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United States Patent 19 11 Patent Number: 5,665,802 Maki Et Al

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United States Patent 19 11 Patent Number: 5,665,802 Maki Et Al US005665802A United States Patent 19 11 Patent Number: 5,665,802 Maki et al. 45 Date of Patent: Sep. 9, 1997 54 POLYMIDE FILM AND MANUFACTURING 56 References Cited METHOD THEREOF U.S. PATENT DOCUMENTS 75) Inventors: Haruhiko Maki, Kyoto; Hirosaku 2,733,226 1/1956 Hunter ................................... 524/15 Nagano, Ohtsu; Yoshiaki Inaba, 3,047,608 7/1962 Friedman et al. ...................... 528/400 Osaka, all of Japan 3.249,588 5/1966 Gall et al. ............................... 528/352 3,551,200 12/1970 Stivers .................................... 528/35 73) Assignee: Kanegafuchi Kagaku Kogyo 3,565,847 2/1971. Dileone ................................... 524/141 Kabushiki Kaisha, Osaka, Japan 3,607,387 9/1971 Lanza et al. ........................... 428/458 3,629,180 12/1971. Yoda et al. ............................. 528/353 3,691,136 9/1972 Serres et al. ... 524/141 (21) Appl. No.:711,072 3,714,116 1/1973 Scalico ..... ... 524/147 4,448,957 5/1984 Nagaoka ..... ... 528/352 (22 Filed: Sep. 9, 1996 4,470,944 9/1984 Asakura et al. ... 524/600 4,508,861 4/1985 Avakian ................................. 524/41 Related U.S. Application Data 4,742,099 5/1988 Nagano et al. ......................... 524/15 63 Continuation of Ser. No. 494,791, Jun. 26, 1995, abandoned, OTHER PUBLICATIONS which is a continuation of Ser. No. 796,915, Nov. 26, 1991, abandoned, which is a continuation of Ser. No. 379.837, Jul. CA 104:34802u (1986) Ittiev, A. B. et al. 14, 1989, abandoned. Primary Examiner-Veronica P. Hoke 30 Foreign Application Priority Data Attorney, Agent, or Firm-Sughrue, Mion, Zinn, Macpeak Jul. 15, 1988 JPl Japan .................................. 63-177526 & Seas (51) Int. Cl. ... C08K 5/523; C08K5/521; 57 ABSTRACT C08K 5/53 The present invention provides an improved grade of poly 52 U.S. Cl. .......................... 524/141; 524/139; 524/145: imide containing an organic phosphorus compound, a film 524/147; 524/414; 524/415: 524/416; 524/417: composed thereof and a method of making the aforemen 524/154; 428/473.5 tioned film. According to the present invention, it is possible (58) Field of Search ................................ 524/141, 145, to obtain a polyimide film improved in mechanical strength. 524/153,414, 600,415, 416, 417, 139, 147, 154; 528/289, 286, 353; 428/473.5 19 Claims, No Drawings 5,665,802 1. 2 POLYMDE FILMAND MANUFACTURING Still further objects and advantages of this invention will METHOD THEREOF be apparent to anybody of ordinary skill by the detailed description below. This is a Continuation of application Ser. No. 08/494.791 As a result of extensive and intensive studies in order to filed Jun. 26, 1995, now abandoned which is a Continuation accomplish the aforementioned objects, the present inven of application Ser. No. 07/796,915 filed Nov. 26, 1991, now tors have discovered that certain compounds have a special abandoned, which is a Continuation of application Ser. No. effect of controlling the process of formation of polyimide 07/379.837 filed Jul 14, 1989, now abandoned. and, after studying the possibility of utilizing it to contribute to improvement of the resin's mechanical strength, they BACKGROUND OF THE INVENTION 10 have succeeded in improving the mechanical strength of 1. Field of the Invention polyimide without changing its molecular structure. The present invention relates to an improved polyimide The essential feature of the improved grade of polyimide and polyimide film prepared therefrom as well as a manu according to the present invention is that an organic phos phorus compound is incorporated in polyimide. facturing method of the polyimide film. 15 2. Description of the Prior Art The essential feature of the invented method of manufac Polyimide is known for its outstanding heat resistance, turing a polyimide film, on the other hand, is that an organic low-temperature resistance, resistance to chemicals, electric phosphorus compound is contained in, at least, either of a insulation property and mechanical strength etc, and has a polyimide precursor or a dehydration-cyclizing agent or the wide scope of use like, among others, electric insulation both before filming thereof. materials, heat insulation materials and base films for flex DETALED DESCRIPTION OF THE ible printed circuitboards (PCB). When used as material for NVENTION flexible PCB, which is an important use for a polyimide film, the manufactured PCB is often used for a prolonged period As polyimide, there may be included, according to the in a deformed state or subjected to repeated contraction or 25 present invention, all known grades of polyimide prepared bending. Hence, in this field of use, mechanical properties of by dehydration-cyclization of an organic solvent solution of a polyimide film are very important, especially its tensile polyamide acid as a precursor of polyimide obtainable strength and anti-bending property are critical. through reaction of an organic solvent solution of organic It is also often the case that polyimide film is used, as in diamine with organic tetracarboxylic acid dianhyhdride the manufacture of flexible PCB, in a form laminated with 30 under heating or by the use of a dehydration-cyclizing agent. a copper foil, adhesive layer and the like. In such a case the As organic diamines, there may be included, according to problem was that a laminated film as such with its thickness the present invention, any organic diamines represented by increased had its physical properties, especially repeated the general formula (I); flexural strength, markedly deteriorated or lowered. HN-R-NH2 (I) Hence, it was strongly desired to have the mechanical 35 strength of polyimide film as a base, flexural failure strength wherein R is an aliphatic group, a phenylene group, a in particular, much more improved when it was to be used naphthalene group, a biphenylene group, a by being laminated with a copperfoil and an adhesive layer. As will be described later, the present invention consists in mixing some organic phosphorus compound to polyimide, but as far as the present inventors investigated -G- group, prior arts involving the use of phosphorus compound as an N additive to heat resistant synthetic high polymer, they found out Japanese Laid-open Application No. 131249/82 and or divalent organic group of the general formula (II): Japanese Laid-open Application No. 221454/85. The 45 former relates to a thermoplastic polyamideimide resin composition in which organic phosphonite is mixed with aromatic polyamideimide and the latter discloses a tech nique relating to thermoplastic polyetherinide incorporating O)--(O) sterically hindered phenol to polyetherimide, aryl 50 where R is an alkylene group having 1 to 4 carbon atoms, phosphonite, organic phosphonite etc. Polyamideimide and O O O O R3 polyetherimide are both thermoplastic resins and, moreover, I both techniques are aimed at preventing thermal decompo -O-, -S.-, -i- -C-, -CO-, -CNH-, -N-, sition of melted thermoplastics. Thus, any of the above identified prior arts neither discloses nor suggests anyway 55 O the technical concept of the present invention. SUMMARY OF THE INVENTION The object of the present invention is to provide a grade O O of polyimide giving a polyimide film improved in mechani cal strength. (where R to R are each an aliphatic or aromatic group) or Another object of this invention is to provide a grade of the compounds thereof. Specific examples thereof are a polyimide film improved in mechanical strength. metaphenylenediamine, paraphenylenediamine, 3,3'- A further object of this invention is to provide a method dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4, for manufacturing a polyimide film improved in mechanical 4'diaminobiphenyl, 4,4'-diaminoparaterphenyl, 44-bis(4- strength. aminophenoxy)biphenyi, 4,4'-diaminooctafluorobiphenyl, 5,665,802 3 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylpropane, 2.2-bis 4-(4-aminophenoxy)phenyl) propane, 2,2-bis(4-(4- aminophenoxy)phenylhexafluoropropane, 2.2-bis(4- aminophenyl)propane, 2,2-bis(4-aminophenyl) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl) propane, 2,2-bis(3-hydroxy-4-aminophenyl) hexafluoropropane, 4,4'-diaminodiphenylmethane, bis(3- ethyl-4-aminophenyl)methane, bis(3-methyl-4- o aminophenyl)methane, bis(3-chloro-4-aminophenyl) methane, benzidine, 4,4'-diaminodiphenylsulfone, 3,3'- 10 diaminodiphenylsulfone, bis(4-(4-aminophenoxy) phenyl O: Sulfone, bis(4-(3-aminophenoxy)phenylsulfone, bis(4-(2- aminophenoxy)phenyl)sulfone, 1.4-bis(4-aminophenoxy) benzene, 1.3-bis(4-aminophenoxy)benzene, 1,3-bis(3- aminophenoxy)benzene, 14-bis(4-aminophenyl)benzene, 15 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 4,4'- or a mixture thereof. Specific examples of the compounds diaminodiphenylsulfide, 3,3'-diaminodiphenylether, 3,4'- are pyromellitic dianhydride, 2, 3, 6, 7-naphthalene tetra diaminobiphenyl ether, bis(4-(4-aminophenoxy)phenyl) carboxylic acid dianhydride, 3,3', 4,4'- ether, 4,4'-diaminodiphenylether, 2,6-diaminopyridine, bis biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'- (4-aminophenyl) diethylsilane, bis(4-aminophenyl) 20 diphenylsilane, 3,3'-dichlorobenzidine, bis(4-aminophenyl) benzophenonetetracarboxylic acid dianhydride, ethylphosfine oxide, bis(4-aminophenyl)-N-phenylamine, naphthalene-1,2,5,6-tetracarboxylic dianhydride, 2.2, 3,3'- bis(4-aminophenyl)-N-methylamine, 1,5- diphyenyltetracarboxylic acid dianhydride, 2,3,5,6- diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, pyridinetetracarboxylic acid dianhydride, 2.2-bis(3,4- 3,3'-dimethoxybenzidine, 4,4'-methylenedianiline,
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