CN1896126A - Polyester thin-film with reinforced surface metal adhesion and its production - Google Patents
Polyester thin-film with reinforced surface metal adhesion and its production Download PDFInfo
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- CN1896126A CN1896126A CN 200510027768 CN200510027768A CN1896126A CN 1896126 A CN1896126 A CN 1896126A CN 200510027768 CN200510027768 CN 200510027768 CN 200510027768 A CN200510027768 A CN 200510027768A CN 1896126 A CN1896126 A CN 1896126A
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Abstract
A polyester thin film with reinforced surface metal adhesion and its production are disclosed. The thin film is prepared by on-line coating a special chemical substance layer. It has better reinforced surface metal adhesion and thermal stability.
Description
Technical field
The present invention relates to a kind of production method of biaxially oriented polyester film, the online coating technique of particularly a kind of employing carries out the film surface chemical treatment, makes film have the bi-directional stretching polyester film preparation method of reinforced surface metal adhesion and thermostability.
Background technology
Biaxially oriented polyester film is through being often used as the base material with metal composite, such as being used to aluminize compound aspect the packing, is used for metallizing powder etc. aspect laser.These matrix materials often will experience the technological process that processing temperature is higher, condition is complicated in processing own or use occasion.This just requires the polyester film surface tool not only high metal adhesion will be arranged, and also requires at high temperature still have stable adhesion property simultaneously, is unlikely in processing or use metal level to be split away off from film surface.
Just be widely used in the laminated film of aluminizing of food product pack aspect at present, will experience the high temperature steaming sterilization process one toward contact after the food product pack,, aluminium coated is split away off and lose provide protection packing material if aluminium plating film is at high temperature unstable.Common aluminizing increases the tack that surface polarity improves film and aluminium lamination with polyester film by corona treatment, this film not only tack with aluminium coated is not high, but also can weaken gradually or disappear along with the growth surface polarity of period of storage and influence film and aluminium lamination plyability.In addition, common aluminium plating film at high temperature performance is also very unstable, is difficult to guarantee that aluminium coated can not split away off in the course of processing.Therefore, general thin can't be used for the packaging aluminium plating basement membrane of high temperature steaming.The online application type polyester film that we produce because its surface-coated has the special chemical substance of one deck, makes film surface have enhanced metal adhesion energy.This kind film is unlike common corona film, and its surface property does not have ageing shortcoming.Simultaneously, because coated chemical substance has good high-temperature stability, the composite performance of aluminizing that aluminium plating film at high temperature still can be shown.This kind film is suitable for requiring the processing temperature packaging relatively harsher than higher, the condition compound basement membrane of aluminizing as coffee, hot pickled mustard tube, meat product etc. very much.
The basic structure of application type polyester film is the biaxially oriented polyester film base material, chemical substance coat, aluminium coated and ink printing layer or other film composite bed.In this composite structure, the most important thing is the second layer, be the chemical substance coat, it not only plays and strengthens the effect of putting forth effort again between washing layer and the film substrate layer, and can guarantee some in particular cases (as high temperature, humidity etc.) make this performance that still keeps stable of putting forth effort again.Common aluminizing with in the polyester film, metal level directly is attached on the film substrate, and its performance is often not fully up to expectations, and can not be used for the special occasions that some is had relatively high expectations.
The polyester film for preparing said structure has the main points of two aspects: being the formulation of processing sequence on the one hand, is the selection of coating material and the exploitation of prescription thereof on the other hand.On technology, also can adopt traditional off-line coating method, but the off-line coating after finishing, film production is carried out again, its technological process is numerous and diverse relatively, it is more to add the coating consumption, causes production cost very high, and the price of the finished product is difficult to be accepted by the user.
Summary of the invention
In order to address the above problem, the present invention discloses a kind of polyester film with reinforced surface metal adhesion.Film has a surface to handle through online coating process and applies last layer vibrin chemical substance through stretch processes production.This film substrate also possesses following performance: tensile strength (laterally, vertically) is greater than 200MPa, elongation at break (laterally, vertically) is greater than 90%, mist degree is less than 3.0%, skin friction coefficient less than the heat shrink rate under 0.5,150 ℃, 30min laterally less than 1.0%, vertically less than 2.5%.This film is applicable to the packing basement membrane of require to aluminize plyability height, stable performance under the high temperature process condition.
Among the present invention, the biaxially oriented polyester film of production is handled through online coating process, at a surface-coated last layer polyester resin material, makes film have special surface property.Thickness is 0.03-0.08 μ m after the coating layer drying, and the moistened surface tension force after the coating is greater than 44mN/m, generally greater than 48mN/m.Polyester film has lower mist degree, and generalized case is less than 3.5%, and best situation is less than 3.0%.The frictional coefficient of polyester film surface is generally less than 0.55, and less than 0.5, low frictional coefficient helps the rolling of polyester film and cuts under the best-case, guarantees the excellent processing characteristics of polyester film.Polyester film has lower percent thermal shrinkage, and at 150 ℃ of following heating 30min, laterally percent thermal shrinkage is less than 1.0%, vertically less than 2.5%.Special surface coated material property and the lower percent thermal shrinkage of film have guaranteed the excellent properties of polyester film in high temperature is aluminized the course of processing, have guaranteed that also aluminium plating film still can show stable performance in the high temperature environment for use.
Among the present invention, be used to produce the polyester raw material of biaxially oriented polyester film, be generally polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-, be preferably PET or PEN (ethylene naphthalate) (PEN) and co-polymerization modified polyester thereof.The second-order transition temperature general requirement of polyester raw material is greater than 65 ℃, and more preferably greater than 70 ℃, the fusing point general requirement is greater than 250 ℃, and more preferably greater than 260 ℃, other performance index must meet national standard.
The general employing of coating material can the water-soluble polymer substance that maybe can be scattered in the water, generally is made into the aqueous solution that weight percent is 5%-30%, and concrete concentration is decided on the performance of raw material.Require coating fluid to have lower viscosity, be easy on film drawout, to film in performances such as the horizontal tensile property that draws the stage are similar.The coating material that uses among the present invention is polyester resin WB 630-100, is mixed with 10% the aqueous solution.If coating material influences the processing characteristics of film, can add an amount of surface slip agent and antiblocking agent in the coating fluid.
The method for producing of polyester adopts stretch processes, can be that individual layer is extruded structure, also can be the polyester film of three-layer co-extruded structure.The present invention uses three-layer co-extruded structure, and the polyester film of three-decker contains two upper layer A and C, and the centre is the B layer.The polyester raw material of three-decker is extruded by three forcing machines respectively, and forcing machine can be a single screw extrusion machine, also can be twin screw extruder.A and C can set extrusion capacity separately respectively, and the thickness of A layer and C layer generally between 0.2 μ m-3.0 μ m, is preferably 0.3 μ m-2.0 μ m usually greater than 0.1 μ m, and the A layer can be different with C layer structure.The thickness of middle layer B is generally 0.5 μ m-15 μ m usually greater than 0.5 μ m, is preferably 1.0 μ m-10 μ m.Middle layer B can be different with the material of upper layer A, C, the general thickness of film uses needs to change according to the user, from 6 μ m-75 μ m, is generally 8 μ m-50 μ m, be preferably 10 μ m-25 μ m, the thickness of middle layer B generally accounts for 50% to 95% of whole film thickness.
Have at least one deck to contain antiblocking agent in two upper layers of three-decker, help the processing and the use of polyester film, the material of every layer of usefulness is polyester.Usually the antiblocking agent of usefulness is inorganic particulate or organic filler, such as inorganic particulate or organic fillers such as crosslinked polystyrene, crosslinked poly-interior olefin(e) acid ester particle such as lime carbonate, silicon-dioxide, clay, magnesiumcarbonate, calcium sulfate, calcium phosphate, alchlors.Can select one or more particles as antiblocking agent, perhaps select one type of identical but mix particles that particle diameter is different, antiblocking agent can be to add to make masterbatch when polyester, also can adopt the mode of extruding blend to add, adopt the method for making masterbatch to add antiblocking agent usually.The antiblocking agent particle adds the concentration 0.01-0.4% that is weight percentage in upper layer A and C., be generally 0.02-0.30%.
The dried moisture content that requires of polyester raw material process is less than 50ppm, preferably less than 30ppm.Polyester raw material melt extrudes in forcing machine after the co-extrusion module and arrives cold founding sheet by T type flat-die die head, and the temperature of cold drum is generally less than 50 ℃, preferably less than 30 ℃.In order to obtain good casting sheet effect, can be preferably the auxiliary casting of static sheet with static auxiliary casting sheet or the auxiliary casting of air-flow sheet, subsequently through longitudinal stretching, coating processing, cross directional stretch, heat setting type handle, lax, cooling, traction, rolling.
Online coating treatment process is carried out after film sheet longitudinal stretching and before the cross directional stretch, and diaphragm is coated with pressing diaphragm during by coating machine on coating roll, and coating roll brings to membrane surface with the coating fluid in the liquid bath.The speed of coating roll is consistent with line speed, and the horizontal drying process afterwards of drawing of drying process after the diaphragm coating and film is together finished.
Two-way stretch is generally one by one and stretches, and preferably carries out earlier carrying out cross directional stretch (TD) behind the longitudinal stretching (MD), makes the polyester molecule chain orientation.Longitudinal stretching can be undertaken by predefined different stretch multiplying power with the roller of two friction-motion speeds, and cross directional stretch generally carries out horizontal the drawing in the baking oven of Band clamp.Draft temperature can require to adjust in the scope of a broad usually according to film performance, vertical La Wendu is generally 80-140 ℃, horizontal La Wendu is 90-150 ℃, indulging draws multiplying power to be generally 2.0: 1 to 6.0: 1, be preferably 2.5: 1 to 5.5: 1, vertical drawing can divide several sections to carry out, and also can one section carries out.The horizontal multiplying power of drawing was generally 3.0: 1 to 5.0: 1, was preferably 3.5: 1 to 4.5: 1.
Heat-setting section temperature after the film stretching generally is controlled between 150 ℃ to 250 ℃, carry out heat setting type more than the second-order transition temperature of polyester and below the fusing point and help changing the stretch orientation in the film into crystalline orientation, reduce the percent thermal shrinkage of film.The time of heat setting type is generally 1s-10s, and at a certain temperature, the time is long more, helps the crystalline orientation of film more.
The lax position and the size of time length and relaxation rate directly influence the percent thermal shrinkage of film.Lax generally can vertical draw and horizontal drawing between, cross directional stretch finish and heat-setting section between, and carry out between heat-setting section and the cooling section.Vertical draw with horizontal between relaxation rate be generally less than 1%, preferably less than 0.8%.Horizontal drawknot bundle is generally 0%-5% to the relaxation rate between the heat setting type, 0.5%-4% preferably, and the time is generally 0.0s-1.5s, is preferably 0.5s-1.5s, and temperature is generally 100 ℃-180 ℃, is preferably 120 ℃-170 ℃.The lax 0%-8% that is generally of heat-setting section is preferably 1%-5%, and the time is generally 0.0s-3s, is preferably 1.5s-3s.The relaxation rate of cooling section is generally 0.5%-8%, 1.0%-6% preferably, and the time is generally 0.0s-5s, is preferably 0.5s-5s.
Biaxially oriented polyester film after the horizontal section of drawing finishes can be handled the non-coated face of film with high-voltage corona to the traction section of rolling, also can decide on the purposes of film without corona treatment.If carry out corona, control the density of corona treatment or surface tension that voltage makes film usually greater than 45mN/m (dyne), more preferably greater than 50mN/m.
Description of drawings
Fig. 1 is the basic structure of online application type polyester film and is used for the metal composite synoptic diagram
Among the figure: biaxially oriented polyester film base material 1 chemical substance coat 2
Washing layer 3 other coat 4
Embodiment:
Further specify the technical solution of invention in conjunction with the embodiments:
The preparation of coating fluid:
Coating fluid is 10% polyester resin solution, and main component is WB 630-100 (100% vibrin), and solvent is the mixed solution of water, Virahol (IPA) and Tert Butyl Cellusolve (ETB, effect is to promote the dissolving power of resin in water).Concrete preparation process is: water, IPA, ETB mixed solution are heated to 80 ℃, add the vibrin solid, continued down heated and stirred 3-5 hour at 90 ℃, cooled and filtered is standby.
The course of processing of polyester film:
By aforesaid processing condition, polyester raw material melt extrudes by forcing machine, by being furnished with the co-extrusion die head of co-extrusion block of ingredient, electrostatic adhesion is at cold bulging direct casting sheet, and sheet is made the polyester film that thickness is 12 μ m through longitudinal stretching, online coating processing, cross directional stretch, heat setting type, lax, traction, rolling.
Table 1-4 is respectively raw materials used in for example, technology and product performance detection case.
Table 1: used coating fluid proportioning raw materials situation (IPA: ETB=2: 1) gives an example
| Vibrin | WB 630-100 | 10％ |
| Solvent | IPA+ETB | 6.7％ |
| Water | 83.3％ | |
| Gross weight | 100％ |
Table 2: the raw materials used situation of giving an example
| The forcing machine feed bin | Raw material type | Ingredient proportion (%) |
| Main squeeze (B layer) | The light material is arranged greatly | 75 |
| Reclaimed materials | 25 | |
| Co-extrusion (A layer) | The light material is arranged greatly | 48 |
| Masterbatch | 52 | |
| Co-extrusion (C layer) | The light material is arranged greatly | 48 |
| Masterbatch | 52 |
Table 3: the used manufacturing condition of giving an example
| Project | Unit | Parameter | |
| Feed circuit | Pre-Tc | ℃ | 160 |
| Drying temperature | ℃ | 150 | |
| Expressing technique | Middle B layer temperature | ℃ | 285 |
| The casting blade technolgy | Cold bulging speed | m/min | 72 |
| Cold bulging temperature | ℃ | 25 | |
| Vertical drawing process | Preheating temperature | ℃ | 58-77 |
| Draft temperature | ℃ | 83 | |
| Stretch ratio | - | 3.3 | |
| Horizontal drawing process | Preheating temperature | ℃ | 84.5-98 |
| Draft temperature | ℃ | 102 | |
| Stretch ratio | - | 4.2 | |
| The heat setting type stage | Setting temperature | ℃ | 230 |
| Shaping time | s | 3 | |
| Relaxation rate | ％ | 2 | |
| Cooling stages | Cooling temperature | ℃ | 130 |
| Cooling time | s | 1 | |
| Relaxation rate | ％ | 5 | |
| Total production rate | - | m/min | 250 |
Table 4: the Key Performance Indicator of giving an example
| Test event | Unit | Performance index | Test result | |
| Thickness deviation | Film thickness 12 μ m | ％ | ±6.0 | 2.6 |
| Tensile strength | Vertically | MPa | ≥200 | 245 |
| Laterally | MPa | ≥200 | 300 | |
| Elongation at break | Vertically | ％ | ≥90 | 149 |
| Laterally | ％ | ≥90 | 117 | |
| Percent thermal shrinkage | Vertically | ％ | ≤2.5 | 1.7 |
| Laterally | ％ | ≤1.0 | 0.1 | |
| Frictional coefficient | Static friction coefficient | - | ≤0.5 | 0.43 |
| Kinetic friction coefficient | - | ≤0.5 | 0.39 | |
| Mist degree | Film thickness 12 μ m | ％ | ≤3.5 | 2.6 |
| Moistened surface tension force | Coated face | mN/m | ≥44 | 50 |
Claims (10)
1. polyester film with reinforced surface metal adhesion, described polyester film is a biaxially oriented polyester film, it is characterized in that: described polyester film is handled through online coating for one side is arranged, another side can corona treatment, also can be without corona treatment, the moistened surface tension force of its online coating treated side is not less than 44mN/m.
2. online coated polyester film according to claim 1 is characterized in that: the second-order transition temperature of described polyester is greater than 75 ℃, and fusing point is greater than 260 ℃.
3. method of producing online coated polyester film as claimed in claim 1 or 2, comprise co-extrusion, casting sheet, vertical draw, online coating, horizontally draw, the treating processes of heat setting type, lax, traction and rolling, it is characterized in that: described polyester film has one side to handle through online coating, another side can corona treatment also can be without corona treatment, used coating material is a polyester resin.
4. the method for production polyester film according to claim 3 is characterized in that: described polyester resin coating material is macromolecular material that can be water-soluble, and its weight water soluble per-cent is greater than 20%.
5. the method for production polyester film according to claim 4 is characterized in that: in the described polyester resin coating fluid, the weight percentage of resin in solution is between 5%-20%.
6. the method for production polyester film according to claim 5 is characterized in that: coating layer thickness is between 0.03 μ m-0.1 μ m after being coated in the coating material drying on the polyester film.
7. the method for production polyester film according to claim 3, it is characterized in that: described polyester film stretch processes is to carry out longitudinal stretching earlier, carry out cross directional stretch then, online coating process carries out after the film longitudinal stretching and before the cross directional stretch.
8. the method for production polyester film according to claim 7 is characterized in that: the temperature of described longitudinal stretching is 80-140 ℃, and the cross directional stretch temperature is 90-150 ℃; The longitudinal stretching multiplying power is 2.5: 1-5.5: 1, and the cross directional stretch multiplying power is 3.5: 1-4.5: 1; Heat setting temperature is 150-240 ℃, and heat-setting time is 1-10 second.
9. the method for production polyester film according to claim 8, it is characterized in that: described relaxation processes technology respectively vertical draw and horizontal drawing between, between horizontal drawknot bundle and the heat setting type and carry out between heat setting type and the cooling, be 120-190 ℃ to the lax temperature between the heat setting type at horizontal drawknot bundle.
10. the method for production polyester film according to claim 9, it is characterized in that: in the described relaxation processes technology, vertical draw and horizontal drawing between relaxation rate less than 1.0%, relaxation rate is 0.01-4.0% between horizontal drawknot bundle and the heat setting type, be 0.0-1.5 second time of relaxation, and the relaxation rate between heat setting type and the cooling is 1.0-6.0%, and be 0.5-3.0 second time of relaxation, the relaxation rate of cooling section is 1.0-6.0%, and be 0.5-3.0 second time of relaxation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510027768 CN1896126A (en) | 2005-07-15 | 2005-07-15 | Polyester thin-film with reinforced surface metal adhesion and its production |
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| CN 200510027768 CN1896126A (en) | 2005-07-15 | 2005-07-15 | Polyester thin-film with reinforced surface metal adhesion and its production |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102768374A (en) * | 2012-07-28 | 2012-11-07 | 江阴金中达新材料有限公司 | Optical-grade coating PET (Polyethylene terephthalate) film and preparation method thereof |
| CN105315627A (en) * | 2014-06-30 | 2016-02-10 | 上海紫东薄膜材料股份有限公司 | Ultrathin polyester thin film used for gold and silver wires and production method thereof |
| CN107236140A (en) * | 2017-06-22 | 2017-10-10 | 张家港康得新光电材料有限公司 | Antibacterial film, its preparation method and the packaging material including it |
-
2005
- 2005-07-15 CN CN 200510027768 patent/CN1896126A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102768374A (en) * | 2012-07-28 | 2012-11-07 | 江阴金中达新材料有限公司 | Optical-grade coating PET (Polyethylene terephthalate) film and preparation method thereof |
| CN102768374B (en) * | 2012-07-28 | 2014-12-03 | 常州钟恒新材料有限公司 | Optical-grade coating PET (Polyethylene terephthalate) film and preparation method thereof |
| CN105315627A (en) * | 2014-06-30 | 2016-02-10 | 上海紫东薄膜材料股份有限公司 | Ultrathin polyester thin film used for gold and silver wires and production method thereof |
| CN107236140A (en) * | 2017-06-22 | 2017-10-10 | 张家港康得新光电材料有限公司 | Antibacterial film, its preparation method and the packaging material including it |
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