Photosensitive resin composition and cured film comprising the same

Abstract

A photosensitive resin composition including a poly(imide-benzoxazine) block copolymer, and a cured film. The poly(imide-benzoxazine) block copolymer included in the photosensitive resin composition enables the formation of a cured film having excellent mechanical and insulation even at a low temperature of less than 200° C.

Claims

1. A photosensitive resin composition comprising: a poly(imide-benzoxazine) block copolymer comprising one or more repeat units selected from the group consisting of a repeat unit represented by the following Chemical Formula 1 and a repeat unit represented by the following Chemical Formula 2; and a photo-curable multifunctional acrylic compound: ##STR00018## in Chemical Formulas 1 and 2, Y.sup.1 is a C6-20 tetravalent aliphatic cyclic group; a C6-20 tetravalent aromatic cyclic group; or a C4-20 tetravalent heteroaromatic cyclic group comprising one or more heteroatoms selected from the group consisting of N, O, and S; the tetravalent aliphatic cyclic group, tetravalent aromatic cyclic group, or tetravalent heteroaromatic cyclic group is unsubstituted or substituted with at least one of —OH, —F, —Cl, —Br, —I, —CF.sub.3, —CCl.sub.3, —CBr.sub.3, —CI.sub.3, —NO.sub.2, —CN, —COCH.sub.3, CH.sub.3COO—, and —CO.sub.2C.sub.2H.sub.5; the aliphatic cyclic group, aromatic cyclic group, or heteroaromatic cyclic group optionally has, two or more rings conjugated to form a condensed ring, or two or more rings linked by —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O).sub.2—, —Si(CH.sub.3).sub.2—, —(CH.sub.2).sub.p, —(CF.sub.2).sub.q—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, or —C(═O)NH—, wherein 1≤p≤10 and 1≤q≤10, Y.sup.2 includes a C6-20 divalent aliphatic cyclic group or a C6-20 divalent aromatic cyclic group; the divalent aliphatic or aromatic cyclic group is unsubstituted or substituted with at least one of —OH, —F, —Cl, —Br, —I, —CF.sub.3, —CCl.sub.3, —CBr.sub.3, —CI.sub.3, —NO.sub.2, —CN, —COCH.sub.3, CH.sub.3COO—, and —CO.sub.2C.sub.2H.sub.5; the divalent aliphatic or aromatic cyclic group optionally has two or more rings conjugated to form a condensed ring, or two or more rings linked by —O—, —S—,—C(═O)—, —CH(OH)—, —S(═O).sub.2—, —Si(CH.sub.3).sub.2—, —(CH.sub.2).sub.p—, —(CF.sub.2).sub.q—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, or —C(═O)NH—, wherein 1≤p≤10 and 1≤q≤10, R.sup.1's are each independently a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl, A.sup.1 and A.sup.2 are each independently a direct bond; a C6-20 divalent aliphatic cyclic group; a C6-20 divalent aromatic cyclic group; or a C4-20 tetravalent heteroaromatic cyclic group comprising one or more heteroatoms selected from the group consisting of N, O, and S, X.sup.1 and X.sup.2 are each independently a group represented by the following Chemical Formula 3a or 3b: ##STR00019## the mark ##STR00020## indicates a part where the group represented by Chemical Formula 3a or 3b is linked to an adjacent atom in the Chemical Formula 1, and m and n are each independently a number of 5 to 10,000.

2. The photosensitive resin composition according to claim 1, wherein Y.sup.1 is a tetravalent group selected from the group consisting of the following structural formulas: ##STR00021## and in the structural formulas, each cyclic group is unsubstituted or substituted with —OH, —F, —Cl, —Br, —I, —CF.sub.3, —CCl.sub.3, —CBr.sub.3, —CI.sub.3, —NO.sub.2, —CN, —COCH.sub.3, CH.sub.3COO—, and —CO.sub.2C.sub.2H.sub.5, each L.sup.1 is independently —O—, —S—,—C(═O)—, —CH(OH)—, —S(═O).sub.2—, —Si(CH.sub.3).sub.2—, —(CH.sub.2).sub.p—, —(CF.sub.2).sub.q—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, or —C(═O)NH—, wherein 1≤p≤10 and 1≤q≤10, and ##STR00022## is a part where the tetravalent group is linked to an adjacent atom in the Chemical Formula 1.

3. The photosensitive resin composition according to claim 1, wherein Y.sup.2 is a divalent group selected from the group consisting of the following structural formulas: ##STR00023## and in the structural formulas, each cyclic group is unsubstituted or substituted with —OH, —F, —Cl, —Br, —I, —CF.sub.3, —CCl.sub.3, —CBr.sub.3, —CI.sub.3, —NO.sub.2, —CN, —COCH.sub.3, CH.sub.3COO—, and —CO.sub.2C.sub.2H.sub.5, each L.sup.2 is independently, a —O—, —S—,—C(═O)—, —CH(OH)—, —S(═O).sub.2—, —Si(CH.sub.3).sub.2—, —(CH.sub.2).sub.p—, —(CF.sub.2).sub.q—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, or —C(═O)NH—, wherein 1≤p≤10 and 1≤q≤10, and ##STR00024## is a part where the divalent group is linked to an adjacent atom in the Chemical Formula 1.

4. The photosensitive resin composition according to claim 1, wherein A.sup.1 and A.sup.2 are each independently a direct bond or a divalent group selected from the group consisting of the following structural formulas: ##STR00025## and in the structural formulas, each L.sup.3 is independently —O—, —S—,—C(═O)—, —CH(OH)—, —S(═O).sub.2—, —Si(CH.sub.3).sub.2—, —(CH.sub.2).sub.p—, —(CF.sub.2).sub.q—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, or —C(═O)NH—, wherein 1≤p≤10 and 1≤q≤10, and ##STR00026## is a part where the divalent group is linked to an adjacent atom in the Chemical Formula 1.

5. The photosensitive resin composition according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 4: ##STR00027## and in Chemical Formula 4, A.sup.1, A.sup.2, X.sup.1, X.sup.2, m, and n are each independently as defined in claim 1, and L.sup.1 and L.sup.2 are each independently —O—, —S—,—C(═O)—, —CH(OH)—, —S(═O).sub.2—, —Si(CH.sub.3).sub.2—, —(CH.sub.2).sub.p—, —(CF.sub.2).sub.q—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, or —C(═O)NH—, wherein 1≤p≤10 and 1≤q≤10.

6. The photosensitive resin composition according to claim 1, wherein in the poly(imide-benzoxazine) block copolymer, the weight ratio of the repeat unit having a polymerization degree m and the repeat unit having a polymerization degree n is 1:0.01 to 1:100.

7. The photosensitive resin composition according to claim 1, wherein the poly(imide-benzoxazine) block copolymer has a weight average molecular weight of 5000 to 100,000 g/mol.

8. The photosensitive resin composition according to claim 1, wherein the photocurable multifunctional acrylic compound includes one or more acrylic compounds selected from the group consisting of an acrylate-based compound, a polyester acrylate based compound, a polyurethane acrylate based compound, an epoxy acrylate based compound, and a caprolactone modified acrylate based compound.

9. The photosensitive resin composition according to claim 1, wherein the composition comprises 1 to 50 parts by weight of the photocurable multifunctional acrylic compounds, based on 100 parts by weight of the poly(imide-benzoxazine) block copolymer.

10. A method of preparing a film comprising curing the photosensitive resin composition of claim 1.

11. The method of claim 10, wherein the curing is performed at a temperature of from 160 to 220° C.

12. A film formed by the method of claim 10.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 shows an NMR spectrum of a material C synthesized in Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) Hereinafter, preferable examples are presented for better understanding of the present invention. However, these examples are presented only as illustrations of the invention, and the present invention is not limited thereby.

Example 1

(3) In a 500 mL round flask equipped with a Dean-Stark apparatus and a condenser, 8 g of 4-aminophenol was dissolved in 100 ml of tetrahydrofuran (THF), and 20 ml of trifluoroacetic anhydride was added dropwise thereto at 0° C. After the mixture was reacted for 2 hours, the solvent was removed, followed by extraction with ethyl acetate and an aqueous solution of NaHCO.sub.3. The obtained organic layer was precipitated in hexane to obtain material A.

(4) 4 g of the material A, 1.9 g of 4,4′-diaminodiphenylmethane, and 1.4 g of paraformaldehyde were dissolved in 15 ml of a solution of chlorobenzene:xylene (1:1), and the mixture was reacted at 120° C. for 3 hours. After the reaction, the mixture was precipitated in hexane and filtered. The obtained solid was dissolved in ethyl acetate and extracted with the aqueous solution of Na.sub.2CO.sub.3. The solvent of the obtained organic layer was removed to obtain material B.

(5) 4 g of the material B was dissolved in 50 ml of a solution of ethyl acetate:methanol (100:1), and NaBH.sub.4 was added thereto. After the mixture was reacted for 7 hours, brine was added for extraction. The obtained organic layer was put in hexane for precipitation. The obtained solid was dried to obtain material C. The .sup.1H NMR spectrum (DMSO-d.sub.6, standard material TMS) of the material C is shown in FIG. 1.

(6) 1 g of the material C and 5 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminophenol) were dissolved in N-methyl-2-pyrrolidone(NMP). Thereto, 3.4 g of dibutyl 5,5′-oxybis(2-(chlorocarbonyl)benzoate) was slowly added dropwise at 0° C. After the mixture was reacted for 2 hours, 1.2 g of maleic anhydride was added and the mixture was additionally reacted for 2 hours. After the reaction, excess distilled water was dripped therein to produce a precipitate. The precipitate was filtered and washed with water three times, and then dried under a 100° C. vacuum condition for 24 hours to obtain 5 g of a poly(imide-benzoxazine) block copolymer (PIBZ-1).

(7) The molecular weight of the copolymer (PIBZ-1) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 7000 g/mol and a weight average molecular weight (Mw) of 12,000 g/mol.

Example 2

(8) 5 g of a poly(imide-benzoxazine) block copolymer (PIBZ-2) was obtained by the same method as Example 1, except that the content of the material C was changed to 3 g, and the content of dibutyl 5,5′-oxybis(2-(chlorocarbonyl)benzoate) was changed to 4.6 g.

(9) The molecular weight of the copolymer (PIBZ-2) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 7500 g/mol and a weight average molecular weight (Mw) of 12,000 g/mol.

Example 3

(10) 5 g of a poly(imide-benzoxazine) block copolymer (PIBZ-3) was obtained by the same method as Example 1, except that 4.8 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminobenzene) was used instead of 5 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminophenol).

(11) The molecular weight of the copolymer (PIBZ-3) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 7000 g/mol and a weight average molecular weight (Mw) of 12,500 g/mol.

Example 4

(12) 5 g of a poly(imide-benzoxazine) block copolymer (PIBZ-4) was obtained by the same method as Example 1, except that 4.0 g of bis(2-(acryloyloxy)ethyl) 5,5′-oxybis(2-(chlorocarbonyl)benzoate) was used instead of 3.4 g of dibutyl 5,5′-oxybis(2-(chlorocarbonyl)benzoate).

(13) The molecular weight of the copolymer (PIBZ-4) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 8000 g/mol and a weight average molecular weight (Mw) of 14,000 g/mol.

Example 5

(14) 10.0 g of the block copolymer (PIBZ-1) according to Example 1 was dissolved in 35 g of N-methyl-2-pyrrolidone (NMP), and 2.1 g of 2-isocyanatoethyl methacrylate was added thereto. The mixture was reacted at 60° C. for 8 hours, and then precipitated with 500 ml of methanol. The precipitate was filtered and washed with water three times, and then dried under a 100° C. vacuum condition for 24 hours to obtain 8 g of a poly(imide-benzoxazine) block copolymer (PIBZ-5).

(15) The molecular weight of the copolymer (PIBZ-5) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 8000 g/mol and a weight average molecular weight (Mw) of 13,000 g/mol.

Example 6

(16) 4.8 g of a poly(imide-benzoxazine) block copolymer (PIBZ-6) was obtained by the same method as Example 1, except that 1.9 g of 4,4′-oxydianiline was used instead of 1.9 g of 4,4′-diaminodiphenyl methane.

(17) The molecular weight of the copolymer (PIBZ-6) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 9000 g/mol and a weight average molecular weight (Mw) of 17,000 g/mol.

Example 7

(18) Material C was obtained by the same method as Example 1.

(19) 1 g of the material C and 5 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminophenol) were dissolved in N-methyl-2-pyrrolidone (NMP). After raising the temperature to 80° C., 3.8 g of 4,4′-oxydiphthalic anhydride was added dropwise, and the mixture was reacted for 2 hours. Thereafter, 0.5 g of pyridine and 2.1 g of acetic anhydride were slowly introduced. After the mixture was reacted for 12 hours, it was precipitated with 500 ml of methanol. The precipitate was filtered and washed with water three times, and then dried under a 100° C. vacuum condition for 24 hours to obtain 8 g of poly(imide-benzoxazine) block copolymer (PIBZ-7).

(20) The molecular weight of the copolymer (PIBZ-7) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 8500 g/mol and a weight average molecular weight (Mw) of 16,500 g/mol.

Example 8

(21) 7.5 g of a poly(imide-benzoxazine) block copolymer (PIBZ-8) was obtained by the same method as Example 7, except that 1.9 g of 4,4′-oxydianiline was used instead of 1.9 g of 4,4′-diaminodiphenyl methane.

(22) The molecular weight of the copolymer (PIBZ-8) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 9000 g/mol and a weight average molecular weight (Mw) of 16,000 g/mol.

Example 9

(23) 7.8 g of a poly(imide-benzoxazine) block copolymer (PIBZ-9) was obtained by the same method as Example 7, except that 4.2 g of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was used instead of 3.8 g of 4,4′-oxydiphthalic anhydride.

(24) The molecular weight of the copolymer (PIBZ-9) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 8500 g/mol and a weight average molecular weight (Mw) of 17,500 g/mol.

Comparative Example 1

(25) 5 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminophenol) was dissolved in N-methyl-2-pyrrolidone (NMP). Thereto, 3.8 g of dibutyl 5,5′-oxybis(2-(chlorocarbonyl)benzoate) was slowly added dropwise at 0° C. After the mixture was reacted for 2 hours, 1.2 g of maleic anhydride was added, and the reaction mixture was additionally reacted for 2 hours. After the reaction, an excess amount of distilled water was dripped therein to produce a precipitate. The precipitate was filtered and washed with water three times, and then dried under a 100° C. vacuum condition for 24 hours to obtain 5 g of a polyimide (PI-1).

(26) The molecular weight of the polyimide (PI-1) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 6500 g/mol and a weight average molecular weight (Mw) of 12,000 g/mol.

Comparative Example 2

(27) 4.8 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminobenzene) was dissolved in N-methyl-2-pyrrolidone(NMP). Thereto, 3.8 g of dibutyl 5,5′-oxybis(2-(chlorocarbonyl)benzoate) was slowly added dropwise at 0° C. After the mixture was reacted for 2 hours, 1.2 g of maleic anhydride was added, and the reaction mixture was additionally reacted for 2 hours. After the reaction, an excess amount of distilled water was dripped thereto to produce a precipitate. The precipitate was filtered and washed with water three times, and then dried under a 100° C. vacuum condition for 24 hours to obtain 5 g of a polyimide (PI-2).

(28) The molecular weight of the polyimide (PI-2) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 6500 g/mol and a weight average molecular weight (Mw) of 12,500 g/mol.

Comparative Example 3

(29) 5 g of 5,5′-(perfluoropropane-2,2-diyl)bis(2-aminophenol) was dissolved in N-methyl-2-pyrrolidone (NMP). After raising the temperature to 80° C., 3.4 g of 4,4′-oxydiphthalic anhydride was added dropwise, and the reaction mixture was reacted for 2 hours. Thereafter, 0.4 g of pyridine and 1.8 g of acetic anhydride were slowly introduced. After the mixture was reacted for 12 hours, it was precipitated with 500 ml of methanol. The precipitate was filtered and washed with water three times, and then dried under a 100° C. vacuum condition for 24 hours to obtain 6 g of a polyimide (PI-3).

(30) The molecular weight of the polyimide (PI-3) was measured by GPC under a THF solvent, and as the result, it was confirmed that the copolymer had a number average molecular weight (Mn) of 7500 g/mol and a weight average molecular weight (Mw) of 15,000 g/mol.

Preparation Examples 1 to 12

(31) The photosensitive resin compositions of Preparation Examples 1 to 12 were respectively prepared by mixing the components shown in the following Table 1. In Table 1, the content of each component was based on 100 parts by weight of the polymer PIBZ-1, PIBZ-2, PIBZ-3, PIBZ-4, PIBZ-5, PIBZ-6, PIBZ-7, PIBZ-8, PIBZ-9, PI-1, PI-2, or PI-3) according to the examples and comparative examples.

(32) In Table 1, each component used for the preparation examples are as follows.

(33) [PIBZ-1] poly(imide-benzoxazine) block copolymer according to Example 1

(34) [PIBZ-2] poly(imide-benzoxazine) block copolymer according to Example 2

(35) [PIBZ-3] poly(imide-benzoxazine) block copolymer according to Example 3

(36) [PIBZ-4] poly(imide-benzoxazine) block copolymer according to Example 4

(37) [PIBZ-5] poly(imide-benzoxazine) block copolymer according to Example 5

(38) [PIBZ-6] poly(imide-benzoxazine) block copolymer according to Example 6

(39) [PIBZ-7] poly(imide-benzoxazine) block copolymer according to Example 7

(40) [PIBZ-8] poly(imide-benzoxazine) block copolymer according to Example 8

(41) [PIBZ-9] poly(imide-benzoxazine) block copolymer according to Example 9

(42) [PI-1] polyimide according to Comparative Example 1

(43) [PI-2] polyimide according to Comparative Example 2

(44) [PI-3] polyimide according to Comparative Example 3

(45) [B] a photoacid generator of the following chemical formulas

(46) ##STR00015##

(47) [C] a photoacid generator of the following chemical formula

(48) ##STR00016##

(49) [D] a photocurable multifunctional acrylic compound according to the following chemical formula

(50) ##STR00017##

(51) [E] gamma-butyrolactone (GBL)

(52) TABLE-US-00001 TABLE 1 Preparation Example 1 2 3 4 5 6 7 8 9 10 11 12 PIBZ-1 100 — — — — — — — — — — — PIBZ-2 — 100 — — — — — — — — — — PIBZ-3 — — 100 — — — — — — — — — PIBZ-4 — — — 100 — — — — — — — — PIBZ-5 — — — — 100 — — — — — — — PIBZ-6 — — — — — 100 — — — — — — PIBZ-7 — — — — — — 100 — — — — — PIBZ-8 — — — — — — — 100 — — — — PIBZ-9 — — — — — — — — 100 — — — PI-1 — — — — — — — — — 100 — — PI-2 — — — — — — — — — — 100 — PI-3 — — — — — — — — — — — 100 B  30  30  30  30 —  30  30  30  30  30  30  30 C — — — —  10 — — — — — — — D  30  30  30  30  30  30  30  30  30  30  30  30 E 150 150 150 150 150 150 150 150 150 150 150 150

Experimental Example 1: Adhesion of a Cured Film

(53) The photosensitive resin compositions according to the preparation examples were respectively coated on a silicon wafer substrate on which a 4-inch silicone wafer and Cu were coated to a thickness of 300 nm by spin coating, and then dried at 120° C. for 2 minutes, and exposed in a broadband aligner exposure apparatus at 500 mJ/cm.sup.2. They were cured again at 200° C. for 2 hours to obtain a substrate on which a cured film with a thickness of about 4.3 to 4.5 μm was formed.

(54) The substrate on which a cured film was formed was evaluated for adhesion of the cured film (cohesion to the substrate) through a taping test according to the TPC-TM-650 method. Specifically, using a knife for a taping test only (Cross Hatch Cutter, YCC-230/1), 10×10 lattice-shaped sheathes were made only on the upper cured film without damaging the lower wafer (the size of each lattice was 100 μm, and the number of lattices was 100), and a Nichibang tape was firmly adhered to the surface of the cured film. 60 seconds after the adhesion, the end of the tape was bent 180 degrees and peeled off with the same force. Here, the number of lattices of the cured film, which were peeled off together with the tape, was counted to evaluate cohesion to the substrate, and the results are shown in the following Table 2.

(55) TABLE-US-00002 TABLE 2 Preparation Example 1 2 3 4 5 6 7 8 9 10 11 12 Number of 0 0 1 0 0 0 0 0 0 2 5 4 lattices peeled off

Experimental Example 2: Chemical Resistance of a Cured Film

(56) The photosensitive resin compositions according to the preparation examples were respectively coated on a 4 inch silicon wafer by spin coating of 800 to 1200 rpm, and then dried at 120° C. for 2 minutes to obtain a substrate on which a photosensitive resin film with a thickness of 5.0 μm was formed.

(57) Further, using a mask on which a micropattern was formed, it was exposed in a broadband aligner exposure apparatus at 500 mJ/cm.sup.2. Thereafter, the exposed wafer was developed in an aqueous solution of 2.39 wt % tetramethyl ammonium hydroxide for 150 seconds, washed with ultrapure water, and then dried under nitrogen to form a pattern on the photosensitive resin film. The substrate was cured again at 200° C. for 2 hours to obtain a substrate on which a cured film was formed.

(58) The obtained substrate was soaked in acetone (AC), dimethylformamide (DMF), or gamma-butyrolactone (GBL) for 30 minutes, and then washed with isopropyl alcohol and dried under nitrogen, and then the surface was observed through a microscope. As results of observance, it was evaluated as “◯” (generated) or “X” (not generated) according to whether or not damage such as molten marks or cracks were generated on the cured film. The results are shown in the following Table 3.

(59) TABLE-US-00003 TABLE 3 Preparation Example 1 2 3 4 5 6 7 8 9 10 11 12 AC X X X X X X X X X X X X DMF X X X X X X X X X ◯ ◯ ◯ GBL X X X X X X X X X ◯ ◯ ◯

Experimental Example 3: Low Temperature Curing Property

(60) In order to evaluate the low temperature curability of each photosensitive resin compositions according to the preparation examples, the same process as Experimental Example 2 was progressed, except that the curing temperatures were changed to 140° C., 160° C., 180° C., 200° C., and 220° C., thus obtaining a substrate on which a cured film was formed.

(61) The obtained substrate was soaked in gamma-butyrolactone (GBL) for 30 minutes, and then washed with isopropyl alcohol and dried under nitrogen, and then the surface was observed with a microscope. As results of observation, it was evaluated as “◯” (generated) or “X” (not generated) according to whether or not damage such as molten marks or cracks were generated. The results are shown in the following Table 4.

(62) TABLE-US-00004 TABLE 4 Preparation Example 1 2 3 4 5 6 7 8 9 10 11 12 140° C. ◯ ◯ ◯ ◯ ◯ ◯ X X X ◯ ◯ X 160° C. X X ◯ X X X X X X ◯ ◯ X 180° C. X X X X X X X X X ◯ ◯ X 200° C. X X X X X X X X X ◯ ◯ X 220° C. X X X X X X X X X ◯ ◯ X

(63) Referring to Tables 1 to 4, it was confirmed that the photosensitive resin compositions of Preparation Examples 1 to 9 including the poly(imide-benzoxazine) block copolymers according to the examples provided cured films having excellent adhesion and chemical resistance, compared to the photosensitive resin compositions of Preparation Examples 10 to 12 including the polyimide according to the comparative examples.

(64) Particularly, it was confirmed that the photosensitive resin compositions of Preparation Examples 1 to 6 can be cured even at a temperature of 160° C. or 180° C., which is remarkably lower than 300° C., the curing temperature of the existing photosensitive resin composition using a polyimide precursor.