CN114456501A - Ultrahigh wear-resistant BOPP film and preparation method thereof - Google Patents
Ultrahigh wear-resistant BOPP film and preparation method thereof Download PDFInfo
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- CN114456501A CN114456501A CN202110154611.1A CN202110154611A CN114456501A CN 114456501 A CN114456501 A CN 114456501A CN 202110154611 A CN202110154611 A CN 202110154611A CN 114456501 A CN114456501 A CN 114456501A
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- 229920006378 biaxially oriented polypropylene Polymers 0.000 title claims abstract description 39
- 239000011127 biaxially oriented polypropylene Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 9
- -1 ethylene-propylene-butadiene Chemical class 0.000 claims abstract description 69
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 35
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 27
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000002981 blocking agent Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001897 terpolymer Polymers 0.000 claims abstract description 23
- 239000002216 antistatic agent Substances 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims abstract description 21
- 239000004743 Polypropylene Substances 0.000 claims abstract description 20
- 239000003208 petroleum Substances 0.000 claims abstract description 19
- 229920001155 polypropylene Polymers 0.000 claims abstract description 18
- 239000002861 polymer material Substances 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 238000005299 abrasion Methods 0.000 claims description 9
- 238000009998 heat setting Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000011325 microbead Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 90
- 235000019504 cigarettes Nutrition 0.000 abstract description 28
- 238000010008 shearing Methods 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 3
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 23
- 238000005266 casting Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000543392 Symplocos Species 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000009517 secondary packaging Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
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- 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
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- 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
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L57/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2457/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Abstract
The invention provides an ultrahigh wear-resistant BOPP film, which consists of an upper layer, a middle layer and a lower layer from top to bottom in sequence; the upper layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer heat-sealing functional master batch, polydimethylsiloxane, silicone high polymer material and anti-blocking agent; the middle layer is formed by blending and extruding homopolymerized polypropylene and an antistatic agent or homopolymerized polypropylene, petroleum resin and an antistatic agent; the lower layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat-sealing functional master batch, polydimethylsiloxane and anti-blocking agent. According to the invention, the auxiliary agent with a high-symmetry flexible molecular chain structure is added on the surface layer of the BOPP cigarette film, so that the shearing force during the surface friction of the cigarette film is reduced, the lubricating effect is increased, the surface tension is reduced, the lower friction coefficient is realized, the wear resistance of the film is improved, and the wear resistance is enabled to be less than or equal to 0.2% under the condition of ensuring lower precipitation performance of the BOPP cigarette film.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to an ultrahigh wear-resistant BOPP film and a preparation method thereof.
Background
The traditional cigarette film product is poor in scratch resistance, scratches are easily generated by dynamic friction between the traditional cigarette film product and machinery in the cigarette packaging process, and scratches are generated by friction between a strip packet and the strip packet, friction between the strip packet and a corrugated case and friction between sorting links after boxing in the logistics link. At a sale terminal, the scratches can cause visual adverse reactions, especially for high-grade cigarettes, which seriously affect the aesthetic feeling of the original design and reduce the purchasing desire of consumers. In order to make up for the technical shortage of BOPP (biaxially-oriented polypropylene) and better show the cigarette packaging design at a consumer terminal, some cigarette factories are forced to reduce the friction between a carton and the outside by increasing plastic bags to isolate the friction between cigarettes and corrugated paper or using PE (polyethylene) bags to perform secondary packaging on each cigarette, but the methods increase the packaging cost and workload on one hand and address the symptoms but not the root causes on the other hand, and the possibility of scratching the product still exists in the terminal sales link.
With the increasing requirements of the cigarette industry on cigarette film products, the cigarette packaging film has the technical problems that the ultra-strong wear-resisting property is urgently needed to be solved at present in addition to low haze and high gloss in vision. In recent years, almost all cigarette film manufacturers invest a great deal of manpower and financial resources to develop the ultra-strong wear-resistant cigarette packaging film according to market demands, but the manufacturers do not make qualitative breakthrough, and the wear-resistant performance of the product still cannot meet the requirements of cigarette production enterprises in the aspect of wear-resistant performance application from the test results of cigarette film samples collected in the tobacco industry at home and abroad.
The existing wear-resistant cigarette film mainly achieves the purpose of improving the wear resistance of the film by means of adding high-molecular silicone smooth master batch and inorganic nano-materials, and has the following defects: 1. the wear resistance is poor, and the general wear resistance index is more than 0.5 percent; 2. the added nanoscale substances are inorganic substances, which can affect the optical performance (glossiness and haze) of the film, the amount of the added nanoscale substances is not controlled well, and the film even can generate appearance defects (crystal points); 3. inorganic nano-scale substances are easy to agglomerate, and the appearance of the film has defects.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide an ultrahigh wear-resistant BOPP film and a preparation method thereof, wherein the prepared BOPP film has high wear resistance.
In order to achieve the purpose, the invention provides an ultrahigh wear-resistant BOPP film which is composed of an upper layer, a middle layer and a lower layer from top to bottom in sequence;
the upper layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer heat-sealing functional master batch, polydimethylsiloxane, silicone high polymer material and anti-blocking agent;
the middle layer is formed by blending and extruding homopolymerized polypropylene and an antistatic agent or homopolymerized polypropylene, petroleum resin and the antistatic agent;
the lower layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat-sealing functional master batch, polydimethylsiloxane and anti-blocking agent.
Preferably, the upper layer comprises the following raw materials:
74 to 85.5 percent of ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat sealing functional master batch;
5 to 10 percent of polydimethylsiloxane;
8% -15% of silicone polymer material;
0.5 to 2 percent of anti-blocking agent.
The total amount of the raw materials meets 100 percent.
More preferably, the upper layer is composed of the following raw materials:
74 to 81.5 percent of ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat sealing functional master batch;
8 to 10 percent of polydimethylsiloxane;
10-14% of silicone polymer material;
1.5 to 2 percent of anti-blocking agent.
Preferably, the intermediate layer comprises the following raw materials:
61.5 to 98.5 percent of homopolymerized polypropylene;
0 to 35 percent of petroleum resin;
1.5 to 3.5 percent of antistatic agent.
The total amount of the raw materials meets 100 percent.
More preferably, the intermediate layer is composed of the following raw materials:
67.0 to 98.2 percent of homopolymerized polypropylene;
0 to 30 percent of petroleum resin;
1.8 to 3.0 percent of antistatic agent.
Preferably, the lower layer comprises the following raw materials:
88 to 94.5 percent of ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat sealing functional master batch;
5 to 10 percent of polydimethylsiloxane;
0.5 to 2 percent of anti-blocking agent.
The total amount of the raw materials meets 100 percent.
More preferably, the lower layer is composed of the following raw materials:
88 to 90.5 percent of ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat sealing functional master batch;
8 to 10 percent of polydimethylsiloxane;
1.5 to 2 percent of anti-blocking agent.
In the invention, the total amount of all the components meets 100 percent.
The invention adopts ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer as heat sealing functional master batch.
Specifically, it may be selected from the group including but not limited to 3C30F, 5C30F of basel, FS5612 of TPC, KS359 of sumitomo, etc.
The invention adopts ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer to be blended and modified with polydimethylsiloxane.
In the invention, the preferred silicone polymer material is a smooth master batch, and the carrier of the silicone polymer material is PP.
Preferably, the number average molecular weight of the silicone-based polymer material is greater than 20 ten thousand. The effective content of silicone in the silicone-based high polymer material is preferably 10-15%.
Specifically, the silicone-based polymer material may be selected from, but not limited to, IL2580SC from surmann, comnstein SAB06554PPR, taiwan ken PSE99RP, and the like.
In the present invention, the anti-blocking agent is preferably an organic anti-blocking agent, and more preferably elastic beads. In some embodiments of the present invention, the anti-blocking agent is glass beads.
The particle size of the anti-blocking agent is preferably 2-4 μm, and more preferably 2-3 μm.
Specifically, the anti-blocking agent is selected from the group consisting of, but not limited to, Schleman's ABVT22SC, Japanese HIS04S, and the like.
Preferably, the antistatic agent is a polyamide antistatic agent.
In particular, the type of antistatic agent may be selected from the group including, but not limited to, Dochman's DS126T, Shelman's FASPA2955, Comstein's AT4023PP, and the like.
Preferably, the melt index of the homo-polypropylene is 3g/10min (230 ℃, 2.16 Kg).
The type of the homo-polypropylene is not particularly limited in the present invention, and may be selected from medium petrochemical polypropylene F03D, F300M, and the like.
Preferably, the petroleum resin is C3 petroleum resin or C5 petroleum resin.
According to the invention, preferably, the petroleum resin is blended with the homopolymerized polypropylene according to the proportion of 50% to prepare the stiffening master batch.
Specifically, the type of the petroleum resin can be selected from the group consisting of, but not limited to, FS600A, which is fine in yin, PPMA66, PPMA66H, ML8002, which is muron, HL8139, which is symplocos in hainan, and the like.
Preferably, the upper layer further comprises the following raw materials:
blending maleic anhydride with modified master batch.
The content of the maleic anhydride blending modified master batch is preferably 10-20%.
Wherein, in the blending modified master batch, the content of the maleic anhydride is preferably 10-20%, and more preferably 15%.
Preferably, the raw materials of the lower layer further include:
blending maleic anhydride with modified master batch.
The content of the maleic anhydride blending modified master batch is preferably 10-20%.
Wherein, in the blending modified master batch, the content of the maleic anhydride is preferably 10-20%, and more preferably 15%.
In the invention, the master batch refers to an ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat-sealing functional master batch.
The addition of the maleic anhydride blending modified master batch is beneficial to improving the compatibility of the polydimethylsiloxane and other components and simultaneously is beneficial to improving the binding force of the anti-blocking agent and the film surface layer.
In the invention, the thickness of the upper layer of the ultrahigh wear-resistant BOPP film is preferably 0.5-1.0 μm, and more preferably 0.5 μm.
Preferably, the thickness of the ultrahigh wear-resistant BOPP film intermediate layer is 16.0-48.8 microns.
In the invention, the thickness of the lower layer of the ultrahigh wear-resistant BOPP film is preferably 0.7-1.0 μm.
The total thickness of the ultrahigh wear-resistant BOPP film is preferably 18-50 microns.
According to the invention, the wear-resisting property of the prepared BOPP film is optimal under the condition that the silicone high polymer material, the polydimethylsiloxane and the elastic anti-adhesion agent with the specific particle size are used in a matching manner.
In the invention, the polydimethylsiloxane can be blended and modified by taking an ethylene-propylene-butadiene terpolymer or an ethylene-propylene binary copolymer as a carrier, wherein the effective content of the polydimethylsiloxane is preferably 15-30%, and more preferably 20%.
Meanwhile, the thickness of the upper layer film is controlled, preferably 0.5 mu m, so that the heat sealing strength is guaranteed, and the wear resistance is optimal.
The contents of the present invention are mass contents unless otherwise specified.
According to the invention, through blending modification of polydimethylsiloxane and ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer, the flexibility of a molecular chain is improved, the wear resistance of the BOPP film is greatly improved, and the wear resistance is less than 0.2% as measured by GB T31727-2015 transparent film abrasion degree test method.
The invention provides a preparation method of the ultrahigh wear-resistant BOPP film, which comprises the following steps:
A) mixing the raw materials of the upper layer, the middle layer and the lower layer respectively, flowing into respective extruders, converging in a die head and then flowing out;
B) and cooling the resin flowing out of the extruder die head into a sheet, and then sequentially carrying out longitudinal stretching, transverse stretching and heat setting to obtain the ultrahigh wear-resistant BOPP film.
Specifically, the raw materials of the upper layer, the middle layer and the lower layer are mixed respectively and flow into an upper layer extruder, a middle layer extruder and a lower layer extruder respectively;
the temperature of the upper layer extruder is preferably 180-240 ℃;
the temperature of the middle layer extruder is preferably 235-260 ℃;
the temperature of the lower layer extruder is preferably 180 ℃ to 230 ℃.
And then cooling the resin flowing out of the extruder die head into a sheet, wherein the cooling temperature is 18-32 ℃. This step is denoted b 1.
Preferably, the sheet is cooled by a sheet casting machine.
Then preheating the cooled sheet at 105-120 ℃, longitudinally stretching at 68-100 ℃, and heat setting at 72-120 ℃, wherein the stretching ratio is 450-620%. This step is denoted b 2.
Then preheating the longitudinally stretched sheet at 168-178 ℃, transversely stretching the sheet at 148-165 ℃, and performing heat setting at 105-165 ℃ with the stretching ratio of 800-1000%. This step is denoted b 3.
The molecular structure of the polymer has a great influence on the coefficient of friction and the wear resistance of the polymer. Linear polymer materials (such as polypropylene) have large molecular chain sizes, and the polymer material structure is mainly characterized by macromolecules consisting of rotatable rigid chain segments, which provides great flexibility for polymers. Another characteristic of a polymer molecular chain is that there is a strong chemical force linking the internal atoms of the molecular chain, while there is another much smaller intermolecular force linking adjacent molecular chains. The structural characteristics of the polymer friction material enable the polymer friction material to have great influence and regulation effect on the tribological behavior of the polymer. Polymers having a smooth, regular molecular structure generally can have a low coefficient of friction. Because the entanglement acting force between polymer molecular chains with higher molecular structure symmetry is small, in the sliding friction process, the flexible high molecular polymer containing linear molecular chain segments has lower shearing strength than the nonlinear and rigid high molecular polymer containing macromolecular side groups, and is easy to shear and slide, thereby showing low friction coefficient. The abrasion of the high molecular material is a process that molecular chain segment fragments move under the action of shearing force and are separated from the body to be transferred to the dual surface, the flexible and smooth molecular chain segments move easily, and the abrasion is correspondingly high. Compared with rigid polymers containing bulky side groups and irregular structures, linear polymers with flexible molecular chains are more easily oriented in the direction of traction force under the action of traction force, and the oriented structure influences the tribological properties of the polymers. The flexible molecular chain with the molecular structure symmetry degree is easy to generate friction induced orientation, the shearing force is small, and the friction coefficient is low in the orientation sliding process.
According to the invention, through the selection of raw materials, high surface tension and antistatic effect can be obtained without corona treatment in the preparation process step.
Compared with the prior art, the invention provides the ultrahigh wear-resistant BOPP film which sequentially consists of an upper layer, a middle layer and a lower layer from top to bottom; the upper layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer heat-sealing functional master batch, polydimethylsiloxane, silicone high polymer material and anti-blocking agent; the middle layer is formed by blending and extruding homopolymerized polypropylene and an antistatic agent or homopolymerized polypropylene, petroleum resin and the antistatic agent; the lower layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat-sealing functional master batch, polydimethylsiloxane and anti-blocking agent. According to the invention, the auxiliary agent with a high-symmetry flexible molecular chain structure is added on the surface layer of the BOPP cigarette film, so that the shearing force during the surface friction of the cigarette film is reduced, the lubricating effect is increased, the surface tension is reduced, the lower friction coefficient is realized, and the wear resistance of the film is improved under the condition of ensuring the lower precipitation performance of the auxiliary agent. The wear resistance can reach less than or equal to 0.2 percent without adding inorganic nano-substances, and the appearance and the optical performance of the film are not negatively influenced. On the premise of meeting the requirements of BOPP cigarette packaging film products on all cigarette packaging machine types, the wear resistance of the cigarette film is enhanced, so that scratches generated in the packaging process and in the logistics link of the cigarette film are reduced, the original design effect of the cigarette package is kept, the purchasing desire of consumers is enhanced, and the value of the cigarette product is ensured to be embodied in the appearance vision of the cigarette product.
Detailed Description
In order to further illustrate the present invention, the ultra-high abrasion-resistant BOPP film and the preparation method thereof provided by the present invention are described in detail below with reference to examples.
In the following examples, the silicone-based polymer is selected from SAB06554PPR produced by Constantol;
the anti-blocking agent is selected from HIS04S produced in Japan;
the antistatic agent is selected from DS126T manufactured by Beijing degree.
Example 1
The upper layer is 0.6 μm thick and is prepared from the following raw materials in percentage by weight: 76% of ethylene-propylene binary copolymer heat-sealing functional master batch, 12% of silicone macromolecules, 10% of polydimethylsiloxane and 2% of anti-blocking agent; the thickness of the middle layer is 16.6 μm, and the middle layer is prepared from the following raw materials in percentage by weight: 78% of homopolymerized polypropylene, 20% of petroleum resin and 2% of antistatic agent; the thickness of the lower layer is 0.8 μm, and the lower layer is prepared from the following raw materials in percentage by weight: 93% of ethylene-propylene-butadiene terpolymer, 5% of polydimethylsiloxane and 2% of antiblocking agent. The total thickness was 18 μm.
The manufacturing method of the ultrahigh wear-resistant BOPP film comprises the following steps:
(1) ingredients
The upper layer, the middle layer and the lower layer are respectively mixed according to the raw materials with the weight ratio, and the materials can be mixed manually or by equipment.
(2) Extrusion
The three layers of raw materials flow into respective extruders after being mixed respectively, and are converged and flow out at a die head after being extruded, the temperature of the upper layer extruder is 220 ℃, the temperature of the middle layer extruder is 245 ℃, and the temperature of the lower layer extruder is 215 ℃.
(3) Casting sheet
And cooling the resin flowing out of the die head into a sheet by a sheet casting machine, wherein the cooling temperature is 22 ℃.
(4) Longitudinal stretching
Preheating the sheet at 108 ℃, and then longitudinally stretching the sheet at a certain speed to longitudinally orient polymer molecules, wherein the stretching temperature is 70 ℃, the setting temperature is 100 ℃, and the stretching ratio is 600%.
(5) Stretching in transverse direction
Preheating the longitudinally stretched sheet at 172 ℃, and then transversely stretching the sheet in a stretching region with a certain expansion angle through a set chain guide rail to ensure that polymer molecules are transversely oriented, wherein the stretching temperature is 154 ℃, the setting temperature is 125 ℃, and the stretching ratio is 850%.
(6) Rolling-up device
The film is flattened by a flattening roller in a traction area and is finally wound by a winding machine.
Example 2
The upper layer is 0.5 μm thick and is prepared from the following raw materials in percentage by weight: 74% of ethylene-propylene binary copolymer heat-sealing functional master batch, 14% of silicone macromolecules, 10% of polydimethylsiloxane and 2% of anti-blocking agent; the thickness of the middle layer is 20.7 μm, and the middle layer is prepared from the following raw materials in percentage by weight: 73% of homopolymerized polypropylene, 15% of petroleum resin and 2% of antistatic agent; the thickness of the lower layer is 0.8 μm, and the lower layer is prepared from the following raw materials in percentage by weight: 98% of ethylene-propylene-butadiene terpolymer and 2% of antiblocking agent. The total thickness was 22 μm.
The manufacturing method of the ultrahigh wear-resistant BOPP film comprises the following steps:
(1) ingredients
The upper layer, the middle layer and the lower layer are respectively mixed according to the raw materials with the weight ratio, and the materials can be mixed manually or by equipment.
(2) Extrusion
The three layers of raw materials flow into respective extruders after being mixed respectively, and are converged and flow out at a die head after being extruded, the temperature of the upper layer extruder is 225 ℃, the temperature of the middle layer extruder is 250 ℃, and the temperature of the lower layer extruder is 210 ℃.
(3) Casting sheet
And cooling the resin flowing out of the die head into a sheet by a sheet casting machine, wherein the cooling temperature is 20 ℃.
(4) Longitudinal stretching
Preheating a sheet at 112 ℃, and longitudinally stretching the sheet at a certain speed to longitudinally orient polymer molecules, wherein the stretching temperature is 70 ℃, the setting temperature is 100 ℃, and the stretching ratio is 580%.
(5) Stretching in transverse direction
Preheating the longitudinally stretched sheet at 175 ℃, and then transversely stretching the sheet in a stretching region with a certain expansion angle through a set chain guide rail to ensure that polymer molecules are transversely oriented, wherein the stretching temperature is 156 ℃, the setting temperature is 130 ℃, and the stretching ratio is 880%.
(6) Rolling-up device
The film is flattened in the traction area through a flattening roller and is finally wound through a winding machine.
Example 3
The upper layer is 0.7 μm thick and is prepared from the following raw materials in percentage by weight: 78% of ethylene-propylene binary copolymer heat-sealing functional master batch, 10% of silicone macromolecules, 10% of polydimethylsiloxane and 2% of anti-blocking agent; the thickness of the middle layer is 38.5 μm, and the middle layer is prepared from the following raw materials in percentage by weight: 67% of homopolymerized polypropylene, 30% of petroleum resin and 3% of antistatic agent; the thickness of the lower layer is 0.8 μm, and the lower layer is prepared from the following raw materials in percentage by weight: 96% of ethylene-propylene-butadiene terpolymer, 2% of polydimethylsiloxane and 2% of antiblocking agent. The total thickness was 40 μm.
The manufacturing method of the ultrahigh wear-resistant BOPP film comprises the following steps:
(1) ingredients
The upper layer, the middle layer and the lower layer are respectively mixed according to the raw materials with the weight ratio, and the materials can be mixed manually or by equipment.
(2) Extrusion
The three layers of raw materials flow into respective extruders after being mixed respectively, and are converged and flow out at a die head after being extruded, the temperature of the upper layer extruder is 220 ℃, the temperature of the middle layer extruder is 240 ℃, and the temperature of the lower layer extruder is 215 ℃.
(3) Casting sheet
And cooling the resin flowing out of the die head into a sheet by a sheet casting machine, wherein the cooling temperature is 18 ℃.
(4) Longitudinal stretching
Preheating the sheet at 115 ℃, and then longitudinally stretching the sheet at a certain speed to longitudinally orient polymer molecules, wherein the stretching temperature is 80 ℃, the setting temperature is 95 ℃, and the stretching ratio is 560%.
(5) Stretching in transverse direction
Preheating the longitudinally stretched sheet at 176 ℃, and transversely stretching the sheet in a stretching region with a certain expansion angle through a set chain guide rail to ensure that polymer molecules are transversely oriented, wherein the stretching temperature is 160 ℃, the setting temperature is 140 ℃, and the stretching ratio is 860%.
(6) Rolling-up device
The film is flattened in the traction area through a flattening roller and is finally wound through a winding machine.
Example 4
The upper layer is 0.5 μm thick and is prepared from the following raw materials in percentage by weight: 68% of ethylene-propylene bipolymer heat-sealing functional master batch, 10% of silicone macromolecules, 10% of polydimethylsiloxane, 10% of maleic anhydride blending modified master batch (wherein the content of maleic anhydride is 15%), and 2% of an anti-blocking agent; the thickness of the middle layer is 23.8 μm, and the middle layer is prepared from the following raw materials in percentage by weight: 67% of homopolymerized polypropylene, 30% of petroleum resin and 3% of antistatic agent; the thickness of the lower layer is 0.7 μm, and the lower layer is prepared from the following raw materials in percentage by weight: 96% of ethylene-propylene-butadiene terpolymer, 2% of polydimethylsiloxane and 2% of antiblocking agent. The total thickness was 25 μm.
The manufacturing method of the ultrahigh wear-resistant BOPP film comprises the following steps:
(1) ingredients
The upper layer, the middle layer and the lower layer are respectively mixed according to the raw materials with the weight ratio, and the materials can be mixed manually or by equipment.
(2) Extrusion
The three layers of raw materials flow into respective extruders after being mixed respectively, and are converged and flow out at a die head after being extruded, the temperature of the upper layer extruder is 220 ℃, the temperature of the middle layer extruder is 240 ℃, and the temperature of the lower layer extruder is 215 ℃.
(3) Casting sheet
And cooling the resin flowing out of the die head into a sheet by a sheet casting machine, wherein the cooling temperature is 18 ℃.
(4) Longitudinal stretching
Preheating the sheet at 115 ℃, and then longitudinally stretching the sheet at a certain speed to longitudinally orient polymer molecules, wherein the stretching temperature is 80 ℃, the setting temperature is 95 ℃, and the stretching ratio is 560%.
(5) Stretching in transverse direction
Preheating the longitudinally stretched sheet at 176 ℃, and transversely stretching the sheet in a stretching region with a certain expansion angle through a set chain guide rail to ensure that polymer molecules are transversely oriented, wherein the stretching temperature is 160 ℃, the setting temperature is 140 ℃, and the stretching ratio is 860%.
(6) Rolling-up device
The film is flattened in the traction area through a flattening roller and is finally wound through a winding machine.
The ultra-high abrasion-resistant BOPP films prepared above were tested using GBT31727-2015 "transparent film graining degree test method", and the results are shown in table 1:
TABLE 1 BOPP film Performance test results
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. An ultrahigh wear-resistant BOPP film consists of an upper layer, a middle layer and a lower layer from top to bottom in sequence;
the upper layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene binary copolymer heat-sealing functional master batch, polydimethylsiloxane, silicone high polymer material and anti-blocking agent;
the middle layer is formed by blending and extruding homopolymerized polypropylene and an antistatic agent or homopolymerized polypropylene, petroleum resin and an antistatic agent;
the lower layer is formed by blending and extruding ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat-sealing functional master batch, polydimethylsiloxane and anti-blocking agent.
2. The ultra-high wear-resistant BOPP film as recited in claim 1, wherein the upper layer comprises the following raw materials by mass:
74 to 85.5 percent of ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat sealing functional master batch;
5 to 10 percent of polydimethylsiloxane;
8% -15% of silicone polymer material;
0.5 to 2 percent of anti-blocking agent;
the middle layer comprises the following raw materials:
61.5 to 98.5 percent of homopolymerized polypropylene;
0 to 35 percent of petroleum resin;
1.5 to 3.5 percent of antistatic agent;
the lower layer comprises the following raw materials:
88 to 94.5 percent of ethylene-propylene-butadiene terpolymer or ethylene-propylene bipolymer heat sealing functional master batch;
5 to 10 percent of polydimethylsiloxane;
0.5 to 2 percent of anti-blocking agent.
3. The ultra-high abrasion-resistant BOPP film according to claim 1, wherein the raw material of the upper layer further comprises:
blending maleic anhydride to modify the master batch;
wherein the content of the maleic anhydride is 10 to 20 percent;
the raw materials of the lower layer also comprise:
blending maleic anhydride to modify the master batch;
wherein the content of the maleic anhydride is 10 to 20 percent.
4. The ultra-high wear-resistant BOPP film according to claim 1, wherein the silicone-based polymer material is a smooth master batch, and the carrier thereof is PP;
the anti-blocking agent is elastic micro-beads;
the particle size of the glass beads is 2-4 microns.
5. The ultra-high abrasion-resistant BOPP film according to claim 1, wherein the antistatic agent is a polyamide antistatic agent.
6. The ultra-high abrasion-resistant BOPP film according to claim 1, wherein the petroleum resin is a C3 petroleum resin or a C5 petroleum resin.
7. The ultra-high abrasion-resistant BOPP film according to claim 1, wherein the thickness of the upper layer is 0.5 to 1.0 μm;
the thickness of the intermediate layer is 16.0-48.8 μm;
the thickness of the lower layer is 0.7-1.0 μm;
the total thickness of the ultrahigh wear-resistant BOPP film is 18-50 microns.
8. The method for preparing the ultra-high wear-resistant BOPP film as recited in any one of claims 1 to 7, comprising the following steps:
A) mixing the raw materials of the upper layer, the middle layer and the lower layer respectively, flowing into respective extruders, converging in a die head and then flowing out;
B) and cooling the resin flowing out of the extruder die head into a sheet, and then sequentially carrying out longitudinal stretching, transverse stretching and heat setting to obtain the ultrahigh wear-resistant BOPP film.
9. The preparation method according to claim 8, wherein the step a) is specifically:
mixing the raw materials of the upper layer, the middle layer and the lower layer respectively, and enabling the mixed raw materials to flow into an upper layer extruder, a middle layer extruder and a lower layer extruder respectively;
the temperature of the upper layer extruder is 180-240 ℃;
the temperature of the middle layer extruder is 235-260 ℃;
the temperature of the lower layer extruder is 180-230 ℃.
10. The preparation method according to claim 8, wherein the step B) is specifically:
b1) cooling the resin flowing out of the extruder die head into a sheet, wherein the cooling temperature is 18-32 ℃;
b2) preheating the cooled sheet at 105-120 ℃, longitudinally stretching at 68-100 ℃, and heat setting at 72-120 ℃, wherein the stretching ratio is 450-620%;
b3) preheating the longitudinally stretched sheet at 168-178 ℃, transversely stretching at 148-165 ℃, and heat setting at 105-165 ℃, wherein the stretching ratio is 800-1000%.
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| PCT/CN2021/086587 WO2022165985A1 (en) | 2021-02-04 | 2021-04-12 | Super wear-resistant bopp thin film and preparation method therefor |
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| SK9122000A3 (en) * | 2000-06-14 | 2002-01-07 | Chemosvit A S | Heat-shrinkable biaxially oriented polypropylene film for use as tobacco pack overwrap |
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| CN110356085B (en) * | 2019-07-11 | 2020-10-30 | 海南赛诺实业有限公司 | Three-layer co-extrusion strip-wrapped naked-wrapped polypropylene film and manufacturing method thereof |
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| US5508090A (en) * | 1993-04-01 | 1996-04-16 | Hoechst Aktiengesellschaft | Heat-sealable, oriented, multilayer polyolefin film, process for the production thereof, and the use thereof |
| CN102079154A (en) * | 2010-08-26 | 2011-06-01 | 湛江包装材料企业有限公司 | Nano wear-resisting BOPP (Biaxially-oriented Polypropylene) thin film for packing barrel cigarettes |
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