CN102602005A - Method for manufacturing PETG (polyethylene terephthalate glycol) heat-shrink film - Google Patents
Method for manufacturing PETG (polyethylene terephthalate glycol) heat-shrink film Download PDFInfo
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- CN102602005A CN102602005A CN2012100704462A CN201210070446A CN102602005A CN 102602005 A CN102602005 A CN 102602005A CN 2012100704462 A CN2012100704462 A CN 2012100704462A CN 201210070446 A CN201210070446 A CN 201210070446A CN 102602005 A CN102602005 A CN 102602005A
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Abstract
The invention discloses a method for manufacturing a PETG (polyethylene terephthalate glycol)-1,4-cyclohexylene dimethylene terephthalate heat-shrink film with low shrink stress, high transverse shrink rate, low longitudinal shrink rate and low haze. PETG materials are plasticized and melted in an extruder after being dried and are extruded into a uniform membrane by a T-shaped die head. The membrane is quenched and shaped on a cooling roller, and is longitudinally stretched by the ratio of 1:1.1-1.5 after being preheated by seven preheating rollers. The membrane is cooled and shaped by four cooling rollers, is transversely stretched by the ratio of 1:3-6 after being longitudinally stretched and preheated, and then is cooled and shaped by the cooling rollers, trimmed, treated by means of corona and coiled into a finished product.
Description
Technical field
The present invention relates to a kind of manufacturing approach of packing with the heat-shrinkable film material, specifically is poly terephthalic acid ethylene glycol-1, the manufacturing approach of 4-cyclohexanedimethanol ester (PETG) heat-shrinkable film.
Background technology
PETG is terephthalic acid (TPA), ethylene glycol, 1, the condensation polymer of 4-cyclohexanedimethanol, and in its production process, because the ethylene glycol of some is by 1, the 4-cyclohexanedimethanol replaces, and polymer can prevent crystallization, is a kind of amorphism copolyester.
Along with the progress of science and technology and improving constantly of people's living standard, people require increasingly high to the external packing of expensive goods.The PETG heat shrink films has nontoxic, and is tasteless, high strength, and percent thermal shrinkage is high, and the packing effect is attractive in appearance.PETG mylar biggest advantage is that heat sealing performance is good, and is easy to operate during involution, and involution is effective and be prone to use the glue bonding, and optical property and mechanical extensibility are all fine simultaneously.PETG about the Food Contact standard, can be applied to the packing in fields such as food and individual health care articles for use, medical and health equipment food through U.S. FDA, also can be used for the electronic device packing, and meets environmental protection recovery demand.
The PETG heat-shrinkable film of being processed by the biaxial tension of PETG material is a kind of high-performance shrink film, and final shrinkage factor can be made into the packing of complex appearance container greater than 70%; Has high plastic uptake power, the high grade of transparency, high glaze; Low haze is easy to printing, difficult drop-off; Nature shrinkage factor low advantage during storage is applied to the shrink label of shrink wrapping and the electronic product etc. of beverage bottle, foods and cosmetics.Compare with the PVC shrink film, the PETG shrink film also has the advantage of environmental protection.So the PETG heat-shrinkable film has obtained extensive use at packaging field.Have only this product of minority enterprise ability processing at present in the world, and these product percent thermal shrinkages are still not high, the product transparency is also lower; Mist degree reaches more than 5%; Shrinkage stress is big, improves the percent thermal shrinkage and the transparency of product, reduce shrinkage stress and be this area the technical barrier that will capture.
Summary of the invention
The purpose of this invention is to provide a kind of have low shrinkage stress, horizontal high shrinkage, vertical low-shrinkage, the poly terephthalic acid ethylene glycol-1 of low haze, the manufacturing approach of 4-cyclohexanedimethanol ester (PETG) heat-shrinkable film.
The present invention includes the following step:
A. select inherent viscosity 0.55 ~ 0.85dL/g for use; 60 ~ 90 ℃ of Vicat softening points; Ethylene glycol and 1 in the polymer, the mol ratio of 4-cyclohexanedimethanol monomer are the PETG material of 1 ︰ 4 ~ 7, oven dry back plastifying fusion in extruder; Extrude the even diaphragm that forms 0.2 ~ 0.5 millimeter of thickness through 260 ~ 280 ℃ T shape die head, diaphragm is the chilling typing on 20 ~ 60 ℃ chill roll;
B. diaphragm carries out the longitudinal stretching of 1.1 ~ 1.5 times of l ︰ after 70 ~ 90 ℃ preheat roll preheating, uses 40 ~ 65 ℃ chill roll cooling and shaping again;
C. the diaphragm behind the longitudinal stretching carries out the cross directional stretch of 3 ~ 6 times of l ︰ after 75 ~ 90 ℃ preheating, uses 50 ~ 70 ℃ of chill roll cooling and shapings again, cut edge, and corona treatment, rolling becomes finished product.
In the PETG resin of the present invention, the mol ratio of ethylene glycol and 1,4 cyclohexanedimethanol monomer is preferably 1 ︰ 4.5 ~ 5.5.
The upper and lower surfaces of diaphragm can also respectively have adherent layer; The material of adherent layer is made up of 90 ~ 97% PETG material and 3 ~ 10% PETG antitack agent by weight percentage, and the typing surface layer of the flow-rate ratio of 0.5 ~ 1.2 ︰, 10 ︰ 0.5 ~ 1.2 of lower floor through die lip closed and extrude during adherent layer was pressed in T shape die head after the injection machine fusion.
2 ~ 5% the PETG antitack agent that also can in diaphragm PETG material, add the PETG material weight.
Longitudinal stretching is 1.1 ~ 1.2 times of preferred l ︰; The cross directional stretch ratio is for being preferably 4 ~ 5 times of l ︰.
PETG antitack agent according to the invention is that be weight percentage 2 ~ 3% nano-kaoline and surplus is the blend composition of PETG material.
The present invention makes at the vertical and horizontal drawing process that polymer molecular chain elongates at this both direction, orientation, makes product have very high lateral shrinkage (99 ℃, 10 seconds, laterally>=78%); Lower vertical shrinkage factor (≤0.5%), transparency high (mist degree≤1.5) has machinery spy preferably; Intensity is high, and firmness is big, the big (vertical MD>=2000MPa of elastic modelling quantity; Horizontal TD>=4000MPa), the hot strength height (vertical MD>=50MPa, horizontal TD>=200MPa).
Especially, the product shrinkage stress of the present invention's production can be low to moderate 6MPa.The advantage of low convergent force is the pack article that can be applied to thinning; Process in shrink wrapping is more even; Can be used as the high-quality base material of industrial circles such as high-grade packing, printing, electronic apparatus, dressing of cable, insulating materials, and external application label such as various canned polyester bottles, various containers.
The specific embodiment
Embodiment 1
Material therefor: PETG: transparent, inherent viscosity 0.7dL/g, 69 ℃ of Vicat softening points;
PETG antitack agent: inherent viscosity 0.62dL/g, 69 ℃ of Vicat softening points, kaolin content 2wt%.
Above-mentioned material is material by weight the preparation intermediate layer: 100 parts of PETG; Upper and lower surfaces layer material: 95 parts of PETG, 5 parts of PETG antitack agents.
After intermediate layer material and skin-material evenly mix respectively; Deliver to 65 ℃ of continuous dryers respectively and dry (about 6 hours of time), remove the raw material surface moisture, pass through apparatus for separating metals then; Metal fillings of carrying secretly in the material or particle separation are come out; Deliver to an extruder plastifying fusion more separately, 275 ℃ of melt temperatures, melt rotates at a high speed down by evenly mixing and conveying at screw rod.At course of conveying, the lower-molecular substance that gasifies in the melt and the gas that decomposes and moisture are pumped into condenser system through the steam vent of extruder by vavuum pump, and separation such as lower-molecular substance is gone out.Refilter and remove plasticizing bad material and impurity, guarantee that the height of melt is pure.Melt in T shape die head by in the typing surface layer of flow-rate ratio through die lip of 3 ︰, 34 ︰ 3 of lower floor close and extrude; Bright and clean through highly again, temperature is 35 ℃ chill roll chilling typing, becomes by three layers to constitute; Thickness is 0.22 millimeter even diaphragm, and diaphragm thickness is regulated by die head and confirmed.
Diaphragm after the chilling typing is through 80 ℃ multiple tracks preheat roll preheating, utilizes the stretching ratio one-off drawing moulding of the speed difference of roller and quick roll at a slow speed by 1 ︰ 1.2, through 60 ℃ of chill roll cooling and shapings, and the completion longitudinal stretching.
Be preheated to 85 ℃ in the diaphragm baking oven behind the longitudinal stretching, utilize adjustable track, accomplish cross directional stretch, use 50 ℃ of cooling and shapings then by the stretching ratio of 1 ︰ 4.5 by chain folder traction diaphragm.
Stretched film excises its both sides with bead cutter earlier, carries out high-frequency corona with corona machine then and handles, to increase the adhesive force and the frictional force of printing-ink.Bundled through the rolling on winder of the film after the corona treatment, place a period of time naturally then, carry out Ageing Treatment, make the performance of products trend stable.
Biaxial tension PETG film after Ageing Treatment utilizes cutting machine to cut into the specification of customer requirements, packs then, promptly obtains biaxial tension PETG heat-shrinkable film finished product.
Above-mentioned finished product is through detecting, thickness 40.7 μ m, each about 3 μ m of two surface layer thicknesses up and down wherein, (99 ℃ of percent thermal shrinkages; 10 seconds) horizontal (TD) 79%, vertical (MD) 0.5%, mist degree 1.2%, glossiness (45 °) 126.4%; Hot strength: vertical (MD) 57.8MPa, horizontal (TD) 223.7MPa, elastic modelling quantity: vertical (MD) 2180MPa; Horizontal (TD) 4360MPa, shrinkage stress 6MPa is the good PETG heat-shrinkable film of performance.
Embodiment 2
Material therefor:
PETG: transparent, inherent viscosity 0.7dL/g, 69 ℃ of Vicat softening points; PETG antitack agent: inherent viscosity 0.62dL/g, 69 ℃ of Vicat softening points, kaolin content 2wt%.
Above-mentioned material is by weight batching, individual layer: 97 parts, and PETG, 3 parts of PETG antitack agents.
Extrude the individual layer diaphragm that forms 0.20 millimeters thick by a double screw extruder plastifying fusion, other processing step is identical with EXAMPLE l, stretching condition:
40 ℃ of chill-roll temperature after T shape die head is extruded;
78 ℃ of longitudinal stretching preheat roll temperature, stretching ratio 1 ︰ 1.15,45 ℃ of longitudinal stretching cooling and shaping temperature;
82 ℃ of cross directional stretch preheat temperatures, stretching ratio 1 ︰ 4.4,65 ℃ of cross directional stretch cooling and shaping temperature.
Above-mentioned finished product is through detecting thickness 39.6 μ m; Percent thermal shrinkage (99 ℃, 10 seconds): horizontal TD:78.2%, vertically MD:0.3%; Mist degree 1.4%; Glossiness (45 °) 121.5%; Hot strength: vertical MD:52.6MPa, laterally TD:208.8MPa; Elastic modelling quantity: vertical MD:2093MPa, horizontal (TD) 4210MPa, shrinkage stress 6MPa is the good PETG heat-shrinkable film of performance.
Claims (6)
1. the manufacturing approach of a PETG heat-shrinkable film is characterized in that, may further comprise the steps:
A. select inherent viscosity 0.55 ~ 0.85dL/g for use; 60 ~ 90 ℃ of Vicat softening points; Ethylene glycol and 1 in the polymer, the mol ratio of 4-cyclohexanedimethanol monomer are the PETG material of 1 ︰ 4 ~ 7, oven dry back plastifying fusion in extruder; Extrude the even diaphragm that forms 0.2 ~ 0.5 millimeter of thickness through 260 ~ 280 ℃ T shape die head, diaphragm is the chilling typing on 20 ~ 60 ℃ chill roll;
B. diaphragm carries out the longitudinal stretching of 1.1 ~ 1.5 times of l ︰ after 70 ~ 90 ℃ preheat roll preheating, uses 40 ~ 65 ℃ chill roll cooling and shaping again;
C. the diaphragm behind the longitudinal stretching carries out the cross directional stretch of 3 ~ 6 times of l ︰ after 75 ~ 90 ℃ preheating, uses 50 ~ 70 ℃ of chill roll cooling and shapings again, cut edge, and corona treatment, rolling becomes finished product.
2. according to the manufacturing approach of the said PETG heat-shrinkable film of claim 1, it is characterized in that, in the said PETG resin, ethylene glycol and 1, the mol ratio of 4-cyclohexanedimethanol monomer is 1 ︰ 4.5 ~ 5.5.
3. according to the manufacturing approach of claim 1 or 2 said PETG heat-shrinkable films, it is characterized in that in the steps A, the upper and lower surfaces of diaphragm also respectively has adherent layer, the adherent layer material is made up of 90 ~ 97% PETG material and 3 ~ 10% PETG antitack agent by weight percentage; During the adherent layer material is pressed in T shape die head after the injection machine fusion typing face of the flow-rate ratio of 0.5 ~ 1.2 ︰, 10 ︰ 0.5 ~ 1.2 of lower floor through die lip and diaphragm simultaneously layer close and extrude.
4. according to the manufacturing approach of claim 1 or 2 said PETG heat-shrinkable films, it is characterized in that, in the said diaphragm, add 2 ~ 5% PETG antitack agent of PETG material weight.
5. according to the manufacturing approach of claim 1 or 2 said PETG heat-shrinkable films, it is characterized in that longitudinal stretching is than being 1.1 ~ 1.3 times of l ︰.
6. according to the manufacturing approach of claim 1 or 2 said PETG heat-shrinkable films, it is characterized in that cross directional stretch is than being 4 ~ 5 times of l ︰.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210070446.2A CN102602005B (en) | 2012-03-17 | 2012-03-17 | Method for manufacturing PETG (polyethylene terephthalate glycol) heat-shrink film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210070446.2A CN102602005B (en) | 2012-03-17 | 2012-03-17 | Method for manufacturing PETG (polyethylene terephthalate glycol) heat-shrink film |
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| CN102602005A true CN102602005A (en) | 2012-07-25 |
| CN102602005B CN102602005B (en) | 2014-05-21 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102848581A (en) * | 2012-10-03 | 2013-01-02 | 广东华业包装材料有限公司 | Tape casting method for thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer |
| CN102848569A (en) * | 2012-10-03 | 2013-01-02 | 广东华业包装材料有限公司 | Production method of two-way stretched thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer |
| CN103483785A (en) * | 2013-09-29 | 2014-01-01 | 太仓市鸿运包装材料有限公司 | PETG (polyethylene terephthalate glycol) heat shrinking film and preparation method thereof |
| CN103522713A (en) * | 2013-10-10 | 2014-01-22 | 宁波东旭成新材料科技有限公司 | Low-shrinkage rate bidirectional stretching plastic thin film and preparation method thereof |
| CN107610585A (en) * | 2017-09-18 | 2018-01-19 | 江苏景宏新材料科技有限公司 | A kind of preparation for washing transparent thermal contraction type beer bottle label and its wash mark technique |
| CN108044919A (en) * | 2017-12-08 | 2018-05-18 | 广州宏信塑胶工业有限公司 | The secondary extension process of PVC adhesive plasters and its application |
| CN115260707A (en) * | 2022-07-02 | 2022-11-01 | 福建晋江宏洋新材料科技有限责任公司 | High-toughness heat-shrinkable battery label film and preparation method thereof |
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| US20070178326A1 (en) * | 2006-01-27 | 2007-08-02 | Kolon Ind. Inc./Kr | Thermo-shrinkable polyester film |
| EP1839849A1 (en) * | 2005-01-11 | 2007-10-03 | Mitsubishi Plastics Inc. | Heat-shrinkable layered film, molded article comprising the film, and heat-shrinkable label and container |
| CN101838445A (en) * | 2010-04-30 | 2010-09-22 | 宜兴市光辉包装材料有限公司 | PETG blow molding film and preparation method thereof |
| CN102152585A (en) * | 2010-12-16 | 2011-08-17 | 浙江强盟实业股份有限公司 | Twistable polyester film and preparation method thereof |
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Patent Citations (5)
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| EP1839849A1 (en) * | 2005-01-11 | 2007-10-03 | Mitsubishi Plastics Inc. | Heat-shrinkable layered film, molded article comprising the film, and heat-shrinkable label and container |
| US20070178326A1 (en) * | 2006-01-27 | 2007-08-02 | Kolon Ind. Inc./Kr | Thermo-shrinkable polyester film |
| CN102196908A (en) * | 2008-10-24 | 2011-09-21 | 埃克森美孚石油公司 | Multilayer shrink, films, labels made therefrom and use thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102848569A (en) * | 2012-10-03 | 2013-01-02 | 广东华业包装材料有限公司 | Production method of two-way stretched thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer |
| CN102848581A (en) * | 2012-10-03 | 2013-01-02 | 广东华业包装材料有限公司 | Tape casting method for thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer |
| CN102848569B (en) * | 2012-10-03 | 2014-12-10 | 广东华业包装材料有限公司 | Production method of two-way stretched thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer |
| CN102848581B (en) * | 2012-10-03 | 2014-12-24 | 广东华业包装材料有限公司 | Tape casting method for thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer |
| CN103483785B (en) * | 2013-09-29 | 2016-03-30 | 太仓卡斯特姆新材料有限公司 | A kind of PETG heat-shrinkable film and preparation method thereof |
| CN103483785A (en) * | 2013-09-29 | 2014-01-01 | 太仓市鸿运包装材料有限公司 | PETG (polyethylene terephthalate glycol) heat shrinking film and preparation method thereof |
| CN103522713A (en) * | 2013-10-10 | 2014-01-22 | 宁波东旭成新材料科技有限公司 | Low-shrinkage rate bidirectional stretching plastic thin film and preparation method thereof |
| CN107610585A (en) * | 2017-09-18 | 2018-01-19 | 江苏景宏新材料科技有限公司 | A kind of preparation for washing transparent thermal contraction type beer bottle label and its wash mark technique |
| CN107610585B (en) * | 2017-09-18 | 2021-04-20 | 江苏景宏新材料科技有限公司 | Preparation of washable transparent heat-shrinkable beer bottle label and label washing process thereof |
| CN108044919A (en) * | 2017-12-08 | 2018-05-18 | 广州宏信塑胶工业有限公司 | The secondary extension process of PVC adhesive plasters and its application |
| CN108044919B (en) * | 2017-12-08 | 2022-08-12 | 无锡宏义高分子材料科技有限公司 | Secondary extension process of PVC (polyvinyl chloride) adhesive tape and application thereof |
| CN115260707A (en) * | 2022-07-02 | 2022-11-01 | 福建晋江宏洋新材料科技有限责任公司 | High-toughness heat-shrinkable battery label film and preparation method thereof |
| CN115260707B (en) * | 2022-07-02 | 2023-10-27 | 福建晋江宏洋新材料科技有限责任公司 | High-toughness heat-shrinkable battery label film and preparation method thereof |
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| CN102602005B (en) | 2014-05-21 |
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Denomination of invention: Method for manufacturing PETG (polyethylene terephthalate glycol) heat-shrink film Effective date of registration: 20150215 Granted publication date: 20140521 Pledgee: Bank of Communications Ltd Chaozhou branch Pledgor: Huaye Packing Materials Co., Ltd., Guangdong Registration number: 2015990000151 |
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Date of cancellation: 20210120 Granted publication date: 20140521 Pledgee: Bank of Communications Ltd Chaozhou branch Pledgor: GUANGDONG HUAYE PACKING MATERIAL Co.,Ltd. Registration number: 2015990000151 |
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