CN103252959A - Polypropylene film and preparation method thereof - Google Patents
Polypropylene film and preparation method thereof Download PDFInfo
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- CN103252959A CN103252959A CN2012100416022A CN201210041602A CN103252959A CN 103252959 A CN103252959 A CN 103252959A CN 2012100416022 A CN2012100416022 A CN 2012100416022A CN 201210041602 A CN201210041602 A CN 201210041602A CN 103252959 A CN103252959 A CN 103252959A
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Abstract
The invention provides a polypropylene film and a preparation method thereof. The film comprises a polypropylene core layer and a smooth surface layer adhered to at least one side surface of the polypropylene core layer. The smooth surface layer is a polypropylene layer with dispersed self-lubricating micro-particles. Fusion index of the polypropylene in the polypropylene core layer and the smooth surface layer under 230 DEG C and 2.16kg are 0.5-5g/10min. The self-lubricating micro-particles are high-molecular micro-particles with melting temperature higher than or equal to 250 DEG C and with both static friction coefficient and dynamic friction coefficient smaller than or equal to 0.6. The polypropylene film provided by the invention has excellent smooth performance, optical performance, and mechanical performance.
Description
Technical field
The present invention relates to a kind of polypropylene film and preparation method thereof.
Background technology
Bidirectional stretching polypropylene film (BOPP film) has that transparency height, glossiness are good, good mechanical performance, molecular structure stabilized, smell and moisture had the advantage of certain iris action, be desirable packaging material, occupy very consequence in Flexible Package Market.Yet the coefficient of friction of BOPP film own is bigger, and frictional static is serious, and adhesion easily between the film requires film to have the Application for Field of good smooth performance at high-speed packaging, cigarette with film, lubricated barrier film etc. thereby limited it.
The defective that generally adopts at present the method for adding slipping agent in the polypropylene film to reduce the coefficient of friction of polypropylene film and improve its easy adhesion improves its smooth property.Slipping agent commonly used is divided into inorganic and organic two classes usually.Inorganic slipping agent comprises calcium carbonate, mica, silica etc.In order to reduce the caking property between the film, the smooth performance on raising top layer, need to improve the addition of inorganic slipping agent usually.But inorganic slipping agent is normally opaque, and the increase of slipping agent consumption can cause the optical property variation of polypropylene film, is not suitable for transparency and glossiness are had the production and processing of the film of requirement.Organic class slipping agent is generally amine or silicone organic matter.Wherein, silicone is liquid, adds and uses inconvenience.The amine slipping agent is the migration-type additive, the method of adding the amine slipping agent in the film is mainly and amine slipping agent and acrylic resin are mixed the back processes film forming, after but gained acrylic resin film must be placed 7-10 days, treat just can reach smooth performance preferably after slipping agent is moved to the surface of acrylic resin film, therefore, production efficiency is lower; What is more important, Qian Yi slipping agent can not remain in the polypropylene film and cause the optical property of film and mechanical property significantly to reduce, thereby has had a strong impact on its application in practice.
Summary of the invention
The objective of the invention is in order to overcome when adopting existing method to prepare polypropylene film, needs placement a period of time just can reach its smooth effect, production efficiency is lower, and the defective that the optical property of the polypropylene film that obtains and mechanical property are not good, and a kind of preparation method that can reach the higher polypropylene film of its smooth effect and productive rate that do not need to place is provided, and the polypropylene film that obtains has excellent smooth performance, optical property and mechanical property concurrently.
The invention provides a kind of polypropylene film, wherein, described film comprises the polypropylene sandwich layer and is attached to the smooth superficial layer of at least one side surface of described polypropylene sandwich layer that described smooth superficial layer is the polypropylene layer that is dispersed with the self-lubricating particulate; Polypropylene in described polypropylene sandwich layer and the smooth superficial layer is 0.5g/10min-5g/10min at 230 ℃, the melt index of 2.16kg; Described self-lubricating particulate be melt temperature more than or equal to 250 ℃, confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle.
The present invention also provides a kind of preparation method of polypropylene film, and wherein, this method comprises sends into melting mixing and extruding pelletization in the extruder after polypropylene and self-lubricating particulate mixed, and obtains smooth superficial layer raw material; Described smooth superficial layer raw material and polypropylene sent into have extruding of multi-layer co-extruded structure and extrude curtain coating in the casting apparatus, obtain the cast-sheet of the smooth superficial layer of at least one side surface of comprising the polypropylene sandwich layer and being attached to described polypropylene sandwich layer; The cast-sheet that obtains is carried out biaxial tension, obtain comprising the bidirectional stretching polypropylene film of polypropylene sandwich layer and the smooth superficial layer of at least one side surface that is attached to described polypropylene sandwich layer; Described smooth superficial layer is the polypropylene layer that is dispersed with the self-lubricating particulate; Polypropylene in described polypropylene sandwich layer and the smooth superficial layer is 0.5g/10min-5g/10min at 230 ℃, the melt index of 2.16kg; Described self-lubricating particulate is that melt temperature is more than or equal to 250 ℃, and confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle.
On the one hand, after the self-lubricating particulate adds smooth superficial layer to, because the incompatibility of described self-lubricating particulate and polypropylene matrix, particulate can be arranged automatically, disperse, and can break through or be embedded on the described film top layer, form the self-lubricating point at film surface, thereby can effectively reduce the coefficient of friction of polypropylene film, and the bonding between the reduction polypropylene film, it is outstanding to make it smooth performance.Further, adopt method of the present invention to prepare polypropylene film, need not to wait for that the self-lubricating particulate migration to the top layer of described film, can improve the production efficiency of film.In addition, because the smooth performance of polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and polyether-ether-ketone particulate is very excellent, melt temperature is higher, optical property is better, therefore, a preferred embodiment of the invention, when described self-lubricating particulate was selected from polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and the polyether-ether-ketone particulate one or more, the combination property of the polypropylene film that obtains was very good.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that the specific embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, described polypropylene film comprises the polypropylene sandwich layer and is attached to the smooth superficial layer of at least one side surface of described polypropylene sandwich layer that described smooth superficial layer is the polypropylene layer that is dispersed with the self-lubricating particulate; Polypropylene in described polypropylene sandwich layer and the smooth superficial layer is 0.5g/10min-5g/10min at 230 ℃, the melt index of 2.16kg; Described self-lubricating particulate be melt temperature more than or equal to 250 ℃, confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle.
Described polypropylene is to be a kind of thermoplastic resin that raw material is produced with the propylene, has good insulation performance performance and corrosion resistance, is widely used in the packing of food.Described polypropylene can be commercially available, for example can be available from Maoming petrochemical industry, Singapore TPC company etc.Under the preferable case, polyacrylic density is that 0.9-0.91 gram/cubic centimetre, melt temperature are 148-165 ℃.
According to the present invention, described self-lubricating particulate refers to have the granular high temperature resistant high molecular particle of self-lubricating property.The adding of self-lubricating particulate in the described smooth top layer can make the coefficient of friction of the polypropylene film of production significantly reduce, and the smooth performance of film increases substantially.
According to the present invention, the content of described self-lubricating particulate can change in relative broad range, it will be understood by those skilled in the art that the content of described self-lubricating particulate is more big, smooth performance is more good, but optical property and mechanical property may descend to some extent, and therefore, performance synthesis is from every side considered, under the preferable case, gross mass with described smooth superficial layer is benchmark, and the content of described self-lubricating particulate is 0.05-10 weight %, more preferably 0.5-3 weight %.
According to the present invention, the thickness of described polypropylene sandwich layer and the thickness of smooth superficial layer can suitably be selected according to the service condition of described polypropylene film, if the described polypropylene film of conditional request of described use has bigger mechanical strength and lower to the optical property requirement, then the thickness of the thickness of described polypropylene sandwich layer and smooth superficial layer can be thicker; If the described polypropylene film of conditional request of described use has preferably light transmission and mechanical strength required lower, then the thickness of the thickness of described polypropylene sandwich layer and smooth superficial layer can be thinner.Generally, the thickness of described polypropylene sandwich layer can be the 5-70 micron, and the thickness of the smooth superficial layer of described polypropylene sandwich layer one side can be the 0.1-10 micron; In order further to improve the combination property of the polypropylene film that obtains, under the preferable case, the thickness of described polypropylene sandwich layer can be the 15-30 micron, and the thickness of the smooth superficial layer of described polypropylene sandwich layer one side can be the 1-3 micron.Correspondingly, the particle diameter of described self-lubricating particulate is the 0.1-20 micron, is preferably the 1-6 micron.When the particle diameter of described self-lubricating particulate was the 100%-200% of thickness of smooth superficial layer of described polypropylene sandwich layer one side, the smooth performance of polypropylene film of the present invention was very good.
According to the present invention, although the kind of described self-lubricating particulate can not cause remarkable influence to the smooth performance of the polypropylene film that obtains, as long as be selected from melt temperature more than or equal to 250 ℃, confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle and get final product, but in order to obtain frictional behaviour, glossiness and mechanical property be more excellent polypropylene film all, and can further guarantee the even dispersion of described self-lubricating particle, under the preferable case, described high molecular particle is selected from the polytetrafluoroethylene (PTFE) particulate, medlin particulate, in polyamide particles and the polyether-ether-ketone particulate one or more.The present inventor finds by further investigation, when described self-lubricating particulate is selected from polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and the polyether-ether-ketone particulate one or more, and when the particle diameter of described self-lubricating particulate was the 100%-200% of thickness of smooth superficial layer of described polypropylene sandwich layer one side, the combination property of the polypropylene film of gained was splendid.Infer that reason may be: described polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and polyether-ether-ketone particulate itself have good self-lubricating property, can give film surface good smooth property, and above several self-lubricating high molecular particle stable in properties, can be high temperature resistant, melt temperature is all more than 250 ℃, therefore, in the process of polypropylene film fusion can not take place, can keep particulate form on the film top layer, thereby stable smooth performance can be provided.In addition, when the particle diameter of described self-lubricating particulate is the 100%-200% of thickness of smooth superficial layer of described polypropylene sandwich layer one side, can guarantee that the self-lubricating particulate is embedded among the superficial layer and has part to protrude from superficial layer, not only can give full play to its smooth characteristic, also be unlikely in processing or use, to fall from the film surface pull-up, thereby make that the smooth performance of film is more lasting.In addition, a preferred embodiment of the invention, when the gross mass with described smooth superficial layer is benchmark, the content of described self-lubricating particulate is 0.05-10 weight %, when being preferably 0.5-3 weight %, not only can the light transmission of film not impacted, can also significantly improve durability and the heat-resistant stability of described film.
According to the present invention, described self-lubricating particulate can be by commercially available and prepare according to existing method, and for example, described polytetrafluoroethylene (PTFE) particulate can be available from Su Wei group, the trade mark is F284, and melt temperature is that 327-333 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.04 and 0.04; Described medlin particulate can be available from Hubei bismaleimide resin factory, and the trade mark is SM003, perhaps can prepare according to the CN101253223A disclosed method, and its melt temperature is that 330-350 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.06 and 0.06; Described polyamide particles can be available from the Guangzhou Long Suliaocailiaochang that escapes, the trade mark is A102F, perhaps can prepare according to CN 101357989A disclosed method, its melt temperature can be respectively 0.42 and 0.35 for 255-265 ℃, confficient of static friction and the coefficient of kinetic friction; Described polyether-ether-ketone particulate can be available from Britain Wei Gesi company, and melt temperature is that 334-340 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.2 and 0.2.
The preparation method of polypropylene film provided by the invention comprises and sends into melting mixing and extruding pelletization in the extruder after polypropylene and self-lubricating particulate mixed, and obtains smooth superficial layer raw material; Described smooth superficial layer raw material and polypropylene sent into have extruding of multi-layer co-extruded structure and extrude curtain coating in the casting apparatus, obtain the cast-sheet of the smooth superficial layer of at least one side surface of comprising the polypropylene sandwich layer and being attached to described polypropylene sandwich layer; The cast-sheet that obtains is carried out biaxial tension, obtain comprising the bidirectional stretching polypropylene film of polypropylene sandwich layer and the smooth superficial layer of at least one side surface that is attached to described polypropylene sandwich layer; Described smooth superficial layer is the polypropylene layer that is dispersed with the self-lubricating particulate; Polypropylene in described polypropylene sandwich layer and the smooth superficial layer is 0.5g/10min-5g/10min at 230 ℃, the melt index of 2.16kg; Described self-lubricating particulate is that melt temperature is more than or equal to 250 ℃, and confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle.Under the preferable case, described high molecular particle is selected from one or more in polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and the polyether-ether-ketone particulate.
According to the present invention; in order to obtain the more excellent polypropylene film of performance; under the preferable case; this method also is included in before polypropylene and the mixing of self-lubricating particulate; and before described smooth superficial layer raw material and acrylic resin are sent into casting machine, polypropylene and self-lubricating particulate are carried out drying.The method of described drying and condition can for example, can be vacuum drying, forced air drying etc. for well known to a person skilled in the art drying means and condition, and baking temperature can be 60-100 ℃.Drying equipment is generally and comprises that heating, heated drying air purge or the drying equipment of vacuum system, for example, can be continuous dryer, vacuum drying oven and hot-air oven etc.
Usually, the mode that mixes of described acrylic resin and self-lubricating particulate can be even for described polypropylene and self-lubricating particulate being joined in the existing various mixing apparatus blended under agitation.Wherein, described mixing apparatus for example can be mixer, kneader, mill and banbury etc.The temperature and time of blended under agitation is conventionally known to one of skill in the art, and for example, the temperature of blended under agitation can be 25-65 ℃, and the time of blended under agitation can be 5-30 minute, and the rotating speed of blended under agitation is 50-300 rev/min; Under the preferable case, under 50-100 rev/min rotating speed, stirred 5-15 minute earlier, and then under 100-200 rev/min rotating speed, stirred 5-15 minute.
According to the present invention, it is conventionally known to one of skill in the art that the described mixture that obtains after polypropylene and self-lubricating particulate are mixed carries out method, condition and used extruder that melting mixing and extruding pelletization obtain smooth superficial layer raw material.For example, double screw extruder can be adopted, also single screw extrusion machine can be adopted, screw speed is 150-360 rev/min, each zone temperatures is respectively 170-230 ℃, 175-240 ℃, 180-250 ℃, 180-250 ℃, 180-250 ℃, 175-240 ℃, and the vacuum of each section is extruding pelletization under the condition of 0.02 to 0.09 MPa.Vacuum in this specification refers to the absolute value of the difference of absolute pressure and atmospheric pressure.
Need to prove, extrude casting apparatus and generally include a plurality of extruders, can different materials be heated in a plurality of extruders, and can comprise that at least two-layer MULTILAYER COMPOSITE die head extrudate flow prolongs by same through the material after the different extruder heating, thereby obtain comprising the cast-sheet of multilayer; Wherein, the material in each extruder is extruded from wherein one deck of described MULTILAYER COMPOSITE die head.Therefore, what those skilled in the art should be readily appreciated that is, when a side surface that obtains the polypropylene sandwich layer when needs is attached with the polypropylene film of smooth superficial layer, can adopt two different extruders with described smooth superficial layer raw material and acrylic resin fusion, and molten product comprised that by same two-layer die head extrudes curtain coating simultaneously, the two membranes that obtains after the extruding cast-sheet that just obtains stacked together just can obtain polypropylene film of the present invention again after biaxial tension; When the both side surface that obtains the polypropylene sandwich layer when needs all is attached with the polypropylene film of smooth superficial layer, can adopt three different extruders with raw materials melt (wherein, add polypropylene in the main extruder, all add smooth superficial layer raw material in the extruder of top layer), and molten product comprised that by same three layers die head extrudes curtain coating simultaneously, the trilamellar membrane that obtains after the extruding cast-sheet that obtains stacked together just can obtain polypropylene film of the present invention again after biaxial tension.
According to the present invention, described condition and the used extruder of extruding curtain coating is as well known to those skilled in the art.For example, can adopt single screw extrusion machine, double screw extruder etc.The condition of extruding generally includes extrusion temperature and curtain coating chilling temperature, and described extrusion temperature comprises extruder temperature, draping district temperature and head temperature, and described extrusion temperature can be 160-250 ℃; Described curtain coating chilling temperature refers generally to the temperature of casting roller, can be 10-95 ℃.
According to the present invention, described biaxial tension can be carried out in biaxial tension equipment, for example carries out biaxial tension in the model available from German Br ü ckner company is the film biaxial orientation stretching machine of Karo IV.Described biaxial tension can adopt synchronous method to stretch, and namely carries out film vertically (MD) and laterally (TD) stretching simultaneously; Also can adopt the method for fractional steps to stretch, namely carry out vertically (MD) stretching of film earlier, carry out laterally (TD) stretching of film then; Perhaps, carry out laterally (TD) stretching of film earlier, carry out vertically (MD) stretching of film then.Particularly, described synchronous method is stretched as: will extrude cast-sheet that curtain coating obtains at 110-80 ℃ down after the abundant preheating, and carry out the synchro-draw of MD and TD direction; Wherein, the MD stretching ratio can be 2-7 times, and the TD stretching ratio can be 4-12 times, and draft temperature can be 110-180 ℃.The described method of fractional steps is stretched as: will extrude cast-sheet that curtain coating obtains at 80-160 ℃ down after the abundant preheating, carry out the stretching of MD direction earlier, stretching ratio can be 2-7 doubly, draft temperature can be 80-160 ℃; And then after abundant preheating under 140-180 ℃, carry out the stretching of TD direction, and stretching ratio can be 4-12 times, draft temperature can be 140-180 ℃.
According to the present invention, the film that obtains can also be carried out annealing in process behind the described drawing and forming, produce bigger contraction with the film that prevents from obtaining; Film after perhaps directly will stretching carries out just can obtaining polypropylene film product of the present invention after cutting edge and the rolling.
According to the present invention, the selection of the thickness of the content of described self-lubricating particulate, the thickness of polypropylene sandwich layer, smooth superficial layer and the particle diameter of self-lubricating particulate is described hereinbefore, here repeats no more.
The used hot-air oven of embodiment and Comparative Examples is available from Beijing Jing Tong instrument plant, and model is DF205; The extruding pelletization device therefor is double screw extruder, and available from German WP company, model is ZSK25; Biaxial orientation stretching machine is available from German Br ü ckner company, and model is Karo IV; Extrude casting apparatus available from Sweden Labtech company, model is LCR400; Polyacrylic melt index is that the fusion index instrument of MP600 is measured by the model available from U.S. TO company.The polytetrafluoroethylene (PTFE) particulate is available from Su Wei group, and melt temperature is that 327-333 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.04 and 0.04; Described medlin particulate is available from Hubei bismaleimide resin factory, and melt temperature is that 330-400 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.06 and 0.06; Polyamide particles is available from the Guangzhou Long Suliaocailiaochang that escapes, and melt temperature is that 255-265 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.42 and 0.35; Described polyether-ether-ketone particulate is available from Britain Wei Gesi company, and melt temperature is that 334-340 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.2 and 0.2; The erucyl amide particulate is available from Britain standing grain major company, and melt temperature is that 79-81 ℃, confficient of static friction and the coefficient of kinetic friction are respectively 0.06 and 0.06.
Embodiment 1
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Among this embodiment, form the polypropylene of polypropylene sandwich layer and smooth superficial layer available from Maoming petrochemical industry, the melt index under 230 ℃, 2.16kg is that 2.8 grams/10 minutes, melt temperature are 160 ℃.
(1) preparation of smooth superficial layer raw material:
Polypropylene is carried out drying in hot-air oven, wherein, purged 8 hours continuously with 80 ℃ heated drying air.The polytetrafluoroethylene (PTFE) particulate (particle diameter is the 2-4 micron) of the dried polypropylene of the process of 99.5 weight portions and 0.5 weight portion joined in the mixer under 25 ℃, stir, mixer is earlier with 100 rev/mins of mixed on low speed 7 minutes, and then with 200 rev/mins of high-speed mixing 8 minutes;
The above-mentioned mixture that stirs is sent in the double screw extruder, and the rotating speed of adjusting screw rod is 360 rev/mins, and each zone temperatures is controlled respectively: 200 ℃, 200 ℃, 215 ℃, 215 ℃, 215 ℃ and 210 ℃; The vacuum of each section remains 0.02 to 0.09 MPa; Mixture after fusion, shearing, dispersion, compression, exhaust, plastifying, extrude, is extruded, after the pelletizing, is finally obtained smooth superficial layer raw material through die head again in the screw rod and cylindrical shell of above-mentioned extruder.
(2) preparation of cast-sheet:
The smooth superficial layer raw material that polypropylene and step (1) are obtained carries out drying respectively in hot-air oven, wherein, dry mode is for 80 ℃ heated drying air purging 8 hours continuously.Dried polypropylene adding is extruded in the main extruder of casting apparatus, the smooth superficial layer raw material adding that step (1) obtains is extruded in the top layer extruder of casting apparatus, melt extrude, and through the casting roller flow casting molding, obtaining skin depth is 70 microns, and core layer thickness is 875 microns raw material sheet material.Wherein, the temperature of two extruders is set consistent, and each zone temperatures of extruder is respectively 230 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, and draping district temperature is 240 ℃, and head temperature is 240 ℃, and the casting roller temperature is 25 ℃.
(3) biaxial tension moulding:
The raw material sheet material that step (2) is obtained carries out biaxial tension with biaxial orientation stretching machine.Used stretching mode stretches for carrying out carrying out TD after MD stretches earlier, and wherein, the preheat temperature that MD stretches is that 150 ℃, draft temperature are that 150 ℃, stretching ratio are 5 times; The preheat temperature that TD stretches is that 172 ℃, draft temperature are that 165 ℃, stretching ratio are 7 times.Formation comprises the polypropylene film X1 of polypropylene sandwich layer and the smooth superficial layer of a side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 25 microns, and the thickness of smooth superficial layer is 2 microns.
Embodiment 2
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Among this embodiment, form the polypropylene of polypropylene sandwich layer and smooth superficial layer available from TPC company, the melt index under 230 ℃, 2.16kg is that 5 grams/10 minutes, melt temperature are 158 ℃.
(1) preparation of smooth superficial layer raw material:
Polypropylene is carried out drying in hot-air oven, wherein, dry mode purged 8 hours continuously for the heated drying air with 80 ℃.With the polytetrafluoroethylene (PTFE) particulate (particle diameter is the 1-2 micron) of the dried polypropylene of the process of 97 weight portions and 3 weight portions add mixer under 25 ℃, stir, mixer is earlier with 120 rev/mins of mixed on low speed 5 minutes, and then with 180 rev/mins of high-speed mixing 6 minutes;
The above-mentioned mixture that stirs is sent in the double screw extruder, and the rotating speed of adjusting screw rod is 150 rev/mins, and each zone temperatures is controlled respectively at 180 ℃, 190 ℃, 200 ℃, 200 ℃, 200 ℃ and 190 ℃; The vacuum of each section remains 0.02 to 0.09 MPa; Mixture after fusion, shearing, dispersion, compression, exhaust, plastifying, extrude, is extruded, after the pelletizing, is finally obtained smooth superficial layer raw material through die head again in the screw rod and cylindrical shell of above-mentioned extruder.
(2) preparation of cast-sheet:
The smooth superficial layer raw material that polypropylene and step (1) are obtained carries out drying respectively in hot-air oven, wherein, dry mode is for 80 ℃ heated drying air purging 8 hours continuously.Dried polypropylene adding is extruded in the main extruder of casting apparatus, the smooth superficial layer raw material adding that step (1) obtains is extruded in the top layer extruder of casting apparatus, melt extrude, and through the casting roller flow casting molding, obtaining skin depth is 35 microns, and core layer thickness is 665 microns raw material sheet material.Wherein, the temperature of two extruders is set consistent, and each zone temperatures of extruder is respectively 190 ℃, 210 ℃, 200 ℃, 200 ℃, 200 ℃,, draping district temperature is 200 ℃, and head temperature is 200 ℃, and the casting roller temperature is 30 ℃.
(3) biaxial tension moulding:
The raw material sheet material that step (2) is obtained carries out biaxial tension with biaxial orientation stretching machine.Used stretching mode is for carrying out film vertically (MD) and laterally (TD) stretching simultaneously, and wherein, the preheat temperature during stretching is that 150 ℃, draft temperature are 160 ℃, and the MD stretching ratio is 5 times, and the TD stretching ratio is 7 times.Formation comprises the polypropylene film X2 of polypropylene sandwich layer and the smooth superficial layer of a side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 15 microns, and the thickness of smooth superficial layer is 1 micron.
Embodiment 3
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Among this embodiment, form the polypropylene of polypropylene sandwich layer and smooth superficial layer available from Maoming petrochemical industry, the melt index under 230 ℃, 2.16kg is that 0.5 gram/10 minutes, melt temperature are 165 ℃.
(1) preparation of smooth superficial layer raw material:
Polypropylene is carried out drying in hot-air oven, wherein, dry mode purged 8 hours continuously for the heated drying air with 80 ℃.The polyether-ether-ketone particulate (particle diameter is the 3-6 micron) of the dried polypropylene of the process of 98.5 weight portions and 1.5 weight portions joined in the mixer under 25 ℃, stir, mixer is earlier with about 5 minutes of 100 rev/mins of mixed on low speed, and then with 200 rev/mins of high-speed mixing 6 minutes;
The above-mentioned mixture that stirs is sent in the double screw extruder, adjusted the rotating speed of screw rod, be 300 rev/mins, each zone temperatures is controlled respectively at 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃ and 210 ℃; The vacuum of each section remains 0.02 to 0.09 MPa; Mixture after fusion, shearing, dispersion, compression, exhaust, plastifying, extrude, is extruded, after the pelletizing, is finally obtained smooth superficial layer raw material through die head again in the screw rod and cylindrical shell of above-mentioned extruder.
(2) preparation of cast-sheet:
The smooth superficial layer raw material that polypropylene and step (1) are obtained carries out drying respectively in hot-air oven, wherein, dry mode is for 80 ℃ heated drying air purging 8 hours continuously.Dried polypropylene adding is extruded in the main extruder of casting apparatus, the smooth superficial layer raw material adding that step (1) obtains is extruded in the upper and lower top layer extruder of casting apparatus, melt extrude, and through the casting roller flow casting molding, obtaining skin depth is 105 microns, and core layer thickness is 1190 microns raw material sheet material.Wherein, the temperature of three extruders is set consistent, and each zone temperatures of extruder is respectively 200 ℃, 230 ℃, 220 ℃, 220 ℃, 220 ℃, and draping district temperature is 220 ℃, and head temperature is 220 ℃, and the casting roller temperature is 25 ℃.
(3) biaxial tension moulding:
The raw material sheet material that step (2) is obtained carries out biaxial tension with biaxial orientation stretching machine.Used stretching mode stretches for carrying out carrying out TD after MD stretches earlier, and wherein, the preheat temperature that MD stretches is that 150 ℃, draft temperature are that 150 ℃, stretching ratio are 5 times; The preheat temperature that TD stretches is that 172 ℃, draft temperature are that 165 ℃, stretching ratio are 7 times.Formation comprises the polypropylene film X3 of polypropylene sandwich layer and the smooth superficial layer of the both side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 30 microns, and the thickness of two-layer smooth superficial layer is 3 microns.
Embodiment 4
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Method according to embodiment 3 prepares polypropylene film, and different is that described polyether-ether-ketone particulate substitutes with medlin particulate (particle diameter is the 3-6 micron).Formation comprises the polypropylene film X4 of polypropylene sandwich layer and the smooth superficial layer of the both side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 30 microns, and the thickness of two-layer smooth superficial layer is 3 microns.
Embodiment 5
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Method according to embodiment 2 prepares polypropylene film, and different is that described polytetrafluoroethylene (PTFE) particulate substitutes with polyamide particles (particle diameter is the 1-2 micron).Formation comprises the polypropylene film X5 of polypropylene sandwich layer and the smooth superficial layer of a side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 15 microns, and the thickness of smooth superficial layer is 1 micron.
Embodiment 6
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Method according to embodiment 3 prepares polypropylene film, different is, described self-lubricating particulate polyether-ether-ketone particulate is with the mixture replacing of medlin particulate (particle diameter is the 3-6 micron) and polytetrafluoroethylene (PTFE) particulate (particle diameter is the 3-6 micron), wherein, the weight ratio of described medlin particulate and polytetrafluoroethylene (PTFE) particulate is 1: 1.Formation comprises the polypropylene film X6 of polypropylene sandwich layer and the smooth superficial layer of the both side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 30 microns, and the thickness of two-layer smooth superficial layer is 3 microns.
Embodiment 7
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Method according to embodiment 2 prepares polypropylene film, and different is, in the preparation process of smooth superficial layer raw material, described polyacrylic addition is 90 weight portions, and the addition of described polytetrafluoroethylene (PTFE) particulate is 10 weight portions.Formation comprises the polypropylene film X7 of polypropylene sandwich layer and the smooth superficial layer of a side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 15 microns, and the thickness of smooth superficial layer is 1 micron.
Embodiment 8
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Method according to embodiment 2 prepares polypropylene film, and different is, in the preparation process of smooth superficial layer raw material, described polyacrylic addition is 88 weight portions, and the addition of described polytetrafluoroethylene (PTFE) particulate is 12 weight portions.Formation comprises the polypropylene film X8 of polypropylene sandwich layer and the smooth superficial layer of a side surface that is attached to described polypropylene sandwich layer, and wherein, the thickness of polypropylene sandwich layer is 15 microns, and the thickness of smooth superficial layer is 1 micron.
Embodiment 9
This embodiment is used for the preparation of explanation polypropylene film provided by the invention.
Method according to embodiment 3 prepares polypropylene film, different is, in the preparation process of polypropylene film, the MD stretching ratio is 4 times in the step (3) by controlling, the TD stretching ratio is 5 times, the thickness of the polypropylene sandwich layer of the polypropylene film X9 that obtains is 60 microns, and the thickness of smooth superficial layer is 5 microns.
Comparative Examples 1
This Comparative Examples is used for the reference preparation of explanation polypropylene film.
Mode according to embodiment 1 prepares polypropylene film, different is, this Comparative Examples does not comprise the step of the preparation of smooth superficial layer raw material, but polypropylene and polytetrafluoroethylene (PTFE) particulate directly mixed and send in the casting machine extrudate flow and delay biaxial tension, obtain the polypropylene film of individual layer, be specially:
(1) preparation of cast-sheet:
The mixture of the polypropylene among the embodiment 1 and polytetrafluoroethylene (PTFE) particulate is carried out drying in hot-air oven, wherein, dry mode purged 8 hours continuously for the heated drying air with 80 ℃.Dried described mixture added extrude in the same extruder of casting apparatus, melt extrude, and through the casting roller flow casting molding, obtain thickness and be 700 microns raw material sheet material.Wherein, each zone temperatures of extruder is respectively 200 ℃, 230 ℃, 220 ℃, 220 ℃, 220 ℃, and draping district temperature is 220 ℃, and head temperature is 220 ℃, and the casting roller temperature is 45 ℃.
(2) biaxial tension moulding:
The raw material sheet material that step (1) is obtained carries out biaxial tension with biaxial orientation stretching machine.Used stretching mode stretches for carrying out carrying out TD after MD stretches earlier, and wherein, the preheat temperature that MD stretches is that 150 ℃, draft temperature are that 150 ℃, stretching ratio are 5 times; The preheat temperature that TD stretches is that 172 ℃, draft temperature are that 172 ℃, stretching ratio are 7 times.Formation contains the polypropylene film D1 of self-lubricating particulate, and wherein, the thickness of polypropylene film D1 is 27 microns.
Comparative Examples 2
This Comparative Examples is used for the reference preparation of explanation polypropylene film.
Method according to Comparative Examples 1 prepares polypropylene film, and different is, does not add the polytetrafluoroethylene (PTFE) particulate when preparing described polypropylene film, forms the polypropylene film D2 of the individual layer that does not contain the self-lubricating particulate.Wherein, the thickness of described polypropylene film is 27 microns.
Comparative Examples 3
This Comparative Examples is used for the reference preparation of explanation polypropylene film.
Method according to Comparative Examples 1 prepares polypropylene film, and different is that described polytetrafluoroethylene (PTFE) particulate substitutes with the erucyl amide particulate, forms polypropylene film D3.Wherein, the thickness of described polypropylene film is 27 microns.
Comparative Examples 4
This Comparative Examples is used for the reference preparation of explanation polypropylene film.
Method according to embodiment 5 prepares polypropylene film, and different is that described polyamide particles substitutes with silicon dioxide microparticle (particle diameter is the 1-2 micron), forms polypropylene film D4.Wherein, the thickness of polypropylene sandwich layer is 15 microns, and the thickness of smooth superficial layer is 1 micron.
Test case 1-9
Test case 1-9 is used for the test of explanation polypropylene film performance.
(1) test of smooth performance:
The smooth performance of film is according to the method for GB/T10006, with the PPT-F1 type friction coefficient instrument test of Jinan blue streak company.The gained result is as shown in table 1.
(2) test of mist degree and glossiness:
The film mist degree is according to the method for GB/T2410, with the A-4725 type transmission mist shadow analyzer test of German BYK company; The film glossiness is according to the method for ASTMD2457-08, with the A-4454 type glossiness tester test of German BYK company.The gained result is as shown in table 1.
(3) test of mechanical property:
Thin film mechanical performance is according to the method for GB/T1040.3-2006, with the Z020 type cupping machine test of German Zwick company.The gained result is as shown in table 1.
Contrast test example 1-4
Contrast test example 1-4 is used for the test of explanation reference polypropylene film performance.
Method according to test case 1-9 is tested the performance of polypropylene film, and different is that described polypropylene film is respectively the polypropylene film D1-D4 that Comparative Examples 1-4 makes.The gained result is as shown in table 1.
From the result of table 1 as can be seen, the polypropylene film that adopts method provided by the invention to prepare has excellent smooth performance, and Film Optics performance and mechanical property are all better.
Claims (13)
1. a polypropylene film is characterized in that, described film comprises the polypropylene sandwich layer and be attached to the smooth superficial layer of at least one side surface of described polypropylene sandwich layer that described smooth superficial layer is the polypropylene layer that is dispersed with the self-lubricating particulate; Polypropylene in described polypropylene sandwich layer and the smooth superficial layer is 0.5g/10min-5g/10min at 230 ℃, the melt index of 2.16kg; Described self-lubricating particulate be melt temperature more than or equal to 250 ℃, confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle.
2. polypropylene film according to claim 1, wherein, described high molecular particle is selected from one or more in polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and the polyether-ether-ketone particulate.
3. polypropylene film according to claim 1 and 2 wherein, is benchmark with the gross mass of described smooth superficial layer, and the content of described self-lubricating particulate is 0.05-10 weight %, is preferably 0.5-3 weight %.
4. polypropylene film according to claim 1 and 2, wherein, the thickness of described polypropylene sandwich layer is the 5-70 micron, and the thickness of the smooth superficial layer of described polypropylene sandwich layer one side is the 0.1-10 micron, and the particle diameter of described self-lubricating particulate is the 0.1-20 micron; Preferably, the thickness of described polypropylene sandwich layer is the 15-30 micron, and the thickness of the smooth superficial layer of described polypropylene sandwich layer one side is the 1-3 micron, and the particle diameter of described self-lubricating particulate is the 1-6 micron.
5. polypropylene film according to claim 4, wherein, the particle diameter of described self-lubricating particulate is the 100%-200% of thickness of the smooth superficial layer of described polypropylene sandwich layer one side.
6. polypropylene film according to claim 1, wherein, the polyacrylic melt temperature in described polypropylene sandwich layer and the smooth superficial layer is 148-165 ℃.
7. the preparation method of a polypropylene film is characterized in that, this method comprises sends into melting mixing and extruding pelletization in the extruder after polypropylene and self-lubricating particulate mixed, and obtains smooth superficial layer raw material; Described smooth superficial layer raw material and polypropylene sent into have extruding of multi-layer co-extruded structure and extrude curtain coating in the casting apparatus, obtain the cast-sheet of the smooth superficial layer of at least one side surface of comprising the polypropylene sandwich layer and being attached to described polypropylene sandwich layer; The cast-sheet that obtains is carried out biaxial tension, obtain comprising the bidirectional stretching polypropylene film of polypropylene sandwich layer and the smooth superficial layer of at least one side surface that is attached to described polypropylene sandwich layer; Described smooth superficial layer is the polypropylene layer that is dispersed with the self-lubricating particulate; Polypropylene in described polypropylene sandwich layer and the smooth superficial layer is 0.5g/10min-5g/10min at 230 ℃, the melt index of 2.16kg; Described self-lubricating particulate is that melt temperature is more than or equal to 250 ℃, and confficient of static friction and the coefficient of kinetic friction all are less than or equal to 0.6 high molecular particle.
8. method according to claim 7, wherein, described high molecular particle is selected from one or more in polytetrafluoroethylene (PTFE) particulate, medlin particulate, polyamide particles and the polyether-ether-ketone particulate.
9. according to claim 7 or 8 described methods, wherein, the feasible gross mass with the smooth superficial layer of described polypropylene of the consumption of described self-lubricating particulate is benchmark, and the content of self-lubricating particulate is 0.05-10 weight %, is preferably 0.5-3 weight %.
10. according to claim 7 or 8 described methods, wherein, the consumption of described polypropylene and self-lubricating particulate and biaxial tension condition make that the thickness of described polypropylene sandwich layer is the 5-70 micron, and the thickness of the smooth superficial layer of described polypropylene sandwich layer one side is the 0.1-10 micron; Under the preferable case, the consumption of described polypropylene and self-lubricating particulate and biaxial tension condition make that the thickness of described polypropylene sandwich layer is the 15-30 micron, and the thickness of the smooth superficial layer of described polypropylene sandwich layer one side is the 1-3 micron.
11. method according to claim 10, wherein, the particle diameter of described self-lubricating particulate is the 100%-200% of thickness of the smooth superficial layer of described polypropylene sandwich layer one side.
12. method according to claim 7, wherein, the cross directional stretch multiplying power of described biaxial tension is 2-7 times, and the longitudinal stretching multiplying power is 4-12 times.
13. one kind by any polypropylene film that described method prepares among the claim 7-12.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106273970A (en) * | 2016-08-03 | 2017-01-04 | 海宁长昆包装有限公司 | Biaxially oriented polypropylene heat-sealing film that a kind of coefficient of friction is low and preparation method thereof |
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