CN107603172A - A kind of thermal contraction type polyester film and preparation method thereof - Google Patents
A kind of thermal contraction type polyester film and preparation method thereof Download PDFInfo
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- CN107603172A CN107603172A CN201711040680.XA CN201711040680A CN107603172A CN 107603172 A CN107603172 A CN 107603172A CN 201711040680 A CN201711040680 A CN 201711040680A CN 107603172 A CN107603172 A CN 107603172A
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Abstract
The present invention relates to a kind of thermal contraction type polyester film and preparation method thereof, and include 60 90 parts of dibasic acid component, 60 90 parts of diol component, 15 30 parts of elastomer components, 0.01 1 parts of silica, wear-resisting shaping dope according to weight proportion is according to parts by weight：30 40 parts of graphene oxide, 250 300 parts of Nafion solution, 58 parts of hydroxymethyl cellulose, 58 parts of nickel acetate, 12 18 parts of potassium borohydride, 8 15 parts of cobalt acetate, 10 15 parts of alundum (Al2O3), 35 parts of phosphorus pentoxide.The present invention adds a kind of elastomeric material by mixing, and can effectively limit film caused excessive crystallographic orientation in process, and then the elongation at break for limiting non-main shrinkage direction reduces suddenly.And during being deposited after film deposits process, set mark process, set mark, elastomer can effectively prevent hot and humid environment, ink printing process, cover the excessive induction crystallization of film caused by mark process, further increase the stability of the elongation at break of its non-main shrinkage direction.
Description
Technical field
The present invention relates to thermal contraction type polyester film technical field, more particularly to a kind of thermal contraction type polyester film and its system
Preparation Method.
Background technology
Heat-shrinkable film, its original shape that can retract after the heating have been widely used, such as：Various containers are packed, are wrapped
Fill a bundle of commodity and capping youngster.
This thermal contraction type film is most common to be made up of polyvinyl chloride, polystyrene, but is existed when polyvinyl chloride burns
There are printing issues in problem of environmental pollution, polystyrene, therefore more meet the thermal contraction type polyester film of environmental requirement in recent years
Receive significant attention and development and application.
Compared with traditional polyvinyl chloride, polystyrene heat shrink films, the universal mistake of the convergent force and shrinkage factor of polyester film
Height, with after 90 DEG C of water process 10s along main shrinkage direction, shrinkage factor >=70%, convergent force >=4N/10mm, be very easy to cause it is non-
Even contraction, and then cause contraction distortion, shrink phenomena such as altering.There are numerous patents to be reported both at home and abroad for this problem
Road, involved solution method include, are controlled by modified component content, be controlled by altered contents species, lead to
Processing technology is crossed to be controlled, it is non-homogeneous to solving to realize the thermal contraction type polyester film of relatively low convergent force and shrinkage factor
Phenomenon, which is altered, in deformation caused by shrinking and contraction plays certain improvement.
But thermal contraction type polyester film is all the altered contents that are known by modified polyester raw material, including two
The one or more of first acid or dihydric alcohol, shrinkage factor is reduced by reducing modified component content, modified segment is reduced and homopolymerization
Segment increase, causes the crystal property of polyester resin to increase.Thermal contraction type polyester film typically uses simple tension, is being modified to
In the case that point content is certain, typically by increasing draft temperature or heat treatment temperature reduces shrinkage factor, but higher stretching
Temperature or heat treatment temperature, it can also produce excessive crystallographic orientation.Due to the excessive crystallographic orientation of above method so that film is deposited
The elongation at break for let off journey, covering mark process, cover the very easy non-main shrinkage direction of generation during being deposited after marking significantly drops
It is low, and there is the phenomenon that label ruptures along not contracted direction, particularly under hot and humid environment, the hair of this phenomenon can be accelerated
It is raw.
The content of the invention
It is an object of the invention to provide a kind of thermal contraction type polyester film and preparation method thereof, to overcome prior art
Technological deficiency.
To achieve the above object, the present invention provides a kind of thermal contraction type polyester film, includes binary acid according to weight proportion
Component 60-90 parts, diol component 60-90 parts, elastomer components 15-30 parts, silica 0.01-1 parts, wear-resisting shaping dope are pressed
It is according to parts by weight：Graphene oxide 30-40 parts, Nafion solution 250-300 parts, hydroxymethyl cellulose 5-8 parts, nickel acetate 5-
8 parts, potassium borohydride 12-18 parts, cobalt acetate 8-15 parts, alundum (Al2O3) 10-15 parts, phosphorus pentoxide 3-5 parts.
Further, the dibasic acid component, is counted by 100mol% of dibasic acid component, and it contains 50-100mol% pair
Phthalic acid；0-50mol% other common binary acid.
Further, the diol component, is counted by 100mol% of diol component, and it contains 50-99mol% second two
Alcohol；1-50mol% other common dihydric alcohols.
Further, the composition of the elastomer, it contains thermoplastic polyolefin elastomer, thermoplastic styrene class elasticity
Body, polyurethane-type thermoplastic elastomer, polyester-type thermoplastic elastomer, thermoplastic polyamide elastomer, ethylene copolymer thermoplastic
Property elastomer etc., the one or more of conventional elastomers.
Further, the thickness of film layer is 80-100nm；The thickness of wear-resisting shape layer is 30-50nm.
The present invention also provides a kind of preparation method of thermal contraction type polyester film, including：
Step a, laminated polyester film make；
Dibasic acid component, diol component, elastomer components are mixed into simultaneously melting extrusion according to parts by weight；Melt by die head and
Sharp cooling roll forms non-stretched slab；
Step b, the manufacturing process of wear-resisting shaping dope；
Step b1, nickel acetate, potassium borohydride, cobalt acetate, alundum (Al2O3), phosphorus pentoxide are obtained according to parts by weight, will be above-mentioned
Material is well mixed, and is placed into vacuum drying chamber and is carried out drying and processing, and high-temperature roasting is carried out in Muffle furnace, and sintering temperature is set
It is set to 1400-1600 DEG C；Above-mentioned material is inserted in closed ball milling machine and carries out smashing processing, and by sieving screening, bulky grain
Material is inserted in ball mill handle again, untill it can all sieve, is sufficiently mixed again uniformly；By all powder shape material
It is covered in smelting furnace, rise smelting temperature stirs to 1600-1750 DEG C, stands 10-20 minutes, treats that temperature is down to
1400~1550 DEG C, insert in closed ball milling machine and carry out smashing processing, and by sieving screening, select particle 5-10 mesh.
Step b2, in the Nafion solution that concentration is 5-15%, add the graphene oxide powder of preset weight part, oxygen
The particle diameter of graphite alkene is 30-40 mesh, and adds the hydroxymethyl cellulose of preset weight part, and in 150-300r/min stirring
Stirred 30 minutes in machine, and stand 3-4 hours；
Step b3, the cemented carbide particle that above-mentioned steps b1 is obtained, using Nafion of the high pressure particle rifle into above-mentioned steps b
High speed cemented carbide particle is injected in solution, jet velocity 400m/s, sprays the cemented carbide particle for specifying quality；Meanwhile
Stirred in 30-50r/min mixer, until particle is completed in injection, wear-resisting shaping dope is made；
Step c, the manufacturing process of thermal contraction type polyester film；
Carried out after the vertical and horizontal of sheet material non-stretched above-mentioned steps a to be carried out to the stretching of certain stretching ratio at thermal finalization
Reason, 150-180 DEG C of melting is heated to, and wear-resisting shaping dope made from above-mentioned steps b is smeared on top layer, keeping temperature 1-2 hours,
Normal temperature is stood, and thermal contraction type polyester film is made.
The beneficial effects of the present invention are the present invention provides a kind of convergent force and shrinkage factor is less compared with prior art
Thermal contraction type polyester film, the shrink film have good contraction uniformity, prevent set mark during contraction distortion, shrink on alter
Phenomena such as.A kind of elastomeric material is added by mixing, can effectively limit film caused excessive orientation in process
Crystallization, and then the elongation at break for limiting non-main shrinkage direction reduces suddenly.And deposit process, set mark process, set in film
During being deposited after mark, elastomer can effectively prevent hot and humid environment, ink printing process, cover film caused by mark process
Excessive induction crystallization, further increase the stability of the elongation at break of its non-main shrinkage direction.
According to the purpose of the present invention, with the percent thermal shrinkage along main shrinkage direction after 100 DEG C of water process 10S with 35-65%,
It is preferred that 40-60%.The contraction demand of some bottle-type can not be met during shrinkage factor ＜ 35%.Convergent force occurs during shrinkage factor ＞ 65%
Excessive phenomenon.
In addition, there is≤4N/10mm thermal shrinkage force along main shrinkage direction with after 100 DEG C of water process 10S, preferably≤
2.5N/10mm.Easily occurring contraction distortion as convergent force ＞ 4N/10mm during set is marked, shrinking phenomena such as altering.
The stabilization of the elongation at break of non-main shrinkage direction during being deposited after film storage process, set mark process, set mark
Property, its detection method is relatively wet using 40 DEG C of temperature come Acceleration study, the hot and humid environment by hot and humid environment
Degree 85%（40℃/85%）The placement of a period of time is carried out in climatic chamber.
According to a kind of thermal contraction type polyester film provided by the present invention, placed in 40 DEG C/85% environment, its non-master receipts
The time of the elongation at break rapid drawdown in contracting direction should be greater than being equal to ≮ 5 days, preferable ≮ 8 days.
The sign of the elongation at break rapid drawdown is, according to GB/T 1040（ASTM D882）Method is tested, and is broken
Elongation is split by >=250%, is reduced to≤10% phenomenon suddenly.
Embodiment
Hereinafter, the forgoing and additional technical features and advantages are described in more detail.
The preferred embodiment of the present invention is described below.It will be apparent to a skilled person that these embodiments
It is used only for explaining the technical principle of the present invention, it is not intended that limit the scope of the invention.
It should be noted that in the description of the invention, term " on ", " under ", "left", "right", " interior ", " outer " etc. refer to
The direction shown or the term of position relationship are based on shown direction or position relationship, and this is intended merely to facilitate description, without
It is instruction or implies that described device or element there must be specific orientation, with specific azimuth configuration and operation, therefore can not
It is interpreted as limitation of the present invention.
In addition it is also necessary to explanation, in the description of the invention, unless otherwise clearly defined and limited, term " peace
Dress ", " connected ", " connection " should be interpreted broadly, for example, it may be fixedly connected or be detachably connected, or integratedly
Connection；Can be mechanical connection or electrical connection；Can be joined directly together, can also be indirectly connected by intermediary,
It can be the connection of two element internals.
The thermal contraction type polyester film of the embodiment of the present invention, include dibasic acid component 60-90 parts, binary according to weight proportion
Alkoxide component 60-90 parts, elastomer components 15-30 parts, silica 0.01-1 parts, wear-resisting shaping dope are according to parts by weight：Oxidation
Graphene 30-40 parts, Nafion solution 250-300 parts, hydroxymethyl cellulose 5-8 parts, nickel acetate 5-8 parts, potassium borohydride 12-
18 parts, cobalt acetate 8-15 parts, alundum (Al2O3) 10-15 parts, phosphorus pentoxide 3-5 parts.
Wherein, the dibasic acid component, is counted by 100mol% of dibasic acid component, and it contains（a）50-100mol% to benzene
Dioctyl phthalate；0-50mol% other common binary acid.
Wherein, the diol component, is counted by 100mol% of diol component, and it contains（a）50-99mol% ethylene glycol；
1-50mol% other common dihydric alcohols.
Wherein, the gross mass of the elastomer components is counted for 100Wt%, and component accounts for the 1-20Wt% of total mass fraction, preferentially
5-10Wt%, the tensile strength of film can be influenceed when elastomer dosage is excessive；The composition of the elastomer, it contains thermoplasticity
It is polyolefin elastomer, thermoplastic styrene class elastomer, polyurethane-type thermoplastic elastomer, polyester-type thermoplastic elastomer, poly-
Acid amides thermoplastic elastomer (TPE), ethylene copolymer thermoplastic elastomer (TPE) etc., the one or more of conventional elastomers.The elastomer
Main function is, caused excessive in process by elastomer molecules chain flexibility and amorphism, limitation film
Crystallographic orientation, and then the elongation at break for limiting non-main shrinkage direction reduces suddenly.Further, process, set are deposited in film
During being deposited after mark process, set mark, elastomer can effectively prevent hot and humid environment, ink printing process, set mark process
The excessive induction crystallization of caused film, further increase the stability of the elongation at break of its non-main shrinkage direction.
Specifically, the dibasic acid component, diol component, the method for elastomer components mixing, including：Blending is mixed
Close, be copolymerized mixing, graft copolymerization, interpenetrating networks blending etc., common mixed method.The thermal contraction type polyester film can be by
Single or multiple lift structure composition, to prevent that adhesion from can add film total amount 0.01-1% silica or other are common inorganic
Inert particle is as antiblocking agent.Film thickness includes various common thickness ranges.The thermal contraction type polyester film may be used also
Mixing adds titanium dioxide and fluorescent whitening agent, to increase the degree that bleaches of film.
In order to increase wearability and processability, in thermal contraction type polyester film manufacturing process, one layer of coating is resistance to wear into
Type layer, wear-resisting shape layer are by the alloy-layer that graphene oxide is matrix, and film layer is applied to by forming resistance to grinding fluid.Specifically
For, the unique two dimension of graphene oxide, cycle alveolate texture, huge specific surface area and excellent performance are made it have,
Contain many oxy radicals on its lamella, there is higher specific surface energy, good hydrophily and mechanical performance, in water and mostly
There is good dispersion stabilization in number polar organic solvent, there is good wettability and surface-active, and can be small
Peel off, played in terms of the combination properties such as the calorifics of improvement material, electricity, mechanics very heavy after molecule or polyalcohol intercalation
The effect wanted；It is bigger away from 0.34nm than graphite layers between graphene oxide interlamellar spacing about 0 .59nm ~ 0.67nm, be advantageous to insert
The progress of layer reaction.The embodiment of the present invention is being aoxidized on the one hand by the use of graphene oxide as matrix by hard alloy envelope
Graphene top layer, because graphene oxide has larger space, by between lamella and outer layer forms continuous hard and closed
Layer gold, the thermal contraction type polyester film of formation is while very fast shaping, hardness and intensity also with consistent.The opposing party
Face, graphene oxide in organic solvent can fine dispersion, graphene oxide can be dispersed, is easy to fill with hard alloy
Divide and combine, form independent graphene oxide hard alloy particle.In the present embodiment, the particle diameter of graphene oxide is 30-40 mesh.
Specifically, the wear-resisting shape layer of the embodiment of the present invention, closed using Nafion solution as graphene oxide hard
The lysate of gold grain, Nafion Chineses:Perfluorinated sulfonic acid-teflon-copolymers, Nafion solution are perfluor sulphur
Acid-based polymer solution.In the present embodiment, using 5-15% perfluorinated sulfonic acid solution, solvent is ethanol, namely perfluorinated sulfonic acid-
The weight part ratio of teflon-copolymers and ethanol is（5-15）:100.Perfluorinated sulfonic acid-teflon-copolymers have various
Organic group, therefore, Nafion solution have fabulous dispersiveness, and the present embodiment is using Nafion solution to dissolving in the inner
Molecule dispersiveness, and there is extremely strong Adhesion property.In the present embodiment, dissolved in Nafion solution aerobic
Graphite alkene powder, it is by the peptizaiton of Nafion solution that graphene oxide powder is dispersed, while used in outer masterpiece
Lower hard alloy enter solution in, in the solution the hard alloy of high-speed motion Nafion solution stick drag effect under,
Gradually it is fitted in the alveolate texture of graphene oxide, and in gradual moderating process, increasing hard alloy is molten
Flocked together in the presence of liquid adhesive force, formed using graphene oxide as the hard alloy thermal contraction type polyester film of core and
Its preparation method.Simultaneously as the alveolate texture of graphene oxide, the Nafion solutions of its surface contact are compared with plane
Structure is more, and therefore, graphene oxide gathers hard alloy along its top layer, and hard alloy outwards extends along cellular, in formation
Outer uniform hard alloy arrangement architecture.The present invention is during graphene oxide hard metal is formed, with Nafion solution
Be integrated for carrier binder, by the bonding of several materials, absorption, aggregation and air-dry after formed wear Protection liquid, be applied to thin
Film layer forms wear-resisting shape layer.
Specifically, hydroxymethyl cellulose plays a part of dispersant, further disperses the oxygen added in Nafion solution
Graphite alkene, form scattered particle.
Specifically, nickel acetate, potassium borohydride, cobalt acetate, alundum (Al2O3), phosphorus pentoxide, above-mentioned material is mixed
Uniformly, it is placed into vacuum drying chamber and carries out drying and processing, carry out high-temperature roasting in Muffle furnace therewith, sintering temperature is set as
1400-1600℃；Then, above-mentioned material is inserted in closed ball milling machine and carries out smashing processing, and by sieving screening, bulky grain
Material is inserted in ball mill handle again, untill it can all sieve, is sufficiently mixed again uniformly；Finally, by all powder
Shape material is covered in smelting furnace, and rise smelting temperature stirs to 1600-1750 DEG C, stands 10-20 minutes, treats temperature
1400~1550 DEG C are down to, inserts in closed ball milling machine and carries out smashing processing, and by sieving screening, select particle 5-10 mesh.
The hard alloy of the embodiment of the present invention has extremely strong wearability, also, comprising soft aluminium, in particle state, has mutual
The performance of absorption.
Thermal contraction type polyester film of the present invention can be prepared by a conventional method, and this method includes：
Step a, laminated polyester film make；
Dibasic acid component, diol component, elastomer components are mixed into simultaneously melting extrusion according to parts by weight；Melt by die head and
Sharp cooling roll forms non-stretched slab；
Step b, the manufacturing process of wear-resisting shaping dope；
Step b1, nickel acetate, potassium borohydride, cobalt acetate, alundum (Al2O3), phosphorus pentoxide are obtained according to parts by weight, will be above-mentioned
Material is well mixed, and is placed into vacuum drying chamber and is carried out drying and processing, and high-temperature roasting is carried out in Muffle furnace, and sintering temperature is set
It is set to 1400-1600 DEG C；Above-mentioned material is inserted in closed ball milling machine and carries out smashing processing, and by sieving screening, bulky grain
Material is inserted in ball mill handle again, untill it can all sieve, is sufficiently mixed again uniformly；By all powder shape material
It is covered in smelting furnace, rise smelting temperature stirs to 1600-1750 DEG C, stands 10-20 minutes, treats that temperature is down to
1400~1550 DEG C, insert in closed ball milling machine and carry out smashing processing, and by sieving screening, select particle 5-10 mesh.
Step b2, in the Nafion solution that concentration is 5-15%, add the graphene oxide powder of preset weight part, oxygen
The particle diameter of graphite alkene is 30-40 mesh, and adds the hydroxymethyl cellulose of preset weight part, and in 150-300r/min stirring
Stirred 30 minutes in machine, and stand 3-4 hours.
Step b3, the cemented carbide particle that above-mentioned steps b1 is obtained, using high pressure particle rifle into above-mentioned steps b
High speed cemented carbide particle is injected in Nafion solution, jet velocity 400m/s, sprays the hard alloy grain for specifying quality
Son；Meanwhile stirred in 30-50r/min mixer, until particle is completed in injection, wear-resisting shaping dope is made.
Step c, the manufacturing process of thermal contraction type polyester film；
Carried out after the vertical and horizontal of sheet material non-stretched above-mentioned steps a to be carried out to the stretching of certain stretching ratio at thermal finalization
Reason, 150-180 DEG C of melting is heated to, and wear-resisting shaping dope made from above-mentioned steps b is smeared on top layer, keeping temperature 1-2 hours,
Normal temperature is stood, and thermal contraction type polyester film is made.
In embodiments of the present invention, the thickness of film layer is 80-100nm；The thickness of wear-resisting shape layer is 30-50nm.
Described stretching includes simple tension and biaxial tension, preferably using bidirectional extending method, certain stretch ratio
Non- main shrinkage direction stretching, strand ordered arrangement in non-main shrinkage direction can be made, it can be restricted in main contraction side
Upward crystallographic orientation degree.Non- 1.1-1.5 times of main shrinkage direction draw ratio, 3-6 times of main shrinkage direction draw ratio.
Described film shrunk power and the less control method of shrinkage factor may include to reduce altered contents content, reduce stretching
Than, rise draft temperature, rise setting temperature.Preferential is controlled using rise setting temperature, reduces altered contents content
Shrinkage factor curve can be changed, the thickness evenness of film can be influenceed by reducing draw ratio and raising draft temperature.
Illustrated below by embodiment：
（1）Comparative example 1：Shrinkage factor and the higher thermal contraction type polyester film of convergent force
（2）Comparative example 2：Shrinkage factor and the relatively low thermal contraction type polyester film of convergent force, but the extension at break of non-main shrinkage direction
Rate is greatly lowered.（Reduce altered contents）
（3）Comparative example 3：Shrinkage factor and the relatively low thermal contraction type polyester film of convergent force, but the extension at break of non-main shrinkage direction
Rate is greatly lowered.（Raise setting temperature）
（4）Embodiment 1：Shrinkage factor and the relatively low thermal contraction type polyester film of convergent force, but the extension at break of non-main shrinkage direction
Rate stability is good.（Reduce altered contents, individual event stretching）
（5）Embodiment 2：Shrinkage factor and the relatively low thermal contraction type polyester film of convergent force, but the extension at break of non-main shrinkage direction
Rate stability is good.（Raise setting temperature, individual event stretching）
（6）Embodiment 3：Shrinkage factor and the relatively low thermal contraction type polyester film of convergent force, but the extension at break of non-main shrinkage direction
Rate stability is good.（Raise setting temperature, double stretchings）
The component of each embodiment of the different materials of table 1
| PTA | IPA | EG | NPG | DEG | Elastomer | |
| Comparative example 1 | 100% | 70% | 25% | 5% | 0 | |
| Comparative example 2 | 95% | 5% | 90% | 10% | 0 | |
| Comparative example 3 | 100% | 70% | 25% | 5% | 0 | |
| Embodiment 1 | 95% | 5% | 90% | 10% | 10wt% | |
| Embodiment 2 | 100% | 70% | 25% | 5% | 15wt% | |
| Embodiment 3 | 100% | 70% | 25% | 5% | 12wt% |
Each embodiment film effect of table 2
| Longitudinal stretching | Cross directional stretch | Setting temperature | Shrinkage factor | Convergent force | Contractive effect | Stability | |
| Comparative example 1 | 0 | 5 times | 70℃ | 77% | 6N/10mm | × | 20 days |
| Comparative example 2 | 0 | 5 times | 70℃ | 60% | 4N/10mm | √ | 3 days |
| Comparative example 3 | 0 | 5 times | 80℃ | 55% | 3N/10mm | √ | 2 days |
| Embodiment 1 | 0 | 5 times | 70℃ | 60% | 3.5N/10mm | √ | 5 days |
| Embodiment 2 | 0 | 5 times | 80℃ | 50% | 2.5N/10mm | √ | 10 days |
| Embodiment 3 | 1.2 | 5 times | 82℃ | 45% | 2N/10mm | √ | 8 days |
According to the purpose of the present invention, with the percent thermal shrinkage along main shrinkage direction after 100 DEG C of water process 10S with 35-65%, preferably
40-60%.The contraction demand of some bottle-type can not be met during shrinkage factor ＜ 35%.Occur that convergent force is excessive during shrinkage factor ＞ 65%
Phenomenon.
In addition, there is≤4N/10mm thermal shrinkage force along main shrinkage direction with after 100 DEG C of water process 10S, preferably≤
2.5N/10mm.Easily occurring contraction distortion as convergent force ＞ 4N/10mm during set is marked, shrinking phenomena such as altering.
The stabilization of the elongation at break of non-main shrinkage direction during being deposited after film storage process, set mark process, set mark
Property, its detection method is relatively wet using 40 DEG C of temperature come Acceleration study, the hot and humid environment by hot and humid environment
Degree 85%（40℃/85%）The placement of a period of time is carried out in climatic chamber.
According to a kind of thermal contraction type polyester film provided by the present invention, placed in 40 DEG C/85% environment, its non-master receipts
The time of the elongation at break rapid drawdown in contracting direction should be greater than being equal to ≮ 5 days, preferable ≮ 8 days.
The sign of the elongation at break rapid drawdown is, according to GB/T 1040（ASTM D882）Method is tested, and is broken
Elongation is split by >=250%, is reduced to≤10% phenomenon suddenly.
So far, technical scheme is described with reference to preferred embodiment, still, those skilled in the art are easy
Understand, protection scope of the present invention is expressly not limited to these embodiments.In the principle without departing from the present invention
Under the premise of, those skilled in the art can make equivalent change or replacement to correlation technique feature, and these are changed or replaced it
Technical scheme afterwards is fallen within protection scope of the present invention.
Claims (6)
1. a kind of thermal contraction type polyester film, it is characterised in that include dibasic acid component 60-90 parts, binary according to weight proportion
Alkoxide component 60-90 parts, elastomer components 15-30 parts, silica 0.01-1 parts, wear-resisting shaping dope are according to parts by weight：Oxidation
Graphene 30-40 parts, Nafion solution 250-300 parts, hydroxymethyl cellulose 5-8 parts, nickel acetate 5-8 parts, potassium borohydride 12-
18 parts, cobalt acetate 8-15 parts, alundum (Al2O3) 10-15 parts, phosphorus pentoxide 3-5 parts.
2. thermal contraction type polyester film according to claim 1, it is characterised in that the dibasic acid component, with binary acid
Component is counted for 100mol%, and it contains 50-100mol% terephthalic acid (TPA)；0-50mol% other common binary acid.
3. thermal contraction type polyester film according to claim 1, it is characterised in that the diol component, with dihydric alcohol
Component is counted for 100mol%, and it contains 50-99mol% ethylene glycol；1-50mol% other common dihydric alcohols.
4. thermal contraction type polyester film according to claim 1, it is characterised in that the composition of the elastomer, it contains
Thermoplastic polyolefin elastomer, thermoplastic styrene class elastomer, polyurethane-type thermoplastic elastomer, polyester-type thermoplastic elasticity
Body, thermoplastic polyamide elastomer, ethylene copolymer thermoplastic elastomer (TPE) etc., the one or more of conventional elastomers.
5. thermal contraction type polyester film according to claim 1, it is characterised in that the thickness of film layer is 80-100nm；
The thickness of wear-resisting shape layer is 30-50nm.
A kind of 6. preparation method of thermal contraction type polyester film, it is characterised in that including：
Step a, laminated polyester film make；
Dibasic acid component, diol component, elastomer components are mixed into simultaneously melting extrusion according to parts by weight；Melt by die head and
Sharp cooling roll forms non-stretched slab；
Step b, the manufacturing process of wear-resisting shaping dope；
Step b1, nickel acetate, potassium borohydride, cobalt acetate, alundum (Al2O3), phosphorus pentoxide are obtained according to parts by weight, will be above-mentioned
Material is well mixed, and is placed into vacuum drying chamber and is carried out drying and processing, and high-temperature roasting is carried out in Muffle furnace, and sintering temperature is set
It is set to 1400-1600 DEG C；Above-mentioned material is inserted in closed ball milling machine and carries out smashing processing, and by sieving screening, bulky grain
Material is inserted in ball mill handle again, untill it can all sieve, is sufficiently mixed again uniformly；By all powder shape material
It is covered in smelting furnace, rise smelting temperature stirs to 1600-1750 DEG C, stands 10-20 minutes, treats that temperature is down to
1400~1550 DEG C, insert in closed ball milling machine and carry out smashing processing, and by sieving screening, select particle 5-10 mesh；
Step b2, in the Nafion solution that concentration is 5-15%, the graphene oxide powder of preset weight part is added, aoxidizes stone
The particle diameter of black alkene is 30-40 mesh, and adds the hydroxymethyl cellulose of preset weight part, and in 150-300r/min mixer
Stirring 30 minutes, and stand 3-4 hours；
Step b3, the cemented carbide particle that above-mentioned steps b1 is obtained, using Nafion of the high pressure particle rifle into above-mentioned steps b
High speed cemented carbide particle is injected in solution, jet velocity 400m/s, sprays the cemented carbide particle for specifying quality；Meanwhile
Stirred in 30-50r/min mixer, until particle is completed in injection, wear-resisting shaping dope is made；
Step c, the manufacturing process of thermal contraction type polyester film；
Carried out after the vertical and horizontal of sheet material non-stretched above-mentioned steps a to be carried out to the stretching of certain stretching ratio at thermal finalization
Reason, 150-180 DEG C of melting is heated to, and wear-resisting shaping dope made from above-mentioned steps b is smeared on top layer, keeping temperature 1-2 hours,
Normal temperature is stood, and thermal contraction type polyester film is made.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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Application publication date: 20180119 |