper substrate, and discoloration evaluation of the copper substrate were performed. The evaluation results are shown in Table 3.

[Comparative Example 2]
Alkali-soluble resin G (3.50 g) obtained in Comparative Example 1, quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) KBM-1003 (50.0 mg) and N- (2-hydroxyethyl) -2-pyrrolidone (0.834 g) were added to GBL (4.73 g) to obtain a varnish of the photosensitive resin composition. Table 2 shows the components of the photosensitive resin composition. As described above, the obtained varnish was evaluated for sensitivity, chemical resistance, adhesion to a copper substrate, and discoloration of the copper substrate. The evaluation results are shown in Table 3.

[Comparative Example 3]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Further, HFHA (19.7 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) were added together with NMP (20.0 g), and 50 ° C. And then stirred for 4 hours at 200 ° C. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate, which was collected by filtration and washed with water three times. And dried for 72 hours in a vacuum dryer at 0 ° C. to obtain a powder of alkali-soluble resin H. The obtained alkali-soluble resin H (3.50 g), the quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g) and KBM-1003 (50.0 mg) were added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. The components of the alkali-soluble resin H are shown in Table 1, and the components of the photosensitive resin composition are shown in Table 2. Using the obtained varnish, as described above, sensitivity, adhesion to the copper substrate, and discoloration evaluation of the copper substrate The evaluation results are shown in Table 3.

[Comparative Example 4]
ODPA (15.5 g (50.0 mmol)) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added MAP (1.09 g (10.0 mmol)) along with NMP (20.0 g). Further, HFHA (19.7 g (32.5 mmol)), ED-600 (6.00 g (10.0 mmol)), SiDA (0.620 g (2.50 mmol)) were added together with NMP (20.0 g), and 50 The reaction was carried out at 0 ° C. for 1 hour and then stirred at 85 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin I powder. Obtained alkali-soluble resin I (3.50 g), quinonediazide compound a (0.500 g) obtained in Synthesis Example 1, HMOM-TPHAP (0.500 g), TrisP-HAP (0.300 g), KBM-1003 (50.0 mg) was added to GBL (5.56 g) to obtain a varnish of the photosensitive resin composition. Table 1 shows components of the alkali-soluble resin I, and Table 2 shows components of the photosensitive resin composition. Using the obtained varnish, as described above, sensitivity, adhesion with a copper substrate, and discoloration evaluation of the copper substrate were performed. The evaluation results are shown in Table 3.

In Examples 1 to 19, (a) the alkali-soluble resin in the photosensitive resin composition has a structural unit represented by the general formula (1) and / or the general formula (2), and the general formula (1) and The organic group represented by R ² in the general formula (2) contains at least one selected from the group consisting of the structures represented by the general formulas (3) to (5). Compared to 4, adhesion after the accelerated life test was improved, and discoloration of the copper substrate could be suppressed.

  In Examples 4 to 7, 9, 10, 12, 13, 15, 16, 18, and 19, the photosensitive resin composition is selected from the group consisting of (c) cyclic amide, cyclic urea, and derivatives thereof. By containing one or more kinds of compounds, the adhesion after the accelerated life test was improved as compared with Examples 3, 8, 11, 14, and 17.

  In Examples 5 and 6, the content of one or more compounds selected from the group consisting of (c) cyclic amide, cyclic urea, and derivatives thereof in the cured film is 0.005% by mass to 5% by mass. By setting it as the following, the adhesiveness after an accelerated life test improved compared with Example 4 and 7. FIG.

DESCRIPTION OF SYMBOLS 1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulating film 4 'Insulating film 4 "Insulating film 5 Metal (Cr, Ti etc.) film 5' Metal (Cr, Ti etc.) film 5" Metal (Cr, Ti etc.) film 6 Metal wiring (Al, Cu, etc.)
6 'Metal wiring (Al, Cu, etc.)
6 "metal wiring (Al, Cu, etc.)
7 Insulating film 8 UBM (under bump metal)
9 Scribe line 10 Solder bump 11 Sealing resin 12 Substrate 13 Insulating film 14 Insulating film 15 Metal (Cr, Ti, etc.) film 16 Metal wiring (Ag, Cu, etc.)
17 Metal wiring (Ag, Cu, etc.)
18 Electrode 19 Sealing resin

Claims (17)

(A) an alkali-soluble resin;
(B) contains a photosensitizer,
The (a) alkali-soluble resin has a structural unit represented by the general formula (1) and / or the general formula (2), and is represented by R ² in the general formula (1) and the general formula (2). The photosensitive resin composition in which an organic group contains at least 1 or more types chosen from the group which consists of a structure represented by General formula (3)-(5).

(R ¹ in the general formula (1) represents a divalent to tetravalent organic group having 2 to 100 carbon atoms, and R ³ is either hydrogen or an organic group having 1 to 20 carbon atoms. A represents an integer satisfying 0 ≦ a ≦ 2.)

(R ⁴ in the general formula (2) represents a tetravalent organic group having 2 to 100 carbon atoms.)

(R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formulas (3) to (5) represent an organic group having 1 to 80 carbon atoms which does not contain a hydroxy group. X in the general formula (5) is hydrogen. An atom, a halogen atom or an organic group having 1 to 10 carbon atoms is shown.) At least one organic group selected from the group consisting of the structures represented by the general formulas (3) to (5) is 40 of all R ^{2 in} the general formula (1) and the general formula (2). It is -90 mol%, The photosensitive resin composition of Claim 1 characterized by the above-mentioned. The photosensitive resin composition according to claim 1, further comprising (c) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is used as an insulating film in contact with a metal wiring containing a copper element. The photosensitive sheet | seat formed from the photosensitive resin composition in any one of Claims 1-4. A cured film obtained by curing the photosensitive resin composition according to claim 1. A cured film obtained by curing the photosensitive sheet according to claim 5. 8. The content of one or more kinds of compounds selected from the group consisting of (c) cyclic amides, cyclic ureas, and derivatives thereof is 0.005% by mass or more and 5% by mass or less. Cured film. The cured film according to claim 8, wherein the boiling point of one or more compounds selected from the group consisting of (c) cyclic amide, cyclic urea, and derivatives thereof is 170 ° C or higher. The cured film according to claim 8, wherein the boiling point of one or more compounds selected from the group consisting of (c) cyclic amide, cyclic urea, and derivatives thereof is 210 ° C. or higher and 400 ° C. or lower. One or more types of compounds selected from the group which consists of said (c) cyclic amide, cyclic urea, and those derivatives have the structure represented by General formula (6) in any one of Claims 6-10 The cured film as described.

(In general formula (6), b shows the integer of 1-4, Y shows CH or a nitrogen atom. R < ⁹ > and R < ¹⁰ > shows a hydrogen atom or a C1-C20 organic group each independently. However, R ⁹ is an organic group having 2 to 20 carbon atoms when Y is CH, and is a hydrogen atom or an organic group having 1 to 20 carbon atoms when Y is a nitrogen atom, and R ¹⁰ is hydrogen when Y is CH. An atom, and when Y is a nitrogen atom, it is a hydrogen atom or an organic group having 1 to 20 carbon atoms.) The interlayer insulation film or semiconductor protective film which consists of a cured film in any one of Claims 6-11. The process of apply | coating the photosensitive resin composition in any one of Claims 1-4 on a base material, or the process of laminating the photosensitive sheet of Claim 5 on a base material, The process of irradiating an ultraviolet-ray, The manufacturing method of a semiconductor device including the process of forming, the process of forming a pattern, and the process of further heating and forming the relief pattern layer of a cured film. The semiconductor electronic component or semiconductor device which has the relief pattern layer of the cured film in any one of Claims 6-11. The semiconductor electronic component or semiconductor device by which the cured film in any one of Claims 6-11 was arrange | positioned as an interlayer insulation film between rewiring. The semiconductor electronic component or the semiconductor device according to claim 15, wherein the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. The semiconductor electronic component or semiconductor device by which the cured film in any one of Claims 6-11 is arrange | positioned as an interlayer insulation film of the adjacent board | substrate comprised with 2 or more types of materials.

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