CA1133644A - High gloss low temperature moldings from filled p.e.t. compositions - Google Patents
High gloss low temperature moldings from filled p.e.t. compositionsInfo
- Publication number
- CA1133644A CA1133644A CA322,519A CA322519A CA1133644A CA 1133644 A CA1133644 A CA 1133644A CA 322519 A CA322519 A CA 322519A CA 1133644 A CA1133644 A CA 1133644A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- component
- carbon atoms
- carboxyl groups
- mixture
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000000465 moulding Methods 0.000 title description 9
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 27
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 27
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 150000002895 organic esters Chemical class 0.000 claims abstract description 5
- 229920000620 organic polymer Polymers 0.000 claims abstract description 5
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 4
- 241000284466 Antarctothoa delta Species 0.000 claims abstract 2
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- RCGZRZBMXNWTFH-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC RCGZRZBMXNWTFH-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure A reinforced or filled polyethylene terephtha-late composition that can be molded at mold temperatures below about 110°C to produce a molded article having a smooth and glossy surface is disclosed. The composition consists essentially of, (A) polyethylene terephthalate having an inherent viscosity of at least about 0.4; (B) between about 10 and about 60 percent by weight reinforcing or filling material; (C) a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, the salt being present in an amount sufficient to provide a .DELTA.HH/.DELTA.HC ratio of less than 0.25 to a mixture of components (A), (B) and (C); and (D) a compound present in an amount sufficient to provide a Tpk at least 4°C
lower than the Tpk of a mixture of components A, B
and C. Compound D is an organic ester selected from the product of an aliphatic carboxylic acid of 1 to 20 carbon atoms containing 1-3 carboxyl groups, and an alcohol of the formula HO?R"O?yR"' wherein R" is a hydrocarbon radical of 2-15 carbon atoms, R"' is -H or a hydrocarbon radical of 2-20 carbon atoms, and when R"' is -H, y is a cardinal number between 2 and 15, and when R"' is a hydrocarbon radical, y is a cardinal number between 1 and 15.
lower than the Tpk of a mixture of components A, B
and C. Compound D is an organic ester selected from the product of an aliphatic carboxylic acid of 1 to 20 carbon atoms containing 1-3 carboxyl groups, and an alcohol of the formula HO?R"O?yR"' wherein R" is a hydrocarbon radical of 2-15 carbon atoms, R"' is -H or a hydrocarbon radical of 2-20 carbon atoms, and when R"' is -H, y is a cardinal number between 2 and 15, and when R"' is a hydrocarbon radical, y is a cardinal number between 1 and 15.
Description
AD~9l~0-B
3~1 ~4 TITLE
PRODUCT AND PROCESS
FIELD OF THE INVENTION
This invention relates to polyethylene terephthalate resins useful in molding applications.
More particularly, this invention relates to polyethylene terephthalate resins containing an inorganic reinforcing or filler material.
BACKGROUND
It is desirable to enhance the strength of articles molded from polyethylene terephthalate resin by employing a reinforcing material, such as glass fibers, asbestos fibers or other fibrous mineral materials with a coupling agent, in the resin. ~urthermore, it is sometimes sufficient to merely increase the modulus by use o~ a filler, such as beads or a mineral of low aspect ratio, in the resin. However, heretofore, it was necessary to use very high~mold temperatures, on the order of 130C, to obtain molded articles from such reinforced or filled resins which had a glossy surface .' , :: . . , ' ' . ' . : , . :
,, - ~ ;
1133tj i4 and which were rot rough in texture. If these high mold temperatures were not employed, the molded articles had a rough surface with poor gloss. It is believed that the crystallization rate of poly-ethylene terephthalate is too slow below about 130Cto result in a molded article having good surface characteristics.
While good surface characteristics can be obtained at molding temperatures of 130C or more, the use of such temperatures is not practical in the molding field, for most molds are heated with water and attain temperatures of only about 85-110C.
A few molding devices employ heating means such as oil to reach temperatures higher than 85-110C but these generally are inconvenient to use and still either do not generally reach such temperatures or reach them unevenly because of inadequate coring. Because of these heating problems, it has proven commercially unattractive to employ these high temperature molding devices with reinforced or filled polyethylene terephthalate resins.
SUMMARY OF THE INVENTION
It is desirable to provide a reinforced or filled polyethylene terephthalate resin ~hat can be molded at mold temperatures below about 110C to produce a molded article having a smooth and glossy surface. The reinforced or filled polyethylene terephthalate resins of this invention achieve the foregoing by having incorpor-ated therein 1) a sodium or potassium salt of a selected organic polymer containing pendant carboxyl g~oups and 2) a selected low molecular weight ~ organic ester.
. .
6 *~
Speci~ically, the resins of this invention are compositions consisting essentially of:
A. polyethylene terephthalate having an inherent viscosity of at least about 0.4;
5B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, said material present in an amount sufficient to provide a ~H~/aHC ratio of less than 0.25 to a mixture of components A, B and C;
D. a compound present in an amount ~u~
cient to provide a Tpk at least 4C lower than the Tpk of a mixture of components A, B and C, said compound being an organic ester selected from the product of an aliphatic carboxylic acid of 1 to 20 carbon atoms containing 1-3 carboxyl groups, and an alcohol of the formula HO~R"O~ "t wherein R" is a hydrocarbon radical of 2-15 carbon atoms (preferably
3~1 ~4 TITLE
PRODUCT AND PROCESS
FIELD OF THE INVENTION
This invention relates to polyethylene terephthalate resins useful in molding applications.
More particularly, this invention relates to polyethylene terephthalate resins containing an inorganic reinforcing or filler material.
BACKGROUND
It is desirable to enhance the strength of articles molded from polyethylene terephthalate resin by employing a reinforcing material, such as glass fibers, asbestos fibers or other fibrous mineral materials with a coupling agent, in the resin. ~urthermore, it is sometimes sufficient to merely increase the modulus by use o~ a filler, such as beads or a mineral of low aspect ratio, in the resin. However, heretofore, it was necessary to use very high~mold temperatures, on the order of 130C, to obtain molded articles from such reinforced or filled resins which had a glossy surface .' , :: . . , ' ' . ' . : , . :
,, - ~ ;
1133tj i4 and which were rot rough in texture. If these high mold temperatures were not employed, the molded articles had a rough surface with poor gloss. It is believed that the crystallization rate of poly-ethylene terephthalate is too slow below about 130Cto result in a molded article having good surface characteristics.
While good surface characteristics can be obtained at molding temperatures of 130C or more, the use of such temperatures is not practical in the molding field, for most molds are heated with water and attain temperatures of only about 85-110C.
A few molding devices employ heating means such as oil to reach temperatures higher than 85-110C but these generally are inconvenient to use and still either do not generally reach such temperatures or reach them unevenly because of inadequate coring. Because of these heating problems, it has proven commercially unattractive to employ these high temperature molding devices with reinforced or filled polyethylene terephthalate resins.
SUMMARY OF THE INVENTION
It is desirable to provide a reinforced or filled polyethylene terephthalate resin ~hat can be molded at mold temperatures below about 110C to produce a molded article having a smooth and glossy surface. The reinforced or filled polyethylene terephthalate resins of this invention achieve the foregoing by having incorpor-ated therein 1) a sodium or potassium salt of a selected organic polymer containing pendant carboxyl g~oups and 2) a selected low molecular weight ~ organic ester.
. .
6 *~
Speci~ically, the resins of this invention are compositions consisting essentially of:
A. polyethylene terephthalate having an inherent viscosity of at least about 0.4;
5B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, said material present in an amount sufficient to provide a ~H~/aHC ratio of less than 0.25 to a mixture of components A, B and C;
D. a compound present in an amount ~u~
cient to provide a Tpk at least 4C lower than the Tpk of a mixture of components A, B and C, said compound being an organic ester selected from the product of an aliphatic carboxylic acid of 1 to 20 carbon atoms containing 1-3 carboxyl groups, and an alcohol of the formula HO~R"O~ "t wherein R" is a hydrocarbon radical of 2-15 carbon atoms (preferably
2-8 carbon atoms), Rtlt is -H or a hydrocarbon radlcal of 2-20 carbon atoms (pre~erably ~-12 carbon atoms), and when R"l is H, y is a cardinal number between 2 ~nd 15 (preferably between 2 and 8) and when R"
i.s a hydrocarbon radical, y is a cardinal number between 1 and 15 (preferably between 2 and 8).
DESCRIPTION OF THE INVENTION
The polyethylene terephthalate employed herein is one which has an inherent viscosity of at least 0.4. The polyethylene terephthalate preferably has an upper limit on inherent viscosity of about 1.2. Inherent viscosity is measured at 30C
using 0.5 g of polyethylene terephthalate per 100 ml of a liquid that is a mixture, at a 3:1 ratio by volume, of methylene chloride and trifluoroacetic acid i.e. using the procedure o~ ASTM D-2857. The polyethylene terephthalate can contain minor amounts of other comonomers such as diethylene glycol or glutaric acid.
.
:
~1336 ~4 The reinforcing or filler material employed herein include glass fibers, glass beads, aluminum silicate, asbestos, mica and the like, or combinations thereof, as for example a mixture of mica and glass fibers.
Materials present in an amount sufficient to cause the compositions of the invention to have a iHH/~HC ratio of less than 0.25 (component C defined above) include the sodium or potassium salts of car-boxyl containing organic polymers, such as copolymersof olefins and acrylic or methacrylic acids, or co-polymers of aromatic olefins and maleic anhydride.
Preferably these materials include the sodium or potassium salt of ethylene/methacrylic acid copolymers (including both wholly or partially neutralized salts e.g., at least about 30%
neutralized), and the sodium salt of styrene/
maleic anhydride copolymers (including both wholly or partially neutralized salts e.g., at least about 30% neutralized). In the co-polymers listed above the olefin or aromatic olefin moiety ordinarily comprises 50-98 percent by weight of the copolymer, and preferably 80-98 percent. An especially preferred material is the sodium salt of ethylene/methacrylic acid copolymer. The copolymers may be prepared by conventional high pressure polymerization technology.
Preferred organic esters of component D
recited above are those in which the aliphatic car-boxylic acids are hydrocarbon acids containing 1-3 carboxyl groups, preferably 1 or 2, and are of 4-10 carbon atoms and the alcohols are aliphatic.
In other words, the R groups in the alcohols are alkyl or alkylene depending upon the particular R group.
Preferably also when the carboxylic acids contain two or more carboxyl groups, the carboxyl groups are all '` 1133~i~4 reacted to ~orm ester (CO0) linkages, that is, there will be no free carboxyl groups present in the ester. Preferably, all the hydroxyl groups of the alcohols will also be reacted to form ester (COO) 5 linkages, that is, there will be no free hydroxyl groups present in the ester.
Specific compounds within these definitions are listed following (The number in parenthesis after each compound is the number of degrees centigrade that 1 percent by weight of the compound present (based on polyethylene terephthalate) in the reinforced or filled polyethylene terephthalate lowers the Tpk): butyl carbitol* adipate (2.9), tri~
ethylene glycol caprate-caprylate (2.7).
Components (C) and (D) in the compositions of this invention aid in obtaininy molded articles of high surface gloss at molding temperatures below 110C by increasing the rate of crystallization of polyethylene terephthalate. Component (C) is believed to primarily aid in increasing the rate of crystallization while component (D) is believed to primarily improve the mobility of the polyethylene terephthalate in its supercooled state by reducing the viscosity of the supercooled mixture. Both are necessary to obtain the high gloss found in the articles molded from the composition.
The amount of component (C) present in the compositions of this invention is an amount which will result in a~HH/~Hc ratio of the composition less than 0.25. To find theaHH/aHc ratio, poly-ethylene terephthalate is molded at 70C into 1/16"
thick bars. The bars are heated and at between 95C and 120C an exotherm (termed ~HH) is recorded on a differential scanning calorimeter (DSC) cell *denotes trade mark , ~ .
.: : :
, ' - :
-" ii33~i~4 attached to a Du Pont 900 Differential Thermal Analysis (DTA) device. Th~ bar is heated to 290 (which is above its melting point) and the melted sample cooled at 10C/minute. Another exotherm at between about 200-220C (termed ~Hc) is the exotherm recorded on freezing of the sample. It has been found that the QHH/~HC ratio is a convenient method of measuring the degree of crystallization.
The Tpk of the composition of this invention is the temperature at which heat evolves most rapidly during the heating cycle recited in the previous paragraph. As stated earlier the amount of component (D) present in the composition of this invention is an amount which lowers the Tpk of the 15 composition by at least 4C over that of an identical composition that does not contain component (D).
The upper limits on the amounts of components C and D are not critical. However, physical properties may become adversely a~fected as amounts increase. In general, the upper amount employed for any one component will usually be about 12 percent by weight based on weight polyethylene terephthalate, while the lower limit will be about 1 percent. For the preferred component (C) salts of ethylene/methacrylic acid copolymer the upper limit on the amount present will be about 12 percent by weight based on weight of polyethylene terephthalate while the lower limit will be about 0.5 percent, but preferably an amount within the range of 2-7 percent will be used.
In addition to the components discussed hereinabove, the compositions of this invention may contain additives commonly employed with poly-35 ester resins, such as colorants, mold release agents, antioxidants, ultraviolet light stabilizers,flame retardants and the like. Additi~es which improve physical properties, such as tensile strength and elongation can also be employed; such additives include epoxy compounds (e.g., an epoxy compound formed from bisphenol-A and epichlorohydrin) present in amounts of from 0.1-1.5 percent by weight based on weight of composition.
The compositions of this invention are prepared by blending the components together by any convenient means. Neither temperature nor pressure are critical. For example, the poly-ethylene terephthalate can be mixed dry in any suitable blender or tumbler with components B, C
and D and the mixture melt-extruded. The extrudate can be chopped and mixed with reinforcing agent and then this mixture melt extruded. More con-veniently, all the components can be mixed dry in any suitable blender or tumbler and the mixture then melt extruded.
Described in the following Example is the best mode of carrying out the invention. The ~HH/aHC ratio and the Tpk were determined as described above. The gloss of molded sample was measured with a Gardner Multi Angle Gloss* (Model GG-9095) set at a selected degree angle set forth in the Examples.
EXAMPLE
Dry polyethylene terephthalate (PET) having an inherent viscosity of about 0.6 was mixed manually with 25~ (based on total weight of OCF
277B glass fiber, 5.7~ (based on weight of PET) ethylene/methacrylic acid copolymer (85/15 by weight) which had been 60 percent neutralized with sodium (which is component C herein) and with 5.7~ (based on weight of PET) triethylene glycol caprate-caprylate *denotes trade mark ,.,;~
,'' ~ ~ ' ~' ; :
- ~ ' .' - . . : - .
~133~4 (which is component D herein), 0.6% (based on total weight) of the product of bisphenol A and epichlor~-hydrin, and 0.3~ (based on total weight) of a phenolic antioxidant. Component C provided a ~ c of 0.16 and Component D provided a Tpk of 15.4~ lower than the Tpk f a mixture the other ingredients.
The resulting mixture was then extruded through a two-stage two inch single screw extruder at a melt temperature of 285C and at a vacuum of 28 inches. The extruded strand was cut and the resulting resin pellets dried at 110C in a vacuum oven for about 16 hours. The resin pellets were then molded into tumblers that were 9.2 cm high, 7.5 cm in diameter at the top, 5.5 cm in diameter at the bottom and which had a wall thickness of 0.19 cm. Melt temperature in the molding machine was 295C; while the surface temperature of the mold was 85C. at a cycle time of 10/20.
Gloss was measured at an angle of 60 by the Gardner Multi Angle Gloss Meter (Model GG-9095) several times for each sample. Gloss was measured around the circumference of the tumbler, at one-third the way down from the top. The highest rea~ing was 64 and the lowest reading was 50.
~5 In a comparison experiment, the identical ingredients were employed except that no triethylene glycol caprate-caprylate was used. The highest gloss reading obtained was 20 and the lowest was 15. Also the molding cycle had to be increased to 10/30 seconds injection over hold to get parts off the mold. Thus, it is seen that component D is necessary to obtain substantially higher gloss values.
i.s a hydrocarbon radical, y is a cardinal number between 1 and 15 (preferably between 2 and 8).
DESCRIPTION OF THE INVENTION
The polyethylene terephthalate employed herein is one which has an inherent viscosity of at least 0.4. The polyethylene terephthalate preferably has an upper limit on inherent viscosity of about 1.2. Inherent viscosity is measured at 30C
using 0.5 g of polyethylene terephthalate per 100 ml of a liquid that is a mixture, at a 3:1 ratio by volume, of methylene chloride and trifluoroacetic acid i.e. using the procedure o~ ASTM D-2857. The polyethylene terephthalate can contain minor amounts of other comonomers such as diethylene glycol or glutaric acid.
.
:
~1336 ~4 The reinforcing or filler material employed herein include glass fibers, glass beads, aluminum silicate, asbestos, mica and the like, or combinations thereof, as for example a mixture of mica and glass fibers.
Materials present in an amount sufficient to cause the compositions of the invention to have a iHH/~HC ratio of less than 0.25 (component C defined above) include the sodium or potassium salts of car-boxyl containing organic polymers, such as copolymersof olefins and acrylic or methacrylic acids, or co-polymers of aromatic olefins and maleic anhydride.
Preferably these materials include the sodium or potassium salt of ethylene/methacrylic acid copolymers (including both wholly or partially neutralized salts e.g., at least about 30%
neutralized), and the sodium salt of styrene/
maleic anhydride copolymers (including both wholly or partially neutralized salts e.g., at least about 30% neutralized). In the co-polymers listed above the olefin or aromatic olefin moiety ordinarily comprises 50-98 percent by weight of the copolymer, and preferably 80-98 percent. An especially preferred material is the sodium salt of ethylene/methacrylic acid copolymer. The copolymers may be prepared by conventional high pressure polymerization technology.
Preferred organic esters of component D
recited above are those in which the aliphatic car-boxylic acids are hydrocarbon acids containing 1-3 carboxyl groups, preferably 1 or 2, and are of 4-10 carbon atoms and the alcohols are aliphatic.
In other words, the R groups in the alcohols are alkyl or alkylene depending upon the particular R group.
Preferably also when the carboxylic acids contain two or more carboxyl groups, the carboxyl groups are all '` 1133~i~4 reacted to ~orm ester (CO0) linkages, that is, there will be no free carboxyl groups present in the ester. Preferably, all the hydroxyl groups of the alcohols will also be reacted to form ester (COO) 5 linkages, that is, there will be no free hydroxyl groups present in the ester.
Specific compounds within these definitions are listed following (The number in parenthesis after each compound is the number of degrees centigrade that 1 percent by weight of the compound present (based on polyethylene terephthalate) in the reinforced or filled polyethylene terephthalate lowers the Tpk): butyl carbitol* adipate (2.9), tri~
ethylene glycol caprate-caprylate (2.7).
Components (C) and (D) in the compositions of this invention aid in obtaininy molded articles of high surface gloss at molding temperatures below 110C by increasing the rate of crystallization of polyethylene terephthalate. Component (C) is believed to primarily aid in increasing the rate of crystallization while component (D) is believed to primarily improve the mobility of the polyethylene terephthalate in its supercooled state by reducing the viscosity of the supercooled mixture. Both are necessary to obtain the high gloss found in the articles molded from the composition.
The amount of component (C) present in the compositions of this invention is an amount which will result in a~HH/~Hc ratio of the composition less than 0.25. To find theaHH/aHc ratio, poly-ethylene terephthalate is molded at 70C into 1/16"
thick bars. The bars are heated and at between 95C and 120C an exotherm (termed ~HH) is recorded on a differential scanning calorimeter (DSC) cell *denotes trade mark , ~ .
.: : :
, ' - :
-" ii33~i~4 attached to a Du Pont 900 Differential Thermal Analysis (DTA) device. Th~ bar is heated to 290 (which is above its melting point) and the melted sample cooled at 10C/minute. Another exotherm at between about 200-220C (termed ~Hc) is the exotherm recorded on freezing of the sample. It has been found that the QHH/~HC ratio is a convenient method of measuring the degree of crystallization.
The Tpk of the composition of this invention is the temperature at which heat evolves most rapidly during the heating cycle recited in the previous paragraph. As stated earlier the amount of component (D) present in the composition of this invention is an amount which lowers the Tpk of the 15 composition by at least 4C over that of an identical composition that does not contain component (D).
The upper limits on the amounts of components C and D are not critical. However, physical properties may become adversely a~fected as amounts increase. In general, the upper amount employed for any one component will usually be about 12 percent by weight based on weight polyethylene terephthalate, while the lower limit will be about 1 percent. For the preferred component (C) salts of ethylene/methacrylic acid copolymer the upper limit on the amount present will be about 12 percent by weight based on weight of polyethylene terephthalate while the lower limit will be about 0.5 percent, but preferably an amount within the range of 2-7 percent will be used.
In addition to the components discussed hereinabove, the compositions of this invention may contain additives commonly employed with poly-35 ester resins, such as colorants, mold release agents, antioxidants, ultraviolet light stabilizers,flame retardants and the like. Additi~es which improve physical properties, such as tensile strength and elongation can also be employed; such additives include epoxy compounds (e.g., an epoxy compound formed from bisphenol-A and epichlorohydrin) present in amounts of from 0.1-1.5 percent by weight based on weight of composition.
The compositions of this invention are prepared by blending the components together by any convenient means. Neither temperature nor pressure are critical. For example, the poly-ethylene terephthalate can be mixed dry in any suitable blender or tumbler with components B, C
and D and the mixture melt-extruded. The extrudate can be chopped and mixed with reinforcing agent and then this mixture melt extruded. More con-veniently, all the components can be mixed dry in any suitable blender or tumbler and the mixture then melt extruded.
Described in the following Example is the best mode of carrying out the invention. The ~HH/aHC ratio and the Tpk were determined as described above. The gloss of molded sample was measured with a Gardner Multi Angle Gloss* (Model GG-9095) set at a selected degree angle set forth in the Examples.
EXAMPLE
Dry polyethylene terephthalate (PET) having an inherent viscosity of about 0.6 was mixed manually with 25~ (based on total weight of OCF
277B glass fiber, 5.7~ (based on weight of PET) ethylene/methacrylic acid copolymer (85/15 by weight) which had been 60 percent neutralized with sodium (which is component C herein) and with 5.7~ (based on weight of PET) triethylene glycol caprate-caprylate *denotes trade mark ,.,;~
,'' ~ ~ ' ~' ; :
- ~ ' .' - . . : - .
~133~4 (which is component D herein), 0.6% (based on total weight) of the product of bisphenol A and epichlor~-hydrin, and 0.3~ (based on total weight) of a phenolic antioxidant. Component C provided a ~ c of 0.16 and Component D provided a Tpk of 15.4~ lower than the Tpk f a mixture the other ingredients.
The resulting mixture was then extruded through a two-stage two inch single screw extruder at a melt temperature of 285C and at a vacuum of 28 inches. The extruded strand was cut and the resulting resin pellets dried at 110C in a vacuum oven for about 16 hours. The resin pellets were then molded into tumblers that were 9.2 cm high, 7.5 cm in diameter at the top, 5.5 cm in diameter at the bottom and which had a wall thickness of 0.19 cm. Melt temperature in the molding machine was 295C; while the surface temperature of the mold was 85C. at a cycle time of 10/20.
Gloss was measured at an angle of 60 by the Gardner Multi Angle Gloss Meter (Model GG-9095) several times for each sample. Gloss was measured around the circumference of the tumbler, at one-third the way down from the top. The highest rea~ing was 64 and the lowest reading was 50.
~5 In a comparison experiment, the identical ingredients were employed except that no triethylene glycol caprate-caprylate was used. The highest gloss reading obtained was 20 and the lowest was 15. Also the molding cycle had to be increased to 10/30 seconds injection over hold to get parts off the mold. Thus, it is seen that component D is necessary to obtain substantially higher gloss values.
Claims (8)
1. A composition consisting essentially of:
A. polyethylene terephthalate having an inherent viscosity of at least about 0.4;
B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, said salt being present in an amount sufficient to provide a .DELTA.HH/.DELTA.HC ratio of less than 0.25 to a mixture of components A, B and C;
D. a compound present in an amount sufficient to provide a Tpk at least 4°C lower than the Tpk of a mixture of components A, B and C, said compound being an organic ester selected from the product of an aliphatic carboxylic acid of 1 to 20 carbon atoms containing 1-3 carboxyl groups, and an alcohol of the formula HO?R"O?yR"' wherein R" is a hydrocarbon radical of 2-15 carbon atoms, R"' is -H or a hydrocarbon rad-ical of 2-20 carbon atoms, and when R"' is -H, y is a cardinal number between 2 and 15, and when R"' is a hydrocarbon radical, y is a cardinal number between 1 and 15.
A. polyethylene terephthalate having an inherent viscosity of at least about 0.4;
B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, said salt being present in an amount sufficient to provide a .DELTA.HH/.DELTA.HC ratio of less than 0.25 to a mixture of components A, B and C;
D. a compound present in an amount sufficient to provide a Tpk at least 4°C lower than the Tpk of a mixture of components A, B and C, said compound being an organic ester selected from the product of an aliphatic carboxylic acid of 1 to 20 carbon atoms containing 1-3 carboxyl groups, and an alcohol of the formula HO?R"O?yR"' wherein R" is a hydrocarbon radical of 2-15 carbon atoms, R"' is -H or a hydrocarbon rad-ical of 2-20 carbon atoms, and when R"' is -H, y is a cardinal number between 2 and 15, and when R"' is a hydrocarbon radical, y is a cardinal number between 1 and 15.
2. The composition of Claim 1 wherein Component C is the sodium or potassium salt of a copolymer of an olefin and acrylic or methacrylic acid.
3. The composition of Claim 1 wherein Component C is the sodium salt of a copolymer of ethylene and methacrylic acid in which at least 30%
of the carboxyl groups are neutralized with sodium.
of the carboxyl groups are neutralized with sodium.
4. The composition of Claim 2 wherein Component D is an ester selected from the product of a hydrocarbon carboxylic acid having 1 or 2 carboxyl groups of 4-10 carbon atoms and the alcohol is an aliphatic alcohol.
5. The composition of Claims 1, 2 or 4 wherein Component B is glass fiber.
6. The composition of Claims 1, 2 or 4 wherein Component B is glass fiber and which contains 0.1 to 1.5 percent by weight of an epoxy compounds.
7. The composition of Claims 1, 2 or 4 wherein Component B is mica.
8. The composition of Claims 1, 2 or 4 wherein Component B is a mixture of glass fiber and mica.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US88221978A | 1978-02-28 | 1978-02-28 | |
US882,219 | 1978-02-28 | ||
US929579A | 1979-02-05 | 1979-02-05 | |
US009,295 | 1979-02-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1133644A true CA1133644A (en) | 1982-10-12 |
Family
ID=26679300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA322,519A Expired CA1133644A (en) | 1978-02-28 | 1979-02-27 | High gloss low temperature moldings from filled p.e.t. compositions |
Country Status (16)
Country | Link |
---|---|
JP (1) | JPS54139654A (en) |
AU (1) | AU520709B2 (en) |
BE (1) | BE874469A (en) |
BR (1) | BR7901205A (en) |
CA (1) | CA1133644A (en) |
CH (1) | CH644617A5 (en) |
DD (1) | DD142200A5 (en) |
DE (1) | DE2907779C2 (en) |
FR (1) | FR2418255A1 (en) |
GB (1) | GB2015013B (en) |
IT (1) | IT1207175B (en) |
LU (1) | LU80980A1 (en) |
NL (1) | NL174473C (en) |
PL (1) | PL120158B1 (en) |
RO (1) | RO78149A (en) |
SE (1) | SE430169C (en) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4223113A (en) | 1976-11-23 | 1980-09-16 | Bayer Aktiengesellschaft | Polyester compositions which crystallize rapidly |
ATE7396T1 (en) | 1979-09-21 | 1984-05-15 | Imperial Chemical Industries Plc | RAPIDLY CRYSTALLIZABLE COMPOSITION BASED ON A BLOCK COPOLYESTER. |
EP0029930B1 (en) * | 1979-11-19 | 1984-02-15 | Bayer Ag | Use of polyethylene terephthalate moulding masses containing an organic imide in the preparation of crystalline mouldings by injection moulding at low mould temperatures |
EP0031201A3 (en) | 1979-12-12 | 1981-07-15 | Imperial Chemical Industries Plc | Fast crystallising polyester compositions |
US4338243A (en) * | 1980-05-07 | 1982-07-06 | E. I. Du Pont De Nemours And Company | Polyethylene terephthalate blends |
US4316866A (en) | 1980-09-26 | 1982-02-23 | R. Martin & Associates | Process and apparatus involving a cutting wire spooling system for cutting brick and tile |
US4327007A (en) * | 1980-12-22 | 1982-04-27 | Allied Chemical Corporation | Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent |
US4357268A (en) | 1980-12-29 | 1982-11-02 | Allied Corporation | Nucleation agents for crystalline polymers |
JPS6479256A (en) * | 1981-03-05 | 1989-03-24 | Kuraray Co | Polyester resin composition of excellent moldability |
US4366273A (en) * | 1981-05-11 | 1982-12-28 | Allied Corporation | Polyester composition with mixed metal ion nucleating agents |
US4349503A (en) | 1981-05-15 | 1982-09-14 | Allied Corporation | Polyester compositions containing sodium nitrite |
WO1983000697A1 (en) * | 1981-08-21 | 1983-03-03 | Ethyl Corp | Polyester composition |
US4539352A (en) * | 1981-08-21 | 1985-09-03 | Ethyl Corporation | Injection-moldable thermoplastic polyester composition |
US4486561A (en) * | 1981-08-21 | 1984-12-04 | Ethyl Corporation | Injection-moldable thermoplastic polyester composition |
US4533679A (en) * | 1982-06-28 | 1985-08-06 | Mobay Chemical Corporation | Reinforced polyester composition having an improved strength |
GB2124637A (en) * | 1982-08-03 | 1984-02-22 | Bip Chemicals Ltd | Polyethylene terephthalate moulding compositions |
US4511527A (en) * | 1982-12-16 | 1985-04-16 | Celanese Corporation | Alkali metal salts of cross-linked polymeric microgels as nucleating agents for polyethylene terephthalate molding compositions and method for molding |
US4451606A (en) * | 1983-02-23 | 1984-05-29 | General Electric Company | Copolymeric nucleating agent for polyester |
EP0146104A3 (en) * | 1983-12-19 | 1986-08-06 | Mobay Corporation | Polyester thermoplastic molding compositions with good mold release |
US4581410A (en) * | 1984-01-09 | 1986-04-08 | Monsanto Company | Hot melt adhesive compositions |
US4548996A (en) * | 1984-01-09 | 1985-10-22 | Monsanto Company | Hot melt adhesive compositions |
US4548978A (en) * | 1984-02-24 | 1985-10-22 | E. I. Du Pont De Nemours And Company | Fast crystallizing polyester resin containing three-component crystallization system |
JPH0660277B2 (en) * | 1984-02-24 | 1994-08-10 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Rapid crystalline polyester resin containing a three-component crystallization system |
IT1216472B (en) * | 1988-02-29 | 1990-03-08 | Montefibre Spa | QUICK CRYSTALLIZATION POLYESTER COMPOSITIONS. |
PL228921B1 (en) | 2015-12-23 | 2018-05-30 | R&D Centre Inventor Spolka Z Ograniczona Odpowiedzialnoscia | Construction of a cutter for harvesting energy crops |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3639527A (en) * | 1967-09-05 | 1972-02-01 | Hoechst Ag | Polyester-ionic copolymer thermoplastic moulding compositions |
US3533994A (en) * | 1968-02-20 | 1970-10-13 | Fmc Corp | Stabilized polyesters |
US3516957A (en) * | 1968-04-29 | 1970-06-23 | Eastman Kodak Co | Thermoplastic polyester composition containing organic ester mold release agent |
BE757093A (en) * | 1969-10-06 | 1971-04-06 | Hoechst Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON POLYESTERS |
AU500523B2 (en) * | 1975-12-08 | 1979-05-24 | General Electric Company | Thermoplastic molding composition |
-
1979
- 1979-02-15 SE SE7901350A patent/SE430169C/en not_active IP Right Cessation
- 1979-02-23 BR BR7901205A patent/BR7901205A/en unknown
- 1979-02-26 FR FR7904844A patent/FR2418255A1/en active Granted
- 1979-02-26 AU AU44593/79A patent/AU520709B2/en not_active Ceased
- 1979-02-27 CH CH192779A patent/CH644617A5/en not_active IP Right Cessation
- 1979-02-27 DD DD79211260A patent/DD142200A5/en unknown
- 1979-02-27 CA CA322,519A patent/CA1133644A/en not_active Expired
- 1979-02-27 BE BE0/193709A patent/BE874469A/en not_active IP Right Cessation
- 1979-02-27 JP JP2149679A patent/JPS54139654A/en active Granted
- 1979-02-27 IT IT7920605A patent/IT1207175B/en active
- 1979-02-28 LU LU80980A patent/LU80980A1/en unknown
- 1979-02-28 RO RO7996739A patent/RO78149A/en unknown
- 1979-02-28 PL PL1979213791A patent/PL120158B1/en unknown
- 1979-02-28 GB GB7907033A patent/GB2015013B/en not_active Expired
- 1979-02-28 DE DE2907779A patent/DE2907779C2/en not_active Expired
- 1979-02-28 NL NLAANVRAGE7901609,A patent/NL174473C/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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SE7901350L (en) | 1979-08-29 |
BE874469A (en) | 1979-08-27 |
SE430169C (en) | 1985-07-22 |
NL174473C (en) | 1988-08-16 |
LU80980A1 (en) | 1979-09-07 |
FR2418255A1 (en) | 1979-09-21 |
PL213791A1 (en) | 1979-12-03 |
NL7901609A (en) | 1979-08-30 |
NL174473B (en) | 1984-01-16 |
PL120158B1 (en) | 1982-02-27 |
SE430169B (en) | 1983-10-24 |
DD142200A5 (en) | 1980-06-11 |
IT1207175B (en) | 1989-05-17 |
JPS5547059B2 (en) | 1980-11-27 |
CH644617A5 (en) | 1984-08-15 |
DE2907779C2 (en) | 1982-06-09 |
AU520709B2 (en) | 1982-02-25 |
DE2907779A1 (en) | 1979-09-06 |
JPS54139654A (en) | 1979-10-30 |
FR2418255B1 (en) | 1981-01-30 |
GB2015013A (en) | 1979-09-05 |
BR7901205A (en) | 1979-10-02 |
AU4459379A (en) | 1980-01-03 |
GB2015013B (en) | 1982-06-03 |
RO78149A (en) | 1982-04-12 |
IT7920605A0 (en) | 1979-02-27 |
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