Low temperature curable polyimide resin and method of preparing the same
In a method for preparing a polyimide resin by reacting diamine and dianhydride, the polyimide resin is polymerized under the presence of a solvent having a boiling point ranging from 130° C. to 180° C. so as to be curable at a low temperature ranging from 150° C. to 250° C. Because the polyimide is curable even at a low temperature, when the polyimide resin is used as an electronic material, damage to equipment due to an otherwise high temperature process can be minimized, and in addition, the polyimide resin can be extensively used as an electronic material such as for a plastic substrate, or the like.
1. A method for preparing a polyimide resin, the method comprising:
a polymerization process resulting in 10 ppm to 200 ppm of the catalyst in the soluble polyimide resin after polymerization process, the polymerization process having the steps of:
polymerizing a soluble polyimide resin using a monomer comprising one or more dianhydrides and aromatic diamines including a phenolic hydroxyl group, a carboxyl group, or a hydroxyl group,
under the presence of a catalyst of triethylamine having a boiling point ranging from about 60° C. to about 100° C. in a solvent having a boiling point ranging from about 130° C. to about 180° C., and
refluxing said soluble polyimide resin in the solvent until the remaining amount of the catalyst in the soluble polyimide resin is 10 ppm to 200 ppm,
wherein the soluble polyimide resin is directly prepared without performing a step for preparing a polyamic acid precursor,
wherein the polymerization is performed at a temperature ranging from 120° C. to 160° C. for five hours or less,
wherein the catalyst is used in the amount of 0.5 weight parts to 30 weight parts over 100 weight parts of the monomers, and
wherein a weight average molecular weight of the polyimide resin ranges from 1,000 to 100,000.
2. The method of claim 1 , wherein the solvent is one or more selected from the group consisting of diethyleneglycol methylethylether, diethyleneglycol dimethylether, diethyleneglycol diethylether, dipropyleneglycol dimethylether, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol methylether propionate, dipropyleneglycol dimethylether, cyclohexanone, and propyleneglycolmonomethyletheracetate (PGMEA).
3. The method of claim 1 , wherein the solvent is used in the amount of 20 weight parts to 2000 weight parts over 100 weight parts of the monomer for preparing a polyimide resin.
4. The method of claim 1 , wherein the aromatic diamines have a bivalent organic group selected from the group consisting of
and a 3,5-diaminobenzoic acid.
5. The method of claim 1 , wherein the monomer further comprises one or more aromatic or aliphatic diamines selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4′-diaminodiphenylether, 3,4′-diaminodiphenylether, 3,3′-diaminodiphenylether, 4,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylmethane, 3,4′-diaminophenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-methylene-bis(2-methylaniline), 4,4′-methylene-bis(2-isopropyl-6-methylaniline), 4,4′-methylene-bis(2,6-didsopropylaniline), 4,4′-methylene-bis(2-isopropyl-6-methylaniline), 4,4′-methylene-bis(2,6-diisopropylaniline), 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3′,5,5′-tetramethylbenzidine, 2,2′-bis(trifluoromethyl)benzidine, 1,4-bis(4-amoniphenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxyl)phenyl]sulfone, bis[4-(3-aminophenoxyl)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxyl)phenyl]propane, 2,2-bis[4-(3-aminophenoxyl)phenyl]propane, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bix(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,2-bis-(2-aminoethoxyl)ethane, bis(3-aminopropyl)ether, 1,4-bis(3-amonipropyl)piperazine, 3,9-bis(3-amonopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, and 1-3-bis(3-aminopropyl)tetramethyldisiloxane.
6. The method of claim 1 , wherein the dianhydrides are selected from the group consisting of one or more acid anhydrides selected from the group consisting of anhydrous pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride, butane-1,2,3,4-tetracarboxylic acid dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride, 3,3′4,4′-diphenylethertetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride, 2,2-bis(3,4,-dicarboxyphenyl)hexafluoroisopropylidine dianhydride, 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic acid dianhyride, 4,4′-hexafluoroisopropylidenediphthalic acid dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,4,-dicarboxy-1,2,3,4-tetrahydro-1-naphthalane succinic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2,-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic acid dianhydride, bicycle[2,2,2]octo-7-en-2,3,5,6-tetracarboxilic acid dianhydride, 2,3,4,5-tetrahydropuranetetracarboxylic acid dianhydride, and 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride, and their derivatives.