CN107962849A - A kind of high-barrier polyester film - Google Patents
A kind of high-barrier polyester film Download PDFInfo
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- CN107962849A CN107962849A CN201711099489.2A CN201711099489A CN107962849A CN 107962849 A CN107962849 A CN 107962849A CN 201711099489 A CN201711099489 A CN 201711099489A CN 107962849 A CN107962849 A CN 107962849A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
Abstract
The present invention relates to a kind of high-barrier polyester film, using individual layer A, bilayer A/B, three layers of A/B/A co-extrusions biaxially oriented polyester film, at least one layer includes graphene polyester barrier layer, and the High barrier PET masterbatch containing graphene is added in the graphene polyester barrier layer.The polyester film of the present invention has high barrier, substantially increases the water oxygen barrier of polyester film, is effectively simplified product processes, considerably reduces production cost.Product can be widely used for the fields such as photovoltaic industry, packing business.
Description
Technical field
The present invention relates to the flexible layered product that thin film technique field, especially plastics are main material.
Background technology
With the development of science and technology the production technology of polyester film is also increasingly perfect, its use scope is also progressively expanding, and gathers
Ester film is with its high mechanical strength, cold-resistant heat-resist, shrinkage is stable and the performance such as excellent electrical insulating property, is widely used in
The field such as packaging, industry, electronics, electric, magnetic, photosensitive.In the fields such as current photovoltaic industry, packing business, especially in liquid
In the application such as brilliant display original set, organic solar batteries, solar energy backboard, organic electroluminescent device, simple polyester film
Easily degrade, it is therefore desirable to using high-barrier polyester film, it is met the performance requirements such as water vapor transmittance.Current solution
Certainly scheme is：1st, with plasma enhanced chemical vapor phase deposition method, vacuum sputtering or evaporation certain is deposited on plastic basis material
Inorganic matter coating；2nd, lotion is configured to PVDC, is coated on polyester film base material；3rd, carried out with PVDC, EVOH with gathering
Ester film carries out MULTILAYER COMPOSITE；4th, combination one or more of in PEN, PBT, PTT is added in polyester film process.
Although technical staff has carried out numerous studies to Obstruct membrane, obstructing membrane technology at present, also there are many problems：
1st, when deposited inorganic coating, the inorganic matter coating surface that is easy to cause deposition is coarse, uneven, leakiness, and holds
Easily there are the disadvantages such as vacuum, crack, cause the inorganic matter coating barrier of production to decline, ultimately result in high-barrier polyester film matter
Amount declines；2nd, Obstruct membrane is produced using PVDC emulsion coatings, coating adhesion easily occurs under adverse circumstances, comes off, directly affect
Polyester film service life；3rd, carry out carrying out MULTILAYER COMPOSITE with polyester film using PVDC, EVOH, not only complex production process,
And production time and raw materials consumption are added, so as to add its production cost；4th, add in polyester film process
Add one or more combination in PEN, PBT, PTT, the working condition of PEN, PBT, PTT in itself is harsh, production difficulty coefficient is high, directly
Connect and result in the production difficulty of polyester film, the production cost increases.
The content of the invention
The purpose of the present invention is intended to overcome deficiency of the prior art, there is provided a kind of high-barrier polyester film and its preparation side
Method.It can effectively solve the problem that existing photovoltaic industry, packing business high-barrier polyester film production and processing complexity, production cost height etc. are asked
A kind of topic, there is provided high-barrier polyester film especially suitable for fields such as photovoltaic industry, packing businesses.
To solve the above problems, the present invention adopts the following technical scheme that：
A kind of high-barrier polyester film, using individual layer A, bilayer A/B, three layers of A/B/A co-extrusions biaxially oriented polyester film,
At least one layer includes graphene polyester barrier layer, and the high-barrier containing graphene is added in the graphene polyester barrier layer
Polyester masterbatch.
Above-mentioned high-barrier polyester film, in the graphene polyester barrier layer content of graphene for 100ppm~
5000ppm。
Above-mentioned high-barrier polyester film, the thickness of the high-barrier polyester film is 23 μm~350 μm.
Above-mentioned high-barrier polyester film, the preparation method of the High barrier PET masterbatch containing graphene are：
(1) graphene prepared is added in ethylene glycol solution, under the conditions of 23 DEG C~27 DEG C, uses homogenizer
1h~2h is stirred, then with ultrasonic disperse 2h~3h, 1000ppm~100000ppm graphenes-ethylene glycol dispersion liquid is made；
(2) in pet reaction kettle add binary acid, dihydric alcohol, catalyst, heat stabilizer, carry out mashing 15min~
20min, and nitrogen protection is passed through, carry out esterification 3h~5h under the conditions of 225 DEG C~265 DEG C, 240KPa~260KPa；
(3) graphene-ethylene glycol dispersion liquid in by described in (1), is added in reaction kettle by nitrogen plunging, is opened
Vacuumize, under the conditions of 265 DEG C~280 DEG C, 20Pa~60Pa, polycondensation reaction 2h~4h, through making silk, cooling, pelletizing, drying,
The High barrier PET masterbatch containing graphene is made.
Above-mentioned high-barrier polyester film, binary acid in the step (2)：Dihydric alcohol molar ratio is 1:1.2~1:2.1.
Above-mentioned high-barrier polyester film, binary acid is terephthalic acid (TPA) and M-phthalic acid in the step (2), both
Molar ratio is 2:1~5:1.
Above-mentioned high-barrier polyester film, the dihydric alcohol are ethylene glycol and Isosorbide-5-Nitrae-cyclohexane diol, both molar ratios are
1:1~3:1.
Above-mentioned high-barrier polyester film, the catalyst are antimony glycol, and the additive amount of the antimony glycol is 100ppm
~500ppm.
Above-mentioned high-barrier polyester film, the stabilizer are trimethyl phosphate, and the additive amount of the trimethyl phosphate is
20ppm~100ppm.
The beneficial effects of the present invention are：
1st, the present invention uses the High barrier PET masterbatch containing graphene, is added directly into polyester film at least one layer,
Integrate vapor water barriers layer, oxygen barrier layer, relative to coating, compound, simple production process, avoid because of coating, again
Layer separation is closed, and causes polyester film service life to shorten；
When the 2nd, preparing the High barrier PET masterbatch containing graphene, using polycondensation section nitrogen plunging, graphene-second is added
Glycol dispersion liquid, while not only having can guarantee that dispersing uniformity of the graphene in masterbatch, but also has been avoided that graphene in high temperature ring
Overlong time in border, causes its performance change；Also reduce influence of the graphene to pet reaction Esterification Stage at the same time.
3rd, the present invention prepares High barrier PET masterbatch using direct synthesis technique, avoids the second melting extrusion of polyester and causes
Polyester is degraded.
4th, the present invention prepares high-barrier polyester film using graphene as additive, with respect to PVDC etc., belongs to environment friend
Good type material.
Embodiment
The present invention using individual layer A, bilayer A/B, three layers of A/B/A co-extrusions biaxially oriented polyester film, thickness 23 μm~350
μm, at least one layer includes graphene polyester barrier layer, and the height containing graphene is added in the graphene polyester barrier layer
Polyester masterbatch is obstructed, wherein the preparation method of the High barrier PET masterbatch containing graphene is as follows：
(1) graphene prepared is added in ethylene glycol solution, under the conditions of 23 DEG C~27 DEG C, uses homogenizer
1h~2h is stirred, then with ultrasonic disperse 2h~3h, 1000ppm~100000ppm graphenes-ethylene glycol dispersion liquid is made.
(2) in pet reaction kettle add binary acid, dihydric alcohol, catalyst, stabilizer, carry out mashing 15min~
20min, and nitrogen protection is passed through, carry out esterification 3h~5h under the conditions of 225 DEG C~265 DEG C, 240KPa~260KPa；
(3) by the graphene in (1)-ethylene glycol dispersion liquid, it is added to by nitrogen plunging in reaction kettle, opens and take out very
Sky, under the conditions of 265 DEG C~280 DEG C, 20Pa~60Pa, polycondensation reaction 2h~4h, through making silk, cooling, pelletizing, drying, is made
High barrier PET masterbatch containing graphene.
Then use by die head co-extrusion, it is thin that High barrier PET is made through slab, vertical drawing, horizontal drawing, sizing and the mode of winding
Film.
The specific preparation method of high-barrier polyester film is in the present invention：
1st, the obtained High barrier PET masterbatch containing graphene is added in polyester film at least one layer, is melted
Extrusion.
2nd, melt through die co-extrusion, is cast on slab roller, forms multi-layer co-extruded slab, and slab roll temperature is 20 DEG C~35
℃。
3rd, slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 2.8~4.0 to indulge Lapie.
4th, vertical pulling-on piece is subjected to cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.3~4.7.
5th, the film after stretching shaped, cooled down, setting temperature be 230 DEG C~240 DEG C, cooling temperature for 45 DEG C~
55℃。
6th, film after cooling drawn, wound.
With reference to embodiment, the present invention will be further described, but the implementation of the present invention and protection domain are not limited to
These embodiments.
Embodiment 1
1st, 0.5g graphenes are added in 499.5g ethylene glycol solutions, under the conditions of 23 DEG C, are stirred with homogenizer
1h, then with ultrasonic disperse 2h, it is 1000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:1.2, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid rubs
You are than being 2:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 1:1 ratio；Antimony glycol additive amount is
100ppm, trimethyl phosphate additive amount are 20ppm, after mixing, are added in polyester synthesis reaction kettle, carry out 15 points of mashing
Clock, and nitrogen protection is passed through, carry out esterification 3h under the conditions of 225 DEG C~265 DEG C, 240KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 20Pa, polycondensation reaction 4h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene and gathers
Ester masterbatch.
3rd, by B layers of normal polyester and containing the present invention the High barrier PET masterbatch containing graphene A layers mixing
Material, is added to corresponding extrusion system, is melted through die head co-extrusion, be cast on slab roller, forms AB layers of co-extrusion slab, casting
Piece roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 3.5 to indulge Lapie；By vertical pulling-on piece into
Row cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.7；Film after stretching is shaped, is cooled down, it is fixed
Type temperature is 235 DEG C, and cooling temperature is 50 DEG C, and it is 23 μm of high-barriers that film after cooling, which is drawn, winds obtained thickness
Polyester film, graphene content is 100ppm in graphene polyester barrier layer.
Embodiment 2
1st, 1.5g graphenes are added in 498.5g ethylene glycol solutions, under the conditions of 24 DEG C, are stirred with homogenizer
1.5h, then with ultrasonic disperse 2h, it is 3000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:1.4, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid rubs
You are than being 3:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 2:1 ratio；Antimony glycol additive amount is
200ppm, trimethyl phosphate additive amount are 50ppm, after mixing, are added in polyester synthesis reaction kettle, carry out 17 points of mashing
Clock, and nitrogen protection is passed through, carry out esterification 3.5h under the conditions of 225 DEG C~265 DEG C, 250KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 35Pa, polycondensation reaction 3.5h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene
Polyester masterbatch.
3rd, by A layers of normal polyester and containing the present invention the High barrier PET masterbatch containing graphene B layers mixing
Material, is added to corresponding extrusion system, is melted through die head co-extrusion, be cast on slab roller, forms ABA layers of co-extrusion slab,
Slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 3.3 to indulge Lapie；By vertical pulling-on piece
Cross directional stretch is carried out, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.7；Film after stretching is shaped, is cooled down,
Setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, and it is 125 μm of high resistants that film after cooling, which is drawn, winds obtained thickness
Every graphene content in polyester film, graphene polyester barrier layer be 250ppm.
Embodiment 3
1st, 4g graphenes are added in 496g ethylene glycol solutions, under the conditions of 25 DEG C, 1.8h are stirred with homogenizer,
Then ultrasonic disperse 2.2h is used, it is 8000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:1.6, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid rubs
You are than being 3.5:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 2.5:1 ratio；Antimony glycol additive amount is
300ppm, trimethyl phosphate additive amount are 60ppm, after mixing, are added in polyester synthesis reaction kettle, carry out 18 points of mashing
Clock, and nitrogen protection is passed through, carry out esterification 3.5h under the conditions of 225 DEG C~265 DEG C, 255KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 45Pa, polycondensation reaction 3h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene and gathers
Ester masterbatch.
3rd, by B layers of normal polyester and containing the present invention the High barrier PET masterbatch containing graphene A layers mixing
Material, is added to corresponding extrusion system, is melted through die head co-extrusion, be cast on slab roller, forms ABA layers of co-extrusion slab,
Slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 3.1 to indulge Lapie；By vertical pulling-on piece
Cross directional stretch is carried out, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.5；Film after stretching is shaped, is cooled down,
Setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, and it is 250 μm of high resistants that film after cooling, which is drawn, winds obtained thickness
Every graphene content in polyester film, graphene polyester barrier layer be 500ppm.
Embodiment 4
1st, 10g graphenes are added in 490g ethylene glycol solutions, under the conditions of 25 DEG C, 2h are stirred with homogenizer,
Then ultrasonic disperse 2.5h is used, it is 20000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:1.8, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid rubs
You are than being 3.5:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 2.5:1 ratio；Antimony glycol additive amount is
350ppm, trimethyl phosphate additive amount are 70ppm, after mixing, are added in polyester synthesis reaction kettle, carry out 18 points of mashing
Clock, and nitrogen protection is passed through, carry out esterification 4h under the conditions of 225 DEG C~265 DEG C, 255KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 50Pa, polycondensation reaction 2.8h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene
Polyester masterbatch.
3rd, by B layers of normal polyester and containing the present invention the High barrier PET masterbatch containing graphene A layers mixing
Material, is added to corresponding extrusion system, is melted through die head co-extrusion, be cast on slab roller, forms ABA layers of co-extrusion slab,
Slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 3.1 to indulge Lapie；By vertical pulling-on piece
Cross directional stretch is carried out, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.5；Film after stretching is shaped, is cooled down,
Setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, and it is 250 μm of high resistants that film after cooling, which is drawn, winds obtained thickness
Every graphene content in polyester film, graphene polyester barrier layer be 1500ppm.
Embodiment 5
1st, 25g graphenes are added in 475g ethylene glycol solutions, under the conditions of 26 DEG C, 2h are stirred with homogenizer,
Then ultrasonic disperse 2.5h is used, it is 50000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:1.9, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid rubs
You are than being 4:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 2.5:1 ratio；Antimony glycol additive amount is
350ppm, trimethyl phosphate additive amount are 80ppm, after mixing, are added in polyester synthesis reaction kettle, carry out 19 points of mashing
Clock, and nitrogen protection is passed through, carry out esterification 4h under the conditions of 225 DEG C~265 DEG C, 255KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 60Pa, polycondensation reaction 2.5h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene
Polyester masterbatch.
3rd, by B layers of normal polyester and containing the present invention the High barrier PET masterbatch containing graphene A layers mixing
Material, is added to corresponding extrusion system, is melted through die head co-extrusion, be cast on slab roller, forms ABA layers of co-extrusion slab,
Slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 3.1 to indulge Lapie；By vertical pulling-on piece
Cross directional stretch is carried out, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.5；Film after stretching is shaped, is cooled down,
Setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, and it is 250 μm of high resistants that film after cooling, which is drawn, winds obtained thickness
Every graphene content in polyester film, graphene polyester barrier layer be 2500ppm.
Embodiment 6
1st, 37.5g graphenes are added in 462.5g ethylene glycol solutions, under the conditions of 26 DEG C, are stirred with homogenizer
2h, then with ultrasonic disperse 3h, it is 75000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:2, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid mole
Than for 4:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 2.5:1 ratio；Antimony glycol additive amount is
400ppm, trimethyl phosphate additive amount are 90ppm, after mixing, are added in polyester synthesis reaction kettle, carry out 19 points of mashing
Clock, and nitrogen protection is passed through, carry out esterification 4h under the conditions of 225 DEG C~265 DEG C, 260KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 35Pa, polycondensation reaction 2.5h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene
Polyester masterbatch.
3rd, by containing the present invention the High barrier PET masterbatch containing graphene B layers mixture and contain the present invention
The High barrier PET masterbatch containing graphene A layers mixture, be added to corresponding extrusion system, melted through mould
Coextrusion head, is cast on slab roller, forms ABA layers of co-extrusion slab, and slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching,
Vertical to draw temperature as 70 DEG C~80 DEG C, it is 3.1 to indulge Lapie；Vertical pulling-on piece is subjected to cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C,
Horizontal Lapie is 3.5；Film after stretching is shaped, is cooled down, setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, will be cooled down
It is 250 μm of high-barrier polyester films that film afterwards, which drawn, winds obtained thickness, and graphene contains in graphene polyester barrier layer
Measure as 5000ppm.
Embodiment 7
1st, 50g graphenes are added in 450g ethylene glycol solutions, under the conditions of 27 DEG C, 2h are stirred with homogenizer,
Then ultrasonic disperse 3h is used, it is 100000ppm graphenes-ethylene glycol dispersion liquid that graphene content, which is made,.
2nd, according to binary acid：Dihydric alcohol molar ratio is 1:2.1, wherein terephthalic acid (TPA) in binary acid：M-phthalic acid rubs
You are than being 5:1, ethylene glycol in dihydric alcohol：1,4- cyclohexane diols molar ratio is 3:1 ratio；Antimony glycol additive amount is
500ppm, trimethyl phosphate additive amount are 100ppm, after mixing, are added in polyester synthesis reaction kettle, carry out mashing 20
Minute, and nitrogen protection is passed through, carry out esterification 5h under the conditions of 225 DEG C~265 DEG C, 260KPa；After esterification, polycondensation starts
Before, the graphene in 1-ethylene glycol dispersion liquid is added in reaction kettle by nitrogen plunging, unlatching vacuumizes, at 265 DEG C
~280 DEG C, under the conditions of 40Pa, polycondensation reaction 2h, through making silk, cooling, pelletizing, drying, is made the high-barrier containing graphene and gathers
Ester masterbatch.
3rd, by B layers of normal polyester and containing the present invention the High barrier PET masterbatch containing graphene A layers mixing
Material, is added to corresponding extrusion system, is melted through die head co-extrusion, be cast on slab roller, forms ABA layers of co-extrusion slab,
Slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, it is 70 DEG C~80 DEG C to indulge and draw temperature, and it is 2.9 to indulge Lapie；By vertical pulling-on piece
Cross directional stretch is carried out, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is 3.47；Film after stretching is shaped, is cooled down,
Setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, and it is 350 μm of high resistants that film after cooling, which is drawn, winds obtained thickness
Every graphene content in polyester film, graphene polyester barrier layer be 2500ppm.
Comparative example 1
A layers, B layers are cut into slices using normal polyester, are added to corresponding extrusion system, are melted through die head co-extrusion, stream
Prolong onto slab roller, form AB layers of co-extrusion slab, slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, vertical drawing temperature is
70 DEG C~80 DEG C, it is 3.5 to indulge Lapie；Vertical pulling-on piece is subjected to cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is
3.7；Film after stretching is shaped, is cooled down, setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, by film after cooling
It is 23 μm of polyester films to be drawn, wind obtained thickness.
Comparative example 2
A layers, B layers are cut into slices using normal polyester, are added to corresponding extrusion system, are melted through die head co-extrusion, stream
Prolong onto slab roller, form ABA layers of co-extrusion slab, slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, vertical drawing temperature is
70 DEG C~80 DEG C, it is 3.3 to indulge Lapie；Vertical pulling-on piece is subjected to cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is
3.7；Film after stretching is shaped, is cooled down, setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, by film after cooling
It is 125 μm of polyester films to be drawn, wind obtained thickness.
Comparative example 3
A layers, B layers are cut into slices using normal polyester, are added to corresponding extrusion system, are melted through die head co-extrusion, stream
Prolong onto slab roller, form ABA layers of co-extrusion slab, slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, vertical drawing temperature is
70 DEG C~80 DEG C, it is 3.1 to indulge Lapie；Vertical pulling-on piece is subjected to cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is
3.5；Film after stretching is shaped, is cooled down, setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, by film after cooling
It is 250 μm of polyester films to be drawn, wind obtained thickness.
Comparative example 4
A layers, B layers are cut into slices using normal polyester, are added to corresponding extrusion system, are melted through die head co-extrusion, stream
Prolong onto slab roller, form ABA layers of co-extrusion slab, slab roll temperature is 25 DEG C；Slab is subjected to longitudinal stretching, vertical drawing temperature is
70 DEG C~80 DEG C, it is 2.9 to indulge Lapie；Vertical pulling-on piece is subjected to cross directional stretch, horizontal drawing temperature is 105 DEG C~120 DEG C, and horizontal Lapie is
3.47；Film after stretching is shaped, is cooled down, setting temperature is 235 DEG C, and cooling temperature is 50 DEG C, will be after cooling thin
It is 350 μm of polyester films that film, which is drawn, winds obtained thickness,.
Effect is embodied
Moisture-vapor transmission test method：Carried out by GB/T21529-2008；
OTR oxygen transmission rate test method：Carried out by GB-T1038-2000.
Claims (9)
1. a kind of high-barrier polyester film, using individual layer A, bilayer A/B, three layers of A/B/A co-extrusions biaxially oriented polyester film, its
It is characterized in that, at least one layer includes graphene polyester barrier layer, is added in the graphene polyester barrier layer and contains graphite
The High barrier PET masterbatch of alkene.
2. high-barrier polyester film according to claim 1, it is characterised in that graphite in the graphene polyester barrier layer
The content of alkene is 100ppm~5000ppm.
3. high-barrier polyester film according to claim 1, it is characterised in that the thickness of the high-barrier polyester film is
23 μm~350 μm.
4. high-barrier polyester film according to claim 1, it is characterised in that the High barrier PET containing graphene
The preparation method of masterbatch is：
(1) graphene prepared is added in ethylene glycol solution, under the conditions of 23 DEG C~27 DEG C, is stirred with homogenizer
1h~2h, then with ultrasonic disperse 2h~3h, is made 1000ppm~100000ppm graphenes-ethylene glycol dispersion liquid；
(2) binary acid, dihydric alcohol, catalyst, heat stabilizer are added in pet reaction kettle, carries out mashing 15min~20min,
And nitrogen protection is passed through, carry out esterification 3h~5h under the conditions of 225 DEG C~265 DEG C, 240KPa~260KPa；
(3) graphene-ethylene glycol dispersion liquid in by described in (1), the reaction kettle of step (2) is added to by nitrogen plunging
In, unlatching vacuumizes, under the conditions of 265 DEG C~280 DEG C, 20Pa~60Pa, polycondensation reaction 2h~4h, through making silk, cooling down, cut
Grain, dry, the obtained High barrier PET masterbatch containing graphene.
A kind of 5. high-barrier polyester film according to claim 4, it is characterised in that binary acid in the step (2)：Two
First alcohol molar ratio is 1:1.2~1:2.1.
6. high-barrier polyester film according to claim 4, it is characterised in that the binary acid for terephthalic acid (TPA) and
Phthalic acid, both molar ratios are 2:1~5:1.
7. high-barrier polyester film according to claim 4, it is characterised in that dihydric alcohol is second two in the step (2)
Alcohol and Isosorbide-5-Nitrae-cyclohexane diol, both molar ratios are 1:1~3:1.
8. high-barrier polyester film according to claim 4, it is characterised in that the catalyst is antimony glycol, described
The additive amount of antimony glycol is 100ppm~500ppm.
9. high-barrier polyester film according to claim 4, it is characterised in that the stabilizer is trimethyl phosphate, institute
The additive amount for stating trimethyl phosphate is 20ppm~100ppm.
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| CN110712412A (en) * | 2019-10-14 | 2020-01-21 | 合肥乐凯科技产业有限公司 | Weather-resistant barrier polyester film and manufacturing method thereof |
| CN112876710A (en) * | 2021-01-18 | 2021-06-01 | 山东阜坤新材料有限公司 | Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof |
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Effective date of registration: 20191217 Address after: A New District Industrial Park Industrial Park Station lucky District of Hefei City, Anhui province 230041 Applicant after: Hefei Lucky Science & Technology Industry Co., Ltd. Applicant after: Kunshan Lekai Jinfu Photoelectric Technology Co.,Ltd. Address before: A New District Industrial Park Industrial Park Station lucky District of Hefei City, Anhui province 230041 Applicant before: Hefei Lucky Science & Technology Industry Co., Ltd. |
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Application publication date: 20180427 |