TWI732855B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition that can be cured by heat treatment at a low temperature while obtaining a cured film excellent in heat resistance, chemical resistance, and breaking elongation.

唑前驅物、聚醯亞胺前驅物、聚醯胺醯亞胺前驅物及該等之共聚物的1種以上而成，且具有苯并

唑前驅物結構及脂肪族基的鹼可溶性樹脂；以及(B)熱酸產生劑及(E)抗氧化劑。 The resin composition of the present invention contains: (A) containing polybenzo

Azole precursor, polyimide precursor, polyimide precursor and one or more of these copolymers, and have benzo

Alkali-soluble resin with azole precursor structure and aliphatic base; and (B) thermal acid generator and (E) antioxidant.

Description

Resin composition

The present invention relates to a resin composition suitable for use in surface protection films of semiconductor elements, interlayer insulating films, and insulating layers of organic electroluminescence elements.

唑系樹脂。 In the past, polyimide resins with excellent heat resistance, electrical insulation, and mechanical properties have been widely used in surface protection films or interlayer insulating films of semiconductor elements, insulating layers of organic electroluminescence elements, or flattening films of TFT substrates. Polybenzo

Azole resin.

唑前驅物、聚醯胺醯亞胺前驅物的塗膜進行熱性脫水閉環以得到耐熱性、機械特性優異之薄膜的情況，通常需要進行350℃左右的高溫燒製。此外，有時將使聚醯亞胺前驅物、聚苯并

唑前驅物、聚醯胺醯亞胺前驅物的塗膜進行熱性脫水閉環以得到耐熱性、機械特性優異之薄膜時的操作稱為燒製，並將塗膜的變化稱為硬化。然而，從近年來所使用的記憶體元件、或半導體封裝體製作時所用的模製樹脂等無法耐受高溫製程的觀點、以及從半導體封裝體可靠度的觀點來看，尋求表面保護膜或層間絕緣膜為可在250℃以下、再佳為220℃以下的低溫下進行燒製而硬化，而且具有高機械特性、熱特性的聚醯亞胺系樹脂、聚苯并

唑系樹脂、聚醯胺醯亞胺系樹脂。 Make polyimide precursors, polybenzo

When the coating film of the azole precursor and polyimide precursor is subjected to thermal dehydration and loop closure to obtain a film with excellent heat resistance and mechanical properties, it is usually necessary to perform high-temperature firing at about 350°C. In addition, sometimes it will make polyimide precursors, polybenzo

The operation when the coating film of the azole precursor and the polyimide precursor is thermally dehydrated and closed to obtain a film with excellent heat resistance and mechanical properties is called firing, and the change of the coating film is called curing. However, from the viewpoint that the memory elements used in recent years or the molding resin used in the production of semiconductor packages cannot withstand high-temperature processes, and from the viewpoint of the reliability of semiconductor packages, there is a need for surface protection films or interlayers. The insulating film is made of polyimide resins and polybenzos that can be fired at a low temperature of 250°C or less, and preferably 220°C or less, and have high mechanical and thermal properties.

Azole-based resins, polyimide-based resins.

唑、聚苯并咪唑、聚苯并噻唑等樹脂及熱交聯劑的樹脂組成物(專利文獻1)；含有鹼可溶性聚醯胺醯亞胺、光酸產生劑、溶劑及交聯劑的正型感光性聚醯胺醯亞胺樹脂組成物(專利文獻2)；含有鹼可溶性聚醯亞胺、醌二疊氮化合物、熱交聯劑、熱酸產生劑及密合改良劑的正型感光性聚醯亞胺樹脂組成物(專利文獻3)等。 As a resin composition that can be cured at a low temperature, it is known that it contains polyimide, polybenzo

Resin composition of resins such as azoles, polybenzimidazoles, polybenzothiazoles, and thermal crosslinking agents (Patent Document 1); a positive composition containing alkali-soluble polyamidoimines, photoacid generators, solvents, and crosslinking agents Type photosensitive polyimide resin composition (Patent Document 2); positive type photosensitive containing alkali-soluble polyimide, quinonediazide compound, thermal crosslinking agent, thermal acid generator, and adhesion improver Polyimide resin composition (Patent Document 3) and the like.

Prior art literature Patent literature

Patent Document 1 JP 2007-16214 A

Patent Document 2 JP 2007-240554 A

Patent Document 3 JP 2013-72935 A

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

The purpose of the present invention is to solve the above-mentioned problems associated with the prior art, and to provide a resin composition that can be cured by heat treatment at a low temperature while obtaining a cured film excellent in heat resistance, chemical resistance, and breaking elongation .

唑前驅物、聚醯亞胺前驅物、聚醯胺醯亞胺前驅物、及該等之共聚物的1種以上而成，且具有苯并

唑前驅物結構及脂肪族基的鹼可溶性樹脂；以及(B)熱酸產生劑及(E)抗氧化劑。 The present invention has the following constitution. That is, a resin composition containing: (A) containing polybenzo

Azole precursor, polyimide precursor, polyimide precursor, and one or more of these copolymers, and have benzo

Alkali-soluble resin with azole precursor structure and aliphatic base; and (B) thermal acid generator and (E) antioxidant.

According to the resin composition of the present invention, it can be cured by heat treatment at a low temperature, and at the same time, a cured film excellent in heat resistance, chemical resistance, and breaking elongation can be obtained.

1‧‧‧Silicon Wafer

2‧‧‧Al gasket

3‧‧‧Passivation film

4‧‧‧Insulation film

5‧‧‧Metal (Cr, Ti, etc.) film

6‧‧‧Metal wiring (Al, Cu, etc.)

7‧‧‧Insulation film

8‧‧‧Barrier metal

9‧‧‧Cutting line

10‧‧‧Soldering bump

11‧‧‧Encapsulation resin

12‧‧‧Substrate

13‧‧‧Insulation film

14‧‧‧Insulation film

15‧‧‧Metal (Cr, Ti, etc.) film

16‧‧‧Metal wiring (Ag, Cu, etc.)

17‧‧‧Metal wiring (Ag, Cu, etc.)

18‧‧‧electrode

19‧‧‧Encapsulation resin

FIG. 1 is an enlarged cross-sectional view showing a pad part of a semiconductor device with bumps.

FIG. 2 is a diagram showing a detailed manufacturing method of a semiconductor device with bumps.

3 is a cross-sectional view showing the manufacturing steps of the semiconductor device according to the embodiment of the present invention.

4 is a cross-sectional view showing the coil part of the induction device of the embodiment of the present invention.

The form used to implement the invention

唑前驅物、聚醯亞胺前驅物、聚醯胺醯亞胺前驅物及該等之共聚物的1種以上而成，且具有苯并

唑前驅物結構及脂肪族基的鹼可溶性樹脂；以及(B)熱酸產生劑及(E)抗氧化劑的樹脂組成物。又，較佳為更含有(C)熱交聯劑及(D)感光性化合物的樹脂組成物。以下，有時分別省略為(A)成分、(B)成分、(C)成分及(D)化合物。 The resin composition of the present invention contains (A) containing selected from polybenzo

Azole precursor, polyimide precursor, polyimide precursor and one or more of these copolymers, and have benzo

Alkali-soluble resin with an azole precursor structure and aliphatic group; and (B) a thermal acid generator and (E) an antioxidant resin composition. Moreover, it is preferable to further contain the resin composition of (C) thermal crosslinking agent and (D) photosensitive compound. Hereinafter, it may be omitted as (A) component, (B) component, (C) component, and (D) compound, respectively.

In the present invention, alkali solubility means that the dissolution rate when the prebaked film formed by the method described below is immersed in the alkaline aqueous solution described below is 50 nm/min or more. In detail, it refers to coating a solution with resin dissolved in γ-butyrolactone on a silicon wafer, and pre-baking at 120°C for 4 minutes to form a pre-baked film with a film thickness of 10μm±0.5μm. When the prebaked film was immersed in a 2.38% by mass tetramethylamine hydroxide aqueous solution at 23±1°C for 1 minute, and then rinsed with pure water, the dissolution rate determined from the reduction in film thickness was 50 nm/min or more.

The alkali-soluble resin used for the component (A) of the present invention preferably has an acidic group in the structural unit of the resin or at the end of the main chain, or both. As an acidic group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, etc. are mentioned, for example. By having this acidic group, it can have good alkali solubility. (A) The content of the acidic group in the component is preferably 1% by mass or more from the viewpoint of improving alkali solubility, and preferably 30% by mass or less from the viewpoint of chemical resistance, water absorption, etc.

The component (A) preferably has a fluorine atom. When the component (A) has a fluorine atom, the formed film has water repellency, and when the alkali aqueous solution is used for development, the penetration of the alkali aqueous solution into the interface between the film and the substrate can be suppressed. In addition, the alkaline aqueous solution used in development may also be described as an alkaline developer. The content of fluorine atoms in the component (A) is preferably 5 mass% or more from the viewpoint of the effect of inhibiting the penetration of the alkali aqueous solution into the interface between the film and the substrate, and from the viewpoint of solubility in the alkali aqueous solution, it is more preferable It is 20% by mass or less.

唑前驅物、聚醯亞胺前驅物、聚醯胺醯亞胺前驅物及該等之共聚物作為較佳例。 (A) The alkali-soluble resin of the component preferably has high heat resistance. In particular, from the viewpoint of obtaining excellent characteristics as a planarization film, insulating layer, partition wall, protective film, and interlayer insulating film used in organic light-emitting devices, display devices, and semiconductor devices, it is preferable that the temperature be above 160°C after heat treatment. Under the temperature conditions, the amount of outgassing is small. Specific examples include polybenzo

Azole precursors, polyimide precursors, polyimide precursors, and copolymers of these are preferred examples.

The component (A) used in the present invention preferably has a structural unit represented by the following general formula (1). In addition, it may have other structural units. As other structural units in this case, for example, an imine structure, a structure having a skeleton in which two cyclic structures are bonded to four-stage carbon atoms constituting a cyclic structure, a siloxane structure, etc., are not mentioned. Limited to this. In the case of further having other structural units, it is preferable to have 50 mol% or more of the structural unit represented by the general formula (1) among the total number of structural units.

(In the general formula (1), X and Y each independently represent an organic group with 2 to 8 valences having 2 or more carbon atoms; R ¹ and R ² each independently represent hydrogen or an organic group with 1 to 20 carbon atoms; n Represents an integer in the range of 10~100,000; r and s represent an integer in the range of 0~2, and p and q represent an integer in the range of 0~4).

唑前驅物結構。藉由具有苯并

唑前驅物結構，其感光性能提高，同時可對於使含有(A)成分之樹脂組成物硬化之硬化膜賦予高伸度性，再者，藉由使苯并

唑前驅物閉環，其耐熱性、化學抗性提高。 Also, component (A) has benzo

The structure of the azole precursor. By having benzo

The azole precursor structure improves the photosensitivity, and at the same time, it can impart high elongation to the cured film that hardens the resin composition containing the component (A). Furthermore, by making benzo

The azole precursor is ring-closed, and its heat resistance and chemical resistance are improved.

In addition, the component (A) has an aliphatic group. The aliphatic group is preferably an organic group having at least one of an alkylene group and an oxyalkylene group. Specific examples include alkylene, cycloalkylene, oxyalkylene, oxycycloalkylene and the like. In addition, the aliphatic group is preferably represented by the following general formula (2).

(In the general formula (2), R ³ to R ⁶ each independently represent an alkylene group with 1 to 6 carbons; R ⁷ to R ¹⁴ each independently represent hydrogen, fluorine, or an alkyl group with 1 to 6 carbons; wherein, The structures shown in parentheses are different; x, y, and z each independently represent an integer from 0 to 35).

唑前驅物結構閉環的情況下所產生的應力增加。因此，可抑制隨著苯并

唑前驅物結構的脫水閉環而對基板晶圓的應力增加。又，脂肪族基為低紫外線吸收性，故藉由該導入，可提高i射線穿透性，同時亦可實現高感度化。 By making (A) component have an aliphatic group, the cured film which hardened the resin composition containing (A) component has high elongation. In addition, by making the component (A) have an aliphatic group, the resin has flexibility, and the benzoic acid in the resin can be suppressed.

When the azole precursor structure is closed, the stress generated increases. Therefore, it can be suppressed with the benzo

The dehydration loop closure of the azole precursor structure increases the stress on the substrate wafer. In addition, the aliphatic group has low ultraviolet absorption, so by this introduction, i-ray penetrability can be improved, and at the same time, high sensitivity can be achieved.

The weight average molecular weight of the component (A) used in the present invention is preferably 600 or more, and more preferably 900 or more from the viewpoint that the cured film has high elongation. Moreover, from the viewpoint of maintaining the solubility to the alkali solution, it is preferably 2,000 or less, more preferably 1,800 or less, and still more preferably 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 be obtained by measuring using N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) in the developing solvent and calculating in terms of polystyrene.

The (A) component used in the present invention preferably has the structural unit represented by the general formula (1). _{(OH) p} -X-(COOR ¹ ) _r in the general formula (1) represents an acid residue. X is a divalent to octal organic group having 2 or more carbon atoms, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or an aliphatic group is preferred.

As the acid component, examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, and diphenylmethyl Ketone dicarboxylic acid, triphenyl dicarboxylic acid, etc.; as examples of tricarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc.; as tetracarboxylic acid Examples include: 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'-benzophenone tetracarboxylic acid, 2,2',3 ,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1- Bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3 -Dicarboxyphenyl) Methane, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl) pyrene, 9,9-bis {4-(3,4-Dicarboxyphenoxy)phenyl}茀, 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, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid of the structure shown below , Aliphatic tetracarboxylic acids such as 1,2,3,4-cyclopentanetetracarboxylic acid, etc., but are not limited to these. Two or more of these can be used.

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 directly or as acid anhydrides, halides, or active esters.

_{In addition, (OH) q} -Y-(COOR ² ) _s in the general formula (1) represents a diamine residue. Y is a divalent to octal organic group having 2 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 preferred.

Specific examples of the diamine used for the component (A) include: 3,4'-diamine diphenyl ether, 4,4'-diamine diphenyl ether, 3,4'-diamine Diphenylmethane, 4,4'-diamine diphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene diamine Amine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl) ether, 1,4-bis(4-amine Phenyloxy)benzene, 2,2'-dimethyl-4,4'-diaminodiphenyl, 2,2'-diethyl-4,4'-diaminodiphenyl, 3,3'- Dimethyl-4,4'-diaminodiphenyl, 3,3'-diethyl-4,4'-diaminodiphenyl, 2,2',3,3'-tetramethyl-4,4 '-Diaminobiphenyl, 3,3',4,4'-Tetramethyl-4,4'-Diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-bis Aminbiphenyl, 9,9-bis(4-aminophenyl) pyrene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or at least a part of the hydrogen atoms of these aromatic rings Compounds substituted with alkyl groups or halogen atoms, aliphatic cyclohexanediamine, methylene bicyclohexylamine, and diamines of the structure shown below, but are not limited to these. Two or more of these can be used.

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.

These can be used as diamines, or as corresponding diisocyanate compounds and trimethylsilyl diamine.

The (A) component used in the present invention has an aliphatic group. Moreover, it is preferable that Y in this general formula (1) has an aliphatic group. Furthermore, the aliphatic groups are more preferably the aliphatic groups represented by the general formula (2).

Since Y in the general formula (1), that is, the diamine side has an aliphatic group, high elongation and low stress in the cured film can be obtained, and at the same time, the resin composition of the present invention can be highly sensitive. In addition, by making Y in the general formula (1) have the aliphatic group represented by the general formula (2), the adhesion between the substrate and the metal (for example, copper) can be improved. Specifically, interactions such as coordination bonds can be obtained between the ether group contained in the general formula (2) and the metal, so that high adhesion between the substrate and the metal can be obtained.

Specific examples of diamines having aliphatic groups include ethylene diamine, 1,3-diamine propane, 2-methyl-1,3-propane diamine, 1,4-diamine butane, 1 ,5-Diaminepentane, 2-methyl-1,5-diaminepentane, 1,6-diaminehexane, 1,7-diamineheptane, 1,8-diamineoctane, 1 ,9-Diaminenonane, 1,10-diaminedecane, 1,11-diamineundecane, 1,12-diaminedodecane, 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, (above are trade names, HUNTSMAN (stock) system), etc. Also, -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N(CH ₂ CH ₃ )-, -N(CH ₂ CH ₂ CH ₃ )-, -N (CH(CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, -NHCONH-, etc. Among them, diamines having an aliphatic group represented by the general formula (2) are preferred, for example, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR are preferred -176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005 , RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, (the above are trade names, HUNTSMAN (stock) system), etc.

All diamine residues preferably contain 5-40 mol% of the aliphatic group, and more preferably contain 10-30 mol%. By including the aliphatic group in this range, the developability during development with an aqueous alkali solution is improved, and the elongation of the cured film obtained by heating is improved.

In addition, the component (A) used in the present invention may contain an aliphatic group having a siloxane structure within a range that does not reduce the heat resistance, thereby improving the adhesion to the substrate. Specifically, as the diamine component, there can be mentioned: 1 to 15 mol% of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octylmethylpentasiloxane, etc. Those obtained by copolymerization, etc. When it contains 1 mol% or more, it is preferable from the viewpoint of improving the adhesion to silicon wafers and other substrates, and when it is 15 mol% or less, it is from the viewpoint of not reducing the solubility to alkaline solutions. Better.

In addition, the alkali-soluble resin of the component (A) is preferably a resin having an acidic group at the end of the main chain. The resin can be obtained by capping the ends of alkali-soluble resins with monoamines, acid anhydrides, chlorinated acids, and monocarboxylic acids having acidic groups.

Preferred examples of monoamines that can be used to obtain alkali-soluble resins having acidic groups 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. Two or more of these can be used.

In addition, preferred examples of acid anhydrides, chlorinates, and monocarboxylic acids that can be used to obtain alkali-soluble resins having acidic groups at the end of the main chain include phthalic anhydride, maleic anhydride, nadic anhydride, and cyclohexane. Acid anhydrides such as dicarboxylic anhydride and 3-hydroxyphthalic anhydride; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1- Monocarboxylic acids such as hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, and the like Carboxyl chlorinated monochloride; terephthalic acid, phthalic acid, maleic acid, cyclohexane dicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7 -Dicarboxynaphthalene, 2,6-dicarboxynaphthalene and other dicarboxylic acid monochloride with only one carboxyl group chlorinated; composed of monochloride and N-hydroxybenzotriazole or N-hydroxy-5 -The active ester compound obtained by the reaction of norbornene-2,3-dicarboxyimide. Two or more of these can be used.

The content of the acidic group at the end of the main chain of the alkali-soluble resin derived from the blocking agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid, etc., relative to the total of the acid and amine components constituting the resin, 100% by mole, is preferably 2~25mol%.

When the alkali-soluble resin of the component (A) has an acidic group at the end of the main chain, it is easy to detect the acidic group at the end of the main chain of the component (A) by the following method. For example, by dissolving a resin with an acidic group at the end of the main chain in an acidic solution, it is decomposed into the amine component and acid component of the resin's constituent units, and then measured by gas chromatography (GC) or NMR, which can be easily detected A blocking agent as a source of acidic groups. In addition, by directly measuring by thermal pyrolysis gas chromatography (PGC) or infrared spectroscopy and ¹³ C-NMR spectroscopy, resins with acidic groups at the end of the main chain can be detected.

唑前驅物結構藉由下述(B)成分的作用而閉環成聚苯并

唑的比例為30%以上。藉由閉環30%以上，可形成逸出氣體量少、高耐熱性、高化學抗性及斷裂伸度高的硬化膜。 In addition, the cured film for curing the resin composition of the present invention is preferably benzo

The structure of the azole precursor is ring-closed into polybenzo

The ratio of azole is 30% or more. With a closed loop of more than 30%, a cured film with low outgassing, high heat resistance, high chemical resistance, and high elongation at break can be formed.

The solvent used when the alkali-soluble resin used in the component (A) of the present invention is polymerized (hereinafter referred to as the polymerization solvent), as long as it can dissolve the tetracarboxylic dianhydrides and diamines of the raw material monomers. The type is not particularly limited. Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone , N,N'-dimethyl allylurea, N,N-dimethyl isobutyrate amide, methoxy-N,N-dimethyl propionamide amides; γ-butyrolactone, Cyclic esters such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc.; ethylene carbonate, propylene carbonate Carbonate esters such as triethylene glycol; phenols such as m-cresol and p-cresol; acetophenone, 1,3-dimethyl-2-imidazolinone, cyclobutane, Dimethyl sulfoxide and so on.

The polymerization solvent can dissolve the component (A) after the reaction. Therefore, it is preferable to use 100 parts by mass relative to 100 parts by mass of the obtained component (A). It is more preferably 150 parts by mass or more. In order to obtain resin powder during precipitation recovery, it is preferably 1,900 parts by mass or less, and more preferably 950 parts by mass or less.

In the present invention, the component (A) having a structural unit represented by the general formula (1) preferably has a weight average molecular weight of 10,000 or more and 50,000 or less. If the weight average molecular weight is 10,000 or more, the mechanical properties after curing can be improved, so it is preferable, and more preferably 20,000 or more. On the other hand, if the weight average molecular weight is 50,000 or less, the alkali aqueous solution can improve developability, which is preferable.

唑前驅物、聚醯胺醯亞胺前驅物或該等之共聚物的情況下，只要至少1種的重量平均分子量在上述範圍內即可。 In addition, it contains two or more alkali-soluble polyimide precursors, polybenzo

In the case of an azole precursor, a polyamide imide precursor, or a copolymer of these, it is sufficient that at least one of the weight average molecular weights is within the above-mentioned range.

The component (A) used in the present invention can be produced by a conventional method.

唑前驅物係由苯并

唑前驅物所構成，作為其製作方法，例如可使雙胺基苯酚化合物與二羧酸進行縮合反應而得。具體有下述方法：使二環己碳二亞胺(DCC)這種脫水縮合劑與酸進行反應，接著加入雙胺基苯酚化合物的方法或於加入吡啶等3級胺的雙胺基苯酚化合物溶液中滴下二羧酸二氯化物之溶液等。又，亦可具有醯亞胺前驅物結構或醯亞胺結構，此情況下，將聚苯并

唑前驅物中的醯亞胺前驅物結構或醯亞胺結構設為100質量份時，苯并

唑前驅物結構的含有比例較佳為101~10000質量份。 Polybenzo used in the present invention

The azole precursor is composed of benzo

It is composed of an azole precursor, and as its production method, for example, it can be obtained by condensation reaction of a diaminophenol compound and a dicarboxylic acid. Specifically, there are the following methods: a method of reacting a dehydrating condensing agent such as dicyclohexamethylene carbodiimide (DCC) with an acid, and then adding a diaminophenol compound, or adding a diaminophenol compound of a tertiary amine such as pyridine A solution of dicarboxylic acid dichloride and the like are dropped into the solution. In addition, it may also have an amide precursor structure or an amide structure. In this case, the polybenzo

When the amide precursor structure or amide structure in the azole precursor is set to 100 parts by mass, the benzo

The content ratio of the azole precursor structure is preferably 101 to 10,000 parts by mass.

唑前驅物結構的情況下，可預先使用具有苯并

唑前驅物的二胺，或藉由應用該聚苯并

唑前驅物之製造方法，於聚醯亞胺前驅物中導入苯并

唑前驅物結構。此情況下，將聚醯亞胺前驅物中的醯亞胺前驅物結構設為100質量份時，苯并

唑前驅物結構的含有比例較佳為1~99質量份。 As a preparation method of the polyimide precursor used in the present invention, for example, the following method can be used for synthesis: a method of reacting tetracarboxylic dianhydride and diamine compound at low temperature; by tetracarboxylic dianhydride and A method of obtaining a diester from alcohol, followed by a reaction in the presence of an amine and a condensing agent; a method of obtaining a diester from tetracarboxylic dianhydride and alcohol, and then chlorinating the remaining dicarboxylic acid and reacting with the amine Wait. With benzo

In the case of the azole precursor structure, it can be used in advance.

Azole precursor diamine, or by using the polybenzo

The manufacturing method of the azole precursor, the polyimide precursor is introduced into the benzo

The structure of the azole precursor. In this case, when the structure of the polyimine precursor in the polyimine precursor is set to 100 parts by mass, the benzo

The content ratio of the azole precursor structure is preferably 1 to 99 parts by mass.

唑前驅物結構的情況下，可預先使用具有苯并

唑前驅物的二胺，或藉由應用該聚苯并

唑前驅物之製造方法，於聚醯胺醯亞胺前驅物中導入苯并

唑前驅物結構。此情況下，將聚醯胺醯亞胺前驅物中的醯亞胺前驅物結構設為100質量份時，苯并

唑前驅物結構的含有比例較佳為50~10000質量份。 As a preparation method of the polyamide imine precursor used in the present invention, it can be synthesized by, for example, the following method: first anhydride the tricarboxylic acid, and make the residual carboxylic acid and the chloride or dicyclohexyl A method in which carbodiimide (DCC), a dehydrating condensing agent, is reacted and then reacted with an amine. With benzo

In the case of the azole precursor structure, it can be used in advance.

Azole precursor diamine, or by using the polybenzo

The manufacturing method of the azole precursor, the polyamide imide precursor is introduced into the benzo

The structure of the azole precursor. In this case, when the structure of the polyimide precursor in the polyimide precursor is set to 100 parts by mass, the benzo

The content ratio of the azole precursor structure is preferably 50 to 10,000 parts by mass.

唑、酚醛樹脂、包含具有鹼可溶性基之自由基聚合性 單體的聚合物、矽氧烷聚合物、環狀烯烴聚合物及卡多樹脂等。該等樹脂可單獨使用，又可組合使用多種樹脂。此情況下，將(A)成分與其它鹼可溶性樹脂的整體設為100質量份時，較佳為使其它鹼可溶性樹脂的含有比例為1~50質量份。 In the present invention, in addition to the (A) component, other alkali-soluble resins may be contained. Specific examples include: polyimide, polybenzo

Azoles, phenolic resins, polymers containing radically polymerizable monomers with alkali-soluble groups, silicone polymers, cyclic olefin polymers, cardo resins, etc. These resins can be used alone, or multiple resins can be used in combination. In this case, when the total of the component (A) and the other alkali-soluble resin is 100 parts by mass, it is preferable to set the content ratio of the other alkali-soluble resin to 1 to 50 parts by mass.

唑前驅物進行環化的的觸媒發揮作用，故可在更低溫下進行環化反應。再者，本發明之樹脂組成物為更含有下述(C)熱交聯劑之樹脂組成物的情況下，其亦作為促進(A)成分之樹脂與(C)熱交聯劑進行交聯反應的觸媒發揮作用。因此，藉由含有(B)熱酸產生劑，硬化後之硬化膜的緻密性提高，結果，其耐熱性、化學抗性提高。 The resin composition of the present invention contains (B) a thermal acid generator. The (B) thermal acid generator used in the present invention generates an acid due to the heat treatment after development, and it acts as a precursor for promoting the (A) component, benzoimide

The catalyst for the cyclization of the azole precursor functions, so the cyclization reaction can be performed at a lower temperature. Furthermore, when the resin composition of the present invention is a resin composition further containing the following (C) thermal crosslinking agent, it also serves to promote the crosslinking of the resin of (A) component and (C) thermal crosslinking agent The catalyst of the reaction comes into play. Therefore, by containing the thermal acid generator (B), the denseness of the cured film after curing is improved, and as a result, the heat resistance and chemical resistance thereof are improved.

The (B) thermal acid generator used in the present invention preferably has a thermal decomposition initiation temperature of 140°C or higher. In addition, the thermal decomposition initiation temperature is preferably 220°C or lower, more preferably 200°C or lower. The thermal decomposition starting temperature mentioned here refers to the boiling point or decomposition temperature, and the decomposition temperature refers to the temperature at which thermal decomposition begins before reaching the melting point.

In addition, if it is selected that "the resin composition of the present invention is applied to the substrate after drying (pre-baking: 70°C to 140°C), acid is not generated, and the patterned after exposure and development Heat hardening (hardening: 140~220℃) produces acid", it can suppress the decrease of sensitivity during development, and can reduce the hardening temperature, so it can suppress the increase of the substrate stress caused by high-temperature heating, so it is preferable. Therefore, the (B) The thermal acid generator, the thermal decomposition initiation temperature is more preferably 140~220℃, and more preferably 140~200℃.

(B) Thermal acid generators include onium salts such as sulfonate compounds and sulfonate salts.

唑前驅物的環化或促進交聯反應之觸媒的功能的觀點來看，較佳為酸解離常數(acid dissociation constant)為2.0以下的強酸。 The acid generated by the thermal acid generator is derived from the precursor of the promotion (A) component, the benzoimide

From the viewpoint of the cyclization of the azole precursor or the function of the catalyst promoting the crosslinking reaction, a strong acid having an acid dissociation constant of 2.0 or less is preferred.

As the acid generated by thermal decomposition, sulfonic acid, boric acid, etc. are preferred.

As the sulfonic acid, for example, aromatic sulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid; alkanesulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, and camphorsulfonic acid or trifluoromethanesulfonic acid are preferred. And other haloalkylsulfonic acid (haloalkylsulfonic acid) and so on.

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

The component (B) used in the present invention is preferably one or more compounds selected from the group consisting of sulfonate compounds represented by general formula (3), sulfonate compounds represented by general formula (4), and onium salts.

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

In general formulas (3) and (4), R ²⁰ to R ²² each independently represent an aliphatic group with 1 to 12 carbons or an aromatic group with 4 to 12 carbons, but aliphatic groups and aromatic groups are part of The hydrogen atom of may be substituted, and examples of the substituent include halogen groups such as an alkyl group, an acyl group, and a fluoro group.

As a specific example of the sulfonate compound represented by the general formula (3), for example, 3-(5-(((phenylsulfonyl)oxy)imino)thiophene-2(5H)-subunit )-2-(o-tolyl)propanenitrile, 3-(5-(((camphorsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl) Propane nitrile, 3-(5-(((trifluoromethanesulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, etc., but not Limited to this. Two or more of these may be contained.

As a specific example of the sulfonic acid ester compound represented by general formula (4), the following structures can be mentioned, for example, but it is not limited to this. Two or more of these may be contained.

As an onium salt, a sulphur salt, an iodonium salt, etc. are mentioned. Specific examples include: benzenesulfonic acid (4-hydroxyphenyl) dimethyl sulfonate, benzenesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonate, benzyl benzenesulfonate (4-Hydroxyphenyl) methyl sulfonic acid, benzyl benzenesulfonate (4-((methoxycarbonyl)oxy) phenyl) methyl sulfonic acid, benzenesulfonic acid (4-hydroxyphenyl) methyl ( (2-Tolyl)methyl) alumium, camphorsulfonic acid (4-hydroxyphenyl) dimethyl sulfonium, camphor sulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonium, Benzyl (4-hydroxyphenyl) methyl benzenesulfonate, benzyl camphorsulfonate (4-((methoxycarbonyl)oxy)phenyl) methyl sulfonic acid, camphorsulfonic acid (4-hydroxyphenyl) Phenyl) methyl ((2-tolyl) methyl) alumite, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethyl alumium, trifluoromethanesulfonate benzyl (4-hydroxyphenyl) methane Ji Yun, Benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl alumium, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-tolyl)methane Base) 鋶, "SAN-AID" (registered trademark), SI-145, SI-200, SI-250, SI-B2A, SI-B3A, SI-B3, SI-B4, SI-B5 (Sanxin Chemical Industry (Share) system), but not limited to this. Two or more of these may be contained.

唑前驅物部分之閉環反應的觀點來看，以及從在本發明之樹脂組成物為更含有下述(C)熱交聯劑之樹脂組成物的情況下進一步促進與(C)熱交聯劑之交聯反應的觀點來看，相對於(A)成分100質量份，較佳為0.1質量份以上，更佳為0.3質量份以上，更佳為0.5質量份以上。另一方面，從維持所得到之硬化膜的電絕緣性、抑制高溫保存性試驗等可靠度試驗後硬化膜與金屬材料之剝離的觀點來看，相對於(A)成分100質量份，較佳為100質量份以下，更佳為8質量份以下，更佳為5質量份以下。 (B) The content of the thermal acid generator can further promote the benzo

From the viewpoint of the ring-closing reaction of the azole precursor part, and from the viewpoint of the resin composition of the present invention being a resin composition further containing the following (C) thermal crosslinking agent, it further promotes the reaction with (C) thermal crosslinking agent From the viewpoint of the crosslinking reaction, relative to 100 parts by mass of the component (A), it is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and even more preferably 0.5 part by mass or more. On the other hand, from the viewpoint of maintaining the electrical insulation of the cured film obtained and suppressing peeling of the cured film from the metal material after reliability tests such as high-temperature storage tests, the ratio is preferably relative to 100 parts by mass of the component (A) It is 100 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.

The resin composition of the present invention preferably further contains (C) a thermal crosslinking agent.

The (C) thermal crosslinking agent used in the present invention refers to a compound having at least two thermally reactive functional groups represented by an alkoxymethyl group, a hydroxymethyl group, and an oxetanyl group in the molecule. (C) The thermal crosslinking agent is strongly crosslinked with the component (A) or other additives including the component (D), and can improve the heat resistance, chemical resistance, hardness, and compactness of the thermally cured film, while suppressing The peeling of the cured film from the metal material after reliability tests such as high temperature storage tests.

When the resin composition of the present invention is a resin composition that further contains (C) a thermal crosslinking agent, the above (B) thermal acid generator serves to promote the crosslinking reaction of the (A) component and (C) the thermal crosslinking agent As the catalyst of the present invention functions, the cured film that hardens the resin composition of the present invention has improved heat resistance, chemical resistance, and compactness.

As the (C) thermal crosslinking agent, preferred examples of compounds having at least two alkoxymethyl groups or hydroxymethyl groups 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 (the above are Trade name, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above are Commodity name, Sanhe Chemical (stock) system), etc.

As the (C) thermal crosslinking agent, preferred examples of compounds having at least two oxetanyl groups include: "Denacol" (registered trademark) EX-212L, Denacol EX-214L, Denacol EX-216L , Denacol EX-850L, Denacol EX-321L (Above is made by Nagase ChemteX Co., Ltd.), GAN, GOT (Above is made by Nippon Kayaku Co., Ltd.), ``EPIKOTE'' (registered trademark) 828, EPIKOTE1002, EPIKOTE1750, EPIKOTE1007, YX8100-BH30, E1256, E4250, E4275 (the above are JER (stock) system), "Epiclon" (registered trademark) 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon HP-4770, Epiclon HP4032 (the above are DIC (Stock)), VG3101 (Mitsui Chemicals (Stock)), "TEPIC" (registered trademark) S, TEPIC G, TEPIC P (the above are Nissan Chemical Industries (Stock) (Nippon Kayaku Co., Ltd.), NC6000 (Nippon Kayaku Co., Ltd.), EPOTOHTOYH-434L (Toto Kasei Co., Ltd.), EPPN502H, NC3000 (Nippon Kayaku Co., Ltd.), Epiclon N695, HP7200 (The above is DIC (stock) (Manufactured), "ETERNACOLL" (registered trademark) EHO, ETERNACOLL OXBP, ETERNACOLL OXTP, ETERNACOLL OXMA (the above are manufactured by Ube Industries Co., Ltd.), oxetane phenol novolac, etc.

When the resin composition of the present invention is a resin composition further containing (C) a thermal crosslinking agent, if the (C) thermal crosslinking agent is a thermal crosslinking agent having a structural unit represented by the following general formula (5) , The elongation of the obtained cured film is improved, and the peeling of the cured film from the metal material after reliability tests such as high-temperature storage tests can be further suppressed due to lower stress and densification, which is preferable.

(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 with 2 or more carbon atoms, which may be linear, branched, and Any of cyclic; R ^{23 can} be enumerated: alkylene, cycloalkylene, oxyalkylene, alkylsilylene, alkoxysilylene, arylene, oxyarylene, oxycarbonyl , Carbonyl, allylene (allylene) group, vinylidene, bonding group containing heterocyclic ring, combinations of these, etc., and may have substituents).

By making the (C) thermal crosslinking agent have a structural unit represented by the above general formula (5), the thermal crosslinking agent itself has a soft alkylene group and a rigid aromatic group, so it has heat resistance, and the obtained The elongation of the cured film can be improved and the stress can be reduced. As a crosslinking group, an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group can be mentioned, but it is not limited to these. Among them, an epoxy group is preferred from the viewpoint that it can react with the phenolic hydroxyl group of the component (A) to improve the heat resistance of the cured film, and from the viewpoint that the reaction can proceed without dehydration.

The compounds represented by the general formula (5) listed above can be exemplified as follows, but are not limited to the following structures.

(In the formula, m is an integer from 1 to 5, and 1 is from 1 to 20).

Among the above-mentioned structures, m is preferably from 1 to 2, and 1 is preferably from 3 to 7 from the viewpoint of having both heat resistance and improved elongation.

(C) The thermal crosslinking agent can be used in combination of two or more types.

The content of the (C) thermal crosslinking agent is preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the component (A). If the content of the (C) thermal crosslinking agent is 1 part by mass or more and 100 parts by mass or less, the chemical resistance and hardness of the film after firing or curing can be improved, and the storage stability of the resin composition can be improved.

In addition, the content of the compound represented by the general formula (5) is preferably 2 to 80 parts by mass, more preferably 5 to 60 parts by mass relative to 100 parts by mass of the total thermal crosslinking agent. By setting the content to 2 parts by mass or more, the effects of improving elongation and reducing stress can be obtained, and by setting the content to 80 parts by mass or less, the sensitivity of the resin composition can be maintained.

The resin composition of the present invention preferably further contains (D) a photosensitive compound. By containing the photosensitive compound (D), photosensitivity can be imparted to the resin composition.

(D) The photosensitive compound includes: a compound containing a group having a naphthoquinonediazide structure (hereinafter sometimes referred to as a naphthoquinonediazide compound), sulfonium salts, phosphonium salts, diazonium salts, and phosphonium Salt etc. It can also contain sensitizers etc. according to demand.

The naphthoquinone diazide compound is preferably a naphthoquinone diazide sulfonyl ester compound in which the sulfonic acid of naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group. Examples of the compound having a phenolic hydroxyl group used here include: Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ , BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene ginseng-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 (commercial Product name, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A , 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxy Methyl-p-cresol, 2,6-Diacetyloxymethyl-p-cresol, naphthol, tetrahydroxytetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E , Methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. Although the naphthoquinone diazide sulfonic acid ester compound in which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced into these compounds having a phenolic hydroxyl group as a preferred example is an ester bond , But other compounds 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 esterified with a naphthoquinone diazide sulfonyl group. By using a naphthoquinone diazide compound in which 50 mol% or more of the phenolic hydroxyl groups of a compound having a phenolic hydroxyl group is esterified with a sulfonyl group, the affinity of the naphthoquinone diazide compound to an aqueous alkali solution is reduced, and the Significantly reduce the solubility of the resin composition in the unexposed part to the aqueous alkali solution, and at the same time, the part of the naphthoquinonediazide structure of the naphthoquinonediazidesulfonyl group can be changed into indene-carboxylic acid by exposure. ), a high dissolution rate of the resin composition in the exposed part to the alkaline aqueous solution is obtained. As a result, the dissolution rate ratio of the exposed part and the unexposed part of the composition becomes larger, and a high-resolution pattern can be obtained. By using this naphthoquinonediazide compound, a resin composition having positive sensitivity to the i-ray (365nm), h-ray (405nm), and g-ray (436nm) of a general mercury lamp can be obtained. In addition, the photosensitive compound may be used alone or in combination of two or more, and a photosensitive resin composition with high sensitivity can be obtained.

In the present invention, as the group having a naphthoquinonediazide structure, it is preferable to use any of 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl. The 5-naphthoquinone diazide sulfonyl ester compound can absorb to extend to the g-ray region of the mercury lamp, which is suitable for g-ray exposure and full-wavelength exposure. The 4-naphthoquinone diazide sulfonyl ester compound can absorb in the i-ray region of a mercury lamp, which is suitable for i-ray exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazidesulfonyl ester compound or a 5-naphthoquinonediazidesulfonyl ester compound in accordance with the wavelength of exposure. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in combination in the same molecule, or 4-naphthoquinone sulfonyl ester compound can also be used in combination. Diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound.

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

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

Among the photosensitive compounds, sulfonium salts, phosphonium salts, and diazonium salts are preferable because they appropriately stabilize the acid component generated by exposure. Among them, aqua salt is preferred.

The content of the (D) compound is preferably 0.1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the component (A). If the content of (D) compound is 0.1 parts by mass or more and 100 parts by mass or less, it can maintain Heat resistance, chemical resistance, mechanical properties of the film after heat treatment, and impart photosensitivity.

When the compound (D) is a naphthoquinone diazide compound, the content of the naphthoquinone diazide compound relative to 100 parts by mass of the component (A) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, It is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less. If it is 1 part by mass or more and 80 parts by mass or less, the heat resistance, chemical resistance, and mechanical properties of the film after the heat treatment can be maintained, and photosensitivity can be imparted.

(D) When the compound is a sulfonium salt, a phosphonium salt, or a diazonium salt, the content of the sulfonium salt, phosphonium salt, and diazonium salt relative to 100 parts by mass of the component (A) is preferably 0.1 parts by mass or more, more preferably It is 1 part by mass or more, more preferably 3 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 50 parts by mass or less. If it is 0.1 parts by mass or more and 80 parts by mass or less, the heat resistance, chemical resistance, and mechanical properties of the film after the heat treatment can be maintained, and photosensitivity can be imparted.

啉、蔥-1,2,10-三元醇、蔥-1,8,9-三元醇、8-羥喹啉等。 For the purpose of enhancing alkali developability, the resin composition of the present invention may contain a compound having a phenolic hydroxyl group. Examples of compounds having phenolic hydroxyl groups 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 (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, Methylene Ginseng-FR-CR, BisRS-26X, BisRS-OCHP, (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR- PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials 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-dihydroxyquinoline, 2,6-Dihydroxyquinoline, 2,3-Dihydroxyquine

Onion, onion-1,2,10-triol, onion-1,8,9-triol, 8-hydroxyquinoline, etc.

The resin composition containing the compound (D) used in the present invention, by containing these compounds having phenolic hydroxyl groups, hardly dissolves in an alkaline developer before exposure, but is easily soluble in an alkaline developer after exposure. The film loss caused by development is less, and it is easy to develop in a short time. Therefore, it is easy to increase the sensitivity.

The resin composition of the present invention further contains (E) antioxidant. By containing (E) antioxidant, the oxidative deterioration of the aliphatic group or phenolic hydroxyl group of (A) component can be suppressed. In addition, the rust-preventing effect on metal materials can suppress metal oxidation caused by external moisture, photosensitizers, thermal acid generators, and the like, and the resulting adhesion drop or peeling can be suppressed. As (E) antioxidant, the compound represented by general formula (6) is preferable. By containing the compound represented by the general formula (6), it is possible to suppress the mechanical properties of the cured film after a reliability test such as a high-temperature storage test, or peeling from a metal material.

(In the general formula (6), R ²⁶ represents a hydrogen atom or an alkylene group with a carbon number of 2 or more, R ²⁷ represents an alkylene group with a carbon number of 2 or more; R ²⁸ represents an alkylene group with a carbon number of 2 or more, containing an O atom and At least any one of the N atoms is a 1- to 4-valent organic group; k represents an integer of 1 to 4; suitable as ^{a monovalent organic group of R 28} , examples include: alkyl, cycloalkyl, alkoxy, and alkane Ether group, alkylsilyl group, alkoxysilyl group, aromatic group, aryl ether group, carboxyl group, allyl group, vinyl group, heterocyclic group, etc. As the divalent organic group, carbonyl group, -O- , -NH-, -NHNH-, -NHCO-, -COO-, etc.; suitable as ^{a trivalent or tetravalent organic group for R 28} , including hydrogen that replaces the above-mentioned monovalent or divalent organic group at the bonding point Groups, etc.; may include combinations of these groups, etc., and may have substituents; among them, from the viewpoint of solubility to the developer or metal adhesion, it is preferable to have an alkyl ether, -NH -, from the viewpoint of the interaction with the component (A) and the metal adhesion due to metal complexation, -NH-) is more preferable.

Examples of the compound represented by the general formula (6) are as follows, but are not limited thereto.

In addition, the content of (E) antioxidant relative to 100 parts by mass of (A) component is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass. By making the content 0.1 parts by mass or more, the metal material can be improved The adhesiveness of the material, while suppressing peeling. In addition, by making the content 10 parts by mass or less, the sensitivity of the resin composition can be maintained.

The resin composition of the present invention may contain a post-development adhesion improver according to needs.

Examples of the adhesion improver after development include: vinyl trimethoxysilane, vinyl triethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- Silane coupling agents such as phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amides with alkoxy-containing silicon compounds Wait. Two or more of these can be contained. By containing these post-development adhesion modifiers, when the resin film is developed, the adhesion to substrate substrates such as _{silicon wafers, ITO, SiO 2, and silicon nitride can be improved.} In addition, the resistance to oxygen plasma and UV ozone treatment used for cleaning etc. can be improved.

The content of the adhesion improver after development is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the component (A). By making it within this range, the effect of each adhesion modifier after development can be fully exhibited.

In addition, the resin composition of the present invention may contain an adhesive modifier after curing.

As a post-curing adhesive modifier, it is preferable to contain a compound represented by the following general formula (7).

(In the general formula (7), R ²⁹ to R ³¹ represent any of O atom, S atom, or N atom ^{, at least one of R 29} to R ³¹ represents S atom; t represents 0 or 1, u and v represent An integer of 1 or 2; R ³² to R ³⁴ each independently represent a hydrogen atom or an organic group with a carbon number of 1 to 20; R ³² to R ³⁴ include hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, Alkyl polyether groups, alkyl silyl groups, alkoxy silyl groups, aromatic groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, combinations thereof, etc., and may have substituents ).

By containing the compound represented by the general formula (7), the adhesion between the film and the metal material, especially copper, after heat curing can be significantly improved, and peeling can be suppressed. This is because the S atom or N atom of the compound represented by the general formula (7) interacts with the metal surface efficiently, and it is easier to interact with the metal surface to form a three-dimensional structure. With these effects, a cured film with excellent adhesion to metal materials can be obtained from the resin composition of the present invention.

Examples of the compound represented by the general formula (7) include the following, but it is not limited to the following structure.

In addition to the compound represented by the general formula (7), the resin composition of the present invention may also contain other post-curing modifiers. Examples of other post-curing adhesive modifiers include aromatic amine compounds containing alkoxysilanes, aromatic amide compounds, or silane compounds not containing aromatics. Two or more of these can be contained. By containing these compounds, the adhesion to the substrate after firing or hardening can be improved.

Specific examples of aromatic amine compounds and aromatic amide compounds containing alkoxysilanes are shown below. In addition, it can also be a compound obtained by reacting an aromatic amine compound with a silicon compound containing an alkoxy group, for example: an aromatic amine compound and a group having an epoxy group, a chloromethyl group, etc., which react with an amine group The compound obtained by the reaction of the alkoxysilane compound, etc.

Examples of non-aromatic silane compounds include: vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl ginseng (β-methoxyethoxy) silane, etc. Vinyl silicon Alkyl compounds; 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropyl Silane compounds containing carbon-carbon unsaturated bonds, such as methyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and the like. Among them, vinyl trimethoxysilane and vinyl triethoxysilane are preferred.

The content of the curing agent represented by the general formula (7) used in the resin composition of the present invention is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A). When the content of the subsequent modifier after curing is 0.1 parts by mass or more with respect to 100 parts by mass of the component (A), the adhesiveness effect to metal materials and the like can be sufficiently obtained, which is preferable. In addition, by making the content of the subsequent modifier after curing 10 parts by mass or less relative to 100 parts by mass of the component (A), when the resin composition used in the present invention is a positive photosensitive resin composition, it can be used The interaction with the sensitizer suppresses the decrease in the sensitivity of the resin composition before curing.

Here, with respect to 100 parts by mass of the component (A), the content of the other modifier after curing is preferably 0.01 to 15 parts by mass. By making it within this range, the adhesion to the substrate after firing or hardening can be improved. In addition, compounds such as vinyl trimethoxysilane, vinyl triethoxysilane, etc., which can function as an adhesion improver after development or as an adhesion improver after curing, may also be contained.

For the purpose of improving the wettability with the substrate or improving the uniformity of the film thickness of the coating film according to demand, the resin composition of the present invention may also contain a surfactant. As the surfactant, commercially available compounds can be used. Specifically, as the silicon-based surfactant, Dow Corning Toray Silicone’s SH series, SD series, ST series, BYK JAPAN’s BYK series, Shin-Etsu Silicone’s KP series, Nippon Oil & Fats Company’s DISFOAM series, Toshiba Silicone’s TSF series, etc.; as a fluorine-based surfactant Examples include: DIC's "MEGAFAC" (registered trademark) series, Sumitomo 3M's FLUORAD series, Asahi Glass's "Surflon" (registered trademark) series, "AsahiGuard" (registered trademark) series, and Shin Akita Kasei's EF series Series, PolyFox series of Omnova Solution, etc.; surfactants obtained from acrylic and/or methacrylic polymers include: Polyflow series of Kyoeisha Chemical Company, "DISPARLON" ( Registered trademark) series, etc., but not limited to this.

The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the component (A). By making it within the above-mentioned range, defects such as bubbles or pinholes can be avoided, and the wettability with the substrate or the uniformity of the film thickness of the coating film can be improved.

唑、將丙烯酸進行共聚合的丙烯酸聚合物、酚醛清漆樹脂、可溶酚醛樹脂、包含具有鹼可溶性基之自由基聚合性單體的聚合物、矽氧烷樹脂、環狀烯烴樹脂、具有卡多結構、亦即於構成環狀結構之4級碳原子上鍵結兩個環狀結構的骨架結構的樹脂等。這種樹脂係溶解於氫氧化四甲胺、膽鹼、三乙胺、二甲胺基吡啶、單乙醇胺、二乙基胺基乙醇、氫氧化鈉、 氫氧化鉀、碳酸鈉等鹼溶液者。藉由含有該等鹼可溶性樹脂，可保持硬化膜的密合性及優異的感度，並賦予各鹼可溶性樹脂的特性。 The resin composition of the present invention may contain other alkali-soluble resins in addition to the component (A). Specific examples include: alkali-soluble polyimide, polybenzo

Azoles, acrylic polymers copolymerized with acrylic acid, novolac resins, resol resins, polymers containing radically polymerizable monomers having alkali-soluble groups, silicone resins, cyclic olefin resins, cardo Structure, that is, a resin with a skeleton structure in which two cyclic structures are bonded to the fourth-level carbon atoms constituting the cyclic structure. This resin is dissolved in alkaline solutions such as tetramethylamine hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. By containing these alkali-soluble resins, the adhesiveness and excellent sensitivity of the cured film can be maintained, and the characteristics of each alkali-soluble resin can be imparted.

烷、丙二醇單甲醚、丙二醇單乙醚等的醚類；丙酮、甲乙酮、二異丁酮等的酮類；乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸丙酯、丙二醇單甲醚乙酸酯、3-甲基-乙酸3-甲氧丁酯等的酯類；乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲基-3-甲氧基丁醇等的醇類；甲苯、二甲苯等的芳香族烴類等。可含有該等2種以上。 The resin composition of the present invention preferably contains a solvent. Examples of solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N- Dimethyl acetamide, dimethyl sulfide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethyl allylurea, N,N-dimethyl isobutyrate , Methoxy-N,N-dimethylpropanamide and other polar aprotic solvents; tetrahydrofuran, two

Ethers such as alkane, propylene glycol monomethyl ether, propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether ethyl Ester, 3-methyl-acetate 3-methoxybutyl ester, etc.; ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, and other alcohols; toluene , Xylene and other aromatic hydrocarbons. Two or more of these can be contained.

The content of the solvent is preferably 100 parts by mass or more relative to 100 parts by mass of the component (A) in order to dissolve the composition, and 1,500 parts by mass or less in order to form a coating film with a film thickness of 1 μm or more.

Next, the manufacturing method of the resin composition of this invention is demonstrated. For example, by making each component of (A), (B) and (E), preferably and each component of (C) ~ (D), and the compound with phenolic hydroxyl group added according to the demand, dense after development A resin composition can be obtained by mixing the modifier, and after curing, the modifier, surfactant, other resins, solvents, etc. are dissolved. As the dissolution method, heating or stirring can be cited. Heating situation Next, it is preferable to set the heating temperature within a range that does not impair the performance of the photosensitive colored resin composition, and it is usually from room temperature to 80°C. In addition, the order of dissolving each component is not particularly limited. For example, there is a method of sequentially dissolving compounds with low solubility. In the case of stirring, it is preferable to set the rotation speed within a range that does not impair the performance of the photosensitive colored resin composition, and it is usually 200 rpm to 2000 rpm. It can also be heated according to demand while stirring, usually from room temperature to 80°C. In addition, for components that are likely to generate bubbles during stirring and dissolution, such as a surfactant or a part of the adhesion modifier after development, can be added last after dissolving other components, thereby preventing the generation of bubbles from causing poor dissolution of other components.

The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa. s. By adjusting the solid content concentration to make the viscosity 2mPa. s or more, it is easy to obtain the expected film thickness. On the other hand, if the viscosity is 5,000mPa. s or less, it is easy to obtain a coating film with high uniformity. For example, by setting the solid content concentration to 5-60% by mass, it is easy to obtain a resin composition having such a viscosity.

The obtained resin composition is preferably filtered with a filter to remove garbage or particles. The pore diameter of the filter is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but it is not limited to these. The material of the filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., but preferably polyethylene or nylon.

Next, the method of manufacturing the resin composition of the present invention, or the resin film formed from the resin composition, or the cured film using the resin sheet will be described.

In addition, here, the resin film is defined as a film obtained by coating the resin composition of the present invention on a substrate and drying it. The resin sheet is defined as a sheet obtained by coating a resin composition on a releasable substrate and drying it. In addition, the cured film system is defined as a film obtained by curing a resin film or a resin sheet.

The resin composition of the present invention is coated on a substrate to obtain a coating film of the resin composition. As the substrate, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and constituent materials for disposing circuits on these substrates can be used, but are not limited to these. Coating methods include spin coating, slit coating, dip coating, spray coating, and printing methods. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but the coating is usually performed so that the film thickness after drying becomes 0.1 to 150 μm.

Before coating, the base material coated with the resin composition may be pre-treated with the above-mentioned post-development adhesion improver. For example, use of 0.5-20% by mass of the post-development adhesion improver dissolved in isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and hexyl alcohol. A solution made of solvents such as diethyl diacid is a method of treating the surface of the substrate by spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment, and other methods. The reduced-pressure drying treatment can be carried out according to the needs, and then the reaction between the substrate and the adhesion modifier after development is carried out by heat treatment at 50°C to 280°C.

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

On the other hand, in the case of using a resin sheet formed from the resin composition of the present invention, when the resin sheet has a protective film, the resin sheet is peeled off, the resin sheet is opposed to the substrate, and the resin sheet is bonded to the substrate by thermocompression. The bonding (the case where the resin sheet is opposed to the substrate and bonded by thermocompression bonding is sometimes described as laminating the resin sheet on the base material). Next, as in the case of obtaining the above-mentioned resin film, the resin sheet laminated on the base material is dried to form a resin film. The resin sheet can be obtained by coating the resin composition of the present invention on a support film composed of polyethylene terephthalate or the like as a peelable base material, and drying it.

Thermal compression bonding can be performed by hot pressing, thermal lamination, thermal vacuum lamination, etc. From the viewpoint of adhesion to the substrate and embedding properties, the bonding temperature is preferably 40°C or higher. In addition, when the resin sheet has photosensitivity, the exposure is reduced in order to prevent the resin sheet from hardening during lamination. The resolution of pattern formation in the development step, and the bonding temperature are preferably 140°C or less.

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

Next, the exposed photosensitive resin film is developed to remove the exposed portion. The developer is preferably tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, acetic acid Dimethylaminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, ring Aqueous solutions of basic compounds such as hexylamine, ethylenediamine, and hexamethylenediamine. Also, depending on the situation, one or more of N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylethyl may be contained in the alkaline aqueous solution. Polar solvents such as amide, dimethyl sulfide, γ-butyrolactone, dimethyl acrylamide, etc.; alcohols such as methanol, ethanol, isopropanol, etc.; ethyl lactate, propylene glycol monomethyl ether acetate, etc. Ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. It is generally rinsed with water after development. Here, alcohols such as ethanol and isopropanol, esters such as ethyl lactate, and propylene glycol monomethyl ether acetate, etc. may also be added to water for rinsing treatment.

A temperature of 140°C to 280°C is applied to the resin film obtained in this way to perform a thermal crosslinking reaction to improve heat resistance and chemical resistance (this step is sometimes referred to as a heat treatment step). This heating treatment can choose to increase the temperature step by step, or select the temperature range to increase the temperature continuously and implement it for 5 minutes to 5 hours. One example is heat treatment at 130°C and 200°C for 30 minutes each. The curing conditions in the present invention are preferably 140°C or higher and 280°C or lower. In order to proceed with the thermal crosslinking reaction, the curing condition is preferably 140°C or higher, more preferably 160°C or higher. In addition, in order to provide an excellent cured film particularly by curing at a low temperature, the present invention is also intended to suppress handling failures following the thermal history of the semiconductor device described below to increase the yield. The curing conditions are preferably 280°C or less, more preferably Below 250°C, more preferably below 220°C.

The cured film obtained by curing the resin composition or resin sheet of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, it is suitable for passivation films (interlayer insulation Film, surface protection film), semiconductor element protection film (sometimes referred to as semiconductor protection film), and interlayer insulating film for multilayer wiring for high-density mounting. Examples of electronic components having a surface protective film or an interlayer insulating film on which the cured film of the present invention is arranged include MRAM with low heat resistance. That is, the cured film of the present invention is suitable for use as a surface protection film of MRAM. Moreover, in addition to MRAM, polymer memory (polymer ferroelectric RAM, PFRAM) or phase change memory (phase change RAM, PCRAM or ovonics unified memory, OUM), which is expected to be a new generation memory, is compared to previous memories. , The possibility of using new materials with low heat resistance is also higher. Therefore, the cured film of the present invention is also suitable for use as such a surface protection film. In addition, it can be used for the insulating layer of the device: a display device including a first electrode formed on a substrate and a second electrode disposed opposite to the first electrode. Specific examples include LCD, ECD, ELD, and Display devices (organic electroluminescence devices) of electroluminescent elements, etc. Especially in recent years, the electrodes of semiconductor elements, multilayer wiring, and circuit board wiring have become the mainstream of semiconductor devices with copper electrodes, copper wiring, and bumps as the structure is further refined. When resisting pattern formation, it will be in contact with a large amount of chemical liquid such as flux. If the resin film formed from the resin composition of the present invention is used as a protective film for such electrodes and wiring, it has high resistance to these chemical liquids, so it is particularly suitable for use.

唑樹脂的機械特性亦為優異，故在安裝時亦可緩和來自封裝樹脂的應力，故可防止損傷low-k層(由用作半導體裝置內部之層間絕緣膜材料的低介電常數材料所構成的層體)，而可提供高可靠度的半導體裝置。 Next, with regard to the cured film obtained by curing the resin composition or resin sheet of the present invention, an application example of a semiconductor device having bumps will be described using drawings. Fig. 1 is an enlarged cross-sectional view of a pad part of a semiconductor device with bumps. As shown in FIG. 1, a passivation film 3 is formed on an aluminum pad (hereinafter referred to as Al pad) 2 for input and output on the silicon wafer 1, and a through hole is formed on the passivation film 3. Then, an insulating film 4 formed using the resin composition or resin sheet of the present invention is formed thereon, and then, a metal film 5 formed of Cr, Ti, etc. is connected to the Al pad 2 to be formed. By etching the periphery of the solder bump 10 of the metal film 5, the pads are insulated. Barrier metal 8 and solder bumps 10 are formed on the insulating gasket. When a soft component is introduced into the resin composition, the warpage of the wafer is small, so exposure and wafer transportation can be performed with high accuracy. Also, polyimide resin or polybenzo

The azole resin also has excellent mechanical properties, so it can relax the stress from the encapsulating resin during installation, so it can prevent damage to the low-k layer (consisting of a low-dielectric constant material used as an interlayer insulating film material inside a semiconductor device的层体), which can provide highly reliable semiconductor devices.

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

Next, as shown in 2e and 2f of FIG. 2, barrier metal 8 and solder bumps 10 are formed. Next, dicing is performed along the dicing line 9 to be divided into wafers. When the insulating film 7 is not patterned on the dicing line 9 or residues remain, cracks or the like are generated during dicing, which affects the reliability of the wafer. Therefore, it is possible to provide pattern processing excellent in thick film processing as in the present invention, which is excellent because of the high reliability of the semiconductor device that can be obtained.

In addition, the resin composition of the present invention can also be applied to fan-out wafer-level packaging (fan-out WLP).

3 is a cross-sectional view showing the manufacturing steps of the semiconductor device according to the embodiment of the present invention. In detail, it is an enlarged cross-sectional view of the pad part of the semiconductor device having the insulating film of the present invention, which is a structure called a fan-out wafer level package (fan-out WLP). In the same manner as in the application example 1, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced to be divided into individual wafers, and then packaged with the resin 11. On the encapsulating resin 11 and the wafer, the photosensitive resin composition of the present invention is patterned to form an insulating film 4, and then a metal (Cr, Ti, etc.) film 5 and metal wiring 6 are formed. After that, barrier metal 8 and solder bumps 10 are formed in the openings of the insulating film 7 formed on the encapsulating resin outside the chip.

Fan-out type WLP is a semiconductor package in which an expansion part is provided around the semiconductor chip using an encapsulating resin such as epoxy resin, rewiring is performed from the electrode on the semiconductor chip to the expansion part, and solder balls are also mounted on the expansion part. This ensures the necessary number of terminals. In the fan-out WLP, wiring is provided so as to straddle the boundary line formed by the main surface of the semiconductor wafer and the main surface of the encapsulating resin. That is, an interlayer insulating film is formed on an adjacent base material (substrate) "consisting of two or more materials: a semiconductor wafer with metal wiring and an encapsulating resin", and wiring is formed on the interlayer insulating film. In addition, in a semiconductor package of the type that "forms a semiconductor chip on a glass epoxy substrate" recessed portion, wiring is arranged so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. In this aspect, an interlayer insulating film is also formed on an adjacent base material (substrate) composed of two or more materials, and wiring is formed on the interlayer insulating film. In this way, in semiconductor electronic parts or semiconductor devices, the cured film formed by curing the resin composition of the present invention has high adhesion to semiconductor wafers with metal wiring, and also has high adhesion to encapsulating resins such as epoxy resins. Therefore, it is suitable for use as an interlayer insulating film provided on an adjacent base material (substrate) composed of two or more materials.

In addition, the resin composition of the present invention is also suitable for use in coil parts of induction devices.

4 is a cross-sectional view showing the coil part of the induction device of the 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 as a pattern is formed thereon. Ferrite or the like can be used for the substrate 12. The photosensitive resin composition of the present invention can be used for either of the insulating film 13 and the insulating film 14. A metal (Cr, Ti, etc.) film 15 is formed in the opening of the pattern, and then metal wiring (Ag, Cu, etc.) 16 is formed by plating thereon. Metal wiring 16 (Ag, Cu, etc.) is formed on a spiral. Repeat the steps of forming 13~16 many times, and make it have the function as a coil by layering. Finally, the metal wiring 16 (Ag, Cu, etc.) is connected to the electrode 18 through the metal wiring 17 (Ag, Cu, etc.), and the sealing resin 19 is used for packaging.

Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, the resin composition in the examples was evaluated by the following method. In addition, for evaluation, a resin composition (hereinafter referred to as varnish) filtered with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries Co., Ltd.) was used in advance.

(1) Calculation of the closed loop rate of the cured film

After pre-baking at 120°C for 3 minutes, the film thickness becomes 11 μm. Using the coating and developing device ACT-8, the varnish is applied to an 8-inch silicon wafer by spin coating and pre-baked. Use an inert gas oven CLH-21CD-S (manufactured by Koyo Thermo Systems), raise the temperature to 200°C or 220°C at an oxygen concentration of 20 ppm or less, 4.0°C/min, and heat treatment at 200°C or 220°C for 1 hour . When the temperature became 50°C or lower, the silicon wafer was taken out to obtain a cured film (A). In addition, a cured film (B) heated at 300 to 350°C was obtained. The infrared absorption spectra of the cured film (A) and the cured film (B) were measured, and the absorbance derived from the peak of the CO stretching vibration in the vicinity of ^{1050 cm -1 was determined.} The infrared absorption spectrum was measured using "FT-720" (trade name, manufactured by Horiba Manufacturing Co., Ltd.) as the measuring device. The closed loop rate of the cured film (B) was set to 100%, and the closed loop rate of the cured film (A) was calculated from the following formula. The ring-closure rate mentioned here refers to the ring-closure rate of the poly(ortho-hydroxyamide) structural unit.

In this example, a cured film was produced from a varnish as described above, and the loop closure ratio was calculated.

Those with a closed loop rate of 40% or more are evaluated as extremely good3, those with 30% or more and less than 40% are evaluated as good2, and those with less than 30% are evaluated as poor1.

The heating temperature for obtaining the cured film (B) is preferably 320°C as long as the cured film does not undergo thermal decomposition. The thermal decomposition temperature of the cured film can be analyzed by thermal weight loss analysis (TGA).

(2) Evaluation of heat resistance

After pre-baking at 120°C for 3 minutes, the film thickness becomes 11 μm. Using the coating and developing device ACT-8, the varnish is applied to an 8-inch silicon wafer by spin coating and pre-baked. Use an inert gas oven CLH-21CD-S (manufactured by Koyo Thermo Systems), raise the temperature to 200°C or 220°C at an oxygen concentration of 20 ppm or less, 4.0°C/min, and heat treatment at 200°C or 220°C for 1 hour . When the temperature became 50°C or lower, the silicon wafer was taken out and immersed in 45% by mass hydrofluoric acid for 5 minutes, thereby peeling the cured film of the resin composition from the wafer. Cut the above film It was formed into a strip with a width of 0.5 cm and a length of 10 cm. Using a thermogravimetric measuring device TGDTA6200 (manufactured by Hitachi High-Tech Science Corporation), the 5% weight when heated from room temperature to 400°C at a heating rate of 10°C/min was used. Reduce the temperature.

If the value of the 5% weight loss temperature is 315°C or higher, it is evaluated as good 2, and if it is less than 315°C, it is evaluated as bad 1.

(3) Evaluation of chemical resistance

After pre-baking at 120°C for 3 minutes, the film thickness becomes 10μm. Using the coating and developing device ACT-8, the varnish is applied on the silicon wafer by the spin coating method. After the pre-baking, an inert gas is used. The oven CLH-21CD-S is heated to 200°C or 220°C with an oxygen concentration of 20 ppm or less and 4.0°C/min under nitrogen flow, and heat treatment is carried out at 200°C or 220°C for 1 hour. Take out the silicon wafer when the temperature becomes below 50°C, and immerse the cured film in an organic chemical solution (dimethyl sulfide: 25% tetramethyl ammonium hydroxide aqueous solution = 92: 2) at 65°C for 100 minutes, and observe Whether there is pattern peeling or dissolution.

As a result, the case where there was no pattern peeling or elution was evaluated as good 2, and the case where peeling or elution of the pattern was observed was evaluated as bad 1.

(4)-1. Evaluation of breaking elongation

After pre-baking at 120°C for 3 minutes, the film thickness becomes 11 μm. Using the coating and developing device ACT-8, the varnish is applied to an 8-inch silicon wafer by spin coating and pre-baked. Use an inert gas oven CLH-21CD-S (manufactured by Koyo Thermo Systems), and raise the temperature to 200°C or 220°C at an oxygen concentration of 20 ppm or less and 4.0°C/min. Or heat treatment at 220°C for 1 hour. When the temperature became 50°C or lower, the silicon wafer was taken out and immersed in 45% by mass hydrofluoric acid for 5 minutes, thereby peeling the cured film of the resin composition from the wafer. The above-mentioned film was cut into strips with a width of 1 cm and a length of 9 cm, using TENSILON RTM-100 (manufactured by ORIENTEC), at room temperature 23.0°C, humidity 45.0% RH, and stretching at a stretching speed of 50 mm/min. Measurement of elongation and breaking elongation. 10 strips are measured for each sample, and the average value of the top 5 is obtained from the results.

Those with a breaking elongation value of 60% or more are evaluated as extremely good3, those with a value of 40% or more and less than 60% are evaluated as good2, and those with less than 40% are evaluated as poor1.

(4)-2. Evaluation of peeling on copper wiring after high temperature storage test (HTS)

When performing peeling evaluation on copper wiring, the following evaluation board|substrates were prepared.

Cylindrical copper wiring with a thickness of 5 μm and a diameter of 90 μm was formed on an 8-inch silicon wafer at equal intervals so that the distance between the centers of the copper wiring was 150 μm. This was used as an evaluation substrate.

After pre-baking at 120°C for 3 minutes, the film thickness becomes 11μm. Using the coating and developing device ACT-8, the varnish was applied to the evaluation substrate by spin coating method and after pre-baking, an inert gas oven was used. CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), heated to 200°C at an oxygen concentration of 20 ppm or less and 4.0°C/min, and heated at 200°C for 1 hour. When the temperature became 50°C or lower, the evaluation substrate (hereinafter referred to as a sample) was taken out. Next, the sample was put into a constant temperature bath at 175°C and processed for 200 hours. After that, take out the sample, in order to observe For the peeling of the copper wiring, a scanning electron microscope FEI Helios650 (manufactured by FEI Co., Ltd.) attached to a focused ion beam processing device was used to cut the sample and observe the cross section at a magnification of 40,000. As an evaluation method, observe the degree of peeling of the side part of the copper wiring, and the peeling of 0% or more and less than 25% is evaluated as extremely good 3, the peeling of 25% or more and less than 50% is evaluated as good 2, and the peeling 50% is evaluated as poor 1.

<Synthesis Example 1 Synthesis of Hydroxyl-Containing Diamine Compound>

18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass, hereinafter referred to as BAHF) was dissolved in 100 mL of acetone, 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and cooled to -15°C. Next, a solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrophenylmethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was dropped. After the dripping is completed, it is stirred at -15°C for 4 hours, and then warmed to room temperature. The precipitated white solid was filtered and vacuum dried at 50°C.

30 g of the obtained white solid was put into a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl ceroxu, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Then hydrogen is introduced in a balloon, and the reduction reaction is carried out at room temperature. After about 2 hours, it was confirmed that the balloon was no longer shrinking and the reaction ended. After the completion of the reaction, filtration was performed to remove the palladium compound of the catalyst, and it was concentrated with a rotary evaporator to obtain a hydroxyl-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'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. Then, together with 50 g of NMP, 39.30 g (0.065 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyl were added. The base disiloxane was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 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 reacted at 50°C for 1 hour. Next, 4.36 g (0.04 mol) of 4-aminophenol as a blocking agent was added together with 5 g of NMP, and reacted at 50° C. for 2 hours. After that, a solution of 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of NMP was dropped over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum drying mechanism at 80° C. for 24 hours to obtain a polyimide precursor (A-1) of the target alkali-soluble resin.

唑前驅物(A-2)的合成> <Synthesis Example 3 Polybenzo

Synthesis of azole precursor (A-2)>

唑前驅物(A-2)的粉末。 Under a stream of dry nitrogen, 27.47 g (0.075 mol) of BAHF was dissolved in 257 g of NMP. Next, 1,1'-(4,4'-oxybenzyl) diimidazole (hereinafter referred to as PBOM) (17.20 g, 0.048 mol) was added together with 20 g of NMP, and reacted at 85°C 3 hours. Then, together with 50 g of NMP, RT-1000 (20.00 g, 0.020 mol) containing propylene oxide and tetramethylene ether glycol structure, 1,3-bis(3-aminopropyl) tetramethyl bis Siloxane (1.24 g, 0.005 mol), PBOM (14.33 g, 0.044 mol), and reacted at 85°C for 1 hour. Furthermore, along with 10 g of NMP, 5-norbornene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol) was added as a blocking agent, and the reaction was carried out at 85° C. for 30 minutes. After the reaction was completed, it was cooled to room temperature, acetic acid (52.82 g, 0.50 mol) was added together with 87 g of NMP, and stirred at room temperature for 1 hour. After the stirring was completed, the solution was poured into 3L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and dried with a ventilated drying mechanism at 50°C for 3 days to obtain polybenzo

The powder of the azole precursor (A-2).

唑前驅物(A-3)的合成> <Synthesis Example 4 Polybenzo

Synthesis of azole precursor (A-3)>

唑前驅物(A-3)的粉末。 According to the synthesis example 3 above, BAHF (27.47g, 0.075 mol), PBOM (30.10g, 0.084 mol), ED-900 (9.00g, 0.020 mol) containing propylene oxide and ethylene glycol structure, 1 , 3-bis(3-aminopropyl) tetramethyldisiloxane (1.24g, 0.0050 mol), 5-norbornene-2,3-dicarboxylic anhydride (5.25g, 0.032 mol), Acetic acid (48.02g, 0.80 mol), 409g of NMP, perform the same operation to obtain polybenzo

A powder of the azole precursor (A-3).

唑前驅物(A-4)的合成> <Synthesis Example 5 Polybenzo

Synthesis of azole precursor (A-4)>

唑前驅物(A-4)的粉末。 According to the synthesis example 3 above, BAHF (32.96g, 0.090 mol), PBOM (29.38g, 0.082 mol), RT-1000 (10.00g, 0.010 mol), 1,3-bis(3-aminopropyl) Base) tetramethyl disiloxane (1.49g, 0.0060 mol), 5-norbornene-2,3-dicarboxylic anhydride (5.91g, 0.036 mol), HFHA (0.60g, 0.0010 mol), ODPA (2.17g, 0.0070 mol), acetic acid (49.22g, 0.82 mol), 360g of NMP, perform the same operation to obtain polybenzo

A powder of the azole precursor (A-4).

<Synthesis Example 6: Synthesis of polyamide imine precursor (A-5)>

Under a stream of dry nitrogen, 27.5 g (0.10 mol) of diphenyl ether tricarboxylic acid anhydride chloride was dissolved in 500 g of NMP. Then, together with 50 g of NMP, 39.30 g (0.065 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyl were added. The base disiloxane was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 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 reacted at 50°C for 1 hour. Next, 4.36 g (0.04 mol) of 4-aminophenol was added together with 5 g of NMP as a blocking agent, and reacted at 50° C. for 2 hours. After that, a solution of 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of NMP was dropped over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum drying mechanism at 80°C for 24 hours to obtain the desired polyimide precursor (A-5).

[Reference example 1~15]

Add 0.2g (0.52 millimoles) of 3-(5-(((benzenesulfonyloxy)imino)thiophene-2 to 10g of (A) component (A-1~5) obtained (5H)-ylidene-2-(o-tolyl)propanenitrile (B-1) or 0.2g (0.53 millimoles) SI-200 (B-2) as (B) thermal acid generator, 2.4g (4.2 millimoles) of HMOM-TPHAP (C-1) and 1.0g (2.6 millimoles) of MW-100LM (C- 2) As (C) a thermal crosslinking agent, 2.0 g (1.8 millimoles) of a photosensitive compound represented by the following formula is used as (D) a photosensitive compound, and 20 g of γ-butyrolactone is added as a solvent to prepare a varnish , Measure these characteristics by the above-mentioned evaluation method. The results obtained are shown in Table 1.

[Reference example 16~20]

Except that (B) the thermal acid generator was not used, varnishes were produced in the same manner as in Reference Examples 1 to 15, and these characteristics were measured by the above-mentioned evaluation method. The results obtained are shown in Table 1.

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

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

[Comparative Examples 10~15]

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

Claims (16)

A resin composition, which contains: (A) containing selected from polybenzo

Azole precursor, polyimide precursor, polyimide precursor and one or more of these copolymers, and have benzo

Azole precursor structure and alkali-soluble resin of aliphatic base; and (B) thermal acid generator and (E) antioxidant, wherein the (A) contains polybenzo

Azole precursor, polyimide precursor, polyimide precursor and one or more of these copolymers, and have benzo

Alkali-soluble resin with azole precursor structure and aliphatic base, having a structural unit represented by the general formula (1);

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

(In the general formula (2), R ³ to R ⁶ each independently represent an alkylene group with 1 to 6 carbons; R ⁷ to R ¹⁴ each independently represent hydrogen, fluorine, or an alkyl group with 1 to 6 carbons; wherein, The structures shown in parentheses are different; x, y, and z each independently represent an integer from 0 to 35). The resin composition of claim 1, wherein the (B) thermal acid generator comprises a sulfonate compound represented by the following general formula (3), a sulfonate compound represented by the general formula (4), and an onium salt More than one compound of

(In general formulas (3) and (4), R ²⁰ to R ²² each independently represent an aliphatic group with 1 to 12 carbons or an aromatic group with 4 to 12 carbons). The resin composition of 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 of claim 1, which further contains (C) a thermal crosslinking agent and (D) a photosensitive compound. The resin composition of claim 4, wherein the (C) thermal crosslinking agent comprises 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 with 2 or more carbon atoms, which may be linear, branched, and Any kind of ring). The resin composition of any one of claims 1 to 5, 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 alkylene group with a carbon number of 2 or more, R ²⁷ represents an alkylene group with a carbon number of 2 or more; R ²⁸ represents an alkylene group with a carbon number of 2 or more, an O atom, and At least any one of 1~4 valence organic groups among N atoms; k represents an integer of 1~4). A resin sheet formed of the resin composition according to any one of claims 1 to 6. A cured film formed by curing the resin composition of any one of claims 1 to 6. A cured film formed by curing a resin sheet as in Claim 7. Such as the hardened film of claim 8 or 9, in which benzo

The structure of the azole precursor is closed to form a polybenzo

The ratio of azole is 30% or more. A method for manufacturing a cured film, characterized by comprising: coating the resin composition according to any one of claims 1 to 6 on a substrate, or laminating the resin sheet according to claim 7 on a substrate, and drying A step 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 heating the developed resin film. The method of manufacturing a cured film of claim 11, wherein the heat treatment step of heat-treating the developed resin film includes a step of heat-treating at 140°C or higher and 220°C or lower. An interlayer insulating film or semiconductor protective film, which is configured with a hardened film as in any one of Claims 8 to 10. A semiconductor electronic component or semiconductor device provided with a cured film as in any one of claims 8 to 10 as an interlayer insulating film between rewiring. For example, the semiconductor electronic component or semiconductor device of claim 14, which is repeatedly arranged with 2-10 layers of the rewiring and interlayer insulating film. A semiconductor electronic component or semiconductor device provided with the cured film of any one of claims 8 to 10 as an interlayer insulating film of adjacent substrates composed of two or more materials.

Images