AU666053B2 - Polypropylene molding composition for producing calendered films - Google Patents
Polypropylene molding composition for producing calendered films Download PDFInfo
- Publication number
- AU666053B2 AU666053B2 AU52037/93A AU5203793A AU666053B2 AU 666053 B2 AU666053 B2 AU 666053B2 AU 52037/93 A AU52037/93 A AU 52037/93A AU 5203793 A AU5203793 A AU 5203793A AU 666053 B2 AU666053 B2 AU 666053B2
- Authority
- AU
- Australia
- Prior art keywords
- weight
- polypropylene
- fluorine
- propylene
- film
- 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.)
- Ceased
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Classifications
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (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 moulding composition containing from 99.5 to 99.999% by weight of a homopolymer or copolymer of propylene having an MFI 230/2.16 of from 2.0 to 25 g/10 min and from 0.01 to 0.5% by weight of a fluorine-containing thermoplastic polymer having a fluorine content of at least 50% and a melting point of below 250@C makes it possible to produce high-quality polypropylene films by the calandering method. The addition of fluoropolymers is not only more effective with respect to the release effect, but also gives significantly less deposits and causes an improved take-off behaviour compared with the use of conventional lubricants.
Description
IUU/ 1 21VS/01 Regulation 3.2(2)
AUSTRALIA
Patents Act 19O
ORIGINAL
COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: 0 4* 0 0 Invention Title: CoPoSWoAj POLYPROPYLENE MOLDING Q.Iy 4,FOR PRODUCING CALENDERED FILMS *0 0 0 0 The following statement is a full description of this invention, including the best method of performing it known to us I V 7
LU
Polypropylene molding composition for producing calendered films The present invention relates to a calendered polypropylene film, which consists essentially of a polypropylene molding composition containing 99.5 to 99.99% by weight of a homopolymer or copolymer of propylene consisting of olefin comonomers with a MFI 230/2.16 of 2.0 to 25 g/10 min and 0.01 to 0.5% by weight of a fluorine-containing thermoplastic polymer consisting of monomers selected from vinylidene fluoride, hexafluoro propylene, and tetra fluoroethylene with a fluorine content of at least 50% by weight and a melting point of below 2500C, said polypropylene molding composition having been plasticated and calendered into a film.
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 S 15 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.
ego 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 S 25 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 candering to those with a high melt viscosity. However, these PP grades have a high tendency to crystallize, leading to disturbing surface structures
I_
2 which reduce the quality.
It is known that polypropylene grades suitable for producing calendered films must have a MFI 230/ 2-/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 230/2.16 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 coiposikon, for producing calendered films, in which suitable polypropylene grades have, for example, a MFI 230/2./6 of 0.5 g/10 min 15 (cf. DE 40 28 407). The said molding composii0ns contain a stabilizer system composed of phosphites or sulfur compounds in conjunction with a phenolic antioxidant Swhich 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 230/2./6 of less :than 5 g/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 chlorotrifluor r.
ethylene (cf. US 31 25 547). The addition of these 7/ ,TA fluoropolymers, in specific polyolefins, preferably in B LLDPE (Linear Low Density Polyethylene), increases the 3 a 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 compositions 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 cocvosiions in such a manner that even polypropylene with a significantly higher MFI can 15 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 coMeposiW for producing calendered films which comprises 99.5 to 99.99/% by weight of a homopolymer or copolymer of polypropylene with a MFI 230/2.16 of 2.0 to 25g/10 min and 0.01 to 0.5% by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least and't melting point of below 250"C.
The polypropylene molding compos i on according to the invention comprises 99.5 to 99.99 by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/10 min, preferably 4 to 15 g/10 min. The copolymers of propylene include, for example, ethylene/propylene copolymers, propylene/l-butene copolymers and propylene/isobutylene copolymers. Mixtures of homopolymers or copolymers of propylene with terpolymers of propylene, ethylene and a Sx diene are also possible.
~Th 'r 0 4 Furthermore, the molding corpost+(on according to the invention consists of 0.0 to 0.5, preferably 0.02 to 0.04%, by weight of a fluorine-containing thermoplastic polymer with a fluorine cpntent of at least 50%,(y wek4 preferably more than 70%,and a melting point below the customary processing temperature of the polypropylene, that is to say below 250°C, preferably below 190 0 C, and in particular from 100 to 130 0
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 50%, weIko by We6POv in particular of more than 68%Aand a melting point below the customary processing temperature of the polypropylene, that is to say less than 250oC. A particularly preferred fluoropolymer is composed of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene with a fluorine content of 68 to 76% and a melting point S. 20 of less than 185 0 C, particularly preferably from 100 to 130°C.
The molding compoeo anr according to the invention can additionally contain further additives, such as, for example, antioxidants, for example alkylated monophenols, 25 alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, benzyl compounds, acylaminophenols, (5-t-butyl-4-hydroxy-3-methylphenyl) propionates, p-(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, 8 antistatic agents, blowing agents, lubricants and I ,I 5 pigments.
For metering in the fluorine-containing polymer, all methods me 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 weir't of fluoropolymer, in particular 1 to 3% by weight of 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 homogeneous distribution 20 of the active substance, even on machines without special mixing elements.
Using the molding coMnos4, according to the invention, it is possible to produce, by calendering, polypropylene films of high quality. The addition of fluoropolymers is 25 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.
00 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 electrically heated. The follow- Rs. ing settings were made for all tests: -pla~ o I 6 Roll Heating roll 1 Heating roll 2 Heating roll 3 Heating roll 4 Cooling roll 1 Cooling roll 2 Temperature 150 170 170 120 15 15 Speed (rpm) 12 18 18 18 The polypropylene was plasticated by means of a twinscrew extruder. The temperature was chosen in dependence on the PP grade used such that the melt temperature at the die outlet was 200 0 C in each case.
Furthermore, a two-roll mill with a roll width of 30 cm and a roll diameter of 15 cm was used. Speed 15/20 rpm, temperature 190 0
C.
s S. 15 Example/Comparative example PP 1 PP 2 AO 1 AO 2 Fluoropolymer Ca stearate Montan wax Amounts in g A 1 B 200 200 200 0.1 0.1 0.1 0.1 0.1 0.1 0.1
C
200 0.1 0.1 D 2 E F 200 0.1 0.1 200 0.1 0.1 0.1 200 0.1 0.1 0-.P 200 0.1 0.1 0.o PP 1 PP 2 AO 1 A02 Fluoropolymer Montan wax PP homopolymer (MFI 230/2.16 5 g/10 min) PP homopolymer (MFI 230/2.16 12 g/10 min) bis[3,3-bis-4-(4'-hydroxy-3'-t-butylphenyl)butanoic acid] ethylene glycol ester tri(2,4-di-t-butylphenyl) phosphite terpolymer of 40% tetrafluoroethylene, vinylidene fluoride and 20% hexafluoropropene partly saponified ester wax of montanic acids with 1,3-butanediol I P 1 II 7 Results: Rolling tests (two-roll mill) Example/ Comp.
A
1 Adhesion-free time (min.) 13 24
B
C
D
2
E
F
Ease of take-off of the roll hide poor good poor moderate poor good very poor moderate 2. Calendering tests 0 a e ft Example/ 15 Comp.
A
1
B
C
D
2
E
F
a a a Ease of take-off of the film moderate good moderate good adheres immediately moderategood adheres immediately adheres immediately Roll deposits none none slight deposit slight deposit none Take-off behavior irregular take-off line smooth, straight take-off line irregular take-off line somewhat irregular take-off line slightly curved take-off line a a
Claims (2)
1. Calendered polypropylene film, which consists essentially of a polypropylene molding composition containing
99.5 to 99.99% by weight of a homopolymer or copolymer of propylene consisting of olefin comonomers with a MFI 230/2.16 of 2.0 to 25 g/10 min and 0.01 to 0.5% by weight of a fluorine-containing thermoplastic polymer consisting of monomers selected from vinylidene fluoride, hexafiuoro propylene, and tetra fluoroethylene with a fluorine content of at least 50% by weight and a melting point of below 2500C, said polypropylene molding Icompound having been plasticated and calendered into a film. 2. The film as claimed in claim 1, wherein the fluorine-containing thermoplastic polymer has a fluorine content of more than 70% by weight and a melting point from 100 to 1500C. 3. The film as claimed in claim 1, which additionally comprises antioxidants, light stabilizers, metal deactivators, phosphates and phosphonites, peroxide- scavenging compounds, basic costabilizers, nucleating agents, fillers and C reinforcing agents, plasticizers, optical brighteners, flameproofing agents, antistatic agents, blowing agents, lubricants or pigments. 4 4. Process for producing calendered films by plasticating a polypropylene molding composition and drawing out in the plastic state on a film calender, hO'' wherein a molding compound is used which comprises X 99.5 to 99.99% by weight of a homopolymer or copolymer of propylene consisting of olefin comonomers with a MFI I -"srCrr 9 230/2.16 of 2.0 to 25 g/10 min and 0.01 to 0.5% by weight of a fluorine-containing thermopistic polymer consisting of monomers selected from vinylidene fluoride,' hexafluoro propylene, and tetra fluoroethylene with a fluorine content of at least 50% by weight and a melting point of below 25000. DA-i ED this 11 th day of October, 1995 WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA o ***AU5203793.WPC[DOC. 01 0000 .0. *0 0 0000: V0040 0 0, 0: 1 HOE 92/F 387 Abstract of the disclosure Polypropylene molding compound for producing calendered films A polypropylene molding compound which comprises 99.5 to 99.9% by weight of a homopolymer or copolymer of propylene with a MFI 230/2.16 of 2.0 to 25 g/10 min and 0.01 to 0.5% by weight of a fluorine-containing thermoplastic polymer with a fluorine content of at least 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. J. o *e 0 *e e
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4240409 | 1992-12-02 | ||
| DE4240409 | 1992-12-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU5203793A AU5203793A (en) | 1994-06-16 |
| AU666053B2 true AU666053B2 (en) | 1996-01-25 |
Family
ID=6474127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU52037/93A Ceased AU666053B2 (en) | 1992-12-02 | 1993-11-30 | 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) |
Families Citing this family (8)
| 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 |
| GB2483245A (en) * | 2010-09-01 | 2012-03-07 | Doosan Power Systems Ltd | Polymer membrane for carbon capture |
| CN114058098A (en) * | 2020-08-03 | 2022-02-18 | Ａｇｃ株式会社 | Membrane, method for the production thereof and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
-
1993
- 1993-11-17 TW TW082109629A patent/TW302384B/zh active
- 1993-11-30 JP JP30007493A patent/JP3464254B2/en not_active Expired - Fee Related
- 1993-11-30 AU AU52037/93A patent/AU666053B2/en not_active Ceased
- 1993-12-01 DE DE59303747T patent/DE59303747D1/en not_active Expired - Fee Related
- 1993-12-01 ZA ZA938977A patent/ZA938977B/en unknown
- 1993-12-01 KR KR1019930026015A patent/KR100296530B1/en not_active IP Right Cessation
- 1993-12-01 BR BR9304908A patent/BR9304908A/en not_active Application Discontinuation
- 1993-12-01 ES ES93119350T patent/ES2092739T3/en not_active Expired - Lifetime
- 1993-12-01 CA CA002110440A patent/CA2110440C/en not_active Expired - Fee Related
- 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 MX MX9307584A patent/MX9307584A/en unknown
- 1993-12-01 AT AT93119350T patent/ATE142674T1/en not_active IP Right Cessation
-
1998
- 1998-06-23 HK HK98106076A patent/HK1006723A1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2092739T3 (en) | 1996-12-01 |
| JPH06234894A (en) | 1994-08-23 |
| ATE142674T1 (en) | 1996-09-15 |
| EP0601455A1 (en) | 1994-06-15 |
| TW302384B (en) | 1997-04-11 |
| CA2110440C (en) | 2005-02-15 |
| ZA938977B (en) | 1994-08-03 |
| DE59303747D1 (en) | 1996-10-17 |
| KR940014585A (en) | 1994-07-18 |
| CA2110440A1 (en) | 1994-06-03 |
| JP3464254B2 (en) | 2003-11-05 |
| BR9304908A (en) | 1994-07-05 |
| AU5203793A (en) | 1994-06-16 |
| HK1006723A1 (en) | 1999-03-12 |
| KR100296530B1 (en) | 2001-10-24 |
| DK0601455T3 (en) | 1997-02-24 |
| MX9307584A (en) | 1994-06-30 |
| EP0601455B1 (en) | 1996-09-11 |
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| PC | Assignment registered |
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| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |