CA2087416A1 - Thermoplastic molding composition - Google Patents
Thermoplastic molding compositionInfo
- Publication number
- CA2087416A1 CA2087416A1 CA002087416A CA2087416A CA2087416A1 CA 2087416 A1 CA2087416 A1 CA 2087416A1 CA 002087416 A CA002087416 A CA 002087416A CA 2087416 A CA2087416 A CA 2087416A CA 2087416 A1 CA2087416 A1 CA 2087416A1
- Authority
- CA
- Canada
- Prior art keywords
- molding composition
- lubricant
- carbon atoms
- weight
- respect
- 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.)
- Abandoned
Links
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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
Abstract
Abstract Thermoplastic molding composition A plastic molding composition which comprises a thermo-plastic, preferably polycarbonate, polyester, polyester carbonate, polymethyl methacrylate or a mixture of these polymers, and an ester of a long-chain, aliphatic carboxylic acid having 24 - 40 carbon atoms with an aliphatic monohydric alcohol having 1 to 5 carbon atoms as lubricant, is distinguished by good flow properties, good mold release properties and very slight impairment of the transparency.
Description
2 ~
HOECHST AKTIENGESELLSC~AFT HOE 92/F 007 Dr. DA/bs Description Thermoplastic molding composition Thermopla~tics are as a rule processed above their melting point or ~ in the case of amorphous types - above their glass transition temperature. A plurality of processes exist for shaping plastics, the selection ultimately depending on the shape of the desired finished article. Films are produced, for example, by extrusion or calendering and hollow bodies by injection molding or extrusion blow molding. On economic grounds, a high material throughput of the processing machines is of interest. However, raising the processing speed comes up against limits where the material properties of the plastics demand compliance with specific conditions. Many plastic melt~ display a severe tendency to adhere to the metal parts of the processing machines, which makes removal of the finished products more difficult, for example in the case of blow-molding or injection molding.
~0 The tendency of the finished produc~s to adhere necessitates, in particular, relatively long cooling times so that the parts acquire sufficient mechanical stability for release from the mold without damage. In order to increase the processing speed, for example by shortening the cooling times, and thus to facilitate removal of the parts at higher temperatures, it is thus desirable to reduce the tendency of the plastic melts to adhere to the processing machines. In the vast majority of cases this is effected by adding lubricants and release agents.
A large number of substances are cu~tomarily used as lubricants and release agents in plastics. These include fatty alcohols, fatt~ acids and their derivatives (salts, esters and amides), montanic acids and their derivatives, ~ , .
~ , . ,.. i~
~7~ ~
polyethylene waxes, oxidized polyethylene waxes and paraffins.
Which of the available lubricants i5 used in a specific plas~ic ultimately depends on the properties of the plastic, the processing method and the processing condi-tions as well as on the demands made on the end product.
The prerequisite for the release effect of a lubricant in a specific plastic is that a certain incompatibility exists between the two, since if the lubricant i~ readily mi~cible or even soluble in the plastic melt there can be no enrichment at ~he interface between the pol~mer melt and the wall of the processin~ machine. Thus, polar compounds, such as, for example, fatty acid esters or fatty acid amides, are used as additives having a relea~e effect in non-polar polyolefin melts, whereas in polar plastics non-polar lubricants, such as, for example, paraffins or polyethylene waxes, have a release effect.
A particular problem arises when lubricants having a release effect are used in highly transpar~nt plastics, such as, for example, polyesters or polymethyl methacrylates. In these plastics, the lubricants, which necessarily have only limited compatibility in order to achieve the release effect, frequently result in substantial turbidity, which impairs the appearance of the end products. The use of lubricants and release agents in amorphous polyesters is particularly critical.
Amongst these polyesters, the type most used is polyethylene terephthalate, which iB obtainable from terephthalic acid and ethylene glycol and, in its amorphous form, is used, for example, to produce highly transparent bottles. With this polyether, in contrast to polycarbonate and polymethyl methacrylate, added lubricants and release agent~ can not only have the effect of producing turbidity because of their incompatibility and the consequent formation of a separate lubricant phase, but readily compatible . -,, .
"
2~7~
HOECHST AKTIENGESELLSC~AFT HOE 92/F 007 Dr. DA/bs Description Thermoplastic molding composition Thermopla~tics are as a rule processed above their melting point or ~ in the case of amorphous types - above their glass transition temperature. A plurality of processes exist for shaping plastics, the selection ultimately depending on the shape of the desired finished article. Films are produced, for example, by extrusion or calendering and hollow bodies by injection molding or extrusion blow molding. On economic grounds, a high material throughput of the processing machines is of interest. However, raising the processing speed comes up against limits where the material properties of the plastics demand compliance with specific conditions. Many plastic melt~ display a severe tendency to adhere to the metal parts of the processing machines, which makes removal of the finished products more difficult, for example in the case of blow-molding or injection molding.
~0 The tendency of the finished produc~s to adhere necessitates, in particular, relatively long cooling times so that the parts acquire sufficient mechanical stability for release from the mold without damage. In order to increase the processing speed, for example by shortening the cooling times, and thus to facilitate removal of the parts at higher temperatures, it is thus desirable to reduce the tendency of the plastic melts to adhere to the processing machines. In the vast majority of cases this is effected by adding lubricants and release agents.
A large number of substances are cu~tomarily used as lubricants and release agents in plastics. These include fatty alcohols, fatt~ acids and their derivatives (salts, esters and amides), montanic acids and their derivatives, ~ , .
~ , . ,.. i~
~7~ ~
polyethylene waxes, oxidized polyethylene waxes and paraffins.
Which of the available lubricants i5 used in a specific plas~ic ultimately depends on the properties of the plastic, the processing method and the processing condi-tions as well as on the demands made on the end product.
The prerequisite for the release effect of a lubricant in a specific plastic is that a certain incompatibility exists between the two, since if the lubricant i~ readily mi~cible or even soluble in the plastic melt there can be no enrichment at ~he interface between the pol~mer melt and the wall of the processin~ machine. Thus, polar compounds, such as, for example, fatty acid esters or fatty acid amides, are used as additives having a relea~e effect in non-polar polyolefin melts, whereas in polar plastics non-polar lubricants, such as, for example, paraffins or polyethylene waxes, have a release effect.
A particular problem arises when lubricants having a release effect are used in highly transpar~nt plastics, such as, for example, polyesters or polymethyl methacrylates. In these plastics, the lubricants, which necessarily have only limited compatibility in order to achieve the release effect, frequently result in substantial turbidity, which impairs the appearance of the end products. The use of lubricants and release agents in amorphous polyesters is particularly critical.
Amongst these polyesters, the type most used is polyethylene terephthalate, which iB obtainable from terephthalic acid and ethylene glycol and, in its amorphous form, is used, for example, to produce highly transparent bottles. With this polyether, in contrast to polycarbonate and polymethyl methacrylate, added lubricants and release agent~ can not only have the effect of producing turbidity because of their incompatibility and the consequent formation of a separate lubricant phase, but readily compatible . -,, .
"
2~7~
lubricants are also able, by virtue o~ their plasticizing effect, to increase the mobility o~ the polymer chains and thus to increase the rate of crystallization. For this reason, lubricants are frequently used in linear polyesters, in particular in polyethyl2ne terephthalate, in order to increase the degree of crystallization.
The use of fatty acid esters of polyethylene glycols as lubrlcants for polyesters has been disclosed (cf. US
The use of fatty acid esters of polyethylene glycols as lubrlcants for polyesters has been disclosed (cf. US
4,795,771, US 4,731,~04).
The synergistic effect of nucleating agents and fatty acid esters, such as, for example, pentaerythritol tetra-stearate and methyl stearate, on the surface quality and mold release properties of injection-molded articles composed of reinforced polyethylene terephthalate has also been disclosed (cf. US 3,516,957).
The use of partial esters of monocarboxylic acids having more than 8 carbon atoms and aliphatic polyols having at least 4 hydroxyl groups (for example pentaerythritol tetrastearate) in biaxially oriented polyester films to improve the surface slip has also been disclosed (cf. US
4,421,887).
Finally, the use of esters of long-chain carboxylic acids, preferably having a chain length of 20 to 32 carbon atoms, with linear or branched monoalcohols or dialcohols in combination with fine fillers to improve the surface quality of biaxially oriented polyester films has been disclosed (cf. US 4,590,119). Examples of suitable esters are, for example, ethylene glycol montanate, ethyl montanate, cetyl montanate and stearyl behenate. Since the effect results from synergy between the filler and the esker, both componenk~ are needed for the onset of action, whereas the use of one component on its own has no effect.
7~ ~
4 - ;
It has now been found that esters of long-shain aliphatic monocarboxylic acids with short-chain aliphatic mono-alcohols improve the mold release properties of polyethylene terephthalate without giving ri82 to turbidity or significant acceleration of crystallization.
The present invention therefore relates to a thermoplastic molding composition composed of 95 to 99.99% by weight, with respect to the molding composition, of a thermoplastic and 0.01 to 5.0% by weight, with respect to the molding composi~ion, of a lubricant in the form of an ester of a long-chain, aliphatic carboxylic acid having 24~40 carbon atoms with an aliphatic monohydric alcohol having 1 to 5 carbon atoms.
The molding composition according to the invention comprises a polymer and a lubrican~.
Suitable polymers are:
1. Polymers which are derived from ~ unsaturated acids, such as polyacrylates and polymethacrylates.
2. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, poly-[2,2-bis(4-hydroxyphenyl)propane] terephthalate, polyhydroxy-benzoates, and also block polyether-esters, which are derived from polyethers having terminal hydroxyl groups.
3. Polycarbonates and polyestercarbona~es.
Preferred polymers are polycarbonate, polyesters, polyester carbonate and polymethyl methacrylate, and polyesters are particularly preferred. ~Ihe polymers can also be used in the form of mixtures.
, , . ~ . .:, .
, ., . , , ~ , .
` ~8~:i 6 -- s --The lubricant to be used according to the invention is an ester of a long-chain carboxylic acid. The alcohol compone~t is derived from an aliphatic monohydric alcohol having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms and in particular 1 carbon atom. Examples are methanol, ethanol, n-propanol, i-propanol, butanols and amyl alcohols and particularly pre~erably methanol. The acid component is derived from a long-chain carboxylic acid having 24 to 40 carbon atoms. Examples are cerotic acid (=C26), montanic acid (=C28), melissic acid (-C30) and dotriacontanoic acid, preferably montanic acid. Technical grade montanic acid, which can be obtained by oxidative bleaching of crude montan wax and comprises a mixture of C24 to C34 carboxylic acids, predominantly C2~ to C32, and approximately 15% by weight of dicarboxylic acids, is particularly preferred. The esters to be used according to the invention are obtained in a known manner by esterification of the carboxylic acids in the presence of an esterification catalyst, such as, for example, sulfuric acid.
The lubricant is incorporated in the polymers using generally customary methods. For examplel the incorporation can be effected by mixing the compounds, and optionally further additives, into the melt prior to shaping. Incorporation can also be effected by applying the dissolved or dispersed compounds directly to the polymer or by mixing into a solution, suspension or emulsion of the polymer, allowing the solvent to evaporate subsequently, if appropriate. The amount to be added to the polymers is 0.01 to 5.0l preferably 0.1 to 1.0% by weight, with respect to the material to be treated.
In addition to the lubricant, the plastic molding composition can comprise the conventional additives, ~uch as, for example, antioxidants, processing stabilizers, light stabilizers, antiskatic agents, processing : .
' .
~7~
auxiliaries, impac~ modifiersl which are added in an amount of 0.01 to 10, pre~erably 0.01 to 5% by weight, with respect to ~he total weight of the molding composi-tion, and 1 to 60, preferably 5 to 40% by weight, with respect to the total molding composition, of fillers, reinforcing agents, flameproofing agents, plasticizers, blowing agents, pigments, colorants or dyes.
The plastic molding composition according to the invention is characterized by good flow properties and good mold release properties. It is therefore used in particular for ~he production of transparent hollow bodies.
The following examples are intended to illustrate the invention:
lS The polymer used was a linear polyethylene terephthalate which has a viscosity number (intrinsic viscosity) of 0.81 + 0.2 (measured in dichloxoacetic acid). The following lubricants were used as test productss Example 1: Methyl esters of montanic acids1 (acid no. 6 mg of KOH/g, dxop point 75C) Example 2: n-Butyl esters of montanic acids (acid no. about 5 mg of KOH/g, drop point 76C) Comparison Octyl esters of montanic acids, ~5 Example A: (acid no. 4 mg of KOH/g, drop point 76C) Comparison Stearyl esters of montanic acids Example B: (acid no. 8 mg of ROH/g, drop point 80C) Comparison Pentaerythritol tetrastearate Example C: (acid no. about 2 mg of KOH/g, drop point about 61C).
1) Here montanic acids are under~tood to be the wax acid mixture ohtained by oxidation of crude mon~an wax.
Prior to pxocessing, the polyester was dried for 8 h at - , , . .. . .
;
, 2~74~6 , 160C in a circulating-air oven and the test products were applied in a drum to the granules while these were still hot. The processing was carried out in an injection molding machine with the following settings:
Temperature profile: 260-270-290-300C
Injection pressure: 400 bar Holding pressure: 500 bar Back-pressure: 0 bar Die temperature: set value 25C, actual value 4~C
Sleeves 7 cm high and having an internal diameter of 6 cm which were cylindrical on the inside and slightly conical on the outside were in~ection-molded. The wall thickness was 3 mm at the sprue and 4 mm remote from the sprue. On ejection of the sleeve, the demolding force arising was measured via a piezoelectric force transducer. Cut sections from the sleeve were used to measure the trans-parency in neutral grey light; the wall thickness at the measurement point was about 3.5 mm.
The measured values obtained are summarized in the following table.
~, ; . ; , 2 ~
Table Additive Demolding ReleaseTransparency 0.2% additionforce [N] effect2 [%] [%~
None 3,200 77.0 Example 1 (Methyl montanate) 925 71 72.0 Example 2 (n~Butyl montanate) 932 71 69.5 Comp. Ex. A
(Octyl montanate) 914 72 46 . 8 Comp. Ex. B
(Stearyl montanate) 1,222 62 20.5 Comp. Ex. C
(Pentaerythritol tetrastearate) 1,681 49 60.0 2~ The release effect can be calculated in accordance with the following equation:
Demolding force with release agent Release = 1 - x 100 effect Demolding force without release agent .~
. . . ~ . .
. .
The synergistic effect of nucleating agents and fatty acid esters, such as, for example, pentaerythritol tetra-stearate and methyl stearate, on the surface quality and mold release properties of injection-molded articles composed of reinforced polyethylene terephthalate has also been disclosed (cf. US 3,516,957).
The use of partial esters of monocarboxylic acids having more than 8 carbon atoms and aliphatic polyols having at least 4 hydroxyl groups (for example pentaerythritol tetrastearate) in biaxially oriented polyester films to improve the surface slip has also been disclosed (cf. US
4,421,887).
Finally, the use of esters of long-chain carboxylic acids, preferably having a chain length of 20 to 32 carbon atoms, with linear or branched monoalcohols or dialcohols in combination with fine fillers to improve the surface quality of biaxially oriented polyester films has been disclosed (cf. US 4,590,119). Examples of suitable esters are, for example, ethylene glycol montanate, ethyl montanate, cetyl montanate and stearyl behenate. Since the effect results from synergy between the filler and the esker, both componenk~ are needed for the onset of action, whereas the use of one component on its own has no effect.
7~ ~
4 - ;
It has now been found that esters of long-shain aliphatic monocarboxylic acids with short-chain aliphatic mono-alcohols improve the mold release properties of polyethylene terephthalate without giving ri82 to turbidity or significant acceleration of crystallization.
The present invention therefore relates to a thermoplastic molding composition composed of 95 to 99.99% by weight, with respect to the molding composition, of a thermoplastic and 0.01 to 5.0% by weight, with respect to the molding composi~ion, of a lubricant in the form of an ester of a long-chain, aliphatic carboxylic acid having 24~40 carbon atoms with an aliphatic monohydric alcohol having 1 to 5 carbon atoms.
The molding composition according to the invention comprises a polymer and a lubrican~.
Suitable polymers are:
1. Polymers which are derived from ~ unsaturated acids, such as polyacrylates and polymethacrylates.
2. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, poly-[2,2-bis(4-hydroxyphenyl)propane] terephthalate, polyhydroxy-benzoates, and also block polyether-esters, which are derived from polyethers having terminal hydroxyl groups.
3. Polycarbonates and polyestercarbona~es.
Preferred polymers are polycarbonate, polyesters, polyester carbonate and polymethyl methacrylate, and polyesters are particularly preferred. ~Ihe polymers can also be used in the form of mixtures.
, , . ~ . .:, .
, ., . , , ~ , .
` ~8~:i 6 -- s --The lubricant to be used according to the invention is an ester of a long-chain carboxylic acid. The alcohol compone~t is derived from an aliphatic monohydric alcohol having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms and in particular 1 carbon atom. Examples are methanol, ethanol, n-propanol, i-propanol, butanols and amyl alcohols and particularly pre~erably methanol. The acid component is derived from a long-chain carboxylic acid having 24 to 40 carbon atoms. Examples are cerotic acid (=C26), montanic acid (=C28), melissic acid (-C30) and dotriacontanoic acid, preferably montanic acid. Technical grade montanic acid, which can be obtained by oxidative bleaching of crude montan wax and comprises a mixture of C24 to C34 carboxylic acids, predominantly C2~ to C32, and approximately 15% by weight of dicarboxylic acids, is particularly preferred. The esters to be used according to the invention are obtained in a known manner by esterification of the carboxylic acids in the presence of an esterification catalyst, such as, for example, sulfuric acid.
The lubricant is incorporated in the polymers using generally customary methods. For examplel the incorporation can be effected by mixing the compounds, and optionally further additives, into the melt prior to shaping. Incorporation can also be effected by applying the dissolved or dispersed compounds directly to the polymer or by mixing into a solution, suspension or emulsion of the polymer, allowing the solvent to evaporate subsequently, if appropriate. The amount to be added to the polymers is 0.01 to 5.0l preferably 0.1 to 1.0% by weight, with respect to the material to be treated.
In addition to the lubricant, the plastic molding composition can comprise the conventional additives, ~uch as, for example, antioxidants, processing stabilizers, light stabilizers, antiskatic agents, processing : .
' .
~7~
auxiliaries, impac~ modifiersl which are added in an amount of 0.01 to 10, pre~erably 0.01 to 5% by weight, with respect to ~he total weight of the molding composi-tion, and 1 to 60, preferably 5 to 40% by weight, with respect to the total molding composition, of fillers, reinforcing agents, flameproofing agents, plasticizers, blowing agents, pigments, colorants or dyes.
The plastic molding composition according to the invention is characterized by good flow properties and good mold release properties. It is therefore used in particular for ~he production of transparent hollow bodies.
The following examples are intended to illustrate the invention:
lS The polymer used was a linear polyethylene terephthalate which has a viscosity number (intrinsic viscosity) of 0.81 + 0.2 (measured in dichloxoacetic acid). The following lubricants were used as test productss Example 1: Methyl esters of montanic acids1 (acid no. 6 mg of KOH/g, dxop point 75C) Example 2: n-Butyl esters of montanic acids (acid no. about 5 mg of KOH/g, drop point 76C) Comparison Octyl esters of montanic acids, ~5 Example A: (acid no. 4 mg of KOH/g, drop point 76C) Comparison Stearyl esters of montanic acids Example B: (acid no. 8 mg of ROH/g, drop point 80C) Comparison Pentaerythritol tetrastearate Example C: (acid no. about 2 mg of KOH/g, drop point about 61C).
1) Here montanic acids are under~tood to be the wax acid mixture ohtained by oxidation of crude mon~an wax.
Prior to pxocessing, the polyester was dried for 8 h at - , , . .. . .
;
, 2~74~6 , 160C in a circulating-air oven and the test products were applied in a drum to the granules while these were still hot. The processing was carried out in an injection molding machine with the following settings:
Temperature profile: 260-270-290-300C
Injection pressure: 400 bar Holding pressure: 500 bar Back-pressure: 0 bar Die temperature: set value 25C, actual value 4~C
Sleeves 7 cm high and having an internal diameter of 6 cm which were cylindrical on the inside and slightly conical on the outside were in~ection-molded. The wall thickness was 3 mm at the sprue and 4 mm remote from the sprue. On ejection of the sleeve, the demolding force arising was measured via a piezoelectric force transducer. Cut sections from the sleeve were used to measure the trans-parency in neutral grey light; the wall thickness at the measurement point was about 3.5 mm.
The measured values obtained are summarized in the following table.
~, ; . ; , 2 ~
Table Additive Demolding ReleaseTransparency 0.2% additionforce [N] effect2 [%] [%~
None 3,200 77.0 Example 1 (Methyl montanate) 925 71 72.0 Example 2 (n~Butyl montanate) 932 71 69.5 Comp. Ex. A
(Octyl montanate) 914 72 46 . 8 Comp. Ex. B
(Stearyl montanate) 1,222 62 20.5 Comp. Ex. C
(Pentaerythritol tetrastearate) 1,681 49 60.0 2~ The release effect can be calculated in accordance with the following equation:
Demolding force with release agent Release = 1 - x 100 effect Demolding force without release agent .~
. . . ~ . .
. .
Claims (8)
1. A thermoplastic molding composition composed of 95 to 99.99% by weight with respect to the molding composition, of a thermoplastic and 0.01 to 5.0% by weight, with respect to the molding composition, of a lubricant in the form of an ester of a long-chain, aliphatic carboxylic acid having 24-40 carbon atoms with an aliphatic monohydric alcohol having 1 to 5 carbon atoms.
2. The molding composition as claimed in claim 1, wherein the lubricant is an ester of technical grade montanic acid with an aliphatic monohydric alcohol having 1 to 5 carbon atoms.
3. The molding composition as claimed in claim 1, wherein the lubricant is technical grade methyl montanate.
4. The molding composition as claimed in claim 1, wherein the lubricant is technical grade ethyl montanate.
5. The molding composition as claimed in claim 1, wherein the polymer is polycarbonate, polyester, polyester carbonate, polymethyl methacrylate or a mixture of these polymers.
6. The molding composition as claimed in claim 1, wherein the polymer is polyethylene terephthalate.
7. The molding composition as claimed in claim 1, which comprises, in addition to the lubricant, antioxidants, processing stabilizers, light stabilizers, antistatic agents, processing auxiliaries, impact modifiers in an amount of 0.01 to 10% by weight, with respect to the molding composition, and 1 to 60% by weight, with respect to the molding composition, fillers, reinforcing agents, flameproofing agents, plasticizers, blowing agents, pigments, colorants or dyes.
8. Use of an ester of a long-chain, aliphatic carboxylic acid having 24 - 40 carbon atoms with an aliphatic monohydric alcohol having 1 to 5 carbon atoms as lubricant when processing plastic molding compositions, in an amount of 0.01 to 5.0% by weight, with respect to the material to be processed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4201190 | 1992-01-18 | ||
| DEP4201190.6 | 1992-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2087416A1 true CA2087416A1 (en) | 1993-07-19 |
Family
ID=6449743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002087416A Abandoned CA2087416A1 (en) | 1992-01-18 | 1993-01-15 | Thermoplastic molding composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0552680B1 (en) |
| JP (1) | JPH05247259A (en) |
| AU (1) | AU662946B2 (en) |
| CA (1) | CA2087416A1 (en) |
| DE (1) | DE59308813D1 (en) |
| ZA (1) | ZA93262B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641348A (en) * | 1992-03-31 | 1994-02-15 | Union Carbide Chem & Plast Technol Corp | Dispersion of polymer additive in fatty acid ester |
| DE10015863A1 (en) * | 2000-03-30 | 2001-10-11 | Bayer Ag | Compositions containing polycarbonate |
| JP2001316577A (en) * | 2000-05-11 | 2001-11-16 | Toyobo Co Ltd | Thermoplastic polyester resin composition |
| CN113167861A (en) * | 2018-11-29 | 2021-07-23 | 科思创知识产权两合公司 | LIDAR sensor system with improved surface quality |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097435A (en) * | 1977-04-11 | 1978-06-27 | Mobay Chemical Corporation | Glass-filled polycarbonate of improved ductility |
| AU527855B2 (en) * | 1978-10-09 | 1983-03-24 | Teijin Limited | Glass fiber-reinforced thermoplastic polyester composition |
| US4686256A (en) * | 1985-12-17 | 1987-08-11 | General Electric Company | Thermoplastically moldable compositions |
| GB9007457D0 (en) * | 1990-04-03 | 1990-05-30 | Shell Int Research | Copolymer compositions |
-
1993
- 1993-01-14 JP JP5005323A patent/JPH05247259A/en not_active Withdrawn
- 1993-01-15 CA CA002087416A patent/CA2087416A1/en not_active Abandoned
- 1993-01-15 DE DE59308813T patent/DE59308813D1/en not_active Expired - Fee Related
- 1993-01-15 ZA ZA93262A patent/ZA93262B/en unknown
- 1993-01-15 EP EP93100565A patent/EP0552680B1/en not_active Expired - Lifetime
- 1993-01-15 AU AU31849/93A patent/AU662946B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0552680B1 (en) | 1998-07-29 |
| AU3184993A (en) | 1993-07-22 |
| AU662946B2 (en) | 1995-09-21 |
| ZA93262B (en) | 1993-08-17 |
| DE59308813D1 (en) | 1998-09-03 |
| EP0552680A1 (en) | 1993-07-28 |
| JPH05247259A (en) | 1993-09-24 |
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