CN117841505B - PET (polyethylene terephthalate) plate film and preparation process thereof - Google Patents
PET (polyethylene terephthalate) plate film and preparation process thereof Download PDFInfo
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- CN117841505B CN117841505B CN202410156268.8A CN202410156268A CN117841505B CN 117841505 B CN117841505 B CN 117841505B CN 202410156268 A CN202410156268 A CN 202410156268A CN 117841505 B CN117841505 B CN 117841505B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 title abstract description 138
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract description 138
- 239000004595 color masterbatch Substances 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 154
- 239000010410 layer Substances 0.000 claims description 75
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 229920006895 TPC ET Polymers 0.000 claims description 14
- 229920006417 TPC-ET Polymers 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920002799 BoPET Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical group [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006344 thermoplastic copolyester Polymers 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
-
- 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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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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
- B32B2250/00—Layers arrangement
- B32B2250/04—4 layers
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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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
The application discloses a PET (polyethylene terephthalate) plate film and a preparation process thereof, and belongs to the field of decorative materials. The utility model provides a PET panel membrane, includes PETG surface course, PET flashing layer, PET color master batch layer and PETG bottom that sets gradually, and PET flashing layer contains PET resin and flashing, and PET color master batch layer contains PET resin and color master batch, and PETG surface course, PET flashing layer, PET color master batch layer and PETG bottom pass through the coextruding complex. The application has the effect of improving the color and mechanical property of the PET film.
Description
Technical Field
The application relates to the field of decorative materials, in particular to a PET (polyethylene terephthalate) plate film and a preparation process thereof.
Background
In the classification of the decorative panel materials, the PET panel film occupies higher positioning and influence, has the advantages of scratch resistance, difficult cracking and environmental protection, thereby endowing the panel with more excellent performance and being applied to the fields of furniture decoration, advertisement, packaging and the like.
The sheet film is usually attached to the decorative face of the sheet, so the decorative function is also a consideration for the quality of the sheet film. The decorative function of the plate film is generally realized by adding flash powder and pigment, for example, the flash powder and pigment are mixed in the melting process of PET resin, and then the PET film is obtained by extrusion, so that the designed color and visual effect are given to the plate film.
However, after the flash powder and the color master batch are blended with PET, the problem of uneven color distribution is easily caused due to poor dispersibility of the flash powder and the color master batch, and the mechanical property of the PET film is easily influenced, so that the comprehensive performance of the PET film is easily influenced.
Disclosure of Invention
In order to improve the color and mechanical property of the PET film, the application provides a PET plate film and a preparation process thereof.
In a first aspect, the present application provides a PET sheet film, which adopts the following technical scheme:
the utility model provides a PET panel membrane, includes PETG surface course, PET powder layer, PET color master batch layer and PETG bottom that flash of standing in proper order, PET powder layer contains PET resin and flash of powder, PET color master batch layer contains PET resin and color master batch, PETG surface course, PET powder layer, PET color master batch layer and PETG bottom pass through the coextruding complex.
By adopting the technical scheme, the flash powder and the color master are respectively combined with different PET layers, so that the flash powder and the color master in the plate film are staggered, the problem of poor dispersibility when the flash powder and the color master are simultaneously blended in a PET resin system is effectively avoided, and therefore, the PET flash powder layer and the PET color master layer have good uniformity, and the plate film can present good color and visual effect while ensuring good mechanical property.
The PETG surface layer and the PETG bottom layer are both composed of PETG resin, the PETG is a product of polycondensation of three monomers of terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol by an ester exchange method, compared with PET, more 1, 4-cyclohexanedimethanol comonomer is used, the PETG has good impact toughness and transparency, can play a good role in protection, does not influence the color and visual effect display of the PET flash powder layer and the PET color master layer, and further improves the comprehensive performance of the plate film.
Optionally, the PET flash powder layer is formed by blending and extruding PET resin and flash powder, wherein the flash powder accounts for 1-5% of the PET resin by mass; the PET color masterbatch layer is formed by blending and extruding PET resin and color masterbatch, and the color masterbatch accounts for 5-12% of the PET resin by mass.
By adopting the technical scheme, the proportion of the flash powder and the color master in the respective layer structure is controlled, so that good appearance is prepared, and good mechanical properties of the plate film can be maintained.
Optionally, the flash powder is one or more of metal flash powder, pearl flash powder, flaky flash powder and fluorescent flash powder.
By adopting the technical scheme, the flash powder of the type can show a flash effect in the plate film, and the glossiness and visual effect of the plate film are improved.
Optionally, the flash powder is modified flash powder, the modified flash powder is prepared from flash powder, a vinyl silane coupling agent, allyl polyoxyethylene ether and an initiator, and the mass ratio of the flash powder to the vinyl silane coupling agent to the allyl polyoxyethylene ether to the initiator is 10 (0.6-1) (0.4-0.7) (0.01-0.03).
By adopting the technical scheme, the vinyl silane coupling agent grafts the surface of the flash powder to obtain a vinyl functional group, and then the initiator grafts the allyl polyoxyethylene ether, so that the surface characteristic of the flash powder is improved by utilizing the grafted polyether segment structure, the flash powder is promoted to be compatible and dispersed in a PET resin system, and the good mechanical property of the PET flash powder layer is maintained.
Optionally, the color masterbatch is prepared from PET resin, TPA-ET, TPC-ET, dispersing agent and pigment, wherein the mass ratio of the PET resin, TPA-ET, TPC-ET, dispersing agent to pigment is 10 (0.2-0.5) (0.3-0.6) (1-2.5).
By adopting the technical scheme, TPA-ET is a thermoplastic polyamide elastomer containing polyether soft segments, TPC-ET is a thermoplastic copolyester elastomer containing polyether soft segments, and TPA-ET, TPC-ET and PET resin are blended to improve the deformation and flow characteristics of the color master, so that the color master can drive pigment to be uniformly dispersed in a PET color master layer, and a good color effect is obtained.
In addition, for the flash powder dispersed at the interface of the PET flash powder layer and the color master batch dispersed at the interface of the PET color master batch layer, the ether segment structure grafted by the flash powder and the ether segment structure of the blending modified color master batch generate good interface compatibility, and the polyether segments can be mutually wound due to the soft characteristic of the polyether segments, so that the PET flash powder layer and the PET color master batch layer are tightly combined, the integral mechanical property of the plate film is improved, the plate film is not easy to deform, the weather resistance of the plate film is improved, the influence of a wet and hot environment can be borne, and good barrier property is kept.
Optionally, the allyl polyoxyethylene ether is one or two of APEG-1200 and APEG-2400.
By adopting the technical scheme, the allyl polyoxyethylene ether with the molecular weight of the model has a good effect of improving the dispersibility of the flash powder in a PET system, and further promotes the interface combination of the PET flash powder layer and the PET color masterbatch layer, so that the water vapor and oxygen barrier property of the plate film is improved.
Optionally, the PETG surface layer accounts for 20% -30% of the thickness of the plate film, the PET flash powder layer accounts for 15% -25% of the thickness of the plate film, the PET color master layer accounts for 40% -50% of the thickness of the plate film, and the PETG bottom layer accounts for 5% -15% of the thickness of the plate film.
By adopting the technical scheme, the PET powder flashing layer and the PET color master layer occupy a higher proportion, so that the appearance and the mechanical property of the plate film are well exerted while the cost is controlled.
In a second aspect, the preparation process of the PET plate film provided by the application adopts the following technical scheme:
a preparation process of a PET plate film comprises the following steps:
mixing PET resin with flash powder, and melting to obtain PET flash powder melt;
Mixing PET resin with a color master batch, and melting to obtain a PET color master batch melt;
melting PETG resin to obtain PETG melt;
And (3) splitting the PETG melt into an inner runner and an outer runner of the co-extrusion die head, respectively flowing the PET flash powder melt and the PET color master melt into the middle two runners of the co-extrusion die head, carrying out composite co-extrusion, calendaring and shaping to obtain the PET plate film.
By adopting the technical scheme, the melt is subjected to composite coextrusion by four runners, which is beneficial to obtaining the plate film with uniform thickness.
Optionally, the flash powder is modified flash powder, and the preparation method of the modified flash powder comprises the following steps:
Dispersing the flash powder in a first solvent, heating, adding a vinyl silane coupling agent, reacting for a certain time, filtering, washing, and collecting a filter body; dispersing the filter body in a second solvent, adding allyl polyoxyethylene ether, heating, adding an initiator, reacting for a certain time, filtering, and washing to obtain the modified flash powder.
By adopting the technical scheme, the grafting of the allyl polyoxyethylene ether is carried out in two steps, so that the modified flash powder with good dispersibility is obtained.
Optionally, the preparation method of the color master batch comprises the following steps:
PET resin, TPA-ET, TPC-ET, dispersing agent and pigment are mixed, melted and extruded to obtain the color master.
In summary, the application has the following beneficial effects:
1. according to the application, by combining the flash powder and the color master batch in different PET layers respectively, the flash powder and the color master batch in the plate film are staggered, so that the problem of poor dispersibility when the flash powder and the color master batch are simultaneously blended in a PET resin system is effectively avoided, and therefore, the PET flash powder layer and the PET color master batch layer have good uniformity, and the plate film can present good color and visual effect while ensuring good mechanical property.
2. The application also adopts modified flash powder and blending modified color master for the structures of the PET flash powder layer and the PET color master layer, so that the PET flash powder layer and the PET color master layer generate good interface compatibility and bonding property, and good weather resistance and barrier property are brought to the plate film.
Drawings
Fig. 1 is a plan view showing the structure of a sheet film layer according to example 1 of the present application.
Reference numerals illustrate:
1. a PETG topcoat; 2. PET powder flashing layer; 3. a PET color master layer; 4. PETG bottom layer.
Detailed Description
The present application will be described in further detail with reference to fig. 1.
The PET resin is selected from DuPont Di 725, the PETG resin is selected from SK chemistry BS 050, TPA-ET is selected from Japanese Kogyo XPA 9048F1, TPC-ET is selected from Selanis 6356, and the manufacturer types mentioned above are used to support embodiments of the application to satisfy the disclosure and are not limited to the listed manufacturer types.
Preparative example 1
The modified flash powder comprises the following raw materials:
1000g of flash powder, 60g of vinyl silane coupling agent and 40g of allyl polyoxyethylene ether.
The flash powder is 1000-mesh aluminum flash powder, the vinyl silane coupling agent is vinyl trimethoxy silane, and the allyl polyoxyethylene ether is APEG-1200.
The preparation method of the modified flash powder comprises the following steps:
dispersing the flash powder in 8L of a first solvent which is 80wt% ethanol solution, heating to 60 ℃, adding a vinyl silane coupling agent, reacting for 1h, filtering, washing, and collecting a filter body; dispersing the filter body in 8L of a second solvent which is a 10wt% ethanol solution, adding allyl polyoxyethylene ether, heating to 85 ℃, then dropwise adding an initiator solution which consists of 1g of potassium persulfate and 300mL of water, continuing to react for 2 hours after the dropwise adding is finished, and then filtering, washing and drying to obtain the modified flash powder.
PREPARATION EXAMPLE 2
The modified flash powder comprises the following raw materials:
1000g of flash powder, 100g of vinyl silane coupling agent and 70g of allyl polyoxyethylene ether.
The flash powder is 1000-mesh pearl flash powder, the pearl flash powder is formed by covering titanium dioxide on the surface of mica, the vinyl silane coupling agent is vinyl trimethoxy silane, and the allyl polyoxyethylene ether is APEG-2400.
The preparation method of the modified flash powder comprises the following steps:
Dispersing the flash powder in 10L of a first solvent which is 80wt% ethanol solution, heating to 65 ℃, adding a vinyl silane coupling agent, reacting for 1h, filtering, washing, and collecting a filter body; dispersing the filter body in 10L of a second solvent which is a10 wt% ethanol solution, adding allyl polyoxyethylene ether, heating to 80 ℃, then dropwise adding an initiator solution which consists of 3g of potassium persulfate and 500mL of water, continuing to react for 2 hours after the dropwise adding is finished, and then filtering, washing and drying to obtain the modified flash powder.
Preparative example 3
The preparation example differs from preparation example 1 in that no allyl polyoxyethylene ether and no initiator are added, specifically:
Dispersing the flash powder in 8L of a first solvent which is 80wt% ethanol solution, heating to 60 ℃, adding a vinyl silane coupling agent, reacting for 1h, filtering, washing, drying, and collecting a filter body to obtain the modified flash powder.
PREPARATION EXAMPLE 4
The preparation example differs from preparation example 1 in that APEG-500 is used as the allyl polyoxyethylene ether.
Preparation example 1
The color master batch comprises the following raw materials: 10kg PET resin, 0.2kg TPA-ET, 0.2kg TPC-ET, 0.3kg dispersant, 1kg pigment.
The dispersing agent is polyethylene wax, and the pigment is phthalocyanine blue.
The preparation method of the color master batch comprises the following steps:
PET resin, TPA-ET, TPC-ET, dispersing agent and pigment are mixed, melted and extruded by a double screw extruder, the extrusion temperature is 270 ℃, and the masterbatch is obtained by pelleting.
Preparation example 2
The present preparation example differs from preparation example 1 in that the raw material composition of the color master is different.
10Kg PET resin, 0.5kg TPA-ET, 0.5kg TPC-ET, 0.6kg dispersant, 2.5kg pigment.
The dispersing agent is polyethylene wax, and the pigment is phthalocyanine blue.
Preparation example 3
The present preparation example differs from preparation example 1 in that the raw material composition of the color master is different.
10Kg PET resin, 0.4kg POE, 0.3kg dispersant and 1kg pigment.
POE is selected from DF740 of Mitsui chemical company, the dispersing agent is polyethylene wax, and the pigment is phthalocyanine blue.
Preparation example 4
The present preparation example differs from preparation example 1 in that the raw material composition of the color master is different.
10Kg PET resin, 0.4kg TPA-ET, 0.3kg dispersant, 1kg pigment.
The dispersing agent is polyethylene wax, and the pigment is phthalocyanine blue.
Preparation example 5
The present preparation example differs from preparation example 1 in that the raw material composition of the color master is different.
10Kg PET resin, 0.4kg TPC-ET, 0.3kg dispersant, 1kg pigment.
The dispersing agent is polyethylene wax, and the pigment is phthalocyanine blue.
Example 1
The preparation process of the PET plate film comprises the following steps:
Mixing PET resin and flash powder, wherein the flash powder is 1000 meshes of aluminum flash powder, the flash powder accounts for 5 mass percent of the PET resin, and putting the mixture into an extruder for melting to obtain a PET flash powder melt;
mixing PET resin with a color master batch, wherein the color master batch is prepared by adopting the color master batch prepared in preparation example 1, and the color master batch accounts for 12 mass percent of the PET resin, and putting the mixture into an extruder for melting to obtain a PET color master batch melt;
Putting PETG resin into an extruder for melting to obtain PETG melt;
And (3) splitting the PETG melt into an inner runner and an outer runner of the co-extrusion die head, respectively flowing the PET flash powder melt and the PET color master melt into the middle two runners of the co-extrusion die head, carrying out composite co-extrusion, calendaring and shaping to obtain the PET plate film.
The thickness of the obtained PET plate film is 1mm, and as shown in figure 1, the plate film sequentially comprises a PETG surface layer 1, a PET flash powder layer 2, a PET color master layer 3 and a PETG bottom layer 4; the PETG surface layer 1 accounts for 20% of the thickness of the plate film, the PET flash powder layer 2 accounts for 25% of the thickness of the plate film, the PET color master layer 3 accounts for 40% of the thickness of the plate film, and the PETG bottom layer 4 accounts for 15% of the thickness of the plate film.
Example 2
The preparation process of the PET plate film comprises the following steps:
mixing PET resin and flash powder, wherein the flash powder is 1000 meshes of aluminum flash powder, the flash powder accounts for 1 mass percent of the PET resin, and putting the mixture into an extruder for melting to obtain a PET flash powder melt;
Mixing PET resin with a color master batch, wherein the color master batch is prepared by adopting the color master batch prepared in preparation example 1, and the color master batch accounts for 5 mass percent of the PET resin, and putting the mixture into an extruder for melting to obtain PET color master batch melt;
Putting PETG resin into an extruder for melting to obtain PETG melt;
And (3) splitting the PETG melt into an inner runner and an outer runner of the co-extrusion die head, respectively flowing the PET flash powder melt and the PET color master melt into the middle two runners of the co-extrusion die head, carrying out composite co-extrusion, calendaring and shaping to obtain the PET plate film.
The thickness of the obtained PET plate film is 1mm, and the plate film sequentially comprises a PETG surface layer, a PET flash powder layer, a PET color master layer and a PETG bottom layer; the PETG surface layer accounts for 30% of the thickness of the plate film, the PET flash powder layer accounts for 15% of the thickness of the plate film, the PET color master layer accounts for 50% of the thickness of the plate film, and the PETG bottom layer accounts for 5% of the thickness of the plate film.
Example 3
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of the same amount, the modified flash powder being from preparation example 1.
Example 4
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of equal amount, the modified flash powder being from preparation 2 and the color master from preparation 2.
Example 5
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of the same amount, the modified flash powder being from preparation example 3.
Example 6
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of the same amount, the modified flash powder being from preparation example 4.
Example 7
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of equal amount, the modified flash powder being from preparation 1 and the color master from preparation 3.
Example 8
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of equal amount, the modified flash powder being from preparation 1 and the color master from preparation 4.
Example 9
This example differs from example 1 in that the flash powder is replaced by a modified flash powder of equal amount, the modified flash powder being from preparation 1 and the color master from preparation 5.
Comparative example 1
The preparation process of the PET plate film comprises the following steps:
Mixing PET resin, flash powder and color master batch, wherein the flash powder is 1000 meshes of aluminum flash powder, the color master batch is prepared by adopting the color master batch prepared in preparation example 1, the flash powder accounts for 5% of the PET resin, the color master batch accounts for 12% of the PET resin, and putting the mixture into an extruder for melting to obtain a PET flash powder-color master batch mixed melt;
Putting PETG resin into an extruder for melting to obtain PETG melt;
And (3) splitting the PETG melt into an inner runner and an outer runner of the co-extrusion die head, enabling the PET flash powder-color master batch mixed melt to flow into the middle runner of the co-extrusion die head, carrying out composite co-extrusion, calendaring and shaping to obtain the PET plate film.
The obtained PET plate film sequentially comprises a PETG surface layer, a PET flash powder-color master layer and a PETG bottom layer; the PETG surface layer accounts for 20% of the thickness of the plate film, the PET flash powder-color master layer accounts for 65% of the thickness of the plate film, and the PETG bottom layer accounts for 15% of the thickness of the plate film.
Comparative example 2
This comparative example differs from comparative example 1 in that the flash powder was replaced with a modified flash powder of the same amount, the modified flash powder being derived from preparation example 1.
Appearance test
The sheet film was evaluated for color and visual effect, and the results are shown in table 1.
TABLE 1
Performance test toughness: the elongation at break of the sheet film was tested with reference to GB/T1040.3 test conditions for determination of tensile Properties of Plastic films and sheets, and the results are shown in Table 2.
Impact resistance: the plate film was placed in an environment of-20 ℃ for cold storage for 12 hours, taken out to room temperature and impacted with free darts, the dart height was 1.5m, the dart weight was 300g, and whether the plate film was broken or not after the dart impact was observed, and the results are shown in table 2.
Water vapor barrier properties: the water vapor permeation amount of the plate film was measured using a water vapor permeation tester, and the test object includes an unaged plate film and a plate film aged for 24 hours at 80.+ -. 2 ℃ under an environment of 85.+ -. 2% humidity, and the results are shown in Table 2.
Oxygen barrier properties: the oxygen permeation amount of the plate film was measured by using an oxygen permeameter, and the test object includes an unaged plate film and a plate film aged for 24 hours at a temperature of 75.+ -. 2 ℃ and a humidity of 85.+ -. 2%, and the results are shown in Table 2.
TABLE 2
As can be seen from table 1, the conventional plate film, taking comparative example 1 as an example, blends the flash powder and the color master batch with PET, so that poor dispersibility of the flash powder and the color master batch is easy to cause defects in appearance such as color with sundry blocks, and as can be seen from table 2, poor dispersibility of the flash powder and the color master batch also affects the combination of interfaces of the PET layer and the PETG layer, so that a stable connection structure is difficult to form between layers in the plate film, and the problems of reduced elongation at break and easy impact damage are caused, namely, the appearance and mechanical properties of the plate film are affected.
In comparison with comparative example 1, the combination of examples 1 to 9 effectively avoids the problem of uneven blending of the flash powder and the color master by adopting the structural forms of the PETG surface layer, the PET flash powder layer, the PET color master layer and the PETG bottom layer, thereby having better color and visual performance and improving the toughness and impact resistance of the plate film, in particular the impact resistance in low-temperature durability.
The panel film is often applied to door panel decoration, such as kitchen cabinet doors and bathroom cabinet doors, and as the kitchen and bathroom belongs to a use scene with high temperature and high humidity, the durability of the material can be negatively affected, and therefore, the panel film has corresponding requirements on the high-temperature and high-humidity resistance and the protective blocking capability of the panel film besides the decoration function.
As can be seen from table 2, the plate films prepared in examples 3 to 4 have lower water vapor transmission amount and lower oxygen transmission amount, i.e., better protective barrier ability, than the plate film prepared in example 1, and the ability to block water vapor and oxygen is not significantly reduced after the humid heat aging treatment, which indicates that the modified flash powder can generate good interfacial compatibility and bonding with the blended modified color master batch, and improve the barrier property and high temperature and high humidity resistance of the plate film.
The sheet films prepared in examples 5 to 6 exhibited poorer barrier properties and high temperature and high humidity resistance than the sheet film prepared in example 3, indicating that the barrier properties and high temperature and high humidity resistance of the sheet film were improved only when the modification of the allyl polyoxyethylene ether was absent or the molecular weight of the allyl polyoxyethylene ether was not satisfactory.
Compared with the plate film prepared in the embodiment 3, the plate films prepared in the embodiments 7-9 are poorer in barrier property and high-temperature and high-humidity resistance, which shows that the TPA-ET and TPC-ET blending modified PET color master batch can improve the matching of the color master batch and the modified flash powder, realize the tight combination of the PET flash powder layer and the PET color master batch layer, and further improve the barrier property and the weather resistance of the plate film.
Further, in example 3, compared with the plate film prepared in comparative example 2, even if the modified flash powder and the blending modified color master batch are adopted under the condition of blending the flash powder and the color master batch with PET, the appearance, the mechanical property and the barrier property of the plate film are not obviously improved, which indicates that the modified flash powder and the blending modified color master batch are suitable for improving the interface property of the PET flash powder layer and the PET color master batch layer.
The present embodiment is merely illustrative of the present application and not limiting, and one skilled in the art, after having read the present specification, may make modifications to the embodiment without creative contribution as required, but is protected by patent law within the scope of the claims of the present application.
Claims (6)
1. A PET sheet film, characterized in that: the PET powder flashing layer comprises PET resin and flashing powder, the PET powder flashing layer comprises PET resin and a color master, and the PETG surface layer, the PET powder flashing layer, the PET color master layer and the PETG bottom layer are compounded through coextrusion;
the flash powder is modified flash powder, the modified flash powder is prepared from flash powder, a vinyl silane coupling agent, allyl polyoxyethylene ether and an initiator, and the mass ratio of the flash powder to the vinyl silane coupling agent to the allyl polyoxyethylene ether to the initiator is 10 (0.6-1) (0.4-0.7) (0.01-0.03);
The preparation method of the modified flash powder comprises the following steps:
Dispersing the flash powder in a first solvent, heating, adding a vinyl silane coupling agent, reacting for a certain time, filtering, washing, and collecting a filter body; dispersing the filter body in a second solvent, adding allyl polyoxyethylene ether, heating, adding an initiator, reacting for a certain time, filtering, and washing to obtain modified flash powder;
The color masterbatch is prepared from PET resin, TPA-ET, TPC-ET, a dispersing agent and pigment, wherein the mass ratio of the PET resin, TPA-ET, TPC-ET, the dispersing agent to the pigment is 10 (0.2-0.5) (0.3-0.6) (1-2.5);
the allyl polyoxyethylene ether is one or two of APEG-1200 and APEG-2400.
2. A PET sheet film as defined in claim 1 wherein: the PET powder flashing layer is formed by blending and extruding PET resin and powder flashing, wherein the powder flashing accounts for 1-5% of the PET resin by mass percent; the PET color masterbatch layer is formed by blending and extruding PET resin and color masterbatch, and the color masterbatch accounts for 5-12% of the PET resin in percentage by mass.
3. A PET sheet film as defined in claim 1 wherein: the flash powder is one or more of metal flash powder, pearl flash powder, flaky flash powder and fluorescent flash powder.
4. A PET sheet film according to any one of claims 1-3, characterized in that: the PETG surface layer accounts for 20% -30% of the thickness of the plate film, the PET flash powder layer accounts for 15% -25% of the thickness of the plate film, the PET color master layer accounts for 40% -50% of the thickness of the plate film, and the PETG bottom layer accounts for 5% -15% of the thickness of the plate film.
5. A process for preparing a PET sheet film according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
mixing PET resin with flash powder, and melting to obtain PET flash powder melt;
Mixing PET resin with a color master batch, and melting to obtain a PET color master batch melt;
melting PETG resin to obtain PETG melt;
And (3) splitting the PETG melt into an inner runner and an outer runner of the co-extrusion die head, respectively flowing the PET flash powder melt and the PET color master melt into the middle two runners of the co-extrusion die head, carrying out composite co-extrusion, calendaring and shaping to obtain the PET plate film.
6. The process for preparing the PET sheet material film as claimed in claim 5, wherein: the preparation method of the color master batch comprises the following steps:
PET resin, TPA-ET, TPC-ET, dispersing agent and pigment are mixed, melted and extruded to obtain the color master.
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CN116604905A (en) * | 2023-05-08 | 2023-08-18 | 安徽金田高新材料股份有限公司 | Extinction type pearlescent color heat-sealing BOPP film and preparation method thereof |
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CN116604905A (en) * | 2023-05-08 | 2023-08-18 | 安徽金田高新材料股份有限公司 | Extinction type pearlescent color heat-sealing BOPP film and preparation method thereof |
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