CA2110440C - Polypropylene molding composition for producing calendered films - Google Patents
Polypropylene molding composition for producing calendered films Download PDFInfo
- Publication number
- CA2110440C CA2110440C CA002110440A CA2110440A CA2110440C CA 2110440 C CA2110440 C CA 2110440C CA 002110440 A CA002110440 A CA 002110440A CA 2110440 A CA2110440 A CA 2110440A CA 2110440 C CA2110440 C CA 2110440C
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- molding composition
- polypropylene
- fluorine
- weight
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Laminated Bodies (AREA)
Abstract
A polypropylene molding composition which comprises 99.5 to 99.999% by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/10 min and 0.001 to 0.5%
by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C makes it possible to produce, by calendering, polypropylene films of high quality. The addition of fluoropolymers is not only effective as regards the release effect, but also results in significantly fewer deposits and brings about an improved take-off behavior in comparison to the use of conventional lubricants.
by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C makes it possible to produce, by calendering, polypropylene films of high quality. The addition of fluoropolymers is not only effective as regards the release effect, but also results in significantly fewer deposits and brings about an improved take-off behavior in comparison to the use of conventional lubricants.
Description
Description Polypropylene molding composition for producing calendered films The present invention relates to a molding composition for producing polypropylene films by calendering, which molding composition consists of a homopolymer or copolymer of propylene and a thermoplastic fluoropolymer with a fluorine content of at least 50o and a melting point below the customary processing temperature of polypropylene.
The production of films from polypropylene is carried out predominantly by extrusion, such as, for example, by film blowing or by extrusion via a slit die with subsequent cooling on metal rolls (chill-roll process). By comparison, the calendering process, which is customary in PVC film production for producing especially high-quality films, has only a minor importance. Although the production of calendered films from polypropylene was described for the first time as long as over 30 years ago, because of unsolved technical problems the process has scarcely become widespread.
Polypropylene molding compositions tend to adhere very intensively at the temperatures customary for calendering.
This makes it necessary to add relatively large amounts of release agents, which lead to undesired secondary effects, such as, for example, to roll deposits and therefore to poor surface qualities of the films or to impairment of the transparency or weldability of the films.
The low melt elasticity of the polypropylene in comparison limits the polypropylene grades coming into consideration for calendering to those with a high melt viscosity.
The production of films from polypropylene is carried out predominantly by extrusion, such as, for example, by film blowing or by extrusion via a slit die with subsequent cooling on metal rolls (chill-roll process). By comparison, the calendering process, which is customary in PVC film production for producing especially high-quality films, has only a minor importance. Although the production of calendered films from polypropylene was described for the first time as long as over 30 years ago, because of unsolved technical problems the process has scarcely become widespread.
Polypropylene molding compositions tend to adhere very intensively at the temperatures customary for calendering.
This makes it necessary to add relatively large amounts of release agents, which lead to undesired secondary effects, such as, for example, to roll deposits and therefore to poor surface qualities of the films or to impairment of the transparency or weldability of the films.
The low melt elasticity of the polypropylene in comparison limits the polypropylene grades coming into consideration for calendering to those with a high melt viscosity.
However, these PP grades have a high tendency to crystallize, leading to disturbing surface structures which reduce the quality.
It is known the polypropylene grades suitable for producing calendered films must have a MFI 230/21.6 of 0.4 to 2.0 g/10 min, and they must be stabilized so that their melt flow index does not rise above 2.4 g/10 min during processing (cf. EP 40 298).
Moreover, a process for producing PP calendered films is known in which the polypropylene has a MFI 230/21.6 of 0.2 to 1.0 g/10 min and additional release agents such as siloxanes, polyoctamers and metal salts of carboxylic acids are added (cf. DE 32 40 338).
Also known is a polyolefin molding composition for producing calenderized films, in which suitable polypropylene grades have, for example, a MFI 230/21.6 of 0.5 g/10 min (cf. DE 40 28 407). The said molding compositions contain a stabilizer system composed of phosphites or sulfur compounds in conjunction with a phenolic antioxidant which has the function of suppressing an increase of the MFI value during the course of processing and thus of suppressing a relatively intense adhesion tendency of the polyolefin.
According to the prior art, PP grades with a high melt viscosity, that is to say with a MFI 230121.6 of less than 5g/10 min, are accordingly necessary for producing calendered films from polypropylene, additional stabilizers and lubricants and release agents being advantageously used.
It is known the polypropylene grades suitable for producing calendered films must have a MFI 230/21.6 of 0.4 to 2.0 g/10 min, and they must be stabilized so that their melt flow index does not rise above 2.4 g/10 min during processing (cf. EP 40 298).
Moreover, a process for producing PP calendered films is known in which the polypropylene has a MFI 230/21.6 of 0.2 to 1.0 g/10 min and additional release agents such as siloxanes, polyoctamers and metal salts of carboxylic acids are added (cf. DE 32 40 338).
Also known is a polyolefin molding composition for producing calenderized films, in which suitable polypropylene grades have, for example, a MFI 230/21.6 of 0.5 g/10 min (cf. DE 40 28 407). The said molding compositions contain a stabilizer system composed of phosphites or sulfur compounds in conjunction with a phenolic antioxidant which has the function of suppressing an increase of the MFI value during the course of processing and thus of suppressing a relatively intense adhesion tendency of the polyolefin.
According to the prior art, PP grades with a high melt viscosity, that is to say with a MFI 230121.6 of less than 5g/10 min, are accordingly necessary for producing calendered films from polypropylene, additional stabilizers and lubricants and release agents being advantageously used.
It is known that the processing behavior of polyolefins is improved by the addition of fluoropolymers, which are obtainable from tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, vinyl fluoride and chlorotrifluoroethylene (cf. US 31 25 547). The addition of these fluoropolymers, in specific polyolefins, preferably in LLDPE (Linear Low Density Polyethylene), increases the flowability of the polymer melt. In addition, in processing operations in which the polymer melt is subject to high shearing, such as, for example, in film blowing through narrow annular dies, they improve the surface quality of the extrudate by preventing the occurrence of melt fracture (shark-skin).
Finally, the addition of small amounts of vinylidene fluoride to PP molding composition has been disclosed (cf.
JP 61/085 457). These small amounts are intended to produce extruded films with improved slipping properties.
It has now been found that specific fluorine-containing polymers, in very small amounts, reduce the adhesion tendency of PP molding compositions in such a manner that even polypropylene with a significantly higher MFI can advantageously be processed on calenders to produce films and the addition of other lubricants and release agents is in general superfluous.
The invention thus relates to a polypropylene molding composition for producing calendered films which comprises 99.5 to 99.999% by weight of a homopolymer or copolymer of polypropylene with a MFI 230/2.16 of 2.0 to 25g/10 min and 0.001 to 0.5% by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50o and a melting point of below 250°C.
The polypropylene molding composition according to the invention comprises 99.5 to 99.999, preferably 98 to 99.5, o by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25g/10 min, preferably 4 to 15 g/10 min. The copolymers of propylene include, for example, ethylene/propylene copolymers, propylene/1-butene copolymers and propylene/isobutylene copolymers. Mixtures of homopolymers or copolymers of propylene with terpolymers of propylene, ethylene and a diene are also possible.
Furthermore, the molding composition according to the invention consists of 0.001 to 0.5, preferably 0.02 to 0.040, by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50%, preferably more than 700, and a melting point below the customary processing temperature of the polypropylene, that is to say below 250°C, preferably below 190°C, and in particular from 100 to 130°C.
Suitable fluorine-containing polymers are produced by copolymerization of vinylidene fluoride and hexafluoropropylene or by terpolymerization of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. Such fluoropolymers preferably have a fluorine content of over 500, in particular of more than 68~ and a melting point below the customary processing temperature of the polypropylene, that is to say less than 230°C. A
particularly preferred fluoropolymer is composed of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene with a fluorine content of 68 to 76~ and a melting point of less than 185°C, particularly preferably from 100 to 130°C.
The molding composition according to the invention can additionally contain further additives, such as, for example, antioxidants, for example alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, benzyl compounds, acylaminophenols, (3-(5-t-butyl-4-hydroxy-3-methylphenyl)-propionates, (3-(3,5-di-t-butyl-4-hydroxyphenyl) propionamides, UV absorbers and light stabilizers, for example 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, oxalic diamides, possibly substituted benzoates, acrylates, nickel compounds, sterically hindered amines (HALS), metal deactivators, phosphates and phosphonites, peroxide-scavenging compounds, basic costabilizers, nucleating agents, fillers and reinforcing agents, plasticizers, optical brighteners, flameproofing agents, antistatic agents, blowing agents, lubricants and pigments.
For metering in the fluorine-containing polymer, all methods come into consideration which are otherwise customary for the addition of additives. For example, it is possible continuously to add the fluoropolymer to the polypropylene during preparation, compounding or processing. It is especially advantageous to choose methods permitting an especially uniform distribution of the fluoropolymers;
incorporation using kneaders, Banbury mixers, or mixing extruders can be quoted as examples in this regard. It is advantageous to produce a more highly concentrated mixture of fluoropolymer and polypropylene which contains, for example, 0.1 to 20~ by weight of fluoropolymer, in particular 1 to 3$ by weight of - 5a -fluoropolymer, and, after its production is in the form of a powder, beads or cylindrical pellets. This master batch can then be metered into the polypropylene, for example in the plastication extruder, in the course of film production and results in a very homogenous distribution of the active substance, even on machines without special mixing elements.
Using the molding composition according to the invention, it is possible to produce, by calendering, polypropylene films of high quality. For example, it is possible to produce calendered films by plasticating a polypropylene molding composition and drawing out the plastic state on a film calender, wherein a molding composition is used which comprises 99.5% to 99.999% by weight of a homopolyer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/
10 min and 0.001 to 0.5% by weight of a fluorine-containing theromplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C. The addition of fluoropolymers is not only effective as regards the release effect, but also results in significantly fewer deposits and provides an improved take-off behavior in comparison to the use of conventional lubricants.
The following examples are intended to explain the invention in greater detail.
A 4-roll, L-type laboratory calender from Schwabenthan with a roll width of 35 cm and a roll diameter of 15 cm was used.
The rolls are electronically heated. The following settings were made for all tests:
2l~Ot~40 Roll Temperature (C) Speed (rpm) Heating roll 1 150 10 Heating roll 2 170 12 Heating roll 3 170 15 Heating roll 4 120 18 Cooling roll 1 15 18 Cooling roll 2 15 18 The polypropylene was plasticated by means of a twin-screw extruder.
The temperature was chosen in dependence on the temperature PP grade at used such that the melt the die outlet 200C in each case.
was Furthermore, a two-roll mill with a roll width of 30 cm and a roll diameter of 15 cm was used. Speed 15120 rpm, temperature 190°C.
Example/Compara-tive Amounts in g example AO 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 AO 2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Fluoropolymer 0.1 0.1 Ca stearate Montan wax 0.2 0.2 0.1 0.1 PP 1 PP homopolymer (1~I 230/2.16 5 g/10 min) PP 2 PP homopolymer (ICI 230/2.16 12 g/10 min) AO 1 bas[3,3-bas-4-(4'-hydroxy-3'-t-butylphenyl) butanoic acid] ethylene glycol ester A02 tri(2,4-di-t-butylphenyl) phosphate Fluoro- terpolymer of 40% tetrafluoroethylene, 40%
polymer vinylidene fluoride and 20% hexafluoropropene Montan partly saponified ester wax of montanic acids wax with 1,3-butanediol Results:
l.) Rollingtests (two-roll mill) Example/ Adhesion-free Ease of take-off of Comp. time (min.) the roll hide A 13 poor 1 24 good B 5 poor C 22 moderate D 6 poor 2 12 good E <1 very poor F il moderate 2. Calendering tests Example/ Ease of Roll Take-off Comp. take-off depositsbehavior of the film A moderate none irregular take-off line 1 good none smooth, straight take-off line 8 moderate slight irregular take-off depositline C good slight somewhat irregular deposittake-o!! line D adheres immediately 2 moderate- cone slightly curved good take-off line E adheres immediately F adheres immediately
Finally, the addition of small amounts of vinylidene fluoride to PP molding composition has been disclosed (cf.
JP 61/085 457). These small amounts are intended to produce extruded films with improved slipping properties.
It has now been found that specific fluorine-containing polymers, in very small amounts, reduce the adhesion tendency of PP molding compositions in such a manner that even polypropylene with a significantly higher MFI can advantageously be processed on calenders to produce films and the addition of other lubricants and release agents is in general superfluous.
The invention thus relates to a polypropylene molding composition for producing calendered films which comprises 99.5 to 99.999% by weight of a homopolymer or copolymer of polypropylene with a MFI 230/2.16 of 2.0 to 25g/10 min and 0.001 to 0.5% by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50o and a melting point of below 250°C.
The polypropylene molding composition according to the invention comprises 99.5 to 99.999, preferably 98 to 99.5, o by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25g/10 min, preferably 4 to 15 g/10 min. The copolymers of propylene include, for example, ethylene/propylene copolymers, propylene/1-butene copolymers and propylene/isobutylene copolymers. Mixtures of homopolymers or copolymers of propylene with terpolymers of propylene, ethylene and a diene are also possible.
Furthermore, the molding composition according to the invention consists of 0.001 to 0.5, preferably 0.02 to 0.040, by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50%, preferably more than 700, and a melting point below the customary processing temperature of the polypropylene, that is to say below 250°C, preferably below 190°C, and in particular from 100 to 130°C.
Suitable fluorine-containing polymers are produced by copolymerization of vinylidene fluoride and hexafluoropropylene or by terpolymerization of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. Such fluoropolymers preferably have a fluorine content of over 500, in particular of more than 68~ and a melting point below the customary processing temperature of the polypropylene, that is to say less than 230°C. A
particularly preferred fluoropolymer is composed of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene with a fluorine content of 68 to 76~ and a melting point of less than 185°C, particularly preferably from 100 to 130°C.
The molding composition according to the invention can additionally contain further additives, such as, for example, antioxidants, for example alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, benzyl compounds, acylaminophenols, (3-(5-t-butyl-4-hydroxy-3-methylphenyl)-propionates, (3-(3,5-di-t-butyl-4-hydroxyphenyl) propionamides, UV absorbers and light stabilizers, for example 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, oxalic diamides, possibly substituted benzoates, acrylates, nickel compounds, sterically hindered amines (HALS), metal deactivators, phosphates and phosphonites, peroxide-scavenging compounds, basic costabilizers, nucleating agents, fillers and reinforcing agents, plasticizers, optical brighteners, flameproofing agents, antistatic agents, blowing agents, lubricants and pigments.
For metering in the fluorine-containing polymer, all methods come into consideration which are otherwise customary for the addition of additives. For example, it is possible continuously to add the fluoropolymer to the polypropylene during preparation, compounding or processing. It is especially advantageous to choose methods permitting an especially uniform distribution of the fluoropolymers;
incorporation using kneaders, Banbury mixers, or mixing extruders can be quoted as examples in this regard. It is advantageous to produce a more highly concentrated mixture of fluoropolymer and polypropylene which contains, for example, 0.1 to 20~ by weight of fluoropolymer, in particular 1 to 3$ by weight of - 5a -fluoropolymer, and, after its production is in the form of a powder, beads or cylindrical pellets. This master batch can then be metered into the polypropylene, for example in the plastication extruder, in the course of film production and results in a very homogenous distribution of the active substance, even on machines without special mixing elements.
Using the molding composition according to the invention, it is possible to produce, by calendering, polypropylene films of high quality. For example, it is possible to produce calendered films by plasticating a polypropylene molding composition and drawing out the plastic state on a film calender, wherein a molding composition is used which comprises 99.5% to 99.999% by weight of a homopolyer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/
10 min and 0.001 to 0.5% by weight of a fluorine-containing theromplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C. The addition of fluoropolymers is not only effective as regards the release effect, but also results in significantly fewer deposits and provides an improved take-off behavior in comparison to the use of conventional lubricants.
The following examples are intended to explain the invention in greater detail.
A 4-roll, L-type laboratory calender from Schwabenthan with a roll width of 35 cm and a roll diameter of 15 cm was used.
The rolls are electronically heated. The following settings were made for all tests:
2l~Ot~40 Roll Temperature (C) Speed (rpm) Heating roll 1 150 10 Heating roll 2 170 12 Heating roll 3 170 15 Heating roll 4 120 18 Cooling roll 1 15 18 Cooling roll 2 15 18 The polypropylene was plasticated by means of a twin-screw extruder.
The temperature was chosen in dependence on the temperature PP grade at used such that the melt the die outlet 200C in each case.
was Furthermore, a two-roll mill with a roll width of 30 cm and a roll diameter of 15 cm was used. Speed 15120 rpm, temperature 190°C.
Example/Compara-tive Amounts in g example AO 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 AO 2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Fluoropolymer 0.1 0.1 Ca stearate Montan wax 0.2 0.2 0.1 0.1 PP 1 PP homopolymer (1~I 230/2.16 5 g/10 min) PP 2 PP homopolymer (ICI 230/2.16 12 g/10 min) AO 1 bas[3,3-bas-4-(4'-hydroxy-3'-t-butylphenyl) butanoic acid] ethylene glycol ester A02 tri(2,4-di-t-butylphenyl) phosphate Fluoro- terpolymer of 40% tetrafluoroethylene, 40%
polymer vinylidene fluoride and 20% hexafluoropropene Montan partly saponified ester wax of montanic acids wax with 1,3-butanediol Results:
l.) Rollingtests (two-roll mill) Example/ Adhesion-free Ease of take-off of Comp. time (min.) the roll hide A 13 poor 1 24 good B 5 poor C 22 moderate D 6 poor 2 12 good E <1 very poor F il moderate 2. Calendering tests Example/ Ease of Roll Take-off Comp. take-off depositsbehavior of the film A moderate none irregular take-off line 1 good none smooth, straight take-off line 8 moderate slight irregular take-off depositline C good slight somewhat irregular deposittake-o!! line D adheres immediately 2 moderate- cone slightly curved good take-off line E adheres immediately F adheres immediately
Claims (4)
1. A polypropylene molding composition for producing calendered films, which comprises 99.5 to 99.999% by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/10 min and 0.001 to 0.5%
by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C.
by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C.
2. The polypropylene molding composition as claimed in claim 1, wherein the fluorine-containing thermoplastic polymer has a fluorine content of more than 70% and a melting point from 100 to 150°C.
3. The molding composition as claimed in claim 1, which additionally comprises antioxidants, light stabilizers, metal deactivators, phosphates, phosphonites, peroxide-scavenging compounds, basic costabilizers, nucleating agents, fillers, reinforcing agents, plasticizers, optical brighteners, flameproofing agents, antistatic agents, blowing agents, lubricants or pigments.
4. Process for producing calendered films by plasticating a polypropylene molding composition and drawing out in the plastic state on a film calender, wherein a polypropylene molding composition is used which comprises 99.5 to 99.999% by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/10 min and 0.001 to 0.5% by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 50% and a melting point of below 250°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4240409.6 | 1992-12-02 | ||
| DE4240409 | 1992-12-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2110440A1 CA2110440A1 (en) | 1994-06-03 |
| CA2110440C true CA2110440C (en) | 2005-02-15 |
Family
ID=6474127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002110440A Expired - Fee Related CA2110440C (en) | 1992-12-02 | 1993-12-01 | Polypropylene molding composition for producing calendered films |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0601455B1 (en) |
| JP (1) | JP3464254B2 (en) |
| KR (1) | KR100296530B1 (en) |
| AT (1) | ATE142674T1 (en) |
| AU (1) | AU666053B2 (en) |
| BR (1) | BR9304908A (en) |
| CA (1) | CA2110440C (en) |
| DE (1) | DE59303747D1 (en) |
| DK (1) | DK0601455T3 (en) |
| ES (1) | ES2092739T3 (en) |
| HK (1) | HK1006723A1 (en) |
| MX (1) | MX9307584A (en) |
| TW (1) | TW302384B (en) |
| ZA (1) | ZA938977B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2483245A (en) * | 2010-09-01 | 2012-03-07 | Doosan Power Systems Ltd | Polymer membrane for carbon capture |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5710217A (en) * | 1995-09-15 | 1998-01-20 | Minnesota Mining And Manufacturing Company | Extrudable thermoplastic hydrocarbon compositions |
| JPH09290424A (en) * | 1996-04-26 | 1997-11-11 | Hoechst Ind Kk | Mold-releasing agent composition |
| DE19801687A1 (en) * | 1998-01-19 | 1999-07-22 | Danubia Petrochem Polymere | Thermoplastic elastomers with good dyeability and high strength and elasticity as well as high impact polymer blends made from them |
| EP1038905A3 (en) * | 1999-03-26 | 2001-01-31 | Mitsubishi Polyester Film GmbH | Transparent, UV-stabilised film from a crystallisable thermoplastic material |
| DE10002153A1 (en) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Amorphous, white, UV-stable thermoformable film, useful in interior or exterior applications, formed from crystallizable resin, e.g. polyester, contains white pigment and soluble flame retardant and UV stabilizer |
| DE10003211A1 (en) * | 2000-01-26 | 2001-08-02 | Mitsubishi Polyester Film Gmbh | Amorphous, structured, opaque colored, UV light absorbing film, a process for its production and its use |
| CN114058098A (en) * | 2020-08-03 | 2022-02-18 | Ａｇｃ株式会社 | Membrane, method for the production thereof and use thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997884A (en) * | 1989-03-01 | 1991-03-05 | Rohm And Haas Company | Polyolefin compositions with improved impact strength |
| US4904735A (en) * | 1988-07-08 | 1990-02-27 | E. I. Du Pont De Nemours And Company | Processing aid for polymers |
| US5106911A (en) * | 1989-10-06 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Process and processing aid for extruding a hydrocarbon polymer |
| JPH06185457A (en) * | 1991-11-27 | 1994-07-05 | Toshiyuki Nozawa | Pressure oil delivery device by magnetic force |
-
1993
- 1993-11-17 TW TW082109629A patent/TW302384B/zh active
- 1993-11-30 AU AU52037/93A patent/AU666053B2/en not_active Ceased
- 1993-11-30 JP JP30007493A patent/JP3464254B2/en not_active Expired - Fee Related
- 1993-12-01 AT AT93119350T patent/ATE142674T1/en not_active IP Right Cessation
- 1993-12-01 CA CA002110440A patent/CA2110440C/en not_active Expired - Fee Related
- 1993-12-01 ZA ZA938977A patent/ZA938977B/en unknown
- 1993-12-01 ES ES93119350T patent/ES2092739T3/en not_active Expired - Lifetime
- 1993-12-01 MX MX9307584A patent/MX9307584A/en unknown
- 1993-12-01 EP EP93119350A patent/EP0601455B1/en not_active Expired - Lifetime
- 1993-12-01 DK DK93119350.2T patent/DK0601455T3/da active
- 1993-12-01 BR BR9304908A patent/BR9304908A/en not_active Application Discontinuation
- 1993-12-01 DE DE59303747T patent/DE59303747D1/en not_active Expired - Fee Related
- 1993-12-01 KR KR1019930026015A patent/KR100296530B1/en not_active IP Right Cessation
-
1998
- 1998-06-23 HK HK98106076A patent/HK1006723A1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2483245A (en) * | 2010-09-01 | 2012-03-07 | Doosan Power Systems Ltd | Polymer membrane for carbon capture |
Also Published As
| Publication number | Publication date |
|---|---|
| TW302384B (en) | 1997-04-11 |
| EP0601455A1 (en) | 1994-06-15 |
| HK1006723A1 (en) | 1999-03-12 |
| BR9304908A (en) | 1994-07-05 |
| JP3464254B2 (en) | 2003-11-05 |
| KR940014585A (en) | 1994-07-18 |
| AU666053B2 (en) | 1996-01-25 |
| ZA938977B (en) | 1994-08-03 |
| JPH06234894A (en) | 1994-08-23 |
| ES2092739T3 (en) | 1996-12-01 |
| EP0601455B1 (en) | 1996-09-11 |
| KR100296530B1 (en) | 2001-10-24 |
| DK0601455T3 (en) | 1997-02-24 |
| ATE142674T1 (en) | 1996-09-15 |
| CA2110440A1 (en) | 1994-06-03 |
| DE59303747D1 (en) | 1996-10-17 |
| MX9307584A (en) | 1994-06-30 |
| AU5203793A (en) | 1994-06-16 |
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