Polyimide-based block copolymer film

Abstract

The present disclosure relates to a polyimide-based block copolymer film. The polyimide-based block copolymer film according to the present disclosure exhibits excellent an ultraviolet shielding property to be suitably used for substrates for displays, protective films for displays, touch panels, and the like.

Claims

1. A polyimide-based block copolymer film including a first repeating unit represented by Chemical Formula 1 and a second repeating unit represented by Chemical Formula 2, wherein transmittance is 13% or less with respect to ultraviolet light having a wavelength of 388 nm at a thickness of 505 m: ##STR00014## wherein, in Chemical Formula 1, each R.sup.1 is the same as or different from each other in each repeating unit, and each is independently a single bond, O, S, C(O), CH(OH), S(O).sub.2, Si(CH.sub.3).sub.2, (CH.sub.2).sub.p (wherein 1p10), (CF.sub.2).sub.q (wherein 1q10), C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, C(O)NH, or a C6 to C30 aromatic organic group; each R.sup.2 is independently H, F, Cl, Br, I, CF.sub.3, CCl.sub.3, CBr.sub.3, CI.sub.3, NO.sub.2, CN, COCH.sub.3, CO.sub.2C.sub.2H.sub.5, a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group; n1 and m1 are independently 0 to 3; each Y.sup.1 is the same as or different from each other in each repeating unit, and each independently comprises a C6 to C30 aromatic organic group, and the aromatic organic group exists alone, or two or more aromatic organic groups are bonded to each other to form a condensed ring, or two or more aromatic organic groups are linked by a single bond, a fluorenyl group, O, S, C(O), CH(OH), S(O).sub.2, Si(CH.sub.3).sub.2, (CH.sub.2).sub.p (wherein 1p10), (CF.sub.2).sub.q (wherein 1q10), C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, or C(O)NH; x is an integer of 2 or more, and each repeating unit which is repeated two or more times by x may be the same as or different from each other; E.sup.1, E.sup.2, and E.sup.3 are independently a single bond, NH, or C(O); and each Z.sup.1 is the same as or different from each other in each repeating unit, and each is independently a trivalent linking group derived from at least one compound selected from the group consisting of triacyl halide, tricarboxylic acid, and tricarboxylate;
*E.sup.4-Y.sup.2-E.sup.5-Z.sup.2-E.sup.6*[Chemical Formula 2] wherein, in Chemical Formula 2, each Y.sup.2 is the same as or different from each other in each repeating unit, and each independently comprises a C6 to C30 aromatic organic group, and the aromatic organic group exists alone, or two or more aromatic organic groups are bonded to each other to form a condensed ring, or two or more aromatic organic groups are linked by a single bond, a fluorenyl group, O, S, C(O), CH(OH), S(O).sub.2, Si(CH.sub.3).sub.2, (CH.sub.2).sub.p (wherein 1p10), (CF.sub.2).sub.q (wherein 1q10), C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, or C(O)NH; E.sup.4, E.sup.5, and E.sup.6 are independently a single bond, NH, or C(O); and each Z.sup.2 is the same as or different from each other in each repeating unit, and each is independently a divalent linking group derived from at least one compound selected from the group consisting of diacyl halide, dicarboxylic acid, and dicarboxylate.

2. The polyimide-based block copolymer film of claim 1, wherein the first repeating unit comprises a repeating unit represented by Chemical Formula 3: ##STR00015## wherein, in Chemical Formula 3, each R.sup.1 is the same as or different from each other in each repeating unit, and each is independently a single bond, O, S, C(O), CH(OH), S(O).sub.2, Si(CH.sub.3).sub.2, (CH.sub.2).sub.p (wherein 1p10), (CF.sub.2).sub.q (wherein 1q10), C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, C(O)NH, or a C6 to C30 aromatic organic group; R.sup.2 is independently H, F, Cl, Br, I, CF.sub.3, CCl.sub.3, CBr.sub.3, CI.sub.3, NO.sub.2, CN, COCH.sub.3, CO.sub.2C.sub.2H.sub.5, a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group; each R.sup.3 is the same as or different from each other in each repeating unit, and each is independently a single bond, O, S, S(O).sub.2, Si(CH.sub.3).sub.2, a C1 to C30 aliphatic organic group, a C3 to C30 alicyclic organic group, a C6 to C30 aromatic organic group, a C2 to C30 heterocyclic group, or a C13 to C20 fluorenyl group; each R.sup.4 is independently CF.sub.3, CCl.sub.3, CBr.sub.3, CI.sub.3, F, Cl, Br, I, NO.sub.2, CN, COCH.sub.3, or CO.sub.2C.sub.2H.sub.5; n1 and m1 are independently 0 to 3; n2 and m2 are independently 1 to 4; x is an integer of 2 or more, and each repeating unit which is repeated two or more times by x may be the same as or different from each other; E.sup.1, E.sup.2, and E.sup.3 are independently a single bond, NH, or C(O); and each Z.sup.1 is the same as or different from each other in each repeating unit, and each is independently a trivalent linking group derived from at least one compound selected from the group consisting of triacyl halide, tricarboxylic acid, and tricarboxylate.

3. The polyimide-based block copolymer film of claim 1, wherein the second repeating unit comprises a repeating unit represented by Chemical Formula 4: ##STR00016## wherein, in Chemical Formula 4, each R.sup.5 is the same as or different from each other in each repeating unit, and each is independently a single bond, O, S, S(O).sub.2, Si(CH.sub.3).sub.2, a C1 to C30 aliphatic organic group, a C3 to C30 alicyclic organic group, a C6 to C30 aromatic organic group, a C2 to C30 heterocyclic group, or a C13 to C20 fluorenyl group; each R.sup.6 is independently H, F, Cl, Br, I, CF.sub.3, CCl.sub.3, CBr.sub.3, CI.sub.3, NO.sub.2, CN, COCH.sub.3, CO.sub.2C.sub.2H.sub.5, a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group; n3 and m3 are independently 1 to 4; E.sup.5, and E.sup.6, and E.sup.7 are independently a single bond, NH, or C(O); and each Z.sup.2 is the same as or different from each other in each repeating unit, and each is independently a divalent linking group derived from at least one compound selected from the group consisting of diacyl halide, dicarboxylic acid, and dicarboxylate.

4. The polyimide-based block copolymer film of claim 1, wherein Z.sup.1 is a trivalent linking group derived from at least one compound selected from the group consisting of 1,3,5-benzenetricarbonyl trichloride, 1,2,4-benzenetricarbonyl trichloride, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, trimethyl 1,3,5-benzenetricarboxylate, and trimethyl 1,2,4-benzenetricarboxylate; and Z.sup.2 is a divalent linking group derived from at least one compound selected from the group consisting of isophthaloyl dichloride (IPC), isophthalic acid, cyclohexane-1,3-dicarbonyl chloride, cyclohexane-1,3-dicarboxylic acid, pyridine-3,5-dicarbonyl chloride, pyridine-3,5-dicarboxylic acid, pyrimidine-2,6-dicarbonyl chloride, pyrimidine-2,6-dicarboxylic acid, terephthaloyl chloride (TPC), terephthalic acid, cyclohexane-1,4-dicarbonyl chloride, cyclohexane-1,4-dicarboxylic acid, pyridine-2,5-dicarbonyl chloride, pyridine-2,5-dicarboxylic acid, pyrimidine-2,5-dicarbonyl chloride, pyrimidine-2,5-dicarboxylic acid, 4,4-biphenyldicarbonyl chloride (BPC), and 4,4-biphenyldicarboxylic acid.

5. The polyimide-based block copolymer film of claim 1, wherein the first repeating unit comprises a repeating unit represented by Chemical Formula 5a, and X.sup.1 of Chemical Formula 5a is a repeating unit represented by Chemical Formula 5b and X.sup.2 is a repeating unit represented by Chemical Formula 5c: ##STR00017## wherein, in Chemical Formulae 5a, 5b, and 5c, each R.sup.4 is independently F, Cl, Br, I, CF.sub.3, CCl.sub.3, CBr.sub.3, CI.sub.3, NO.sub.2, CN, COCH.sub.3, or CO.sub.2C.sub.2H.sub.5; n2 and m2 are independently 1 to 4; and xb and xc are independently an integer of 1 or more.

6. The polyimide-based block copolymer film of claim 5, wherein an equivalent ratio of the repeating unit represented by Chemical Formula 5b and the repeating unit represented by Chemical Formula 5c is 1:1.1 to 1:2.0.

7. The polyimide-based block copolymer film of claim 1, wherein the second repeating unit comprises a repeating unit represented by Chemical Formula 6: ##STR00018## wherein, in Chemical Formula 6, each R.sup.6 is independently H, F, Cl, Br, I, CF.sub.3, CCl.sub.3, CBr.sub.3, CI.sub.3, NO.sub.2, CN, COCH.sub.3, CO.sub.2C.sub.2H.sub.5, a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group; n3 and m3 are independently 1 to 4; and A is a C6 to C20 divalent aromatic organic group, a C4 to C20 divalent heteroaromatic organic group, a C6 to C20 divalent alicyclic organic group, or a divalent organic group in which two or more of the organic groups are linked by a single bond, a fluorenyl group, O, S, C(O), CH(OH), S(O).sub.2, Si(CH.sub.3).sub.2, (CH.sub.2).sub.p (wherein 1p10), (CF.sub.2).sub.q (wherein 1q10), C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, or C(O)NH.

8. The polyimide-based block copolymer film of claim 1, wherein a weight ratio of the first repeating unit to the second repeating unit is 1:0.25 to 1:4.

9. The polyimide-based block copolymer film of claim 1, wherein a weight average molecular weight of the polyimide-based block copolymer is 100,000 to 5,000,000 g/mol.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an NMR spectrum of the polyimide-based copolymer obtained in Example 1.

(2) FIG. 2 is a graph showing the measurement results of the total light transmittance of the polyimide-based films according to Example 4 and Comparative Example 2.

(3) FIG. 3 is a graph showing the measurement results of the total light transmittance of the polyimide-based films according to Example 5, Comparative Example 2, and Reference Example 2.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(4) Hereinafter, preferred examples are provided for better understanding. However, these examples are for illustrative purposes only, and the invention is not intended to be limited by these examples.

Example 1

(5) 1.01 eq. of 2,2-bis(trifluoromethyl)benzidine; 0.3275 eq. of 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA); 0.655 eq. of 4,4-biphthalic anhydride (BPDA); 0.005 eq. of benzene-1,3,5-tricarbonyl trichloride; and 14 wt % of dimethylacetamide were placed to a 250 mL round flask equipped with a Dean-Stark apparatus and a condenser, and the reaction was initiated at room temperature. The reaction mixture was stirred at 0 C. using ice water under a nitrogen atmosphere.

(6) After 4 hours, the reaction product was taken out and allowed to return to room temperature, 0.99 eq. of 2,2-bis(trifluoromethyl)benzidine, 1.01 eq. of terephthaloyl chloride (TPC), and 120 ml of dimethylacetamide were added thereto, and the reaction was initiated under a nitrogen atmosphere at room temperature.

(7) After forming the polyamic acid polymer by reaction for 4 hours, 14 mL (10 eq., 0.15 mol) of acetic anhydride and 12 mL (10 eq., 0.15 mol) of pyridine were added to the reaction mixture, and the mixture was stirred in an oil bath at 40 C. for 15 hours to carry out the chemical imidization reaction.

(8) After completion of the reaction, the mixture was precipitated with water and ethanol to obtain a polyimide-based block copolymer having the following repeating units (with a weight average molecular weight of 490,000 g/mol, and a ratio of the first repeating unit to the second repeating unit of 1:1).

(9) ##STR00012##

(10) .sup.1H NMR (DMSO-d6, TMS as standard material) (ppm): 10.818 (s), 8.534 (s), 8.460 (s), 8.379 (s), 8.266 (d), 8.169 (s), 8.104 (d), 7.941 (d), 7.798 (s), 7.708 (s), 7.416 (s)

Example 2

(11) 1.01 eq. of 2,2-bis(trifluoromethyl)benzidine; 0.4323 eq. of 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA); 0.5502 eq. of 4,4-biphthalic anhydride (BPDA); 0.005 eq. of benzene-1,3,5-tricarbonyl trichloride; and 14 wt % of dimethylacetamide were placed to a 250 mL round flask equipped with a Dean-Stark apparatus and a condenser, and the reaction was initiated at room temperature. The reaction mixture was stirred at 0 C. using ice water under a nitrogen atmosphere.

(12) After 4 hours, the reaction product was taken out and allowed to return to room temperature, 0.99 eq. of 2,2-bis(trifluoromethyl)benzidine, 1.01 eq. of terephthaloyl chloride (TPC), and 120 ml of dimethylacetamide were added thereto, and the reaction was initiated under a nitrogen atmosphere at room temperature.

(13) After forming the polyamic acid polymer by reaction for 4 hours, 14 mL (10 eq., 0.15 mol) of acetic anhydride and 12 mL (10 eq., 0.15 mol) of pyridine were added to the reaction mixture, and the mixture was stirred in an oil bath at 40 C. for 15 hours to carry out the chemical imidization reaction.

(14) After completion of the reaction, the mixture was precipitated with water and ethanol to obtain a polyimide-based block copolymer having the same repeating units as in Example 1 (with a weight average molecular weight of 490,000 g/mol, and a ratio of the first repeating unit to the second repeating unit of 1:1).

Example 3

(15) 1.01 eq. of 2,2-bis(trifluoromethyl)benzidine; 0.3275 eq. of 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA); 0.655 eq. of 4,4-biphthalic anhydride (BPDA); 0.005 eq. of benzene-1,3,5-tricarbonyl trichloride; and 14 wt % of dimethylacetamide were placed to a 250 mL round flask equipped with a Dean-Stark apparatus and a condenser, and the reaction was initiated at room temperature. The reaction mixture was stirred at 0 C. using ice water under a nitrogen atmosphere.

(16) After 4 hours, the reaction product was taken out and allowed to return to room temperature, 0.99 eq. of 2,2-bis(trifluoromethyl)benzidine, 0.5 eq. of isophthaloyl dichloride (IPC), 0.5 eq. of 4,4-biphenyldicarbonyl chloride (BPC), and 120 ml of dimethylacetamide were added thereto, and the reaction was initiated under a nitrogen atmosphere at room temperature.

(17) After forming the polyamic acid polymer by reaction for 4 hours, 14 mL (10 eq., 0.15 mol) of acetic anhydride and 12 mL (10 eq., 0.15 mol) of pyridine were added to the reaction mixture, and the mixture was stirred in an oil bath at 40 C. for 15 hours to carry out the chemical imidization reaction.

(18) After completion of the reaction, the mixture was precipitated with water and ethanol to obtain a polyimide-based block copolymer having the following repeating units (with a weight average molecular weight of 490,000 g/mol, and a ratio of the first repeating unit to the second repeating unit of 1:1).

(19) ##STR00013##

Comparative Example 1

(20) A polyimide-based copolymer (with a weight average molecular weight of 160,000 g/mol, and a ratio of the first repeating unit to the second repeating unit of 1:1) was obtained in the same manner as in Example 1, except that the 4,4-biphthalic anhydride (BPDA) was not used.

Reference Example 1

(21) 1.01 eq. of 2,2-bis(trifluoromethyl)benzidine; 0.49125 eq. of 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA); 0.49125 eq. of 4,4-biphthalic anhydride (BPDA); 0.005 eq. of benzene-1,3,5-tricarbonyl trichloride; and 14 wt % of dimethylacetamide were placed to a 250 mL round flask equipped with a Dean-Stark apparatus and a condenser, and the reaction was initiated at room temperature. The reaction mixture was stirred at 0 C. using ice water under a nitrogen atmosphere.

(22) After 4 hours, the reaction product was taken out and allowed to return to room temperature, 0.99 eq. of 2,2-bis(trifluoromethyl)benzidine, 1.01 eq. of terephthaloyl chloride, and 120 ml of dimethylacetamide were added thereto, and the reaction was initiated under a nitrogen atmosphere at room temperature.

(23) After forming the polyamic acid polymer by reaction for 4 hours, 14 mL (10 eq., 0.15 mol) of acetic anhydride and 12 mL (10 eq., 0.15 mol) of pyridine were added to the reaction mixture, and the mixture was stirred in an oil bath at 40 C. for 15 hours to carry out the chemical imidization reaction.

(24) After completion of the reaction, the mixture was precipitated with water and ethanol to obtain a polyimide-based block copolymer having the same repeating units as in Example 1 with a (weight average molecular weight of 490,000 g/mol).

Example 4

(25) A film was prepared using the polyimide-based copolymer obtained in Example 1. Specifically, the polyimide-based copolymer was dissolved in dimethylacetamide to prepare a polymer solution of about 25% (w/V). The polymer solution was poured on a glass plate, the thickness of the polymer solution was uniformly adjusted using a film applicator, and was dried in a vacuum oven at 100 C. for 12 hours or more to obtain a polyimide-based film.

Example 5

(26) A polyimide-based film having a thickness of 50 m was obtained in the same manner as in Example 4, except that the polyimide-based copolymer obtained in Example 2 was used in place of the copolymer obtained in Example 1.

Example 6

(27) A polyimide-based film having a thickness of 50 m was obtained in the same manner as in Example 4, except that the polyimide-based copolymer obtained in Example 3 was used in place of the copolymer obtained in Example 1.

Comparative Example 2

(28) A polyimide-based film having a thickness of 50 m was obtained in the same manner as in Example 4, except that the polyimide-based copolymer obtained in Comparative Example 1 was used in place of the copolymer obtained in Example 1.

Reference Example 2

(29) A polyimide-based film having a thickness of 50 m was obtained in the same manner as in Example 4, except that the polyimide-based copolymer obtained in Reference Example 1 was used in place of the copolymer obtained in Example 1.

EXPERIMENTAL EXAMPLES

(30) The total light transmittance of the films according to the examples and comparative examples was measured using a UV-VIS-NIR spectrophotometer (SolidSpec-3700, SHIMADZU).

(31) The measurement results of the total light transmittance of the films of Example 4 and Comparative Example 2 are shown in FIG. 2.

(32) The measurement results of the total light transmittance of the films of Example 5, Comparative Example 2, and Reference Example 2 are shown in FIG. 3.

(33) In addition, the transmittance values of the films of Example 4, Example 5, and Comparative Example 2 with respect to ultraviolet light having a wavelength of 388 nm are shown in Table 1 below.

(34) TABLE-US-00001 TABLE 1 Comparative Example 4 Example 5 Example 2 Transmittance 12.10 11.09 82.58 (%, @ 388 nm)

(35) Referring to Table 1, it was confirmed that the films according to the above examples exhibit a remarkably excellent ultraviolet shielding property compared with the film of Comparative Example 2.

(36) In addition, referring to FIG. 3, it was confirmed that the film according to Reference Example 2 had a transmittance value of 38.92% with respect to ultraviolet light having a wavelength of 388 nm. Thus, it was confirmed that its ultraviolet shielding property was worse than that of the films of the above examples.