CN102336042A - Polyester composite film and its preparation method - Google Patents
Polyester composite film and its preparation method Download PDFInfo
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- CN102336042A CN102336042A CN2010102287493A CN201010228749A CN102336042A CN 102336042 A CN102336042 A CN 102336042A CN 2010102287493 A CN2010102287493 A CN 2010102287493A CN 201010228749 A CN201010228749 A CN 201010228749A CN 102336042 A CN102336042 A CN 102336042A
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Abstract
The invention relates to a polyester composite film, concretely relates to a composite film composited by a modified copolyester film and a polyolefin film through an adhesive layer, and a preparation method. The composite film comprises a modified copolyester film layer, a polyolefin film layer positioned on one surface or upper and lower surfaces of the modified copolyester film, and an adhesive layer positioned between the polyester layer and the polyolefin layer. According to the invention, the modified copolyester is used in the composite film, wherein a melt-strength reinforcer is introduced in the modified copolyester, so that the melt strength is enhanced, the composite film can be prepared by the modified copolyester through a double-bubble blown film moulding method, thereby the secondary composite processing procedure is reduced. The polyester composite film is used for packaging food, medicines and biological products, and overcomes the disadvantage that the copolyester is unsuitable for preparing the membrane.
Description
Technical field
The present invention relates to a kind of polyester composite sheet, specifically, relate to the laminated film that a kind of modified copolymer ester film and polyolefin film are composited through adhesive phase, with and preparation method thereof.
Background technology
The normal polyester raw material is because its melt strength is low, and degree of crystallinity is high, only limits to use the processing method of extruding the curtain coating biaxial tension to prepare at present.The polyester composite sheet that uses in the packaging for foodstuff field also only limits to the processing method of using dry method compound.Therefore exist equipment investment big, power consumption is high, to disadvantages such as environment pollute.
Patent ZL200610155089.4 discloses a kind of composite packing film with very high oxygen inhibition and boiling resistance, and this composite membrane comprises base material-high resistant oxygen glue-polyolefinic 3-tier architecture, and this base material can be selected polyester material for use; Extrude the preparation of curtain coating processing method but the polyester film of this patent adopts,, adopt the composite dry process preparation to form laminated film again through applying high resistant oxygen glue.
The present invention adopts the copolyesters raw material is carried out the modification processing; Improve its melt strength through adding the melt strength hardening agent; Reduce its degree of crystallinity; Destroy its macromolecular regularity, make it reduce crystallization or non-crystallizable, the modified copolyester of handling like this can use two bubble inflation film moulding process to prepare polyester composite sheet.
Summary of the invention
Primary goal of the invention of the present invention is to provide a kind of polyester composite sheet.
Second goal of the invention of the present invention is to provide the preparation method of this laminated film.
In order to accomplish the present invention's purpose, the technical scheme that the present invention adopts is:
The present invention relates to a kind of polyester composite sheet, described laminated film comprises one deck modified copolyester film, is positioned at the polyolefm film layer of these modified copolyester film one or both sides, and is positioned at the adhesive phase in the middle of said polyester layer and the said polyolefin layer.
First preferred version of the present invention is that described polyolefin is selected from metallocene PE or low density polyethylene (LDPE).
Second preferred version of the present invention does, described adhesive is olefin-modified adhesive, at least a in optimal ethylene acrylic copolymer (EAA), vinyl-vinyl acetate copolymers (EVA) or the ethylene-vinyl alcohol copolymer (EVOH).
The 3rd preferred version of the present invention does, described modified copolyester layer proportion is 20～50%, and the polyolefin layer proportion is 48～78%, and the adhesive phase proportion is 2～5%; Be preferably, modified copolyester layer proportion is 22～48%, and the polyolefin layer proportion is 50～75%, and the adhesive phase proportion is 2～4%.
The 4th preferred version of the present invention does, the raw material of the modified copolyester in the described laminated film comprises smart para Toluic Acid, second diester, modified monomer, melt strength hardening agent, additive and catalyst, and wherein the melt strength hardening agent is selected from 1; 2,4-benzenetricarboxylic acid, 1,2; 4-benzenetricarboxylic anhydride, 1,2,4; At least a in 5-benzenetetracarboxylic acid dianhydride, trimethylolpropane, glycerine, pentaerythrite, citric acid, tartaric acid, the 3-hydroxy dibasic acid, preferred pentaerythrite.
Wherein, modified monomer is selected from aliphatic or aromatic binary carboxylic acid, the dihydroxylic alcohols except that ethylene glycol except that terephthalic acid (TPA), preferred M-phthalic acid, diglycol, 1,4-cyclohexanedimethanol (CHDM) etc.
The 5th preferred version of the present invention does, the weight ratio that described melt strength hardening agent is added is 0.05 ‰～0.25 ‰ of a copolyesters, and is preferred 0.1 ‰～0.2 ‰, more preferably 0.125 ‰～0.175 ‰.
The 6th preferred version of the present invention does, described catalyst is selected from least a in antimony, antimony glycol or the antimony acetate, and wherein, the weight ratio that antimony added is 0.1 of copolyesters～0.3 ‰, and is preferred 0.15 ‰～0.25 ‰, most preferably 0.2 ‰; The weight ratio that antimony glycol or antimony acetate added is 0.2 ‰ of copolyesters～0.8 ‰, and is preferred 0.25 ‰～0.75 ‰, more preferably 0.3 ‰～0.5 ‰, further preferred 0.35 ‰～0.45 ‰.
The invention still further relates to the preparation method of modified copolyester, comprise that steps such as esterification, polycondensation, pelletizing are prepared from, wherein, enzymatic synthesis condition is 210 ℃～260 ℃, 2～3 atmospheric pressure; The polycondensation condition is a vacuum less than 100Pa, 275 ℃～285 ℃; Melt strength hardening agent in the described modified copolyester joins respectively in the said raw material in Esterification Stage or polycondensation phase, or adds in Esterification Stage or polycondensation phase in batches.
Invention also relates to the preparation method of polyester composite sheet, adopts the preparation of two bubble inflation film moulding technique, and its technological process is as shown in Figure 3.
Wherein, the concrete steps of described two bubble inflation film moulding process are:
(1) the modified copolyester raw material is transported in the closed drying hopper, drying is 6～12 hours under 60～70 ℃ of temperature, makes its water content be lower than 0.1 ‰;
(2) carry out fusion plastification in the single screw extrusion machine with dried modified copolyester raw material adding intermediate layer and extrude, extruder temperature is controlled at 180 ℃～220 ℃, and preferred 190 ℃～220 ℃, more preferably 200 ℃～220 ℃, most preferably 200 ℃～210 ℃; Carry out fusion plastification in the single screw extrusion machine with polyethylene raw material adding skin and/or internal layer and extrude, extruder temperature is controlled at 165 ℃～215 ℃, and preferred 175 ℃～215 ℃, more preferably 185 ℃～215 ℃, most preferably 190 ℃～210 ℃; Adhesive is added carry out fusion plastification in the interbed single screw extrusion machine of polyethylene and copolyesters and extrude, extruder temperature is controlled at 160 ℃～180 ℃, and preferred 165 ℃～180 ℃, more preferably 170 ℃～180 ℃; All melts gets into die head, and die head temperature is controlled at 180 ℃～220 ℃, and preferred 190 ℃～220 ℃, more preferably 200 ℃～220 ℃, most preferably 200 ℃～210 ℃; Upwards carry out inflation and obtain first film bubble;
(3) first films bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls; The first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 80 ℃～95 ℃, preferred 85 ℃～95 ℃; To elastomeric state, the secondary inflation obtains second film bubble then after post bake;
(4) second films bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls;
(5) second bubble two-fold films are introduced coiling machine through deflector roll and are accomplished last rolling.
Wherein, modified copolyester used additive in synthetic generally adds according to requirement of products, ratio as, membrane will add anti-ether agent silica, need add toner sometimes, for example blue degree agent and red degree agent etc.
Polyester composite sheet of the present invention can be used for the packing of food, medicine, biological products.
Further describe in the face of technical scheme of the present invention down.
Composite membrane of the present invention can be 3-tier architecture, is followed successively by: modified copolyester film-adhesive phase-polyolefin film, and structural representation is as shown in Figure 1; Or be 5 layers of structure, be followed successively by: polyolefin layer-adhesive phase-polyester layer-adhesive phase-polyolefin layer, structural representation is as shown in Figure 2.
Direct esterification (PTA) method route is adopted in the preparation of modified copolyester raw material: PTA, EG, modified monomer are added melt strength hardening agent, additive, catalyst etc.; Under 210 ℃～260 ℃ 2～3 atmospheric pressure, carry out esterification; Add portions additive after the esterification again; Carry out polycondensation in vacuum under less than 100Pa, 275 ℃～285 ℃ conditions, carry out pelletizing, packaging and other steps after the completion again.
Direct esterification (PTA) method route can also adopt following steps; PTA, EG, modified monomer are added additive and catalyst; Under 210 ℃～260 ℃ 2～3 atmospheric pressure, carry out esterification; Add melt strength hardening agent, portions additive after the esterification again, carry out polycondensation under less than 100Pa, 275 ℃～285 ℃ conditions, carry out pelletizing, packaging and other steps after the completion again in vacuum.
Modified copolyester layer of the present invention has adopted modified copolyester, and modified copolyester is in the copolyesters polymerization process, improves its melt strength through adding the melt strength hardening agent; Reduce its degree of crystallinity; Destroy its macromolecular regularity, make it reduce crystallization or non-crystallizable, thereby make the structure of molecular structure and original copolyesters of copolyesters different; The mobile variation of copolyesters melt, intensity enhancing.The modified copolyester for preparing like this can adopt secondary inflation blow molding process processing film forming.The melt strength hardening agent can add in the Esterification Stage or the polycondensation phase of polyester manufacture, participates in pet reaction.
The copolyesters that non-modified is handled can not be used the film of the prepared of two bubble inflation film moulding because melt strength is not enough.Modified copolyester of the present invention has overcome copolyesters and has not been suitable for the shortcoming of making film, makes the film of preparation have the advantage that hot strength strengthens, the fracture growth rate strengthens, oxygen permeating amount is lower than the common PET polyester, heat seal strength is high simultaneously; And be specially adapted to as material of preparing.Prepared film can be used for the packing of food, medicine, biological products.
The preparation flow of the two bubble inflation film moulding process that adopted of preparation laminated film is:
(1) the modified copolyester raw material is transported in the closed drying hopper, dry more than 6 hours under 65 ℃ of temperature, water content is lower than 0.1 ‰.
(2) carry out fusion plastification in the single screw extrusion machine with dried modified copolyester raw material adding intermediate layer and extrude, extruder temperature is controlled at 200 ℃～210 ℃; Carry out fusion plastification in the single screw extrusion machine with polyethylene raw material adding skin and/or internal layer and extrude, 190 ℃～210 ℃ of extruder temperature controls; Adhesive is added carry out fusion plastification in the interbed single screw extrusion machine of polyethylene and copolyesters and extrude, extruder temperature is controlled at 170 ℃～180 ℃; All melts gets into die head, and die head temperature is controlled at 200 ℃～210 ℃; Upwards carry out inflation and obtain first film bubble;
(3) first films bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls; The first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 85 ℃～95 ℃; To elastomeric state, the secondary inflation obtains second film bubble then after post bake;
(4) second films bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls.
(5) second bubble two-fold films are introduced coiling machine through deflector roll and are accomplished last rolling.
The polyester composite sheets of two bubble inflation film moulding techniques preparation that the present invention describes have solved that the equipment investment that conventional dry method Compound Machining brings is big, power consumption is high, to disadvantages such as environment pollute.Simultaneously, polyester composite sheet processing method described in the invention has reduced intermediate link for system film, compound once completion, has reduced production cost, has improved operating efficiency.In today of Market competition, for we have brought competitiveness and benefit.
Description of drawings
The formation sketch map of Fig. 1 laminated film, three-decker; Wherein 1 is polyethylene layer, and 2 is the modified copolyester layer, and 3 is adhesive phase;
The formation sketch map of Fig. 2 laminated film, five-layer structure; Wherein 1 is polyethylene layer, and 2 is the modified copolyester layer, and 3 is adhesive phase;
The process chart of the two bubble of Fig. 3 laminated film inflation film moulding.
The specific embodiment
The present invention provides following examples for further describing the present invention, but described embodiment only is used to explain the present invention rather than restriction the present invention.
1. the preparation of modified copolyester raw material
On 1 cube semicrystalline polyester continuous apparatus, according to the method that this device is produced, cut into slices and 108 kilograms ethylene glycol and an amount of alcoholysis catalysts with about 665 kilograms light that has much, under 260 ℃, carry out alcoholysis, with the preparation mother liquor; In the making beating still with every batch of modified monomer CHDM that adds 300 kilograms PTA (or quite binary acid of molal quantity), 150 kilograms of EG and certain molal quantity; And appropriate amount of catalysts and melt strength hardening agent; The weight ratio that catalyst glycol antimony added is 0.35 ‰ of a copolyesters; The melt strength hardening agent is 1,2, and the weight ratio that the 4-benzenetricarboxylic anhydride is added is 0.125 ‰ of a copolyesters; Every batch of slurry adds esterifying kettle with certain speed, makes the reaction temperature in the esterifying kettle be controlled at 250 ℃; Material adds in the esterifying kettle and after reacting completely fully in the every batch of making beating still, and the esterifying kettle thing that lactonizes partly is pressed in the polycondensation vessel, and vacuum is to carry out polycondensation reaction under the state below the 100Pa in melt temperature is 280 ℃, still; Judge the viscosity of copolyesters according to the power of agitator of polycondensation vessel, confirm discharging power, through supercooling, blank, sub-sieve, drying and pack.1.2M
3Production technology on the semicontinuous device is seen table 1.
Table 1:1.2M
3Production technology on the semicontinuous device
| Esterification temperature ℃ | Esterification pressure p a | Condensation temperature ℃ | Polycondensation pressure pa | Discharging electric current A |
| 250～260 | 2～3 atmospheric pressure | 280 | ＜100 | ?23 |
1.2M
3The production technology with common PET is identical basically for the production technology of copolyesters on the semicontinuous device.
2. the preparation of laminated film
1) the modified copolyester raw material is transported in the closed drying hopper, dry more than 6 hours under 65 ℃ of temperature.
2) carry out fusion plastification in the single screw extrusion machine of dried modified copolyester raw material adding internal layer and extrude, extruder temperature is controlled at 215 ℃; The polyethylene raw material added carry out fusion plastification in the outer field single screw extrusion machine and extrude, extruder temperature is controlled at 185 ℃; Adhesive added carry out fusion plastification in the single screw extrusion machine of intermediate layer and extrude, extruder temperature is controlled at 165 ℃.All melts gets into and contains three laminar flow road die heads, and die head temperature is controlled at 210 ℃.Upwards carry out inflation and obtain first film bubble.First film bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls.
3) the first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 85 ℃, and to elastomeric state, the secondary inflation obtains second film bubble then after post bake; Second film bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls;
4) the second bubble two-fold film is introduced coiling machine through deflector roll and is accomplished last rolling.
Three layers of composite membrane thickness of preparation are 40 μ m, and wherein copolyester layer thickness is 15 μ m, and polyethylene layer thickness is 24 μ m, and adhesive phase thickness is 1 μ m.The performance of composite membrane is referring to table 2:
The performance of table 2 composite membrane
1. the preparation of modified copolyester raw material
On 1 cube semicrystalline polyester continuous apparatus, according to the method that this device is produced, cut into slices and 108 kilograms ethylene glycol and an amount of alcoholysis catalysts with about 665 kilograms light that has much, under 260 ℃, carry out alcoholysis, with the preparation mother liquor; In the making beating still with every batch of modified monomer CHDM that adds 300 kilograms PTA (or quite binary acid of molal quantity), 150 kilograms of EG and certain molal quantity, and appropriate amount of catalysts, the weight ratio that catalyst acetic acid antimony is added is 0.45 ‰ of a copolyesters; Every batch of slurry adds esterifying kettle with certain speed, makes the reaction temperature in the esterifying kettle be controlled at 250 ℃; Material adds in the esterifying kettle and after reacting completely fully in the every batch of making beating still, and the esterifying kettle thing that lactonizes partly is pressed in the polycondensation vessel, adds an amount of melt strength hardening agent pentaerythrite again, and the weight ratio that pentaerythrite added is 0.125 ‰ of a copolyesters; Vacuum is to carry out polycondensation reaction under the state below the 100Pa in melt temperature is 280 ℃, still; Judge the viscosity of copolyesters according to the power of agitator of polycondensation vessel, confirm discharging power, through supercooling, blank, sub-sieve, drying and pack.1.2M
3Production technology on the semicontinuous device is seen table 3.
Table 31.2M
3Production technology on the semicontinuous device
| Esterification temperature ℃ | Esterification pressure p a | Condensation temperature ℃ | Polycondensation pressure pa | Discharging electric current A |
| 250～260 | 2～3 atmospheric pressure | 280 | ＜100 | ?23 |
1.2M
3The production technology with common PET is identical basically for the production technology of copolyesters on the semicontinuous device.
2. the preparation of laminated film
1) the modified copolyester raw material is transported in the closed drying hopper, dry more than 6 hours under 65 ℃ of temperature.
2) dried modified copolyester raw material adds and carries out fusion plastification in the single screw extrusion machine in intermediate layer and extrude, and extruder temperature is controlled at 215 ℃; Carry out fusion plastification in the single screw extrusion machine with polyethylene raw material adding skin and internal layer and extrude, extruder temperature is controlled at 185 ℃; Adhesive added carry out fusion plastification in the interbed single screw extrusion machine and extrude, extruder temperature is controlled at 165 ℃.All melts gets into and contains five laminar flow road die heads, and die head temperature is controlled at 205 ℃.Upwards carry out inflation and obtain first film bubble.First film bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls.
3) the first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 85 ℃, and to elastomeric state, the secondary inflation obtains second film bubble then after post bake.Second film bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls.
4) the second bubble two-fold film is introduced coiling machine through deflector roll and is accomplished last rolling.
Three layers of composite membrane thickness of preparation are 40 μ m, and wherein copolyester layer thickness is 10 μ m, and polyethylene layer thickness is 28 μ m, and adhesive phase thickness is 2 μ m.The performance of composite membrane is referring to table 4:
The performance of table 4 composite membrane
1. the preparation of modified copolyester raw material
On 1 cube semicrystalline polyester continuous apparatus, according to the method that this device is produced, cut into slices and 108 kilograms ethylene glycol and an amount of alcoholysis catalysts with about 665 kilograms light that has much, under 260 ℃, carry out alcoholysis, with the preparation mother liquor; In the making beating still with every batch of CHDM that adds 300 kilograms PTA (or quite binary acid of molal quantity), 150 kilograms of EG and certain molal quantity; And appropriate amount of catalysts and melt strength hardening agent; The weight ratio that catalyst antimony is added is 0.2 ‰ of a copolyesters, and the weight ratio that melt strength hardening agent glycerine is added is 0.05 ‰ of a copolyesters; Every batch of slurry adds esterifying kettle with certain speed, makes the reaction temperature in the esterifying kettle be controlled at 250 ℃; Material adds in the esterifying kettle and after reacting completely fully in the every batch of making beating still, and the esterifying kettle thing that lactonizes partly is pressed in the polycondensation vessel, and vacuum is to carry out polycondensation reaction under the state below the 100Pa in melt temperature is 285 ℃, still; Judge the viscosity of copolyesters according to the power of agitator of polycondensation vessel, confirm discharging power, through supercooling, blank, sub-sieve, drying and pack.1.2M
3Production technology on the semicontinuous device is seen table 5.
Table 5:1.2M
3Production technology on the semicontinuous device
| Esterification temperature ℃ | Esterification pressure p a | Condensation temperature ℃ | Polycondensation pressure pa | Discharging electric current A |
| 250～260 | 2～3 atmospheric pressure | 285 | ＜100 | ?23 |
1.2M
3The production technology with common PET is identical basically for the production technology of copolyesters on the semicontinuous device.
3. the preparation of laminated film
5) the modified copolyester raw material is transported in the closed drying hopper, dry more than 6 hours under 65 ℃ of temperature.
6) carry out fusion plastification in the single screw extrusion machine of dried modified copolyester raw material adding internal layer and extrude, extruder temperature is controlled at 205 ℃; The polyethylene raw material added carry out fusion plastification in the outer field single screw extrusion machine and extrude, extruder temperature is controlled at 190 ℃; Adhesive added carry out fusion plastification in the single screw extrusion machine of intermediate layer and extrude, extruder temperature is controlled at 170 ℃.All melts gets into and contains three laminar flow road die heads, and die head temperature is controlled at 205 ℃.Upwards carry out inflation and obtain first film bubble.First film bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls.
7) the first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 80 ℃, and to elastomeric state, the secondary inflation obtains second film bubble then after post bake; Second film bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls;
8) the second bubble two-fold film is introduced coiling machine through deflector roll and is accomplished last rolling.
Three layers of composite membrane thickness of preparation are 50 μ m, and wherein copolyester layer thickness is 12 μ m, and polyethylene layer thickness is 36 μ m, and adhesive phase thickness is 2 μ m.The performance of composite membrane is referring to table 6:
The performance of table 6 composite membrane:
Embodiment 4
1. the preparation of modified copolyester raw material
On 1 cube semicrystalline polyester continuous apparatus, according to the method that this device is produced, cut into slices and 108 kilograms ethylene glycol and an amount of alcoholysis catalysts with about 665 kilograms light that has much, under 260 ℃, carry out alcoholysis, with the preparation mother liquor; In the making beating still with every batch of CHDM that adds 300 kilograms PTA (or quite binary acid of molal quantity), 150 kilograms of EG and certain molal quantity; And appropriate amount of catalysts and melt strength hardening agent; The weight ratio that catalyst antimony is added is 0.2 ‰ of a copolyesters, and the weight ratio that melt strength hardening agent-glycerine is added is 0.05 ‰ of a copolyesters; Every batch of slurry adds esterifying kettle with certain speed, makes the reaction temperature in the esterifying kettle be controlled at 250 ℃; Material adds in the esterifying kettle and after reacting completely fully in the every batch of making beating still, and the esterifying kettle thing that lactonizes partly is pressed in the polycondensation vessel, and vacuum is to carry out polycondensation reaction under the state below the 100Pa in melt temperature is 285 ℃, still; Judge the viscosity of copolyesters according to the power of agitator of polycondensation vessel, confirm discharging power, through supercooling, blank, sub-sieve, drying and pack.1.2M
3Production technology on the semicontinuous device is seen table 7.
Table 7:1.2M
3Production technology on the semicontinuous device
| Esterification temperature ℃ | Esterification pressure p a | Condensation temperature ℃ | Polycondensation pressure pa | Discharging electric current A |
| 250～260 | 2～3 atmospheric pressure | 285 | ＜100 | ?23 |
1.2M
3The production technology with common PET is identical basically for the production technology of copolyesters on the semicontinuous device.
4. the preparation of laminated film
9) the modified copolyester raw material is transported in the closed drying hopper, dry more than 6 hours under 65 ℃ of temperature.
10) carry out fusion plastification in the single screw extrusion machine of dried modified copolyester raw material adding internal layer and extrude, extruder temperature is controlled at 220 ℃; The polyethylene raw material added carry out fusion plastification in the outer field single screw extrusion machine and extrude, extruder temperature is controlled at 210 ℃; Adhesive added carry out fusion plastification in the single screw extrusion machine of intermediate layer and extrude, extruder temperature is controlled at 180 ℃.All melts gets into and contains three laminar flow road die heads, and die head temperature is controlled at 200 ℃.Upwards carry out inflation and obtain first film bubble.First film bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls.
11) the first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 95 ℃, and to elastomeric state, the secondary inflation obtains second film bubble then after post bake; Second film bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls;
12) the second bubble two-fold film is introduced coiling machine through deflector roll and is accomplished last rolling.
Three layers of composite membrane thickness of preparation are 50 μ m, and wherein copolyester layer thickness is 16.5 μ m, and polyethylene layer thickness is 32 μ m, and adhesive phase thickness is 1.5 μ m.The performance of composite membrane is referring to table 8:
Table 8: the performance of composite membrane
Embodiment 5
1. the preparation of modified copolyester raw material
On 1 cube semicrystalline polyester continuous apparatus, according to the method that this device is produced, cut into slices and 108 kilograms ethylene glycol and an amount of alcoholysis catalysts with about 665 kilograms light that has much, under 260 ℃, carry out alcoholysis, with the preparation mother liquor; In the making beating still with every batch of CHDM that adds 300 kilograms PTA (or quite binary acid of molal quantity), 150 kilograms of EG and certain molal quantity; And appropriate amount of catalysts and melt strength hardening agent; The weight ratio that catalyst antimony is added is 0.2 ‰ of a copolyesters, and the weight ratio that melt strength hardening agent glycerine is added is 0.05 ‰ of a copolyesters; Every batch of slurry adds esterifying kettle with certain speed, makes the reaction temperature in the esterifying kettle be controlled at 250 ℃; Material adds in the esterifying kettle and after reacting completely fully in the every batch of making beating still, and the esterifying kettle thing that lactonizes partly is pressed in the polycondensation vessel, and vacuum is to carry out polycondensation reaction under the state below the 100Pa in melt temperature is 285 ℃, still; Judge the viscosity of copolyesters according to the power of agitator of polycondensation vessel, confirm discharging power, through supercooling, blank, sub-sieve, drying and pack.1.2M
3Production technology on the semicontinuous device is seen table 9.
Table 9:1.2M
3Production technology on the semicontinuous device
| Esterification temperature ℃ | Esterification pressure p a | Condensation temperature ℃ | Polycondensation pressure pa | Discharging electric current A |
| 250～260 | 2～3 atmospheric pressure | 285 | ＜100 | ?23 |
1.2M
3The production technology with common PET is identical basically for the production technology of copolyesters on the semicontinuous device.
5. the preparation of laminated film
1) the modified copolyester raw material is transported in the closed drying hopper, dry more than 6 hours under 65 ℃ of temperature.
2) carry out fusion plastification in the single screw extrusion machine of dried modified copolyester raw material adding internal layer and extrude, extruder temperature is controlled at 205 ℃; The polyethylene raw material added carry out fusion plastification in the outer field single screw extrusion machine and extrude, extruder temperature is controlled at 190 ℃; Adhesive added carry out fusion plastification in the single screw extrusion machine of intermediate layer and extrude, extruder temperature is controlled at 170 ℃.All melts gets into and contains five laminar flow road die heads, and die head temperature is controlled at 205 ℃.Upwards carry out inflation and obtain first film bubble.First film bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls.
3) the first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 80 ℃, and to elastomeric state, the secondary inflation obtains second film bubble then after post bake; Second film bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls;
4) the second bubble two-fold film is introduced coiling machine through deflector roll and is accomplished last rolling.
Five layers of composite membrane thickness of preparation are 60 μ m, and wherein copolyester layer thickness is 12 μ m, and the every layer thickness of polyethylene layer is 22 μ m, and the every layer thickness of adhesive phase is 2 μ m.The performance of composite membrane is referring to table 10:
Table 10: the performance of composite membrane
Claims (10)
1. polyester composite sheet; It is characterized in that; Described laminated film comprises one deck modified copolyester film, is positioned at the polyolefm film layer of said modified copolyester film one or both sides; And being positioned at the adhesive phase in the middle of said polyester layer and the said polyolefin layer, described laminated film is to be prepared from two bubble inflation film moulding process.
2. polyester composite sheet according to claim 1 is characterized in that described polyolefin is selected from metallocene PE or low density polyethylene (LDPE).
3. polyester composite sheet according to claim 1 is characterized in that, described adhesive is olefin-modified adhesive, at least a in optimal ethylene acrylic copolymer, vinyl-vinyl acetate copolymers or the ethylene-vinyl alcohol copolymer.
4. polyester composite sheet according to claim 1 is characterized in that, described modified copolyester layer proportion is 20～50%, and the polyolefin layer proportion is 48～78%, and the adhesive phase proportion is 2～5%; Be preferably, modified copolyester layer proportion is 22～48%, and the polyolefin layer proportion is 50～75%, and the adhesive phase proportion is 2～4%.
5. polyester composite sheet according to claim 1 is characterized in that, the raw material of the modified copolyester in the described laminated film comprises smart para Toluic Acid, second diester, modified monomer, melt strength hardening agent, additive and catalyst.
6. polyester composite sheet according to claim 5 is characterized in that, described melt strength hardening agent is selected from 1; 2,4-benzenetricarboxylic acid, 1,2; 4-benzenetricarboxylic anhydride, 1,2,4; At least a in 5-benzenetetracarboxylic acid dianhydride, trimethylolpropane, glycerine, pentaerythrite, citric acid, tartaric acid, the 3-hydroxy dibasic acid, preferred pentaerythrite.
7. polyester composite sheet according to claim 5 is characterized in that, the weight ratio that described melt strength hardening agent is added is 0.05 ‰～0.25 ‰ of a copolyesters, and is preferred 0.1 ‰～0.2 ‰, more preferably 0.125 ‰～0.175 ‰.
8. polyester composite sheet according to claim 5 is characterized in that, described catalyst is selected from least a in antimony, antimony glycol or the antimony acetate; Wherein, The weight ratio that antimony added is 0.1 of copolyesters～0.3 ‰, and is preferred 0.15 ‰～0.25 ‰, most preferably 0.2 ‰; The weight ratio that antimony glycol or antimony acetate added is 0.2 ‰ of copolyesters～0.8 ‰, and is preferred 0.25 ‰～0.75 ‰, more preferably 0.3 ‰～0.5 ‰, further preferred 0.35 ‰～0.45 ‰.
9. polyester composite sheet according to claim 5 is characterized in that described modified copolyester is prepared from through esterification, polycondensation, and wherein, enzymatic synthesis condition is 210 ℃～260 ℃, 2～3 atmospheric pressure; The polycondensation condition is a vacuum less than 100Pa, 275 ℃～285 ℃; Melt strength hardening agent in the described modified copolyester joins respectively in the said raw material in Esterification Stage or polycondensation phase, or adds in Esterification Stage or polycondensation phase in batches.
10. polyester composite sheet according to claim 1 is characterized in that, described two bubble inflation film moulding process may further comprise the steps:
(1) the modified copolyester raw material is transported in the closed drying hopper, drying is 6～12 hours under 60～70 ℃ of temperature, and water content is lower than 0.1 ‰;
(2) carry out fusion plastification in the single screw extrusion machine with dried modified copolyester raw material adding intermediate layer and extrude, extruder temperature is controlled at 180 ℃～220 ℃, and preferred 190 ℃～220 ℃, more preferably 200 ℃～220 ℃, most preferably 200 ℃～210 ℃; The polyethylene raw material is added carry out fusion plastification in the single screw extrusion machine of skin and/or internal layer and extrude, extruder temperature is controlled at 165 ℃～215 ℃, and is preferred 175～215, and more preferably 185 ℃～215 ℃, most preferably 190 ℃～210 ℃; Adhesive is added carry out fusion plastification in the interbed single screw extrusion machine of polyethylene and copolyesters and extrude, extruder temperature is controlled at 160 ℃～180 ℃, and preferred 165 ℃～180 ℃, more preferably 170 ℃～180 ℃; All melts gets into die head, and die head temperature is controlled at 180 ℃～220 ℃, and preferred 190 ℃～220 ℃, more preferably 200 ℃～220 ℃, most preferably 200 ℃～210 ℃; Upwards carry out inflation and obtain first film bubble;
(3) first films bubble forms the first bubble two-fold film through the first letter stencil folding with pressures first carry-over pinch rolls; The first bubble two-fold film gets into heater through the deflector roll and second carry-over pinch rolls, and temperature is controlled at 80 ℃～95 ℃, preferred 85 ℃～95 ℃; To elastomeric state, the secondary inflation obtains second film bubble then after post bake;
(4) second films bubble forms the second bubble two-fold film of final fabric width and final thickness through second collapser folding with pressures the 3rd carry-over pinch rolls;
(5) second bubble two-fold films are introduced coiling machine through deflector roll and are accomplished last rolling.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106626638A (en) * | 2016-12-07 | 2017-05-10 | 滁州瑞林包装材料有限公司 | Composite film for medicine package |
| CN111300945A (en) * | 2020-04-14 | 2020-06-19 | 四川汇利实业有限公司 | Medicine packaging bag and preparation process thereof |
| CN111409344A (en) * | 2020-04-14 | 2020-07-14 | 四川汇利实业有限公司 | Medicine packaging film and preparation method thereof |
| CN111849026A (en) * | 2020-08-27 | 2020-10-30 | 华润化学材料科技股份有限公司 | Method and system for producing rPET bottle grade polyester chip |
| CN113043701A (en) * | 2021-04-22 | 2021-06-29 | 青岛海益塑业有限责任公司 | Composite degradable mulching film and preparation method thereof |
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| CN86108901A (en) * | 1985-11-29 | 1987-12-23 | 美国制罐公司 | The packing that multilayered packaging film and current film form |
| CN101134810A (en) * | 2006-09-01 | 2008-03-05 | 远东纺织股份有限公司 | Modified copolyester, thermal shrinkage polyester film produced thereby and method for preparing same |
| CN101502997A (en) * | 2009-02-27 | 2009-08-12 | 北京化工大学 | Double-bubble blown film moulding method for producing polyester thermal contraction film |
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| CN86108901A (en) * | 1985-11-29 | 1987-12-23 | 美国制罐公司 | The packing that multilayered packaging film and current film form |
| CN101134810A (en) * | 2006-09-01 | 2008-03-05 | 远东纺织股份有限公司 | Modified copolyester, thermal shrinkage polyester film produced thereby and method for preparing same |
| CN101502997A (en) * | 2009-02-27 | 2009-08-12 | 北京化工大学 | Double-bubble blown film moulding method for producing polyester thermal contraction film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106626638A (en) * | 2016-12-07 | 2017-05-10 | 滁州瑞林包装材料有限公司 | Composite film for medicine package |
| CN111300945A (en) * | 2020-04-14 | 2020-06-19 | 四川汇利实业有限公司 | Medicine packaging bag and preparation process thereof |
| CN111409344A (en) * | 2020-04-14 | 2020-07-14 | 四川汇利实业有限公司 | Medicine packaging film and preparation method thereof |
| CN111849026A (en) * | 2020-08-27 | 2020-10-30 | 华润化学材料科技股份有限公司 | Method and system for producing rPET bottle grade polyester chip |
| CN113043701A (en) * | 2021-04-22 | 2021-06-29 | 青岛海益塑业有限责任公司 | Composite degradable mulching film and preparation method thereof |
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| CN102336042B (en) | 2014-04-09 |
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