Energy-sensitive resin composition

Abstract

An energy-sensitive resin composition with which it is possible, even if the precursor polymer is heat-treated at low temperatures, to produce a film or molded article comprising an imide ring-containing polymer having excellent heat resistance, tensile elongation and chemical resistance with a low dielectric constant, or a film or molded article comprising an oxazole ring-containing polymer having excellent heat resistance, tensile elongation and chemical resistance. A method of manufacturing the film or molded article; a method of forming a pattern using the energy-sensitive resin composition; and a permanent film having excellent heat resistance, tensile elongation and chemical resistance. The energy-sensitive resin composition includes an imidazole compound, a resin precursor component, and a solvent, the resin precursor component being at least one of a monomer component including a diamine compound, a dicarbonyl compound and/or a tetracarboxylic acid dianhydride; and a precursor polymer having a repeating unit.

Claims

1. An energy-sensitive resin composition comprising an imidazole compound (A) represented by the following formula (1a), a resin precursor component (B), and a solvent (S), wherein the resin precursor component (B) is at least one selected from the group consisting of a monomer component and a precursor polymer, wherein the monomer component comprises (i) a diamine compound represented by the following formula (2) and (ii) a dicarbonyl compound represented by the following formula (3a) and/or a tetracarboxylic dianhydride represented by the following formula (3b), and the precursor polymer is a precursor polymer having a repeating unit represented by the following formula (4): ##STR00102## wherein one R represents a hydrogen atom and the other R represents a monovalent organic group; R.sup.2 represents an optionally substituted aromatic group; each R.sup.4 independently represents a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group; n is an integer from 0 to 3; and the R which represents a monovalent organic group may be bonded to R.sup.2 to form a cyclic structure; ##STR00103## wherein R.sup.BN represents an organic group having a valence of (2+q), and q is an integer from 0 to 2; ##STR00104## wherein R.sup.BCa represents a divalent organic group; A.sup.1 and A.sup.2 each independently represents a hydrogen atom or a halogen atom; ##STR00105## wherein R.sup.BCb represents a tetravalent organic group; ##STR00106## wherein R.sup.BN and q are as defined above; R.sup.BC represents an organic group having a valence of (2+m); R.sup.B3 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; and m is an integer from 0 to 2, wherein m+q>0 is satisfied.

2. The energy-sensitive resin composition according to claim 1, wherein the imidazole compound (A) comprises a compound represented by the following formula (1): ##STR00107## wherein R.sup.2, R.sup.4, and n are as defined for the formula (1a); R.sup.1 represents a hydrogen atom or an alkyl group; R.sup.3 represents an optionally substituted alkylene group, and R.sup.3 may be bonded to R.sup.2 to form a cyclic structure.

3. The energy-sensitive resin composition according to claim 1, wherein the resin precursor component (B) is at least one selected from the group consisting of: (B1) an imide ring forming polymer (excluding a polymer of the following (B3)) obtained by reacting the tetracarboxylic dianhydride and the diamine compound with each other; (B2) an oxazole ring forming polymer (excluding a polymer of the following (B3)) obtained by reacting a diamine diol represented by the following formula (2a) and the dicarbonyl compound represented by the formula (3a) with each other; and (B3) an imide ringoxazole ring forming polymer comprising a repeating unit represented by the following formula (4c) as a main component: ##STR00108## wherein R.sup.BNa represents a tetravalent organic group having adjacent two carbon atoms to which each pair of an amino group and a hydroxyl group of two pairs of amino groups and hydroxyl groups included in the diamine diol represented by the formula (2a) are bonded; ##STR00109## wherein R.sup.BNa, R.sup.BCa, R.sup.BCb and R.sup.B3 are each independently as defined above; R.sup.BNb represents a divalent organic group; R.sup.BNd represents an organic group having a valence of (2+q2); R.sup.BCd represents an organic group having a valence of (2+m2); m2 and q2 are each independently 1 or 2; a, b, and c are each independently an integer of 0 or more, and a bonding order among repeating units of a pieces of repeating units, b pieces of repeating units, and c pieces of repeating units is not limited to the order described in the formula (4c), wherein a>0 and b>0 are satisfied, or c>0 is satisfied.

4. The energy-sensitive resin composition according to claim 1, wherein the imidazole compound (A) comprises a compound represented by the following formula (1-1a): ##STR00110## wherein in the formula (1-1a), R.sup.4, and n are as defined for the formula (1a) and R is the monovalent organic group; R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, wherein at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is a group other than a hydrogen atom; at least two of R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 may be bonded to each other to form a cyclic structure; and R may be bonded to R.sup.7 to form a cyclic structure.

5. The energy-sensitive resin composition according to claim 1, wherein the imidazole compound (A) is a compound represented by the following formula (1-1): ##STR00111## wherein in the formula (1-1), R.sup.1 represents a hydrogen atom or an alkyl group; R.sup.3 represents an optionally substituted alkylene group; each R.sup.4 independently represents a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group; n is an integer from 0 to 3; R.sup.7, R.sup.8, and R.sup.9 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group; at least two of R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 may be bonded to each other to form a cyclic structure; and R.sup.3 may be bonded to R.sup.7 to form a cyclic structure.

6. The energy-sensitive resin composition according to claim 1, wherein the solvent (S) is a solvent comprising a compound (Si) represented by the following formula (5): ##STR00112## wherein, in the formula (5), R.sup.S1 and R.sup.S2 each independently represents an alkyl group having 1 to 3 carbon atoms; and R.sup.S3 is a group represented by the following formula (5-1) or the following formula (5-2); ##STR00113## wherein in the formula (5-1), R.sup.S4 is a hydrogen atom or a hydroxyl group; R.sup.S5 and R.sup.S6 each independently represents an alkyl group having 1 to 3 carbon atoms, and in the formula (5-2), R.sup.S7 and R.sup.S8 each independently represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms.

7. The energy-sensitive resin composition according to claim 1, further comprising a base generator component that generates a base by exposure.

8. A method of manufacturing a film or a molded article comprising an imide ring- and/or oxazole ring-containing polymer, the method comprising: forming a coating film or a molded article comprising the energy-sensitive resin composition according to claim 1; and ring-closing the resin precursor component (B) in the coating film or the molded article by exposing or heating the coating film or the molded article; wherein the resin precursor component (B) is the precursor polymer having a repeating unit represented by formula (4).

9. A method of forming a pattern, the method comprising: a formation step of forming a coating film or a molded article comprising the energy-sensitive resin composition according to claim 1; selectively exposing the coating film or the molded article; developing the coating film or the molded article after the exposing, and heating the coating film or the molded article after the developing.

10. A permanent film comprising: an imidazole compound (A) represented by the following formula (1a); an imide ring- and/or oxazole ring-containing polymer obtained by ring-closing a precursor polymer comprising a repeating unit represented by the following formula (4) as a main component: ##STR00114## wherein one R represents a hydrogen atom and the other R represents a monovalent organic group; R.sup.2 represents an optionally substituted aromatic group; each R.sup.4 independently represents a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group; n is an integer from 0 to 3; and the R which represents a monovalent organic group may be bonded to R.sup.2 to form a cyclic structure; ##STR00115## wherein R.sup.BN represents an organic group having a valence of (2+q); q is an integer from 0 to 2; R.sup.BC represents an organic group having a valence of (2+m); R.sup.B3 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; and m is an integer from 0 to 2, wherein m+q>0 is satisfied.

11. The permanent film according to claim 10, wherein the imidazole compound (A) comprises a compound represented by the following formula (1): ##STR00116## wherein R.sup.2, R.sup.4 and n are as defined for the formula (1a), R.sup.1 represents a hydrogen atom or an alkyl group, R.sup.3 represents an optionally substituted alkylene group; and R.sup.3 may be bonded to R.sup.2 to form a cyclic structure.

12. The energy-sensitive resin composition according to claim 1, wherein, in the formula (1a), the monovalent organic group as the other R is an optionally substituted alkyl group or an optionally substituted aromatic group.

13. The energy-sensitive resin composition according to claim 4, wherein the monovalent organic group is an optionally substituted alkyl group or an optionally substituted aromatic group.

14. The energy-sensitive resin composition according to claim 1, wherein, in the formula (1a), the monovalent organic group as the other R is an optionally substituted alkyl group.

15. The energy-sensitive resin composition according to claim 4, wherein the monovalent organic group is an optionally substituted alkyl group.

16. The energy-sensitive resin composition according to claim 1, wherein n is zero.

17. The permanent film according to claim 10, wherein n is zero.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described more specifically by way of Examples, but the present invention is not limited to these Examples.

Examples 1 to 27 and Comparative Examples 1 to 14

(2) In the Examples and the Comparative Examples, the diamine compounds (2b), the carboxylic anhydrides, the diamine diols, the dicarbonyl compounds, the solvents, the imidazole compounds (A), and the comparative compounds shown below were used.

(3) Diamine Compounds (2b)

(4) DA1: ODA: 4,4-diaminodiphenyl ether

(5) DA2: PPD: p-phenylenediamine

(6) DA3: MPD: m-phenylenediamine

(7) DA4: 2,4-TDA: 2,4-diaminotoluene

(8) DA5: BAFL: 9,9-bis(4-aminophenyl)fluorene

(9) DA6: BTFL: 9,9-bis(4-amino-3-methylphenyl)fluorene

(10) DA7: BisA-P: 4,4-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline

(11) DA8: MDA: 4,4-diaminodiphenylmethane

(12) ##STR00095##
DA9: 2,2-bis[4-(4-aminophenoxy)phenyl]propane
DA10: 1,4-bis(4-amino-a,-dimethyl benzyl)benzene
DA11: 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indene-5-amine
DA12: 2,2-bis[4-(4-amino phenoxy)phenyl]hexafluoropropane

(13) Carboxylic Anhydrides

(14) TC1: PMDA: pyromellitic acid dianhydride

(15) TC2: s-BPDA: 3,3,4,4-biphenyltetracarboxylic dianhydride

(16) TC3: -BPDA: 2,3,3,4-biphenyltetracarboxylic dianhydride

(17) TC4: THPA: cis-4-cyclohexane-1,2-dicarboxylic anhydride

(18) TC5: 1,2,4,5-cyclohexane tetracarboxylic dianhydride

(19) PD1: following compound

(20) ##STR00096##

(21) Diamine Diols

(22) DD1: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

(23) DD2: 3,3-dihydroxybenzidine

(24) ##STR00097##

(25) Dicarbonyl Compounds

(26) DK1: isophthalaldehyde

(27) DK2: terephthalic acid dichloride

(28) ##STR00098##

(29) Solvent

(30) NMP: N-methyl-2-pyrrolidone

(31) TMU: N,N,N,N-tetramethylurea

(32) DMAc: N,N-dimethylacetamide

(33) DMIB: N,N,2-tirmethyl propionamide

(34) Imidazole compounds (A)

(35) Compound 1: following chemical formula

(36) Compound 2: following chemical formula

(37) Comparative Compounds

(38) Compound 3: following chemical formula

(39) Compound 4: 2-ethyl-1-methylimidazole

(40) Compound 5: 1-ethyl-2-methylimidazole

(41) ##STR00099##

Synthesis Examples of Imidazole Compound (A)

1. Synthesis Example of Compound 1

(42) Firstly, 30 g of cinnamic acid derivative having a structure of the following formula was dissolved in 200 g of methanol, and 7 g of potassium hydroxide was added in the methanol. Then, the methanol solution was stirred at 40 C. The methanol was distilled, and residue was suspended in 200 g of water. To the resulting suspension, 200 g of tetrahydrofuran was mixed, and the mixture was stirred, followed by separation of a water phase. Under cooling in ice, 4 g of hydrochloric acid was added, and the mixture was stirred. After stirring, 100 g of ethyl acetate was mixed thereto, and the mixture was stirred. The mixed solution was allowed to stand still, followed by separation of an oil phase. A target product was crystallized from the oil phase, and precipitate was recovered to obtain an imidazole compound having the above-mentioned structure (Compound 1).

(43) ##STR00100##

(44) .sup.1H-NMR measurement results of the compound 1 follow.

(45) .sup.1H-NMR (DMSO): 11.724 (s, 1H), 7.838 (s, 1H), 7.340 (d, 2H, J=4.3 Hz), 7.321 (d, 1H, J=7.2 Hz), 6.893 (d, 2H, J=4.3 Hz), 6.876 (d, 1H, J=6.1 Hz), 5.695 (dd, 1H, J=4.3 Hz, 3.2 Hz), 3.720 (s, 3H), 3.250 (m, 2H)

2. Synthesis Example of Compound 2

(46) Specifically, the same Synthesis Example as for the compound 1 was carried out except that the raw material compound was changed to cinnamic acid derivative having a structure of the following formula to obtain the compound 2.

(47) ##STR00101##

Preparation Example of Imide Ring and/or Oxazole Ring Forming Polymer

1. Imide Ring Forming Polymer (B1)

(48) To a 5 L separable flask equipped with a stirrer, impellers, a reflux condenser, and a nitrogen gas inlet tube, carboxylic anhydride and a diamine compound (2b), of types and amounts mentioned in Table 1, respectively, and 2951 g of solvent (however, 73 g of solvent in Examples 30 to 35) were added. Nitrogen gas was introduced into the flask through the nitrogen gas inlet tube to provide the inside of the flask with an atmosphere of nitrogen. Then, the carboxylic anhydride and the diamine compound (2b) were reacted with each other at 50 C. for 20 hours while stirring the reaction mixture in the flask to obtain a solution of imide ring forming polymer (B1) (polyamic acid).

2. Oxazole Ring Forming Polymer (B2)

(49) Preparation was carried out according to the following method. Regarding the preparation method of an oxazole ring forming polymer (B2), reaction between diamine diol and a dialdehyde compound, and the reaction between diamine diol and dicarboxylic acid dihalide are described below.

(50) (Reaction Between Diamine Diol and Dialdehyde Compound)

(51) To an Erlenmeyer flask provided with a rotor, diamine diol of types and amounts mentioned in Table 1, 2951 g of solvent of types and amounts mentioned in Table 1, were added. The content of the flask was stirred for 5 minutes using a magnetic stirrer. Thereafter, a dialdehyde compound (DK1) of an amount mentioned in Table 1 was added into the flask, the content of the flask was refluxed under nitrogen atmosphere for 3 hours, and reaction was performed. Next, a reaction solution was dehydrated by distillation under reduced pressure to obtain a solution of an oxazole ring forming polymer (B2) (polybenzoxazole resin). As one example, in Example 17, a number average molecular weight of the oxazole ring forming polymer (B2) was about 1500.

(52) (Reaction Between Diamine Diol and Dicarboxylic Acid Dihalide)

(53) To an Erlenmeyer flask provided with a rotor, diamine diol of types and amounts mentioned in Table 1, triethylamine of an amount being two times larger than the amount of diamine diol, a solvent of types mentioned in Table 1 (the amount was half of 2951 g) were added. Next, dicarboxylic acid dihalide (DK2) in an amount mentioned in Table 1 was dissolved in a solvent of types mentioned in Table 1 (the amount was half of 2951 g). The resulting solution was dropped into the Erlenmeyer flask under a nitrogen atmosphere at 0 C. for 30 minutes. After dripping, at room temperature, the reaction solution inside the Erlenmeyer flask was stirred for further 5 hours to obtain a solution of the oxazole ring forming polymer (B2).

3. Imide RingOxazole Ring Forming Polymer

(54) A solution of an imide ring-oxazole ring forming polymer was obtained in the same manner as in the preparation method of the above-mentioned 1. Imide ring forming polymer (B1) except that PD1 was used as the carboxylic anhydride. [Preparation example of energy-sensitive resin composition]

Examples 1 to 25

(55) To the solutions of the imide ring and/or oxazole ring forming polymer obtained in the preparation examples, any of the compounds 1 to 5 in amounts mentioned in Table 1 were added, and the mixture was stirred to prepare energy-sensitive resin compositions.

Example 26

(56) A solution of imide ring forming polymer (B1) (polyamic acid in which component (A) remains) was obtained in the same manner as in 1. imide ring forming polymer (B1) except that carboxylic anhydride of type and amount in Example 2, and diamine compound (2b), 2951 g of solvent were added, and further, 49.22 g of the compound 1 was added. Note here that in the solution of Example 26, since the compound 1 as the component (A) had been added in advance, unlike the above Examples (Examples 1 to 25), evaluation was carried out without further adding compound 1 after preparation of the imide ring forming polymer (B1).

Example 27

(57) After imide ring forming polymer (B1) solution similar to that of Example 26, a base generator component (D1) was added at 5% by mass relative to the (B1) component.

(58) [Preparation and Evaluation of Film]

(59) Films were formed using energy-sensitive resin compositions obtained in each Example and Comparative Example according to the below-mentioned method, heat resistance, tensile elongation, chemical resistance (NMP), and dielectric constant of films were evaluated. Results are shown in Table 1. Note here that although not shown in Table 1, the energy-sensitive resin compositions of Example 27 and Example 29 are the same and include the (D1) component. The energy-sensitive resin composition of Example 28 is the same as that of Example 2.

(60) (Heat Resistance)

(61) The resulting energy-sensitive resin composition was applied on a wafer substrate using a spin coater (manufactured by Mikasa, 1H-360S). The applied film on the wafer substrate was heated at heating temperatures and conditions mentioned in Table 1 to form a film having a film thickness of about 0.9 m. From the resulting film, 5 g of film sample was scraped off for the evaluation of heat resistance. The film sample for the evaluation of heat resistance was measured on a differential thermal/thermogravimetry instrument (TG/DTA-6200, manufactured by Seiko Instruments Inc.) in an air flow, at a temperature increasing rate of 10 C./min. to obtain a TG curve. From the resulting TG curve, a 5% thermogravimetric reduction temperature of the sample was obtained. A case where the 5% thermogravimetric reduction temperature was 350 C. or higher was evaluated as good (A+; a case where it was 300 C. or higher and lower than 350 C. was evaluated as substantially good (A); a case where it was lower than 300 C. was evaluated as bad (B).

(62) (Evaluation of Tensile Elongation)

(63) The resulting energy-sensitive resin composition was applied on a wafer substrate using an applicator (manufactured by YOSHIMITSU SEIKI, TBA-7). The applied film on the wafer substrate was heated under conditions mentioned in Table 1 to form a film having a film thickness of about 10 m. From the resulting film, a dumbbell test piece having a shape according to IEC450 specification was punched out to obtain a test piece for measurement of tensile elongation. The resulting test piece was subjected to measurement of rupture elongation of a film using a universal testing machine (TENSILON, manufactured by Orientec Corporation) with a distance between chucks of 20 mm and at a drawing speed of 2 mm/min. A case where the rupture elongation was 10% or more was evaluated as A, and a case where it was less than 10% was evaluated as B.

(64) (Chemical Resistance/NMP Resistance)

(65) A film thickness of about 0.9 m was formed in the same manner as in the evaluations of the tensile elongation. On the formed film, 1 cc of NMP was dropped, the film was stood still for one minute and two minutes, and then NMP was removed. The surface state of the film after NMP had been removed was visually observed. A case where the surface of the film was not changed even after the film had been stood still for two minutes was evaluated as A, a case where depression traces were observed on the surface after two minutes, but no change was found on the surface of the film after one minute was evaluated as B+, and a case where depression traces remain on the surface even after one minute was evaluated as B.

(66) (Dielectric Constant)

(67) A case where the dielectric constant was 3.5 or less was evaluated as very good (A+); a case where the dielectric constant was not more than 3.8 and more than 3.5 was evaluated as good (A); a case where the dielectric constant was more than 3.8 and not more than 4.2 was evaluated as slightly bad (B+); and a case where the dielectric constant was more than 4.2 was evaluated as bad (B).

Patterning Characteristic of Example 27

(68) The resulting energy-sensitive resin composition of Example 27 was applied on a wafer substrate using a spin coater (manufactured by Mikasa Co., Ltd., 1H-360S) and pre-baked at 80 C. for 5 minutes to form a coating film having a film thickness of 1 m. By using a mask with line and space pattern, the coating film was exposed using a high-pressure mercury lamp in the condition of 300 mJ/cm.sup.2. The exposed coating film was dipped in a developing solution (a solution in which a 2.38% by mass aqueous solution of tetramethylammonium hydroxide and isopropanol are blended in a ratio of 9:1). As a result, a pattern (5 m of 1:1 line and space pattern) in which the exposed portions, which did not dissolve in the developing solution, remained was obtained. Next, the resulting pattern was heated at 140 C. for two hours (post baking, described in the heating temperature section in Table 1).

(69) TABLE-US-00001 TABLE 1 Carboxylic anhydride Diamine imidazole Dicarbonyl compound compound compound diamine diol (A) Solvent Heating Heat Tensile NMP Dielectric Types (g) Types (g) Types (g) Types temperature resistance elongation resistance constrant Example 1 TC1 653.1 DA1 672.30 Compound 1 49.22 NMP 140 C. 2h A+ A A A Example 2 TC1 653.1 DA1 672.30 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 3 TC1 653.1 DA1 672.30 Compound 1 49.22 DMAc 140 C. 2h A+ A A A Example 4 TC1 653.1 DA1 672.30 Compound 1 49.22 DMIB 140 C. 2h A+ A A A Example 5 TC2 882.06 DA1 672.30 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 6 TC3 882.06 DA1 672.30 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 7 TC4 + 228.07/ DA1 672.30 Compound 1 49.22 TMU 140 C. 2h A+ A A A TC2 441.03 Example 8 TC1 653.1 DA2 363.35 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 9 TC1 653.1 DA3 363.35 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 10 TC1 653.1 DA4 410.49 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 11 TC1 653.1 DA5 1170.75 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 12 TC1 653.1 DA6 1265 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 13 TC1 653.1 DA7 1157.48 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 14 TC1 653.1 DA8 666.15 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 15 TC1 653.1 DA1 672.3 Compound 1 49.22 TMU 140 C. 2h A A A A Example 16 TC1 653.1 DA1 672.3 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 17 DK1 402.39 DD1 1230.63 Compound 1 49.22 TMU 140 C. 2h A+ A A Example 18 DK1 402.39 DD1 1230.63 Compound 1 49.22 NMP 140 C. 2h A+ A A Example 19 DK1 402.39 DD1 1230.63 Compound 1 49.22 DMAc 140 C. 2h A+ A A Example 20 DK1 402.39 DD1 1230.63 Compound 1 49.22 DMIB 140 C. 2h A+ A A Example 21 DK2 609.06 DD2 726.56 Compound 1 49.22 TMU 140 C. 2h A+ A A Example 22 PD1 714.07 DA1 224.1 Compound 1 49.22 TMU 140 C. 2h A+ A A Example 23 PD1 714.07 DA1 224.1 Compound 1 49.22 NMP 140 C. 2h A+ A A Example 24 PD1 714.07 DA1 224.1 Compound 1 49.22 DMAc 140 C. 2h A+ A A Example 25 PD1 714.07 DA1 224.1 Compound 1 49.22 DMIB 140 C. 2h A+ A A Example 26 TC1 653.1 DA1 672.3 Compound 1 49.22 TMU 140 C. 2h A+ A A A Example 27 TC1 653.1 DA1 672.3 Compound 1 49.22 TMU 140 C. 2h A A A A Example 28 TC1 653.1 DA1 672.3 Compound 1 49.22 TMU After A+ A A A+ heating at 140 C. 2h 320 C. 30m Example 29 TC1 653.1 DA1 672.3 Compound 1 49.22 TMU After A+ A A A+ heating at 140 C. 2h 320 C. 30m Example 30 TC5 11.2 DA9 20.5 Compound 1 1 NMP 140 C. 2h A+ A A A Example 31 TC5 11.2 DA9 20.5 Compound 1 1 TMU 140 C. 2h A+ A A A Example 32 TC5 11.2 DA10 + 12.1/4.0 Compound 1 1 NMP 140 C. 2h A+ A A A DA11 Example 33 TC5 11.2 DA10 + 12.1/4.0 Compound 1 1 TMU 140 C. 2h A+ A A A DA11 Example 34 TC5 11.2 DA12 25.9 Compound 1 1 NMP 140 C. 2h A+ A A A Example 35 TC5 11.2 DA12 25.9 Compound 1 1 TMU 140 C. 2h A+ A A A Comparative TC1 653.1 DA1 672.3 Not Added TMU 140 C. 2h B B B B Example 1 Comparative TC1 653.1 DA1 672.3 Compound 3 TMU 140 C. 2h B B B B Example 2 Comparative TC1 653.1 DA1 672.3 Compound 4 22.03 TMU 140 C. 2h B B B B Example 3 Comparative TC1 653.1 DA1 672.3 Compound 5 22.03 TMU 140 C. 2h B B B B Example 4 Comparative TC1 653.1 DA1 672.3 Not Added TMU 140 C. 2h A+ A A B Example 5 Comparative DK1 402.39 DD1 1230.63 Not Added TMU 140 C. 2h B B B Example 6 Comparative DK1 402.39 DD1 1230.63 Not Added NMP 140 C. 2h B B B Example 7 Comparative DK1 402.39 DD1 1230.63 Not Added DMAc 140 C. 2h B B B Example 8 Comparative DK1 402.39 DD1 1230.63 Not Added DMIB 140 C. 2h B B B Example 9 Comparative DK2 609.06 DD2 726.56 Not Added TMU 140 C. 2h B B B Example 10 Comparative PD1 714.07 DA1 224.1 Not Added TMU 140 C. 2h B B B Example 11 Comparative PD1 714.07 DA1 224.1 Not Added NMP 140 C. 2h B B B Example 12 Comparative PD1 714.07 DA1 224.1 Not Added DMAc 140 C. 2h B B B Example 13 Comparative PD1 714.07 DA1 224.1 Not Added DMIB 140 C. 2h B B B Example 14

(70) According to Examples 1 to 25 and Examples 30 to 35, it was shown that addition of the of the imidazole compound (A) enabled a film comprising an imide ring- and/or oxazole ring-containing polymer having excellent heat resistance, tensile elongation, and chemical resistance (NMP) to be obtained from an energy-sensitive resin composition comprising imide ring and/or oxazole ring forming polymer even if heat treatment was carried out at such a low temperature as 140 C. Further, from Examples 1 to 16, it was found that dielectric constant of the film comprising the imide ring-containing polymer (B1) was low. From Example 26, it was shown that also in a case where the imidazole compound (A) had been added in advance, a film comprising an imide ring- and/or oxazole ring-containing polymer having excellent heat resistance, tensile elongation, chemical resistance (NMP) was obtained. Furthermore, from Example 27, it was shown that patterns comprising an imide ring- and/or oxazole ring-containing polymer having excellent heat resistance, tensile elongation, and chemical resistance (NMP) were obtained. It is considered that remaining of component (D1) have an influence on the results of the heat resistance. In Examples 28 and 29 in which further high-temperature baking was carried out, improvement of dielectric constant was verified. From the comparison between Example 28 in which high-temperature baking was carried out after low-temperature baking and Example 2 in which low-temperature baking was carried out and high-temperature baking was not carried out, it was found that dielectric constant was more improved in the former case. The improvement of the dielectric constant seems to be because high-temperature baking promotes ring closure reaction of the resin precursor component (B). From the comparison between Examples 28 and 29 in which high-temperature baking was carried out after low-temperature baking in the presence of the imidazole compound (A) and Comparative Example 5 in which high-temperature baking was carried out in the absence of an imidazole compound (A) without carrying out low-temperature baking, it was shown that the dielectric constant was more improved in the former case. The improvement of the dielectric constant seems to be because low-temperature baking in the presence of an imidazole compound (A) promotes the increase of the molecular weight of the resin precursor component (B).

(71) According to Comparative Examples 1 to 4 and 6 to 14, it was found that when the imidazole compound (A) was not added, a film with inferior heat resistance, tensile elongation, and chemical resistance (NMP) was obtained. Furthermore, from Comparative Examples 1 to 5, it was found that the dielectric constant of the film comprising an imide ring-containing polymer was high. From the comparison between Comparative Example 5 and Example 2, it was found that in order to obtain a film comprising the imide ring-containing polymer (B1) having the same level of the heat resistance, tensile elongation, and chemical resistance (NMP) as those in Example 2 for the same heating time, heating at such a high temperature as 320 C. was required. Furthermore, from Comparative Example 5, it was found that even in a film obtained in such a heating condition, when the imidazole compound (A) was not added, the dielectric constant was high.