CA2110708C - Liquid crystalline polyester - Google Patents
Liquid crystalline polyesterInfo
- Publication number
- CA2110708C CA2110708C CA002110708A CA2110708A CA2110708C CA 2110708 C CA2110708 C CA 2110708C CA 002110708 A CA002110708 A CA 002110708A CA 2110708 A CA2110708 A CA 2110708A CA 2110708 C CA2110708 C CA 2110708C
- Authority
- CA
- Canada
- Prior art keywords
- molar ratio
- liquid crystalline
- crystalline polyester
- transition temperature
- isotropic transition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 59
- 239000007788 liquid Substances 0.000 title claims abstract description 44
- 230000007704 transition Effects 0.000 claims abstract description 36
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 21
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims abstract description 17
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims description 4
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000000071 blow moulding Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- HGXJNYNUTHMEOS-UHFFFAOYSA-N (4-propanoyloxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC=C(OC(=O)CC)C=C1 HGXJNYNUTHMEOS-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- RQMBBMQDXFZFCC-UHFFFAOYSA-N [4-(4-acetyloxyphenyl)phenyl] acetate Chemical compound C1=CC(OC(=O)C)=CC=C1C1=CC=C(OC(C)=O)C=C1 RQMBBMQDXFZFCC-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKOGNYJNGMLDOA-UHFFFAOYSA-N (4-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C=C1 AKOGNYJNGMLDOA-UHFFFAOYSA-N 0.000 description 1
- DIRCLGLKRZLKHG-UHFFFAOYSA-N 4-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C(O)C=C1 DIRCLGLKRZLKHG-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 aliphatic monocarboxylic acid esters Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Liquid Crystal Substances (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to liquid crystalline polyesters which have surprisingly low isotropic transition temperatures.
The invention further relates to a new process for preparing containers which have more uniform properties made from certain liquid crystalline polyesters. Also, the present invention relates to molded objects comprising certain liquid crystalline polyesters.
The liquid crystalline polyesters disclosed herein are derived from 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid.
The invention further relates to a new process for preparing containers which have more uniform properties made from certain liquid crystalline polyesters. Also, the present invention relates to molded objects comprising certain liquid crystalline polyesters.
The liquid crystalline polyesters disclosed herein are derived from 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid.
Description
W093/~382 1 ~ t. ~: PCT/US92/~909 ~110708 LIQUID CRYSTALLINE POLYESTER
Field of Invention This invention concerns certain liquid crystalline polyesters having a low isbtropic transition temperature.
Backqround of the Invention It is well known in the art that liquid crystalline polyesters (LCP's) give anisotropic mechanical properties when injection molded or extruded. This behavior can be attributed to processing the LCP in its liquid crystalline or thermotropic state, resulting in the molded or extruded article being highly oriented with very high mechanical properties in the direction of flow and poorly oriented with low properties across the direction of flow. Such properties are said to be anisotropic.
The isotropic transition temperature of a polymer is the temperature at which the polymer melt changes from an opaque, thermotropic, anisotropic state to a clear, isotropic state. For some applications, it would be highly advantageous if polyester compositions were available which had isotropic transition temperatures low enough for them to be processed in their isotropic state. Such compositions should give much less anisotropic properties under certain processing conditions.
U.S. Patent 4,067,852 broadly discloses certain melt processable, wholly aromatic polyesters, but no mention is made of low isotropic transition temperatures. Additionally, European Patent Application 0,356,226 discloses certain aromatic polyesters and polyester-amides, but again, no mention is made of low isotropic transition temperatures.
W093/~382 ~ PCT/US92/~ ~9 ~0~ 0~ - 2 -Summary of the Invention The present invention relates to new LCP's which have surprisingly low isotropic transition temperatures.
The invention further relatè~ to a new process for preparing containers mad~rom certain liquid crystalline polyesters~which have more uniform properties. Also, the present invention relates to molded objects comprising certain liquid crystalline polyesters.
Detailed DescriPtion of the Invention The present invention provides all-aromatic, liquid crystalline polyester compositions which have surprisingly low isotropic transition temperatures even though all chemical bonds between repeating units are either opposite and coaxial or opposite and parallel.
The invention concerns all-aromatic, liquid crystalline compositions based on 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid in molar amounts such that the isotropic transition temperatures of the resulting polyesters are less than 380~C and are typically equal to or less than 350~C.
The chemical bonds extending from the 2,6-naphthalenedicarboxylic acid repeating units are opposite and parallel, and the bonds extending from the 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid units are opposite and coaxial. The advantage of the bonds between repeating units being either opposite and parallel or opposite and coaxial is that a higher degree of crystallinity (and, therefore, higher heat distortion temperature) can be obtained than in compositions containing kinking units in the chain (such as isophthalic acid).
The liquid crystalline polyesters of the invention 3S comprise repeating units from:
W093/00382 ~ iPCT/US92/~909 211~708 . , ,,.. ~ ,p (a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone~ and (d) p-hydroxybenz~ic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380~C, provided that said liquid crystalline polyester is not a polyester consisting of:
(a), at a molar ratio of 0.30, (b), at a molar ratio of 0.15, (c), at a molar ratio of 0.15, and (d), at a molar ratio of 0.70.
The LCP's of the invention typically have an inherent viscosity of at least 2, and preferably 2 to 6, as determined in a 60~40 weight~weight solution of pentafluorophenol~1,2,4-trichlorobenzene at 25~C at a concentration of 0.1 g polyester per 100 ml solvent.
Preferred LCP's of the invention are as follows:
wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.2, the molar ratio of (c) is 0.2, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.3, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.25, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.6, ~ ~ ~07 ~h wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.25, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.3, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.3, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.7, and wherein the molar ratio of (a) is 0.2, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.8.
The LCP's of the invention can be prepared by conventional melt- and solid-state acidolysis methods, such as from the free acids and lower aliphatic monocarboxylic acid esters of the aromatic hydroxyl groups involved. Such methods are generally disclosed in U.S. Patent 4,169,933.
The all-aromatic LCP's of the invention having isotropic transition temperatures of 3500C or less have utility in processes where they can be processed above their isotropic transition temperature in the isotropic state so that the mechanical properties of the finished item are more uniform (less anisotropic) in all directions. Thus, the present invention is also directed to a process for preparing a container comprising:
(A) extruding a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, W093/~382 PCT/US92/~909 2i10708 -- s ., wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380~C or less, above its isotropic transition temperature to form a parison, (B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation, and (C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
This process for preparing a container is preferably performed at a temperature of 300~C to 350~C. It is further preferred that the container is a bottle. By the term "relax" and cognatic terms thereof is meant that the degree of polymer chain alignment, possibly introduced during initial stages of processing, assumes a less aligned (more random coil) configuration.
Although the above-described method for preparing a container is a preferred embodiment of the invention, the present invention is also directed to molded objects regardless of the specific methodology employed for their preparation. Such molded objects comprise a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and W093/~382 PCT/US92/~909 , .
. . . ~.
~o~ o~
(d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar r~o of (d) is 0.6 to 0.8, the molar ratio of (a) i~ equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380OC or less. Of course, it is preferred that the molded object is a parison, or a container made from the parison such as a bottle.
This invention is illustrated by the following examples but should not be interpreted as a limitation thereon.
Examples In the examples, the inherent viscosities (I. V.'s) are determined in 60~40 w~w pentafluorophenol~1,2,4-trichlorobenzene at 25~C and 0.1 g~100 mL in a Schott Gerate viscometer. The polymers are dissolved at 25~C.
The isotropic transition temperatures are determined on a Fisher-Johns Hot-Stage apparatus and are defined as the temperature at which the molten polymer observably changes from an opaque, thermotropic, anisotropic state to a mostly clear, isotropic state. Films are melt-pressed using dry polymer in a Hannafin press at the final temperature used in the preparation of the polyester.
ExamPle 1 This example illustrates the preparation of one liquid crystalline polyester which has an isotropic transition temperature less than 350~C.
To a 1000-mL, single-necked flask equipped with stainless steel stirrer, provisions for maintaining a W093/00382 PCT/US92/~ ~9 , ~ I , . . .
7 _ nitrogen atmosphere and applying vacuum, and a trap system for removing the volatiles from the polymeriza-tion are added 40.50 grams (0.15 mole) 4,4'-biphenol diacetate, 36.63 grams (0.165 mole) p-phenylene diacetate, 64.80 grams (0.30 mole) 2,6-naphthalene-dicarboxylic acid, and 81.00 grams (0.45 mole) p-acetoxybenzoic acid. The flask is then evacuated and purged three times with nitrogen, a slow nitrogen sweep of the flask contents is begun, and the flask is partly immersed in a metal bath maintained at 280~C. After the starting materials are mostly melted, stirring is begun.
The mixture is heated at 280~C for 65 minutes, at 300~C
for 60 minutes, and at 340~C for 15 minutes. The polymerization mixture is an opaque, low melt viscosity material at this time. Vacuum is then applied from atmospheric to <0.5 torr (0.067 kPa) during 10 minutes, and stirring is continued for 65 minutes to obtain a very high melt viscosity product. After being cooled to 25~C, the polymer is opaque-tan, gives a very tough melt-pressed film, and has an I. V. of 2.70. The isotropic transition temperature (Ti) of the polyester is 290-295~C.
Comparative Exam~le 2 This example illustrates the very high isotropic transition temperature obtained when the liquid crystalline polyester is prepared from four monomers (only one of which is different from the four monomers used to prepare the compositions of the invention) which give only opposite and coaxial or opposite and parallel bonds in the polyester chain; but, in contrast to the compositions of the invention, the isotropic transition temperature is still very high.
W093/00~2 PCT/US92/~
~0~
Example 1 is repeated using a final buildup temperature of 370~C and the following starting materials:
28.22 grams (0.170 mol~terephthalic acid 36.72 grams (0.170 ~ j 2,6-naphthalenedicarboxylic acid ~' 83.03 grams (0.374 mole) p-phenylene dipropionate 91.80 grams (0.510 mole) p-acetoxybenzoic acid The polymer thus prepared has an I. V. of 7.66, has an isotropic transition temperature of >420~C, and gives a very tough, melt-pressed film.
Comparative Example 3 This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol diacetate, and p-acetoxybenzoic acid (no p-phenylene dipropionate used).
Example 1 is repeated using 400~C as the final buildup temperature and the following starting materials:
64.80 grams (0.300 mole) 2,6-naphthalenedicarboxylic acid 81.00 grams (0.300 mole) 4,4'-biphenol diacetate 81.00 grams (0.450 mole) p-acetoxybenzoic acid The polymer thus prepared has an I. V. of 7.48, has an isotropic transition temperature of >420~C, and gives a very tough melt-pressed film.
W093/~382 ~ PCT/US92/~909 Comparative ExamPle 4 This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6-naphthalenedicarboxylic acid, p-phenylene dipropionate, and p-acetoxybenzoic acid (no 4,4'-biphenol diacetate used).
Example 1 is repeated using 390~C as the final buildup temperature and the following starting materials:
69.12 grams (0.320 mole) 2,6-naphthalenedicarboxylic acid 78.14 grams (0.352 mole) p-phenylene dipropionate 86.40 grams (0.480 mole) p-acetoxybenzoic acid The polymer thus prepared has an I. V. of 5.96, has an isotropic transition temperature of >420~C, and gives a very tough melt-pressed film.
Comparative Examples 5-9 Comparative Examples 5-9 illustrate other liquid crystalline polyesters outside the scope of the present invention which have high isotropic transition temperatures. The polyesters were prepared using techniques similar to those disclosed in Examples 1-4.
Examples 10-15 Example 1 is repeated except using different amounts of the same starting materials and various final buildup temperatures between 340~C and 380~C, as required, to prepare various high-melt-viscosity, liquid crystalline polyesters having the Ti's indicated in Table 1. The data for the other examples are also given for comparison.
W093/~382 PCT/US92/~909 a Examples 10-15 illustrate that liquid crystalline polyester compositions having low isotropic transition temperatures can be prepared containing a certain range of monomer segments derive~* from 2,6-naphthalene-dicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid.
Table 1 uses the following nomenclature:
'N' = mole ratio of repeat units derived from 2,6-naphthalenedicarboxylic acid.
'HQ' = mole ratio of repeat units derived from hydroquinone.
'BP' = mole ratio of repeat units derived from 4,4'-biphenol.
'PHB' = mole ratio of repeat units derived from p-hydroxybenzoic acid.
'T' = mole ratio of repeat units derived from terephthalic acid.
NOTES:
1. 'N' + 'T' = 'HQ' + 'BP'.
2. 'N' + 'T' + 'PHB' = 1Ø
W093/00382 ~PCT/US92/W909 ExamPle # 'N' 'T' 'H0' 'BP' 'PHB' Ti, oc 1 0.40 None 0.20 0.20 0.60295 Comparative 2 0.20 0.20 0.40 None 0.60>420 Comparative 3 0.40 None None 0.40 0.60>420 Comparative 4 0.40 None 0.40 None 0.60>420 Comparative 5 0.50 None 0.25 0.25 0.50>420 10Comparative 6 0.60 None 0.30 0.30 0.40>420 Comparative 7 0.40 None 0.05 0.35 0.60>420 Comparative 8 0.20 None None 0.20 0.80>420 Comparative 9 0.15 0.15 0.15 0.15 0.70>420 0.40 None 0.10 0.30 0.60310 1511 0.40 None 0.15 0.25 0.60305 12 0.40 None 0.25 0.15 0.60320 13 0.40 None 0.30 0.10 0.60345 14 0.30 None 0.15 0.15 0.70350 0.20 None 0.10 0.10 0.80335 The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Field of Invention This invention concerns certain liquid crystalline polyesters having a low isbtropic transition temperature.
Backqround of the Invention It is well known in the art that liquid crystalline polyesters (LCP's) give anisotropic mechanical properties when injection molded or extruded. This behavior can be attributed to processing the LCP in its liquid crystalline or thermotropic state, resulting in the molded or extruded article being highly oriented with very high mechanical properties in the direction of flow and poorly oriented with low properties across the direction of flow. Such properties are said to be anisotropic.
The isotropic transition temperature of a polymer is the temperature at which the polymer melt changes from an opaque, thermotropic, anisotropic state to a clear, isotropic state. For some applications, it would be highly advantageous if polyester compositions were available which had isotropic transition temperatures low enough for them to be processed in their isotropic state. Such compositions should give much less anisotropic properties under certain processing conditions.
U.S. Patent 4,067,852 broadly discloses certain melt processable, wholly aromatic polyesters, but no mention is made of low isotropic transition temperatures. Additionally, European Patent Application 0,356,226 discloses certain aromatic polyesters and polyester-amides, but again, no mention is made of low isotropic transition temperatures.
W093/~382 ~ PCT/US92/~ ~9 ~0~ 0~ - 2 -Summary of the Invention The present invention relates to new LCP's which have surprisingly low isotropic transition temperatures.
The invention further relatè~ to a new process for preparing containers mad~rom certain liquid crystalline polyesters~which have more uniform properties. Also, the present invention relates to molded objects comprising certain liquid crystalline polyesters.
Detailed DescriPtion of the Invention The present invention provides all-aromatic, liquid crystalline polyester compositions which have surprisingly low isotropic transition temperatures even though all chemical bonds between repeating units are either opposite and coaxial or opposite and parallel.
The invention concerns all-aromatic, liquid crystalline compositions based on 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid in molar amounts such that the isotropic transition temperatures of the resulting polyesters are less than 380~C and are typically equal to or less than 350~C.
The chemical bonds extending from the 2,6-naphthalenedicarboxylic acid repeating units are opposite and parallel, and the bonds extending from the 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid units are opposite and coaxial. The advantage of the bonds between repeating units being either opposite and parallel or opposite and coaxial is that a higher degree of crystallinity (and, therefore, higher heat distortion temperature) can be obtained than in compositions containing kinking units in the chain (such as isophthalic acid).
The liquid crystalline polyesters of the invention 3S comprise repeating units from:
W093/00382 ~ iPCT/US92/~909 211~708 . , ,,.. ~ ,p (a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone~ and (d) p-hydroxybenz~ic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380~C, provided that said liquid crystalline polyester is not a polyester consisting of:
(a), at a molar ratio of 0.30, (b), at a molar ratio of 0.15, (c), at a molar ratio of 0.15, and (d), at a molar ratio of 0.70.
The LCP's of the invention typically have an inherent viscosity of at least 2, and preferably 2 to 6, as determined in a 60~40 weight~weight solution of pentafluorophenol~1,2,4-trichlorobenzene at 25~C at a concentration of 0.1 g polyester per 100 ml solvent.
Preferred LCP's of the invention are as follows:
wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.2, the molar ratio of (c) is 0.2, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.3, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.25, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.6, ~ ~ ~07 ~h wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.25, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.3, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.3, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.7, and wherein the molar ratio of (a) is 0.2, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.8.
The LCP's of the invention can be prepared by conventional melt- and solid-state acidolysis methods, such as from the free acids and lower aliphatic monocarboxylic acid esters of the aromatic hydroxyl groups involved. Such methods are generally disclosed in U.S. Patent 4,169,933.
The all-aromatic LCP's of the invention having isotropic transition temperatures of 3500C or less have utility in processes where they can be processed above their isotropic transition temperature in the isotropic state so that the mechanical properties of the finished item are more uniform (less anisotropic) in all directions. Thus, the present invention is also directed to a process for preparing a container comprising:
(A) extruding a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, W093/~382 PCT/US92/~909 2i10708 -- s ., wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380~C or less, above its isotropic transition temperature to form a parison, (B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation, and (C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
This process for preparing a container is preferably performed at a temperature of 300~C to 350~C. It is further preferred that the container is a bottle. By the term "relax" and cognatic terms thereof is meant that the degree of polymer chain alignment, possibly introduced during initial stages of processing, assumes a less aligned (more random coil) configuration.
Although the above-described method for preparing a container is a preferred embodiment of the invention, the present invention is also directed to molded objects regardless of the specific methodology employed for their preparation. Such molded objects comprise a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and W093/~382 PCT/US92/~909 , .
. . . ~.
~o~ o~
(d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar r~o of (d) is 0.6 to 0.8, the molar ratio of (a) i~ equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380OC or less. Of course, it is preferred that the molded object is a parison, or a container made from the parison such as a bottle.
This invention is illustrated by the following examples but should not be interpreted as a limitation thereon.
Examples In the examples, the inherent viscosities (I. V.'s) are determined in 60~40 w~w pentafluorophenol~1,2,4-trichlorobenzene at 25~C and 0.1 g~100 mL in a Schott Gerate viscometer. The polymers are dissolved at 25~C.
The isotropic transition temperatures are determined on a Fisher-Johns Hot-Stage apparatus and are defined as the temperature at which the molten polymer observably changes from an opaque, thermotropic, anisotropic state to a mostly clear, isotropic state. Films are melt-pressed using dry polymer in a Hannafin press at the final temperature used in the preparation of the polyester.
ExamPle 1 This example illustrates the preparation of one liquid crystalline polyester which has an isotropic transition temperature less than 350~C.
To a 1000-mL, single-necked flask equipped with stainless steel stirrer, provisions for maintaining a W093/00382 PCT/US92/~ ~9 , ~ I , . . .
7 _ nitrogen atmosphere and applying vacuum, and a trap system for removing the volatiles from the polymeriza-tion are added 40.50 grams (0.15 mole) 4,4'-biphenol diacetate, 36.63 grams (0.165 mole) p-phenylene diacetate, 64.80 grams (0.30 mole) 2,6-naphthalene-dicarboxylic acid, and 81.00 grams (0.45 mole) p-acetoxybenzoic acid. The flask is then evacuated and purged three times with nitrogen, a slow nitrogen sweep of the flask contents is begun, and the flask is partly immersed in a metal bath maintained at 280~C. After the starting materials are mostly melted, stirring is begun.
The mixture is heated at 280~C for 65 minutes, at 300~C
for 60 minutes, and at 340~C for 15 minutes. The polymerization mixture is an opaque, low melt viscosity material at this time. Vacuum is then applied from atmospheric to <0.5 torr (0.067 kPa) during 10 minutes, and stirring is continued for 65 minutes to obtain a very high melt viscosity product. After being cooled to 25~C, the polymer is opaque-tan, gives a very tough melt-pressed film, and has an I. V. of 2.70. The isotropic transition temperature (Ti) of the polyester is 290-295~C.
Comparative Exam~le 2 This example illustrates the very high isotropic transition temperature obtained when the liquid crystalline polyester is prepared from four monomers (only one of which is different from the four monomers used to prepare the compositions of the invention) which give only opposite and coaxial or opposite and parallel bonds in the polyester chain; but, in contrast to the compositions of the invention, the isotropic transition temperature is still very high.
W093/00~2 PCT/US92/~
~0~
Example 1 is repeated using a final buildup temperature of 370~C and the following starting materials:
28.22 grams (0.170 mol~terephthalic acid 36.72 grams (0.170 ~ j 2,6-naphthalenedicarboxylic acid ~' 83.03 grams (0.374 mole) p-phenylene dipropionate 91.80 grams (0.510 mole) p-acetoxybenzoic acid The polymer thus prepared has an I. V. of 7.66, has an isotropic transition temperature of >420~C, and gives a very tough, melt-pressed film.
Comparative Example 3 This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol diacetate, and p-acetoxybenzoic acid (no p-phenylene dipropionate used).
Example 1 is repeated using 400~C as the final buildup temperature and the following starting materials:
64.80 grams (0.300 mole) 2,6-naphthalenedicarboxylic acid 81.00 grams (0.300 mole) 4,4'-biphenol diacetate 81.00 grams (0.450 mole) p-acetoxybenzoic acid The polymer thus prepared has an I. V. of 7.48, has an isotropic transition temperature of >420~C, and gives a very tough melt-pressed film.
W093/~382 ~ PCT/US92/~909 Comparative ExamPle 4 This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6-naphthalenedicarboxylic acid, p-phenylene dipropionate, and p-acetoxybenzoic acid (no 4,4'-biphenol diacetate used).
Example 1 is repeated using 390~C as the final buildup temperature and the following starting materials:
69.12 grams (0.320 mole) 2,6-naphthalenedicarboxylic acid 78.14 grams (0.352 mole) p-phenylene dipropionate 86.40 grams (0.480 mole) p-acetoxybenzoic acid The polymer thus prepared has an I. V. of 5.96, has an isotropic transition temperature of >420~C, and gives a very tough melt-pressed film.
Comparative Examples 5-9 Comparative Examples 5-9 illustrate other liquid crystalline polyesters outside the scope of the present invention which have high isotropic transition temperatures. The polyesters were prepared using techniques similar to those disclosed in Examples 1-4.
Examples 10-15 Example 1 is repeated except using different amounts of the same starting materials and various final buildup temperatures between 340~C and 380~C, as required, to prepare various high-melt-viscosity, liquid crystalline polyesters having the Ti's indicated in Table 1. The data for the other examples are also given for comparison.
W093/~382 PCT/US92/~909 a Examples 10-15 illustrate that liquid crystalline polyester compositions having low isotropic transition temperatures can be prepared containing a certain range of monomer segments derive~* from 2,6-naphthalene-dicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid.
Table 1 uses the following nomenclature:
'N' = mole ratio of repeat units derived from 2,6-naphthalenedicarboxylic acid.
'HQ' = mole ratio of repeat units derived from hydroquinone.
'BP' = mole ratio of repeat units derived from 4,4'-biphenol.
'PHB' = mole ratio of repeat units derived from p-hydroxybenzoic acid.
'T' = mole ratio of repeat units derived from terephthalic acid.
NOTES:
1. 'N' + 'T' = 'HQ' + 'BP'.
2. 'N' + 'T' + 'PHB' = 1Ø
W093/00382 ~PCT/US92/W909 ExamPle # 'N' 'T' 'H0' 'BP' 'PHB' Ti, oc 1 0.40 None 0.20 0.20 0.60295 Comparative 2 0.20 0.20 0.40 None 0.60>420 Comparative 3 0.40 None None 0.40 0.60>420 Comparative 4 0.40 None 0.40 None 0.60>420 Comparative 5 0.50 None 0.25 0.25 0.50>420 10Comparative 6 0.60 None 0.30 0.30 0.40>420 Comparative 7 0.40 None 0.05 0.35 0.60>420 Comparative 8 0.20 None None 0.20 0.80>420 Comparative 9 0.15 0.15 0.15 0.15 0.70>420 0.40 None 0.10 0.30 0.60310 1511 0.40 None 0.15 0.25 0.60305 12 0.40 None 0.25 0.15 0.60320 13 0.40 None 0.30 0.10 0.60345 14 0.30 None 0.15 0.15 0.70350 0.20 None 0.10 0.10 0.80335 The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims (19)
1. A liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380°C, provided that said liquid crystalline polyester is not a polyester consisting of:
(a), at a molar ratio of 0.30, (b), at a molar ratio of 0.15, (c), at a molar ratio of 0.15, and (d), at a molar ratio of 0.70.
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380°C, provided that said liquid crystalline polyester is not a polyester consisting of:
(a), at a molar ratio of 0.30, (b), at a molar ratio of 0.15, (c), at a molar ratio of 0.15, and (d), at a molar ratio of 0.70.
2. The liquid crystalline polyester of Claim 1 having an isotropic transition temperature of 350°C or less.
3. The liquid crystalline polyester of Claim 1 having an inherent viscosity of at least 2 as determined in a 60/40 weight/weight solution of pentafluoro-phenol/1,2,4-trichlorobenzene at 25°C at a concentration of 0.1 g polyester per 100 ml solvent.
4. The liquid crystalline polyester of Claim 1 having an inherent viscosity of 2 to 6 as determined in a 60/40 weight/weight solution of pentafluoro-phenol/1,2,4-trichlorobenzene at 25°C at a concentration of 0.1 g polyester per 100 ml solvent.
5. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.2, the molar ratio of (c) is 0.2, and the molar ratio of (d) is 0.6.
6. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.3, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.6.
7. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.25, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.6.
8. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.25, and the molar ratio of (d) is 0.6.
9. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.3, and the molar ratio of (d) is 0.6.
10. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.3, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.7.
11. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.2, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.8.
12. A molded object comprising a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less.
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less.
13. The molded object of Claim 12 which is a parison.
14. The molded object of Claim 12 which is a container.
15. The molded object of Claim 12 wherein said liquid crystalline polyester has an isotropic transition temperature of less than 350°C.
16. A process for preparing a container comprising:
(A) extruding a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less, above its isotropic transition temperature to form a parison, (B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation, and (C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
(A) extruding a liquid crystalline polyester comprising repeating units from:
(a) 2,6-naphthalenedicarboxylic acid, (b) 4,4'-biphenol, (c) hydroquinone, and (d) p-hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c), and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less, above its isotropic transition temperature to form a parison, (B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation, and (C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
17. The process of Claim 16 carried out at a temperature of 300°C to 350°C.
18. The process of Claim 16 wherein said container is a bottle.
19. The process of Claim 16 wherein said liquid crystalline polyester has an isotropic transition temperature of less than 350°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71869291A | 1991-06-21 | 1991-06-21 | |
| US07/718,692 | 1991-06-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2110708A1 CA2110708A1 (en) | 1993-01-07 |
| CA2110708C true CA2110708C (en) | 1998-01-06 |
Family
ID=24887111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002110708A Expired - Fee Related CA2110708C (en) | 1991-06-21 | 1992-06-12 | Liquid crystalline polyester |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0590028A1 (en) |
| JP (1) | JP3174330B2 (en) |
| KR (1) | KR940701416A (en) |
| CA (1) | CA2110708C (en) |
| WO (1) | WO1993000382A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5771449A (en) * | 1994-03-17 | 1998-06-23 | Endlink, Inc. | Sectorized multi-function communication system |
| JP2001114890A (en) * | 1999-10-18 | 2001-04-24 | Polyplastics Co | Method for producing liquid crystalline polymer |
| RU2729113C2 (en) | 2014-11-21 | 2020-08-04 | Оккам Байолэбс, Инк. | System and method of collecting a nucleic acid sample |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4067852A (en) * | 1976-05-13 | 1978-01-10 | Celanese Corporation | Melt processable thermotropic wholly aromatic polyester containing polybenzoyl units |
| US5025082A (en) * | 1988-08-24 | 1991-06-18 | Mitsubishi Kasei Corporation | Aromatic polyester, aromatic polyester-amide and processes for producing the same |
-
1992
- 1992-06-12 WO PCT/US1992/004909 patent/WO1993000382A1/en not_active Ceased
- 1992-06-12 KR KR1019930703970A patent/KR940701416A/en not_active Abandoned
- 1992-06-12 CA CA002110708A patent/CA2110708C/en not_active Expired - Fee Related
- 1992-06-12 EP EP92913524A patent/EP0590028A1/en not_active Withdrawn
- 1992-06-12 JP JP50151193A patent/JP3174330B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993000382A1 (en) | 1993-01-07 |
| JP3174330B2 (en) | 2001-06-11 |
| CA2110708A1 (en) | 1993-01-07 |
| EP0590028A1 (en) | 1994-04-06 |
| JPH06508395A (en) | 1994-09-22 |
| KR940701416A (en) | 1994-05-28 |
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