POLYIMIDE RESIN AND POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPRISING THE SAME

Abstract

An exemplary embodiment of the present application provides a polyimide resin in which the functional group represented by Chemical Formula 1 or 2 is bonded to at least one end of the polyimide resin.

Claims

1. A polyimide resin in which a functional group represented by the following Chemical Formula 1 or 2 is bonded to at least one end of the polyimide resin: ##STR00016## in Chemical Formulae 1 and 2, denotes a position to be bonded to the polyimide resin, respectively, R1 to R3 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R2 and R3 are optionally linked to each other to form a ring, and Ar1 and Ar2 are each independently a substituted or unsubstituted heteroaryl group.

2. The polyimide resin of claim 1, where Chemical Formula 1 is represented by the following Chemical Formula 3 or 4: ##STR00017## in Chemical Formulae 3 and 4, denotes a position to be bonded to the polyimide resin, respectively, R4 and R5 are each independently hydrogen, or a substituted or unsubstituted alkyl group, and Ar1 is a substituted or unsubstituted heteroaryl group.

3. The polyimide resin of claim 1, wherein Chemical Formula 2 is any one of the following Chemical Formulae 5 to 9: ##STR00018## in Chemical Formulae 5 to 9, denotes a position to be bonded to the polyimide resin, respectively, and Ar2 is a substituted or unsubstituted heteroaryl group.

4. The polyimide resin of claim 1, wherein Ar1 and Ar2 of Chemical Formulae 1 and 2 are each independently represented by any one of the following structural formulae: ##STR00019## in the structural formulae, * denotes a position to be bonded to Chemical Formula 1 or 2.

5. The polyimide resin of claim 1, wherein the polyimide resin comprises a polymer product of an amine-based monomer and an anhydride-based monomer.

6. The polyimide resin of claim 5, wherein the amine-based monomer is selected from the following structural formulae: ##STR00020##

7. The polyimide resin of claim 5, wherein the anhydride-based monomer is selected from the following structural formulae: ##STR00021##

8. A method for preparing a polyimide resin, the method comprising: preparing a polyimide resin in which a functional group represented by the following Chemical Formula 10 or 11 is bonded to at least one end of the polyimide resin; and reacting the polyimide resin to which the functional group represented by Chemical Formula 10 or 11 is bonded with a heterocyclic compound comprising a thiol group (—SH): ##STR00022## in Chemical Formulae 10 and 11, denotes a position to be bonded to the polyimide resin, respectively, and R1 to R3 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R2 and R3 are optionally linked to each other to form a ring.

9. The method of claim 8, wherein the heterocyclic compound comprising a thiol group (—SH) is selected from the following compounds: ##STR00023##

10. 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.

11. The positive-type photosensitive resin composition of claim 10, 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.

Description

EXAMPLES

Synthesis Example 1

Synthesis of Polyimide Resin A1

[0103] 100 mmol of Bis-APAF and 300 g of propylene glycol methyl ether acetate (PGMEA) were sequentially added to a 1,000-mL round bottom flask, the temperature was increased to 120° C., and the resulting mixture was stirred and completely dissolved. The flask was cooled to 80° C., 97 mmol of PMDA and 6 mmol of MA having the following structural formula were added thereto, and the resulting mixture was stirred 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 were diluted with 10 g of propylene glycol monomethyl acetate, 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, the solution was cooled to room temperature and recovered. The weight average molecular weight (Mw) of the recovered polymer was confirmed using gel permeation chromatography (GPC), and was determined to be 16,112 g/mol. In addition, the polydispersity index (PDI) of the prepared polymer was 2.18.

##STR00013##

Synthesis Example 2

Synthesis of Polyimide Resin B1

[0104] Polyimide resin B1 was synthesized in the same manner as in the synthesis of polyimide resin A1, except that TFMB and BPDA were used instead of Bis-APAF and PMDA, respectively. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 15,998 g/mol and 2.16, respectively.

Synthesis Example 3

Synthesis of Polyimide Resin C1

[0105] Polyimide resin C1 was synthesized in the same manner as in the synthesis of polyimide resin A1, except that 50 mmol of Bis-APAF and 50 mmol of ODA were used instead of 100 mmol of Bis-APAF, and 47 mmol of PMDA and 50 mmol of ODPA were used instead of 97 mmol of PMDA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 18,055 g/mol and 2.29, respectively.

Synthesis Example 4

Synthesis of Polyimide Resin D1

[0106] Polyimide resin D1 was synthesized in the same manner as in the synthesis of polyimide resin Al, except that 50 mmol of TFMB and 50 mmol of HAB were used instead of 100 mmol of Bis-APAF, and 47 mmol of BPDA and 50 mmol of ODPA were used instead of 97 mmol of PMDA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 14,911 g/mol and 2.62, respectively.

Synthesis Example 5

Synthesis of Polyimide Resin E1

[0107] Polyimide resin E1 was synthesized in the same manner as in the synthesis of polyimide resin A1, except that 50 mmol of Bis-APAF and 50 mmol of polyetheramine (ED-900, Jeffamine) were used instead of 100 mmol of Bis-APAF, and ODPA was used instead of PMDA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 15,618 g/mol and 2.26, respectively.

Synthesis Example 6

Synthesis of Polyimide Resin A2

[0108] Polyimide resin A2 was synthesized in the same manner as in the synthesis of polyimide resin Al, except that iBF of the following structural formula was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 18,485 g/mol and 2.46, respectively.

##STR00014##

Synthesis Example 7

Synthesis of Polyimide Resin B2

[0109] Polyimide resin B2 was synthesized in the same manner as in the synthesis of polyimide resin B1, except that iBF was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,489 g/mol and 2.41, respectively.

Synthesis Example 8

Synthesis of Polyimide Resin C2

[0110] Polyimide resin C2 was synthesized in the same manner as in the synthesis of polyimide resin C1, except that iBF was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,918 g/mol and 2.45, respectively.

Synthesis Example 9

Synthesis of Polyimide Resin D2

[0111] Polyimide resin D2 was synthesized in the same manner as in the synthesis of polyimide resin D1, except that iBF was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 18,007 g/mol and 2.46, respectively.

Synthesis Example 10

Synthesis of Polyimide Resin E2

[0112] Polyimide resin E2 was synthesized in the same manner as in the synthesis of polyimide resin El, except that iBF was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 15,152 g/mol and 2.12, respectively.

Synthesis Example 11

Synthesis of Polyimide Resin A3

[0113] Polyimide resin A3 was synthesized in the same manner as in the synthesis of polyimide resin A1, except that 3AP was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 17,475 g/mol and 2.35, respectively.

Synthesis Example 12

Synthesis of Polyimide Resin B3

[0114] Polyimide resin B3 was synthesized in the same manner as in the synthesis of polyimide resin B 1, except that PA was used instead of MA. The weight average molecular weight (Mw) and polydispersity index (PDI) of the recovered polymer were 16,341 g/mol and 2.23, respectively.

Examples 1 to 20

1) Synthesis of Polyimide Resin and Thiol

[0115] 2 equivalents of the thiol compound and 1 equivalent of the polyimide resin shown in the following Table 1, and 0.1 equivalent of the photoinitiator (benzophenone) were put into a flask and irradiated with 350 nm UV at room temperature for 4 hours. After the reaction, the polyimide was dissolved in THF and the precipitate was captured using hexane to remove unreacted materials and impurities.

2) Preparation of Positive-Type Photosensitive Resin Composition

[0116] 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 prepared in 1).

Comparative Examples 1 to 5

[0117] Positive-type photosensitive resin compositions were prepared in the same manner as in the Examples, except that the polyimide resins shown in the following Table 1 were applied.

Comparative Examples 6 and 7

[0118] Positive-type photosensitive resin compositions were prepared in the same manner as in the Examples, except that the polyimide resins shown in the following Table 1 were applied and 2 equivalents of thiol compound T1 based on 1 equivalent of the polyimide resin were added.

Experimental Example

[0119] The positive-type photosensitive resin compositions prepared in the Examples and Comparative Examples were allowed to pass through a 0.2-μm filter and evaluated by removing impurities in the solution.

[0120] After a wafer was spin-coated with the prepared positive-type photosensitive resin composition using a wafer 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 solvent remaining on the wafer was completely removed by baking at a temperature of 105° C. or more in order to remove the solvent. After the wafer was 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 wafer was 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]

[0121] Prebake: 105° C./120 s

[0122] Exposure: i-line Stepper, 100 mJ/cm.sup.2 to 900 mJ/cm.sup.2

[0123] Development: 2.38 wt % tetramethylammonium hydroxide (TMAH) solution 23° C./120 s

[0124] Rinse: DI water rinse

[0125] Post Bake: 200° C./2 hrs

[0126] 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.

[0127] 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]

[0128] The shape and size of the pattern were measured by measuring a completely developed part from a thickness of 5 μm to a contact hole pattern lower part of 10 μm using the SEM, and a case where the hole pattern of 10 μm was completely developed was described as good. The case where the pattern lower part was not developed was described as poor.

[0129] Good: ⊚

[0130] Fair: Δ

[0131] Poor: X

[Adhesion Strength]

[0132] 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.

[0133] Less than 10: ⊚

[0134] 10 or more and less than 20: Δ

[0135] 20 or more: X

TABLE-US-00001 TABLE 1 Binder resin Thiol Pattern Adhesion Polyimide resin compound developability strength Example 1 A1 T1 ⊚ ⊚ Example 2 B1 T1 ⊚ ⊚ Example 3 C1 T1 ⊚ ⊚ Example 4 D1 T1 ⊚ ⊚ Example 5 E1 T1 ⊚ ⊚ Example 6 A2 T1 ⊚ ⊚ Example 7 B2 T1 ⊚ ⊚ Example 8 C2 T1 ⊚ ⊚ Example 9 D2 T1 ⊚ ⊚ Example 10 E2 T1 ⊚ ⊚ Example 11 A1 T2 ⊚ ⊚ Example 12 B1 T2 ⊚ ⊚ Example 13 C1 T2 ⊚ ⊚ Example 14 D1 T2 ⊚ ⊚ Example 15 E1 T2 ⊚ ⊚ Example 16 A2 T2 Δ ⊚ Example 17 B2 T2 ⊚ ⊚ Example 18 C2 T2 Δ ⊚ Example 19 D2 T2 ⊚ ⊚ Example 20 E2 T2 ⊚ ⊚ Comparative A1 X X X Example 1 Comparative B1 X Δ X Example 2 Comparative C1 X X X Example 3 Comparative D1 X Δ X Example 4 Comparative E1 X Δ X Example 5 Comparative A3 X Δ Δ Example 6 Comparative B3 X X Δ Example 7

[Thiol Compound]

[0136] ##STR00015##

[0137] As shown in the results, the polyimide resin according to an exemplary embodiment of the present application is characterized in that the adhesion strength to a metal can be improved by directly comprising a functional group having excellent adhesion to the metal in the polyimide resin.

[0138] Furthermore, Comparative Examples 6 and 7 are the cases where a thiol compound is separately comprised in a photosensitive resin composition instead of applying a polyimide resin in which a thiol-based functional group is directly bonded to the polyimide resin as in the examples of the present application. As shown in the results, it can be confirmed that in the case of Comparative Examples 6 and 7, pattern developability and adhesion strength characteristics are not good when compared to the examples of the present application.

[0139] Therefore, a photosensitive resin composition comprising the polyimide resin according to an exemplary embodiment of the present application can improve the adhesion strength to a metal even when the photosensitive resin composition does not comprise a separate adhesion promoter.