CN104044281B - The preparation method of heat shrinkable polyester film - Google Patents
The preparation method of heat shrinkable polyester film Download PDFInfo
- Publication number
- CN104044281B CN104044281B CN201310078258.9A CN201310078258A CN104044281B CN 104044281 B CN104044281 B CN 104044281B CN 201310078258 A CN201310078258 A CN 201310078258A CN 104044281 B CN104044281 B CN 104044281B
- Authority
- CN
- China
- Prior art keywords
- polyester film
- heat shrinkable
- preparation
- shrinkable polyester
- annealing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
A preparation method for heat shrinkable polyester film, comprises: the polyester film that (a) provides to have a glass transition temperature of X DEG C; B () carries out preheating under making the preheat temperature range of this polyester film in (X+20) DEG C to (X+30) DEG C, obtain once preheating polyester film; (c) in draw ratio scope be 2.7 to 7.7 and stretching time under being not more than 15 seconds, make this stretch along the direction perpendicular to machine direction through preheating polyester film, obtain once oriented film; (d) make this drawn film in the annealing region of (X-10) DEG C to X DEG C and be not more than 10 seconds annealing time under anneal, obtain once annealing thin film; And (e) makes this be cooled to environment temperature through annealing thin film, with this heat shrinkable polyester film obtained.Heat shrinkable polyester film obtained by preparation method of the present invention has lower shrinkage temperature in label thermal contraction operation, and also has good dimensional stability in time transporting.
Description
Technical field
The present invention relates to a kind of preparation method of heat shrinkable polyester film, particularly relate to a kind of preparation method of heat shrinkable polyester film comprising preheating, stretching and annealing steps.
Background technology
Heat shrink films is widely used packaging and label material, wherein, heat shrinkable polyester film due to tasteless, nontoxic, engineering properties is good and have advantages such as being easy to recovery, be used at present replacing the polyvinyl chloride film comparatively not meeting environmental requirement.Thermal contracting polyester film, as PETG (PET), during packaging and label for PET beverage bottle, together can reclaim with beverage bottle body, more meet market and ecological requirements.
Shrinkage factor generally without the polyester film of upgrading is no more than 30%, therefore when being applied to heat shrink films, known techniques generally can add modification agent in polyester, as M-phthalic acid (IPA), neopentyl glycol (neopentylglycol, NPG), 1,4-cyclohexanedimethanol (1,4 – Cyclohexanedimethanol, CHDM) etc.Moreover, polyester film is in subsequent packages and label thermal contraction operation, must carry out at higher than the temperature of 100 DEG C, and in order to reach energy-conservation object, current industry all wishes the shrinkage temperature of thermal contracting polyester film and time to be reduced, such as, below 80 DEG C and 10 seconds, just can reach required percent thermal shrinkage.According to aforementioned various problem, US7,008,698B2 just propose a kind of heat shrink polymer film, comprise by diacid and containing 2-methyl isophthalic acid, the glycol of ammediol be polymerized through upgrading mylar; This polymeric membrane is by melting and extruding in flakes, then carries out made by multi-drawing to the temperature of softening melting lower than macromolecule through cooling and in high molecular glass transition temperature.The operation of this patent needs the stretching step through at least 2 times, and the shrinkage factor of obtained polymeric membrane under 80 DEG C and 10 seconds just can be allowed to be 50%.For industry, the operation of this Patent Case does not still meet economic benefit and haves much room for improvement.
EP1055506B1 also utilizes operation to improve mode to reduce shrinkage temperature, under its operation comprises and makes the temperature of polyester film in [Tg-5] DEG C to [Tg+15] DEG C and the draw ratio (drawratio) of 1.05-1.2, first time stretching is carried out, to obtain drawn polyester film along machine direction (MD); Make this drawn polyester film preheating and carry out second time and third time stretching along the direction (TD) perpendicular to machine direction respectively, the shrinkage factor of obtained thermal contracting polyester film at 80 DEG C reaches 50-60%.Above-mentioned Patent Case only uses two benches stretching process, reduces the demand of shrinkage temperature though meet, but still cannot effectively carbon reduction and reduction manufacturing cost.In addition, thermal contracting polyester film obtained by above-mentioned Patent Case has the shrinkage factor >20% under 70 DEG C and 5 seconds and the shrinkage factor >35% under 75 DEG C and 5 seconds respectively, may when container transport heat shrinkable and be out of shape (goods in-cabinet temperature during general transport may up to 70 DEG C), cause the dimensional stability of thermal contracting polyester film not good.
As shown in the above description, the dimensional stability that when how to reduce the shrinkage temperature of thermal contracting polyester film and meet container transport simultaneously, needs maintain, still has very big demand for current industry.
Summary of the invention
In view of the power consumption that EP1055506B1 uses two benches stretching process to produce, and its dimensional stability problem when cannot meet container transport, present invention applicant proposes one and utilizes one-off drawing step, to arrange in pairs or groups again the operation of preheating and annealing steps (EP1055506B1 does not propose these steps), to overcome aforementioned proposed all problems, meet the demand of industry simultaneously.
The object of the present invention is to provide and a kind ofly reduce shrinkage temperature and in time transporting, there is the preparation method of the heat shrinkable polyester film of excellent dimensions stability.
The preparation method of heat shrinkable polyester film of the present invention, comprises:
A polyester film that () provides one to have a glass transition temperature of X DEG C;
B () carries out preheating under making the preheat temperature range of this polyester film in (X+20) DEG C to (X+30) DEG C, obtain once preheating polyester film;
(c) in draw ratio scope be 2.7 to 7.7 and stretching time under being not more than 15 seconds, make this stretch along the direction perpendicular to machine direction through preheating polyester film, obtain once oriented film;
(d) make this drawn film in the annealing region of (X-10) DEG C to X DEG C and be not more than 10 seconds annealing time under anneal, obtain once annealing thin film; And
E () makes this be cooled to environment temperature through annealing thin film, with this heat shrinkable polyester film obtained.
Beneficial effect of the present invention is: preparation method of the present invention is by the control of preheat temperature, stretching condition and annealing temperature, make the shrinkage factor <0.5% of obtained heat shrinkable polyester film under 70 DEG C and 5 seconds, and good dimensional stability can be had when container transport, and the shrinkage factor >60% under 80 DEG C and 5 seconds, by the reduction of shrinkage temperature, label thermal contraction process temperature is reduced, and reduces power consumption simultaneously.
Detailed description of the invention
The preparation method of heat shrinkable polyester film of the present invention, comprises:
A polyester film that () provides one to have a glass transition temperature of X DEG C;
B () carries out preheating under making the preheat temperature range of this polyester film in (X+20) DEG C to (X+30) DEG C, obtain once preheating polyester film;
(c) in draw ratio scope be 2.7 to 7.7 and stretching time under being not more than 15 seconds, make this stretch along the direction perpendicular to machine direction through preheating polyester film, obtain once oriented film;
(d) make this drawn film in the annealing region of (X-10) DEG C to X DEG C and be not more than 10 seconds annealing time under anneal, obtain once annealing thin film; And
E () makes this be cooled to environment temperature through annealing thin film, with this heat shrinkable polyester film obtained.
The polyester film of this step (a) can be prepared according to current known method, such as, make polyester or through upgrading polyester by single screw extrusion machine or double screw extruder, and melting is carried out under 200 to 300 DEG C of processing temperatures, then form polyester film by a die head (T-die) again.
Preferably, the polyester film of this step (a) is by made by upgrading polyester, and this is made by a constituent is polymerized through upgrading polyester, and this constituent comprises diacid, glycol and for destroying the modification agent of degree of crystallinity.This kind through upgrading polyester can the content that discloses of the patent such as such as TWI335922, US6939616 and US7829655, is wherein preferably the PETG through upgrading.This diacid can such as but not limited to terephthalic acid (TPA) (TPA); This glycol such as but not limited to ethylene glycol (EG), propane diols (PG), butanediol (BG) etc., can be preferably EG.Preferably, this modification agent is selected from M-phthalic acid (IPA), 2-methyl isophthalic acid, ammediol (MPDO), neopentyl glycol (NPG), 1,4-CHDM (CHDM) and a described combination are wherein preferred with NPG.
Preferably, the scope of the glass transition temperature X of the polyester film of step (a) is 70 to 80 DEG C.In preferred concrete example of the present invention, the scope of X is 73 to 79 DEG C.
According to the preferable range of above-mentioned X, preferably, the preheat temperature range of this step (b) is 90 to 110 DEG C.In preferred concrete example of the present invention, the preheat temperature range of this step (b) is 93 to 109 DEG C.In more preferably concrete example of the present invention, the preheat temperature range of this step (b) is 99 to 108 DEG C.
Step (b) mainly makes this polyester film preheating, has uniform temperature to make film surface.In the warm of step (b), this polyester film does not stretch simultaneously, and preferably, the draw ratio of this step (b) is for being not more than 1.05; More preferably, this draw ratio is 1 (namely complete tensionless winkler foundation).
Preferably, scope preheating time of this step (b) is 5 to 9 seconds; More preferably, this, scope was 7 to 9 seconds preheating time.
Preferably, the temperature range of this step (c) is 70 to 90 DEG C.In preferred concrete example of the present invention, the temperature range of this step (c) is 80 to 85 DEG C.
Preferably, the draw ratio of this step (c) is 3.5 to 6.5; More preferably, this draw ratio is 4.5 to 5.2.
The stretching time of this step (c) is for being not more than 15 seconds; Preferably, this stretching time is 1 to 12 second; More preferably, this stretching time is 5 to 11 seconds.
According to the preferable range of above-mentioned X, preferably, the annealing region of this step (d) is 60 to 80 DEG C.In preferred concrete example of the present invention, the annealing region of this step (d) is 63 to 79 DEG C.In more preferably concrete example of the present invention, the annealing region of this step (d) is 70 to 78 DEG C.
Preferably, the draw ratio of this step (d) is for being not more than 1.05; More preferably, this draw ratio is 1.
The annealing time of this step (d) is for being not more than 10 seconds; Preferably, annealing time is 1 to 8 second.
Preferably, the ambient temperature range of this step (e) is 20 to 30 DEG C.
The shrinkage factor <0.5% of heat shrinkable polyester film obtained by preparation method of the present invention under 70 DEG C and 5 seconds, and the shrinkage factor >60% under 80 DEG C and 5 seconds, meet industry demand completely.
The present invention will be described further with regard to following examples, but it is to be understood that this embodiment is only and illustrates, and should not be interpreted as restriction of the invention process.
< embodiment >
[preparation example 1] is through upgrading polyester
By 80%(molar percentage) TPA, 100%(molar percentage) EG and 20%(molar percentage) IPA pour in tank diameter stir formed pastel, and add the thermal stabilizer (phosphoric acid) of 75ppm, then being poured into by this pastel in esterification groove heats up stirs, carry out esterification, in groove, Stress control is at 3kg/cm simultaneously
2within, and the water allowing reaction generate distillates collection via bead tube.After lasting 6-7 hour, the carboxylate in reactive tank, to 250 DEG C, is moved to condensation reaction grain by final esterification end temperature subsequently, then the antimony oxide adding 300ppm is as catalyst, and is progressively warming up to 285 DEG C, is evacuated to about 1torr in 2 hours simultaneously.To limit viscosity between 0.6-0.9, last 4-5 hour, carry out drainage, cooling, pelletizing subsequently, with obtained through upgrading polyester ester grain.
[preparation example 2 and 3] is through upgrading polyester
Except changing except reactant and ratio according to following table 1, all the other method for makings and flow process are all identical with preparation example 1, finally obtained through upgrading polyester.
[character test]
1. thermal property: utilize heat difference scanning analysis instrument (DSC, TAInstruments company manufactures, and model is DSC2910ModulatedDSC) to carry out tested glass transition temperature Tg (DEG C).
2. limit viscosity [intrinsicviscosity, IV (ml/g)]: 1g is dissolved in 100g and weight ratio is in the phenol/tetrachloroethanes mixed solvent of 50/50 through upgrading polyester, and uses Ubbelohde viscometer (Ubbelohde-viscometer) to record at 30 DEG C.
Table 1
[embodiment 1] heat shrinkable polyester film
(a) first, make preparation example 2 through upgrading polyester by single screw extrusion machine, and carry out melting under higher than 200 DEG C of processing temperatures, then form a polyester film by a die head again;
B () makes this polyester film carry out preheating under the preheat temperature of 99 DEG C and do not stretch (draw ratio is 1), obtain once preheating polyester film after 7.2 seconds;
C (), at draw ratio 4.7 and draft temperature 80 DEG C, makes this stretch along the direction perpendicular to machine direction through preheating polyester film, obtains once oriented film after 10.8 seconds to be tensioned;
D () makes this drawn film anneal under the annealing temperature of 76 DEG C and do not stretch (draw ratio is 1), obtain once annealing thin film after 7.2 seconds; And
E () makes this be cooled to environment temperature (about 25 DEG C) through annealing thin film, with this heat shrinkable polyester film obtained.
[embodiment 2 to 5 and comparative example 1 to 6]
Except changing process conditions according to following table 2, all the other operations are identical with embodiment 1, finally obtain the heat shrinkable polyester film of embodiment 2 to 5 and comparative example 1 to 6 respectively.
Percent thermal shrinkage is tested: the heat shrinkable polyester film of embodiment 1 to 5 and comparative example 1 to 6 is carried out following steps test respectively.With reference to JISZ1709 standard method, polyester film is cut along MD and TD respectively and is of a size of 100mm × 100mm rectangle sample and goes forward side by side row labels.Sample to be positioned over respectively in the water bath with thermostatic control of 60 DEG C, 70 DEG C and 80 DEG C and to last 5 seconds and test, then take out sample and carried out the calculating of percent thermal shrinkage by following formula: percent thermal shrinkage=[(L
0-L
1)/L
0] × 100% (L
0represent sample original length, L
1represent that sample shrinks rear length).According to industry demand, the shrinkage factor the best being 0%, 70 DEG C in shrinkage factor the bests of 60 DEG C is < 0.5%, and shrinkage factor the best of 80 DEG C is > 60%.
Table 2
As seen from the results in Table 2, the shrinkage factor of sample under 70 DEG C and 5 seconds of embodiment 1 to 5 be all less than 0.5% and shrinkage factor under 80 DEG C and 5 seconds be all greater than 60%, the annealing region that to prove by the preheat temperature range of rate-determining steps (b) be (X+20) to (X+30) DEG C and step (d) is (X-10) to (X) DEG C, really effectively shrinkage temperature can be reduced, dimensional stability during lifting container transport simultaneously.
The preheat temperature of comparative example 1 is lower than (X+20) DEG C, and the shrinkage factor at 70 DEG C is then greater than 0.5%, dimensional stability required when cannot meet container transport.Comparative example 5 also has same situation.
The preheat temperature of comparative example 2 is lower than (X+20) DEG C, and annealing temperature is for being greater than X, and the shrinkage factor at 80 DEG C, lower than 60%, cannot meet the requirement of shrinkage factor.Comparative example 4 also has same situation.
The annealing temperature of comparative example 3 is for being greater than X, and the shrinkage factor at 80 DEG C, lower than 60%, cannot meet the requirement of shrinkage factor.The annealing temperature of comparative example 6 lower than (X-10) DEG C, the shrinkage factor at 70 DEG C much larger than 0.5%, dimensional stability required when cannot meet container transport.
In sum, preparation method of the present invention is by controlling the temperature range of preheating step and annealing steps, coordinate one-off drawing step simultaneously, allow the shrinkage factor <0.5% of obtained heat shrinkable polyester film under 70 DEG C and 5 seconds, and the shrinkage factor >60% under 80 DEG C and 5 seconds, and good dimensional stability can be had when container transport, reduce the shrinkage temperature in packaging and label thermal contraction operation simultaneously.
Be as described above, be only the preferred embodiments of the present invention, when not limiting scope of the invention process with this, the simple equivalence namely done according to claims of the present invention and patent specification content changes and modifies, and all still belongs to the scope that patent of the present invention contains.
Claims (8)
1. a preparation method for heat shrinkable polyester film, is characterized in that comprising:
A polyester film that () provides one to have a glass transition temperature of X DEG C;
B () carries out preheating under making the preheat temperature range of this polyester film in (X+20) DEG C to (X+30) DEG C, obtain once preheating polyester film;
(c) in draw ratio scope be 2.7 to 7.7 and stretching time under being not more than 15 seconds, make this stretch along the direction of extruding direction perpendicular to machine through preheating polyester film, obtain once oriented film;
(d) make this drawn film in the annealing region of (X-10) DEG C to X DEG C and be not more than 10 seconds annealing time under anneal, obtain once annealing thin film; And
E () makes this be cooled to environment temperature through annealing thin film, with this heat shrinkable polyester film obtained.
2. the preparation method of heat shrinkable polyester film according to claim 1, it is characterized in that: the polyester film of this step (a) is by made by upgrading polyester, this is made by a constituent is polymerized through upgrading polyester, and this constituent comprises diacid, glycol and for destroying the modification agent of degree of crystallinity; This modification agent is selected from M-phthalic acid, 2-methyl isophthalic acid, ammediol, neopentyl glycol, 1,4-CHDM and a described combination.
3. the preparation method of heat shrinkable polyester film according to claim 1, is characterized in that: the scope of X is 70 to 80 DEG C.
4. the preparation method of heat shrinkable polyester film according to claim 1, is characterized in that: the draw ratio of this step (b) is for being not more than 1.05.
5. the preparation method of heat shrinkable polyester film according to claim 1, is characterized in that: scope preheating time of this step (b) is 5 to 9 seconds.
6. the preparation method of heat shrinkable polyester film according to claim 1, is characterized in that: the temperature range of this step (c) is 80 to 85 DEG C.
7. the preparation method of heat shrinkable polyester film according to claim 1, is characterized in that: the draw ratio of this step (d) is for being not more than 1.05.
8. the preparation method of heat shrinkable polyester film according to claim 1, is characterized in that: this ambient temperature range is 20 to 30 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078258.9A CN104044281B (en) | 2013-03-11 | 2013-03-11 | The preparation method of heat shrinkable polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078258.9A CN104044281B (en) | 2013-03-11 | 2013-03-11 | The preparation method of heat shrinkable polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104044281A CN104044281A (en) | 2014-09-17 |
| CN104044281B true CN104044281B (en) | 2016-04-13 |
Family
ID=51497885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310078258.9A Active CN104044281B (en) | 2013-03-11 | 2013-03-11 | The preparation method of heat shrinkable polyester film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104044281B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107639821B (en) * | 2016-07-20 | 2019-10-18 | 颖台投资控股股份有限公司 | The manufacturing method and its phase difference film of phase difference film are manufactured in such a way that Biaxial synchronous extends |
| CN113997608A (en) * | 2021-10-21 | 2022-02-01 | 上海晶路电子科技有限公司 | Production method of high-temperature-resistant polyester film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253074A (en) * | 1998-09-24 | 2000-05-17 | 东丽株式会社 | Double axial orientated polyester film |
| JP2000273208A (en) * | 1999-03-25 | 2000-10-03 | Toyobo Co Ltd | Aliphatic polyester-based resin film |
| CN1665859A (en) * | 2002-06-26 | 2005-09-07 | 伊斯曼化学公司 | Biaxially oriented polyester film and laminates thereof with copper |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5411419B2 (en) * | 2007-10-11 | 2014-02-12 | 積水化学工業株式会社 | Stretched thermoplastic polyester resin sheet and method for producing the same |
-
2013
- 2013-03-11 CN CN201310078258.9A patent/CN104044281B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253074A (en) * | 1998-09-24 | 2000-05-17 | 东丽株式会社 | Double axial orientated polyester film |
| JP2000273208A (en) * | 1999-03-25 | 2000-10-03 | Toyobo Co Ltd | Aliphatic polyester-based resin film |
| CN1665859A (en) * | 2002-06-26 | 2005-09-07 | 伊斯曼化学公司 | Biaxially oriented polyester film and laminates thereof with copper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104044281A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101134810B (en) | Modified copolyester, thermal shrinkage polyester film produced thereby and method for preparing same | |
| JP6359555B2 (en) | Copolyesters for shrink film applications plasticized with polymer plasticizers | |
| CN109476857B (en) | Sealant film and method for producing the same | |
| JP2001081210A (en) | Heat-shrinkable polyester-based film and its preparation | |
| CN103154101B (en) | Heat-shrinkable polyester film | |
| US8557951B2 (en) | Copolymer polyester resin and molded product using same | |
| CN101134820A (en) | Thermal contracting polyester film and method for preparing same | |
| CN1276009C (en) | Heat-shrinkable polyester film | |
| EP2300512B1 (en) | Copolyester for shrink film applications | |
| CN104044281B (en) | The preparation method of heat shrinkable polyester film | |
| TW201833218A (en) | Mdo thermoresistant heat-shrinkable film | |
| TWI454371B (en) | Preparation of Heat Shrinkable Polyester Films | |
| TWI335922B (en) | ||
| CN102964576A (en) | Modified polyester and preparation method thereof | |
| TW200813117A (en) | Thermal-shrinkage polyester film and manufacturing method of the same | |
| JP3949565B2 (en) | Heat-shrinkable polyester film and method for producing the same | |
| CN102964575A (en) | Modified polyester and preparation method thereof | |
| JP2010150488A (en) | Ethylene terephthalate based polyester resin for molding heat-resistant container and preform consisting of the resin | |
| JPH04164929A (en) | Shrink polyester film | |
| WO2010064811A2 (en) | Heat-shrinkable polyester film | |
| KR20020008899A (en) | A high shrinkage and drawn polyester film, and a process of preparing for the same | |
| JPH0976333A (en) | Polyester hollow container | |
| JPH02289626A (en) | Polyester shrink film | |
| CN115678213A (en) | Heat-shrinkable polyester film and method for producing same | |
| JP3742505B2 (en) | Polyester and hollow molded container comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |