POLYIMIDE RESIN AND POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPRISING THE SAME

Abstract

An exemplary embodiment of the present application provides a polyimide resin comprising a structure represented by Chemical Formula 1 and a positive-type photosensitive resin composition comprising the same.

Claims

1. A polyimide resin comprising a structure represented by the following Chemical Formula 1: ##STR00011## in Chemical Formula 1, A1 is a tetravalent organic group, A2 is a divalent organic group, at least one of R.sub.1 and R.sub.2 is an acetylacetone group, and the other is independently hydrogen, an acetylacetone group, a hydroxyl group, or a substituted or unsubstituted alkyl group, o and p are the same as or different from each other, and are each independently an integer from 0 to 10, and o+p≥1, when o is 2 or higher, R.sub.1's are the same as or different from each other, and when p is 2 or higher, R.sub.2's are the same as or different from each other, and n is an integer from 1 to 90, and when n is 2 or higher, structures in the parenthesis are the same as or different from each other.

2. The polyimide resin of claim 1, wherein Al is a substituted or unsubstituted aliphatic ring, or a substituted or unsubstituted aromatic ring.

3. The polyimide resin of claim 1, wherein A2 is represented by (L1)a, L1 is a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group, and a is an integer from 1 to 3, and when a is 2 or higher, L1's are the same as or different from each other.

4. A positive-type photosensitive resin composition comprising: a binder resin comprising the polyimide resin of claim 1; a photo active compound; a cross-linking agent; a surfactant; and a solvent.

5. The positive-type photosensitive resin composition of claim 4, wherein based on 100 parts by weight of the binder resin comprising the polyimide resin, 1 part by weight to 40 parts by weight of the photo active compound; 5 parts by weight to 50 parts by weight of the cross-linking agent; 0.05 part by weight to 5 parts by weight of the surfactant; and 50 parts by weight to 500 parts by weight of the solvent are comprised.

6. A method for preparing a polyimide resin, the method comprising: preparing a polyimide resin comprising a structure represented by the following Chemical Formula 2; and reacting the polyimide resin with a compound comprising an acetylacetone group: ##STR00012## in Chemical Formula 2, A1 is a tetravalent organic group, A2 is a divalent organic group, at least one of R.sub.3 and R.sub.4 is a hydroxyl group, and the other is independently hydrogen, a hydroxyl group, or a substituted or unsubstituted alkyl group, o and p are the same as or different from each other, and are each independently an integer from 0 to 10, and o+p≥1, when o is 2 or higher, R.sub.3's are the same as or different from each other, and when p is 2 or higher, R.sub.4's are the same as or different from each other, and n is an integer from 1 to 90, and when n is 2 or higher, structures in the parenthesis are the same as or different from each other.

7. The method of claim 6, wherein the compound comprising the acetylacetone group is ethoxyacetylacetone.

Description

EXAMPLES

Synthesis Example 1

Synthesis of Polyimide Resin A1

[0118] After 100 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Bis-APAF) and 300 g of propylene glycol methyl ether acetate (PGMEA) were sequentially introduced into a 1,000-mL round bottom flask and completely dissolved by increasing the temperature to 120° C. and stirring the flask, the flask was cooled to 80° C., 97 mmol of tetrahydro-[3,3′-bifuran]-2,2′,5,5′-tetraone (BT-100) and 6 mmol of trimellitic anhydride (TMA) were introduced thereto, and then the resulting mixture was stirred along with 30 g of toluene at 150° C. After the components were completely dissolved, the resulting solution was cooled to 50° C., and then 3 mmol of gamma valerolactone (r-VL) and 7 mmol of triethyl amine (TEA) were diluted with 10 g of propylene glycol monomethyl acetate (PGMEA), and the resulting solution was introduced thereinto. After a Dean-Stark distillation apparatus was installed such that water could be removed in the reaction by the apparatus, the mixture was stirred at 175° C. for 16 hours. After the toluene added to the mixed solution was removed, a polymer was recovered by cooling the solution to room temperature. The weight average molecular weight (Mw) of the recovered polymer was confirmed using gel permeation chromatography (GPC), and was determined to be 23,900 g/mol. In addition, the polydispersity index (PDI) of the prepared polymer was 1.54.

Synthesis Example 2

Synthesis of Polyimide Resin B1

[0119] Polymer resin B1 was synthesized in the same manner as in the method of Synthesis Example 1, except that 4,4′-oxydiphthalic anhydride (ODPA) was used instead of BT-100. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,202 g/mol and 2.46, respectively.

Synthesis Example 3

Synthesis of Polyimide Resin C1

[0120] Polymer resin C1 was synthesized in the same manner as in the method of Synthesis Example 1, except that biphenyl-tetracarboxylic acid dianhydride (BPDA) was used instead of BT-100. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,766 g/mol and 2.40, respectively.

Synthesis Example 4

Synthesis of Polyimide Resin D1

[0121] Polymer resin D1 was synthesized in the same manner as in the method of Synthesis Example 1, except that 2,2-dihydroxybenzidine was used instead of Bis-APAF. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 20,500 g/mol and 1.58, respectively.

Synthesis Example 5

Synthesis of Polyimide Resin E1

[0122] Polyimide resin E1 was synthesized in the same manner as in the method of Synthesis Example 4, except that ODPA was used instead of BT-100. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,898 g/mol and 2.57, respectively.

Synthesis Example 6

Synthesis of Polyimide Resin F1

[0123] Polyimide resin F1 was synthesized in the same manner as in the method of Synthesis Example 4, except that BPDA was used instead of BT-100. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 20,679 g/mol and 2.49, respectively.

Synthesis Example 7

Synthesis of polyimide resin G1

[0124] Polyimide resin G1 was synthesized in the same manner as in the method of Synthesis Example 1, except that 60 mmol of Bis-APAF and 40 mmol of O,O′-Bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol (ED-600) were used instead of 100 mmol of Bis-APAF, and 47 mmol of BT-100 and 50 mmol of ODPA were used instead of 97 mmol of BT-100. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 20,751 g/mol and 2.74, respectively.

Synthesis Example 8

Synthesis of Polyimide Resin H1

[0125] Polyimide resin H1 was synthesized in the same manner as in the method of Synthesis Example 7, except that BPDA was used instead of BT-100. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 14,793 g/mol and 2.65, respectively.

Synthesis Example 9

Synthesis of Polyimide Resin I1

[0126] Polyimide resin I1 was synthesized in the same manner as in the method of Synthesis Example 7, except that 2,2′-dihydroxybenzidine was used instead of Bis-APAF. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,257 g/mol and 2.81, respectively.

Synthesis Example 10

Synthesis of Polyimide Resin J1

[0127] Polyimide resin J1 was synthesized in the same manner as in the method of Synthesis Example 8, except that 2,2′-dihydroxybenzidine was used instead of Bis-APAF. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 16,855 g/mol and 2.48, respectively.

Synthesis Example 11

Synthesis of Polyimide Resins A2 to J2

[0128] As shown in the following General Synthesis Example, an acetylacetone group can be easily introduced into the molecule by a reaction of ethoxyacetylacetone and a hydroxyl group.

General Synthesis Example

Synthesis of acetylacetone group

[0129] ##STR00010##

[0130] Polyimide resins A2 to J2 were synthesized by the following General Synthesis Example Each of the polymide resins Al to Jl and ethoxyacetylacetone were dissolved in anhydrous tetrahydrofuran (THF), the temperature was lowered to 0° C. using an ice bath, and nitrogen atmosphere was prepared. While nitrogen atmosphere at 0° C. was maintained in other flasks, POCl.sub.3 and dimethylformamide (DMF) were mixed in anhydrous THF and maintained in the flask for 30 minutes. A mixture of POCl.sub.3 and DMF was slowly added to the flask in which the resin was dissolved using a syringe. After the addition was completed, the resulting mixture was slowly warmed to room temperature, and then heated and stirred at 60° C. for 15 hours using an oil bath. After the reaction was completed, the mixture was cooled to room temperature and washed with a basic solution using sodium bicarbonate and distilled water. The obtained organic solution was distilled under reduced pressure to remove THE

[0131] The polymer in which an acetylacetone group was introduced into the polyimide resin A1 is marked as polyimide resin A2. Polymers in which an acetylacetone group was introduced into the above-described polyimide resins B1 to J1 using the same method are marked as polyimide resins B2 to J2, respectively.

Examples 1 to 10 and Comparative Examples 1 to 4

Preparation of positive-type photosensitive resin composition

[0132] A positive-type photosensitive resin composition was prepared by mixing 15 parts by weight of a photo active compound (TPA529), 25 parts by weight of a cross-linking agent (2-[[4-[2-[4-[1,1-bis[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenyl]propan-2-yl]phenoxy]methyl]oxirane), 0.1 part by weight of a surfactant (BYK-307, manufactured by BYK-Chemie) and 200 parts by weight of a solvent (PGMEA) based on 100 parts by weight of the polyimide resin shown in the following Table 1. The positive-type photosensitive resin composition prepared as described above were allowed to pass through a 0.2-μm filter and evaluated by removing impurities in the solution.

Experimental Example

[0133] After wafers were spin-coated with the positive-type photosensitive resin compositions prepared in the Examples and Comparative Examples using wafers on which Ti and Cu were vapor-deposited to a thickness of 100 nm or more, and coated to a thickness of 6 μm, the solvents remaining on the wafers were completely removed by baking at a temperature of 105° C. or more in order to remove the solvent. After the wafers were irradiated with a constant exposure of 100 mJ/cm.sup.2 to 900 mJ/cm.sup.2 using a stepper that emits i-line wavelength, the wafers were developed with a developer for 120 seconds, subjected to a rinsing process with a rinse solution, and then post baked at a temperature of 200° C. or less for 2 hours.

Evaluation conditions of positive-type photosensitive resin composition

[0134] Prebake: 105° C./120 s

[0135] Exposure: i-line Stepper, 100 mJ/cm.sup.2 to 900 mJ/cm.sup.2

[0136] Development: 2.38 wt% tetramethylammonium hydroxide (TMAH) solution 23° C./120 s

[0137] Rinse: DI water rinse

[0138] Post Bake: 200° C./2 hrs

[0139] The pattern characteristics were confirmed using a wafer that had been completely post baked, the photosensitive resin composition coated on the wafer was cured and then formed into a film, and the mechanical properties and thermal characteristics thereof were measured.

[0140] For pattern developability, the shape and size of the pattern were measured using a scanning electron microscope (SEM), and mechanical properties were measured using a universal testing machine (UTM).

Pattern Developability

[0141] The shape and size of the pattern were measured by measuring a completely developed part from a thickness of 5 pm to a contact hole pattern lower part of 10 μm using the SEM, and a case where the hole pattern of 10 pm was completely developed was described as good. The case where the pattern lower part was not developed was described as poor.

[0142] Good: ⊚

[0143] Fair: Δ

[0144] Poor: X

Adhesion Strength

[0145] A check shape of 10 rows, 10 columns was incised at an interval of 2 mm using a single-edged blade on a film after the wafer was coated with the resin and the resin was cured. The number of cells peeled out of 100 cells on top of this was counted by peeling with a cellophane tape (registered trademark) to evaluate the adhesion characteristics between the metal material and the resin-cured film.

[0146] Less than 10: ⊚

[0147] 10 or more and less than 20: Δ

[0148] 20 or more: X

TABLE-US-00001 TABLE 1 Pattern Adhesion Polyimide resin developability strength Example 1 Polyimide resin A2 Δ ⊚ Example 2 Polyimide resin B2 ⊚ ⊚ Example 3 Polyimide resin C2 ⊚ ⊚ Example 4 Polyimide resin D2 Δ ⊚ Example 5 Polyimide resin E2 ⊚ ⊚ Example 6 Polyimide resin F2 ⊚ ⊚ Example 7 Polyimide resin G2 ⊚ ⊚ Example 8 Polyimide resin H2 ⊚ ⊚ Example 9 Polyimide resin I2 ⊚ ⊚ Example 10 Polyimide resin J2 ⊚ ⊚ Comparative Polyimide resin A1 Δ Δ Example 1 Comparative Polyimide resin D1 X Δ Example 2 Comparative Polyimide resin G1 Δ Δ Example 3 Comparative Polyimide resin I1 Δ Δ Example 4

[0149] As described in the results, the polyimide resin according to an exemplary embodiment of the present application is characterized in that even when a separate additive is not added, the adhesion strength to a metal can be improved by comprising an acetylacetone group in the polyimide resin.