WO2020087849A1 - 高熔体强度聚丙烯薄膜组合物和薄膜及其应用 - Google Patents

高熔体强度聚丙烯薄膜组合物和薄膜及其应用 Download PDF

Info

Publication number
WO2020087849A1
WO2020087849A1 PCT/CN2019/079473 CN2019079473W WO2020087849A1 WO 2020087849 A1 WO2020087849 A1 WO 2020087849A1 CN 2019079473 W CN2019079473 W CN 2019079473W WO 2020087849 A1 WO2020087849 A1 WO 2020087849A1
Authority
WO
WIPO (PCT)
Prior art keywords
extruded layer
polypropylene
layer
melt strength
film
Prior art date
Application number
PCT/CN2019/079473
Other languages
English (en)
French (fr)
Inventor
韦丽明
梁雁扬
Original Assignee
上海若祎新材料科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海若祎新材料科技有限公司 filed Critical 上海若祎新材料科技有限公司
Priority to MYPI2021002368A priority Critical patent/MY197918A/en
Publication of WO2020087849A1 publication Critical patent/WO2020087849A1/zh

Links

Images

Classifications

    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/412—Transparent
    • 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
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the technical field of processing high-melt strength polypropylene films, and discloses a high-melt strength polypropylene film composition and films and applications thereof.
  • Biaxially stretched film, blown tube film, and cast film are common packaging materials with excellent performance, and are widely used in clothing, cosmetics, food, books, paper towels, industry, pharmaceuticals, electronic protection, coating (glue), etc. field.
  • China's total packaging film production capacity exceeded 10 million tons, and it is expected to increase at an average annual compound growth rate of 5% within five years.
  • thermal shrinkage rate is used to characterize the dimensional stability of the film under heating, that is, the degree of thermal deformation of the film, which can also reflect the temperature resistance of the film.
  • GB / T 21302 "Composite Films and Bags for Packaging” does not clearly specify the curling and shrinkage rates.
  • GB / T 4456 Polyethylene Blown Films for Packaging” and GB / T 27740 "Casting Polypropylene (CPP) Films ⁇ The size and test method of heat shrinkage rate are not clearly defined.
  • GB / T10003 “General Purpose Biaxially Stretched Polypropylene (BOPP) Film” makes clear provisions with reference to YC / T 266 “Packaging Film for Cigarettes”. The downstream processing companies usually choose three grades of 80 °C, 120 °C and 135 °C for testing the heat shrinkage temperature.
  • the macromolecules of the film are in a state of natural curl, and when heated, they produce a very small thermal shrinkage rate (thermal deformation rate).
  • thermal deformation rate polypropylene (PP) and polyethylene (PE) are semi-crystalline polymer materials.
  • PP polypropylene
  • PE polyethylene
  • the production process of biaxially stretched and blown tube foam film has experienced longitudinal stretching and transverse stretching.
  • the production width, speed, and heat shrinkage rate requirements Different stretch ratios are set; the cast film has different degrees of longitudinal stretching due to the position of the die and casting roll, and the speed difference between the rolls. Under the action of external force, the molecular chains are forced to stretch, and the macromolecules cannot slip with each other.
  • the molecular chains that are forcibly stretched are frozen when the shaped area is cooled.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, such as biaxially stretched film, blown tube bubble film, cast film, poor heat resistance, low dimensional stability, many appearance defects and precipitation of migration.
  • High melt strength polypropylene through blending method, column reactor method with long branched structure (electron beam irradiation, peroxide treatment, reactive extrusion) and internal reactor polymerization method (direct copolymerization, macromolecularization) ), Cross-linking method, improve the weight average molecular weight of polypropylene (PP) and widen the molecular weight distribution, so that it has a long-chain branched structure, this structural material can significantly improve the rheological properties of linear polypropylene materials, so that this class
  • the melt strength of polypropylene is generally 1.5-50 times that of ordinary polypropylene.
  • the long branched structure changes the strain softening characteristics of ordinary polypropylene and improves the defects of polypropylene during processing.
  • a high melt strength polypropylene film prepared by adding a high melt strength polypropylene composition, a biaxial stretching method, a blown film method, and a casting method has heat resistance, extremely high dimensional stability, Low thermal deformation rate, few appearance defects, no migration of precipitation, function and appearance meet the advantages of high-end electronic protection, flexible packaging batteries, printing compound, plating, coating (adhesive), advertising decoration and other market needs, and no need to modify the existing device.
  • the first aspect of the present invention provides a high melt strength polypropylene film composition, wherein the composition includes a first extruded layer, a second extruded layer and a third extruded layer , And at least the first extruded layer material or the third extruded layer material contains a non-migrating inorganic slip agent, wherein the non-migrating inorganic slip agent is prepared by blending and modifying Blend A
  • Blend A contains high melt strength polypropylene and an auxiliary agent
  • the auxiliary agent contains activated glass spheres, the activated glass spheres are silane coupling agent and hexafluorocarbon polymer surface
  • the glass solid sphere obtained after the treatment.
  • a polypropylene film made from the composition described above, wherein the polypropylene film includes a first extrusion layer, a second extrusion layer and a third extrusion sequentially stacked Layer, wherein the first extrusion layer is obtained by extrusion of the first extrusion layer, the second extrusion layer is obtained by extrusion of the second extrusion layer, and The third extruded layer is obtained by extruding the third extruded layer.
  • the third aspect of the present invention provides the application of the aforementioned polypropylene film in the fields of electronic protection, flexible packaging batteries, printed composites, plating, coating, or advertising decoration.
  • the present invention uses non-migrating inorganic slip agent and high melt strength polypropylene as components of the polypropylene film, which can greatly improve the heat resistance of the film, maintain dimensional stability, reduce thermal deformation rate, reduce Appearance flaws, no migration of precipitates, high transparency, and can be produced online on the existing biaxially stretched, blown tube bubble, cast film production line, without the need to modify existing equipment.
  • Example 1 is a SEM photograph of the surface of the film after rubbing the film prepared in Example 1 of the present invention
  • Example 2 is a SEM photograph of the film surface after rubbing the film prepared in Example 2 of the present invention.
  • Example 4 is a SEM photograph of the first extruded layer and the third extruded layer used to prepare the film in Example 1 of the present invention
  • Example 5 is a SEM photograph of the first extruded layer and the third extruded layer used to prepare the film in Example 2 of the present invention
  • FIG. 7 is a schematic view of the present invention using a two-way stretching method to prepare high melt strength polypropylene film
  • FIG. 8 is a schematic view of the present invention using a blown tube bubble method to prepare high melt strength polypropylene film
  • FIG. 9 is a schematic view of the present invention using a casting method to prepare high melt strength polypropylene film.
  • the first aspect of the present invention provides a high melt strength polypropylene film composition, wherein the composition includes a first extruded layer, a second extruded layer and a third extruded layer, and at least the The first extruded layer material or the third extruded layer material contains a non-migrating inorganic slip agent, wherein the non-migrating inorganic slip agent is a product prepared by blending and modifying Blend A, so
  • the blend A contains high melt strength polypropylene and an auxiliary agent, the auxiliary agent contains an activated glass sphere, the activated glass sphere is a glass solid sphere obtained by surface treatment of a silane coupling agent and a hexafluorocarbon polymer .
  • Blend modification specifically means that the components in Blend A are fed in proportion, melted and extruded in a screw extruder, cooled, and pelletized.
  • the average particle diameter of the activated glass sphere may be 2.5-3.5 ⁇ m, preferably 2.8-3.2 ⁇ m.
  • the hexafluorocarbon polymer is 1,1,2,3,3,3-hexafluoro-1-propene polymer
  • the bulk density is 0.6-1.0g / cm 3
  • the average particle size is less than or equal to 25
  • the volatile content is less than or equal to 1%.
  • the silane coupling agent is 3-aminopropyltriethoxysilane
  • the viscosity value measured at 25 ° C is 1.5-1.7cs, preferably 1.6cs
  • the density is 0.94-0.95g / cm 3 , preferably 0.946g / cm 3
  • the flash point (closed cup) is 96 °C, where, in the present invention, the closed cup flash point refers to heating the sample under specified conditions, when the sample reaches a certain temperature, try The mixture of the sample steam and the surrounding air flashes once it comes into contact with the flame, and the minimum temperature of the sample when flashing occurs.
  • the weight ratio of the content of the activated glass sphere, the hexafluorocarbon polymer, and the silane coupling agent is 1: (0.1-0.5): (0.01-0.5), preferably 1: (0.2 -0.4): (0.01-0.4), more preferably 1: 0.25: 0.05.
  • the additive may be self-made or commercially available.
  • it may be purchased from Shanghai Ruoyi New Material Technology Co., Ltd. Model MB3050PB non-migrating inorganic slip additive, in which Contains the activated glass sphere defined in the present invention, the activated glass sphere is a glass solid sphere obtained by surface treatment of a silane coupling agent and a hexafluorocarbon polymer, wherein the silane coupling agent is 3-aminopropyl Triethoxysilane, the hexafluorocarbon polymer is 1,1,2,3,3,3-hexafluoro-1-propene polymer, and the average particle size of the activated glass sphere is 2.5-3.5 ⁇ m; And in the surface treatment process, the weight ratio of the activated glass sphere, the hexafluorocarbon polymer, and the silane coupling agent is 1: (0.1-0.5): (0.01-0.5).
  • the melt flow rate of the high melt strength polypropylene at 230 ° C under a load of 2.16 kg is 1.7-2.5g / 10min
  • the density is 0.9-0.915g / cm 3
  • the isotactic index is greater than or equal to 95%
  • the tensile modulus of elasticity is greater than or equal to 1000 MPa.
  • “greater than or equal to” means both “greater than” and “equal to”, for example, an isotactic index greater than or equal to 95% means that the isotactic index All values of 95% and greater than 95%; tensile modulus of elasticity greater than or equal to 1000 MPa means that the tensile modulus of elasticity can be all values of 1000 MPa and greater than 1000 MPa.
  • the high melt strength polypropylene has a melt flow rate of 1.7-2.3g / 10min at 230 ° C under a load of 2.16kg, a density of 0.905-0.91g / cm 3 , and an isotactic index of 95-97% ,
  • the tensile modulus of elasticity is 1000-1500MPa; preferably, the melt flow rate of the high melt strength polypropylene at 230 ° C under a load of 2.16kg is 1.7-2.2g / 10min, and the density is 0.905-0.91g / cm 3 , the isotacticity is 96%, and the tensile elastic modulus is 1450 MPa.
  • the high-melt-strength polypropylene can be commercially obtained from the manufacturer of Zhenhai Refinery and Chemicals Branch of China Petroleum & Chemical Corporation, for example, HMS20Z and E02ES, wherein
  • the body flow rate is 2.2g / 10min, the density is 0.905g / cm 3 , the refractive index is 1.49, the isotacticity is 96.6%, the tensile elastic modulus is 1410MPa; the melt flow of E02ES at 230 °C under a load of 2.16kg
  • the rate is 1.7 g / 10 min, the density is 0.905 g / cm 3 , the refractive index is 1.50, and the tensile elastic modulus is 1020 MPa.
  • the content of the auxiliary agent is 5-20% by weight, and the content of the high melt strength polypropylene is 80-95% by weight.
  • the first extruded layer material contains high melt strength polypropylene, non-migrating inorganic slip agent and with or without homopolypropylene or copolymer polypropylene, and the first extruded layer material
  • the total weight is based on the content of the high melt strength polypropylene is 20-99.5% by weight, the content of the non-migrating inorganic slip agent is 0.5-30% by weight, the content of homopolypropylene or copolymer polypropylene 0-50% by weight; preferably, the first extruded layer contains high melt strength polypropylene and non-migrating inorganic slip agent, and based on the total weight of the first extruded layer as a benchmark,
  • the content of the high melt strength polypropylene is 20-99.5 wt%, and the content of the non-migrating inorganic slip agent is 0.5-80 wt%; more preferably, the total weight of the first extruded layer is As a benchmark, the content of the
  • the second extruded layer contains high melt strength polypropylene and with or without homopolypropylene or copolymer polypropylene, and based on the total weight of the second extruded layer, the high melt
  • the content of strength polypropylene is 50-100% by weight, and the content of homopolypropylene or copolymer polypropylene is 0-50% by weight.
  • the third extruded layer material contains high melt strength polypropylene, non-migrating inorganic slip agent and with or without homopolypropylene or copolymer polypropylene, and the total weight of the third extruded layer material is As a benchmark, the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migrating inorganic slip agent is 0.5-30 wt%, and the content of the homopolypropylene or copolymerized polypropylene is 0-50 % By weight; preferably, the third extruded layer material contains high melt strength polypropylene and non-migrating inorganic slip agent, and based on the total weight of the third extruded layer material, the high melt The content of strength polypropylene is 20-97.5 wt%, and the content of the non-migrating inorganic slip agent is 2.5-30 wt%.
  • the inventors of the present invention have found through a large number of scientific experiments that a non-migrating inorganic slip agent is added, and the activated glass spheres contained therein have a good binding force with polypropylene, and the surface of the spheres provides suitable slip properties. Under the appropriate film production process conditions, the film friction coefficient can be reduced, it is not easy to fall off, and it does not pollute the packaged object; the activated glass sphere has a refractive index close to that of polypropylene, and the film has high transparency and low haze.
  • the inventors of the present invention have found through a large number of scientific experiments that a non-migrating inorganic slip agent is added, and the hexafluorocarbon polymer contained in the polypropylene matrix is a small liquid incompatible with the matrix
  • the shape of the drop exists, and the die and the metal die wall have a strong affinity and low surface energy, forming a kinetic coating to reduce the flow damping of the polypropylene melt, while improving the film gloss and reducing haze.
  • a second aspect of the present invention provides a polypropylene film of the aforementioned composition, wherein the polypropylene film includes a first extrusion layer, a second extrusion layer, and a third extrusion layer that are sequentially stacked, wherein , The first extrusion layer is obtained by extruding the first extrusion layer, the second extrusion layer is obtained by extruding the second extrusion layer, and the third The extruded layer is obtained by extruding the third extruded layer.
  • the thickness of the first extruded layer is 0.5-45 ⁇ m
  • the thickness of the second extruded layer is 8-60 ⁇ m
  • the thickness of the third extruded layer is 0.5-45 ⁇ m
  • the thickness of the polypropylene film is 9-100 ⁇ m, preferably 12-85 ⁇ m, more preferably 25-60 ⁇ m.
  • the polypropylene film is produced by co-extrusion, biaxial stretching, blown tube, or casting.
  • the method of preparing the high melt strength polypropylene film by the bidirectional stretching method can refer to the schematic diagram of the preparation process shown in FIG. 7:
  • the content of the high melt strength polypropylene is 20-99.5 wt%, and the content of the non-migrating inorganic slip agent is 0.5-30 wt%, both
  • the content of polypropylene or copolymer polypropylene is 0-50% by weight;
  • the content of the high melt strength polypropylene is 50-100% by weight, and the content of the homopolypropylene or copolymerized polypropylene is 0-50% by weight;
  • the content of the high melt strength polypropylene is 20-100% by weight, and the content of the non-migrating inorganic slip agent is 0.5-30% by weight.
  • the content of polypropylene or copolymer polypropylene is 0-50% by weight.
  • Prefabricated ingredients Put the components of the first extruded layer, second extruded layer and third extruded layer into the corresponding low speed mixers according to the weight percentages mentioned above, and premix for 30 minutes;
  • the pre-mixed first extruded layer, second extruded layer, and third extruded layer are suctioned into the barrel of the three-layer extruder under negative pressure, through the first extrusion
  • the thickness of the first extrusion layer, the second extrusion layer, and the third extrusion layer is determined by the amount of the layer material, the second extrusion layer material, and the third extrusion layer material.
  • Plastic extrusion multiple extruders are used to extrude the resins of the first extrusion layer, the second extrusion layer, and the third extrusion layer separately, and the molten resin is rationally layered by a distributor. Among them:
  • the components of the first extruded layer and the third extruded layer are in a single screw extruder, and the components of the second extruded layer are melt extruded in a twin screw extruder at a temperature of 210-245 ° C;
  • Defect-resistant melt filtration mesh filters with mesh numbers of 80, 150, 300, 150, and 80 are stacked in sequence, arranged in a column shape, and the melt squeezes the outermost filter from the middle mandrel;
  • Cooling crystallization and sheet setting the extruder extruded the melt through the hanger die head, air knife air cooling, chilling roller cooling, sink water bath cooling into a thick piece with fine spherical crystal, die lip gap 0.5mm, laser
  • the water temperature of the cold roller is controlled at 15-35 °C, and the water temperature difference between the inlet and outlet is controlled at ⁇ 2 °C; the water temperature of the cooling water tank is controlled at 25-35 °C;
  • Longitudinal stretching and longitudinal stretching setting two-stage stretching, the total stretching ratio is controlled between 4.0-5.0; longitudinal stretching setting area: temperature is controlled at 120-150 °C;
  • Transverse stretching and transverse stretching setting the transverse stretching ratio is between 7-11; transverse stretching setting area: the temperature is controlled at 170-190 °C;
  • Traction thickness measurement: measure the total thickness of the polypropylene film.
  • Corona treatment can be selected according to the use of the film or not.
  • the film is corona treated by a high-frequency electronic discharger, and the surface tension value of the lower line should reach 40mN / m; the film is wound after being shaped.
  • the winding device is automatically controlled by the winding surface tension control device to achieve the best winding effect; the production line speed: 200 ⁇ 500m / min.
  • Aging, slitting and rewinding In a temperature environment of 25 ⁇ 5 °C and 60% RH, it is allowed to stand for 1-2 days to play a role in further stabilizing the size and performance; cutting out the corresponding width specifications of the finished product.
  • the method of preparing the high melt strength polypropylene film by the blown tube bubble method can refer to the schematic diagram of the preparation process shown in FIG. 8:
  • the content of the high melt strength polypropylene is 20-99.5 wt%, and the content of the non-migrating inorganic slip agent is 0.5-30 wt%, both
  • the content of polypropylene or copolymer polypropylene is 0-50% by weight;
  • the content of the high melt strength polypropylene is 50-100% by weight, and the content of the homopolypropylene or copolymerized polypropylene is 0-50% by weight;
  • the content of the high melt strength polypropylene is 20-100% by weight, and the content of the non-migrating inorganic slip agent is 0.5-30% by weight.
  • the content of polypropylene or copolymer polypropylene is 0-50% by weight.
  • Prefabricated ingredients Put the components of the first extruded layer, second extruded layer and third extruded layer into the corresponding low speed mixers according to the weight percentages mentioned above, and premix for 30 minutes;
  • the pre-mixed first extruded layer, second extruded layer, and third extruded layer are suctioned into the barrel of the three-layer extruder under negative pressure, through the first extrusion
  • the thickness of the first extrusion layer, the second extrusion layer, and the third extrusion layer is determined by the amount of the layer material, the second extrusion layer material, and the third extrusion layer material.
  • Plastic extrusion Multiple extruders are used to extrude the resins of the first extrusion layer, the second extrusion layer, and the third extrusion layer separately.
  • the molten resin is rationally layered through independent channels in the die cavity, among which:
  • the components of the first extrusion layer, the second extrusion layer, and the third extrusion layer are melt extruded in a single screw extruder at a temperature of 160-230 ° C;
  • Defect-resistant melt filtration mesh number 100, 150, 150, 80 are stacked in sequence, porous plate filter, the melt squeezes the outermost filter from the inner layer;
  • Transverse inflation stretching the transverse stretching ratio is between 1.2-3.5; transverse stretching setting area: the temperature is controlled at 160-230 °C;
  • Cooling crystallization and sheet setting the extruder extruded the melt through the die head, air cooling or wind cooling ring into the cold air cooling, setting.
  • the cold air passing through the air cooling ring is controlled at 20 °C ⁇ 1 °C;
  • Thickness measurement corona: The total thickness of the polypropylene film is measured. Corona treatment can be selected according to the application of the film or not. Corona treatment of the film by high-frequency electronic discharger, the surface tension value of the lower line should reach 40mN / m;
  • the film is wound after setting.
  • the winding device is automatically controlled by the winding surface tension control device to achieve the best winding effect; production line speed: 50-150m / min.
  • Aging, slitting and rewinding In a temperature environment of 25 ⁇ 5 °C and 60% RH, it is allowed to stand for 1-2 days to play a role in further stabilizing the size and performance; cutting out the corresponding width specifications of the finished product.
  • the content of the high melt strength polypropylene is 20-99.5 wt%, and the content of the non-migrating inorganic slip agent is 0.5-30 wt%, both Polypropylene or copolymer polypropylene content is 0-50% by weight;
  • the content of the high melt strength polypropylene is 50-100% by weight, and the content of the homopolypropylene or copolymerized polypropylene is 0-50% by weight;
  • the third extruded layer contains high melt strength polypropylene and non-migrating inorganic slip agent, and based on the total weight of the third extruded layer, the content of the high melt strength polypropylene is 20-100% by weight, the content of the non-migrating inorganic slip agent is 0.5-30% by weight, and the content of homopolypropylene or copolymerized polypropylene is 0-50% by weight.
  • Prefabricated ingredients Put the components of the first extruded layer, second extruded layer and third extruded layer into the corresponding low speed mixers according to the weight percentages mentioned above, and premix for 30 minutes;
  • the pre-mixed first extruded layer, second extruded layer, and third extruded layer are suctioned into the barrel of the three-layer extruder under negative pressure, through the first extrusion
  • the thickness of the first extrusion layer, the second extrusion layer, and the third extrusion layer is determined by the amount of the layer material, the second extrusion layer material, and the third extrusion layer material.
  • Plastic extrusion multiple extruders are used to extrude the resins of the first extrusion layer, the second extrusion layer, and the third extrusion layer separately, and the molten resin is rationally layered by a distributor. Among them:
  • the components of the first extrusion layer, the second extrusion layer, and the third extrusion layer are melt extruded in a single screw extruder at a temperature of 195-260 ° C;
  • Defect-resistant melt filtration mesh filters with mesh numbers of 80, 150, 300, 150, and 80 are stacked in sequence, arranged in a column shape, and the melt squeezes the outermost filter from the middle mandrel;
  • Cooling crystallization and sheet shaping the extruder extruded the melt through the hanger die or T-die die, air knife air cooling, chilling roller cooling into a thick piece with fine spherical crystal, die lip gap 0.5mm,
  • the water temperature of the chill roll is controlled at 15-35 °C, and the temperature difference between the inlet and outlet is controlled at ⁇ 2 °C;
  • Thickness measurement The total thickness of the polypropylene film is measured.
  • Heating setting, corona hot water roller setting, water temperature controlled at 35-55 °C, water temperature difference between inlet and outlet is controlled at ⁇ 2 °C; corona treatment can be selected or not according to film application. Corona treatment of the film by high-frequency electronic discharger, the surface tension value of the lower line should reach 40mN / m;
  • Cooling and setting cooling and setting by cooling water roller, the water temperature is controlled at 20-35 °C, and the temperature difference between the inlet and outlet is controlled at ⁇ 2 °C;
  • Winding The film is wound after setting.
  • the winding device is automatically controlled by the winding surface tension control device to achieve the best winding effect; the production line speed: 25-250m / min.
  • Aging, slitting and rewinding In a temperature environment of 25 ⁇ 5 °C and 60% RH, it is allowed to stand for 1-2 days to play a role in further stabilizing the size and performance; cutting out the corresponding width specifications of the finished product.
  • the third aspect of the present invention provides an application of the aforementioned polypropylene film in the fields of electronic protection, flexible packaging batteries, printed composites, plating, coating, or advertising decoration.
  • the coating can also be called glue.
  • the inventor of the present invention has unexpectedly discovered that a high-melt strength polypropylene is added to the biaxially stretched film, blown tube film, and cast film processing technology, and the film has high temperature resistance under specific process conditions.
  • the hexafluorocarbon polymer contained in the polypropylene matrix exists in the form of small droplets that are incompatible with the matrix, and has a strong affinity with the metal die wall and
  • Thermal shrinkage rate test The standard environment for sample condition adjustment and test is conducted according to GB / T 2918.
  • the test environment conditions are temperature 23 °C ⁇ 2 °C, relative humidity 50% ⁇ 1%, and under this condition the sample Place and process for 8hr; test and compare the heat shrinkage of the film at 80 °C, 120 °C, 135 °C according to the 5.7 oven method of GB / T 10003 "Bidirectional Stretched Polypropylene (BOPP) Film".
  • the specific method is: place a 100mm ⁇ 100mm square sample on a stainless steel plate in a constant temperature oven at a specific temperature of °C ⁇ 3 °C, heat for 2min, take out the sample, cool it to the temperature of the test environment, and measure the vertical and horizontal dimensions Changes with dimensions before heating.
  • Test of friction coefficient of hot slip according to GB / T 10006 "Method for Measuring the Coefficient of Friction of Plastic Films and Sheets", compare the data of friction coefficient of hot slip at 80 °C.
  • the specific method is: the constant temperature of the metal plate of the friction coefficient meter is heated to 80 °C, the film is placed on the instrument, the friction coefficient between the film and the heated metal is tested, and the smoothness of the film sliding on the guide roller after simulating the friction heat of the high-speed packaging machine is simulated status.
  • This example is to illustrate the preparation of a high melt strength polypropylene film by a two-way stretching method.
  • the film is prepared according to the schematic diagram of the preparation process of the high melt strength polypropylene film shown in FIG.
  • the first extruded layer material 97.5% by weight of HMS20Z, 2.5% by weight of non-migrating inorganic slip agent MB3050PB;
  • Second extruded layer material 100% by weight of HMS20Z;
  • the third extruded layer material 98% by weight of HMS20Z, 2% by weight of non-migrating inorganic slip agent MB3050PB.
  • Prefabricated ingredients Put the components of the first extruded layer, second extruded layer and third extruded layer into the corresponding low speed mixers according to the weight percentages mentioned above, and premix for 30 minutes;
  • the pre-mixed first extruded layer, second extruded layer, and third extruded layer are suctioned into the barrel of the three-layer extruder under negative pressure, through the first extrusion
  • the thickness of the first extrusion layer, the second extrusion layer, and the third extrusion layer is determined by the amount of the layer material, the second extrusion layer material, and the third extrusion layer material.
  • Plastic extrusion multiple extruders are used to extrude the resins of the first extrusion layer, the second extrusion layer, and the third extrusion layer separately, and the molten resin is rationally layered by a distributor. Among them:
  • the components of the first extruded layer and the third extruded layer are in a single-screw extruder, and the components of the second extruded layer are melt-extruded in a twin-screw extruder at a temperature of 235 ° C;
  • Defect-resistant melt filtration mesh filters with mesh numbers of 80, 150, 300, 150, and 80 are stacked in sequence, arranged in a column shape, and the melt squeezes the outermost filter from the middle mandrel;
  • Cooling crystallization and sheet setting the extruder extruded the melt through the hanger die head, air knife air cooling, chilling roller cooling, sink water bath cooling into a thick piece with fine spherical crystal, die lip gap 0.5mm, laser
  • the water temperature of the cold roller is controlled at 25 °C, and the temperature difference between the inlet and outlet is controlled at ⁇ 2 °C; the temperature of the cooling water tank is controlled at 25 °C;
  • Longitudinal stretching and longitudinal stretching setting two-stage stretching, the total stretching ratio is controlled between 4.8; longitudinal stretching setting area: temperature is controlled at 148 °C;
  • Horizontal stretching and transverse stretching setting transverse stretching ratio between 10; transverse stretching setting area: temperature control at 190 °C;
  • Traction thickness measurement: measure the total thickness of the polypropylene film.
  • Corona treatment can be selected according to the use of the film or not.
  • the film is corona treated by a high-frequency electronic discharger, and the surface tension value of the lower line should reach 40mN / m; the film is wound after being shaped.
  • the winding device is automatically controlled by the winding surface tension control device to achieve the best winding effect; production line speed: 480m / min.
  • the total thickness of the high-melt strength polypropylene film prepared by the bidirectional stretching method was 48 ⁇ m, and the thickness of the first extruded layer was 1 ⁇ m, the thickness of the second extruded layer was 46 ⁇ m, and the third extruded layer The thickness is 1 ⁇ m;
  • FIG. 1 is an SEM photograph of the surface of the film after rubbing the film prepared in Example 1 of the present invention.
  • Example 4 is the first extrusion used for preparing the film in Example 1 of the present invention SEM photographs of the layer and the third extruded layer, where the first extruded layer: no agglomeration point, no crystal point; the third extruded layer: no agglomeration point, no crystal point.
  • the biaxially oriented high-melt-strength polypropylene film was prepared in the same manner as in Example 1, except that the preparation was different, that is, HMS20Z was replaced with E02ES, specifically:
  • First extruded layer material 97.5% by weight E02ES, 2.5% by weight non-migrating inorganic slip agent MB3050PB;
  • Second extrusion layer 100% by weight E02ES
  • Third extrusion layer 98% by weight E02ES, 2% by weight non-migrating inorganic slip agent MB3050PB.
  • the total thickness of the high-melt strength polypropylene film prepared by the bidirectional stretching method was 48 ⁇ m, and the thickness of the first extruded layer was 1 ⁇ m, the thickness of the second extruded layer was 46 ⁇ m, and the third extruded layer The thickness is 1 ⁇ m;
  • FIG. 2 is an SEM photograph of the surface of the film after rubbing the film prepared in Example 2 of the present invention, as can be seen from FIG. 2 Out: S2 grade: It can be observed that there are many, foggy scratches, and the falling point of the hollow glass sphere contained in the non-migrating inorganic slip agent is ⁇ 1 point / 50cm 2 ; In addition, FIG.
  • Example 5 is prepared in Example 2 of the present invention SEM photographs of the first extruded layer and the third extruded layer used in the film, where the first extruded layer: few agglomeration points, no crystal points; the third extruded layer: no agglomeration points, no crystal points.
  • the biaxially oriented high-melt-strength polypropylene film was prepared according to the same method as Example 1, except that the preparation materials were different; specifically:
  • the first extruded layer material 99.5% by weight of HMS20Z, 0.5% by weight of non-migrating inorganic slip agent MB3050PB;
  • Second extruded layer material 100% by weight of HMS20Z;
  • Third extrusion layer 99.5% by weight of HMS20Z, 0.5% by weight of non-migrating inorganic slip agent MB3050PB.
  • the total thickness of the high-melt strength polypropylene film prepared by the bidirectional stretching method was 48 ⁇ m, and the thickness of the first extruded layer was 1 ⁇ m, the thickness of the second extruded layer was 46 ⁇ m, and the third extruded layer The thickness is 1 ⁇ m.
  • the biaxially oriented high-melt-strength polypropylene film was prepared in the same manner as in Example 1, except that the preparation materials were different. specifically:
  • the first extruded layer material 97.5% by weight of HMS20Z, 2.5% by weight of non-migrating inorganic slip agent MB3050PB;
  • Second extruded layer material 100% by weight of HMS20Z;
  • the third extruded layer material 98% by weight of HMS20Z, 2% by weight of non-migrating inorganic slip agent MB3050PB.
  • the total thickness of the high-melt strength polypropylene film prepared by the biaxial stretching method was 80 ⁇ m, and the thickness of the first extruded layer was 0.8 ⁇ m, the thickness of the second extruded layer was 78.4 ⁇ m, and the third extruded The thickness of the layer is 0.8 ⁇ m.
  • the biaxially oriented high-melt-strength polypropylene film was prepared according to the same method as Example 1, except that the preparation materials were different; specifically:
  • First extruded layer material 97.5% by weight E02ES, 2.5% by weight non-migrating inorganic slip agent MB3050PB;
  • Second extrusion layer 100% by weight E02ES
  • Third extrusion layer 98% by weight E02ES, 2% by weight non-migrating inorganic slip agent MB3050PB.
  • the total thickness of the high-melt-strength polypropylene film prepared by the two-way stretching method was 80 ⁇ m, and the thickness of the first extruded layer was 1 ⁇ m, the thickness of the second extruded layer was 78.4 ⁇ m, and the third extruded The thickness of the layer is 1 ⁇ m.
  • Polypropylene films were prepared according to the same ingredients as in Examples 1-5, respectively, except for: using the blown tube method; wherein, the thickness ratios were: the thickness of the first extruded layer accounted for 20% of the total thickness; The thickness of the second extruded layer accounts for 60% of the total thickness; the thickness of the third extruded layer accounts for 20% of the total thickness.
  • Polypropylene films were prepared according to the same ingredients as in Examples 1-5, respectively, except that: the casting method was used; wherein, the thickness ratios were: the thickness of the first extruded layer accounted for 20% of the total thickness; the second extruded The thickness of the out layer accounts for 60% of the total thickness; the thickness of the third extruded layer accounts for 20% of the total thickness.
  • An ordinary biaxially oriented polypropylene film was prepared in the same manner as in Example 1, except that the preparation materials were different. specifically:
  • the first extruded layer material 97.5% by weight of ordinary homopolypropylene T30S, 2.5% by weight of amorphous silica anti-sticking masterbatch;
  • Second extruded layer material 100% by weight of ordinary homopolypropylene T30S;
  • Third extrusion layer 98% by weight T30S, 2% by weight amorphous silica anti-sticking masterbatch.
  • the total thickness of the ordinary biaxially oriented polypropylene film is 48 ⁇ m, and the thickness of the first extruded layer is 1 ⁇ m, the thickness of the second extruded layer is 1 ⁇ m, and the thickness of the third extruded layer is 46 ⁇ m;
  • FIG. 3 is an SEM photograph of the surface of the film after rubbing the film prepared in Comparative Example 1 of the present invention, as can be seen from FIG. 3 : S4 grade: It can be observed that there are many, foggy scratches, the anti-sticking masterbatch falling point is less than 5 points / 50cm 2 ; In addition, FIG. 3
  • the biaxially oriented high-melt-strength polypropylene film was prepared in the same manner as in Example 1, except that the preparation materials were different. specifically:
  • the first extruded layer material 97.5% by weight of E02ES, 2.5% by weight of amorphous silica anti-sticking masterbatch;
  • Second extrusion layer 100% by weight E02ES
  • Third extrusion layer 98% by weight E02ES, 2% by weight amorphous silica anti-sticking masterbatch.
  • the total thickness of the high-melt strength polypropylene film prepared by the bidirectional stretching method was 48 ⁇ m, and the thickness of the first extruded layer was 1 ⁇ m, the thickness of the second extruded layer was 46 ⁇ m, and the third extruded layer The thickness is 1 ⁇ m.
  • the biaxially oriented high-melt-strength polypropylene film was prepared in the same manner as in Example 1, except that the preparation materials were different. specifically:
  • the first extruded layer material 100% by weight of E02ES, 0.5% by weight of non-migrating inorganic slip agent MB3050PB;
  • Second extrusion layer 100% by weight E02ES
  • the third extruded layer 100% by weight of E02ES, 0% by weight of non-migrating inorganic slip agent MB3050PB.
  • the total thickness of the high-melt strength polypropylene film prepared by the bidirectional stretching method was 48 ⁇ m, and the thickness of the first extruded layer was 1 ⁇ m, the thickness of the second extruded layer was 46 ⁇ m, and the third extruded layer The thickness is 1 ⁇ m.
  • Example 1 First extruded layer / third extruded layer 0.23 / 0.22
  • Example 1 First extrusion layer / First extrusion layer 0.22 / 0.20
  • Example 2 First extruded layer / third extruded layer 0.25 / 0.24
  • Example 2 First extrusion layer / First extrusion layer 0.22 / 0.21
  • Example 3 First extruded layer / third extruded layer 0.35 / 0.34
  • Example 3 First extrusion layer / First extrusion layer 0.33 / 0.33
  • Example 4 First extruded layer / third extruded layer 0.25 / 0.24
  • Example 4 First extrusion layer / First extrusion layer 0.22 / 0.21
  • Example 5 First extruded layer / third extruded layer 0.26 / 0.26
  • Example 5 First extrusion layer / First extrusion layer 0.24 / 0.23
  • Example 6 First extruded layer / third extruded layer 0.25 / 0.24
  • Example 15 First extruded layer / third extruded layer 0.28 / 0.26
  • Example 15 First extrusion layer / First extrusion layer 0.27 / 0.25
  • Comparative Example 1 First extruded layer / third extruded layer 0.68 / 0.67 Comparative Example 1 First extrusion layer / First extrusion layer 0.65 / 0.63
  • Comparative Example 2 First extruded layer / third extruded layer 0.65 / 0.64 Comparative Example 2 First extrusion layer / First extrusion layer 0.63 / 0.63
  • Example 3 First extruded layer / third extruded layer 0.55 / 0.54 Comparative Example 3 First extrusion layer / First extrusion layer 0.42 / 0.40
  • Remark 1 The standard environment for sample condition adjustment and testing is carried out in accordance with the provisions of GB / T2918.
  • the test environment conditions are temperature 23 °C ⁇ 2 °C, relative humidity 50% ⁇ 1%, and the sample is pre-treated for 8 hours under this condition.
  • Examples 1, 2, 4, 5, 6, 7, 9, 10, 11, 12, 14, and 15 add a high proportion of non-migrating inorganic slip agent MB3050PB, and the friction is hot at 80 °C The coefficient is low; while the amorphous silica anti-adhesion masterbatch added in Comparative Examples 1 and 2 has a high heat-slip friction coefficient at 80 ° C, which is a scrap product in actual production; and Examples 3, 8, and 13 add non-migrating inorganic
  • the proportion of slip agent MB3050PB is low, and the friction coefficient of hot slip at 80 ° C is relatively high.
  • a high-temperature resistant ultra-low thermal deformation biaxial stretching method prepared in Examples 1-5 and Comparative Examples 2 and 3 of the present invention is a high-melt strength polypropylene (BOPP) and an ordinary biaxially oriented polypropylene (BOPP) film of Comparative Example , 48 hours off the line, the heat shrinkage test is shown in Table 3.
  • BOPP high-melt strength polypropylene
  • BOPP ordinary biaxially oriented polypropylene
  • Remark 2 The standard environment for sample condition adjustment and test is carried out according to GB / T2918.
  • the test environment conditions are temperature 23 °C ⁇ 2 °C, relative humidity 50% ⁇ 1%, and under this condition, the sample is pre-treated for 8hr.
  • Examples 1, 3 and 4 add high melt strength polypropylene HMS20Z, and the ratio of added HMS20Z and non-migrating inorganic slip agent MB3050PB is within the range defined by the present invention, at 80 , 120 °C, 135 °C longitudinal and transverse thermal shrinkage rate (thermal deformation rate) is the lowest, the transverse thermal shrinkage rate (thermal deformation rate) is lower than the longitudinal thermal shrinkage rate;
  • Example 4 is thicker than Example 1 , High temperature resistance, lower thermal deformation rate than Example 1 and others using HMS20Z (Example 3).
  • Example 2 Example 5, Comparative Example 2, Comparative Example 3 Adding high melt strength polypropylene E02ES at 80 °C longitudinal and transverse thermal shrinkage rate (thermal deformation rate) is low, 120 °C, 135 °C transverse thermal shrinkage rate (Thermal deformation rate) is low, and the longitudinal thermal shrinkage rate (thermal deformation rate) gradually increases;
  • Example 5 has a thick thickness and high temperature resistance, and the thermal deformation rate is lower than that of other E02ES.
  • Example 4 has the best heat resistance and thermal shrinkage rate. (Thermal deformation rate) is the lowest, and the longitudinal and lateral thermal deformation rates are the most balanced, which is not easy to cause film warpage.
  • the high-melt-strength polypropylene film prepared by the blow molding tube method of Examples 6-10 of the present invention and the high-melt-strength polypropylene (CPP) film prepared by the casting method of Examples 11-15 were off-line for 48 hours and were thermally contracted The rate test is shown in Table 4.
  • Examples 1-15, Comparative Examples 2 and 3 of the present invention prepared a high temperature resistant ultra-low thermal deformation polypropylene film and Comparative Example 1 ordinary biaxially oriented polypropylene (BOPP) film, offline 48 hours, haze test as Table 5 shows.
  • BOPP biaxially oriented polypropylene
  • Example 1 Serial number Nominal thickness ( ⁇ m) Turbidity (haze) (%) Example 1 48 1.21 Example 2 48 1.25 Example 3 48 1.12 Example 4 80 1.58 Example 5 80 1.62 Example 6 48 8.0 Example 7 48 8.2 Example 8 48 7.8 Example 9 80 8.6 Example 10 80 8.8 Example 11 48 1.56 Example 12 48 1.60 Example 13 48 1.48 Example 14 80 1.70 Example 15 80 1.72 Comparative Example 1 48 2.98 Comparative Example 2 48 1.60 Comparative Example 3 48 1.22
  • Remark 3 The standard environment for sample condition adjustment and testing is carried out according to GB / T2918.
  • the test environment conditions are temperature 23 °C ⁇ 2 °C, relative humidity 50% ⁇ 1%, and the sample is pre-treated for 8 hours under this condition.
  • Example 3 Example 1 ⁇ Example 4.
  • Example 2 Example 5.
  • Example 1 Adding HMS20Z film, adding E02ES film, adding T30S ordinary biaxially oriented film, the haze changes from small to large in order:
  • Example 1 ⁇ Example 2 ⁇ Comparative Example 1.
  • the polypropylene film with excellent properties can be prepared by the biaxial stretching method, the blown tube method, or the casting method.
  • a high melt strength polypropylene is added to the processing process of the polypropylene film prepared by the biaxial stretching, blow molding tube method or casting method, and under the specific process conditions, the poly Propylene (BOPP) film has high temperature resistance, ultra-low thermal deformation rate, and few appearance defects; added a non-migrating inorganic slip agent, which contains activated glass spheres and polypropylene with good binding force, the sphere surface provides a suitable Smoothness, can reduce the film friction coefficient under the appropriate film production process conditions, no migration is not easy to fall off, does not pollute the packaging; activated glass sphere has a refractive index close to polypropylene, the film has high transparency and low haze; in addition, The added non-migrating inorganic slip agent contains hexafluorocarbon polymer in the form of small droplets incompatible with the matrix in the polypropylene matrix, and has strong affinity and low surface energy with the metal die wall , Forming a kinetic coating to reduce the flow

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明涉及高熔体强度聚丙烯薄膜加工技术领域，公开了一种高熔体强度聚丙烯薄膜组合物和薄膜及其应用。其中，该组合物包括第一挤出层料、第二挤出层料和第三挤出层料，且至少第一挤出层料或第三挤出层料含有非迁移无机增滑剂，其中，非迁移无机增滑剂为共混物A经共混改性制备而得到的产物。含有该非迁移无机增滑剂的高熔体强度聚丙烯薄膜具有耐高温、超低热变形率、无晶点、极少外观瑕疵点、高透明度，功能和外观符合高端电子保护、软包装电池、印刷复合、镀层、涂布或广告装饰等市场需求的优点。

Description

高熔体强度聚丙烯薄膜组合物和薄膜及其应用 技术领域
本发明涉及高熔体强度聚丙烯薄膜加工技术领域，公开了一种高熔体强度聚丙烯薄膜组合物和薄膜及其应用。
背景技术
双向拉伸薄膜、吹塑管泡薄膜、流延薄膜是常见的性能优良的包装材料，被广泛应用于服装、化妆品、食品、书籍、纸巾、工业、药品、电子保护、涂布(胶)等领域。中国包装联合会塑包委专家最新统计数据指出，至2018年1月末，中国包装薄膜总产能超1000万吨，预计五年内将以平均5％复合年增长速率递增。
在生产应用中，常规的聚丙烯或聚乙烯薄膜通常会出现翘曲、卷边。这主要是因为薄膜在受拉伸、受热过程中耐高温性差、收缩而导致的现象。薄膜收缩、卷边会影响到生产效率等，因此企业要求热变形率越低越好。特别是电子保护领域薄膜要求必须有耐热性，极高的尺寸稳定性，低热变形率、极少外观瑕疵点，无迁移物析出、不污染电路板及电子元器件等。通常通过检测热收缩率(热变形率)是表征薄膜在受热情况下尺寸稳定性，也即薄膜受热变形的程度，亦可反映薄膜的耐温性能。目前GB/T 21302《包装用复合膜、袋》对卷边、收缩率没有明确规定，GB/T 4456《包装用聚乙烯吹塑薄膜》、GB/T 27740《流延聚丙烯(CPP)薄膜》对热收缩率的大小及测试方法没有明确规定，GB/T10003《普通用途双向拉伸聚丙烯(BOPP)薄膜》参考YC/T 266《烟用包装膜》做出明确规定。下游加工企业测试热收缩率温度通常选择80℃、120℃、135℃三档。
通常情况下，薄膜的大分子处于自然卷曲的状态，受热时产生非常小的热收缩率(热变形率)。然而聚丙烯(PP)、聚乙烯(PE)是半结晶高分子材料，双向拉伸、吹塑管泡薄膜生产过程经历了纵向拉伸和横向拉伸，生产幅宽、速度、热收缩率要求不同而设置不同的拉伸倍率；流延薄膜因为模头与流延辊位置，以及各辊之间速差也有不同程度的纵向拉伸。在外力作用下使分子链受到强制拉伸，大分子彼此之间不能相互滑移，在定型区冷却时被强制拉伸的分子链被冻结起来。在室温下，高分子材料大分子的活动能力差，因而不能靠分子运动来消除这种强制拉伸状态，当薄膜受热情况下，其冻结了的大分子会重新开始活动起来，从不自然状态力图恢复到自然状态，结果就产生了收缩。热变形率大的薄膜应用受到了限制。
因此，研究和开发具有耐热性，极高的尺寸稳定性，低热变形率、极少外观瑕疵点，无迁移物析出的薄膜具有重要意义。
发明内容
本发明的目的是为了克服现有技术存在的双向拉伸薄膜、吹塑管泡薄膜、流延薄膜耐热性差、尺寸稳定性不高、外观瑕疵点多以及有迁移物析出的缺点，而提供一种高熔体强度聚丙烯薄膜组合物和薄膜及其应用。高熔体强度聚丙烯通过掺混法、导入长支化结构的柱式反应器法(电子束辐照、过氧化物处理、反应挤出)及内反应器聚合法(直接共聚、大分子化)、交联法，提高聚丙烯(PP)重均分子量与加宽分子量分布，使其具有长链支化结构，这种结构材料能够明显提高线性聚丙烯材料的流变性能，从而使该类聚丙烯熔体强度一般是普通聚丙烯的1.5-50倍，长支链结构改变了普通聚丙烯所具有的应变软化的特征，改善了聚丙烯在加工过程中的缺陷。具有较宽范围的机械性能、热稳定性以及化学稳定性等传统聚丙烯所不具备的性能优势。本发明通过添加高熔体强度聚丙烯组合物，通过双向拉伸方法、吹塑薄膜方法、流延方法制取的高熔体强度聚丙烯薄膜，具有耐热性、极高的尺寸稳定性、低热变形率、极少外观瑕疵点、无迁移物析出、功能和外观符合高端电子保护、软包装电池、印刷复合、镀层、涂布(胶)、广告装饰等市场需求的优点，并且无需改造现有设备。
为了实现上述目的，本发明第一方面提供了一种高熔体强度聚丙烯薄膜组合物，其中，该组合物包括第一挤出层料、第二挤出层料和第三挤出层料，且至少所述第一挤出层料或所述第三挤出层料含有非迁移无机增滑剂，其中，所述非迁移无机增滑剂为共混物A经共混改性制备而得到的产物，其中，所述共混物A含有高熔体强度聚丙烯和助剂，所述助剂含有活化玻璃球体，所述活化玻璃球体为经硅烷偶联剂及六氟碳聚合物表面处理后得到的玻璃实体球体。
本发明第二方面提供了一种含有上述所述的组合物制得的聚丙烯薄膜，其中，所述聚丙烯薄膜包括依次叠加的第一挤出层、第二挤出层和第三挤出层，其中，所述第一挤出层由所述第一挤出层料挤出而得到的，所述第二挤出层由所述第二挤出层料挤出而得到的，以及所述第三挤出层由所述第三挤出层料挤出而得到的。
本发明第三方面提供了前述所述的聚丙烯薄膜在电子保护、软包装电池、印刷复合、镀层、涂布或广告装饰领域中的应用。
通过上述技术方案，本发明以非迁移无机增滑剂和高熔体强度聚丙烯作为该聚丙 烯薄膜的组分，能够大幅度提高薄膜耐热性，保持尺寸稳定性，降低热变形率、减少外观瑕疵点，无迁移物析出，高透明度，并且，可以在现有双向拉伸、吹塑管泡、流延薄膜生产线上能够在线生产，无需改造现有设备。
附图说明
构成本公开的一部分的附图用来提供对本公开的进一步理解，本公开的示意性实施例及其说明用于解释本公开，并不构成对本公开的不当限定。在附图中：
图1是本发明实施例1制备的薄膜摩擦后的薄膜表面的SEM相片；
图2是本发明实施例2制备的薄膜摩擦后的薄膜表面的SEM相片；
图3是本发明对比例1制备的薄膜摩擦后的薄膜表面的SEM相片；
图4是本发明实施例1中制备薄膜所用的第一挤出层和第三挤出层的SEM相片；
图5是本发明实施例2中制备薄膜所用的第一挤出层和第三挤出层的SEM相片；
图6是本发明对比例1中制备薄膜所用的第一挤出层和第三挤出层的SEM相片；
图7是本发明采用双向拉伸方法制备高熔体强度聚丙烯薄膜的示意图；
图8是本发明采用吹塑管泡方法制备高熔体强度聚丙薄膜的示意图；
图9是本发明采用流延方法制备高熔体强度聚丙烯薄膜的示意图。
附图标记说明：
1第一挤出层 2第三挤出层
具体实施方式
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明第一方面提供了一种高熔体强度聚丙烯薄膜组合物，其中，该组合物包括第一挤出层料、第二挤出层料和第三挤出层料，且至少所述第一挤出层料或所述第三挤出层料含有非迁移无机增滑剂，其中，所述非迁移无机增滑剂为共混物A经共混改性制备而得到的产物，所述共混物A含有高熔体强度聚丙烯和助剂，所述助剂含有活化玻璃球体，所述活化玻璃球体为经硅烷偶联剂及六氟碳聚合物表面处理后得到的玻璃实体球体。
根据本发明，所述第一挤出层料和所述第三挤出层料均含有非迁移无机增滑剂时， 效果更好。
根据本发明，“共混改性”具体地指将共混物A中的各组分，按比例投料，在螺杆挤出机熔融塑炼挤出、冷却、切粒。
根据本发明，所述活化玻璃球体的平均粒径可以为2.5-3.5μm，优选为2.8-3.2μm。
优选地，所述六氟碳聚合物为1,1,2,3,3,3-六氟-1-丙烯聚合物，堆积密度为0.6-1.0g/cm 3，平均粒径小于或等于25目，在105℃下1小时测试挥发份小于或等于1％。
优选地，所述硅烷偶联剂为3-氨丙基三乙氧基硅烷，在25℃下测粘度值为1.5-1.7cs，优选为1.6cs，密度为0.94-0.95g/cm 3，优选为0.946g/cm 3，以及闪点(闭杯)为96℃，其中，在本发明中，闭杯闪点是指在规定的条件下，加热试样，当试样达到某温度时，试样的蒸汽和周围空气的混合气，一旦与火焰接触，即发生闪燃现象，发生闪燃时试样的最低温度。
根据本发明，所述活化玻璃球体和所述六氟碳聚合物、所述硅烷偶联剂的含量的重量比为1：(0.1-0.5)：(0.01-0.5)，优选为1：(0.2-0.4):(0.01-0.4)，更优选为1：0.25：0.05。
根据本发明，所述助剂可以自制，也可以通过商购获得，例如，可以购自上海若祎新材料科技有限公司生产的型号为MB3050PB非迁移无机增滑助剂，其中，该助剂中含有本发明所限定的活化玻璃球体，所述活化玻璃球体为经硅烷偶联剂及六氟碳聚合物表面处理后得到的玻璃实体球体，其中，所述硅烷偶联剂为3-氨丙基三乙氧基硅烷，所述六氟碳聚合物为1,1,2,3,3,3-六氟-1-丙烯聚合物，以及该活化玻璃球体的平均粒径为2.5-3.5μm；以及在表面处理过程中，所述活化玻璃球体和所述六氟碳聚合物、所述硅烷偶联剂的重量比为1：(0.1-0.5)：(0.01-0.5)。
根据本发明，所述高熔体强度聚丙烯在2.16kg载荷下230℃时的熔体流动速率为1.7-2.5g/10min，密度为0.9-0.915g/cm 3，等规指数大于等于95％，拉伸弹性模量大于等于1000MPa，具体地，在本发明中，“大于等于”即指即包括“大于”又包括“等于”，例如，等规指数大于等于95％是指等规指数可以为95％以及大于95％的所有数值；拉伸弹性模量大于等于1000MPa是指拉伸弹性模量可以为1000MPa以及大于1000MPa的所有数值。
优选地，所述高熔体强度聚丙烯在2.16kg载荷下230℃时的熔体流动速率为1.7-2.3g/10min，密度为0.905-0.91g/cm 3，等规指数为95-97％，拉伸弹性模量为1000-1500MPa；优选地，所述高熔体强度聚丙烯在2.16kg载荷下230℃时的熔体流动速 率为1.7-2.2g/10min，密度为0.905-0.91g/cm 3，等规度为96％，拉伸弹性模量为1450MPa。在本发明中，所述高熔体强度聚丙烯可以商购自中国石油化工股份有限公司镇海炼化分公司厂家获得，例如，HMS20Z和E02ES，其中，HMS20Z在2.16kg载荷下230℃时的熔体流动速率为2.2g/10min，密度为0.905g/cm 3，折射率为1.49，等规度为96.6％，拉伸弹性模量为1410MPa；E02ES在2.16kg载荷下230℃时的熔体流动速率为1.7g/10min，密度为0.905g/cm 3，折射率为1.50，拉伸弹性模量为1020MPa。
根据本发明，以所述共混物A的总重量为基准，所述助剂的含量为5-20重量％，所述高熔体强度聚丙烯的含量为80-95重量％。
根据本发明，所述第一挤出层料含有高熔体强度聚丙烯、非迁移无机增滑剂以及含有或不含有均聚聚丙烯或共聚聚丙烯，且以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；优选地，所述第一挤出层料含有高熔体强度聚丙烯和非迁移无机增滑剂，且以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-80重量％；更优选地，以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-97.5重量％，所述非迁移无机增滑剂的含量为2.5-80重量％。
所述第二挤出层料含有高熔体强度聚丙烯以及含有或不含有均聚聚丙烯或共聚聚丙烯，且以所述第二挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为50-100重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％。
所述第三挤出层料含有高熔体强度聚丙烯、非迁移无机增滑剂以及含有或不含有均聚聚丙烯或共聚聚丙烯，且以所述第三挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；优选地，所述第三挤出层料含有高熔体强度聚丙烯和非迁移无机增滑剂，且以所述第三挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-97.5重量％，所述非迁移无机增滑剂的含量为2.5-30重量％。
根据本发明，本发明的发明人经过大量的科学实验发现：添加了一种非迁移无机增滑剂，以及其所含活化玻璃球体与聚丙烯结合力好，球体表面提供合适的爽滑性，在适当薄膜生产工艺条件下可降低薄膜摩擦系数，不易脱落，不污染被包装物；活化玻璃球体具有与聚丙烯接近的折射率，薄膜透明度高，雾度低。
根据本发明，本发明的发明人经过大量的科学实验发现：添加了一种非迁移无机 增滑剂，以及其所含六氟碳聚合物在聚丙烯基体中以与基体不相容的小液滴的形态存在，口模与金属口模壁有较强的亲和力和低表面能，形成动力学涂层降低聚丙烯熔体的流动阻尼，同时提高薄膜光泽度，降低雾度。
本发明第二方面提供了一种前述所述的组合物的聚丙烯薄膜，其中，所述聚丙烯薄膜包括依次叠加的第一挤出层、第二挤出层和第三挤出层，其中，所述第一挤出层由所述第一挤出层料挤出而得到的，所述第二挤出层由所述第二挤出层料挤出而得到的，以及所述第三挤出层由所述第三挤出层料挤出而得到的。
根据本发明，所述第一挤出层的厚度为0.5-45μm，所述第二挤出层的厚度为8-60μm，所述第三挤出层的厚度为0.5-45μm。
优选地，所述聚丙烯薄膜的厚度为9-100μm，优选为12-85μm，更优选为25-60μm。
根据本发明，该聚丙烯薄膜通过共挤出以及双向拉伸法、吹塑管泡法或流延法制得的。
(一)双向拉伸方法
其中，在本发明中，采用双向拉伸方法制备高熔体强度聚丙烯薄膜的方法可以参考图7所示的制备流程示意图：
备料：
以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；
以所述第二挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为50-100重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；
以所述第三挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-100重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％。
预制配料：将第一挤出层、第二挤出层、第三挤出层的各组分按前述所述的重量百分比分别投入到各自对应的低速混拌料器，预混30分钟；
投料：将已预混好的第一挤出层料、第二挤出层料、第三挤出层料负压吸至三层挤出机料筒内其中，通过所投的第一挤出层料、第二挤出层料、第三挤出层料的用量来确定第一挤出层、第二挤出层、第三挤出层的厚度。
塑炼挤出：采用多台挤出机分别挤出第一挤出层、第二挤出层、第三挤出层的树 脂，熔融的树脂通过分配器合理分层，其中：
第一挤出层和第三挤出层各组分在单螺杆挤出机中，第二挤出层组分在双螺杆挤出机中，在210-245℃的温度条件熔融挤出；
阻瑕疵熔体过滤：目数为80、150、300、150、80波浪式过滤网依次叠加，按柱形排列，熔体从中间芯棒挤压出最外层过滤网；
冷却结晶和片材定型：挤出机挤出熔体经衣架模头挤出，风刀风冷、激冷辊冷却、水槽水浴冷却成具有细微球晶体的厚片，模唇缝隙0.5mm，激冷辊的水温控制在15-35℃，进、出水口水温差控制在±2℃；冷却水槽水温控制在25-35℃；
纵向拉伸及纵向拉伸定型：双级拉伸，总拉伸倍率控制在4.0-5.0之间；纵向拉伸定型区：温度控制在120-150℃；
横向拉伸及横向拉伸定型：横向拉伸倍率7-11之间；横向拉伸定型区：温度控制在170-190℃；
牵引、测厚：测量所述聚丙烯薄膜的总厚度。
电晕、收卷：根据薄膜用途可选择电晕处理，或不选择电晕处理。通过高频电子放电器对薄膜进行电晕处理，下线表面张力值应达40mN/m；薄膜经过定型后进行收卷。收卷装置由收卷表面张力控制装置自动控制，以达到最佳收卷效果；生产线速度：200～500m/min。
时效、分切、收卷：在温度25±5℃、温度60％RH温度环境下，静置1-2天，起到了尺寸和性能进一步稳定作用；分切出相应的成品宽度规格。
(二)吹塑管泡方法
其中，在本发明中，采用吹塑管泡方法制备高熔体强度聚丙烯薄膜的方法可以参考图8所示的制备流程示意图：
备料：
以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；
以所述第二挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为50-100重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；
以所述第三挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-100重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量 为0-50重量％。
预制配料：将第一挤出层、第二挤出层、第三挤出层的各组分按前述所述的重量百分比分别投入到各自对应的低速混拌料器，预混30分钟；
投料：将已预混好的第一挤出层料、第二挤出层料、第三挤出层料负压吸至三层挤出机料筒内其中，通过所投的第一挤出层料、第二挤出层料、第三挤出层料的用量来确定第一挤出层、第二挤出层、第三挤出层的厚度。
塑炼挤出：采用多台挤出机分别挤出第一挤出层、第二挤出层、第三挤出层的树脂，熔融的树脂通过模腔内独立流道合理分层，其中：
第一挤出层、第二挤出层、第三挤出层各组分在单螺杆挤出机中，在160-230℃的温度条件熔融挤出；
阻瑕疵熔体过滤：目数为100、150、150、80依次叠加，多孔板式过滤器，熔体从内层挤压出最外层过滤网；
横向吹胀拉伸：横向拉伸倍率1.2-3.5之间；横向拉伸定型区：温度控制在160-230℃；
冷却结晶和片材定型：挤出机挤出熔体经模头挤出，空气冷却或风冷却环通入冷空气冷却、定型。风冷却环通入的冷空气控制在20℃±1℃；
纵向牵引拉伸：牵引速度8-40m/min；
测厚、电晕：测量所述聚丙烯薄膜的总厚度。根据薄膜用途可选择电晕处理，或不选择电晕处理。通过高频电子放电器对薄膜进行电晕处理，下线表面张力值应达40mN/m；
定型、收卷：薄膜经过定型后进行收卷。收卷装置由收卷表面张力控制装置自动控制，以达到最佳收卷效果；生产线速度：50-150m/min。
时效、分切、收卷：在温度25±5℃、温度60％RH温度环境下，静置1-2天，起到了尺寸和性能进一步稳定作用；分切出相应的成品宽度规格。
(三)流延方法
其中，在本发明中，采用流延方法制备高熔体强度聚丙烯薄膜的方法可以参考图9所示的制备流程示意图：
备料：
以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯含量为0-50重量％；
以所述第二挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为50-100重量％，均聚聚丙烯或共聚聚丙烯含量为0-50重量％；
所述第三挤出层料含有高熔体强度聚丙烯和非迁移无机增滑剂，且以所述第三挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-100重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯含量为0-50重量％。
预制配料：将第一挤出层、第二挤出层、第三挤出层的各组分按前述所述的重量百分比分别投入到各自对应的低速混拌料器，预混30分钟；
投料：将已预混好的第一挤出层料、第二挤出层料、第三挤出层料负压吸至三层挤出机料筒内其中，通过所投的第一挤出层料、第二挤出层料、第三挤出层料的用量来确定第一挤出层、第二挤出层、第三挤出层的厚度。
塑炼挤出：采用多台挤出机分别挤出第一挤出层、第二挤出层、第三挤出层的树脂，熔融的树脂通过分配器合理分层，其中：
第一挤出层、第二挤出层、第三挤出层各组分在单螺杆挤出机中，在195-260℃的温度条件熔融挤出；
阻瑕疵熔体过滤：目数为80、150、300、150、80波浪式过滤网依次叠加，按柱形排列，熔体从中间芯棒挤压出最外层过滤网；
冷却结晶和片材定型：挤出机挤出熔体经衣架模头或T型模头挤出，风刀风冷、激冷辊冷却成具有细微球晶体的厚片，模唇缝隙0.5mm，激冷辊的水温控制在15-35℃，进、出水口水温差控制在±2℃；
测厚：测量所述聚丙烯薄膜的总厚度。
加温定型、电晕：通热水辊定型，水温控制在35--55℃，进、出水口水温差控制在±2℃；根据薄膜用途可选择电晕处理，或不选择电晕处理。通过高频电子放电器对薄膜进行电晕处理，下线表面张力值应达40mN/m；
冷却定型：通冷水辊冷却定型，水温控制在20-35℃，进、出水口水温差控制在±2℃；
收卷：薄膜经过定型后进行收卷。收卷装置由收卷表面张力控制装置自动控制，以达到最佳收卷效果；生产线速度：25-250m/min。
时效、分切、收卷：在温度25±5℃、温度60％RH温度环境下，静置1-2天，起到了尺寸和性能进一步稳定作用；分切出相应的成品宽度规格。
本发明第三方面提供了一种前述所述的聚丙烯薄膜在电子保护、软包装电池、印刷复合、镀层、涂布或广告装饰领域中的应用。
其中，涂布也可以称为涂胶。
本发明的发明人意外发现：在双向拉伸薄膜、吹塑管泡薄膜、流延薄膜加工工艺中添加了一种高熔体强度聚丙烯，在特定的工艺条件下，使薄膜具有耐高温性、超低热变形率、极少外观瑕疵点；添加了一种非迁移无机增滑剂，其所含活化玻璃球体与聚丙烯结合力好，球体表面提供合适的爽滑性，在适当薄膜生产工艺条件下可降低薄膜摩擦系数，无迁移不易脱落，不污染被包装物；活化玻璃球体具有与聚丙烯接近的折射率，薄膜透明度高，雾度低；添加了一种非迁移无机增滑剂，其所含六氟碳聚合物在聚丙烯基体中以与基体不相容的小液滴的形态存在，与金属口模壁有较强的亲和力和低表面能，形成动力学涂层降低聚丙烯熔体的流动阻尼，同时提高薄膜光泽度，降低雾度。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中：
(1)热收缩率测试：样品状态调节和试验的标准环境按GB/T 2918规定进行，试验环境条件为温度23℃±2℃，相对湿度50％±1％，并在此条件下样品预放置处理8hr；依据GB/T 10003《普通用途双向拉伸聚丙烯(BOPP)薄膜》之5.7条烘箱法测试对比80℃、120℃、135℃时薄膜的热收缩率。具体方法是：将100mm×100mm正方形试样平置于特定温度℃±3℃的恒温烘箱中的不锈钢板上，加热时间2min，取出试样，将其冷却到试验环境温度，测量纵向、横向尺寸与加热前尺寸的变化。
(2)热爽滑摩擦系数测试：依据GB/T 10006《塑料薄膜和薄片摩擦系数测定方法》对比80℃热爽滑摩擦系数数据。具体方法是：摩擦系数仪金属定板加热恒温至80℃，薄膜放置在仪器上，测试薄膜与加热金属之间的摩擦系数，模拟高速包装机摩擦生热后薄膜在导辊上滑动顺畅与否状态。
(3)薄膜磨花程度测试：依据GB/T 31727《透明薄膜磨花程度试验方法》对比薄膜磨花程度。本试验按标准中4.2条“方法A-观察法评定磨花程度”。具体方法是：调整磨擦试验仪状态：硅橡胶垫洛氏硬度20，磨块4Ib(1.8KG)，磨块速度85次/分；取薄膜样品7张，去除上、下各一张，磨块在薄膜表面上摩擦平行测试5次，在40W日光灯下，沿与试样观察磨擦测试后的样品的表面质量。以5个试样评定结果中最高等级为试样的磨花程度等级如表1所示。
表1
磨花程度等级 外观
s0 观察不到擦伤
s1 可观察到极少量擦伤
s2 可观察到少量擦伤
s3 可观察到有较多擦伤，但无雾状的擦伤
s4 可观察到有较多擦伤，且有雾状擦伤
s5 可观察到密集有雾的擦伤
实施例1
本实施例在于说明采用双向拉伸方法制备高熔体强度聚丙烯薄膜。
按照图7所示的双向拉伸方法高熔体强度聚丙烯薄膜的制备流程示意图制备薄膜。
备料(重量百分比)：
第一挤出层料：97.5重量％的HMS20Z、2.5重量％的非迁移无机增滑剂MB3050PB；
第二挤出层料：100重量％的HMS20Z；
第三挤出层料：98重量％的HMS20Z、2重量％的非迁移无机增滑剂MB3050PB。
预制配料：将第一挤出层、第二挤出层、第三挤出层的各组分按前述所述的重量百分比分别投入到各自对应的低速混拌料器，预混30分钟；
投料：将已预混好的第一挤出层料、第二挤出层料、第三挤出层料负压吸至三层挤出机料筒内其中，通过所投的第一挤出层料、第二挤出层料、第三挤出层料的用量来确定第一挤出层、第二挤出层、第三挤出层的厚度。
塑炼挤出：采用多台挤出机分别挤出第一挤出层、第二挤出层、第三挤出层的树脂，熔融的树脂通过分配器合理分层，其中：
第一挤出层和第三挤出层各组分在单螺杆挤出机中，第二挤出层组分在双螺杆挤出机中，在235℃的温度条件熔融挤出；
阻瑕疵熔体过滤：目数为80、150、300、150、80波浪式过滤网依次叠加，按柱形排列，熔体从中间芯棒挤压出最外层过滤网；
冷却结晶和片材定型：挤出机挤出熔体经衣架模头挤出，风刀风冷、激冷辊冷却、水槽水浴冷却成具有细微球晶体的厚片，模唇缝隙0.5mm，激冷辊的水温控制在25℃，进、出水口水温差控制在±2℃；冷却水槽水温控制在25℃；
纵向拉伸及纵向拉伸定型：双级拉伸，总拉伸倍率控制在4.8之间；纵向拉伸定型区：温度控制在148℃；
横向拉伸及横向拉伸定型：横向拉伸倍率10之间；横向拉伸定型区：温度控制在190℃；
牵引、测厚：测量所述聚丙烯薄膜的总厚度。
电晕、收卷：根据薄膜用途可选择电晕处理，或不选择电晕处理。通过高频电子放电器对薄膜进行电晕处理，下线表面张力值应达40mN/m；薄膜经过定型后进行收卷。收卷装置由收卷表面张力控制装置自动控制，以达到最佳收卷效果；生产线速度：480m/min。
时效、分切、收卷：在温度25±5℃、温度60％RH温度环境下，静置2天，起到了尺寸和性能进一步稳定作用；分切出相应的成品宽度规格。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为48μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为46μm，所述第三挤出层的厚度为1μm；
将所制备的双向拉伸方法高熔体强度聚丙烯薄膜进行磨花程度测试，结果如图1所示；其中，图1为本发明实施例1制备的薄膜摩擦后的薄膜表面的SEM相片，从图1中可以看出：S3级，可观察到有较多擦伤，但无雾状的擦伤，非迁移无机增滑剂中所含活化玻璃球体脱落点＜2点/50cm 2(备注：采用磨擦试验仪或者按照GB/T31727-2015附录A标准，磨擦仪荷重块质量为(1800±1)g，按规定的磨擦条件，在一定时间、一定速度沿着纵向和横向分别在薄膜上进行相互往返磨擦；如果助剂与有机树脂结合力差，则易从膜面上脱落，也称之为掉粉)；另外，图4是本发明实施例1中制备薄膜所用的第一挤出层和第三挤出层的SEM相片，其中，第一挤出层：无团聚点，无晶点；第三挤出层：无团聚点，无晶点。
实施例2
按照与实施例1相同的方法制备双向拉伸方法高熔体强度聚丙烯薄膜，所不同之处在于：备料不同，即，将HMS20Z替换为E02ES，具体地：
第一挤出层料：97.5重量％的E02ES、2.5重量％的非迁移无机增滑剂MB3050PB；
第二挤出层料：100重量％的E02ES；
第三挤出层料：98重量％的E02ES、2重量％的非迁移无机增滑剂MB3050PB。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为48μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为46μm，所述第三挤出层的厚度为1μm；
将所制备的双向拉伸聚丙烯薄膜进行磨花程度测试，结果如图2所示；其中，图2是本发明实施例2制备的薄膜摩擦后的薄膜表面的SEM相片，从图2可以看出：S2级： 可观察到有较多，有雾的擦伤，非迁移无机增滑剂所含空心玻璃球体脱落点＜1点/50cm 2；另外，图5是本发明实施例2中制备薄膜所用的第一挤出层和第三挤出层的SEM相片，其中，第一挤出层：极少团聚点，无晶点；第三挤出层：无团聚点，无晶点。
实施例3
按照与实施例1相同的方法制备双向拉伸方法高熔体强度聚丙烯薄膜，所不同之处在于：备料不同；具体地：
第一挤出层料：99.5重量％的HMS20Z、0.5重量％的非迁移无机增滑剂MB3050PB；
第二挤出层料：100重量％的HMS20Z；
第三挤出层料：99.5重量％的HMS20Z、0.5重量％的非迁移无机增滑剂MB3050PB。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为48μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为46μm，所述第三挤出层的厚度为1μm。
实施例4
按照与实施例1相同的方法制备双向拉伸方法高熔体强度聚丙烯薄膜，所不同之处在于：备料不同。具体地：
第一挤出层料：97.5重量％的HMS20Z、2.5重量％的非迁移无机增滑剂MB3050PB；
第二挤出层料：100重量％的HMS20Z；
第三挤出层料：98重量％的HMS20Z、2重量％的非迁移无机增滑剂MB3050PB。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为80μm，以及第一挤出层的厚度为0.8μm，所述第二挤出层的厚度为78.4μm，所述第三挤出层的厚度为0.8μm。
实施例5
按照与实施例1相同的方法制备双向拉伸方法高熔体强度聚丙烯薄膜，所不同之处在于：备料不同；具体地：
第一挤出层料：97.5重量％的E02ES、2.5重量％的非迁移无机增滑剂MB3050PB；
第二挤出层料：100重量％的E02ES；
第三挤出层料：98重量％的E02ES、2重量％的非迁移无机增滑剂MB3050PB。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为80μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为78.4μm，所述第三挤出层的厚度为1μm。
实施例6-10
分别按照与实施例1-5相同的配料制备聚丙烯薄膜，所不同之处在于：采用吹塑管泡法制备；其中，厚度比例分别为：第一挤出层厚度占总厚度20％；第二挤出层厚度占 总厚度60％；第三挤出层厚度占总厚度20％。
实施例11-15
分别按照与实施例1-5相同的配料制备聚丙烯薄膜，所不同之处在于：采用流延法制备；其中，厚度比例分别为：第一挤出层厚度占总厚度20％；第二挤出层厚度占总厚度60％；第三挤出层厚度占总厚度20％。
对比例1
按照与实施例1相同的方法制备普通双向拉伸聚丙烯薄膜，所不同之处在于：备料不同。具体地：
第一挤出层料：97.5重量％的普通均聚聚丙烯T30S、2.5重量％的无定型二氧化硅抗粘母料；
第二挤出层料：100重量％的普通均聚聚丙烯T30S；
第三挤出层料：98重量％的T30S、2重量％的无定型二氧化硅抗粘母料。
普通双向拉伸聚丙烯薄膜的总厚度为48μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为1μm，所述第三挤出层的厚度为46μm；
将该普通双向拉伸聚丙烯薄膜进行磨花程度测试，结果如图3所示；其中，图3是本发明对比例1制备的薄膜摩擦后的薄膜表面的SEM相片，从图3可以看出：S4级：可观察到有较多，有雾状的擦伤，抗粘母料脱落点＜5点/50cm 2；另外，图6是本发明对比例1中制备薄膜所用的第一挤出层和第三挤出层的SEM相片，其中，第一挤出层：无团聚点，有大晶点；第三挤出层：少量团聚点，无晶点。
对比例2
按照与实施例1相同的方法制备双向拉伸方法高熔体强度聚丙烯薄膜，所不同之处在于：备料不同。具体地：
第一挤出层料：97.5重量％的E02ES、2.5重量％的无定型二氧化硅抗粘母料；
第二挤出层料：100重量％的E02ES；
第三挤出层料：98重量％的E02ES、2重量％的无定型二氧化硅抗粘母料。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为48μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为46μm，所述第三挤出层的厚度为1μm。
对比例3
按照与实施例1相同的方法制备双向拉伸方法高熔体强度聚丙烯薄膜，所不同之处在于：备料不同。具体地：
第一挤出层料：100重量％的E02ES、0.5重量％的非迁移无机增滑剂MB3050PB；
第二挤出层料：100重量％的E02ES；
第三挤出层料100重量％的E02ES、0重量％的非迁移无机增滑剂MB3050PB。
结果制备的双向拉伸方法高熔体强度聚丙烯薄膜的总厚度为48μm，以及第一挤出层的厚度为1μm，所述第二挤出层的厚度为46μm，所述第三挤出层的厚度为1μm。
测试例1
本发明实施例1-5、6-10、11-15制备的一种耐高温超低热变形聚丙烯薄膜与对比例1-3的普通双向拉伸聚丙烯薄膜，下线48小时，80℃热爽滑摩擦系数数据如表2所示。
表2
实施例 测试面 80℃热爽滑摩擦系数(静摩擦/动摩擦)
实施例1 第一挤出层/第三挤出层 0.23/0.22
实施例1 第一挤出层/第一挤出层 0.22/0.20
实施例2 第一挤出层/第三挤出层 0.25/0.24
实施例2 第一挤出层/第一挤出层 0.22/0.21
实施例3 第一挤出层/第三挤出层 0.35/0.34
实施例3 第一挤出层/第一挤出层 0.33/0.33
实施例4 第一挤出层/第三挤出层 0.25/0.24
实施例4 第一挤出层/第一挤出层 0.22/0.21
实施例5 第一挤出层/第三挤出层 0.26/0.26
实施例5 第一挤出层/第一挤出层 0.24/0.23
实施例6 第一挤出层/第三挤出层 0.25/0.24
实施例6 第一挤出层/第一挤出层 0.25/0.23
实施例7 第一挤出层/第三挤出层 0.27/0.26
实施例7 第一挤出层/第一挤出层 0.28/0.26
实施例8 第一挤出层/第三挤出层 0.35/0.34
实施例8 第一挤出层/第一挤出层 0.35/0.34
实施例9 第一挤出层/第三挤出层 0.26/0.25
实施例9 第一挤出层/第一挤出层 0.26/0.25
实施例10 第一挤出层/第三挤出层 0.29/0.27
实施例10 第一挤出层/第一挤出层 0.28/0.27
实施例11 第一挤出层/第三挤出层 0.26/0.25
实施例11 第一挤出层/第一挤出层 0.24/0.23
实施例12 第一挤出层/第三挤出层 0.27/0.26
实施例12 第一挤出层/第一挤出层 0.26/0.25
实施例13 第一挤出层/第三挤出层 0.36/0.35
实施例13 第一挤出层/第一挤出层 0.37/0.35
实施例14 第一挤出层/第三挤出层 0.27/0.26
实施例14 第一挤出层/第一挤出层 0.27/0.26
实施例15 第一挤出层/第三挤出层 0.28/0.26
实施例15 第一挤出层/第一挤出层 0.27/0.25
对比例1 第一挤出层/第三挤出层 0.68/0.67
对比例1 第一挤出层/第一挤出层 0.65/0.63
对比例2 第一挤出层/第三挤出层 0.65/0.64
对比例2 第一挤出层/第一挤出层 0.63/0.63
对比例3 第一挤出层/第三挤出层 0.55/0.54
对比例3 第一挤出层/第一挤出层 0.42/0.40
备注1：样品状态调节和试验的标准环境按GB/T2918规定进行，试验环境条件为温度23℃±2℃，相对湿度50％±1％，并在此条件下样品预放置处理8hr。
从表2可以看出：实施例1、2、4、5、6、7、9、10、11、12、14和15添加非迁移无机增滑剂MB3050PB比例高，在80℃热爽滑摩擦系数低；而对比例1、2添加无定型二氧化硅抗粘母料，在80℃热爽滑摩擦系数高，在实际生产中属于报废品；以及实施例3、8、13添加非迁移无机增滑剂MB3050PB比例低，在80℃热爽滑摩擦系数偏高，在实际生产中应用于高摩擦系数要求的产品品种；以及对比例3添加非迁移无机增滑剂MB3050PB比例非常低，在80℃热爽滑摩擦系数高，在实际生产中属于报废品；以及从实施例1、2、4、5、6、7、9、10、11、12、14和15可以看出，采用双向拉伸法、吹塑管泡法或流延法均能够制备性能优良的聚丙烯薄膜。
测试例2
本发明实施例1-5、对比例2、3制备的一种耐高温超低热变形双向拉伸方法高熔体强度聚丙烯(BOPP)与对比例1的普通双向拉伸聚丙烯(BOPP)薄膜，下线48小时，热收缩率测试如表3所示。
表3
Figure PCTCN2019079473-appb-000001
Figure PCTCN2019079473-appb-000002
备注2：样品状态调节和试验的标准环境按GB/T2918规定进行，试验环境条件为温度23℃±2℃，相对湿度50％±1％，并在此条件下样品预放置处理8hr。
从表3可以看出：实施例1、3和4添加高熔体强度聚丙烯HMS20Z，且添加的HMS20Z和非迁移无机增滑剂MB3050PB比例均在本发明所限定的范围之内，在80℃、120℃、135℃的纵向及横向热收缩率(热变形率)最低，其中横向热收缩率(热变形率)较纵向热收缩率低；实施例4相对于实施例1而言，厚度厚，耐温性高，热变形率较实施例1以及其它使用HMS20Z的(实施例3)更低。
实施例2、实施例5、对比例2、对比例3添加高熔体强度聚丙烯E02ES在80℃的纵向及横向热收缩率(热变形率)低，120℃、135℃的横向热收缩率(热变形率)低，纵向热收缩率(热变形率)逐渐提高；实施例5厚度厚，耐温性高，热变形率较其它使用E02ES的更低。
而对比例1在80℃、120℃、135℃的纵向及横向热收缩率(热变形率)高。
从表3可以看出，实施例1-5的耐热性，热收缩率低，纵、横向热变形率好，不易造成薄膜翘曲，尤其是实施例4耐热性最好，热收缩率(热变形率)最低，纵、横向热变形率最平衡，不易造成薄膜翘曲。
测试例3
本发明实施例6-10吹塑管泡法制备的高熔体强度聚丙烯薄膜与实施例11-15流延法制备的高熔体强度聚丙烯(CPP)薄膜，下线48小时，热收缩率测试如表4所示。
表4
Figure PCTCN2019079473-appb-000003
Figure PCTCN2019079473-appb-000004
从表4可以看出：本发明实施例6-10吹塑管泡法制备的高熔体强度聚丙烯薄膜与实施例11-15流延法制备的高熔体强度聚丙烯(CPP)薄膜的热收缩率，相对于实施例1-5双向拉伸法制备的高熔体强度聚丙烯(BOPP)的热收缩率差一些，但是，相对于对比例1而言，热收缩率较好。
测试例4
本发明实施例1-15、对比例2、3制备的一种耐高温超低热变形聚丙烯薄膜与对比例1的普通双向拉伸聚丙烯(BOPP)薄膜，下线48小时，雾度测试如表5所示。
表5
序号 公称厚度(μm) 浊度(雾度)(％)
实施例1 48 1.21
实施例2 48 1.25
实施例3 48 1.12
实施例4 80 1.58
实施例5 80 1.62
实施例6 48 8.0
实施例7 48 8.2
实施例8 48 7.8
实施例9 80 8.6
实施例10 80 8.8
实施例11 48 1.56
实施例12 48 1.60
实施例13 48 1.48
实施例14 80 1.70
实施例15 80 1.72
对比例1 48 2.98
对比例2 48 1.60
对比例3 48 1.22
备注3：样品状态调节和试验的标准环境按GB/T2918规定进行，试验环境条件为温度23℃±2℃，相对湿度50％±1％，并在此条件下样品预放置处理8hr。
从表5可以得出以下测试规律：
1、薄膜厚度越厚，雾度越大。
2、同一品种聚丙烯条件下，添加助剂比例越多雾度越大。
3、通过实施例和对比例的对比可知：助剂在同一添加比例条件下，添加无定形二氧化硅抗粘连剂薄膜雾度比添加非迁移无机增滑剂薄膜雾度大。
4、助剂在同一添加比例条件下，雾度由小变大依次为：高熔体强度聚丙烯HMS20Z薄膜＜高熔体强度聚丙烯E02ES薄膜＜普通聚丙烯薄膜。
同样添加HMS20Z的薄膜，雾度由小变大依次为：实施例3＜实施例1＜实施例4。
同样添加E02ES的薄膜，雾度由小变大依次为：实施例2＜实施例5。
添加HMS20Z薄膜、添加E02ES薄膜、添加T30S普通双向拉伸薄膜，雾度由小变大依次为：实施例1＜实施例2＜对比例1。
5、以及从实施例1-5、6-10、11-15可以看出，采用双向拉伸法、吹塑管泡法或流延法均能够制备性能优良的聚丙烯薄膜。
综上，在本发明中：在双向拉伸、吹塑管泡法或流延法制备的聚丙烯薄膜加工工艺中添加了一种高熔体强度聚丙烯，在特定的工艺条件下，使聚丙烯(BOPP)薄膜具有耐高温性、超低热变形率、极少外观瑕疵点；添加了一种非迁移无机增滑剂，其所含活化玻璃球体与聚丙烯结合力好，球体表面提供合适的爽滑性，在适当薄膜生产工艺条件下可降低薄膜摩擦系数，无迁移不易脱落，不污染被包装物；活化玻璃球体具有与聚丙烯接近的折射率，薄膜透明度高，雾度低；另外，所添加的非迁移无机增滑剂其所含六氟碳聚合物在聚丙烯基体中以与基体不相容的小液滴的形态存在，与金属口模壁有较强的亲和力和低表面能，形成动力学涂层降低聚丙烯熔体的流动阻尼，同时提高薄膜光泽度，降低雾度。
以上结合附图详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个具体技术特征以任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。但这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种高熔体强度聚丙烯薄膜组合物，其特征在于，该组合物包括第一挤出层料、第二挤出层料和第三挤出层料，且至少所述第一挤出层料或所述第三挤出层料含有非迁移无机增滑剂，其中，所述非迁移无机增滑剂为共混物A经共混改性制备而得到的产物，所述共混物A含有高熔体强度聚丙烯和助剂，所述助剂含有活化玻璃球体，所述活化玻璃球体为经硅烷偶联剂及六氟碳聚合物表面处理后得到的玻璃实体球体。
  2. 根据权利要求1所述的组合物，其中，所述第一挤出层料和所述第三挤出层料均含有非迁移无机增滑剂；
    优选地，所述活化玻璃球体的平均粒径为2.5-3.5μm；
    优选地，所述六氟碳聚合物为1,1,2,3,3,3-六氟-1-丙烯聚合物；
    优选地，所述硅烷偶联剂为3-氨丙基三乙氧基硅烷。
  3. 根据权利要求1或2所述的组合物，其中，所述活化玻璃球体和所述六氟碳聚合物、所述硅烷偶联剂的重量比为1：(0.1-0.5)：(0.01-0.5)。
  4. 根据权利要求1所述的组合物，其中，所述高熔体强度聚丙烯在2.16kg载荷下230℃时的熔体流动速率为1.7-2.5g/10min，密度为0.9-0.915g/cm 3，等规指数大于等于95％，拉伸弹性模量大于等于1000MPa；优选地，所述高熔体强度聚丙烯在2.16kg载荷下230℃时的熔体流动速率为1.7-2.2g/10min，密度为0.905-0.91g/cm 3，等规指数为95-97％，拉伸弹性模量为1000-1500MPa。
  5. 根据权利要求1-4中任意一项所述的组合物，其中，以所述共混物A的总重量为基准，所述助剂的含量为5-20重量％，所述高熔体强度聚丙烯的含量为80-95重量％。
  6. 根据权利要求1所述的组合物，其中，所述第一挤出层料含有高熔体强度聚丙烯、非迁移无机增滑剂以及含有或不含有均聚聚丙烯或共聚聚丙烯，且以所述第一挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％
    所述第二挤出层料含有高熔体强度聚丙烯以及含有或不含有均聚聚丙烯或共聚聚 丙烯，且以所述第二挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为50-100重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％；
    所述第三挤出层料含有高熔体强度聚丙烯、非迁移无机增滑剂以及含有或不含有均聚聚丙烯或共聚聚丙烯，且以所述第三挤出层料的总重量为基准，所述高熔体强度聚丙烯的含量为20-99.5重量％，所述非迁移无机增滑剂的含量为0.5-30重量％，均聚聚丙烯或共聚聚丙烯的含量为0-50重量％。
  7. 一种含有权利要求1-6中任意一项所述的组合物的聚丙烯薄膜，其特征在于，所述聚丙烯薄膜包括依次叠加的第一挤出层、第二挤出层和第三挤出层，其中，所述第一挤出层由所述第一挤出层料挤出而得到的，所述第二挤出层由所述第二挤出层料挤出而得到的，以及所述第三挤出层由所述第三挤出层料挤出而得到的。
  8. 根据权利要求7所述的聚丙烯薄膜，其中，所述第一挤出层的厚度为0.5-45μm，所述第二挤出层的厚度为8-60μm，所述第三挤出层的厚度为0.5-45μm；优选地，所述聚丙烯薄膜的厚度为9-150μm。
  9. 根据权利要求7或8所述的聚丙烯薄膜，其中，该聚丙烯薄膜通过共挤出以及双向拉伸法、吹塑管泡法或流延法制得的。
  10. 权利要求7-9中任意一项所述的聚丙烯薄膜在电子保护、软包装电池、印刷复合、镀层、涂布或广告装饰领域中的应用。
PCT/CN2019/079473 2018-10-29 2019-03-25 高熔体强度聚丙烯薄膜组合物和薄膜及其应用 WO2020087849A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
MYPI2021002368A MY197918A (en) 2018-10-29 2019-03-25 High melt strength polypropylene thin film composition, thin film and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811269458.1A CN109280273B (zh) 2018-10-29 2018-10-29 高熔体强度聚丙烯薄膜组合物和薄膜及其应用
CN201811269458.1 2018-10-29

Publications (1)

Publication Number Publication Date
WO2020087849A1 true WO2020087849A1 (zh) 2020-05-07

Family

ID=65178290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/079473 WO2020087849A1 (zh) 2018-10-29 2019-03-25 高熔体强度聚丙烯薄膜组合物和薄膜及其应用

Country Status (3)

Country Link
CN (1) CN109280273B (zh)
MY (1) MY197918A (zh)
WO (1) WO2020087849A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109280273B (zh) * 2018-10-29 2020-03-27 上海若祎新材料科技有限公司 高熔体强度聚丙烯薄膜组合物和薄膜及其应用
CN114552081B (zh) * 2021-12-14 2023-08-15 万向一二三股份公司 一种高安全性锂电池软包铝塑膜

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1428747A (en) * 1973-08-07 1976-03-17 Ici Ltd Polymeric films
CN101791889A (zh) * 2010-01-29 2010-08-04 浙江凯利包装材料有限公司 耐高温隔离双向拉伸聚丙烯薄膜及其制造方法
CN102806735A (zh) * 2012-08-30 2012-12-05 江苏奔多新材料有限公司 一种高牢度镀铝聚丙烯薄膜及其生产工艺
CN103029396A (zh) * 2012-12-25 2013-04-10 海南赛诺实业有限公司 一种香烟包装用双向拉伸聚丙烯收缩膜及其制造方法和应用
CN103895298A (zh) * 2014-04-12 2014-07-02 广东威孚包装材料有限公司 完全生物降解流涎聚丙烯薄膜及其制造方法
CN104986437A (zh) * 2015-05-29 2015-10-21 桐城市福润包装材料有限公司 一种抗紫外线未拉伸聚丙烯镀铝薄膜的生产方法
CN105172284A (zh) * 2015-07-30 2015-12-23 中山火炬职业技术学院 具备耐久爽滑特性的bopp薄膜及其制备方法
CN106541661A (zh) * 2016-10-27 2017-03-29 上海若祎新材料科技有限公司 一种免电晕双向拉伸聚丙烯包装薄膜及其制造方法
CN109280273A (zh) * 2018-10-29 2019-01-29 上海若祎新材料科技有限公司 高熔体强度聚丙烯薄膜组合物和薄膜及其应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321301A (zh) * 2011-08-19 2012-01-18 刘文敏 一种模口润滑防粘母料及其生产工艺
CN102602106A (zh) * 2012-03-16 2012-07-25 浙江绍兴华东包装有限公司 超透双向拉伸聚丙烯薄膜的生产工艺
CN103331974B (zh) * 2013-07-11 2016-02-24 中山北化高分子材料有限公司 一种时效稳定型高光泽、低雾度、超爽滑bopp薄膜
CN103435911B (zh) * 2013-08-28 2016-05-18 余小双 抗粘连bopp母料及其制备方法
CN105348624A (zh) * 2015-08-31 2016-02-24 无锡市嘉邦电力管道厂 热塑性抗开裂型低烟无卤阻燃聚烯烃电缆护套料及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1428747A (en) * 1973-08-07 1976-03-17 Ici Ltd Polymeric films
CN101791889A (zh) * 2010-01-29 2010-08-04 浙江凯利包装材料有限公司 耐高温隔离双向拉伸聚丙烯薄膜及其制造方法
CN102806735A (zh) * 2012-08-30 2012-12-05 江苏奔多新材料有限公司 一种高牢度镀铝聚丙烯薄膜及其生产工艺
CN103029396A (zh) * 2012-12-25 2013-04-10 海南赛诺实业有限公司 一种香烟包装用双向拉伸聚丙烯收缩膜及其制造方法和应用
CN103895298A (zh) * 2014-04-12 2014-07-02 广东威孚包装材料有限公司 完全生物降解流涎聚丙烯薄膜及其制造方法
CN104986437A (zh) * 2015-05-29 2015-10-21 桐城市福润包装材料有限公司 一种抗紫外线未拉伸聚丙烯镀铝薄膜的生产方法
CN105172284A (zh) * 2015-07-30 2015-12-23 中山火炬职业技术学院 具备耐久爽滑特性的bopp薄膜及其制备方法
CN106541661A (zh) * 2016-10-27 2017-03-29 上海若祎新材料科技有限公司 一种免电晕双向拉伸聚丙烯包装薄膜及其制造方法
CN109280273A (zh) * 2018-10-29 2019-01-29 上海若祎新材料科技有限公司 高熔体强度聚丙烯薄膜组合物和薄膜及其应用

Also Published As

Publication number Publication date
CN109280273A (zh) 2019-01-29
CN109280273B (zh) 2020-03-27
MY197918A (en) 2023-07-25

Similar Documents

Publication Publication Date Title
KR101577394B1 (ko) 무기 물질 분말 고배합 박막 시트의 제조 방법
CN104553218B (zh) 超低温热封双向拉伸聚丙烯薄膜及其制造方法
CN110774713A (zh) 一种涂布型高阻隔双向拉伸聚乳酸薄膜及其制备方法
TW201801928A (zh) 雙軸配向聚丙烯膜
TWI404750B (zh) Polyamide-based mixed resin film roll and its manufacturing method
CN109181242B (zh) 塑料薄膜用开口剂母粒及其制备方法
WO2020087849A1 (zh) 高熔体强度聚丙烯薄膜组合物和薄膜及其应用
CN107849399A (zh) 粘结膜和粘结膜筒
CN111423647B (zh) 一种双向拉伸聚乙烯柔面哑光薄膜组合物和薄膜及其应用
TW200827143A (en) Method for texturing polymeric films and articles comprising the same
JP4650019B2 (ja) ポリプロピレン系積層フィルム及びそれを用いた包装体
WO2005090073A1 (ja) ポリプロピレン系積層フィルム及びそれを用いた包装体
CN105235336A (zh) 一种耐低温的双向拉伸聚丙烯薄膜及其制备方法
CN108602968B (zh) 无光泽的聚酰胺系膜及其制造方法
US5853638A (en) Process for producing stretched porous film
JPH05200858A (ja) シンジオタクティックポリスチレン系フィルム
CN114043794A (zh) 一种粗糙度及光学性能可调的聚酯基膜及其制备方法
CN109605886A (zh) 一种耐高温纳米级自粘性光学保护膜及其生产方法
TWI492977B (zh) 袋用尼龍薄膜
CN112405935A (zh) 锂离子电池用哑光黑色聚酰胺薄膜及其黑色母粒和制备方法
CN110429210A (zh) 一种锂电池软包装用的聚酰胺薄膜及其制备工艺
CN115534464A (zh) 一种高光泽高透明bopp薄膜及其制备方法和应用
Melkar et al. Effect of antiblock and slip additives on the properties of tubular quenched polypropylene film
JPS59215833A (ja) 超高分子量ポリエチレン多孔質フイルムの製造方法
JP2020151907A (ja) 二軸延伸多層フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19878973

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19878973

Country of ref document: EP

Kind code of ref document: A1