POLYIMIDE FILM, METHOD OF PREPARING POLYIMIDE FILM, OPTICAL DEVICE INCLUDING POLYIMIDE FILM
A colorless transparent polyimide having a thickness of about 1 micrometer to about 250 micrometers, an average coefficient of thermal expansion measured in a machine direction and a transverse direction of less than or equal to about 80 parts per million/° C., an average in-plane retardation of less than or equal to about 20 nanometers, an average Yellowness Index of less than or equal to 6, and a transmittance for light at a wavelength of 370 nanometers to 740 nanometers of greater than or equal to about 80%.
1 . A colorless transparent polyimide film having:
a thickness of about 1 micrometer to about 250 micrometers;
an average coefficient of thermal expansion measured in a machine direction and a transverse direction of less than or equal to about 80 parts per million/° C., measured using thermo-mechanical analyzer at a temperature range of 50° C. to 250° C. by a method comprising:
heating the film from 25° C. to 260° C. at a heating rate of 10° C./minute, cooling the film to 40° C. at a cooling rate of 10° C./min, and heating the film from 25° C. to 250° C. at a heating rate of 10° C./minute;
an average in-plane retardation of less than or equal to about 20 nanometers, measured by Axoscan at a wavelength of 550 nanometers throughout the area of the film;
an average Yellowness Index of less than or equal to 6, measured using a spectrophotometer, and
a transmittance for light at a wavelength of 370 nanometers to 740 nanometers of greater than or equal to about 80%, measured by using CIE standard, Illuminant D65.
2 . The polyimide film according to claim 1 , comprising:
a structure unit represented by Chemical Formula 1, a structure unit represented by Chemical Formula 2, or a combination thereof:
wherein in Chemical Formulae 1 or 2,
R 10 is the same or different in each structure unit, and is independently a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic organic group,
R 11 is the same or different in each structure unit, and independently comprises a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the aromatic organic group comprises one aromatic ring, two or more aromatic rings fused together to provide a condensed ring system, or two or more moieties independently selected from one aromatic ring and two or more aromatic rings fused together to provide a condensed ring system, which are linked through a single bond or through a functional group selected from a fluorenylene group, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p wherein 1≦p≦10, (CF 2 ) q wherein 1≦q≦10, C(CH 3 ) 2 , C(CF 3 ) 2 , and C(═O)NH,
R 12 and R 13 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n7 and n8 are each independently integers ranging from 0 to 3.
3 . The polyimide film according to claim 2 , wherein the structure unit represented by Chemical Formula 1 is represented by Chemical Formula 3:
wherein in Chemical Formula 3,
R 11 , R 12 , R 13 , n7, and n8 are the same as in Chemical Formula 1.
4 . The polyimide film according to claim 2 , wherein R 11 is represented by Chemical Formula 4, Chemical Formula 5, or Chemical Formula 6:
wherein in Chemical Formula 4,
R a is selected from chemical formulae:
wherein in the chemical formulae,
R 7 and R 8 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n1 and n2 are each independently integers ranging from 0 to 4;
wherein, in Chemical Formula 5,
R 3 and R 4 are the same or different, and are independently electron withdrawing groups selected from —CF 3 , —CCl 3 , —CBr 3 , —Cl 3 , —NO 2 , —CN, —COCH 3 , and —CO 2 C 2 H 5 ,
R 5 and R 6 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n3 is an integer ranging from 1 to 4, n5 is an integer ranging from 0 to 3, provided that n3+n5 is an integer ranging from 1 to 4, and
n4 is an integer ranging from 1 to 4, n6 is an integer ranging from 0 to 3, provided that n4+n6 is an integer ranging from 1 to 4; and
wherein in Chemical Formula 6,
R 14 is O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p wherein, 1≦p≦10, (CF 2 ) q wherein, 1≦q≦10, C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, or a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the aromatic organic group comprises one aromatic ring, two or more aromatic rings fused together to provide a condensed ring system, or two or more moieties independently selected from one aromatic ring and two or more aromatic rings fused together to provide a condensed ring system, which are linked through a single bond or through a functional group selected from a fluorenylene group, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p wherein 1≦p≦10, (CF 2 ) q wherein 1≦q≦10, C(CH 3 ) 2 , C(CF 3 ) 2 , and C(═O)NH,
R 16 and R 17 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n9 and n10 are each independently integers ranging from 0 to 4.
5 . The polyimide film according to claim 2 , wherein in Chemical Formulae 1 or 2, R 11 is represented by Chemical Formula 7, and both n7 and n8 are 0:
6 . The polyimide film according to claim 1 , wherein the film comprises a structure unit represented by Chemical Formula 8, a structure unit represented by Chemical Formula 9, or a combination thereof:
7 . The polyimide film according to claim 2 , wherein the film further comprises at least one of the structure unit represented by Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, or a combination thereof:
wherein in Chemical Formula 10,
R a , R 7 , R 8 , n1, and n2 are the same as in Chemical Formula 4, and
R 1 is the same or different in each structure unit, and is independently a substituted or unsubstituted C6 to C30 aromatic organic group;
wherein in Chemical Formula 11,
R 3 , R 4 , R 5 , R 6 , n3, n4, n5, and n6 are the same as in Chemical Formula 5, and
R 2 is the same or different in each structure unit, and is independently a substituted or unsubstituted C6 to C30 aromatic organic group; and
wherein in Chemical Formula 12,
R 14 , R 16 , R 17 , n9, and n10 are the same as described in Chemical Formula 6, and
R 15 is the same or different in each structure unit, and is independently a substituted or unsubstituted C6 to C30 aromatic organic group.
8 . The polyimide film according to claim 7 , wherein in Chemical Formulae 10 to 12, R 1 , R 2 , and R 15 are the same or different, and are independently selected from chemical formulae:
wherein in the chemical formulae,
R 18 to R 29 are the same or different, and are independently deuterium, a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group,
n11 and n14 to n20 are independently integers ranging from 0 to 4, and
n12 and n13 are independently integers ranging from 0 to 3.
9 . The polyimide film according to claim 8 , wherein R 1 , R 2 , and R 15 are the same or different, and are independently selected from chemical formulae:
10 . The polyimide film according to claim 7 , wherein the structure unit represented by Chemical Formula 10 comprises a structure unit represented by Chemical Formulae 13, 14, 15, or a combination thereof, the structure unit represented by Chemical Formula 11 comprises a structure unit represented by Chemical Formulae 16, 17, 18, or a combination thereof, the structure unit represented by Chemical Formula 12 comprises a structure unit represented by Chemical Formulae 19, 20, 21, or a combination thereof:
11 . A method of preparing a colorless transparent polyimide comprising:
reacting at least one diamine selected from Chemical Formulae 22 to 24 with at least one dianhydride selected from Chemical Formulae 25 and 26 to provide a polyamic acid solution,
coating the polyamic acid solution on a surface of a polyimide-containing film, and heating to a temperature of less than 300° C. to form a polyamic acid layer on the polyimide-containing film,
heating and curing the polyamic acid layer on the polyimide-containing film to a temperature of less than 500° C. to form a polyimide film, and
separating the obtained polyimide film from the polyimide-containing film:
wherein in Chemical Formula 22,
R a is selected from chemical formulae:
wherein in chemical formulae,
R 7 and R 8 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n1 and n2 are each independently integers ranging from 0 to 4;
wherein in Chemical Formula 23,
R 3 and R 4 are the same or different, and are independently electron withdrawing groups selected from —CF 3 , —CCl 3 , —CBr 3 , —Cl 3 , —NO 2 , —CN, —COCH 3 , and —CO 2 C 2 H 5 ,
R 5 and R 6 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n3 is an integer ranging from 1 to 4, n5 is an integer ranging from 0 to 3, provided that n3+n5 is an integer ranging from 1 to 4, and
n4 is an integer ranging from 1 to 4, n6 is an integer ranging from 0 to 3, provided that n4+n6 is an integer ranging from 1 to 4;
wherein in Chemical Formula 24,
R 14 is O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p wherein, 1≦p≦10, (CF 2 ) q wherein, 1≦q≦10, C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, or a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the aromatic organic group comprises one aromatic ring, two or more aromatic rings fused together to provide a condensed ring system, or two or more moieties independently selected from one aromatic ring and two or more aromatic rings fused together to provide a condensed ring system, which are linked through a single bond or through a functional group selected from a fluorenylene group, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p wherein 1≦p≦10, (CF 2 ) q wherein 1≦q≦10, C(CH 3 ) 2 , C(CF 3 ) 2 , and C(═O)NH,
R 16 and R 17 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n9 and n10 are each independently integers ranging from 0 to 4;
wherein in Chemical Formulae 25 or 26,
R 10 is the same or different in each structure unit, and is independently a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic organic group,
R 12 and R 13 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n7 and n8 are each independently integers ranging from 0 to 3.
12 . The method according to claim 11 , wherein the diamine is represented by Chemical Formula 23, wherein both R 3 and R 4 are —CF 3 , both n3 and n4 are 1, and both n5 and n6 are 0.
13 . The method according to claim 11 , wherein the Chemical Formula 25 is represented by a structure unit represented by Chemical Formula 27:
wherein in Chemical Formulae 27, R 12 , R 13 , n7, and n8 are the same as in Chemical Formula 25.
14 . The method according to claim 11 , wherein the solid content in the polyamic acid solution is about 5 percent by weight to about 30 percent by weight, and the viscosity of the polyamic acid solution is about 1 poise to about 10,000 poise at 25° C.
15 . The method according to claim 11 , wherein the polyamic acid solution is partially imidized before coating on a surface of the polyimide-containing film.
16 . The method according to claim 11 , wherein the polyimide-containing film comprises a structure unit represented by Chemical Formula 1, a structure unit represented by Chemical Formula 2, or a combination thereof:
wherein in Chemical Formulae 1 or 2,
R 10 is the same or different in each structure unit, and is independently a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic organic group,
R 11 is the same or different in each structure unit, and independently comprises a substituted or unsubstituted C6 to C30 aromatic organic group, wherein the aromatic organic group comprises one aromatic ring, two or more aromatic rings fused together to provide a condensed ring system, or two or more moieties independently selected from one aromatic ring and two or more aromatic rings fused together to provide a condensed ring system, which are linked through a single bond or through a functional group selected from a fluorenylene group, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p wherein 1≦p≦10, (CF 2 ) q wherein 1≦q≦10, C(CH 3 ) 2 , C(CF 3 ) 2 , and C(═O)NH,
R 12 and R 13 are the same or different, and are independently a halogen, a hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic organic group, a substituted or unsubstituted C6 to C20 aromatic organic group, an alkoxy group of formula —OR 208 , wherein R 208 is a substituted or unsubstituted C1 to C10 aliphatic organic group, or a silyl group of formula —SiR 209 R 210 R 211 , wherein R 209 , R 210 , and R 211 are the same or different, and are independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group, and
n7 and n8 are each independently integers ranging from 0 to 3.
17 . The method according to claim 11 , wherein the polyimide-containing film has a thickness of about 1 micrometer to about 1,000 micrometers.
18 . The method according to claim 11 , wherein the polyimide-containing film is UPILEX X film, which is a product of UBE Industries, Ltd.
19 . The method according to claim 11 , wherein the polyimide-containing film extends longitudinally, whereby the polyimide film prepared on the polyimide-containing film is separated from the polyimide-containing film in a roll-to-roll process.
20 . An optical device comprising a polyimide film according to claim 1 .