POLYAMIC ACID COMPOSITION FOR PRODUCING POLYIMIDE RESIN WITH SUPERIOR ADHESION AND POLYIMIDE RESIN PRODUCED THEREFROM

Abstract

The present invention provides a polyamic acid composition comprising: a polyamic acid in which a dianhydride monomer comprising a first dianhydride having one benzene ring and a second dianhydride having a benzophenone structure, and a diamine monomer comprising a compound represented by Formula (1) are polymerized; and an organic solvent, wherein the mole ratio of the second dianhydride to the first dianhydride (the mole number of the second dianhydride/the mole number of the first dianhydride) is 0.2 to 1.2.

Claims

1. A polyamic acid composition for producing a polyimide resin, comprising a polyamic acid in which a dianhydride monomer comprising a first dianhydride having one benzene ring and a second dianhydride having a benzophenone structure, and a diamine monomer comprising a compound represented by the following formula (1) are polymerized; and an organic solvent, wherein the mole ratio of the second dianhydride to the first dianhydride (=the mole number of the second dianhydride/the mole number of the first dianhydride) is 0.2 to 1.2. ##STR00003## wherein, R is —C.sub.n1(CH.sub.3).sub.2n1—, —C.sub.n2(CF.sub.3).sub.2n2—, —(CH.sub.2).sub.n3—, or —O(CH.sub.2).sub.n4O—, and n1 to n4 are each independently an integer of 1 to 4.

2. The polyamic acid composition according to claim 1, wherein the mole ratio of the second dianhydride to the first dianhydride is 0.4 to 1.

3. The polyamic acid composition according to claim 1, wherein the content of the first dianhydride is 40 mol % to 80 mol % and the content of the second dianhydride is 20 mol % to 60 mol %, based on the total mole number of the dianhydride monomer.

4. The polyamic acid composition of claim 1, wherein the first dianhydride is pyromellitic dianhydride (PMDA).

5. The polyamic acid composition of claim 1, wherein the second dianhydride is 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA).

6. The polyamic acid composition according to claim 1, wherein the content of the compound of Formula (1) above is 70 mol % to 100 mol %, based on the total mole number of the diamine monomer.

7. The polyamic acid composition according to claim 1, wherein R in Formula (1) above is —C(CH.sub.3).sub.2— or —C(CF.sub.3).sub.2—.

8. The polyamic acid composition according to claim 1, wherein R in Formula (1) above is —C(CH.sub.3).sub.2—.

9. The polyamic acid composition according to claim 1, further comprising at least one additive selected from acetic anhydride (AA), propionic acid anhydride, and lactic acid anhydride, quinoline, isoquinoline, β-picoline (BP) and pyridine.

10. The polyamic acid composition according to claim 9, wherein the additive is contained in an amount of 0.05 moles to 0.1 moles per 1 mole of the amic acid group in the polyamic acid.

11. The polyamic acid composition according to claim 1, wherein when the solid content of the polyamic acid is 15%, the viscosity measured at 23° C. is 400 cP to 1,000 cP.

12. A polyimide resin prepared by imidizing the polyamic acid composition according to claim 1.

13. The polyimide resin according to claim 12, wherein an area removed when measuring adhesion according to ASTM D 3359 on an inorganic substrate is less than 5% of the total.

14. The polyimide resin according to claim 12, wherein the glass transition temperature is 280° C. or more, and the coefficient of thermal expansion is 40 ppm/° C. or more.

15. The polyimide resin according to claim 12, wherein the tensile strength is 140 MPa or more, and the elongation is 100% or more.

16. A polyimide film made of the polyimide resin according to claim 12.

17. An electronic component comprising the polyimide resin according to claim 12.

18. The electronic component according to claim 17, wherein the electronic component is a semiconductor that the polyimide resin is encapsulated in a bonded state.

Description

DESCRIPTION OF DRAWING

[0103] FIG. 1 is a photograph that the polyimide resin of Example 1 is tested for adhesion and then the surface of the resin is photographed.

[0104] FIG. 2 is a photograph that the polyimide resin of Comparative Example 1 is tested for adhesion and then the surface of the resin is photographed.

[0105] FIG. 3 is a photograph that the polyimide resin of Comparative Example 5 is tested for adhesion and then the surface of the resin is photographed.

[0106] FIG. 4 is a photograph that the polyimide resin of Comparative Example 6 is tested for adhesion and then the surface of the resin is photographed.

MODE FOR INVENTION

[0107] Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, these examples are merely illustrative of the invention, and the scope of the invention is not determined thereby.

Example 1

[0108] To a 40° C. reactor filled with NMP, PMDA as the first dianhydride, BTDA as the second dianhydride and BAPP as the diamine were added in the mole ratio shown in Table 1 below, stirred for about 30 minutes to polymerize a polyamic acid and isoquinoline was introduced thereto in an amount of 0.05 to 0.1 moles per 1 mole of the amic acid group, and then the aging process was performed at 80° C. for about 2 hours to prepare a final polyamic acid composition.

Example 2

[0109] A polyamic acid composition was prepared in the same manner as in Example 1, except that the polyamic acid was polymerized by changing PMDA as the first dianhydride and BTDA as the second dianhydride in the mole ratio shown in Table 1 below.

Example 3

[0110] A polyamic acid composition was prepared in the same manner as in Example 1, except that the polyamic acid was polymerized by changing PMDA as the first dianhydride and BTDA as the second dianhydride in the mole ratio shown in Table 1 below.

Comparative Example 1

[0111] A polyamic acid composition was prepared in the same manner as in Example 1, except that the polyamic acid was polymerized by changing PMDA as the first dianhydride and BTDA as the second dianhydride in the mole ratio shown in Table 1 below.

Comparative Example 2

[0112] A polyamic acid composition was prepared in the same manner as in Example 1, except that the polyamic acid was polymerized by changing PMDA as the first dianhydride and BTDA as the second dianhydride in the mole ratio shown in Table 1 below.

Comparative Example 3

[0113] A polyamic acid composition was prepared in the same manner as in Example 1, except that the polyamic acid was polymerized by changing PMDA as the first dianhydride and BTDA as the second dianhydride in the mole ratio shown in Table 1 below.

Comparative Example 4

[0114] A polyamic acid composition was prepared in the same manner as in Example 1, except that the polyamic acid was polymerized by changing PMDA as the first dianhydride and BTDA as the second dianhydride in the mole ratio shown in Table 1 below.

Comparative Example 5

[0115] As compared with Example 1, the first dianhydride was omitted, BTDA of the second dianhydride as the dianhydride monomer was used in a single component, and BAPP and ODA were used together as the diamine monomer.

[0116] Specifically, BTDA, BAPP as the first diamine and ODA as the second diamine were added in the mole ratio shown in Table 1 below to a 40° C. reactor filled with NMP, and stirred for about 30 minutes to polymerize a polyamic acid, and except for this, a polyamic acid composition was prepared in the same manner as in Example 1.

Comparative Example 6

[0117] As compared with Example 1, the first dianhydride was omitted, BTDA of the second dianhydride as the dianhydride monomer was used as a single component, and ODA as the diamine monomer was used in a single component.

[0118] Specifically, BTDA and ODA were added in the mole ratio shown in Table 1 below to a 40° C. reactor filled with NMP, and stirred for about 30 minutes to polymerize a polyamic acid, and except for this, a polyamic acid composition was prepared in the same manner as in Example 1.

Comparative Example 7

[0119] As compared with Example 1, the second dianhydride was omitted, and PMDA of the first dianhydride as the dianhydride monomer was used in a single component.

[0120] Specifically, PMDA and BAPP were added in the mole ratio shown in Table 1 below to a reactor at 40° C. filled with NMP, and stirred for about 30 minutes to polymerize a polyamic acid, and except for this, a polyamic acid composition was prepared in the same manner as in Example 1.

Comparative Example 8

[0121] As compared with Example 1, the first dianhydride was omitted, and BPDA of the second dianhydride as the dianhydride monomer was used in a single component.

[0122] Specifically, BPDA and BAPP were added in the mole ratio shown in Table 1 below to a 40° C. reactor filled with NMP, and stirred for about 30 minutes to polymerize a polyamic acid, and except for this, a polyamic acid composition was prepared in the same manner as in Example 1.

Comparative Example 9

[0123] As compared with Example 1, the first dianhydride was omitted, and only BTDA of the second dianhydride as the dianhydride monomer was used in a single component.

[0124] Specifically, BTDA and BAPP were added in the mole ratio shown in Table 1 below to a 40° C. reactor filled with NMP, and stirred for about 30 minutes to polymerize a polyamic acid, and except for this, a polyamic acid composition was prepared in the same manner as in Example 1.

Comparative Example 10

[0125] As compared with Example 1, the first dianhydride was omitted BTDA of the second dianhydride as the dianhydride monomer was used in a single component, and BAPP and PPD were used together as the diamine monomer.

[0126] Specifically, BTDA. BAPP as the first diamine and PPD as the second diamine were added in the mole ratio shown in Table 1 below to a 40° C. reactor filled with NMP, and stirred for about 30 minutes to polymerize a polyamic acid, and except for this, a polyamic acid composition was prepared in the same manner as in Example 1.

Comparative Example 11

[0127] A polyamic acid composition was prepared in the same manner as in Example 1, except that BPDA was used instead of BTDA as the second dianhydride, and the mole ratios of the first dianhydride and the second dianhydride were changed as shown in Table 1 below.

TABLE-US-00001 TABLE 1 Composition Mole ratio Mole number of second Dianhydride Diamine Dianhydride Diamine dianhydride/mole number 1 2 1 2 1 2 1 2 of first dianhydride Example  1 PDMA BTDA BAPP —  50  50 100 — 1.00  2 PDMA BTDA BAPP —  70  30 100 — 0.42  3 PDMA BTDA BAPP —  60  40 100 — 0.67 Comparative  1 PDMA BTDA BAPP —  90  10 100 — 0.11 Example  2 PDMA BTDA BAPP —  75  25 100 — 0.33  3 PDMA BTDA BAPP —  30  70 100 — 2.33  4 PDMA BTDA BAPP —  43  57 100 — 1.32  5 — BTDA BAPP ODA — 100  50  50 —  6 — BTDA — ODA — 100 — 100 —  7 PMDA — BAPP — 100 — 100 — —  8 — BPDA BAPP — — 100 100 — —  9 — BTDA BAPP — — 100 100 — — 10 — BTDA BAPP PPD — 100  90  10 — 11 PMDA BPDA BAPP —  70  30 100 — 0.42

Experimental Example 1: Physical Property Test of Polyimide Resin

[0128] The polyamic acid compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 11 were each applied to a support in the form of a thin film and then imidized to prepare a polyimide resin in the form of a film having an average thickness of about 21 μm.

[0129] For the polyimide resin thus prepared, physical properties were tested in the following methods, and the results were shown in Table 2 below.

[0130] (1) Coefficient of Thermal Expansion (CTE)

[0131] The coefficient of thermal expansion was measured using TMA.

[0132] (2) Glass Transition Temperature (Tg)

[0133] As for the glass transition temperature, the loss elastic modulus and storage elastic modulus of each film were obtained using DMA, and the inflection point was measured as the glass transition temperature in their tangent graph.

[0134] (3) Tensile Strength

[0135] The tensile strength was measured by the method presented in KS6518.

[0136] (4) Elongation

[0137] The elongation was measured by the method presented in ASTM D1708.

TABLE-US-00002 TABLE 2 Coefficient Glass of thermal transition Tensile expansion temperature strength Elongation (ppm/° C.) (° C.) (MPa) (%) Example 1 49 282 141 106 2 44 302 146 128 3 45 297 145 115 Comparative 1 31 307 131 94 Example 2 38 304 146 112 3 54 262 135 25 4 49 271 136 19 5 38 365 121 45 6 43 277 128 25 7 34 315 138 15 8 58 257 132 75 9 60 254 135 81 10 42 281 132 21 11 38 298 141 84

[0138] As shown in Table 2, the examples showed a very good elongation of 100% or more.

[0139] In addition, the examples have a glass transition temperature of 280° C. or more and a tensile strength of 140 MPa or more, thereby satisfying the compliant heat resistance and mechanical properties, and also satisfy a thermal expansion coefficient of 40 ppm/° C. to 50 ppm/° C. suitable for semiconductor bonding.

[0140] That is, it can be seen that in the examples carried out according to the present invention, the glass transition temperature, and the elongation and the predetermined coefficient of thermal expansion related to the dimensional stability, which are difficult to be compatible with each other, are compatible at desirable levels.

[0141] On the other hand, in Comparative Examples 1 to 4 that the content ratios of the first dianhydride and the second dianhydride were out of the scope of the present invention, most of the physical properties were poor as compared to the examples, and in particular, the glass transition temperature, and the physical properties related to the dimensional stability were not compatible.

[0142] Meanwhile, in Comparative Examples 5 to 11, the polyimide resins were prepared by using conventional polyamic acid compositions prepared using monomers different from the present invention, and as in Comparative Examples 1 to 4, most of the physical properties were poor as compared to the examples.

Experimental Example 2: Adhesion Test of Polyimide Resin

[0143] The polyamic acid compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 11 were each cast on a silicon-based inorganic substrate at 35 μm and dried at a temperature range of 50° C. to 350° C. to prepare a polyimide resin in the form of a film having an average thickness of about 21 μm.

[0144] For the polyimide resin thus prepared, the adhesion was measured using the method set forth in ASTM D 3359 below, and the results were shown in Table 3 below:

[0145] A step of cutting the surface of a polyimide resin in a bonded state according to a cross cutter guide to form a grid pattern;

[0146] a step of rubbing the surface of the polyimide resin using a brush or the like, and then attaching and removing a tape on the grid pattern; and

[0147] a step of visually checking the gap pattern to calculate an area corresponding to the part removed due to the bonding release by the tape.

TABLE-US-00003 TABLE 3 Adhesion** Example 1 5B 2 5B 3 5B Comparative 1 2B Example 2 4B 3 3B 4 3B 5 3B 6 1B 7 0B 8 2B 9 5B 10 1B 11 3B **5B: smooth state substantially without any removed area; 4B: the removed area is about 5% of the total; 3B: the removed area is 5 to 15%; 2B: the removed area is 15 to 35%; 1B: the removed area is 35 to 65%; 0B: most have been removed.

[0148] In the examples, the smooth surface state was maintained without a part that the bonding was released by the tape, and the highest level of adhesion was shown among the grades according to ASTM D 3359.

[0149] In response, FIG. 1 shows a photograph that the polyimide resin of Example 1 is tested for adhesion and then the surface of the resin is photographed (an enlarged photograph at the lower right).

[0150] Referring to FIG. 1, it can be confirmed that even though the tape has been attached to the grid pattern and removed therefrom, there is substantially no removed part due to the bonding release.

[0151] It can be expected therefrom that the polyamic acid compositions and the polyimide resins according to the embodiments of the present invention can be preferably used as an adhesive for circuit bonding, in detail, a semiconductor including a silicon-based inorganic substrate, out of the limit on the adhesion of the conventional polyimide resin.

[0152] On the other hand, Comparative Examples 1 to 4, in which the content ratio of the first dianhydride and the second dianhydride was out of the scope of the present invention, exhibited remarkably poor adhesion as compared to the examples.

[0153] In this regard, FIG. 2 shows a photograph that the polyimide resin of Comparative Example 1 is tested for adhesion and then the surface of the resin is photographed. Referring to FIG. 2, it can be confirmed from Comparative Example 1 that the area removed after bonding is remarkably wide.

[0154] Consequently, it can be understood from Comparative Examples 1 to 4 that when the content of the first dianhydride and the second dianhydride falls within the scope of the present invention and they are used in an optimal ratio, excellent adhesion is finally expressed.

[0155] Other Comparative Examples except Comparative Example 9 also showed poor adhesion as compared to the examples.

[0156] In this regard, FIG. 3 shows a photograph that the polyimide resin of Comparative Example 5 is tested for adhesion and then the surface of the resin is photographed, and FIG. 4 shows a photograph that the polyimide resin of Comparative Example 6 is tested for adhesion and then the surface of the resin is photographed.

[0157] Referring to these drawings, it can be seen from Comparative Example 5 and Comparative Example 6 that the area removed after bonding is wide, whereby there is a limit to being used as an adhesive.

[0158] Although the foregoing has been described with reference to the examples of the present invention, those having ordinary knowledge in the field to which the present invention belongs will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

INDUSTRIAL APPLICABILITY

[0159] As described above, the polyamic acid composition according to the present invention has an advantage in producing a polyimide resin that physical properties related to dimensional stability, such as a coefficient of thermal expansion and an elongation, and a glass transition temperature, which are difficult to be compatible with each other, can be compatible at desirable levels, and having the highest level of adhesion.

[0160] The present invention also provides a polyimide resin prepared from the polyamic acid composition, wherein the polyimide resin has the highest level of adhesion that an area removed when measuring adhesion according to ASTM D 3359 on an inorganic substrate is less than 5% of the total, and simultaneously has a glass transition temperature of 280° C. or more, a coefficient of thermal expansion of 40 ppm/° C. or more, a tensile strength of 140 MPa or more, and an elongation of 100% or more, which may indwell very excellent characteristics.