KR102277707B1 - resin composition - Google Patents

Abstract

While hardening is possible by heat processing at low temperature, it makes it a subject to provide the resin composition which can obtain the cured film excellent in heat resistance, chemical-resistance, and elongation at break. (A) an alkali-soluble resin comprising at least one selected from polybenzoxazole precursors, polyimide precursors, polyamideimide precursors, and copolymers thereof, and also having a benzoxazole precursor structure and an aliphatic group, and ( B) A resin composition containing a thermal acid generator and (E) an antioxidant.

Description

resin composition

BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates to a 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, or the like.

Conventionally, polyimide-based resins and polybenzoxazole-based resins excellent in heat resistance, electrical insulation, mechanical properties, and the like have been widely used for surface protective films and interlayer insulating films of semiconductor devices, insulating layers of organic electrolytic devices, and flattening films of TFT substrates.

When thermally dehydrating and ring-closing the coating film of the polyimide precursor, polybenzoxazole precursor, or polyamideimide precursor to obtain a thin film excellent in heat resistance and mechanical properties, high-temperature firing at around 350° C. is usually required. In addition, the operation at the time of thermally dehydrating and ring-closing the coating film of the polyimide precursor, polybenzoxazole precursor, and polyamideimide precursor to obtain a thin film excellent in heat resistance and mechanical properties is sometimes called firing, and the change of the coating film is sometimes called curing. By the way, memory devices used in recent years, mold resins used in the production of semiconductor packages, etc. are weak to high-temperature processes, and from the viewpoint of semiconductor package reliability, the surface protective film or the interlayer insulating film is 250° C. or less, more preferably Polyimide-based resins, polybenzoxazole-based resins, and polyamideimide-based resins that can be cured by firing at a low temperature of 220° C. or less and have higher mechanical and thermal properties are required.

Examples of the resin composition that can be cured at a low temperature include a resin composition containing a resin such as polyimide, polybenzoxazole, polybenzoimidazole, and polybenzothiazole and a thermal crosslinking agent (Patent Document 1), alkali-soluble polyamideimide, and mineral acid. A positive photosensitive polyamide-imide resin composition containing a generator, a solvent and a crosslinking agent (Patent Document 2), an alkali-soluble polyimide, a quinonediazide compound, a thermal crosslinking agent, a thermal acid generator and a positive photosensitive polyimide containing an adhesion improving agent A resin composition (patent document 3) etc. are known.

Japanese Patent Laid-Open No. 2007-16214 Japanese Patent Laid-Open No. 2007-240554 Japanese Patent Laid-Open No. 2013-72935

However, as disclosed in Patent Documents 1 to 3, a resin composition that can be cured by heat treatment at a low temperature of 250° C. or less has problems in terms of properties such as heat resistance and chemical resistance.

The present invention solves the above problems accompanying the prior art, and provides a resin composition capable of obtaining a cured film excellent in heat resistance, chemical resistance, and elongation at break while being able to be cured by heat treatment at a low temperature. do.

The present invention has the following configuration. In other words,

(A) an alkali-soluble resin comprising at least one selected from polybenzoxazole precursors, polyimide precursors, polyamideimide precursors, and copolymers thereof, and also having a benzoxazole precursor structure and an aliphatic group, and

(B) It is a resin composition containing a thermal acid generator and (E) antioxidant.

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, while hardening is possible by heat processing at low temperature, the cured film excellent in heat resistance, chemical-resistance, and elongation at break can be obtained.

1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps.
2 is a diagram illustrating a detailed manufacturing method of a semiconductor device having bumps.
3 is a cross-sectional view of a manufacturing process of a semiconductor device according to an embodiment of the present invention.
4 is a cross-sectional view of a coil component of an inductor device according to an embodiment of the present invention.

The resin composition of the present invention comprises (A) at least one selected from a polybenzoxazole precursor, a polyimide precursor, a polyamideimide precursor, and a copolymer thereof, and further comprises a benzoxazole precursor structure and an aliphatic group. It is a resin composition containing alkali-soluble resin which has, and (B) a thermal acid generator, and (E) antioxidant. Moreover, it is preferable that it is a resin composition further containing (C) a thermal crosslinking agent and (D) a photosensitive compound. Hereinafter, it may abbreviate as (A) component, (B) component, (C)component, and (D) compound, respectively.

Alkali solubility in this invention means that the dissolution rate at the time of immersing the prebaked film formed by the method described next in the aqueous alkali solution described next is 50 nm/min or more in this invention. Specifically, a solution in which a resin is dissolved in γ-butyrolactone is applied on a silicon wafer, and prebaked at 120° C. for 4 minutes to form a prebaked film having a thickness of 10 μm±0.5 μm, and the prebaked film After being immersed in 23±1 degreeC 2.38 mass % tetramethylammonium hydroxide aqueous solution for 1 minute, the dissolution rate calculated|required from the film thickness reduction at the time of rinsing with pure water means 50 nm/min or more.

It is preferable that alkali-soluble resin which is (A) component used for this invention has an acidic group in the structural unit of resin, or main chain terminal, or both. As an acidic group, a carboxyl group, phenolic hydroxyl group, a sulfonic acid group, a thiol group, etc. are mentioned, for example. By having such an acidic group, it can have good alkali solubility. (A) From a viewpoint of improving alkali solubility, 1 mass % or more is preferable, and, as for content of the acidic group in (A) component, 30 mass % or less is preferable from viewpoints, such as chemical-resistance and water absorption.

It is preferable that (A) component has a fluorine atom. When component (A) has a fluorine atom, the formed film|membrane becomes what has water repellency, and when developing with aqueous alkali solution, permeation of the aqueous alkali solution to the interface of a film|membrane and a base material is suppressed. In addition, the aqueous alkali solution used at the time of developing may be described as an alkali developing solution. The content of fluorine atoms in the component (A) is preferably 5 mass % or more from the viewpoint of the effect of suppressing permeation of the aqueous alkali solution to the interface between the film and the substrate, and preferably 20 mass % or less from the viewpoint of solubility in aqueous alkali solution. Do.

It is preferable that alkali-soluble resin which is (A) component has high heat resistance. In particular, from the viewpoint of obtaining excellent properties as a planarization film, an insulating layer, a barrier rib, a protective film, and an interlayer insulating film used in an organic light emitting device, a display device, and a semiconductor element, it is preferable that the amount of outgas under the temperature condition of 160 ° C. Do. Specifically, a polybenzoxazole precursor, a polyimide precursor, a polyamideimide precursor, and those copolymers are mentioned as a preferable example.

It is preferable that component (A) used for this invention has a structural unit represented by following General formula (1). Moreover, you may have another structural unit further. Other structural units in this case include, for example, an imide structure, a structure having a skeleton in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure, a siloxane structure, etc., but are limited to these doesn't happen When it further has another structural unit, it is preferable to have 50 mol% or more of the structural unit represented by General formula (1) in the total number of structural units.

(In the general formula (1), X and Y each independently represent a 2 to 8 valent organic group having 2 or more carbon atoms. R ¹ and R ² each independently represent hydrogen or an organic group having 1 to 20 carbon atoms. n represents an integer within the range of 10 to 100,000. r and s represent integers within the range of 0 to 2, and p and q represent integers within the range of 0 to 4.)

Moreover, (A) component has a benzoxazole precursor structure. By having a benzoxazole precursor structure, while photosensitive performance improves, high elongation can be provided with respect to the cured film which hardened the resin composition containing (A) component, Furthermore, when a benzoxazole precursor is ring-closing, heat resistance , the chemical resistance is improved.

Moreover, (A) component has an aliphatic group. The aliphatic group preferably has at least one organic group of an alkylene group and an oxyalkylene group. Specifically, an alkylene group, a cycloalkylene group, an oxyalkylene group, an oxycycloalkylene group, etc. are mentioned. Moreover, it is preferable that the said aliphatic group is what is represented by the following general formula (2).

(In the general formula (2), R ³ to R ⁶ each independently represents an alkylene group having 1 to 6 carbon atoms. R ⁷ to R ¹⁴ each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms. However, the structures shown in parentheses are different. Each of x, y, and z independently represents an integer of 0 to 35.)

When the component (A) has an aliphatic group, the cured film obtained by curing the resin composition containing the component (A) has high elongation. Moreover, when (A) component has an aliphatic group, flexibility arises in resin, and the increase of the stress which arises when the benzoxazole precursor structure of resin is ring-closed can be suppressed. For this reason, the increase in the stress to the substrate wafer accompanying the dehydration ring closure of the benzoxazole precursor structure can be suppressed. In addition, since the aliphatic group has low ultraviolet absorptivity, i-ray permeability is improved by its introduction, and high sensitivity can be realized at the same time.

It is preferable that it is 600 or more, and, as for the weight average molecular weight of (A) component used for this invention, it is more preferable that it is a point from which a cured film has high elongation. Moreover, it is preferable that it is 2,000 or less at the point which solubility with respect to an alkali solution is maintained, It is more preferable that it is 1,800 or less, It is still more preferable that it is 1,500 or less.

In the present invention, the weight average molecular weight (Mw) can be confirmed using GPC (gel permeation chromatography). For example, it can measure using N-methyl-2-pyrrolidone (it may abbreviate as NMP hereafter) as a developing solvent, and can calculate and calculate|require it in polystyrene conversion.

It is preferable that (A) component used for this invention has a structural unit represented by the said General formula (1). The (OH) in the formula ^{_{(1) p -X- (COOR 1}} ) r represents the residue of an acid. X is a divalent to octavalent organic group having two or more carbon atoms, and among these, an aromatic ring or an aliphatic group-containing organic group having 5 to 40 carbon atoms is preferable.

As the acid component, examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, and triphenyl. As examples of tricarboxylic acids such as dicarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., as examples of tetracarboxylic acid, pyromellitic acid, 3; 3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3 ,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid , 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1 ,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether , 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis{4-(3,4-dicarboxyphenoxy) Phenyl}fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 2, 2-bis(3,4-dicarboxyphenyl)hexafluoropropane and aromatic tetracarboxylic acid having the structure shown below, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4- Although aliphatic tetracarboxylic acids, such as cyclopentane tetracarboxylic acid, etc. are mentioned, It is not limited to these. You may use 2 or more types of these.

R ¹⁵ represents an oxygen atom, C(CF ₃ ) ₂ , or C(CH ₃ ) ₂ . R ¹⁶ and R ¹⁷ represent a hydrogen atom or a hydroxyl group.

These acids can be used as such or as acid anhydrides, halides, or active esters.

Further, in the general formula _{(1), (OH) q} -Y- (COOR 2) s represents a residue of a diamine. Y is a divalent to octavalent organic group having two or more carbon atoms, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or an aliphatic group described later is preferable.

(A) Specific examples of the diamine used in the component include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis( 4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4, 4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-dia Minobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino -4-hydroxyphenyl) hexafluoropropane or a compound in which at least part of the hydrogen atoms of these aromatic rings is substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines having the structures shown below; can, but is not limited to these. You may use 2 or more types of these.

R ¹⁵ represents an oxygen atom, C(CF ₃ ) ₂ , or C(CH ₃ ) ₂ . R ¹⁶ to R ¹⁹ each independently represent a hydrogen atom or a hydroxyl group.

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

The component (A) used for this invention has an aliphatic group. And it is preferable to have an aliphatic group in Y in the said General formula (1). Moreover, it is more preferable that these aliphatic groups are the aliphatic groups represented by the said General formula (2).

By having an aliphatic group in Y in the said General formula (1), ie, the diamine side, while high elongation in a cured film and stress reduction are acquired, the resin composition of this invention can be made highly sensitive. Moreover, when Y in the said General formula (1) has the aliphatic group represented by the said General formula (2), adhesiveness with the metal (for example, copper) of a board|substrate can be improved. Specifically, since interaction, such as a coordination bond, is obtained between the ether group contained in the said General formula (2) and a metal, high adhesiveness with the metal of a board|substrate can be acquired.

Specific examples of the diamine having an aliphatic group include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, and 2-methyl- 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1 ,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl) Cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2- methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, (or higher A brand name, HUNTSMAN Co., Ltd. product) etc. are mentioned. In addition, -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N(CH ₂ CH ₃ )-, -N(CH ₂ CH ₂ CH ₃ )-, -N(CH (CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, bonds, such as -NHCONH-, may be included. Among these, the diamine which has an aliphatic group represented by General formula (2) is preferable, For example, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT- 1000, HE-1000, HT-1100, HT-1700, (above trade name, HUNTSMAN Co., Ltd. product) etc. are preferable.

It is preferable that 5-40 mol% is contained in all the diamine residues, and, as for the said aliphatic group, it is more preferable that it is contained 10-30 mol%. When an aliphatic group is contained in this range, developability at the time of developing with aqueous alkali solution becomes high, and the elongation of the cured film obtained by heating improves.

Moreover, (A) component used for this invention may contain the aliphatic group which has a siloxane structure in the range which does not reduce heat resistance, and can improve adhesiveness with a board|substrate by this. Specific examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylheptasiloxane, and the like. When it contains 1 mol% or more, it is preferable from the point of adhesive improvement with base materials, such as a silicon wafer, and when it is 15 mol% or less, it is preferable at the point which does not reduce solubility in alkaline solution.

Moreover, it is preferable that alkali-soluble resin which is (A) component is resin which has an acidic group at the main chain terminal. Such resin can be obtained by sealing the terminal of alkali-soluble resin with the monoamine which has an acidic group, an acid anhydride, an acid chloride, or a monocarboxylic acid.

Preferred examples of the monoamine that can be used to obtain an alkali-soluble resin having an acidic group at the end of the main chain include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, and 1-hydroxy-6-aminonaphthalene. , 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 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-aminonaphthalene, 2-carboxy- 5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2 -aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. You may use 2 or more types of these.

Moreover, as preferable examples of the acid anhydride, acid chloride, and monocarboxylic acid that can be used to obtain an alkali-soluble resin having an acidic group at the end of the main chain, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, Acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6- Monocarboxylic acids, such as carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, and 1-mercapto-5-carboxynaphthalene, and these Monoacid chloride compound in which the carboxyl group is acid chlorided, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2 A monoacid chloride compound in which only one carboxyl of dicarboxylic acids such as ,6-dicarboxynaphthalene is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene The active ester compound obtained by reaction of -2,3-dicarboxyimide is mentioned. You may use 2 or more types of these.

The content of the acid group at the main chain terminal of the alkali-soluble resin derived from the terminal blocker such as monoamine, acid anhydride, acid chloride, and monocarboxylic acid is 2 with respect to 100 mol% of the total of the acid and amine components constituting the resin. to 25 mol% is preferred.

(A) When alkali-soluble resin which is component is resin which has an acidic group in the main chain terminal, the acidic group of the main chain terminal of (A) component can be detected easily with the following method. For example, by dissolving a resin having an acidic group at the end of the main chain in an acidic solution, decomposing it into an amine component and an acid component, which are structural units of the resin, and measuring this by gas chromatography (GC) or NMR, End sealants can be easily detected. Apart from this, it is possible to directly detect the resin having an acidic group at the end of the main chain ^{by measuring a thermal decomposition gas chromatograph (PGC), infrared spectrum, and 13} C-NMR spectrum.

Moreover, as for the cured film which hardened the resin composition of this invention, it is preferable that the ratio by which the benzoxazole precursor structure is ring-closed with polybenzoxazole is 30 % or more by the effect|action of (B) component mentioned later. When 30% or more is ring-closed, there is little amount of outgas, and it can be set as the cured film with high heat resistance, high chemical-resistance, and breaking elongation.

The solvent (hereinafter referred to as a polymerization solvent) used for polymerizing the alkali-soluble resin as component (A) used in the present invention should be capable of dissolving tetracarboxylic dianhydrides and diamines as raw material monomers, and the The kind is not particularly limited. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene Urea, N,N-dimethylisobutyric acid amide, amides of methoxy-N,N-dimethylpropionamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε- Cyclic esters such as caprolactone and α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, m-cresol, p-cresol, etc. phenols, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like.

In order to dissolve (A) component after reaction, as for a polymerization solvent, it is preferable to use 100 mass parts or more with respect to 100 mass parts of (A) component obtained, It is more preferable to use 150 mass parts or more, At the time of precipitation collection|recovery In order to obtain resin as powder, it is preferable to use 1,900 mass parts or less, and it is more preferable to use 950 mass parts or less.

It is preferable that the weight average molecular weights of (A) component which has a structural unit represented by General formula (1) in this invention are 10,000 or more and 50,000 or less. Since the mechanical properties after hardening can be improved as a weight average molecular weight is 10,000 or more, it is preferable, and it is more preferable that it is 20,000 or more. On the other hand, since the developability by aqueous alkali solution can be improved that a weight average molecular weight is 50,000 or less, it is preferable.

Moreover, when 2 or more types of alkali-soluble polyimide precursor, polybenzoxazole precursor, polyamideimide precursor, or those copolymers are contained, the weight average molecular weight of at least 1 sort(s) should just exist in the said range.

(A) component used for this invention can be produced by a well-known method.

Although the polybenzoxazole precursor used for this invention is comprised from a benzoxazole precursor, as a preparation method, it can obtain by making a bisaminophenol compound and dicarboxylic acid condensation-react, for example. Specifically, a method in which a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. A solution of dicarboxylic acid dichloride is dripped, etc. In addition, you may have an imide precursor structure or an imide structure, in that case, when the imide precursor structure in a polybenzoxazole precursor or an imide structure is 100 mass parts, the content rate of a benzoxazole precursor structure It is preferable that it is 101-10000 mass parts of silver.

As a method for producing the polyimide precursor used in the present invention, for example, a method in which tetracarboxylic dianhydride and a diamine compound are reacted at a low temperature, a diester is obtained by using tetracarboxylic dianhydride and an alcohol, and then condensed with an amine It can be synthesized by a method of reacting in the presence of an agent, a method in which a diester is obtained by using tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorided and reacted with an amine. In the case of having a benzoxazole precursor structure, a benzoxazole precursor structure may be introduced into the polyimide precursor by using a diamine having a benzoxazole precursor in advance or by applying the method for preparing the polybenzoxazole precursor. In that case, when the imide precursor structure in a polyimide precursor is 100 mass parts, it is preferable that the content rate of a benzoxazole precursor structure is 1-99 mass parts.

As a method for producing the polyamideimide precursor used in the present invention, for example, first, tricarboxylic acid is acid anhydride, and the remaining carboxylic acid is subjected to dehydration condensation such as acid chloride or dicyclohexylcarbodiimide (DCC). It can be synthesized by a method of reacting with an agent and reacting with an amine. In the case of having a benzoxazole precursor structure, a benzoxazole precursor structure can be introduced into the polyamideimide precursor by using a diamine having a benzoxazole precursor in advance or by applying the method for preparing the polybenzoxazole precursor. . In that case, when the imide precursor structure in a polyamideimide precursor is 100 mass parts, it is preferable that the content rate of a benzoxazole precursor structure is 50-10000 mass parts.

In this invention, you may contain other alkali-soluble resin other than (A) component. Specifically, a polyimide, polybenzoxazole, a phenol resin, the polymer containing the radically polymerizable monomer which has an alkali-soluble group, a siloxane polymer, a cyclic olefin polymer, cardo resin, etc. are mentioned. These resins may be used independently and may be used combining some resin. In that case, when the whole of (A) component and other alkali-soluble resin is 100 mass parts, it is preferable to make the content rate of other alkali-soluble resin into 1-50 mass parts.

The resin composition of this invention contains (B) a thermal acid generator. The (B) thermal acid generator used in the present invention generates an acid by heat treatment after image development and acts as a catalyst for accelerating the cyclization of the imide precursor and the benzoxazole precursor of the component (A), so a cyclization reaction can be carried out at a lower temperature. Moreover, when the resin composition of this invention is a resin composition which further contains the (C) thermal crosslinking agent mentioned later, it acts also as a catalyst which accelerates|stimulates the crosslinking reaction of the resin of (A) component and (C) thermal crosslinking agent. For this reason, by containing (B) a thermal acid generator, the compactness of the cured film after hardening improves, as a result, heat resistance and chemical-resistance improve.

As for the (B) thermal acid generator used for this invention, it is more preferable that the thermal decomposition start temperature is 140 degreeC or more. Moreover, it is preferable that thermal decomposition start temperature is 220 degrees C or less, and it is more preferable that it is 200 degrees C or less. The thermal decomposition initiation temperature here refers to a boiling point or a decomposition temperature, and the decomposition temperature is a temperature at which thermal decomposition starts before reaching the melting point.

In addition, no acid is generated during drying (pre-baking: 70 ° C. to 140 ° C.) after application of the resin composition of the present invention to a substrate, and heat curing (cure: 140 to 220 ° C.) after patterning in subsequent exposure and development ), it is preferable to select one that generates an acid at the time of development, since a decrease in sensitivity during development can be suppressed, and the curing temperature can be lowered, so that an increase in stress on the substrate due to high-temperature heating can be suppressed. Therefore, as for (B) thermal acid generator used for this invention, it is more preferable that it is 140-220 degreeC of thermal decomposition initiation temperature, and it is still more preferable that it is 140-200 degreeC.

(B) Examples of the thermal acid generator include onium salts such as sulfonic acid ester compounds and sulfonium salts.

The acid generated by the thermal acid generator is preferably a strong acid having an acid dissociation constant of 2.0 or less from the viewpoint of a function as a catalyst for promoting cyclization and crosslinking of the imide precursor or benzoxazole precursor of component (A).

As an acid generated by thermal decomposition, sulfonic acid, boric acid, or the like is preferable.

As the sulfonic acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, camphorsulfonic acid, and haloalkylsulfonic acids such as trifluoromethanesulfonic acid are preferable.

As boric acid, tetrafluoroboric acid, tetrakis(pentafluorophenyl)boric acid, etc. are preferable, for example.

The component (B) used in the present invention is preferably at least one compound selected from the group consisting of a sulfonic acid ester compound represented by the general formula (3), a sulfonic acid ester compound represented by the general formula (4), and an onium salt.

(In general formulas (3) and (4), R ²⁰ to R ²² each independently represent an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 4 to 12 carbon atoms.)

In the general formulas (3) and (4), R ²⁰ to R ²² each independently represent an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 4 to 12 carbon atoms, but the aliphatic group and the aromatic group are partially substituted with hydrogen atoms may be used, and halogen groups, such as an alkyl group, an acyl group, and a fluorine group, are mentioned as a substituent.

Specific examples of the sulfonic acid ester compound represented by the general formula (3) include, for example, 3-(5-(((phenylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-( o-Tolyl)propanenitrile, 3-(5-(((camphorsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, 3-(5 -(((trifluoromethylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile etc. are mentioned, However, It is not limited to these. You may contain these 2 or more types.

As a specific example of the sulfonic acid ester compound represented by General formula (4), although the following structure is mentioned, for example, It is not limited to these. You may contain these 2 or more types.

As an onium salt, a sulfonium salt, an iodonium salt, etc. are mentioned. Specifically, for example, benzenesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, benzenesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, benzyl benzenesulfonate (4-hydroxyphenyl) Methylsulfonium, benzyl benzenesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, benzenesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, camphorsulfonic acid (4 -Hydroxyphenyl)dimethylsulfonium, camphorsulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, benzyl benzenesulfonate (4-hydroxyphenyl)methylsulfonium, camphorsulfonic acid benzyl (4-( (methoxycarbonyl)oxy)phenyl)methylsulfonium, camphorsulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl)dimethylsulfonium , benzyl trifluoromethanesulfonate (4-hydroxyphenyl)methylsulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, trifluoromethanesulfonic acid (4- Hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, "Sanade" (registered trademark), SI-145, SI-200, SI-250, SI-B2A, SI-B3A, SI-B3, SI -B4, SI-B5 (manufactured by Sanshin Chemical Co., Ltd.) etc. are mentioned, However, It is not limited to these. You may contain these 2 or more types.

(B) The content of the thermal acid generator is, from the viewpoint of further accelerating the ring closure reaction of the benzoxazole precursor moiety, and when the resin composition of the present invention is a resin composition further containing (C) a thermal crosslinking agent described later (C ) From a viewpoint of further promoting a crosslinking reaction with a thermal crosslinking agent, 0.1 mass part or more is preferable with respect to 100 mass parts of (A) component, 0.3 mass part or more is more preferable, and 0.5 mass part or more is more preferable. On the other hand, from the viewpoint of suppression of peeling from the metal material in the cured film after reliability tests such as maintenance of electrical insulation of the obtained cured film and high temperature storage test, 100 parts by mass or less is preferable with respect to 100 parts by mass of component (A), , 8 parts by mass or less is more preferable, and 5 parts by mass or less is more preferable.

It is preferable that the resin composition of this invention contains (C) thermal crosslinking agent further.

The (C) thermal crosslinking agent used for this invention refers to the compound which has at least two thermally-reactive functional groups, including an alkoxymethyl group, a methylol group, and an oxetanyl group, in a molecule|numerator. (C) The thermal crosslinking agent strongly crosslinks with the component (A) or other additive components including component (D), and improves the heat resistance, chemical resistance, hardness, and compactness of the film after thermal curing, and at the same time, a reliability test such as a high temperature storage test Peeling with the metal material in a later cured film can be suppressed.

When the resin composition of the present invention is a resin composition further containing (C) a thermal crosslinking agent, the above-described (B) thermal acid generator acts as a catalyst for accelerating the crosslinking reaction between the component (A) and the (C) thermal crosslinking agent, Thereby, the heat resistance, chemical-resistance, and compactness of the cured film which hardened the resin composition of this invention improve.

(C) Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups as the thermal crosslinking agent 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, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, Honshu Chemical High School) ), "NIKALAC" (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like.

(C) Preferred examples of the compound having at least two oxetanyl groups as the thermal crosslinking agent include "Denacol" (registered trademark) EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L, Denacol EX-321L (above, manufactured by Nagase Chemtex Co., Ltd.), GAN, GOT (above, manufactured by Nippon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, E4275 (above, manufactured by Japan Epoxy Resin Co., Ltd.), "Epiclon" (registered trademark) 850-S, Epiclone HP-4032, Epiclone HP-7200, Epi Clone HP-820, Epiclone HP-4700, Epiclone HP-4770, Epiclone HP4032 (above, manufactured by Dainippon Ink Chemicals Co., Ltd.), VG3101 (manufactured by Mitsui Chemicals Co., Ltd.), "Tepic" ( Registered trademarks) S, Tepic G, Tepic P (above, manufactured by Nissan Chemical Co., Ltd.), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), EPOTOT YH-434L (manufactured by Toto Kasei Corporation), EPPN502H , NC3000 (manufactured by Nippon Kayaku Co., Ltd.), Epiclone N695, HP7200 (or higher, manufactured by Dai Nippon Ink Chemical Co., Ltd.), "Etanacol" (registered trademark) EHO, Etanacol OXBP, Etanacol OXTP, Etanacol OXMA (above, Ube Kosan Co., Ltd. product), an oxetane phenol novolak, etc. are mentioned.

When the resin composition of the present invention is a resin composition further containing (C) a thermal crosslinking agent, if (C) the thermal crosslinking agent is a thermal crosslinking agent having a structural unit represented by the following general formula (5), the elongation of the resulting cured film is improved and low It is preferable at the point which suppression of peeling with the metallic material in the cured film after reliability tests, such as a high temperature storage test by stress increase and densification, is further possible.

(In the general formula (5), R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group. R ²³ is a divalent organic group having an alkylene group having 2 or more carbon atoms, and any of linear, branched and cyclic R ²³ is an alkylene group, a cycloalkylene group, an oxyalkylene group, an alkylsilylene group, an alkoxysilylene group, an arylene group, an oxyarylene group, an oxycarbonyl group, a carbonyl group, an allylene group, a vinylene group, a linking group including a heterocycle; Combinations thereof, etc. are mentioned, and may have a substituent.)

(C) Since the thermal crosslinking agent has a structural unit represented by the above general formula (5), the thermal crosslinking agent itself has a flexible alkylene group and a rigid aromatic group, so it has heat resistance and improved elongation and low stress of the resulting cured film can be angry Although an acryl group, a methylol group, an alkoxymethyl group, and an epoxy group are mentioned as a crosslinking group, it is not limited to this. Among these, it reacts with the phenolic hydroxyl group of (A) component, the point which can improve the heat resistance of a cured film, and the point which can react without dehydration, an epoxy group is preferable.

The compound represented by the following general formula (5) includes, for example, the following, but is not limited to the following structure.

(Wherein, m is an integer from 1 to 5, and l is from 1 to 20.)

It is preferable that m is 1-2, and l is 3-7 at the point which makes heat resistance and an elongation improvement compatible among the said structure.

(C) You may use a thermal crosslinking agent in combination of 2 or more types.

(C) As for content of a thermal crosslinking agent, 1 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of (A) component. (C) Chemical resistance and hardness of the film|membrane after baking or hardening as content of a thermal crosslinking agent is 1 mass part or more and 100 mass parts or less can be improved, and storage stability of a resin composition can be improved.

Moreover, 2-80 mass parts is preferable with respect to 100 mass parts of all the thermal crosslinking agents, and, as for content of the compound represented by General formula (5), 5-60 mass parts is more preferable. When the content is 2 parts by mass or more, the effect of improving elongation and reducing stress is obtained, and by setting it as 80 parts by mass or less, it becomes possible to maintain the sensitivity of the resin composition.

It is preferable that the resin composition of this invention contains the (D) photosensitive compound further. (D) By containing a photosensitive compound, photosensitivity can be provided to a resin composition.

(D) As the photosensitive compound, a compound having a group having a naphthoquinonediazide structure (hereinafter, sometimes referred to as a naphthoquinonediazide compound), a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. can be heard Moreover, you may contain a sensitizer etc. as needed.

As a naphthoquinone diazide compound, the naphthoquinone diazide sulfonyl ester compound which the sulfonic acid of naphthoquinone diazide sulfonic acid couple|bonded with the compound which has a phenolic hydroxyl group by ester is preferable. Examples of the compound having a phenolic hydroxyl group used herein 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, Methyleneless-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical High School Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, Asahi Yukizai High School Co., Ltd.) ) agent), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzo Phenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Co., Ltd. product) etc. are mentioned. Although 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid is introduced as an ester bond to these compounds having a phenolic hydroxyl group, naphthoquinonediazidesulfonyl ester compounds are exemplified as preferred, but compounds other than this can also be used.

Moreover, it is preferable that 50 mol% or more of the whole phenolic hydroxyl group of the compound which has a phenolic hydroxyl group is naphthoquinonediazidesulfonyl-esterified. By using the naphthoquinone diazide compound in which 50 mol% or more of the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group are sulfonyl esterified, the affinity of the naphthoquinone diazide compound to aqueous alkali solution is reduced, While the solubility of the resin composition of the miner in aqueous alkali solution is greatly reduced, the part of the naphthoquinonediazide structure of the naphthoquinonediazidesulfonyl group is changed to indenecarboxylic acid by exposure, and the resin composition of the exposed part is changed to indenecarboxylic acid. A large dissolution rate in aqueous alkali solution can be obtained, and as a result, the dissolution rate ratio of the exposed portion and the unexposed portion of the composition can be increased, and a pattern can be obtained with high resolution. By using such a naphthoquinonediazide compound, the resin composition which has positive photosensitivity which is photosensitive to the i line|wire (365 nm), h line|wire (405 nm), g line|wire (436 nm) of a common mercury vapor lamp can be obtained. Moreover, a photosensitive compound may be used independently, or may be used in combination of 2 or more types, and the resin composition which has highly sensitive photosensitivity can be obtained.

In the present invention, as the group having a naphthoquinone diazide structure, both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferably used. The 5-naphthoquinonediazidesulfonyl ester compound has increased absorption up to the g-ray region of a mercury lamp, and is suitable for g-ray exposure and full-wavelength exposure. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp, and is suitable for i-line exposure. In this invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or 5-naphthoquinone diazide sulfonyl ester compound according to the wavelength to expose. Moreover, a naphthoquinone diazide sulfonyl ester compound using a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group together in the same molecule can also be used, and 4-naphthoquinone diazide sulfonyl An ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can also be used together.

The said naphthoquinone diazide compound can be synthesize|combined by the esterification reaction of the compound which has a phenolic hydroxyl group, and a naphthoquinone diazide sulfonic acid compound, and can be synthesize|combined by a well-known method. By using these naphthoquinonediazide compounds, a resolution, a sensitivity, and a remaining-film rate improve more.

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

Among the photosensitive compounds, sulfonium salts, phosphonium salts and diazonium salts are preferable in order to appropriately stabilize the acid component generated by exposure. Among them, a sulfonium salt is preferable.

(D) As for content of a compound, 0.1 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of (A) component. (D) Photosensitivity can be provided, maintaining the heat resistance of the film|membrane after heat processing, chemical-resistance, and mechanical characteristics as content of a compound is 0.1 mass part or more and 100 mass parts or less.

(D) When the compound is a naphthoquinone diazide compound, the content of the naphthoquinone diazide compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the component (A). , Preferably it is 100 mass parts or less, More preferably, it is 80 mass parts or less. If it is 1 mass part or more and 80 mass parts or less, photosensitivity can be provided, maintaining the heat resistance of the film|membrane after heat processing, chemical-resistance, and mechanical characteristic.

(D) When the compound is a sulfonium salt, phosphonium salt, or diazonium salt, the content of the sulfonium salt, phosphonium salt or diazonium salt is preferably 0.1 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the component (A). Preferably it is 1 mass part or more, More preferably, it is 3 mass parts or more, Preferably it is 100 mass parts or less, More preferably, it is 80 mass parts or less, More preferably, it is 50 mass parts or less. If it is 0.1 mass part or more and 80 mass parts or less, photosensitivity can be provided, maintaining the heat resistance of the film|membrane after heat processing, chemical-resistance, and mechanical characteristic.

The resin composition of this invention may contain the compound which has a phenolic hydroxyl group for the purpose of supplementing alkali developability. 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, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T- OCHP, methyleneless-FR-CR, BisRS-26X, BisRS-OCHP, (trade name, manufactured by Honshu Chemical Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Yukizai Kogyo Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-di Hydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol and the like.

Since the resin composition containing the compound (D) used in the present invention contains a compound having these phenolic hydroxyl groups, it hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer when exposed, so that it is suitable for development. There is little film|membrane reduction|decrease by this, and image development becomes easy in a short time. Therefore, it becomes easy to improve a sensitivity.

The resin composition of this invention also contains (E) antioxidant. (E) By containing antioxidant, oxidative deterioration of the aliphatic group and phenolic hydroxyl group of (A) component is suppressed. Moreover, by the rust preventive action with respect to a metallic material, metal oxidation by external moisture, a photosensitizer, a thermal acid generator, etc., and the adhesion fall and peeling accompanying it can be suppressed. (E) As antioxidant, the compound represented by General formula (6) is preferable. By containing the compound represented by General formula (6), peeling with the mechanical characteristic or metallic material in the cured film after reliability tests, such as a high temperature storage test, can be suppressed.

(In the general formula (6), R ²⁶ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ²⁷ is an alkylene group ^{having 2 or more carbon atoms. R 28} is at least any one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. represents an organic group containing 1 to tetravalent.k represents an integer of 1 to 4. ^Examples of suitable monovalent organic groups for R 28 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkylether group, an alkylsilyl group, an alkoxysilyl group, An aryl group, an arylether group, a carboxyl group, an allyl group, a vinyl group, a heterocyclic group, etc. are mentioned as a carbonyl group, -O-, -NH-, -NHNH-, -NHCO-, -COO- etc. as a divalent organic group. Examples of the trivalent or tetravalent organic group suitable for R ²⁸ include groups in which hydrogen is substituted for the above-described monovalent or divalent organic group at a bonding point, etc. Further, a combination of these groups is exemplified; Among these, from the viewpoint of solubility to a developer and metal adhesion, it is preferable to have an alkyl ether or -NH-, and (A) metal adhesion due to interaction with component and metal complex formation. -NH- is more preferable from the point of

Although the following are mentioned as an example of the compound represented by General formula (6), It is not limited to this.

Moreover, 0.1-10 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (E) antioxidant, 0.2-5 mass parts is more preferable. When content is 0.1 mass part or more, while improving the adhesiveness with respect to a metal material, peeling is suppressed. Moreover, sensitivity maintenance of a resin composition becomes possible because content is 10 mass parts or less.

The resin composition of this invention may contain the adhesion improving agent after image development as needed.

As the adhesion improving agent after development, vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p -Styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc. Silane coupling agent, titanium chelating agent, aluminum chelate and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. You may contain these 2 or more types. For example, when developing these phenomena by containing an adhesion-improving agent after the resin film, it is possible to increase the adhesion to the silicon wafer, ITO, SiO _2, silicon nitride substrate of not. In addition, resistance to oxygen plasma and UV ozone treatment used for cleaning and the like can be improved.

As for content of the adhesion improving agent after image development, 0.01-50 mass parts is preferable with respect to 100 mass parts of (A) component. By setting it as such a range, the effect of the adhesion improving agent after each image development can fully be expressed.

Moreover, the resin composition of this invention may contain the adhesion improving agent after hardening.

It is preferable to contain the compound represented by the following general formula (7) as an adhesion improving agent after hardening.

(In the general formula (7), R ²⁹ to R ³¹ represents an O atom, an S atom, or an N atom, and ^{at least one of R 29} to R ³¹ represents an S atom. t represents 0 or 1, and u , v represents an integer of 1 or 2. R ³² to R ³⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ³² to R ³⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, An alkyl polyether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, combinations thereof, etc. are mentioned, and they may have a substituent.)

By containing the compound represented by General formula (7), the adhesiveness of the film|membrane after heat-hardening and a metal material, especially copper, can be improved remarkably, and peeling can be suppressed. This is derived from the efficient interaction of the S atom and the N atom of the compound represented by the general formula (7) with the metal surface, and is derived from the fact that the compound has a three-dimensional structure that is easy to interact with the metal surface. By these effects, the resin composition of this invention can obtain the cured film excellent in adhesiveness with a metal material.

Although the following are mentioned as an example of the compound represented by General formula (7), It is not limited to the following structure.

The resin composition of the present invention may contain other post-curing adhesion improving agents in addition to the compound represented by the general formula (7). Examples of the other post-curing adhesion improving agent include an alkoxysilane-containing aromatic amine compound, an aromatic amide compound, or an aromatic-free silane compound. You may contain these 2 or more types. By containing these compounds, the adhesiveness with the base material after baking or hardening can be improved.

Specific examples of the alkoxysilane-containing aromatic amine compound and the aromatic amide compound are shown below. In addition, it may be a compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound, for example, an aromatic amine compound and an alkoxysilane compound having a group that reacts with an amino group such as an epoxy group or a chloromethyl group A compound obtained by reacting, etc. can be heard

Examples of the aromatic-free silane compound include vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinyltris(βmethoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane , 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane containing carbon-carbon unsaturated bonds compounds, and the like. Among these, vinyl trimethoxysilane and vinyl triethoxysilane are preferable.

As for content of the adhesion improving agent after hardening represented by General formula (7) used for the resin composition of this invention, 0.1-10 mass parts is preferable with respect to 100 mass parts of (A) component. When content of the adhesion improving agent after hardening shall be 0.1 mass part or more with respect to 100 mass parts of (A) component, since the adhesive effect with respect to a metal material etc. can fully be acquired, it is preferable. In addition, when the content of the adhesion improving agent after curing is 10 parts by mass or less with respect to 100 parts by mass of the component (A), when the resin composition used in the present invention is a positive photosensitive resin composition, by interaction with the photosensitive agent, A decrease in the sensitivity of the resin composition before curing can be suppressed.

Here, as for content of another post-hardening adhesion improving agent, 0.01-15 mass parts is preferable with respect to 100 mass parts of (A) component. By setting it as such a range, adhesiveness with the base material after baking or hardening can be improved. In addition, it may contain a compound that acts as an adhesion improving agent after development and also as an adhesion improving agent after curing, such as vinyltrimethoxysilane and vinyltriethoxysilane.

The resin composition of this invention may contain surfactant in order to improve wettability with a board|substrate as needed, or to improve the film thickness uniformity of a coating film. As the surfactant, a commercially available compound can be used. Specifically, as the silicone-based surfactant, the SH series, SD series, ST series of Toray Dow Corning Silicone, the BYK series of Big Chemi Japan, KP series of Shin-Etsu Silicone, and Japan Disform series by Yushi Corporation, TSF series by Toshiba Silicone Corporation, etc. are mentioned, As a fluorine-type surfactant, "Megapack" (registered trademark) series of Dainippon Ink Kogyo Corporation, Florad series of Sumitomo 3M Corporation, Asahi Glass Corporation, etc. are mentioned. "Suflon" (registered trademark) series, "Asahigard" (registered trademark) series, Saeakita Kasei's EF series, Omnova Solutions' Polyfox series, etc. are mentioned, Acrylic and/or methacrylic type Examples of the surfactant obtained from the polymer include, but are not limited to, the Polyflow series by Kyoeisha Chemical, the "Dispalon" (registered trademark) series by Kusumoto Chemicals, and the like.

As for content of surfactant, 0.001 mass part or more and 1 mass part or less are preferable with respect to 100 mass parts of (A) component. By setting it as the above-mentioned range, problems, such as a bubble and a pinhole, do not generate|occur|produce, but wettability with a board|substrate and the film thickness uniformity of a coating film can be improved.

The resin composition of this invention may contain other alkali-soluble resin other than (A) component. Specifically, alkali-soluble polyimide, polybenzoxazole, acrylic polymer copolymerized with acrylic acid, novolak resin, resol resin, polymer containing a radically polymerizable monomer having an alkali-soluble group, siloxane resin, cyclic olefin resin, cardo and resins having a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the structure, that is, the cyclic structure. Such resin is dissolved in an alkaline solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. By containing these alkali-soluble resins, the characteristic of each alkali-soluble resin can be provided, maintaining the adhesiveness of a cured film and the outstanding sensitivity.

It is preferable that the resin composition of this invention contains a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. Polar aprotic solvents such as , 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide , ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate , esters such as propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol, toluene, xylene Aromatic hydrocarbons, such as these, etc. are mentioned. You may contain these 2 or more types.

In order that content of a solvent may melt|dissolve a composition with respect to 100 mass parts of (A) component, it is preferable to contain 100 mass parts or more, and in order to form a coating film with a film thickness of 1 micrometer or more, it is preferable to contain 1,500 mass parts or less. .

Next, the resin composition manufacturing method of this invention is demonstrated. For example, each component of said (A), (B), and (E), Preferably each component of (C)-(D), further, if necessary, a compound having a phenolic hydroxyl group, and adhesion after development A resin composition can be obtained by dissolving an improving agent, an adhesion improving agent after curing, a surfactant, other resin, a solvent, and the like. Heating and stirring are mentioned as a melt|dissolution method. When heating, it is preferable to set heating temperature in the range which does not impair the performance of the photosensitive colored resin composition, and it is room temperature - 80 degreeC normally. In addition, the dissolution order of each component is not specifically limited, For example, there exists a method of dissolving one by one from a low solubility compound. When stirring, it is preferable to set rotation speed in the range which does not impair the performance of the photosensitive colored resin composition, and it is 200 rpm - 2000 rpm normally. When stirring, you may heat as needed, and it is room temperature - 80 degreeC normally. In addition, for components that are likely to generate bubbles during stirring and dissolution, such as surfactants and some post-development adhesion improving agents, it is possible to prevent poor dissolution of other components due to the generation of bubbles by adding them last after dissolving the other components. can

As for the viscosity of the resin composition of this invention, 2-5,000 mPa*s is preferable. It becomes easy to obtain a desired film thickness by adjusting solid content concentration so that a viscosity may become 2 mPa*s or more. On the other hand, if the viscosity is 5,000 mPa·s or less, it becomes easy to obtain a coating film with high uniformity. The resin composition which has such a viscosity can be obtained easily by making solid content concentration into 5-60 mass %, for example.

It is preferable to filter the obtained resin composition using a filtration filter, and to remove dust and particle|grains. The filter pore diameter includes, for example, 0.5 µm, 0.2 µm, 0.1 µm, 0.05 µm, 0.02 µm, and the like, but is not limited thereto. Although there exist polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc. as a material of a filtration filter, polyethylene and nylon are preferable.

Next, the resin composition of this invention, the resin film formed from the resin composition, or the manufacturing method of the cured film using the resin sheet is demonstrated.

In addition, here, a resin film is defined as the film|membrane obtained by apply|coating the resin composition of this invention on a board|substrate, and making it dry. A resin sheet is defined as a sheet obtained by applying and drying a resin composition on a releasable substrate. In addition, a cured film is defined as the film|membrane obtained by hardening|curing a resin film or a resin sheet.

The resin composition of this invention is apply|coated to a board|substrate, and the coating film of the resin composition is obtained. Examples of the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and those in which circuit constituent materials are arranged on these substrates. As a coating method, there exist methods, such as a spin coating method, the slit coating method, the dip coating method, the spray coating method, and the printing method. In addition, although the coating film thickness changes with the coating method, the solid content concentration of a composition, a viscosity, etc., it apply|coats so that the film thickness after drying may be normally set to 0.1-150 micrometers.

Prior to application, the substrate to which the resin composition is applied may be pre-treated with the above-described post-development adhesion improving agent. For example, 0.5 to 20% by mass of the adhesion improving agent after development in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. A method of treating the surface of a substrate by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment using the dissolved solution is exemplified. If necessary, a reduced pressure drying treatment may be performed, followed by heat treatment at 50° C. to 280° C. to advance the reaction of the adhesion improving agent after development with the substrate.

Next, the coating film of the resin composition is dried to obtain a resin film. Drying is preferably performed in a range of 50°C to 140°C for 1 minute to several hours using an oven, a hot plate, infrared rays, or the like.

On the other hand, when using a resin sheet formed from the resin composition of the present invention, when the resin sheet has a protective film, it is peeled off, the resin sheet and the substrate are opposed, and the resin sheet and the substrate are bonded by thermocompression bonding (resin sheet and substrate). It is sometimes described that a resin sheet is laminated on a base material to face and join by thermocompression bonding). Next, the resin sheet laminated on the base material is dried in the same manner as in obtaining the above resin film to form a resin film. A resin sheet can be obtained by apply|coating and drying the resin composition of this invention on the support film comprised with the polyethylene terephthalate etc. which are a peelable base material.

The thermocompression bonding can be performed by a hot press process, a hot lamination process, a hot vacuum lamination process, etc. As for bonding temperature, 40 degreeC or more is preferable at the point of the adhesiveness to a board|substrate, and embedding property. Moreover, when a resin sheet has photosensitivity, in order to prevent that a resin sheet hardens at the time of bonding, and the resolution of pattern formation in an exposure and image development process falls, 140 degrees C or less of bonding temperature is preferable.

When the resin film has photosensitivity, actinic rays are irradiated through a mask having a desired pattern on the film. Actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays. In the present invention, it is preferable to use general exposure wavelengths of g-ray (436 nm), h-ray (405 nm), and i-ray (365 nm). .

Next, the exposed resin film having photosensitivity is developed, and the exposed portion is removed. The developer is tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound exhibiting alkalinity, such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine, is preferable. In addition, in some cases, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, etc. polar solvents, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone 1 You may contain the species or 2 or more types. After development, it is common to rinse with water. Here too, alcohols, such as ethanol and isopropyl alcohol, esters, such as ethyl lactate, propylene glycol monomethyl ether acetate, etc. may be added to water, and you may rinse process.

The resin film thus obtained is subjected to a temperature of 140°C to 280°C to advance a thermal crosslinking reaction to improve heat resistance and chemical resistance (this step is sometimes referred to as a heat treatment step). This heat treatment is performed for 5 minutes to 5 hours while selecting a temperature and increasing the temperature stepwise, or selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. As curing conditions in this invention, 140 degreeC or more and 280 degrees C or less are preferable. In order to advance a thermal crosslinking reaction, 140 degreeC or more is preferable, and, as for curing conditions, 160 degreeC or more is more preferable. In addition, in order to provide an excellent cured film especially by curing at a low temperature, and to suppress the operation failure accompanying the thermal history of a semiconductor device described later, and to improve the yield, 280° C. or less is preferable, and 250° C. or less is more preferable, and 220°C or less is still more preferable.

The cured film which hardened|cured the resin composition or resin sheet of this invention can be used for electronic components, such as a semiconductor device and a multilayer wiring board. Specifically, it is suitably used for applications such as a passivation film (interlayer insulating film, surface protective film) for semiconductors, a protective film for semiconductor devices (sometimes referred to as a semiconductor protective film), and an interlayer insulating film for high-density mounting multilayer wiring. As an electronic device which has a surface protection film, an interlayer insulating film, etc. which arrange|positioned the cured film of this invention, MRAM etc. with low heat resistance are mentioned, for example. That is, the cured film of this invention is suitable as objects for surface protective films of MRAM. In addition to MRAM, promising next-generation memories such as Polymer Ferroelectric RAM (PFRAM) and Phase Change RAM (PCRAM, or Ovonics Unified Memory: OUM) may use new materials with lower heat resistance than conventional memories. this is high Therefore, the cured film of this invention is suitable also as objects for these surface protective films. In addition, a display device including a first electrode formed on a substrate and a second electrode provided to face the first electrode, specifically, for example, LCD, ECD, ELD, a display device using an organic electroluminescent element ( It can be used for insulating layers, such as an organic electroluminescent device). In particular, in recent years, with the further miniaturization of structures, semiconductor devices with copper electrodes, copper wirings, and bumps have become mainstream in the electrode, multilayer wiring, and circuit board wiring of semiconductor elements. During etching and resist pattern formation, it is in contact with many chemical solutions such as flux. When a resin film formed from the resin composition of the present invention is used as a protective film for such an electrode and wiring, it has high resistance to these chemicals, and therefore is particularly preferably used.

Next, about the cured film which hardened|cured the resin composition or resin sheet of this invention, the application example to the semiconductor device which has a bump is demonstrated using drawings. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps. 1, a passivation film 3 is formed on an input/output aluminum pad (hereinafter referred to as an Al pad) 2 on a silicon wafer 1, and a via hole is formed in the passivation film 3, have. Further, an insulating film 4 formed by using the resin composition or resin sheet of the present invention is formed thereon, and a metal film 5 made of Cr, Ti or the like is formed so as to be connected to the Al pad 2 . By etching the periphery of the solder bump 10 of the metal film 5, each pad is insulated. A barrier metal 8 and solder bumps 10 are formed on the insulated pad. When a flexible component is introduce|transduced into a resin composition, since the curvature of a wafer is small, exposure and conveyance of a wafer can be performed with high precision. In addition, since polyimide resins and polybenzoxazole resins have excellent mechanical properties, stress from the sealing resin can be relieved even during mounting, so that the low-k layer (the dielectric constant used as an inner interlayer insulating film material of a semiconductor device has a lower dielectric constant). By preventing damage to the layer containing low material), it is possible to provide a highly reliable semiconductor device.

Next, the detailed manufacturing method of a semiconductor device is described. In the process of 2a of FIG. 2, the resin composition of the present invention is applied on the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed, and the insulating film 4 is patterned through a photolithography process. to form Subsequently, in the step 2b, the metal film 5 is formed by sputtering. As shown in 2C of FIG. 2 , a metal wiring 6 is formed on the metal film 5 by a plating method. Next, as shown in 2d' of FIG. 2, the resin composition of the present invention is applied or a resin sheet is attached, and through a photolithography process, the insulating film 7 is formed in a pattern as shown in 2d of FIG. . At this time, the resin composition of the insulating film 7 is subjected to thick film processing in the scribe line 9 . A wiring (so-called rewiring) can also be formed on the insulating film 7 . In the case of forming a multilayer wiring structure of two or more layers, by repeating the above steps, the two or more layers of rewiring are separated by the interlayer insulating film obtained from the resin composition or resin sheet of the present invention (that is, the rewiring and the interlayer insulating film). It is possible to form a semiconductor electronic component or semiconductor device having a multilayer wiring structure (which is repeatedly arranged in two or more layers). At this time, the formed insulating film comes into contact with various chemical liquids several times, but since the insulating film obtained from the resin composition of the present invention has excellent adhesion and chemical resistance, a good multilayer wiring structure can be formed. Although there is no upper limit to the number of layers of a multilayer wiring structure, 10 or less layers are often used.

Next, as shown to 2e and 2f of FIG. 2, the barrier metal 8 and the solder bump 10 are formed. Then, it is diced along the scribe line 9 and cut out for each chip. When the insulating film 7 is not patterned in the scribe line 9 or a residue remains, cracks or the like occur during dicing, affecting the reliability of the chip. For this reason, like the present invention, it is very desirable to be able to provide pattern processing excellent in thick film processing in order to obtain high reliability of the semiconductor device.

Moreover, the resin composition of this invention is used suitably also for a fan-out wafer level package (fan-out WLP).

3 is a cross-sectional view of a manufacturing process of a semiconductor device according to an embodiment of the present invention. Specifically, it is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film of the present invention, and has a structure called a fan-out wafer level package (fan-out WLP). As in the above application example 1, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 were formed was diced, cut into chips, and then sealed with a resin 11 . Over this sealing resin 11 and the chip, an insulating film 4 is formed as a pattern by the photosensitive resin composition of the present invention, and further, a metal (Cr, Ti, etc.) film 5 and metal wiring 6 are formed. this is formed Thereafter, a barrier metal 8 and solder bumps 10 are formed in the openings of the insulating film 7 formed on the sealing resin outside the chip.

In the fan-out WLP, an extension portion is provided around the semiconductor chip using a sealing resin such as an epoxy resin, rewiring is performed from the electrode on the semiconductor chip to the extension portion, and a solder ball is also mounted on the extension portion, so that the necessary terminals It is a semiconductor package that has secured a number. In the fan-out WLP, wiring is provided so as to cross the boundary line formed by the main surface of the semiconductor chip and the main surface of the encapsulating resin. That is, an interlayer insulating film is formed on an adjacent base material (substrate) composed of two or more types of materials such as a semiconductor chip to which metal wiring has been applied and a sealing resin, and wiring is formed on the interlayer insulating film. In addition to this, in a semiconductor package of a type in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is provided so as to span the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. Also in this aspect, an interlayer insulating film is formed on the adjacent base material (substrate) which consists of 2 or more types of materials, and wiring is formed on this interlayer insulating film. Thus, in a semiconductor electronic component or semiconductor device, the cured film formed by curing the resin composition of the present invention has high adhesion to a semiconductor chip provided with metal wiring, and also has a high adhesion to a sealing resin with an epoxy resin or the like. It is suitably used as an interlayer insulating film provided on the adjacent base material (substrate) which consists of 2 or more types of materials.

Moreover, the resin composition of this invention is used suitably also for the coil component of an inductor device.

4 is a cross-sectional view of a coil component of an inductor device according to an embodiment of the present invention.

As shown in FIG. 4 , 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 resin composition having photosensitivity 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 by plating thereon. The metal wiring 16 (Ag, Cu, etc.) is formed in a spiral shape. By repeatedly laminating the steps of forming 13 to 16 a plurality of times, the function as a coil can be provided. Finally, the metal wiring 16 (Ag, Cu, etc.) is connected to the electrode 18 by the metal wiring 17 (Ag, Cu, etc.), and is sealed by the sealing resin 19 .

Example

Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. In addition, evaluation of the resin composition in an Example was performed with the following method. In addition, the resin composition (henceforth a varnish) filtered previously with the 1 micrometer polytetrafluoroethylene filter (made by Sumitomo Denki Kogyo Co., Ltd.) was used for evaluation.

(1) Calculation of exchange rate closing of cured film

The varnish was applied and pre-baked on an 8-inch silicon wafer by spin coating using a coating and developing device ACT-8 so that the film thickness after prebaking at 120° C. for 3 minutes was 11 μm, followed by inert oven CLH Using -21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200°C or 220°C at 4.0°C/min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 200°C or 220°C for 1 hour. When temperature became 50 degrees C or less, the silicon wafer was taken out and the cured film (A) was obtained. Furthermore, the cured film (B) heated at 300-350 degreeC was obtained. The infrared absorption spectra of these cured films (A) and cured films (B) were measured, and the absorbance of the peak resulting from CO stretching vibration of ^{1050 cm -1 vicinity was calculated|required.} For the measurement of the infrared absorption spectrum, "FT-720" (trade name, manufactured by Horiba, Ltd.) was used as a measuring device. The exchange rate of the cured film (B) was 100%, and the exchange rate of the cured film (A) was computed from the following formula. The ring-closure rate as used herein is the ring-closure rate of the poly(o-hydroxyamide) structural unit.

In the present Example, the cured film was produced from the varnish as mentioned above, and calculation of the exchange rate was performed.

The thing having a closure rate of 40% or more was regarded as very good, the thing of 3, 30% or more and less than 40% was regarded as good, and the thing of 2 and 30% was regarded as bad and evaluated as 1.

As for the heating temperature for obtaining a cured film (B), if a cured film does not thermally decompose, it is preferable to heat at 320 degreeC. The thermal decomposition temperature of the cured film can be analyzed by thermogravimetric reduction measurement (TGA).

(2) Evaluation of heat resistance

The varnish was applied and pre-baked on an 8-inch silicon wafer by spin coating using a coating and developing device ACT-8 so that the film thickness after prebaking at 120° C. for 3 minutes was 11 μm, followed by inert oven CLH Using -21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200°C or 220°C at 4.0°C/min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 200°C or 220°C for 1 hour. The cured film of the resin composition was peeled from the wafer by taking out a silicon wafer when temperature became 50 degrees C or less, and immersing in 45 mass % hydrofluoric acid for 5 minutes. This film was cut into a rectangle having a width of 0.5 cm and a length of 10 cm, and when heated from room temperature to 400° C. at a temperature increase rate of 10° C./min using a thermogravimetric measurement device TGDTA6200 (manufactured by Hitachi High-Tech Science, Ltd.) 5% weight The decreasing temperature was measured.

The value of the 5% weight loss temperature evaluated 315 degreeC or more as favorable, and made a thing below 2, 315 degreeC bad, and evaluated it as 1.

(3) Evaluation of chemical resistance

The varnish was applied on a silicon wafer by a spin coating method using a coating and developing device ACT-8 so that the film thickness after prebaking at 120°C for 3 minutes was 10 µm, and after prebaking, inert oven CLH Using -21CD-S, the temperature was raised to 200°C or 220°C at 4.0°C/min with an oxygen concentration of 20 ppm or less under a nitrogen stream, and heat treatment was performed at 200°C or 220°C for 1 hour. When the temperature reached 50° C. or less, the silicon wafer was taken out, and the cured film was immersed in an organic chemical solution (dimethyl sulfoxide: 25% aqueous tetramethylammonium hydroxide = 92: 2) at 65° C. for 100 minutes, and the pattern was peeled off or The presence or absence of elution was observed.

As a result, when there was no peeling or elution of a pattern, it was set as 2 as favorable, and when peeling or elution of a pattern was observed, it was set as bad and evaluated as 1.

(4)-1. Elongation at break evaluation

The varnish was applied and pre-baked on an 8-inch silicon wafer by spin coating using a coating and developing device ACT-8 so that the film thickness after prebaking at 120° C. for 3 minutes was 11 μm, followed by inert oven CLH Using -21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200°C or 220°C at 4.0°C/min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 200°C or 220°C for 1 hour. The cured film of the resin composition was peeled from the wafer by taking out a silicon wafer when temperature became 50 degrees C or less, and immersing in 45 mass % hydrofluoric acid for 5 minutes. The film was cut into a rectangle having a width of 1 cm and a length of 9 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the film was pulled at a tensile rate of 50 mm/min at room temperature 23.0° C. and humidity 45.0% RH, and the break point Elongation was measured. The measurement was performed with respect to 10 rectangles per sample, and the average value of the top 5 points was calculated|required from the result.

The value of the elongation at break made 60% or more very good, 3, 40% or more and less than 60% made good, 2, 40% or less made bad, and evaluated it as 1.

(4)-2. Peel evaluation on copper wiring after High Temperature Storage (HTS)

In performing peeling evaluation in copper wiring, the following evaluation board|substrates were prepared.

On an 8-inch silicon wafer, cylindrical copper wirings having a thickness of 5 µm and a diameter of 90 µm were produced at equal intervals so that the distance between the centers of the copper wirings was set to 150 µm. This was used as an evaluation substrate.

The varnish was applied and prebaked on the evaluation substrate by spin coating using a coating and developing device ACT-8 so that the film thickness after prebaking at 120° C. for 3 minutes was 11 μm, followed by prebaking in Inert Oven CLH-21CD Using -S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200°C at 4.0°C/min with an oxygen concentration of 20 ppm or less, and heat treatment was performed at 200°C for 1 hour. When the temperature became 50 degrees C or less, the evaluation board|substrate (hereafter referred to as a sample) was taken out. Next, the sample was put into a thermostat at 175° C. and treated for 200 hours. Then, in order to take out a sample and observe peeling in a copper wiring, using the scanning electron microscope FEI Helios650 (made by FEI Co., Ltd.) attached to a converging ion beam processing apparatus, cutting of a sample, and cross-sectional observation at 40,000 times magnification. was done. As an evaluation method, the degree of peeling of the copper wiring side part is observed, peeling 0% or more and less than 25% is considered very good 3, peeling 25% or more and less than 50% is considered good 2, and peeling 50% is considered bad 1 was evaluated as

<Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound>

18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter referred to as BAHF), 100 mL of acetone, and propylene oxide (Tokyo) It was dissolved in 17.4 g (0.3 mol) of Kasei Co., Ltd. and cooled to -15°C. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dripping, it stirred at -15 degreeC for 4 hours, and returned to room temperature after that. The precipitated white solid was separated by filtration and vacuum dried at 50°C.

30 g of the obtained white solid was put in a 300 mL stainless steel autoclave, it was dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into this by a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon was no longer extinguished and the reaction was terminated. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated in a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

<Synthesis Example 2 Synthesis of polyimide precursor (A-1)>

Under a stream of dry nitrogen, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. To this were added 39.30 g (0.065 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane together with 50 g of NMP, 20 It was reacted at ℃ for 1 hour, and then reacted at 50℃ for 2 hours. Then, RT-1000 (10.00 g, 0.010 mol) containing a propylene oxide and tetramethylene ether glycol structure was added together with 10 g of NMP, and it was made to react at 50 degreeC for 1 hour. Then, 4.36 g (0.04 mol) of 4-aminophenol as a terminal blocker was added together with 5 g of NMP, and the reaction was carried out at 50°C for 2 hours. Thereafter, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours. After completion of stirring, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor (A-1), which is the target alkali-soluble resin.

<Synthesis Example 3 Synthesis of polybenzoxazole precursor (A-2)>

Under a stream of dry nitrogen, 27.47 g (0.075 mol) of BAHF was dissolved in 257 g of NMP. Here, 1,1'-(4,4'-oxybenzoyl)diimidazole (hereinafter referred to as PBOM) (17.20 g, 0.048 mol) was added along with 20 g of NMP, followed by reaction at 85°C for 3 hours. Subsequently, RT-1000 (20.00 g, 0.020 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.005 mol), PBOM containing propylene oxide and tetramethylene ether glycol structure (14.33 g, 0.044 mol) was added together with 50 g of NMP, and reacted at 85°C for 1 hour. Further, as a terminal blocker, 5-norbornene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol) was added together with 10 g of NMP, and reacted at 85°C for 30 minutes. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (52.82 g, 0.50 mol) was added along with 87 g of NMP, followed by stirring at room temperature for 1 hour. After completion of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water 3 times, and then dried in a ventilation dryer at 50°C for 3 days to obtain a powder of a polybenzoxazole precursor (A-2).

<Synthesis Example 4 Synthesis of polybenzoxazole precursor (A-3)>

According to Synthesis Example 3, ED-900 (9.00 g, 0.020 mol), 1,3- containing BAHF (27.47 g, 0.075 mol), PBOM (30.10 g, 0.084 mol), propylene oxide and ethylene glycol structure Bis(3-aminopropyl)tetramethyldisiloxane (1.24 g, 0.0050 mol), 5-norbornene-2,3-dicarboxylic anhydride (5.25 g, 0.032 mol), acetic acid (48.02 g, 0.80 mol) , it carried out similarly using 409 g of NMP, and obtained the powder of a polybenzoxazole precursor (A-3).

<Synthesis Example 5 Synthesis of polybenzoxazole precursor (A-4)>

According to Synthesis Example 3, BAHF (32.96 g, 0.090 mol), PBOM (29.38 g, 0.082 mol), RT-1000 (10.00 g, 0.010 mol), 1,3-bis (3-aminopropyl) tetramethyldi Siloxane (1.49 g, 0.0060 mol), 5-norbornene-2,3-dicarboxylic anhydride (5.91 g, 0.036 mol), HFHA (0.60 g, 0.0010 mol), ODPA (2.17 g, 0.0070 mol), It carried out similarly using acetic acid (49.22 g, 0.82 mol) and NMP 360g, and obtained the powder of polybenzoxazole precursor (A-4).

<Synthesis Example 6 Synthesis of polyamideimide precursor (A-5)>

Under a dry nitrogen stream, 27.5 g (0.10 mol) of anhydrous diphenyl ether tricarboxylic acid chloride was dissolved in 500 g of NMP. To this were added 39.30 g (0.065 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane together with 50 g of NMP, 20 The reaction was carried out at ℃ for 1 hour, followed by reaction at 50 ℃ for 2 hours. Then, RT-1000 (10.00 g, 0.010 mol) containing a propylene oxide and tetramethylene ether glycol structure was added together with 10 g of NMP, and it was made to react at 50 degreeC for 1 hour. Then, 4.36 g (0.04 mol) of 4-aminophenol as a terminal blocker was added together with 5 g of NMP, and the reaction was carried out at 50°C for 2 hours. Thereafter, a solution obtained by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours. After completion of stirring, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyamideimide precursor (A-5).

[Reference Examples 1 to 15]

To 10 g of the obtained (A) component (A-1 to 5), (B) 3-(5-(((phenylsulfonyloxy)imino)thiophene-2(5H)-ylidene-2- as a thermal acid generator 0.2 g (0.52 mmol) of (o-tolyl) propanenitrile (B-1), or 0.2 g (0.53 mmol) of SI-200 (B-2), (C) HMOM-TPHAP (C-1) as a thermal crosslinking agent ) 2.4 g (4.2 mmol) and MW-100LM (C-2) 1.0 g (2.6 mmol), (D) 2.0 g (1.8 mmol) of a photosensitive compound represented by the following formula as a photosensitive compound, and as a solvent 20 g of γ-butyrolactone was added to prepare varnishes, and their properties were measured by the above evaluation method.The results obtained are shown in Table 1.

[Reference Examples 16 to 20]

(B) Varnishes were produced in the same manner as in Reference Examples 1 to 15 except that no thermal acid generator was used, and their properties were measured by the above evaluation method. The obtained results are shown in Table 1.

[Examples 1 to 8, Comparative Examples 1 to 9]

To 10 g of the obtained (A) component (A-1 to 5), (B) 3-(5-(((phenylsulfonyloxy)imino)thiophene-2(5H)-ylidene-2- as a thermal acid generator (o-tolyl)propanenitrile (B-1) 0.2 g (0.52 mmol), or SI-200 (B-2) 0.2 g (0.53 mmol), or 0.5 g (1.3 mmol), or 0.8 g (2.1 mmol), (C) 2.4 g (4.2 mmol) of HMOM-TPHAP (C-1) and 1.0 g (2.6 mmol) of MW-100LM (C-2) as a thermal crosslinking agent, or a thermal crosslinking agent represented by the following formula ( C-3) 0.2 g (0.25 mmol), or 1.5 g (1.9 mmol), or 5.1 g (6.5 mmol), (D) 2.0 g (1.8 mmol) of the photosensitive compound represented by the following formula as the photosensitive compound, ( E) 0.15 g (0.26 mmol) of compound (E-1) represented by the following formula as an antioxidant or 0.15 g (0.27 mmol) of (E-2) is added, and 20 g of γ-butyrolactone is added as a solvent. The varnish was produced, and these properties were measured by the above evaluation method.The results obtained are shown in Table 2.

[Comparative Examples 10 to 15]

(B) A varnish was prepared in the same manner as in Comparative Examples 2 and 6 to 9 except that a thermal acid generator was not used (Comparative Examples 10 to 14), or (B) SI-200 (B-2) was used as a thermal acid generator A varnish was produced in the same manner as in Comparative Example 2 (Comparative Example 15) except that 1.2 g (3.2 mmol) was added, and these properties were measured by the above evaluation method. The obtained results are shown in Table 2.

1: Silicon wafer
2: Al pad
3: passivation film
4: insulating film
5: Metal (Cr, Ti, etc.) film
6: Metal wiring (Al, Cu, etc.)
7: insulating film
8: barrier 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 (20)

(A) a polybenzoxazole precursor, a polyimide precursor, a polyamideimide precursor, and at least one selected from copolymers thereof, has a benzoxazole precursor structure, and is represented by the following general formula (1) Alkali-soluble resin having the structural unit shown, and
(B) A resin composition containing a thermal acid generator and (E) antioxidant.

(In the general formula (1), each X independently represents a 2 to 8 valent organic group having 2 or more carbon atoms. Y represents a 2 to 8 valent organic group having 2 or more carbon atoms, wherein the following general formula ( 2) has an aliphatic group represented by R ¹ and R ² each independently represents hydrogen or an organic group having 1 to 20 carbon atoms n represents an integer within the range of 10 to 100,000 r and s are 0 to 2 Integers within the range, p and q represent integers within the range of 0 to 4.)

(In the general formula (2), R ³ to R ⁶ each independently represents an alkylene group having 1 to 6 carbon atoms. R ⁷ to R ¹⁴ each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms. However, the structures shown in parentheses are different. Each of x, y, and z independently represents an integer of 0 to 35.) delete delete delete delete The method according to claim 1, wherein the (B) thermal acid generator comprises at least one compound selected from a sulfonic acid ester compound represented by the following general formula (3), a sulfonic acid ester compound represented by the general formula (4), and an onium salt. Including, a resin composition.

(In general formulas (3) and (4), R ²⁰ to R ²² each independently represent an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 4 to 12 carbon atoms.) The resin composition according to claim 1, wherein the thermal decomposition initiation temperature of the (B) thermal acid generator is 140°C or more and 220°C or less. The resin composition according to claim 1, further comprising (C) a thermal crosslinking agent and (D) a photosensitive compound. The resin composition according to claim 8, wherein the thermal crosslinking agent (C) contains a thermal crosslinking agent having a structural unit represented by the general formula (5).

(In the general formula (5), R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group. R ²³ is a divalent organic group having an alkylene group having 2 or more carbon atoms, and any of linear, branched and cyclic Any.) The resin composition according to claim 1, wherein the (E) antioxidant contains a compound represented by the general formula (6).

(In the general formula (6), R ²⁶ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ²⁷ is an alkylene group ^{having 2 or more carbon atoms. R 28} is at least any one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. A 1-4 valent organic group is represented. k represents an integer of 1-4.) A resin sheet formed from the resin composition according to claim 1 . The cured film which hardened the resin composition of Claim 1. The cured film which hardened the resin sheet of Claim 11. The cured film of Claim 12 or 13 whose ratio by which the benzoxazole precursor structure is ring-closed with polybenzoxazole is 30 % or more. The resin composition according to any one of claims 1 and 6 to 10 is applied on a substrate and dried to form a resin film, or the resin sheet according to claim 11 is laminated on a substrate and dried a process of forming a resin film,
An exposure step of exposing the dried resin film, a developing step of developing the exposed resin film,
and a heat treatment step of heat treatment of the developed resin film. The manufacturing method of the cured film of Claim 15 in which the heat processing process of heat-processing the said developed resin film includes the process of heat-processing at 140 degreeC or more and 220 degrees C or less. The interlayer insulating film or semiconductor protective film in which the cured film of Claim 12 or 13 was arrange|positioned. A semiconductor electronic component or semiconductor device in which the cured film according to claim 12 or 13 is disposed as an interlayer insulating film between rewiring. The semiconductor electronic component or semiconductor device according to claim 18, wherein the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. A semiconductor electronic component or semiconductor device, wherein the cured film according to claim 12 or 13 is disposed as an interlayer insulating film of an adjacent substrate composed of two or more kinds of materials.

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