CN101927590A - Multilayer coextruded polyethylene film processed in down-blowing water-cooling ring film method - Google Patents
Multilayer coextruded polyethylene film processed in down-blowing water-cooling ring film method Download PDFInfo
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Abstract
The invention discloses a multilayer coextruded polyethylene film processed in a down-blowing water-cooling ring film method. The multilayer coextruded polyethylene film comprises a corona disposal layer and a heat seal layer, and can also consist of a core layer, wherein the formula for each layer comprises: 60-95 parts of polyethylene, 5-40 parts of butylene polymer or propylene polymer, 0.005-1 part of anti-blocking agent, 0.005-1 part of slipping agent, 0.005-0.5 part of nucleating agent, and 0-0.5 part of fluorocarbon resin. By introducing sphaerocrystal through adding the butylene polymer or the propylene polymer in the formula, improving the crystallinity under the effect of the nucleating agent, and regulating the microcosmic planeness of the film surface in the present of fluorocarbon resin, the film has both the high composite strength and good anti-blocking property of a composite film and high transparency, can withstand water boiling sterilization at a temperature over 100 DEG C and stewing sterilization at a temperature below 121 DEG C, has low friction coefficient and attractive appearance. The product prepared in the formula reaches the ideal mutual balance among processability, optical property, mechanical property and temperature tolerance, and can be used for mass production with low industrial production cost.
Description
Technical field
The present invention relates to a kind of polyethylene film, especially a kind of utilize have excellent optical property after the downward-blowing water-cooling ring film method processing, the multi-layer co-extruded polyethylene film of easily processing, combined strength bination height, anti-poach sterilization and thermophilic digestion sterilizations below 121 degrees centigrade more than 100.
Background technology
Ring film blow moulding is to use extruder, by the annular port mould, adopts the method that membrane process is made film that is blown into.
At present, in the film production field, main film forming method has The tape casting and ring film blow moulding etc.
The tape casting is mainly used in processing polypropylene, the advantage of this method is: the film flatness is good, good in optical property, shortcoming is: the equipment cost height, product cost height, opening difficulty, coefficient of friction are big etc., and to be it does not obtain the reason that maximum magnitude is used in the polyethylene film production technology in that China is compound for this.The The tape casting polyethylene film is poor because of opening, the deflection deficiency, easily produce brilliant point, can not satisfy water boiling resistance sterilization requirement seldom with the processing of this method;
This manufacturing technique method of ring film blow moulding mainly is divided into two kinds of methods for cooling of up-draught cold-peace downward-blowing water-cooling: the up-draught cold process, be polyolefin through extruder, annular die head moulding extrude, the method for film forming after air-cooled, be mainly used in the processing polyethylene, polypropylene is slow because of crystallization rate, shear shinning is fast, and can't use this method processing.Its advantage is: film forming is easy, and cost is low, but shortcoming is: cooling is slow, the Film Optics poor performance.
The lower blowing water cold type, the basic module of equipment is identical with upward type, and different is to blow with the form of recirculated cooling water as cooling medium down.In the poly prescription of existing downward-blowing water-cooling ring embrane method, usually the corona layer is a polyethylene, sandwich layer is a polyethylene, hot sealing layer comprises polyethylene, Si oxide and erucyl amide, the problem that the multi-layer co-extruded film that existing traditional downward-blowing water-cooling ring embrane method polyethylene prescription obtains exists is: (1) fracture strength is low, poor mechanical property, (2) corona synchronously, corona rear film appearance poor synchronously, combined strength bination is low, can not do composite membrane, (3) rolling be very easy to wrinkling, can't industrial-scale production, (4) opening poor performance, be difficult to take into account simultaneously opening performance and composite performance, (5) not anti-high temperature more than 100 degrees centigrade.Thereby can not be applied to exigent composite soft packaging industry.
Summary of the invention
The technical problem to be solved in the present invention is: the above-mentioned shortcoming that exists at present traditional downward-blowing water-cooling ring embrane method polyethylene prescription, but for providing a kind of, the user has high combined strength bination and good opening concurrently, have the multi-layer co-extruded polyethylene film of the high grade of transparency and lower temperature resistance, low-friction coefficient, easily processing, anti-poach sterilization and the large-scale production of thermophilic digestion sterilizations below 121 degrees centigrade more than 100 concurrently simultaneously.
The inventor finds: it mainly is in order to obtain high optical property or flexibility that existing common polythene prescription film uses the downward-blowing water-cooling method, but this method for rapid cooling degree of crystallinity that has been independent reduction, the reduction of degree of crystallinity is accompanied by the decline of mechanical property, thereby cause film deflection deficiency, easy sticking to mould, be difficult for processing and the above high temperature of ability 100 degree, opening is bad, occurs behind the corona being clamminess; In order to improve degree of crystallinity, simple adding PE nucleator does not have the good mechanical performance too, because adding along with the PE nucleator, just produced more polyethylene sheet crystal, the mechanical property of product can not obtain the raising of essence, if can introduce spherocrystal, cooperates the use of nucleator again, then can take into account nucleation rate and crystal size simultaneously, make product have good optical performance, mechanical property and heat-resisting quantity concurrently.
Therefore the inventor passes through repetition test, determine to introduce sphaerocrystal as the seed of spherocrystal by adding butene polymers or acrylic polymers, therefore just there have been the seed of spherocrystal, seed, spherocrystal and the platelet zone of intersection of platelet in the product, use in conjunction with nucleator increases degree of crystallinity again, thereby mechanical property and heat-resisting quantity improve, grain refinement simultaneously makes film have the good optical performance concurrently, improve film surface microcosmic planarization by introducing fluorocarbon resin simultaneously, reached the balance of desirable processability, optical, mechanicalness, rub resistance.
In sum, technical scheme of the present invention is as follows:
A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, hot sealing layer, and by mass parts, the prescription of described corona processing layer, hot sealing layer comprises:
Corona processing layer: polyethylene 60-95 part; Butene polymers or acrylic polymers 5-40 part; Opening agent 0.005-1 part; Slipping agent 0.005-1 part; Nucleator 0.005-0.5 part; Fluorocarbon resin 0-0.5 part;
Hot sealing layer: polyethylene 60-95 part; Butene polymers or acrylic polymers 5-40 part; Opening agent 0.005-1 part; Slipping agent 0.005-1 part; Nucleator 0.005-0.5 part; Fluorocarbon resin 0-0.5 part.
As preferably, be provided with sandwich layer between corona processing layer and hot sealing layer: by mass parts, the prescription of described sandwich layer comprises: polyethylene 60-95 part; Butene polymers or acrylic polymers 5-40 part; Opening agent 0.005-1 part; Slipping agent 0.005-1 part; Nucleator 0.005-0.5 part; Fluorocarbon resin 0-0.5 part.
As preferably, described nucleator is a benzyl class nucleator.
As preferably, the polyethylene of described corona processing layer can be: high density polyethylene (HDPE), low density polyethylene (LDPE), one or more of LLDPE.
As preferably, the polyethylene of described hot sealing layer can be: metallocene high density polyethylene (HDPE), metallocene low density polyethylene (LDPE), one or more of metallocene medium density polyethylene.
As preferably, the polyethylene of described sandwich layer, one or more in available high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), ultra-low density polyethylene, LLDPE, linear density polyethylene, linear high-density polyethylene, metallocene low density polyethylene (LDPE), metallocene medium density polyethylene, the metallocene high density polyethylene (HDPE).
As preferably, described opening agent is silica, magnesia, PMMA.
As preferably, described silica and magnesian particle diameter are 5-15um.
As preferably, the particle diameter of described PMMA is 10-20um.
The particle diameter of opening agent is so set, and has avoided the opening agent excessive and influence transparency, and if opening agent particle diameter too small, then can be embedded in the film the inside and can not form pit at film surface, finally influence the opening of film.
As preferably, described slipping agent, available erucyl amide or oleamide.
The multi-layer co-extruded polyethylene film that prescription disclosed by the invention uses downward-blowing water-cooling ring embrane method to obtain, introduced sphaerocrystal by adding butene polymers or acrylic polymers, make the seed that has spherocrystal in the product, the seed of platelet, the spherocrystal and the platelet zone of intersection, under the effect of nucleator, improved degree of crystallinity, under the fluorocarbon resin effect, adjust film surface microcosmic flatness simultaneously, make film have energy Compound Machining and high combined strength bination and good opening concurrently, has the high grade of transparency simultaneously, ability is poach sterilization and 121 degrees centigrade following cooking disinfections more than 100, and film friction coefficient is low, product appearance is good; The particle diameter of opening agent is set moderate, can not influence transparency because opening agent particle diameter is excessive, again can be because of the too small opening that finally influences film of opening agent.The product of this prescription has reached the mutual balance of desirable processability, optical, mechanicalness, heat-resisting quantity, but and large-scale production, industrial production cost is low.
This prescription and regular convention formula see Table 1 with the film performance correction data that the processing of downward-blowing water-cooling ring embrane method obtains.As can be seen from Table 1, it is 124 degree that this prescription film is difficult for exfoliation temperature, so the distortion of film and heatproof can satisfy the requirement of the following thermophilic digestion sterilization of 121 degree.
Table 1
The specific embodiment
Following non-limiting example is used to illustrate the present invention:
Process equipment of the present invention is general downward-blowing water-cooling inflation film manufacturing machine.
Use three-layer co-extruded downward-blowing water-cooling film blow molding machine group when containing sandwich layer, process conditions such as table 2:
Table 2
| Outer heating one district | Outer heating two districts | Outer heating three districts | The outer joint thermal treatment zone |
| 160－170℃ | 180－225℃ | 180－225℃ | 180－225℃ |
| Heating one district, middle level | Heating two districts, middle level | Heating three districts, middle level | The joint thermal treatment zone, middle level |
| 160－170℃ | 180－225℃ | 180－225℃ | 180－225℃ |
| Internal layer heating one district | Internal layer heating two districts | Internal layer heating three districts | The internal layer joint thermal treatment zone |
| 160－170℃ | 180－225℃ | 180－225℃ | 180－225℃ |
| The die head thermal treatment zone | Die head heating one district | Die head heating two districts | Die head heating three districts |
| 180－230℃ | 180－230℃ | 180－230℃ | 180－230℃ |
| Outer main frame speed governing | Middle level main frame speed governing | The speed governing of internal layer main frame | The electric rotating machine speed governing |
| 15－45RPM | 15－45RPM | 15－45RPM | 10-30 |
| ? | Corona output is provided with | Circulating water temperature | ? |
| ? | 2.3-3.5 | 15－25℃ | ? |
When not containing sandwich layer, use two-layer co-extrusion downward-blowing water-cooling film blow molding machine group, process conditions such as table 3:
Table 3
| Outer heating one district | Outer heating two districts | Outer heating three districts | The outer joint thermal treatment zone |
| 160－170℃ | 180－225℃ | 180－225℃ | 180－225℃ |
| Internal layer heating one district | Internal layer heating two districts | Internal layer heating three districts | The internal layer joint thermal treatment zone |
| 160－170℃ | 180－225℃ | 180－225℃ | 180－225℃ |
| The die head thermal treatment zone | Die head heating one district | Die head heating two districts | Die head heating three districts |
| 180－230℃ | 180－230℃ | 180－230℃ | 180－230℃ |
| Outer main frame speed governing | Middle level main frame speed governing | The speed governing of internal layer main frame | The electric rotating machine speed governing |
| 15－45RPM | 15－45RPM | 15－45RPM | 10-30 |
| ? | Corona output is provided with | Circulating water temperature | ? |
| ? | 2.3-3.5 | 15－25℃ | ? |
The following example is used to illustrate different prescriptions:
Embodiment 1A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, hot sealing layer, and by mass parts, the prescription of described corona processing layer, hot sealing layer comprises:
(1) corona processing layer:
95 parts of LLDPEs; 5 parts of butene polymers; 0.005 part of the silica of particle diameter 5um; 0.005 part of erucyl amide; 0.005 part of benzyl class nucleator; 0.5 part of fluorocarbon resin;
(2) hot sealing layer:
95 parts of metallocene high density polyethylene (HDPE)s; 5 parts of butene polymers; 0.005 part of the silica of particle diameter 5um; 0.005 part of erucyl amide; 0.005 part of benzyl class nucleator; 0.5 part of fluorocarbon resin.
Embodiment 2A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, hot sealing layer, and by mass parts, the prescription of described corona processing layer, hot sealing layer comprises:
(1) corona processing layer:
60 parts of high density polyethylene (HDPE)s; 40 parts of acrylic polymers; 1 part in the magnesia of particle diameter 15um; 1 part of oleamide; 0.5 part of benzyl class nucleator;
(2) hot sealing layer:
60 parts of metallocene medium density polyethylenes; 40 parts of acrylic polymers; 1 part in the magnesia of particle diameter 15um; 0.005 part of oleamide; 0.5 part of benzyl class nucleator;
Embodiment 3A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, hot sealing layer, and by mass parts, the prescription of described corona processing layer, hot sealing layer comprises:
(1) corona processing layer:
80 parts of low density polyethylene (LDPE)s; 20 parts of acrylic polymers; PMMA0.2 part of particle diameter 10um; 1 part of erucyl amide; 0.2 part of benzyl class nucleator;
(2) hot sealing layer:
80 parts of metallocene low density polyethylene (LDPE)s; 20 parts of acrylic polymers; PMMA0.2 part of particle diameter 10um; 1 part of erucyl amide; 0.2 part of benzyl class nucleator;
Embodiment 4A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, sandwich layer, hot sealing layer, and by mass parts, the prescription of each layer comprises:
(1) corona processing layer:
80 parts of low density polyethylene (LDPE)s; 20 parts of butene polymers; PMMA0.2 part of particle diameter 20um; 1 part of oleamide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin;
(2) sandwich layer:
80 parts of low density polyethylene (LDPE)s; 20 parts of butene polymers; PMMA0.2 part of particle diameter 20um; 1 part of oleamide; 0.2 part of benzyl class nucleator;
(3) hot sealing layer:
80 parts of metallocene low density polyethylene (LDPE)s; 20 parts of butene polymers; PMMA0.2 part of particle diameter 20um; 1 part of oleamide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin.
Embodiment 5A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, sandwich layer, hot sealing layer, and by mass parts, the prescription of each layer comprises:
(1) corona processing layer:
80 parts of low density polyethylene (LDPE)s; 40 parts of butene polymers; PMMA0.2 part of particle diameter 15um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin;
(2) sandwich layer:
20 parts of high density polyethylene (HDPE)s, 30 parts of medium density polyethylenes, 20 parts of ultra-low density polyethylenes; 30 parts of butene polymers; PMMA0.2 part of particle diameter 15um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.5 part of fluorocarbon resin;
(3) hot sealing layer:
80 parts of metallocene low density polyethylene (LDPE)s; 20 parts of butene polymers; PMMA0.2 part of particle diameter 15um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin.
Embodiment 6A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, sandwich layer, hot sealing layer, and by mass parts, the prescription of each layer comprises:
(1) corona processing layer:
80 parts of low density polyethylene (LDPE)s; 5 parts of acrylic polymers; 0.005 part of the silica of particle diameter 5um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin;
(2) sandwich layer:
30 parts of LLDPEs, 20 parts of linear density polyethylenes, 45 parts of linear high-density polyethylenes, 5 parts of acrylic polymers; 0.005 part of the silica of particle diameter 5um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin;
(3) hot sealing layer:
80 parts of metallocene low density polyethylene (LDPE)s; 5 parts of acrylic polymers; 0.005 part of the silica of particle diameter 5um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin.
Embodiment 7A kind of multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, sandwich layer, hot sealing layer, and by mass parts, the prescription of each layer comprises:
(1) corona processing layer:
80 parts of low density polyethylene (LDPE)s; 20 parts of butene polymers; 1 part in the magnesia of particle diameter 15um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin;
(2) sandwich layer:
30 parts of metallocene low density polyethylene (LDPE)s, 20 parts of metallocene medium density polyethylenes, 10 parts of metallocene high density polyethylene (HDPE)s; 30 parts of butene polymers; 1 part in the magnesia of particle diameter 15um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin;
(3) hot sealing layer:
80 parts of metallocene low density polyethylene (LDPE)s; 20 parts of butene polymers; 1 part in the magnesia of particle diameter 15um; 0.2 part of erucyl amide; 0.2 part of benzyl class nucleator; 0.2 part of fluorocarbon resin.
Claims (10)
1. a multi-layer co-extruded polyethylene film that utilizes the processing of downward-blowing water-cooling ring embrane method comprises corona processing layer, hot sealing layer, it is characterized in that by mass parts, the prescription of described corona processing layer, hot sealing layer comprises:
Corona processing layer: polyethylene 60-95 part; Butene polymers or acrylic polymers 5-40 part; Opening agent 0.005-1 part; Slipping agent 0.005-1 part; Nucleator 0.005-0.5 part; Fluorocarbon resin 0-0.5 part;
Hot sealing layer: polyethylene 60-95 part; Butene polymers or acrylic polymers 5-40 part; Opening agent 0.005-1 part; Slipping agent 0.005-1 part; Nucleator 0.005-0.5 part; Fluorocarbon resin 0-0.5 part.
2. according to the described multi-layer co-extruded polyethylene film of claim 1, it is characterized in that: between corona processing layer and hot sealing layer, be provided with sandwich layer:
By mass parts, the prescription of described sandwich layer comprises:
Polyethylene 60-95 part; Butene polymers or acrylic polymers 5-40 part; Opening agent 0.005-1 part; Slipping agent 0.005-1 part; Nucleator 0.005-0.5 part; Fluorocarbon resin 0-0.5 part.
3. according to claim 1 or 2 described multi-layer co-extruded polyethylene films, it is characterized in that: described nucleator is a benzyl class nucleator.
4. according to the described multi-layer co-extruded polyethylene film of claim 1, it is characterized in that: the polyethylene of described corona processing layer can be: high density polyethylene (HDPE), low density polyethylene (LDPE), one or more of LLDPE.
5. according to the described multi-layer co-extruded polyethylene film of claim 1, it is characterized in that: the polyethylene of described hot sealing layer can be: metallocene high density polyethylene (HDPE), metallocene low density polyethylene (LDPE), one or more of metallocene medium density polyethylene.
6. according to the described multi-layer co-extruded polyethylene film of claim 2, it is characterized in that: the polyethylene of described sandwich layer, one or more in available high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), ultra-low density polyethylene, LLDPE, linear density polyethylene, linear high-density polyethylene, metallocene low density polyethylene (LDPE), metallocene medium density polyethylene, the metallocene high density polyethylene (HDPE).
7. according to claim 1 or 2 described multi-layer co-extruded polyethylene films, it is characterized in that: described opening agent is silica, magnesia, PMMA.
8. according to the described multi-layer co-extruded polyethylene film of claim 7, it is characterized in that: described silica and magnesian particle diameter are 5-15um.
9. according to the described multi-layer co-extruded polyethylene film of claim 7, it is characterized in that: the particle diameter of described PMMA is 10-20um.
10. according to claim 1 or 2 described multi-layer co-extruded polyethylene films, it is characterized in that: described slipping agent, available erucyl amide or oleamide.
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| CN109203616B (en) * | 2018-07-11 | 2021-01-08 | 银金达(上海)新材料有限公司 | Three-layer co-extrusion casting film and preparation method thereof |
| CN110588115A (en) * | 2018-10-08 | 2019-12-20 | 林文茂 | High-low temperature resistant high-barrier safety sealing film |
| CN111231462A (en) * | 2019-03-22 | 2020-06-05 | 上海灵博塑料包装有限公司 | Easy-to-open transparent polyethylene blown film with thickness of less than 45 micrometers and preparation method thereof |
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| CN114728509A (en) * | 2020-09-10 | 2022-07-08 | 哈里哈兰·克里希南·奈尔 | Recyclable packaging material and preparation method thereof |
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Application publication date: 20101229 |