Negative Photosensitive Resin Composition, Patterning Process, Interlayer Insulating Film, Surface Protection Film, And Electronic Component

Abstract

A negative photosensitive resin composition having a high resolution, mechanical strength, adhesion and the like, as well as excellent storage stability. A negative photosensitive resin composition, including: (A) one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a photoacid generator; (C) one or more kinds of crosslinking agent selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on average two or more methylol groups or alkoxymethylol groups within one molecule, a compound in which a hydrogen atom of a hydroxyl group of polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of polyhydric phenol is substituted with a substituent represented by the formula (C-1), a compound represented by the formula (C-15), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the formula (C-2); (D) an onium salt represented by the formula (1); and (E) a solvent.

Claims

1. A negative photosensitive resin composition, comprising: (A) an alkali-soluble resin including at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a photoacid generator; (C) one or two or more kinds of crosslinking agent selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on average two or more methylol groups or alkoxymethylol groups within one molecule, a compound in which a hydrogen atom of a hydroxyl group of polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of polyhydric phenol is substituted with a substituent represented by the following formula (C-1), a compound represented by the following formula (C-15) having a substituent (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2); ##STR00130## wherein the broken line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; s represents 1 or 2; u is a number satisfying 1≤u≤3, (D) an onium salt represented by the following general formula (1); and ##STR00131## wherein A represents iodine, sulfur, phosphorus, or nitrogen; each Q is identical to or different from one another and represents a monovalent hydrocarbon group having 1 to 100 carbon atoms, which may be linked, substituted, or intervened by a heteroatom; E.sup.− represents an anion of an organic or inorganic acid salt; and m represents 2 when A is iodine, m represents 3 when A is sulfur, and m represents 4 when A is phosphorus or nitrogen, (E) a solvent.

2. The negative photosensitive resin composition according to claim 1, wherein the component (D) is a quaternary ammonium salt represented by the following general formula (1-1), in which A in the general formula (1) is nitrogen, ##STR00132## wherein each of Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 is identical to or different from one another and represents a monovalent hydrocarbon group having 1 to 100 carbon atoms, which may be linked, substituted, or intervened by a heteroatom; and E.sup.− represents an anion of an organic or inorganic acid salt as defined above.

3. The negative photosensitive resin composition according to claim 1, wherein, in the component (D), E.sup.− in the general formula (1) is an anion of an organic carboxylic acid represented by the following general formula (6), ##STR00133## wherein R.sup.E represents a hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom.

4. The negative photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product of a diamine comprising one or more of a diamine represented by the following general formula (2) and a diamine represented by the following general formula (3), and one or more of a tetracarboxylic acid dianhydride represented by the following general formula (4) and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5), ##STR00134## wherein L.sub.1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom, wherein L.sub.2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom, T represents any of a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —OCO.sub.2R.sup.T, —OSO.sub.2R.sup.T, and —OSO.sub.3R.sup.T, provided that R.sup.T represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom.

5. The negative photosensitive resin composition according to claim 1, wherein, in the component (B), an acid generated by a photoacid generator is an organic sulfonic acid represented by the following general formula (7), ##STR00135## wherein R.sup.U represents a hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom.

6. The negative photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product of one or more of a tetracarboxylic acid dianhydride represented by the following general formula (8) and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (9), ##STR00136## wherein Z represents an alicyclic structure, an alicyclic structure connected to an aromatic ring, a heteroatom-containing or heteroatom-intervened alicyclic structure, or a heteroatom-containing or heteroatom-intervened alicyclic structure connected to an aromatic ring, each of which has 3 to 20 carbon atoms, T represents any of a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —OCO.sub.2R.sup.T, —OSO.sub.2R.sup.T, and —OSO.sub.3R.sup.T; j represents 0 or 1; when j is 0, the phthalic anhydride structure and the cyclic structure Z in the general formula (8) and the benzoic acid structure and the cyclic structure Z in the general formula (9) are directly bonded; and when j is 1, X.sub.1 and X.sub.2 represent a divalent linkage group.

7. The negative photosensitive resin composition according to claim 6, wherein the alicyclic structure Z in the general formulae (8) and (9) is a structure represented by the following general formula (10) or (11), ##STR00137## wherein the broken line represents a bond; and k represents 0 or an integer of 1 or more, when k=0, Y2 represents a divalent group selected from any of the following general formulae (13), (14), (15), and (16), when k=1, Y1 represents a divalent group selected from any of the following general formulae (17), (18), and (19), and Y.sub.2 represents a divalent group selected from any of the following general formulae (13), (14), (15), and (16), when k is 2 or more, Y.sub.1 represents the following general formula (17), and Y2 represents a divalent group selected from any of the following general formulae (13), (14), (15), and (16), R.sup.1, R.sup.2, R.sup.3, and R.sup.4, and R.sup.5 and R.sup.6 in the following formula (16) represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are bonded together to form an alicyclic or aromatic ring, ##STR00138## wherein the broken line represents a bond, and R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, and R.sup.15 represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms, m and p represent 0 or an integer of 1 to 9; and n represents 0 or 1, Y.sub.3 represents a divalent group selected from any of the following general formulae (12), (13), (14), (15), (16), (17), (18) and (19), ##STR00139## wherein the broken line represents a bond; and R.sup.5 and R.sup.6 are as defined above, R.sup.7 represents a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms.

8. The negative photosensitive resin composition according to claim 6, wherein divalent linkage groups X.sub.1 and X2 in the general formulae (8) and (9) have a structure represented by any of the following general formulae (20), (21), (22), (23), (24), and (25), ##STR00140## wherein the broken line represents a bond.

9. The negative photosensitive resin composition according to claim 4, wherein the diamine represented by the general formula (2) is a diamine represented by the following general formula (26). ##STR00141##

10. The negative photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product further comprising a tetracarboxylic acid diester compound represented by the following general formula (27), ##STR00142## wherein W1 is a tetravalent organic group; and R.sup.16 is represented by the following general formula (28), ##STR00143## wherein the broken line represents a bond; V.sub.1 represents a (r+1)-valent organic group; Rf represents a linear, branched or cyclic alkyl group or an aromatic group having 1 to 20 carbon atoms in which a part or all of the hydrogen atoms are substituted with a fluorine atom; r represents 1, 2 or 3; and q represents 0 or 1.

11. The negative photosensitive resin composition according to claim 10, wherein R.sup.16 in the general formula (27) is an organic group selected from any of groups represented by the following general formulae (29), (30), (31), and (32), ##STR00144## wherein the broken line represents a bond; and Rf is as defined above; each of Ra and Rb is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; each of V.sub.2 and V.sub.3 is a linear or branched alkylene group having 1 to 6 carbon atoms; n1 is an integer of 0 to 6; n2 is an integer of 1 to 6; n3 is an integer of 0 to 6; n4 is an integer of 1 to 6; n5 is an integer of 0 to 6; and n6 is 0 or 1.

12. The negative photosensitive resin composition according to claim 10, wherein R.sup.16 in the general formula (27) is a group represented by the following general formula (28-1),
.Math.—CH.sub.2—CH.sub.2—Rf  (28-1) wherein the broken line represents a bond; and Rf is as defined above.

13. The negative photosensitive resin composition according to claim 6, wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product of one or more of a tetracarboxylic acid dianhydride in which the alicyclic structure Z of the general formula (8) is represented by the following general formula (33) or (34) and/or a dicarboxylic acid or dicarboxylic acid halide in which the alicyclic structure Z of the general formula (9) is selected from any of structures represented by the following general formulae (35), (36), (37), (38), (39), and (40), ##STR00145## wherein the broken line represents a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are bonded together to form an alicyclic or aromatic ring, R.sup.7 represents a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms, wherein R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, and R.sup.15 represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms.

14. A patterning process, comprising the steps of: (1) applying the negative photosensitive resin composition according to claim 1 onto a substrate to form a photosensitive material film; (2) after heating the photosensitive material film, exposing the photosensitive material film to a high-energy beam having a wavelength of 190 to 500 nm or an electron beam through a photomask; and (3) developing the exposed photosensitive material film using an aqueous alkaline solution as a developer.

15. The patterning process according to claim 14, further comprising the step of: (4) post-curing the developed photosensitive material film by heating at a temperature of 100 to 300° C.

16. An interlayer insulating film, comprising a cured product of the negative photosensitive resin composition according to claim 1.

17. A surface protection film, comprising a cured product of the negative photosensitive resin composition according to claim 1.

18. An electronic component, comprising the interlayer insulating film according to claim 16.

19. An electronic component, comprising the surface protection film according to claim 17.

Description

EXAMPLE

[0242] The present invention is specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to these Examples.

[0243] Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples are shown below to specifically describe the present invention. However, the present invention is not limited to these Examples.

I. Synthesis of Resin

[0244] In Synthesis Examples below, the compounds having the following chemical structures and names were used.

##STR00097## ##STR00098##

6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
BPS: bis(3-amino-4-hydroxyphenyl)sulfone
s-ODPA: 3,3′,4,4′-oxydiphthalic acid dianhydride
s-BPDA: 3,3′,4,4′-biphenyl tetracarboxylic acid
dianhydride
DC-1: Dichloride sebacate
PAP: 4-aminophenol
Rf-1: 4,4,5,5,5-pentafluoropentanol

Synthesis Example 1: Synthesis of Polyimide Resin (A-1)

[0245] 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 170 g of N-methyl-2-pyrrolidone were placed in a 1 L flask equipped with a stirrer and a thermometer, and dissolved by stirring at room temperature. Subsequently, a solution obtained by dissolving 12.7 g (41.0 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA), and 18.8 g (41.0 mmol) of tetracarboxylic acid dianhydride (AN-1) in 320 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. Following completion of the dropwise addition, the mixture was stirred for 3 hours at room temperature. Thereafter, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux at 170° C. for 3 hours while removing the produced water from the system. After cooling to room temperature, the resulting reaction solution was added dropwise to 2 L of ultrapure water under stirring, and the precipitate was collected by filtration and washed with water as necessary, followed by drying under reduced pressure at 40° C. for 48 hours to obtain a polyimide resin (A-1). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 35,000 on polystyrene basis.

Synthesis Example 2: Synthesis of Polyimide Resin (A-2)

[0246] The same formulation as that in Synthesis Example 1 was used, except that 26.3 g of the tetracarboxylic acid dianhydride (AN-2) having the weight shown in Table 1 below was used instead of 18.8 g of the tetracarboxylic acid dianhydride (AN-1) to obtain a polyimide resin (A-2). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 34,000 on polystyrene basis.

Synthesis Example 3: Synthesis of Polyimide Resin (A-3)

[0247] The same formulation as that in Synthesis Example 1 was used, except that 23.0 g of bis(3-amino-4-hydroxyphenyl)sulfone (BPS) was used instead of 30.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) to obtain a polyimide resin (A-3). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 33,000 on polystyrene basis as shown in Table 1.

Synthesis Example 4: Synthesis of Tetracarboxylic Acid Diester Dichloride (X-1)

[0248] 100 g (322 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were placed in a 3 L flask equipped with a stirrer and a thermometer, and, during the stirring of the mixture at room temperature, 114.7 g (644 mmol) of 4,4,5,5,5-pentafluoropentanol (Rf-1) was added dropwise, followed by stirring at room temperature for 24 hours. The reaction was then stopped by adding 370 g of 10% aqueous hydrochloric acid solution dropwise under ice-cooling. 800 g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated and washed six times with 600 g of ultrapure water. The solvent of the obtained organic layer was removed by distillation to obtain 193 g of tetracarboxylic acid diester compound (X-1). 772 g of N-methyl-2-pyrrolidone was added to the obtained tetracarboxylic acid diester compound and the compound was dissolved by stirring at room temperature. Next, under ice-cooling, 75.8 g (637 mmol) of thionyl chloride was added dropwise to keep the temperature of the reaction solution at 10° C. or less. After completion of the dropwise addition, the reaction solution was stirred under ice-cooling for 2 hours to obtain a tetracarboxylic acid diester dichloride (X-1) dissolved in N-methyl-2-pyrrolidone.

Synthesis Example 5: Synthesis of Polyamideimide Resin (A-4)

[0249] 30.0 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 170 g of N-methyl-2-pyrrolidone were placed in a 500 ml flask equipped with a stirrer and a thermometer, and dissolved by stirring at room temperature. Subsequently, a solution obtained by dissolving 12.7 g (41.0 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA), and 5.6 g (12.3 mmol) of tetracarboxylic acid dianhydride (AN-1) in 185 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. Following completion of the dropwise addition, the mixture was stirred for 3 hours at room temperature. Thereafter, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux at 170° C. for 3 hours while removing the produced water from the system. After cooling to room temperature, 1.4 g (18.0 mmol) of pyridine was added, and a separately prepared mixed solution of 14.7 g (4.1 mmol on the basis of tetracarboxylic acid diester dichloride) of tetracarboxylic acid diester dichloride (X-1) dissolved in N-methyl-2-pyrrolidone and 5.9 g (24.6 mmol) of sebacic acid dichloride (DC-1) was added dropwise to keep the mixture at 5° C. or less. After the dropwise addition, the reaction solution was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water under stirring, and the precipitate was collected by filtration and washed with water as necessary, followed by drying under reduced pressure at 40° C. for 48 hours to obtain a polyamideimide resin (A-4). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 38,000 on polystyrene basis.

Synthesis Example 6: Synthesis of Polyamideimide Resin (A-5)

[0250] The same formulation as that in Synthesis Example 5 was used, except that 7.9 g of the tetracarboxylic acid dianhydride (AN-2) was used instead of 5.6 g of the tetracarboxylic acid dianhydride (AN-1) to obtain a polyimide resin (A-5). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 39,000 on polystyrene basis as shown in Table 1.

Synthesis Example 7: Synthesis of Polyamideimide Resin (A-6)

[0251] The same formulation as that in Synthesis Example 5 was used, except that 23.0 g of bis(3-amino-4-hydroxyphenyl)sulfone (BPS) was used instead of 30 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) to obtain a polyimide resin (A-6). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 35,000 on polystyrene basis as shown in Table 1.

Synthesis Example 8: Synthesis of Polyamideimide Resin (A-7)

[0252] 27.0 g (73.7 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 108 g of N-methyl-2-pyrrolidone were placed in a 500 ml flask equipped with a stirrer and a thermometer, and dissolved by stirring at room temperature. Subsequently, a solution obtained by dissolving 12.7 g (41.0 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA), and 5.6 g (12.3 mmol) of tetracarboxylic acid dianhydride (AN-1) in 185 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. Following completion of the dropwise addition, the mixture was stirred for 3 hours at room temperature. Thereafter, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux at 170° C. for 3 hours while removing the produced water from the system. After cooling to room temperature, 0.9 g (8.2 mmol) of 4-aminophenol (PAP) and 1.4 g (18.0 mmol) of pyridine were added, and a separately prepared mixed solution of 14.7 g (4.1 mmol on the basis of tetracarboxylic acid diester dichloride) of tetracarboxylic acid diester dichloride (X-1) dissolved in N-methyl-2-pyrrolidone and 5.9 g (24.6 mmol) of sebacic acid dichloride (DC-1) was added dropwise to keep the mixture at 5° C. or less. After the dropwise addition, the reaction solution was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water under stirring, and the precipitate was collected by filtration and washed with water as necessary, followed by drying under reduced pressure at 40° C. for 48 hours to obtain a polyamideimide resin (A-7). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 30,000 on polystyrene basis as shown in Table 1.

Synthesis Example 9: Synthesis of Polyamideimide Resin (A-8)

[0253] The same formulation as that in Synthesis Example 8 was used, except that not 12.7 g (41.0 mmol) but 14.0 g (45.1 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA) was used without using the tetracarboxylic acid diester dichloride (X-1) dissolved in N-methyl-2-pyrrolidone to obtain a polyimide resin (A-8). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 31,000 on polystyrene basis as shown in Table 1.

Synthesis Example 10: Synthesis of Polyamideimide Resin (A-9)

[0254] The same formulation as that in Synthesis Example 8 was used, except that not 12.7 g (41.0 mmol) but 11.4 g (36.9 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA) was used and 1.2 g (4.1 mmol) of 3,3′,4,4′-biphenyl tetracarboxylic acid dianhydride was added to obtain a polyimide resin (A-9). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 30,000 on polystyrene basis as shown in Table 1.

Synthesis Example 11: Synthesis of Polyamideimide Resin (A-10)

[0255] The same formulation as that in Synthesis Example 10 was used, except that not 11.4 g (36.9 mmol) but 12.6 g (40.6 mmol) of 3,3′,4,4′-oxydiphthalic acid dianhydride (s-ODPA) was used and not 1.2 g (4.1 mmol) but 1.35 g (4.6 mmol) of 3,3′,4,4′-biphenyl tetracarboxylic acid dianhydride was used without using the tetracarboxylic acid diester dichloride (X-1) dissolved in N-methyl-2-pyrrolidone to obtain a polyimide resin (A-10). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 30,000 on polystyrene basis as shown in Table 1.

TABLE-US-00001 TABLE 1 Tetracarboxylic Acid Diester Dichloride NMP Solution (Molar Amount of Tetracarboxylic Di- Acid carboxylic Dichloride) Monoamine Acid Synthesis Mole- Diamine Compound Compound Tetracarboxylic Acid Dianhydride Dichloride Example 4 cular 6FAP BPS PAP s-ODPA s-BPDA AN-1 AN-2 DC-1 X-1 Weight Synthesis A-1 30.0 g 12.7 g 18.8 g 35,000 Example 1 (81.9 mmol) (41.0 mmol) (41.0 mmol) Synthesis A-2 30.0 g 12.7 g 26.3 g 34,000 Example 2 (81.9 mmol) (41.0 mmol) (41 mmol) Synthesis A-3 23.0 g 12.7 g 18.8 g 33,000 Example 3 (81.9 (41.0 mmol) (41.0 mmol) mmol Synthesis A-4 30.0 g 12.7 g 5.6 g 5.9 g 14.7 g 38,000 Example 5 (81.9 mmol) (41.0 mmol) (12.3 mmol) (24.6 mmol) (4.1 mmol) Synthesis A-5 30.0 g 12.7 g 7.9 g 5.9 g 14.7 g 39,000 Example 6 (81.9 mmol) (41.0 mmol) (12.3 (24.6 mmol) (4.1 mmol) mmo Synthesis A-6 23.0 g 12.7 g 5.6 g 5.9 g 14.7 g 35,000 Example 7 (81.9 (41.0 mmol) (12.3 mmol) (24.6 mmol) (4.1 mmol) mmol Synthesis A-7 27.0 g 0.9 g 12.7 g 5.6 g 5.9 g 14.7 g 30,000 Example 8 (73.7 mmol) (8.2 mmol) (41.0 mmol) (12.3 mmol) (24.6 mmol) (4.1 mmol) Synthesis A-8 27.0 g 0.9 g 14.0 g 5.6 g 5.9 g 31,000 Example 9 (73.7 mmol) (8.2 mmol) (45.1 mmol) (12.3 mmol) (24.6 mmol) Synthesis A-9 27.0 g 0.9 g 11.4 g 1.2 g 5.6 g 5.9 g 14.7 g 30,000 Example 10 (73.7 mmol) (8.2 mmol) (36.9 mmol) (4.1 (12.3 mmol) (24.6 mmol) (4.1 mmol) mmol) Synthesis A-10 27.0 g 0.9 g 12.6 g 1.35 g 5.6 g 5.9 g 30,000 Example 11 (73.7 mmol) (8.2 mmol) (40.6 mmol) (4.6 (12.3 mmol) (24.6 mmol) mmol)

II. Preparation of Photosensitive Resin Composition

[0256] Resin compositions with a resin equivalent of 20 mass % were prepared according to the formulations and incorporation amounts in Tables 2 and 3 using the polyimide resins (A-1) to (A-3) synthesized in Synthesis Examples 1 to 3 above and polyamideimide resins (A-4) to (A-10) synthesized in Synthesis Examples 5 to 11 above as base resins. After subsequent stirring and mixing for dissolution, precision filtering through a Teflon (registered trademark) filter with a pore size of 0.5 μm was performed to obtain a photosensitive resin composition. In the Tables, the solvent PGMEA stands for propylene glycol monomethyl ether acetate and CyPn stands for cyclopentanone.

TABLE-US-00002 TABLE 2 Photoacid Crosslinking Crosslinking Resin Generator Agent-1 Agent-2 Onium Salt Solvent-1 Solvent-2 Component (A) Component (B) Component (C) Component (D) Component (E) Photosensitive A-1 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 1 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-2 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By 15 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 2 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-3 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 3 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-4 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 4 Weight) Weight) Weight) Weight) Weight Weight) Weight) Photosensitive A-5 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 5 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-6 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 6 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-7 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 7 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-8 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 8 Weight) Weight) Weight) Weight) Weight Weight) Weight) Photosensitive A-9 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 9 Weight) Weight) Weight) Weight) Weight) Weight) Weight) Photosensitive A-10 B-1 CL-1 CL-2 D-1 PGMEA CyPn Resin (100 Parts By (2 Parts By (5 Parts By (10 Parts By (0.5 Parts By (96 Parts By (24 Parts By Composition 10 Weight) Weight) Weight) Weight) Weight) Weight) Weight)

TABLE-US-00003 TABLE 3 Photoacid Crosslinking Crosslinking Crosslinking Basic Resin Generator Agent-1 Agent-2 Agent-3 Onium Salt Com- Solvent-1 Solvent-2 Component (A) Component (B) Component (C) Component (D) pound Component (E) Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-1 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.5 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 11 Photosensitive A-7 B-1 CL-1 CL-2 CL-4 D-1 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.5 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 12 Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-2 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.3 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 13 Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-3 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.6 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 14 Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-4 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.9 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 15 Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-5 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.3 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 16 Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-6 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.5 Parts By 196 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight) By Weight) By Weight) 17 Photosensitive A-7 B-1 CL-1 CL-2 CL-3 D-7 PGMEA CyPn Resin (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.6 Parts By (96 Parts (24 Parts Composition By Weight) Weight) Weight) Weight) Weight) Weight By Weight) By Weight) 18 Comparative A-7 B-1 CL-1 CL-2 CL-3 Amine-1 PGMEA CyPn Photosensitive (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.5 (96 Parts (24 Parts Resin By Weight) Weight) Weight) Weight) Weight) Parts By By Weight) By Weight) Composition 1 Weight) Comparative A-7 B-1 CL-1 CL-2 CL-3 Amine-2 PGMEA CyPn Photosensitive (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.5 (96 Parts (24 Parts Resin By Weight) Weight) Weight) Weight) Weight) Parts By By Weight) By Weight) Composition 2 Weight) Comparative A-7 B-1 CL-1 CL-2 CL-3 Amine-3 PGMEA CyPn Photosensitive (100 Parts (2 Parts By (5 Parts By (10 Parts By (15 Parts By (0.5 196 Parts (24 Parts Resin By Weight) Weight) Weight) Weight Weight) Parts By By Weight) By Weight) Composition 3 Weight)

[0257] The details of the acid generator (B-1), the crosslinking agent (CL-1), (CL-2), (CL-3), and (CL-4), the ammonium and sulfonium salts (D-1) to (D-7), the basic compounds (Amine-1), (Amine-2), and (Amine-3) used as comparative photosensitive resin compositions in Table 2 are as follows.

[0258] Acid Generator (B-1)

##STR00099##

[0259] Crosslinking Agent (CL-1)

##STR00100##

[0260] Crosslinking Agent (CL-2)

##STR00101##

[0261] Crosslinking Agent (CL-3)

##STR00102##

(n=0.9 to 1)
Epoxy resin: EP4000L manufactured by Adeka Corporation

[0262] Crosslinking Agent (CL-4)

##STR00103##

(n=1 to 3)
OXT-121 manufactured by Toagosei Co., Ltd.

[0263] Onium Salt (D-1)

##STR00104##

[0264] Onium Salt (D-2)

##STR00105##

[0265] Onium Salt (D-3)

##STR00106##

[0266] Onium Salt (D-4)

##STR00107##

[0267] Onium Salt (D-5)

##STR00108##

[0268] Onium Salt (D-6)

##STR00109##

[0269] Onium Salt (D-7)

##STR00110##

[0270] Basic Compound (Amine-1)

##STR00111##

[0271] Basic Compound (Amine-2)

##STR00112##

[0272] Basic Compound (Amine-3)

##STR00113##

III. Storage Stability

[0273] After the photosensitive resin compositions 1-18 and the comparative photosensitive resin compositions 1-3 were stirred, mixed, and dissolved as described above, precision filtering through a Teflon (registered trademark) filter with a pore size of 0.5 μm was performed; then, immediately after that, 5 mL of the mixture was dispensed onto a silicon wafer, followed by rotation, i.e., spin coating of the wafer to form a film. Subsequently, prebaking was performed on a hotplate at 100° C. for 2 minutes. The rotation number was adjusted so that the film thickness after prebaking was 6 μm. The film thickness was measured and this thickness was used as the initial film thickness.

[0274] The filtered solutions of the photosensitive resin compositions 1-18 and the comparative photosensitive resin compositions 1-3 were stored at room temperature for 3 weeks, and films were formed at the same rotation number as above so that the film thickness after prebaking was 6 μm. Subsequently, prebaking was performed on a hotplate at 100° C. for 2 minutes. The film thicknesses after the solutions were stored for 3 weeks were measured and the amount of change was evaluated using the following formula. The results are summarized in Table 4 below.

Amount of change (%)=film thickness after 3 weeks−initial film thickness Initial film thickness×100

IV. Patterning

[0275] 5 mL each of the photosensitive resin compositions 1-18 and the comparative photosensitive resin compositions 1-3 were applied by dispensing onto a silicon wafer, followed by rotation, i.e., spin coating, so that the film thickness was 6 μm after heating for post-curing, which is performed after the patterning. Specifically, considering the expected decrease in film thickness after the post-curing step, the rotation number during the application was adjusted so that the finished film thickness after the post-curing was 5 μm.

[0276] Subsequently, prebaking was performed on a hotplate at 100° C. for 2 minutes. Next, exposure to i-line and patterning were performed using an AP-300E i-line exposure machine manufactured by Veeco Japan. In the patterning, negative pattern masks were used. Each of the mask has a pattern enabling formation of holes in a 1:1 vertical and horizontal array, with 10-μm increments from 50 μm to 20 μm, 5-μm increments from 20 μm to 10 μm, and 1-μm increments from 10 μm to 1 μm for hole pattern formation.

[0277] In the development step, an aqueous alkaline solution was used as the developer, and a 2.38% aqueous tetramethyl ammonium hydroxide solution was used as the developer. A 1-minute puddle development with the 2.38% aqueous tetramethyl ammonium hydroxide (TMAH) solution was performed for appropriate number of times as shown in Table 4, followed by rinsing with ultrapure water.

[0278] Then, the obtained pattern on the wafer was post-cured in an oven at 180° C. for 2 hours while the oven was purged with nitrogen.

[0279] To observe the shape of the resulting hole pattern, each substrate was sectioned, and the hole pattern shape was observed using a scanning electron microscope (SEM). The pattern shape was evaluated by determining the diameter of the smallest aperture hole at a film thickness of 5 μm after the post-curing. Together with these results, Table 4 shows the sensitivity with which the minimum pattern was formed.

[0280] The hole pattern shapes were evaluated using the following criteria, and the evaluation results are shown in Table 4. [0281] Good: rectangular or forward-tapered (the top dimension of the hole is larger than the bottom dimension) holes were observed. [0282] Defective: inverse-tapered (the top dimension of the hole is smaller than the bottom dimension) holes, overhang-shaped (a shape with the top of the hole protruding) holes, significant film loss, or residues at the bottom of the hole were observed.

V. Breaking Elongation, Breaking Strength

[0283] Each of the photosensitive resin compositions 1-18 and the comparative photosensitive resin compositions 1-3 was spin-coated onto an aluminum substrate so that the finished film thickness was 10 μm after curing. Next, the coated substrate was pre-baked on a hotplate at 110° C. for 4 minutes to obtain a photosensitive resin film.

[0284] Thereafter, the obtained photosensitive resin film was cured at 200° C. for 2 hours using an oven while the oven was purged with nitrogen to obtain a photosensitive resin cured film. Next, the wafer with the cured film was broken into strips each having a width of 10 mm and a length of 60 mm, and the cured film was peeled off from the substrate by immersing it in 20 mass % hydrochloric acid. The breaking elongation and the breaking strength of the obtained cured films were measured using Autograph AGX-1KN (manufactured by Shimadzu Corporation). The measurements were performed ten times for each sample. Table 4 shows the average values. A large breaking elongation is preferable; specifically, a breaking elongation of 20% or more is more preferable. A large breaking strength is preferable; specifically, a breaking strength of 100 MPa or more is more preferable.

TABLE-US-00004 TABLE 4 Amount of Change in Minimum Storage Hole Breaking Breaking Stability Hole Dimension Sensitivity Strength Elongation (%) Shape (um) (mJ/cm2) (Mpa) (%) Example 1 Photosensitive Resin 0.3 Good 5.0 900 111 30 Composition 1 Example 2 Photosensitive Resin 0.5 Good 5.0 850 113 32 Composition 2 Example 3 Photosensitive Resin −0.1 Good 5.0 800 110 33 Composition 3 Example 4 Photosensitive Resin 0.1 Good 5.0 900 111 30 Composition 4 Example 5 Photosensitive Resin 0.2 Good 5.0 900 113 30 Composition 5 Example 6 Photosensitive Resin 0.4 Good 5.0 850 115 32 Composition 6 Example 7 Photosensitive Resin 0.2 Good 4.0 800 110 35 Composition 7 Example 8 Photosensitive Resin −0.1 Good 5.0 800 115 30 Composition 8 Example 9 Photosensitive Resin −0.3 Good 5.0 850 117 32 Composition 9 Example 10 Photosensitive Resin 0.1 Good 5.0 750 111 33 Composition 10 Example 11 Photosensitive Resin 0.3 Good 5.0 800 120 38 Composition 11 Example 12 Photosensitive Resin 0.8 Good 5.0 800 107 30 Composition 12 Example 13 Photosensitive Resin 0.9 Good 5.0 850 121 38 Composition 13 Example 14 Photosensitive Resin −0.2 Good 5.0 900 120 37 Composition 14 Example 15 Photosensitive Resin 0 Good 5.0 800 122 36 Composition 15 Example 16 Photosensitive Resin 0.5 Good 5.0 900 120 38 Composition 16 Example 17 Photosensitive Resin 0.1 Good 5.0 850 121 38 Composition 17 Example 18 Photosensitive Resin 0.2 Good 5.0 800 120 35 Composition 18 Comparative Comparative 10.2 Good 5.0 900 122 38 Example 1 Photosensitive Resin Composition 1 Comparative Comparative 9.8 Good 5.0 950 123 36 Example 2 Photosensitive Resin Composition 2 Comparative Comparative 11.0 Good 5.0 900 121 36 Example 3 Photosensitive Resin Composition 3

[0285] As shown in Table 4, it was found that the negative photosensitive resin composition of the present invention exhibits desirable pattern shapes in alkaline solvent development, and the minimum hole dimension, i.e., the opening, was 5 μm or less at a finished film thickness of 5 μm, thereby capable of achieving an aspect ratio 1.

[0286] The above results revealed that the present invention is comparable to the comparative photosensitive resin compositions in which a basic compound was added to achieve high resolution.

[0287] More specifically, by using an onium salt which can improve the resolution performance in the negative photosensitive resin composition of the present invention using a polymer containing a polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor as the base resin, it is possible to ensure resolution performance equivalent to that in the case of using a basic compound; further, by using the onium salt of the present invention, it is also possible to prevent poor storage stability that occurs when the polymer containing a polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor is used as the base resin in a combination with a basic compound.

[0288] Further, since the base resin of the negative photosensitive resin composition of the present invention is a polymer containing a polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, it exhibits desirable mechanical strength and can be suitably used for an interlayer insulating film or a surface protection film.

[0289] Furthermore, it was also revealed that the polymer containing a polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor used as the base resin of the negative photosensitive resin composition of the present invention is easily soluble in versatile and safe organic solvents.

[0290] The present invention encompasses the following embodiments. [0291] [1]: A negative photosensitive resin composition, comprising: [0292] (A) an alkali-soluble resin including at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; [0293] (B) a photoacid generator; [0294] (C) one or two or more kinds of crosslinking agent selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on average two or more methylol groups or alkoxymethylol groups within one molecule, a compound in which a hydrogen atom of a hydroxyl group of polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of polyhydric phenol is substituted with a substituent represented by the following formula (C-1), a compound represented by the following formula (C-15) having a substituent (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2);

##STR00114## [0295] wherein the broken line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; s represents 1 or 2; u is a number satisfying 1≤u≤3, [0296] (D) an onium salt represented by the following general formula (1); and

##STR00115## [0297] wherein A represents iodine, sulfur, phosphorus, or nitrogen; each Q is identical to or different from one another and represents a monovalent hydrocarbon group having 1 to 100 carbon atoms, which may be linked, substituted, or intervened by a heteroatom; E.sup.− represents an anion of an organic or inorganic acid salt; and m represents 2 when A is iodine, m represents 3 when A is sulfur, and m represents 4 when A is phosphorus or nitrogen, [0298] (E) a solvent. [0299] [2]: The negative photosensitive resin composition of the [1], wherein the component (D) is a quaternary ammonium salt represented by the following general formula (1-1), in which A in the general formula (1) is nitrogen,

##STR00116## [0300] wherein each of Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 is identical to or different from one another and represents a monovalent hydrocarbon group having 1 to 100 carbon atoms, which may be linked, substituted, or intervened by a heteroatom; and E.sup.− represents an anion of an organic or inorganic acid salt as defined above. [0301] [3]: The negative photosensitive resin composition of the [1] or [2], wherein, in the component (D), E.sup.− in the general formula (1) is an anion of an organic carboxylic acid represented by the following general formula (6),

##STR00117## [0302] wherein R.sup.E represents a hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom. [0303] [4]: The negative photosensitive resin composition of the [1], [2], or [3], wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product of a diamine comprising one or more of a diamine represented by the following general formula (2) and a diamine represented by the following general formula (3), and one or more of a tetracarboxylic acid dianhydride represented by the following general formula (4) and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5),

##STR00118## [0304] wherein L.sub.1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom, wherein L.sub.2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom, T represents any of a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —OCO.sub.2R.sup.T, —OSO.sub.2R.sup.T, and —OSO.sub.3R.sup.T, provided that R.sup.T represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom. [0305] [5]: The negative photosensitive resin composition of the [1], [2], [3], or [4], wherein, in the component (B), an acid generated by a photoacid generator is an organic sulfonic acid represented by the following general formula (7),

##STR00119## [0306] wherein R.sup.U represents a hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a heteroatom or intervened by a heteroatom. [0307] [6]: The negative photosensitive resin composition of the [1], [2], [3], [4], or [5], wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product of one or more of a tetracarboxylic acid dianhydride represented by the following general formula (8) and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (9),

##STR00120## [0308] wherein Z represents an alicyclic structure, an alicyclic structure connected to an aromatic ring, a heteroatom-containing or heteroatom-intervened alicyclic structure, or a heteroatom-containing or heteroatom-intervened alicyclic structure connected to an aromatic ring, each of which has 3 to 20 carbon atoms, T represents any of a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —OCO.sub.2R.sup.T, —OSO.sub.2R.sup.T, and —OSO.sub.3R.sup.T; j represents 0 or 1; when j is 0, the phthalic anhydride structure and the cyclic structure Z in the general formula (8) and the benzoic acid structure and the cyclic structure Z in the general formula (9) are directly bonded; and when j is 1, X.sub.1 and X.sub.2 represent a divalent linkage group. [0309] [7]: The negative photosensitive resin composition of the [6], wherein the alicyclic structure Z in the general formulae (8) and (9) is a structure represented by the following general formula (10) or (11),

##STR00121## [0310] wherein the broken line represents a bond; and k represents 0 or an integer of 1 or more, [0311] when k=0, Y2 represents a divalent group selected from any of the following general formulae (13), (14), (15), and (16), [0312] when k=1, Y.sub.1 represents a divalent group selected from any of the following general formulae (17), (18), and (19), and Y.sub.2 represents a divalent group selected from any of the following general formulae (13), (14), (15), and (16), [0313] when k is 2 or more, Y.sub.1 represents the following general formula (17), and Y2 represents a divalent group selected from any of the following general formulae (13), (14), (15), and (16), [0314] R.sup.1, R.sup.2, R.sup.3, and R.sup.4, and R.sup.5 and R.sup.6 in the following formula (16) represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are bonded together to form an alicyclic or aromatic ring,

##STR00122## [0315] wherein the broken line represents a bond, and R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, and R.sup.15 represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms, [0316] m and p represent 0 or an integer of 1 to 9; and n represents 0 or 1, [0317] Y.sub.3 represents a divalent group selected from any of the following general formulae (12), (13), (14), (15), (16), (17), (18) and (19),

##STR00123## [0318] wherein the broken line represents a bond; and R.sup.5 and R.sup.6 are as defined above, R.sup.7 represents a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. [0319] [8]: The negative photosensitive resin composition of the [6] or [7], wherein divalent linkage groups X.sub.1 and X.sub.2 in the general formulae (8) and (9) have a structure represented by any of the following general formulae (20), (21), (22), (23), (24), and (25),

##STR00124## [0320] wherein the broken line represents a bond. [0321] [9]: The negative photosensitive resin composition of the [4], [5], [6], [7], or [8], wherein the diamine represented by the general formula (2) is a diamine represented by the following general formula (26).

##STR00125## [0322] [10]: The negative photosensitive resin composition of the [1], [2], [3], [4], [5], [6], [7], [8], or [9], wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product further comprising a tetracarboxylic acid diester compound represented by the following general formula (27),

##STR00126## [0323] wherein W1 is a tetravalent organic group; and R.sup.16 is represented by the following general formula (28),

##STR00127## [0324] wherein the broken line represents a bond; V.sub.1 represents a (r+1)-valent organic group; Rf represents a linear, branched or cyclic alkyl group or an aromatic group having 1 to 20 carbon atoms in which a part or all of the hydrogen atoms are substituted with a fluorine atom; r represents 1, 2 or 3; and q represents 0 or 1. [0325] [11]: The negative photosensitive resin composition of the [10], wherein R.sup.16 in the general formula (27) is an organic group selected from any of groups represented by the following general formulae (29), (30), (31), and (32),

##STR00128## [0326] wherein the broken line represents a bond; and Rf is as defined above; each of Ra and Rb is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; each of V2 and V.sub.3 is a linear or branched alkylene group having 1 to 6 carbon atoms; n1 is an integer of 0 to 6; n2 is an integer of 1 to 6; n3 is an integer of 0 to 6; n4 is an integer of 1 to 6; n5 is an integer of 0 to 6; and n6 is 0 or 1. [0327] [12]: The negative photosensitive resin composition of the [10], wherein R.sup.16 in the general formula (27) is a group represented by the following general formula (28-1),

.Math.—CH.sub.2—CH.sub.2—Rf  (28-1) [0328] wherein the broken line represents a bond; and Rf is as defined above. [0329] [13]: The negative photosensitive resin composition of the [6], [7], [8], [9], [10], [11], or [12], wherein the component (A) is an alkali-soluble resin, comprising at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, each of which is a reaction product of one or more of a tetracarboxylic acid dianhydride in which the alicyclic structure Z of the general formula (8) is represented by the following general formula (33) or (34) and/or a dicarboxylic acid or dicarboxylic acid halide in which the alicyclic structure Z of the general formula (9) is selected from any of structures represented by the following general formulae (35), (36), (37), (38), (39), and (40),

##STR00129## [0330] wherein the broken line represents a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are bonded together to form an alicyclic or aromatic ring, R.sup.7 represents a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms, wherein R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, and R.sup.15 represent identical or different substituents, each representing a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. [0331] [14]: A patterning process, comprising the steps of: [0332] (1) applying the negative photosensitive resin composition of the [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], or [13] onto a substrate to form a photosensitive material film; [0333] (2) after heating the photosensitive material film, exposing the photosensitive material film to a high-energy beam having a wavelength of 190 to 500 nm or an electron beam through a photomask; and [0334] (3) developing the exposed photosensitive material film using an aqueous alkaline solution as a developer. [0335] [15]: The patterning process of the [14], further comprising the step of: [0336] (4) post-curing the developed photosensitive material film by heating at a temperature of 100 to 300° C. [0337] [16]: An interlayer insulating film, comprising a cured product of the negative photosensitive resin composition of the [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], or [13]. [0338] [17]: A surface protection film, comprising a cured product of the negative photosensitive resin composition of the [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], or [13]. [0339] [18]: An electronic component, comprising the interlayer insulating film of the [16]. [0340] [19]: An electronic component, comprising the surface protection film of the [17].

[0341] It should be noted that the present invention is not limited to the above-described embodiments. The embodiments are just examples, and any examples that substantially have the same feature and demonstrate the same functions and effects as those in the technical concept disclosed in claims of the present invention are included in the technical scope of the present invention.