CN103172990B - Preparation method of heat shrinkable polyester film - Google Patents
Preparation method of heat shrinkable polyester film Download PDFInfo
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- CN103172990B CN103172990B CN201310101373.3A CN201310101373A CN103172990B CN 103172990 B CN103172990 B CN 103172990B CN 201310101373 A CN201310101373 A CN 201310101373A CN 103172990 B CN103172990 B CN 103172990B
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- copolyester
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention discloses a preparation method of a heat shrinkable polyester film. The method comprises the following steps of: carrying out esterification and condensation polymerization reaction on multi-component dicarboxylic acid and multi-component dihydric alcohol in the presence of a catalyst, a stabilizing agent, an antistatic agent, a chain extender, an anti-caking agent or a modifying agent to prepare a multi-component polyester; carrying out melt extrusion, extension and pelleting on the multi-component polyester to prepare a multi-component polyester slice; and carrying out melted extrusion, die head casting, transverse far infrared drawing, cooling molding, rolling and cutting on the multi-component polyester slice to prepare the heat shrinkable polyester film. The heat shrinkable polyester film with high shrinkage percentage prepared by using the method is pretty high in strength and heat shrinkage performance, excellent in transparency, malleability, and toughness, good in glossiness, uniform in shrinkage, non-toxic, odorless, and easy to recycle, and a product of the film is suitable for labels for various containers and direct packaging of a food product, a beverage product, an electronic product, an electric product, a mechanical product, a hardware product and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Heat shrinkage copolyester film, more particularly, the present invention relates to a kind of preparation method of copolyester film of horizontal high shrinkage, belong to technical field of polymer materials.
Background technology
In recent years, the heat-shrinkable film of polyvinyl chloride (PVC), polystyrene (PS), the material produce such as polyethylene terephthalate (PET) is adopted to be widely used in the fields such as the label of various container and food-drink, electronic apparatus, machinery.
Thermal contraction polyvinyl chloride film because of its excellence shrinkage and the transparency and used the earliest, but owing to often producing a large amount of hydrogenchloride with gases such as dioxin when burning, be unfavorable for recycling, do not meet environmental requirement, therefore, application is now restricted.
Thermal contraction polystyrene film has satisfactory stability and outward appearance in contraction process, but due in chemical resistant properties performance not good, less stable, and intensity is low, not shock-resistant, therefore, seldom use at present.
Heat shrinkable polyester (PET) film has and is easy to reclaim, nontoxic, tasteless, good mechanical property, meets the features such as environment protection service requirements, has become the ideal substitute replacing thermal contraction polyvinyl chloride film and thermal contraction polystyrene film in developed country thus at present.But, because common PET polyester is crystal type superpolymer, and the heat-shrinkable film adopting it to prepare, though through special process process, at most can only obtain the percent thermal shrinkage of less than 30%, and the rigidity of product, transparency are all not high yet.In order to prepare the polyester film of high percent thermal shrinkage, usually need to carry out modification by copolymerization to conventional polyester (polyethylene terephthalate).Current employing terephthalic acid, ethylene glycol and 1, PETG Polyester heat shrinkable film prepared by the monomer copolymerization superpolymer such as 4-cyclohexanedimethanol or neopentyl glycol, percent thermal shrinkage is up to more than 70%, but this series products exists the deficiencies such as the transparency, ductility and poor toughness, thus affects the quality of film.
In order to overcome the deficiency existing for existing ordinary hot shrinkable polyester film, produce the copolyester film meeting the percent thermal shrinkage that user requires, some technician of this area have done many research work, and have applied for the patent of following aspect:
Chinese patent 201210017355.2 discloses a kind of ecological multifunction terpolymer PETG preparation process of polyester and by the method for this polyester for unilateral stretching heat-shrinkable film; PETG polyester described in this patent is formed by terephthalic acid, neopentyl glycol, the copolymerization of ethylene glycol termonomer, and the mol ratio of terephthalic acid, neopentyl glycol and ethylene glycol is 1: (0.1 ~ 0.65): (1.2 ~ 1.75); Described preparation method comprises esterification and polyreaction, and the temperature of esterification is 220 ~ 265 DEG C, and the temperature of polyreaction is 270 DEG C ~ 280 DEG C, and the vacuum tightness of polyreaction is 0.098MPa ~ 0.1MPa; PETG polyester thermal contraction film described in this patent has good transparency and percent thermal shrinkage, but tensile strength, contraction homogeneity are then undesirable.
Chinese patent 200980125580.4 discloses a kind of copolyesters for shrinkable film.Polyester described in this patent is obtained by terephthalic acid and a small amount of m-phthalic acid and ethylene glycol and a small amount of glycol ether copolymerization.Described copolyesters is lower due to percent thermal shrinkage, is thus generally used for production ordinary hot shrinkable polyester film.
Chinese patent 201110363014.6 discloses a kind of polyester film for electronic tag and preparation method thereof, described polyester film raw materials comprises 0.1 ~ 35.6% functional polyester chip A, 0.1 ~ 42.2% functional polyester chip B, 20 ~ 68% polyester regenrated slices, 40 ~ 90% conventional polyester sections, 1 ~ 12% containing the polyester slice of IPA, 5 ~ 92% silicon system polyester slices; Wherein, in functional polyester chip A, sea shell micropowder mass percentage is 0.1 ~ 13.5%, in functional polyester chip B, nano imvite mass percentage is 0.5 ~ 32.6%, be 0.2 ~ 7.8% containing IPA mass percentage in the polyester slice of IPA, in silicon system polyester slice, siliconoxide mass content is 200 ~ 1890PPM.Compared with existing polyester film for electronic tag, longitudinal percent thermal shrinkage is in 0 ~ 1% scope under 180 DEG C of high temperature for this polyester film for electronic tag, and under 1GHz test condition, its specific inductivity is in 1 ~ 3 scope, dielectric loss angle tangent 0.2% ~ 0.8%.The described film of this invention is non-heat-shrinkable material, almost without percent thermal shrinkage, thus can only be used for electronic tag.
Summary of the invention
Technical problem to be solved by this invention is: overcome the deficiency that existing heat shrinkable polyester film exists, the preparation method of a kind of preparation method of effective multi component copolyester and a kind of simple and easy to do Heat shrinkage copolyester film is provided, and it is good by the aforesaid method preparation transparency, shrink evenly, horizontal percent thermal shrinkage reaches the Heat shrinkage copolyester film of the high shrinkage of more than 75%.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of Heat shrinkage copolyester film, the steps include: polycomponent diprotic acid and multicomponent binary alcohol, through esterification, polycondensation, and obtained multi component copolyester; Wherein, esterification temperature is 210 ~ 275 DEG C, and esterification absolute pressure is 0.1 ~ 0.4MPa, and esterification time is 1 ~ 5h; Condensation temperature is 250 ~ 295 DEG C, polycondensation absolute pressure≤100Pa, and the polycondensation time is 1 ~ 4h; In described copolyesters preparation process, catalyzer need be added, stablizer, static inhibitor, chainextender, caking inhibiter or properties-correcting agent; Described multi component copolyester is by melt extrusion, stretching, granulating working procedure, and obtained multi component copolyester cuts into slices (its limiting viscosity is 0.58 ~ 0.70dl/g); Described multi component copolyester section adds in screw extrusion press, by melt extruding, die head slab, horizontal far infrared stretch (far-infrared heating raw material, stretch with equipment), cooling and shaping, rolling, point cutting process, obtained horizontal percent thermal shrinkage reaches more than 75% Heat shrinkage copolyester film.
Described polycomponent diprotic acid is selected from following two or more material: terephthalic acid, m-phthalic acid, biphenyl dicarboxylic acid, naphthalic acid; Described multicomponent binary alcohol is selected from following two or more material: ethylene glycol, Isosorbide, butyleneglycol, glycol ether, triglycol, 1,4 cyclohexane dimethanol, neopentyl glycol.
In described polycomponent diprotic acid, preferred version is at least containing terephthalic acid, and its mass percent > 60%; In described multicomponent binary alcohol, preferred version is at least containing ethylene glycol, and its mass percent > 50%.
In the esterification of described multi component copolyester, polycondensation process, esterification temperature is 210 ~ 275 DEG C, and esterification absolute pressure is 0.1 ~ 0.4MPa, and esterification time is 1 ~ 5h; Condensation temperature is 250 ~ 295 DEG C, polycondensation absolute pressure≤100Pa, and the polycondensation time is 1 ~ 4h.
The catalyzer adopted in described multi component copolyester preparation process is antimony acetate, antimony glycol, tetrabutyl titanate compound, antimony acetate organic complex, antimony glycol organic complex, tetrabutyl titanate organic complex compounds; Its add-on accounts for 0.01 ~ 0.1% of copolyesters quality.
The caking inhibiter adopted in described copolyesters preparation process or properties-correcting agent are selected from one or more in following substances: titanium dioxide, silicon-dioxide, calcium carbonate, calcium phosphate, calcium acetate, barium sulfate, kaolin, silicate, silicates composite granule; Described caking inhibiter or the median size of properties-correcting agent are 100 ~ 280nm; Its add-on accounts for 2.0 ~ 8% of copolyesters quality.
The stablizer adopted in described copolyester section preparation process is phosphoric acid, phosphorous acid, Tripyrophosphoric acid, trimethyl phosphite 99 or triethyl phosphate; Its add-on accounts for 0.0005 ~ 0.035% of copolyesters quality.
The static inhibitor adopted in described multi component copolyester preparation process is stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate or stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate; Its add-on accounts for 0.005 ~ 0.02% of copolyesters quality.
The chainextender adopted in described multi component copolyester preparation process is isocyanic ester, carbon two subunit or pyromellitic acid anhydride; Its add-on accounts for 0.001 ~ 0.06% of copolyesters quality.
The temperature that melt extrudes of described copolyesters is 265 DEG C ~ 295 DEG C, and the draft temperature of described film is 100 DEG C ~ 120 DEG C, and preheating temperature is 70 DEG C ~ 90 DEG C, and cross directional stretch multiplying power is 3.9 ~ 4.1, and thickness is 20 ~ 60 μm.
Beneficial effect of the present invention: the present invention is by the multi component copolyester described in preparation, and by the optimization of film production process and the control of the processing parameter such as film draw temperature, stretching ratio, finally obtain the Heat shrinkage copolyester film that horizontal percent thermal shrinkage reaches the high shrinkage of more than 75%.The Heat shrinkage copolyester film of high shrinkage prepared by the present invention is single layer structure, and tensile strength is between 220 ~ 300MPa, and skin friction coefficient≤0.5, thickness is between 20 ~ 60 μm, and fabric width reaches 8700mm.Compared with conventional heat shrinkable polyester film, the Heat shrinkage copolyester film of high shrinkage prepared by the present invention has higher intensity and heat-shrinkable, the excellent transparency, ductility and toughness, glossiness is good, shrink evenly, and nontoxic, tasteless, be easy to recycle, product is particularly useful for the direct packaging of the goods such as the label of various container and food-drink, electronic apparatus, machinery, five metals.
Accompanying drawing illustrates:
Fig. 1 is preparation technology's schema of disclosed a kind of Heat shrinkage copolyester film of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
2.5Kg pure terephthalic acid is added in the universal reactor of 20L, 2.5Kg polycomponent diprotic acid is (comprising naphthalic acid, m-phthalic acid, biphenyl dicarboxylic acid), 2.8Kg ethylene glycol, 0.5Kg multicomponent binary alcohol is (comprising Isosorbide, butyleneglycol, glycol ether, triglycol, 1, 4-cyclohexanedimethanol, neopentyl glycol) and 9g glycol antimony catalyst, 160g titanium dioxide caking inhibiter, silicate modified dose of 10g, 1.2g stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.9g isocyanic ester chainextender, at 230 ~ 260 DEG C, esterification is carried out under 0.2 ~ 0.3Mpa condition, when aquifer yield reaches 1100mL theoretical value, system pressure is let out to normal pressure.
React with this understanding, add 1.6g triethyl phosphate stablizer, atmospheric agitation 7min, by temperature rise to 285 DEG C in reactor, pressure drops to below 100Pa, carry out reaction 3h with this understanding, then the polymer melt of preparation extruded, pelletizing, drying, obtain limiting viscosity be 0.65dl/g multi component copolyester section.
Above-mentioned copolyester section is melt extruded, die head slab, the stretching of horizontal far infrared, cooling and shaping, rolling, to cut, make the Heat shrinkage copolyester film of horizontal high shrinkage.Wherein, melt extruding temperature is 285 DEG C, and draft temperature is 100 DEG C, and preheating temperature is 80 DEG C, stretching ratio 3.9; Film thickness is 20 μm, and fabric width reaches 8700mm, and horizontal percent thermal shrinkage reaches more than 75%.
Embodiment 2
2.6Kg pure terephthalic acid is added in the universal reactor of 20L, 2.4Kg polycomponent diprotic acid is (comprising naphthalic acid, m-phthalic acid, biphenyl dicarboxylic acid), 2.7Kg ethylene glycol, 0.6Kg multicomponent binary alcohol is (comprising Isosorbide, butyleneglycol, glycol ether, triglycol, 1, 4-cyclohexanedimethanol, neopentyl glycol) and 8g tetrabutyl titanate catalyst, 150g titanium dioxide caking inhibiter, silicate modified dose of 20g, 1.1g stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.8g isocyanic ester chainextender, at 230 ~ 260 DEG C, esterification is carried out under 0.2 ~ 0.3Mpa condition, when aquifer yield reaches 1100mL theoretical value, system pressure is let out to normal pressure.
React with this understanding, add 1.5g triethyl phosphate stablizer, atmospheric agitation 7min, by temperature rise to 285 DEG C in reactor, pressure drops to below 100Pa, carry out reaction 3h with this understanding, then the polymer melt of preparation extruded, pelletizing, drying, obtain the copolyester section that limiting viscosity is 0.63dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, the stretching of horizontal far infrared, cooling and shaping, rolling, to cut, make the Heat shrinkage copolyester film of horizontal high shrinkage.Wherein, melt extruding temperature is 285 DEG C, and draft temperature is 110 DEG C, and preheating temperature is 85 DEG C, stretching ratio 3.9; Film thickness is 30 μm, and fabric width reaches 8700mm, and horizontal percent thermal shrinkage reaches more than 75%.
Embodiment 3
2.7Kg pure terephthalic acid is added in the universal reactor of 20L, 2.3Kg polycomponent diprotic acid is (comprising naphthalic acid, m-phthalic acid, biphenyl dicarboxylic acid), 2.6Kg ethylene glycol, 0.7Kg multicomponent binary alcohol is (comprising Isosorbide, butyleneglycol, glycol ether, triglycol, 1, 4-cyclohexanedimethanol, neopentyl glycol) and 9g antimony acetate catalyzer, 130g titanium dioxide caking inhibiter, silicate modified dose of 30g, 1.2g stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.9g isocyanic ester chainextender, at 230 ~ 260 DEG C, esterification is carried out under 0.2 ~ 0.3Mpa condition, when aquifer yield reaches 1100ml theoretical value, system pressure is let out to normal pressure.
React with this understanding, add 1.6g triethyl phosphate stablizer, atmospheric agitation 9min, by temperature rise to 285 DEG C in reactor, pressure drops to below 100Pa, carry out reaction 3h with this understanding, then the polymer melt of preparation extruded, pelletizing, drying, obtain the copolyester section that limiting viscosity is 0.61dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, the stretching of horizontal far infrared, cooling and shaping, rolling, to cut, make the Heat shrinkage copolyester film of horizontal high shrinkage, wherein, melt extruding temperature is 285 DEG C, and draft temperature is 120 DEG C, and preheating temperature is 90 DEG C, stretching ratio 3.9, thickness is 40 μm, and fabric width reaches 8700mm, and horizontal percent thermal shrinkage reaches more than 75%.
Embodiment 4
2.7Kg pure terephthalic acid is added in the universal reactor of 20L, 2.2Kg polycomponent diprotic acid is (comprising naphthalic acid, m-phthalic acid, biphenyl dicarboxylic acid), 2.5Kg ethylene glycol, 0.8g multicomponent binary alcohol is (comprising Isosorbide, butyleneglycol, glycol ether, triglycol, 1, 4-cyclohexanedimethanol, neopentyl glycol) and 9g antimony acetate catalyzer, 120g titanium dioxide caking inhibiter, silicate modified dose of 40g, 1.2g stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.9g isocyanic ester chainextender, at 230 ~ 260 DEG C, esterification is carried out under 0.2 ~ 0.3Mpa condition, when aquifer yield reaches 1100ml theoretical value, system pressure is let out to normal pressure.
React with this understanding, add 1.6g triethyl phosphate stablizer, atmospheric agitation 9min, by temperature rise to 285 DEG C in reactor, pressure drops to below 100Pa, carry out reaction 3h with this understanding, then the polymer melt of preparation extruded, pelletizing, drying, obtain the copolyester section that limiting viscosity is 0.60dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, the stretching of horizontal far infrared, cooling and shaping, rolling, to cut, make the Heat shrinkage copolyester film of horizontal high shrinkage.Wherein, melt extruding temperature is 285 DEG C, and draft temperature is 120 DEG C, and preheating temperature is 90 DEG C, stretching ratio 3.9; Film thickness is 60 μm, and fabric width reaches 8700mm, and horizontal percent thermal shrinkage reaches more than 75%.
Claims (9)
1. a preparation method for Heat shrinkage copolyester film, is characterized in that: polycomponent diprotic acid and multicomponent binary alcohol, at catalyzer, stablizer, static inhibitor, chainextender, under caking inhibiter or properties-correcting agent exist, through esterification, polycondensation, obtained multi component copolyester; Described multi component copolyester is by melt extrusion, pelletizing, drying process, and obtained multi component copolyester is cut into slices; Described multi component copolyester section again by melt extruding, die head slab, laterally with far-infrared heating raw material, with equipment carry out stretching, cooling and shaping, rolling, point cutting process, the Heat shrinkage copolyester film that obtained horizontal percent thermal shrinkage reaches more than 75%, thickness in monolayer is 20 ~ 60 μm; Wherein, the draft temperature of described Heat shrinkage copolyester film is 100 DEG C ~ 120 DEG C, and preheating temperature is 70 DEG C ~ 90 DEG C, and cross directional stretch multiplying power is 3.9 ~ 4.1.
2. the preparation method of a kind of Heat shrinkage copolyester film according to claim 1, is characterized in that: described polycomponent diprotic acid is selected from following two or more material: terephthalic acid, m-phthalic acid, biphenyl dicarboxylic acid, naphthalic acid; Described multicomponent binary alcohol is selected from following two or more material: ethylene glycol, Isosorbide, butyleneglycol, glycol ether, triglycol, 1,4 cyclohexane dimethanol, neopentyl glycol.
3. the preparation method of Heat shrinkage copolyester film according to claim 2, is characterized in that: in described polycomponent diprotic acid, preferred version is at least containing terephthalic acid, and its mass percent > 60%; In described multicomponent binary alcohol, preferred version is at least containing ethylene glycol, and its mass percent > 50%.
4. the preparation method of the Heat shrinkage copolyester film according to claim 1,2 or 3, it is characterized in that: in the esterification of described multi component copolyester, polycondensation process, esterification temperature is 210 ~ 275 DEG C, and esterification absolute pressure is 0.1 ~ 0.4MPa, and esterification time is 1 ~ 5h; Condensation temperature is 250 ~ 295 DEG C, polycondensation absolute pressure≤100Pa, and the polycondensation time is 1 ~ 4h.
5. the preparation method of the Heat shrinkage copolyester film according to claim 1,2 or 3, is characterized in that: the catalyzer adopted in described multi component copolyester preparation process is the organic complex of antimony acetate, antimony glycol, tetrabutyl titanate compound, the organic complex of antimony acetate, the organic complex of antimony glycol or tetrabutyl titanate; Its add-on is account for copolyesters quality 0.01 ~ 0.1%.
6. the preparation method of the Heat shrinkage copolyester film according to claim 1,2 or 3, is characterized in that: the caking inhibiter adopted in described copolyesters preparation process or properties-correcting agent are selected from one or more in following substances: titanium dioxide, silicon-dioxide, calcium carbonate, calcium phosphate, calcium acetate, barium sulfate, kaolin, silicate, silicates composite granule; Described caking inhibiter or the median size of properties-correcting agent are 100 ~ 280nm; Its add-on accounts for 2.0 ~ 8% of copolyesters quality.
7. the preparation method of the Heat shrinkage copolyester film according to claim 1,2 or 3, is characterized in that: the stablizer adopted in described copolyester section preparation process is phosphoric acid, phosphorous acid, Tripyrophosphoric acid, trimethyl phosphite 99 or triethyl phosphate; Its add-on accounts for 0.0005 ~ 0.035% of copolyesters quality.
8. the preparation method of the Heat shrinkage copolyester film according to claim 1,2 or 3, is characterized in that: the static inhibitor adopted in described multi component copolyester preparation process is stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate or stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate; Its add-on accounts for 0.005 ~ 0.02% of copolyesters quality.
9. the preparation method of the Heat shrinkage copolyester film according to claim 1,2 or 3, is characterized in that: the chainextender adopted in described multi component copolyester preparation process is isocyanic ester, carbon two subunit or pyromellitic acid anhydride; Its add-on accounts for 0.001 ~ 0.06% of copolyesters quality.
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| CN201310101373.3A CN103172990B (en) | 2013-03-26 | 2013-03-26 | Preparation method of heat shrinkable polyester film |
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| CN201310101373.3A CN103172990B (en) | 2013-03-26 | 2013-03-26 | Preparation method of heat shrinkable polyester film |
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| CN103172990B true CN103172990B (en) | 2015-04-01 |
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| CN112724375A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Preparation method of polyester for large-capacity container |
| CN111205441A (en) * | 2019-12-30 | 2020-05-29 | 长垣县源宏包装新材料有限公司 | Preparation process of high-shrinkage high-heat-seal-viscosity polyester product for packaging |
| CN114075342B (en) * | 2020-08-11 | 2023-11-17 | 中国石油化工股份有限公司 | Preparation method of PET film and PET-based printing paper coating film |
| CN112194808A (en) * | 2020-09-28 | 2021-01-08 | 内蒙古广播电视大学(内蒙古现代远程开放教育中心、内蒙古老年开放大学) | Art design packaging film material and preparation method thereof |
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| CN113321829B (en) * | 2021-06-02 | 2023-03-24 | 山东圣和薄膜新材料有限公司 | Low-shrinkage-force polyester shrink film and preparation method thereof |
| CN115703893A (en) * | 2021-08-13 | 2023-02-17 | 江苏双星彩塑新材料股份有限公司 | Preparation method of thermochromic polyester film |
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|---|---|---|---|---|
| CN1860152A (en) * | 2003-07-31 | 2006-11-08 | 纳幕尔杜邦公司 | Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom |
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