Polyimide-polybenzoxazole precursor solution, polyimide-polybenzoxazole film, and preparation method therefor

Abstract

This invention relates to a polyimide-polybenzoxazole precursor solution, a polyimide-polybenzoxazole film, and a method of manufacturing the same, wherein a film manufactured using the polyimide-polybenzoxazole precursor solution of the invention is formed by copolymerizing a unit structure of diamine and dianhydride and a unit structure of diaminophenol and dicarbonyl chloride in an organic solvent, and is colorless and transparent, like conventional polyimide films, and can exhibit improved heat resistance and low birefringence.

1 . A polyimide-polybenzoxazole precursor solution, comprising polyhydroxyamide, which is a polymer of a diaminophenol compound and a dicarbonyl chloride compound; and polyamic acid, which is a polymer of a dianhydride compound and a diamine compound. 
     
     
         2 . The polyimide-polybenzoxazole precursor solution of  claim 1 , wherein the polyhydroxyamide is contained in an amount of 20 to 80 mol % based on a total molar amount of polyhydroxyamide and polyamic acid. 
     
     
         3 . The polyimide-polybenzoxazole precursor solution of  claim 1 , wherein the polyhydroxyamide is contained in an amount of 40 to 60 mol % based on a total molar amount of polyhydroxyamide and polyamic acid. 
     
     
         4 . The polyimide-polybenzoxazole precursor solution of  claim 1 , wherein the diaminophenol compound is at least one selected from the group consisting of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), bis(3-amino-4-hydroxyphenyl)sulfone (BAS), 3,3′ -dihydroxybenzidine (HAB), 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene. 
     
     
         5 . The polyimide-polybenzoxazole precursor solution of  claim 1 , wherein the dicarbonyl chloride compound is at least one selected from the group consisting of phthaloyl chloride, terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 4,4′ -biphenyldicarbonyl chloride (DPDOC), 4,4′ -oxybis(benzoyl chloride) (OBBOC), and naphthalene-2,3-dicarbonyl dichloride. 
     
     
         6 . The polyimide-polybenzoxazole precursor solution of  claim 1 , wherein the dianhydride compound is at least one selected from the group consisting of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), pyromellitic dianhydride (PMDA, 1,2,4,5-benzene tetracarboxylic dianhydride), 3,3,4,4-benzophenone tetracarboxylic dianhydride (BTDA), 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA), 4,4-oxydiphthalic dianhydride (ODPA), bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride (SiDA), 4,4-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride (BDSDA), sulfonyldiphthalic anhydride (SO 2 DPA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), and 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) (6HBDA). 
     
     
         7 . The polyimide-polybenzoxazole precursor solution of  claim 1 , wherein the diamine compound is at least one selected from the group consisting of 4,4′-oxydianiline (ODA), para-phenylene diamine (pPDA), meta-phenylene diamine (mPDA), para-methylene dianiline (pMDA), meta-methylene dianiline (mMDA), 1,3-bis(3-aminophenoxy)benzene (133APB), 1,3-bis(4-aminophenoxy)benzene (134APB), 2,2′-bis [4(4-aminophenoxy)phenyl]hexafluoropropane (4BDAF), 2,2′-bis(3-aminophenyl)hexafluoropropane (33-6F), 2,2′-bis(4-aminophenyl)hexafluoropropane (44-6F), bis(4-aminophenyl)sulfone (4DDS), bis(3-aminophenyl) sulfone (3DDS), 2,2′-bis(trifluoromethyl)benzidine (TFDB), 1,3-cyclohexanediamine (13CHD), 1,4-cyclohexanediamine (14CHD), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (6HMDA), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (DBOH), and 4,4′-bis(3-aminophenoxy)diphenyl sulfone (DBSDA). 
     
     
         8 . A polyimide-polybenzoxazole film, comprising a first repeating unit, obtained by a ring-closing dehydration of a polymer of a diaminophenol compound and a dicarbonyl chloride compound; and a second repeating unit, obtained by a ring-closing dehydration of a polymer of a dianhydride compound and a diamine compound. 
     
     
         9 . The polyimide-polybenzoxazole film of  claim 8 , wherein the first repeating unit is contained in an amount of 20 to 80 mol % based on a total molar amount of the first repeating unit and the second repeating unit. 
     
     
         10 . The polyimide-polybenzoxazole film of  claim 8 , wherein the first repeating unit is contained in an amount of 40 to 60 mol % based on a total molar amount of the first repeating unit and the second repeating unit. 
     
     
         11 . The polyimide-polybenzoxazole film of  claim 8 , wherein the polyimide-polybenzoxazole film has a birefringence of 0.010 or less. 
     
     
         12 . The polyimide-polybenzoxazole film of  claim 8 , wherein the polyimide-polybenzoxazole film has a coefficient of linear thermal expansion (CTE) of 55 ppm/° C. or less. 
     
     
         13 . The polyimide-polybenzoxazole film of  claim 8 , wherein the polyimide-polybenzoxazole film has a transmittance of 88% or more and a yellow index of 10 or less. 
     
     
         14 . A method of manufacturing a polyimide-polybenzoxazole film, comprising:
 polymerizing a diaminophenol compound and a dicarbonyl chloride compound, thus preparing a polyhydroxyamide solution (S1);   adding the polyhydroxyamide solution of S1 with a diamine compound and a dianhydride compound and performing polymerization to give a polyamic acid solution, thus preparing a polyimide-polybenzoxazole precursor solution (S2); and   casting the polyimide-polybenzoxazole precursor solution on a support and performing ring-closing dehydration through thermal treatment (S3).   
     
     
         15 . The method of  claim 14 , wherein the polymerizing in Si is performed at 0° C. to 20° C. for 1 to 2 hr. 
     
     
         16 . The method of  claim 14 , wherein the polymerization in S2 is performed at 25° C. to 45° C. for 2 to 5 hr. 
     
     
         17 . The method of  claim 14 , wherein the thermal treatment in S3 is performed for 60 min to 180 min through heating in a temperature range of 80° C. to 300° C. 
     
     
         18 . The method of  claim 14 , wherein an equivalent ratio of the diaminophenol compound and the dicarbonyl chloride compound in S1 is 1:0.8-1.2, and an equivalent ratio of the diamine compound and the dianhydride compound in S2 is 1:0.8-1.2. 
     
     
         19 . The method of  claim 14 , wherein an equivalent ratio of the polyhydroxyamide solution in S1 and the polyamic acid solution in S2 is 0.2-0.8:0.8-0.2.