CN103738015A - Transverse-thermal-shrinkage bidirectional stretching polyester thin film and preparation method thereof - Google Patents
Transverse-thermal-shrinkage bidirectional stretching polyester thin film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transverse-thermal-shrinkage bidirectional stretching polyester thin film. The polyester thin film includes an upper layer, a middle layer and a lower layer, the middle layer covers on the lower layer, the upper layer covers on the middle layer, and the upper layer, the middle layer and the lower layer are respectively extruded by an extruder in a molten state and then together go into a three-layer co-extrusion die head to be composited into the polyester thin film; the mass parts of the upper layer, the middle layer and the lower layer comprise that the upper layer comprises 30-40 parts of a master batch A, the middle layer comprises 20-30 parts of a master batch B, and the lower layer comprises 30-40 parts of a master batch C. A certain proportion of a recycled material can be added in the production process, the cost of production can be greatly reduced, and industrialization requirements are well adopted; and with adopting of an internal addition production technology, a stabilizer is introduced into the formulation, so that the low-cost transverse-thermal-shrinkage bidirectional stretching polyester thin film has better shrinkage performance, and has the shrinkage rate of up to 30% and the longitudinal thermal shrinkage rate of 5%.
Description
(1) technical field
The invention belongs to packet industry, relate to a kind of biaxially oriented polyester film and production method thereof, relate in particular to biaxially oriented polyester film and the production method thereof of the horizontal thermal contraction of a kind of low cost.
(2) background technology
The biaxially oriented polyester film of the horizontal thermal contraction of low cost apply very extensively, can be applicable to the packing outside beverage bottle, the composite print of various food outer bags, also be widely used in food that the shelf-life grows as outer package products such as coffee, milk, anti-false trademark purposes is a kind of polyester film product of high added value.
The biaxially oriented polyester film mode of production of the horizontal thermal contraction of low cost at present is mainly carried out biaxial tension with PETG raw material, on POF membrane process basis, improves.But this method requires specially for dry, and raw material is relatively high, and continuity is poor in process of production.And directly with PET raw material, produce, effect is comparatively obvious, and the biaxially oriented polyester film of the horizontal thermal contraction of producing is fit transparent for rear processing, embodies commodity image; Tight bundle packing material, anti-scattered property is good; Without restoration, there is certain antiforge function.It is its topmost application that heat shrinkable polyester film is usually used in instant food, beverage market, electronic apparatus, metallic article, particularly shrink label.
(3) summary of the invention
Technical problem to be solved by this invention is to provide raw material proportioning and the preparation method of the biaxially oriented polyester film of the horizontal thermal contraction of low cost, has both guaranteed the brightness of film in production process, guarantees again the shrinkage of film, prepares stay-in-grade polyester film.
The technical solution used in the present invention is:
The invention provides a kind of biaxially oriented polyester film of horizontal thermal contraction, described polyester film comprises the upper, middle and lower, described middle level covers in lower floor, described upper strata covers on middle level, and described upper strata, middle level, lower floor jointly enters respectively the triple extrusion die head described polyester film that is composited after molten condition is extruded by extruder; The mass fraction of described the upper, middle and lower is: upper strata is 30～40 parts of masterbatch A, and middle level is 20～30 parts of masterbatch B, and lower floor is 30～40 parts of masterbatch C;
Based on described masterbatch A, described masterbatch A quality group becomes: 100 parts of polyester a, 50～80 parts of filler a and 1～5 part of stabilizing agent a, and the particle diameter of described filler a is that preferably 1 μ is m) for 0.5～3 μ m(;
Based on described masterbatch B, described masterbatch B quality group becomes: 100 parts of polyester b and 0.2～0.4 part of stabilizing agent b;
Described masterbatch C is identical with masterbatch A quality composition;
Described polyester a is PETG, polybutylene terephthalate, or both copolymers, preferably PETG (PET), and its inherent viscosity (unit: dl/g) is preferably 0.6～0.70; Described polyester b is identical with polyester a;
Described stabilizing agent a is four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, and described stabilizing agent b is identical with stabilizing agent a;
Described filler a is the mixing of one or more arbitrary proportions in zinc oxide, barium sulfate or kaolin, and preferential oxidation zinc can meet the requirement of cost and production performance two aspects.
Further, described upper strata is 30 parts of masterbatch A, and described middle level is 20 parts of masterbatch B, and described lower floor is 30 parts of masterbatch C.
Further, preferred described masterbatch A quality group becomes: 100 parts of polyester a, 60～70 parts of filler a and 1～5 part of stabilizing agent a, and the particle diameter of described filler a is 0.5～3 μ m; Described filler a is zinc oxide.
Further, the biaxially oriented polyester film quality group of described horizontal thermal contraction becomes:
Masterbatch A quality group based on described becomes: 100 parts of polyester a, 50 parts of filler a and 4 parts of stabilizing agent a, and the particle diameter of described filler a is 1 μ m;
Masterbatch B quality group based on described becomes: 100 parts of polyester b and 0.4 part of stabilizing agent b;
Described masterbatch C is identical with masterbatch A quality composition;
Described polyester a is PETG; Described polyester b is identical with polyester a;
Described stabilizing agent a is four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, and described stabilizing agent b is identical with stabilizing agent a;
Described filler a is zinc oxide.
In addition, in the biaxially oriented polyester film of horizontal thermal contraction of the present invention, described masterbatch B(is intermediate layer) middle with 15～30 parts of reclaimed materials instead of polyesters b, described reclaimed materials is to cut the leftover pieces of generation after the biaxially oriented polyester film finished product of the horizontal thermal contraction of preparation, and preferred described reclaimed materials mass parts is 20～25 parts.
The present invention also provides a kind of method of the biaxially oriented polyester film of preparing described horizontal thermal contraction, and described method is:
(1) raw material preparation: described polyester film comprises the upper, middle and lower, and described upper strata is 30～40 parts of masterbatch A of mass parts, and described middle level mass parts is 20～30 parts of masterbatch B, and described lower floor mass parts is 30～40 parts of masterbatch C;
Based on described masterbatch A, described masterbatch A quality group becomes: 100 parts of polyester a, 50～80 parts of filler a and 1～5 part of stabilizing agent a, and the particle diameter of described filler a is 0.5～3 μ m;
Based on described masterbatch B, described masterbatch B quality group becomes: 100 parts of polyester b and 0.2～0.4 part of stabilizing agent b;
Described masterbatch C is identical with masterbatch A quality composition;
(2) polyester film: masterbatch A and masterbatch C are sent into double screw extruder separately, extrusion temperature is 255～285 ℃, masterbatch B is sent into single screw extrusion machine at 180～190 ℃ after dry 2～3 hours through turnover plate type drying tower, extrusion temperature is 255～285 ℃, three extruders after molten condition is extruded from top to bottom by upper strata, it is compound that the order of middle level and lower floor enters triple extrusion die head, melt is evenly extruded through die lip mouth, extrusion temperature is 255～285 ℃, then pass through slab, stretch, sizing, rolling and cutting, obtain the biaxially oriented polyester film of horizontal thermal contraction, 65～110 ℃ of drawing zone temperature, 65～150 ℃ of setting temperatures.
Stabilizing agent a of the present invention, stabilizing agent b are stabilizing agent, for ease of distinguishing different step institute consumption difference, name, described polyester a, polyester b are the dissimilar polyester that different step is used, for ease of distinguishing each step use amount difference, name, described masterbatch A, masterbatch B and masterbatch C are the masterbatch of different compositions, and letter itself does not have implication.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
(1) production technology can have been added a certain proportion of reclaimed materials, greatly reduces production cost, has adapted to well industrialized requirement.
(2) adopted the production technology of interior interpolation, introduced the biaxially oriented polyester film that stabilizing agent makes the horizontal thermal contraction of low cost and have good shrinkage in formula, horizontal shrinkage factor is up to 30%, and longitudinal thermal contraction is 5%.
(4) specific embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
(1) raw material preparation
Upper strata (masterbatch A): (degree of polymerization is 100 to 100 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company), (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 50 parts of zinc oxide.
Lower floor (masterbatch C): (degree of polymerization is 100 to 100 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company), (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 50 parts of zinc oxide.
Middle level (masterbatch B): 100 parts of PETGs (degree of polymerization is 100, and molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company) and 0.4 part of four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester.
(2) polyester film
By step (1) formula ratio, respectively 30 parts of masterbatch A and 30 parts of masterbatch C are sent into two double screw extruder (model ZE60A-34D-UTX, producer is German Kraussmaffei Berstorff company), fully be uniformly mixed, extrusion temperature is 275 ℃, then by 20 parts of masterbatch B through turnover plate type drying tower (model DHP-3500, producer is Beijing moral bark of official magnolia company) at 150 ℃, send into single screw extrusion machine (model BS-PETP275/30D after dry 3 hours, producer Germany BBEngineering company), extrusion temperature is 275 ℃, three extruders after molten condition is extruded from top to bottom by upper strata, the order of middle level and lower floor enters triple extrusion die head, melt is evenly extruded through die lip mouth, extrusion temperature is 275 ℃, then pass through slab, stretch, sizing, rolling and cutting, obtain the biaxial tension pet film of horizontal thermal contraction, 110 ℃ of drawing zone temperature, 110 ℃ of setting temperatures record the horizontal percent thermal shrinkage 20% of film that thickness is 30 μ m, longitudinally percent thermal shrinkage 5% under 150 ℃ of environment of baking oven (model ed53#04-59955, producer is German Bin get company).
Embodiment 2:
(1) raw material preparation
Upper strata (masterbatch A): (degree of polymerization is 100 to 100 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company), (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 70 parts of zinc oxide.
Lower floor (masterbatch C): (degree of polymerization is 100 to 100 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company), (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 70 parts of zinc oxide.
Middle level (masterbatch B): 100 parts of PETGs (degree of polymerization is 100, and molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company) and 0.4 part of four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester.
(2) pet film
By step (1) formula ratio, respectively 35 parts of masterbatch A and 35 parts of masterbatch C are sent into two double screw extruder (model ZE60A-34D-UTX, producer is German Kraussmaffei Berstorff company), fully be uniformly mixed, extrusion temperature be 275 ℃ then by 25 parts of masterbatch B through turnover plate type drying tower (model DHP-3500, producer is Beijing moral bark of official magnolia company) at 150 ℃, send into single screw extrusion machine (model BS-PETP 275/30D after dry 3 hours, producer Germany BBEngineering company), extrusion temperature is 275 ℃, three extruders after molten condition is extruded from top to bottom by upper strata, the order of middle level and lower floor enters triple extrusion die head, melt is evenly extruded through die lip mouth, extrusion temperature is 275 ℃, then pass through slab, stretch, sizing, rolling and cutting, obtain the biaxial tension pet film of horizontal thermal contraction, 100 ℃ of drawing zone temperature, 100 ℃ of setting temperatures record the horizontal percent thermal shrinkage 25% of film that thickness is 25 μ m, longitudinally percent thermal shrinkage 5% under 150 ℃ of environment of baking oven (model ed53#04-59955, producer is German Bin get company).
Embodiment 3:
(1) raw material preparation
Upper strata (masterbatch A): (degree of polymerization is 100 to 100 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company), (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 70 parts of zinc oxide.
Lower floor (masterbatch C): 100 parts of PETGs, (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 70 parts of zinc oxide.
Middle level (masterbatch B): 100 parts of PETGs (degree of polymerization is 100, and molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company) and 0.4 part of four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester.
(2) polyester film
By step (1) formula ratio, respectively 40 parts of masterbatch A and 40 parts of masterbatch C are sent into two double screw extruder (model ZE60A-34D-UTX, producer is German Kraussmaffei Berstorff company), fully be uniformly mixed, extrusion temperature be 275 ℃ then by 30 parts of masterbatch B through turnover plate type drying tower (model DHP-3500, producer is Beijing moral bark of official magnolia company) at 150 ℃, send into single screw extrusion machine (model BS-PETP 275/30D after dry 2.5 hours, producer Germany BBEngineering company), extrusion temperature is 275 ℃, three extruders after molten condition is extruded from top to bottom by upper strata, the order of middle level and lower floor enters triple extrusion die head, melt is evenly extruded through die lip mouth, extrusion temperature is 275 ℃, then pass through slab, stretch, sizing, rolling and cutting, obtain the biaxial tension pet film of horizontal thermal contraction, 100 ℃ of drawing zone temperature, 80 ℃ of setting temperatures record the horizontal percent thermal shrinkage 30% of film that thickness is 20 μ m, longitudinally percent thermal shrinkage 5% under 150 ℃ of environment of baking oven (model ed53#04-59955, producer is German Bin get company).
Embodiment 4:
(1) raw material preparation
Upper strata (masterbatch A): (degree of polymerization is 100 to 100 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company), (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 70 parts of zinc oxide.
Lower floor (masterbatch C): 100 parts of PETGs, (particle diameter is m) He 4 part four of 1 μ [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester to 70 parts of zinc oxide.
Middle level (masterbatch B): (degree of polymerization is 100 to 80 parts of PETGs, molecular weight is 30,000, purchased from Chinese Yizheng Fiber Optical plant company) and 0.4 part of four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, the embodiment 1 of 20 parts prepares the leftover pieces of cutting generation after the biaxially oriented polyester film finished product of horizontal thermal contraction.
(2) polyester film
By step (1) formula ratio, respectively 40 parts of masterbatch A and 40 parts of masterbatch C are sent into two double screw extruder (model ZE60A-34D-UTX, producer is German Kraussmaffei Berstorff company), fully be uniformly mixed, extrusion temperature be 275 ℃ then by 30 parts of masterbatch B through turnover plate type drying tower (model DHP-3500, producer is Beijing moral bark of official magnolia company) at 150 ℃, send into single screw extrusion machine (model BS-PETP 275/30D after dry 2.5 hours, producer Germany BBEngineering company), extrusion temperature is 275 ℃, three extruders after molten condition is extruded from top to bottom by upper strata, the order of middle level and lower floor enters triple extrusion die head, melt is evenly extruded through die lip mouth, extrusion temperature is 275 ℃, then pass through slab, stretch, sizing, rolling and cutting, obtain the biaxial tension pet film of horizontal thermal contraction, 100 ℃ of drawing zone temperature, 80 ℃ of setting temperatures, at baking oven (model ed53#04-59955, producer is German Bin get company) record the horizontal percent thermal shrinkage 30% of film that thickness is 20 μ m under 150 ℃ of environment, longitudinally percent thermal shrinkage 5%, add after the reclaimed materials of 20 parts, the main performance of heat shrink films meets the requirements.
Claims (7)
1. the biaxially oriented polyester film of a horizontal thermal contraction, it is characterized in that described polyester film comprises the upper, middle and lower, described middle level covers in lower floor, described upper strata covers on middle level, and described upper strata, middle level, lower floor jointly enters respectively the triple extrusion die head described polyester film that is composited after molten condition is extruded by extruder; The mass fraction of described the upper, middle and lower is: upper strata is 30～40 parts of masterbatch A, and middle level is 20～30 parts of masterbatch B, and lower floor is 30～40 parts of masterbatch C;
Based on described masterbatch A, described masterbatch A quality group becomes: 100 parts of polyester a, 50～80 parts of filler a and 1～5 part of stabilizing agent a, and the particle diameter of described filler a is 0.5～3 μ m;
Based on described masterbatch B, described masterbatch B quality group becomes: 100 parts of polyester b and 0.2～0.4 part of stabilizing agent b;
Described masterbatch C is identical with masterbatch A quality composition;
Described polyester a is PETG, polybutylene terephthalate, or both copolymers; Described polyester b is identical with polyester a;
Described stabilizing agent a is four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, and described stabilizing agent b is identical with stabilizing agent a;
Described filler a is the mixing of one or more arbitrary proportions in zinc oxide, barium sulfate or kaolin.
2. the horizontal biaxially oriented polyester film of thermal contraction as claimed in claim 1, is characterized in that described upper strata is 30 parts of masterbatch A, and described middle level is 20 parts of masterbatch B, and described lower floor is 30 parts of masterbatch C.
3. the horizontal biaxially oriented polyester film of thermal contraction as claimed in claim 1, is characterized in that described masterbatch A quality group becomes: 100 parts of polyester a, 60～70 parts of filler a and 1～5 part of stabilizing agent a, and the particle diameter of described filler a is 0.5～3 μ m; Described filler a is zinc oxide.
4. the horizontal biaxially oriented polyester film of thermal contraction as claimed in claim 1, is characterized in that:
Masterbatch A quality group based on described becomes: 100 parts of polyester a, 50 parts of filler a and 4 parts of stabilizing agent a, and the particle diameter of described filler a is 1 μ m;
Masterbatch B quality group based on described becomes: 100 parts of polyester b and 0.4 part of stabilizing agent b;
Described masterbatch C is identical with masterbatch A quality composition;
Described polyester a is PETG; Described polyester b is identical with polyester a;
Described stabilizing agent a is four [α-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, and described stabilizing agent b is identical with stabilizing agent a;
Described filler a is zinc oxide.
5. the horizontal biaxially oriented polyester film of thermal contraction as claimed in claim 1, it is characterized in that in described masterbatch B with 15～30 parts of reclaimed materials instead of polyesters b, described reclaimed materials is the leftover pieces of cutting generation after the biaxially oriented polyester film finished product of the horizontal thermal contraction of preparation.
6. the horizontal biaxially oriented polyester film of thermal contraction as claimed in claim 5, is characterized in that described reclaimed materials mass parts is 20～25 parts.
7. prepare described in claim 1 a laterally method for the biaxially oriented polyester film of thermal contraction, it is characterized in that described method is:
(1) raw material preparation: described polyester film comprises the upper, middle and lower, and described upper strata is 30～40 parts of masterbatch A of mass parts, and described middle level mass parts is 20～30 parts of masterbatch B, and described lower floor mass parts is 30～40 parts of masterbatch C;
Based on described masterbatch A, described masterbatch A quality group becomes: 100 parts of polyester a, 50～80 parts of filler a and 1～5 part of stabilizing agent a, and the particle diameter of described filler a is 0.5～3 μ m;
Based on described masterbatch B, described masterbatch B quality group becomes: 100 parts of polyester b and 0.2～0.4 part of stabilizing agent b;
Described masterbatch C is identical with masterbatch A quality composition;
(2) polyester film: masterbatch A and masterbatch C are sent into double screw extruder separately, extrusion temperature is 255～285 ℃, masterbatch B is sent into single screw extrusion machine at 180～190 ℃ after dry 2～3 hours through turnover plate type drying tower, extrusion temperature is 255～285 ℃, three extruders after molten condition is extruded from top to bottom by upper strata, it is compound that the order of middle level and lower floor enters triple extrusion die head, melt is evenly extruded through die lip mouth, extrusion temperature is 255～285 ℃, then pass through slab, stretch, sizing, rolling and cutting, obtain the biaxially oriented polyester film of horizontal thermal contraction, 65～110 ℃ of drawing zone temperature, 65～150 ℃ of setting temperatures.
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| CN104890332A (en) * | 2015-05-30 | 2015-09-09 | 汕头市金品塑胶实业有限公司 | High-barrier coated sheet and production method thereof |
| CN105504253A (en) * | 2016-01-22 | 2016-04-20 | 四川东材绝缘技术有限公司 | Siloxane-polyester copolymer resin, siloxane-polyester copolymer compound substrate membrane, and methods for preparing siloxane-polyester copolymer resin and siloxane-polyester copolymer compound substrate membrane |
| CN106827568A (en) * | 2017-02-08 | 2017-06-13 | 营口康辉石化有限公司 | A kind of polyester film production technology of use reclaimed materials |
| CN111421779A (en) * | 2020-03-31 | 2020-07-17 | 南京兰埔成新材料有限公司 | Preparation method of high-thermal-shrinkage BOPET film |
| CN111823679A (en) * | 2020-06-09 | 2020-10-27 | 山东圣和塑胶发展有限公司 | Light-blocking shrink film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104890332A (en) * | 2015-05-30 | 2015-09-09 | 汕头市金品塑胶实业有限公司 | High-barrier coated sheet and production method thereof |
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| CN111421779A (en) * | 2020-03-31 | 2020-07-17 | 南京兰埔成新材料有限公司 | Preparation method of high-thermal-shrinkage BOPET film |
| CN111823679A (en) * | 2020-06-09 | 2020-10-27 | 山东圣和塑胶发展有限公司 | Light-blocking shrink film and preparation method thereof |
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| CN103738015B (en) | 2016-08-17 |
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