CN103172990A - Preparation method of heat shrinkable polyester film - Google Patents
Preparation method of heat shrinkable polyester film Download PDFInfo
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- CN103172990A CN103172990A CN2013101013733A CN201310101373A CN103172990A CN 103172990 A CN103172990 A CN 103172990A CN 2013101013733 A CN2013101013733 A CN 2013101013733A CN 201310101373 A CN201310101373 A CN 201310101373A CN 103172990 A CN103172990 A CN 103172990A
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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
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 thermal contraction 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, adopt the heat-shrinkable film of the material produce such as polyvinyl chloride (PVC), polystyrene (PS), polyethylene terephthalate (PET) to be widely used in the fields such as the label of various containers and food-drink, electronic apparatus, machinery.
The thermal contraction polyvinyl chloride film is used the earliest because of its excellent shrinkage and the transparency, but often produce a large amount of hydrogenchloride during due to burning with the gases such as dioxin are unfavorable for recycling, do not meet environmental requirement, therefore, now be restricted in application.
The thermal contraction polystyrene film has satisfactory stability and outward appearance in contraction process, but due to not good in performance aspect chemical resistant properties, less stable, and intensity is low, and 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 characteristics such as environment protection service requirements, thereby has become in developed country the ideal substitute that replaces thermal contraction polyvinyl chloride film and thermal contraction polystyrene film at present.But, because the common PET polyester is the crystal type superpolymer, and adopt the heat-shrinkable film of its preparation, though process through special process, can only obtain at most the percent thermal shrinkages below 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).Adopt at present terephthalic acid, ethylene glycol and 1, the PETG Polyester heat shrinkable film of the monomer copolymerization superpolymer such as 4-cyclohexanedimethanol or neopentyl glycol preparation, percent thermal shrinkage is up to more than 70%, but there are the deficiencies such as the transparency, ductility and poor toughness in this series products, thereby affects the quality of film.
In order to overcome the existing existing deficiency of ordinary hot shrinkable polyester film, produce the copolyester film of the percent thermal shrinkage that satisfies customer requirements, 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 the standby unilateral stretching heat-shrinkable film of this polyester; The described PETG polyester of 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 ℃, and the temperature of polyreaction is 270 ℃～280 ℃, and the vacuum tightness of polyreaction is 0.098MPa～0.1MPa; The described PETG polyester thermal contraction film of this patent has transparency and percent thermal shrinkage preferably, but tensile strength, to shrink homogeneity undesirable.
Chinese patent 200980125580.4 discloses a kind of copolyesters for shrinkable film.The described polyester of this patent is made 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 because percent thermal shrinkage is lower, thereby is 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% contains the polyester slice of IPA, and 5～92% silicon are polyester slice; Wherein, in functional polyester chip A, sea shell micropowder quality percentage composition is 0.1～13.5%, in functional polyester chip B, nano imvite quality percentage composition is 0.5～32.6%, contain that in the polyester slice of IPA, IPA quality percentage composition is 0.2～7.8%, silicon is that in polyester slice, siliconoxide mass content is 200～1890PPM.Compare with existing polyester film for electronic tag, this polyester film for electronic tag under 180 ℃ of high temperature vertically percent thermal shrinkage in 0～1% scope, at its specific inductivity under the 1GHz test condition in 1～3 scope, dielectric loss angle tangent 0.2%～0.8%.The described film of this invention is non-heat-shrinkage material, almost without percent thermal shrinkage, thereby 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, a kind of preparation method of effective multi-component copolymer ester and a kind of preparation method of simple and easy to do thermal contraction copolyester film are provided, and it is good to prepare the transparency by aforesaid method, shrink evenly, laterally percent thermal shrinkage reaches the thermal contraction copolyester film of the high shrinkage 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 thermal contraction copolyester film, the steps include: polycomponent diprotic acid and multicomponent binary alcohol, and through esterification, polycondensation, make the multi-component copolymer ester; Wherein, esterification temperature is 210～275 ℃, and the esterification absolute pressure is 0.1～0.4MPa, and esterification time is 1～5h; Condensation temperature is 250～295 ℃, polycondensation absolute pressure≤100Pa, and the polycondensation time is 1～4h; In described copolyesters preparation process, need add catalyzer, stablizer, static inhibitor, chainextender, caking inhibiter or properties-correcting agent; Described multi-component copolymer ester is by melt extrusion, stretching, granulating working procedure, and (its limiting viscosity is 0.58～0.70dl/g) to make the section of multi-component copolymer ester; Described multi-component copolymer ester section adds in screw extrusion press, by melt extrude, die head slab, horizontal far infrared (the far-infrared heating raw material that stretches, stretch with equipment), cooling and shaping, rolling, minute cutting process, make horizontal percent thermal shrinkage and reach 75% above thermal contraction 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 contains terephthalic acid at least, and its mass percent＞60%; In described multicomponent binary alcohol, preferred version contains ethylene glycol at least, and its mass percent＞50%.
In the esterification of described multi-component copolymer ester, polycondensation process, esterification temperature is 210～275 ℃, and the esterification absolute pressure is 0.1～0.4MPa, and esterification time is 1～5h; Condensation temperature is 250～295 ℃, polycondensation absolute pressure≤100Pa, and the polycondensation time is 1～4h.
The catalyzer that adopts in described multi-component copolymer ester 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 that adopts 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; The median size of described caking inhibiter or properties-correcting agent is 100～280nm; Its add-on accounts for 2.0～8% of copolyesters quality.
The stablizer that adopts 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 that adopts in described multi-component copolymer ester preparation process is stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate or stearamide propyl dimethyl-beta-hydroxyethyl ammonium nitrate; Its add-on accounts for 0.005～0.02% of copolyesters quality.
The chainextender that adopts in described multi-component copolymer ester preparation process is isocyanic ester, carbon two subunits 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 ℃～295 ℃, and the draft temperature of described film is 100 ℃～120 ℃, and preheating temperature is 70 ℃～90 ℃, and the cross directional stretch multiplying power is 3.9～4.1, and thickness is 20～60 μ m.
Beneficial effect of the present invention: the present invention is by the described multi-component copolymer ester of preparation, and by the control to processing parameters such as the optimization of film production process and film stretching temperature, stretching ratios, finally obtain the thermal contraction copolyester film that horizontal percent thermal shrinkage reaches the high shrinkage more than 75%.The thermal contraction copolyester film of the high shrinkage of the present invention preparation is single layer structure, tensile strength between 220～300MPa, skin friction coefficient≤0.5, thickness is between 20～60 μ m, fabric width reaches 8700mm.Compare with conventional heat shrinkable polyester film, the thermal contraction copolyester film of the high shrinkage of the present invention's preparation has higher intensity and heat-shrinkable, the good transparency, ductility and toughness, glossiness is good, shrink evenly, and nontoxic, tasteless, be easy to recycle, product is particularly useful for the direct packing of the goods such as the label of various containers and food-drink, electronic apparatus, machinery, five metals.
Description of drawings:
Fig. 1 is preparation technology's schema of disclosed a kind of thermal contraction copolyester film of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
add the 2.5Kg pure terephthalic acid in the universal reactor of 20L, 2.5Kg the 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, the 4-cyclohexanedimethanol, neopentyl glycol) and the 9g glycol antimony catalyst, 160g titanium dioxide caking inhibiter, silicate modified dose of 10g, 1.2g stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.9g isocyanic ester chainextender, at 230～260 ℃, 0.2 carry out esterification under～0.3Mpa condition, when aquifer yield reaches the 1100mL theoretical value, system pressure is let out to normal pressure.
Reaction with this understanding, add 1.6g triethyl phosphate stablizer, normal pressure stirs 7min, with temperature rise to 285 in reactor ℃, pressure drops to below 100Pa, react with this understanding 3h, then the polymer melt of preparation is extruded, pelletizing, drying, obtaining limiting viscosity is the multi-component copolymer ester section of 0.65dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, laterally far infrared stretching, cooling and shaping, rolling, cuts, make the thermal contraction copolyester film of horizontal high shrinkage.Wherein, melt extruding temperature is 285 ℃, and draft temperature is 100 ℃, and preheating temperature is 80 ℃, stretching ratio 3.9; Film thickness is 20 μ m, and fabric width reaches 8700mm, and laterally percent thermal shrinkage reaches more than 75%.
Embodiment 2
add the 2.6Kg pure terephthalic acid in the universal reactor of 20L, 2.4Kg the 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, the 4-cyclohexanedimethanol, neopentyl glycol) and 8g tetrabutyl titanate catalyzer, 150g titanium dioxide caking inhibiter, silicate modified dose of 20g, 1.1g stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.8g isocyanic ester chainextender, at 230～260 ℃, 0.2 carry out esterification under～0.3Mpa condition, when aquifer yield reaches the 1100mL theoretical value, system pressure is let out to normal pressure.
Reaction with this understanding, add 1.5g triethyl phosphate stablizer, normal pressure stirs 7min, with temperature rise to 285 in reactor ℃, pressure drops to below 100Pa, react with this understanding 3h, then the polymer melt of preparation is extruded, pelletizing, drying, obtain the copolyester section that limiting viscosity is 0.63dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, laterally far infrared stretching, cooling and shaping, rolling, cuts, make the thermal contraction copolyester film of horizontal high shrinkage.Wherein, melt extruding temperature is 285 ℃, and draft temperature is 110 ℃, and preheating temperature is 85 ℃, stretching ratio 3.9; Film thickness is 30 μ m, and fabric width reaches 8700mm, and laterally percent thermal shrinkage reaches more than 75%.
Embodiment 3
add the 2.7Kg pure terephthalic acid in the universal reactor of 20L, 2.3Kg the 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, the 4-cyclohexanedimethanol, neopentyl glycol) and 9g antimony acetate catalyzer, 130g titanium dioxide caking inhibiter, silicate modified dose of 30g, 1.2g stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.9g isocyanic ester chainextender, at 230～260 ℃, 0.2 carry out esterification under～0.3Mpa condition, when aquifer yield reaches the 1100ml theoretical value, system pressure is let out to normal pressure.
Reaction with this understanding, add 1.6g triethyl phosphate stablizer, normal pressure stirs 9min, with temperature rise to 285 in reactor ℃, pressure drops to below 100Pa, react with this understanding 3h, then the polymer melt of preparation is extruded, pelletizing, drying, obtain the copolyester section that limiting viscosity is 0.61dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, laterally far infrared stretching, cooling and shaping, rolling, cuts, make the thermal contraction copolyester film of horizontal high shrinkage, wherein, melt extruding temperature is 285 ℃, and draft temperature is 120 ℃, and preheating temperature is 90 ℃, stretching ratio 3.9, thickness is 40 μ m, and fabric width reaches 8700mm, and laterally percent thermal shrinkage reaches more than 75%.
Embodiment 4
add the 2.7Kg pure terephthalic acid in the universal reactor of 20L, 2.2Kg the 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, the 4-cyclohexanedimethanol, neopentyl glycol) and 9g antimony acetate catalyzer, 120g titanium dioxide caking inhibiter, silicate modified dose of 40g, 1.2g stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate static inhibitor, 0.9g isocyanic ester chainextender, at 230～260 ℃, 0.2 carry out esterification under～0.3Mpa condition, when aquifer yield reaches the 1100ml theoretical value, system pressure is let out to normal pressure.
Reaction with this understanding, add 1.6g triethyl phosphate stablizer, normal pressure stirs 9min, with temperature rise to 285 in reactor ℃, pressure drops to below 100Pa, react with this understanding 3h, then the polymer melt of preparation is extruded, pelletizing, drying, obtain the copolyester section that limiting viscosity is 0.60dl/g.
Above-mentioned copolyester section is melt extruded, die head slab, laterally far infrared stretching, cooling and shaping, rolling, cuts, make the thermal contraction copolyester film of horizontal high shrinkage.Wherein, melt extruding temperature is 285 ℃, and draft temperature is 120 ℃, and preheating temperature is 90 ℃, stretching ratio 3.9; Film thickness is 60 μ m, and fabric width reaches 8700mm, and laterally percent thermal shrinkage reaches more than 75%.
Claims (10)
1. the preparation method of a thermal contraction copolyester film is characterized in that: polycomponent diprotic acid and multicomponent binary alcohol, at catalyzer, stablizer, static inhibitor, chainextender, caking inhibiter or properties-correcting agent through esterification, polycondensation, make the multi-component copolymer ester under existing; Described multi-component copolymer ester makes the section of multi-component copolymer ester by melt extrusion, stretching, granulating working procedure; The section of described multi-component copolymer ester again by melt extrude, die head slab, laterally far infrared stretching, cooling and shaping, rolling, minute cutting process, make the thermal contraction copolyester film.
2. the preparation method of a kind of thermal contraction copolyester film according to claim 1, it 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 thermal contraction copolyester film according to claim 2, it is characterized in that: in described polycomponent diprotic acid, preferred version contains terephthalic acid at least, and its mass percent＞60%; In described multicomponent binary alcohol, preferred version contains ethylene glycol at least, and its mass percent＞50%.
4. the preparation method of according to claim 1,2 or 3 described thermal contraction copolyester films, it is characterized in that: in the esterification of described multi-component copolymer ester, polycondensation process, esterification temperature is 210～275 ℃, and the esterification absolute pressure is 0.1～0.4MPa, and esterification time is 1～5h; Condensation temperature is 250～295 ℃, polycondensation absolute pressure≤100Pa, and the polycondensation time is 1～4h.
5. the preparation method of according to claim 1,2 or 3 described thermal contraction copolyester films, it is characterized in that: the catalyzer that adopts in described multi-component copolymer ester preparation process is the machine complex compound of antimony acetate, antimony glycol, tetrabutyl titanate compound, antimony acetate, the machine complex compound of antimony glycol or the machine complex compound of tetrabutyl titanate; Its add-on is to account for 0.01～0.1% of copolyesters quality.
6. the preparation method of according to claim 1,2 or 3 described thermal contraction copolyester films, it is characterized in that: the caking inhibiter that adopts 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; The median size of described caking inhibiter or properties-correcting agent is 100～280nm; Its add-on accounts for 2.0～8% of copolyesters quality.
7. the preparation method of according to claim 1,2 or 3 described thermal contraction copolyester films, it is characterized in that: the stablizer that adopts 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 according to claim 1,2 or 3 described thermal contraction copolyester films, it is characterized in that: the static inhibitor that adopts in described multi-component copolymer ester preparation process is stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate or stearamide propyl dimethyl-beta-hydroxyethyl ammonium nitrate; Its add-on accounts for 0.005～0.02% of copolyesters quality.
9. the preparation method of according to claim 1,2 or 3 described thermal contraction copolyester films, it is characterized in that: the chainextender that adopts in described multi-component copolymer ester preparation process is isocyanic ester, carbon two subunits or pyromellitic acid anhydride; Its add-on accounts for 0.001～0.06% of copolyesters quality.
10. the preparation method of thermal contraction copolyester film according to claim 1, it is characterized in that: the temperature that melt extrudes of described copolyesters is 265 ℃～295 ℃, the draft temperature of described film is 100 ℃～120 ℃, preheating temperature is 70 ℃～90 ℃, the cross directional stretch multiplying power is 3.9～4.1, and thickness is 20～60 μ m.
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| CN104072737A (en) * | 2014-05-30 | 2014-10-01 | 江苏光辉包装材料有限公司 | Method for preparing modified polyester for easily machined type high-shrinkage film |
| CN104804177A (en) * | 2015-04-09 | 2015-07-29 | 中国纺织科学研究院 | Modified PET (polyethylene terephthalate) copolymer for high-toughness heat-shrinkable film and preparation method of modified PET copolymer |
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