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1、精选文档 United States PatentUnited States Patent Kumagawa ,Kumagawa , et al. et al. 4,725,4844,725,484 February 16, 1988February 16, 1988 Dimensionally stablepolyimide filmpolyimide filmand process for preparation thereof AbstractAbstract A dimensionally stable polyimidefilmfilm and processes for the p
2、reparation thereof. The polyimidefilmfilmis composed of an aromatic polyimide obtained from a solution of a polymer formed by polymerization of a biphenyl-tetracarboxylic acid and a phenylene diamine, wherein the average linear expansion coefficient of the polyimidefilmfilm in the temperature range
3、of from 50.degree. C. to 300.degree. C. is 0.1.times.10.sup.-5 to 2.5.times.10.sup.-5 cm/cm.degree.C., the ratio of the linear expansion coefficient in the machine direction of thefilmfilm to the linear expansion coefficient in the transverse direction of the filmfilmis in the range of from 1/5 to 4
4、, and the thermal dimension stability expressed by the ratio of the change of the size of thefilmfilm at normal temperature after the heat treatment where the temperature is elevated to 400.degree. C. from normal temperature and thefilmfilm is maintained at 400.degree. C. for 2 hours is less than 0.
5、3%. Kumagawa; KiyoshiKumagawa; Kiyoshi (Ube, JPJP), Kuniyasu; Kenji, Kuniyasu; Kenji (Ube, JPJP), , Inventors: Nishino; ToshiyukiNishino; Toshiyuki (Ube, JPJP), Matsui; Yuji, Matsui; Yuji (Ube, JPJP) Assignee: Ube Industries, Ltd.Ube Industries, Ltd. (Yamaguchi, JPJP) Appl. No.: 06/864,29906/864,299
6、 Filed:May 16, 1986May 16, 1986 Foreign Application Priority DataForeign Application Priority Data 精选文档 精选文档 May 17, 1985 JP May 17, 1985 JP Current U.S. Class:Current U.S. Class: 60-103674 60-103675 428/220428/220 ; 428/473.5; 428/901; 528/353 CurrentCurrent InternationalInternational Class:Class:C
7、08J 5/18(20060101); B32B 027/28(); B32B 027/34(); C08G 069/26() Field of Search:Field of Search:428/473.5,220,901 528/353 264/212 References CitedReferences Cited Referenced ByReferenced By Foreign Patent DocumentsForeign Patent Documents Jan., 1980 Jan., 1980 007805 0007805 JP JP Primary Examiner:
8、Herbert; Thomas J. Attorney, Agent or Firm: Burgess, Ryan cm/cm/.degree.C.)wasdetermined according to the following procedures. Namely, a test piece (5 mm.times.20 mm) was set at a thermal mechanical analysis apparatus (supplied by Rigaku Denki K. K.) adopting the tensile load method, and the temper
9、ature was elevated at a rate of 10.degree. C./min to 300.degree. C. from normal temperature. The test piece was maintained at 300.degree. C. for 1 minute, and the temperature was lowered to normal temperature at a rate of 5.degree. to 20.degree. C./min. The average linear expansion coefficient calcu
10、lated from the change (.DELTA.L.sub.1) of the length observed when the temperature was lowered from 300.degree. C. to 50.degree. C. and the original length (L.sub.1 ; 10 mm) of the test piece according to the following calculation formula: The thermal dimension stability was determined according to
11、the following procedures. A dehydrated test piece (5 mm.times.20 mm) was set at the same thermal mechanical analysis apparatus as described above, and the temperature was elevated at a rate of 10.degree. C./min from normal 精选文档 精选文档 temperature to 400.degree. C. The test piece was maintained at 400.
12、degree. C. for 2 hours and the temperature was lowered at a rate of 5.degree. to 20.degree. C./min to normal temperature. The thermal dimension stability was calculated from the difference (.DELTA.L.sub.2) between the length of the test piece at normal temperature before the heating and the length o
13、f the test piece at normal temperature after the heating and the original length (L.sub.2 ; 10 mm) of the test piece according to the following calculation formula: EXAMPLE 1 (Preparation of Dope) A cylindrical polymerization tank having an inner capacity of 50 l was chargedwith38.1kgofN,N-dimethyla
14、cetamide,and5.2959kgof 3,3,4,4-biphenyltetracarboxylic dianhydride was added and 1.9466 kg of p-phenylene diamine was gradually added with stirring. The reaction liquid was stirred at 30.degree. C. for about 10 hours to effect polymerization between both the components and form a polyamic acid. The
15、logarithmic viscosity number (as determined at 30.degree. C.) of the polyamic acid formed by the polymerization reaction was 3.10, and the rotation viscosity (as determined at 30.degree. C.) of the solution of the polyamic acid was 25,000 poise. (Formation of theFilmFilm) The solution of thepolyamic
16、 acid wasused as thefilmfilm-forming dope. The dope was extruded at 30.degree. C. in the form of a thin layer through a slit of T-die (lip distance =0.5 mm, lip width =650 mm), and the thin layer of the dopewas continuously supplied onto a smooth metalbelt and was subjected to the drying of the firs
17、t stage on the belt by hot air maintained at about 120.degree. C. to form a solidifiedfilmfilmmember. Then, the solidifiedfilmfilm member was peeled from the belt and was cut into a square piece having a side of 200 mm. One side of the square piece of the filmfilm member was secured to a frame by a
18、pin sheet, and a load of about 35 g was uniformly applied to the opposite sides of the square piece along the entire width thereof by dancers to place the square piece under a low tension (a tension of 7.0 g/mm.sup.2 with respect to the machine direction of the solidifiedfilmfilmmember). In this sta
19、te, the temperature was elevated to 190.degree. C. over a period of about 30 seconds and the drying of the second stage was carried out at 190.degree. C. for 5 minutes to form a solidifiedfilmfilm. The four sides of the square piece of the solidifiedfilmfilm were held and fixed by pin tenter, and th
20、e temperature 精选文档 精选文档 of the solidifiedfilmfilm was elevated at a rate of about10.degree. C./min and thefilmfilmwas dried and heat-treated (imidized) at 450.degree. C. for 30 minutes to form an aromatic polyimidefilmfilm having a thickness of 25 .mu.m. The contents of the volatile components such
21、as the solvent and formed water in the solidifiedfilmfilm member after the drying ofthe first stage, the solidifiedfilmfilm after the drying of the second stage under a low tension and the aromatic polyimidefilm,film,and the properties of the obtained aromatic polyimidefilmfilm are shown in Table 1.
22、 COMPARATIVE EXAMPLE 1 An aromatic polyimidefilmfilm was prepared in the same manner as described in Example 1 except that the square piece of the solidifiedfilmfilm member was not subjected tc the drying of the second stage but was directly dried and heat-treated in the high-temperature heat treatm
23、ent apparatus. The obtained results are shown in Table 1. EXAMPLE 2 A solution of a polyamic acid prepared in the same manner as described in Example 1 was used as thefilmfilm-forming dope, and the dope was extruded at about 30.degree. C. in the form of a thin layer through a slip of a T-die (lip di
24、stance =0.5 mm, lip width =650 mm) and the thin layer of the dope was continuously placed on a smooth metal belt. Thefilmfilmwas subjected to the drying of the first stage on the belt by hot air maintained at about 120.degree. C. to form a solidifiedfilmfilm member continuously. Then, the solidified
25、filmfilm member was peeled from the belt and was supplied to a longitudinal furnace (drying temperature =180.degree. C.) under a low tension (shown in Table 1) produced by dancers and passed through the furnace over a period of about 4 minutes to effect the drying of the second stage and form a soli
26、difiedfilmfilm. Then, the solidifiedfilmfilmwas supplied into a high-temperature heating furnace, and in this furnace, both the end edges in the machine direction of thefilmfilmwere held by a lateral tenter and thefilmfilm was dried and heat-treated by hot air, the temperature of which was gradually
27、 elevated from about 250.degree. C. to about 450.degree. C., while moving thefilmfilm through the furnace, whereby imidization was effected and an aromatic polyimidefilmfilmwas continuously prepared. Finally, thefilmfilm was wound in the form of a roll under cooling. Wrinkles were not formed when th
28、e dried and heat-treated aromatic polyimidefilmfilmwas wound in the form of a roll, and the appearance of the 精选文档 精选文档 rolledfilmfilm was good. In the aromatic polyimidefilmfilmobtained according to the above-mentioned filmfilm-forming process, the imidization degree was at least 95%, and the heatr
29、esistanceexpressedbythethermaldecomposition-initiating temperature was higher than 450.degree. C. Furthermore, when the physical properties of thefilmfilm in the MD direction were measured at the tensile test at 20.degree. C., it was found that the tensile strength was 55 kg/mm.sup.2, the elongation
30、 was 47% and the initial tensile elasticity modulus was 870 kg/mm.sup.2. Thepropertiesofthefilmsattherespectivestagesofthe above-mentionedfilmfilm-forming process and the properties of the obtained aromatic polyimidefilmfilm are shown in Table 1. Comparative Example 2 An aromatic polyimidefilmfilm w
31、as prepared in the same manner as described in Example 2 except that the drying of the second stage was not carried out at all. The obtained results are shown in Table 1. EXAMPLE 3 An aromatic polyimidefilmfilm having a thickness of 25 .mu.m was prepared in the same manner as described in Example 2
32、except that the tension applied at the drying of the second stage was changed to 40 g/mm.sup.2. When the dried and heat-treated aromatic polyimidefilmfilmwas wound in the form of a roll, wrinkles were not formed at all, and the appearance of the rolledfilmfilm was good. In the obtained aromatic poly
33、imidefilm,film, the imidization degree was at least 95%, and the heat resistance of thefilmfilm expressed by the thermal decomposition-initiating temperature was higher than 450.degree. C. When the physical propertiesof thefilmfilmin the MD directionwere measured at the tensile test at 20.degree. C.
34、, it was found that the tensile strength was 50 kg/mm.sup.2, the elongation was 44% and the initial tensile elasticity modulus was 940 kg/mm.sup.2. The volatile component contents and properties of the films at the respective stages of the above-mentionedfilmfilm-forming process are shown in Table 1
35、. EXAMPLE 4 精选文档 精选文档 An aromatic polyimidefilmfilm having a thickness of 25 .mu.m was prepared in the same manner as described in Example 2 except that at the drying of the second stage, both the end edges of the solidifiedfilmfilm member in the machine direction were held at a certain distance so
36、that a tension of about 80 g/mm.sup.2 was imposed on thefilmfilm member. When the dried and heat-treated aromatic polyimidefilmfilmwas wound in the form of a roll, wrinkles were not formed at all and the appearance of the filmfilm in the rolled state was very good. In the obtained aromatic polyimide
37、film,film, the imidization degree was at least 95%, and the heat resistance of thefilmfilm expressed by the thermal decomposition-initiating temperature was higher than 450.degree. C. When the physical properties of thefilmfilm in the MD direction were determined at the tensile test at 20.degree. C.
38、, it was found that the tensile strength was 52 kg/mm.sup.2, the elongation was 37% and the initial tensile elasticity modulus was 1010 kg/mm.sup.2. The obtained results are shown in Table 1. EXAMPLE 5 An aromatic polyimidefilmfilm was prepared in the same manner as described in Example 2 except tha
39、t the width of the lateral pin tenter in the high-temperature heat treatment furnace was gradually increased so that the width of the pin tenter at the maximum temperature zone of the furnace was about 1.04 times the width at the outlet of the furnace. The obtained results are shown in Table 1. TABL
40、E1 _ _ Content (% by weight) of Volatile Components Tension (g/mm.sup.2) on Linear Expansion Thermal SolidifiedFilmFilm Aromatic Poly- Solidified FilmFilmCoefficient Dimension Member after SolidifiedFilmFilmimideFilmFilmMember at Drying (cm/cm/.degree.C.) Stability Drying of First after Drying of af
41、ter Heat of Second Stage (.times. 10.sup.-5) (%) Stage Second Stage TreatmentMDTDMDTDMDTD _ _ Example 1 35 13.0 below 0.01 7.0 free 1.8 2.0 0.18 0.27 Comparative 35 - below 0.01 - - 1.1 1.3 0.50 0.47 Example 1 Example 2 33 17.0 below 0.01 10 free 1.6 1.7 0.15 0.09 Comparative 33 - below 0.01 - - 0.5
42、 0.8 0.52 0.42 Example 2 Example 3 33 17.5 below 0.01 40 free 1.0 1.8 0.21 0.10 精选文档 精选文档 Example 4 33 18.0 below 0.01 80 free 1.1 1.3 0.23 0.18 Example 5 33 18.0 below0.0110free1.41.20.180.17 _ _ EXAMPLE 6 (Preparation of Dope) A cylindrical polymerization tank having an inner capacity of 50 l was
43、chargedwith38.1kgofN,N-dimethylacetamide,and5.2959kgof 3,3,4,4-biphenyltetracarboxylic dianhydride was added and 1.9466 kg of p-phenylene diamine was gradually added with stirring. The reaction liquid was stirred at 30.degree. C. for about 10 hours to effect polymerization between both the component
44、s and form a polyamic acid. The logarithmic viscosity number (as determined at 30.degree. C.) of the polyamic acid formed by the polymerization reaction was 3.10, and the rotation viscosity (as determined at 30.degree. C.) of the solution of the polyamic acid was 25,000 poise. (Formation ofFilmFilm)
45、 The solution of the polyamicacid was used as thefilmfilm-forming dope. The dope was extruded at 30.degree. C. in the form of a thin layer through a slit of a T-die (lip distance =0.5 mm, lip width =650 mm), and the thin layer of the dopewas continuously supplied onto a smooth metal belt and was sub
46、jected to the drying of the first stage on the belt by hot air maintained at about 120.degree. C. to form a solidifiedfilmfilm. Then, the solidifiedfilmfilmwaspeeledfromthebeltandwasfedintoa high-temperature heating furnace. In this furnace, both the end edges in the machine direction of thefilmfilm
47、 were held by a lateral tenter and the filmfilm was dried andheat-treated by hot air, the temperature of which was gradually elevated from about 250.degree. C. to about 450.degree. C., while moving thefilmfilmthrough the furnace, whereby imidization was effected and an aromatic polyimidefilmfilmwas
48、continuously prepared. Finally, thefilmfilmwas supplied to a longitudinal high-temperature heating furnace under a low tension of 100 g/mm.sup.2 applied to the longitudinal direction of thefilmfilmby dancers to heat thefilmfilmat a heating temperature of about 350.degree. C. for 4 min., cooled and t
49、hen wound in the form of a rool. Wrinkles were not formed when the dried and heattreated aromatic polyimide filmfilm was wound in the form of a roll, and the appearance of the rolled 精选文档 精选文档 filmfilm was good. In the aromatic polyimidefilmfilmobtained according to the above-mentioned filmfilm-forming process, the imidization degree was at least 95%, and the heatre