CN109280273B - High melt strength polypropylene film compositions and films and uses thereof - Google Patents

High melt strength polypropylene film compositions and films and uses thereof Download PDF

Info

Publication number
CN109280273B
CN109280273B CN201811269458.1A CN201811269458A CN109280273B CN 109280273 B CN109280273 B CN 109280273B CN 201811269458 A CN201811269458 A CN 201811269458A CN 109280273 B CN109280273 B CN 109280273B
Authority
CN
China
Prior art keywords
polypropylene
layer material
extrusion layer
melt strength
film
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN201811269458.1A
Other languages
Chinese (zh)
Other versions
CN109280273A (en
Inventor
韦丽明
梁雁扬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
If Shanghai Yi New Mstar Technology Ltd
Original Assignee
If Shanghai Yi New Mstar Technology Ltd
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 If Shanghai Yi New Mstar Technology Ltd filed Critical If Shanghai Yi New Mstar Technology Ltd
Priority to CN201811269458.1A priority Critical patent/CN109280273B/en
Publication of CN109280273A publication Critical patent/CN109280273A/en
Priority to PCT/CN2019/079473 priority patent/WO2020087849A1/en
Priority to MYPI2021002368A priority patent/MY197918A/en
Application granted granted Critical
Publication of CN109280273B publication Critical patent/CN109280273B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

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

The invention relates to the technical field of processing of high-melt-strength polypropylene films, and discloses a high-melt-strength polypropylene film composition, a high-melt-strength polypropylene film and application of the high-melt-strength polypropylene film composition and the high-melt-strength polypropylene film. The composition comprises a first extrusion layer material, a second extrusion layer material and a third extrusion layer material, wherein at least the first extrusion layer material or the third extrusion layer material contains a non-migration inorganic slipping agent, and the non-migration inorganic slipping agent is a product prepared by blending and modifying a blend A. The high melt strength polypropylene film containing the non-migrating inorganic slip agent has the advantages of high temperature resistance, ultralow heat deformation rate, no crystal point, few appearance flaws and high transparency, and the function and the appearance of the film meet the market requirements of high-end electronic protection, flexible package batteries, printing and compounding, plating, coating or advertisement decoration and the like.

Description

High melt strength polypropylene film compositions and films and uses thereof
Technical Field
The invention relates to the technical field of processing of high-melt-strength polypropylene films, and discloses a high-melt-strength polypropylene film composition, a high-melt-strength polypropylene film and application of the high-melt-strength polypropylene film composition and the high-melt-strength polypropylene film.
Background
Biaxially oriented films, blown bubble films and cast films are common packaging materials with excellent performance, and are widely applied to the fields of clothing, cosmetics, food, books, tissues, industry, medicines, electronic protection, coating (glue) and the like. The latest statistical data of the plastic package committee experts of the China packaging Association indicate that the total yield of Chinese packaging films exceeds 1000 million tons by 1 month in 2018, and the average 5% composite year growth rate is expected to increase gradually in five years.
In production applications, conventional polypropylene or polyethylene films often suffer from warping, curling. This is mainly due to the phenomenon of the film being poor in resistance to high temperatures and shrinkage during stretching and heating. Film shrinkage, curling and the like affect production efficiency, and therefore, enterprises demand that the lower the heat deformation rate, the better. In particular, the film in the field of electronic protection is required to have heat resistance, extremely high dimensional stability, low thermal deformation rate, extremely few appearance flaws, no precipitate precipitation, no pollution to circuit boards, electronic components and the like. The dimensional stability of the film under heating, that is, the degree of deformation of the film under heating, can also reflect the temperature resistance of the film by detecting the thermal shrinkage (thermal deformation rate). At present, GB/T21302 composite films and bags for packaging have no clear regulations on curling and shrinkage, GB/T4456 polyethylene blown films for packaging and GB/T27740 cast polypropylene (CPP) films have no clear regulations on the size and the test method of the thermal shrinkage, and GB/T10003 biaxially oriented polypropylene (BOPP) films for general use refer to YC/T266 packaging films for cigarettes. The temperature for testing the heat shrinkage rate of the downstream processing enterprises is usually 80 ℃, 120 ℃ and 135 ℃.
In general, the macromolecules of the film are in a state of natural curling, and very little thermal shrinkage (thermal deformation rate) occurs when heated. However, polypropylene (PP) and Polyethylene (PE) are semi-crystalline polymer materials, and the biaxially oriented and blown tube bubble film undergoes longitudinal stretching and transverse stretching during the production process, and the requirements for production width, speed and heat shrinkage rate are different, so that different stretching ratios are set; the cast film also has varying degrees of machine direction stretch due to die to casting roll position, and speed differences between the rolls. The molecular chains are forced to be stretched under the action of external force, the macromolecules cannot slide mutually, and the forced stretched molecular chains are frozen when the shaping area is cooled. At room temperature, the macromolecular material has poor activity, so that the forced stretching state cannot be eliminated by molecular motion, and when the film is heated, the frozen macromolecular material can start to move again, tries to recover to the natural state from the natural state, and generates shrinkage as a result. The use of films having a large thermal deformation rate is limited.
Therefore, it is important to research and develop a film having heat resistance, extremely high dimensional stability, low thermal deformation rate, extremely few appearance defects, and no precipitate.
Disclosure of Invention
The invention aims to overcome the defects of poor heat resistance, low dimensional stability, more appearance defects and precipitate of a migration object of a biaxially oriented film, a blown tube film and a cast film in the prior art, and provides a high-melt-strength polypropylene film composition, a high-melt-strength polypropylene film and application thereof. The high melt strength polypropylene is prepared through a blending method, a column reactor method (electron beam irradiation, peroxide treatment and reactive extrusion) introducing a long-branched structure, an internal reactor polymerization method (direct copolymerization, macromolerization) and a crosslinking method, so that the weight average molecular weight and the broadened molecular weight distribution of the polypropylene (PP) are improved, the polypropylene has a long-chain branched structure, and the structural material can obviously improve the rheological property of a linear polypropylene material, so that the melt strength of the polypropylene is generally 1.5-50 times of that of common polypropylene, the strain softening characteristic of the common polypropylene is changed by the long-branched chain structure, and the defects of the polypropylene in the processing process are overcome. Has the performance advantages which are not possessed by the traditional polypropylene, such as wide range of mechanical properties, thermal stability, chemical stability and the like. The high melt strength polypropylene film prepared by adding the high melt strength polypropylene composition and by a biaxial stretching method, a blown film method and a casting method has the advantages of heat resistance, extremely high dimensional stability, low thermal deformation rate, few appearance flaw points, no precipitate precipitation, and capability of meeting the market requirements of high-end electronic protection, flexible package batteries, printing compounding, plating, coating (glue), advertisement decoration and the like, and does not need to transform the existing equipment.
In order to achieve the above object, a first aspect of the present invention provides a high melt strength polypropylene film composition, where the composition includes a first extruded layer material, a second extruded layer material, and a third extruded layer material, and at least the first extruded layer material or the third extruded layer material contains a non-migrating inorganic slip agent, where the non-migrating inorganic slip agent is a product prepared by blending and modifying a blend a, where the blend a contains a high melt strength polypropylene and an auxiliary agent, the auxiliary agent contains activated glass spheres, and the activated glass spheres are glass solid spheres obtained by surface treatment of a silane coupling agent and a hexafluoro carbon polymer.
The second aspect of the present invention provides a polypropylene film prepared from the composition, wherein the polypropylene film comprises a first extrusion layer, a second extrusion layer and a third extrusion layer which are sequentially stacked, wherein the first extrusion layer is obtained by extruding the first extrusion layer material, the second extrusion layer is obtained by extruding the second extrusion layer material, and the third extrusion layer is obtained by extruding the third extrusion layer material.
The third aspect of the invention provides the application of the polypropylene film in the fields of electronic protection, flexible package battery, printing and compounding, plating, coating or advertising decoration.
By adopting the technical scheme, the non-migratory inorganic slip agent and the high-melt-strength polypropylene are used as the components of the polypropylene film, so that the heat resistance of the film can be greatly improved, the dimensional stability is kept, the thermal deformation rate is reduced, appearance flaw points are reduced, no migratory substances are separated out, the transparency is high, and the film can be produced on line on the existing production lines of biaxially oriented, blown tube bulbs and cast films without modifying the existing equipment.
Drawings
FIG. 1 is an SEM photograph of the surface of a film after rubbing of the film prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of the surface of the film after rubbing of the film prepared in example 2 of the present invention;
FIG. 3 is an SEM photograph of the surface of the film after rubbing of the film prepared in comparative example 1 of the present invention;
FIG. 4 is SEM photographs of the first extruded layer and the third extruded layer used to prepare the film in example 1 of the present invention;
FIG. 5 is SEM photographs of the first extruded layer and the third extruded layer used to prepare the film in example 2 of the present invention;
FIG. 6 is SEM photographs of the first extruded layer and the third extruded layer used to prepare the film in comparative example 1 of the present invention;
FIG. 7 is a schematic diagram of a biaxial stretching process for preparing a high melt strength polypropylene film according to the present invention;
FIG. 8 is a schematic representation of the present invention of a blown tube process for producing a high melt strength polypropylene film;
FIG. 9 is a schematic diagram of the casting method of the present invention for preparing high melt strength polypropylene film.
Description of the reference numerals
1 first extruded layer 2 third extruded layer
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a high melt strength polypropylene film composition, which comprises a first extrusion layer material, a second extrusion layer material and a third extrusion layer material, wherein at least the first extrusion layer material or the third extrusion layer material contains a non-migration inorganic slipping agent, wherein the non-migration inorganic slipping agent is a product prepared by blending and modifying a blend A, the blend A contains high melt strength polypropylene and an auxiliary agent, the auxiliary agent contains an activated glass sphere, and the activated glass sphere is a glass entity sphere obtained by surface treatment of a silane coupling agent and a hexafluorocarbon polymer.
According to the invention, the effect is better when the first extruded layer material and the third extruded layer material both contain non-migrating inorganic slip agents.
According to the invention, "blending modification" specifically means that the components in the blend A are fed in proportion, melted and plasticated in a screw extruder, extruded, cooled and cut into granules.
According to the invention, the mean particle diameter of the activated glass spheres may be between 2.5 and 3.5. mu.m, preferably between 2.8 and 3.2. mu.m.
Preferably, the hexafluoro-carbon polymer is a 1,1,2,3,3, 3-hexafluoro-1-propene polymer having a bulk density of 0.6 to 1.0g/cm3Average particle diameterLess than or equal to 25 mesh, less than or equal to 1% volatile matter at 105 ℃ for 1 hour.
Preferably, the silane coupling agent is 3-aminopropyltriethoxysilane having a viscosity value of 1.5-1.7cs, preferably 1.6cs, and a density of 0.94-0.95g/cm measured at 25 ℃3Preferably 0.946g/cm3And a flash point (closed cup) of 96 ℃, wherein in the present invention, the closed cup flash point is the lowest temperature of the sample when the sample is heated under a predetermined condition and when the sample reaches a certain temperature, a flash-off phenomenon occurs when a mixture of the vapor of the sample and the ambient air comes into contact with a flame, and the flash-off occurs.
According to the invention, the weight ratio of the contents of the activated glass spheres, 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.
according to the invention, the auxiliary agent can be prepared by self or obtained by commerce, for example, the auxiliary agent can be a non-migration inorganic slip additive with the model number of MB3050PB, which is produced by Shanghai Ruan Yi New Material science and technology Limited company, wherein the auxiliary agent contains the activated glass spheres defined by the invention, the activated glass spheres are glass solid spheres obtained by surface treatment of a silane coupling agent and a hexafluoro carbon polymer, the silane coupling agent is 3-aminopropyl triethoxysilane, the hexafluoro carbon polymer is 1,1,2,3,3, 3-hexafluoro-1-propylene polymer, and the average particle size of the activated glass spheres is 2.5-3.5 μm; and in the surface treatment process, the weight ratio of the activated glass spheres to the hexafluorocarbon polymer to the silane coupling agent is 1: (0.1-0.5): (0.01-0.5).
According to the invention, the high melt strength polypropylene has a melt flow rate of 1.7-2.5g/10min at 230 ℃ under a load of 2.16kg and a density of 0.9-0.915g/cm3The isotactic index is 95% or more and the tensile elastic modulus is 1000MPa or more, specifically, in the present invention, "greater than or equal to" means both "greater than" and "equal to" are included, for example, an isotactic index of 95% or greater means all values where the isotactic index can be 95% and greater than 95%; pulling deviceThe tensile modulus of elasticity of 1000MPa or more means that the tensile modulus of elasticity may be all values of 1000MPa or more and 1000MPa or more.
Preferably, the high melt strength polypropylene has a melt flow rate of 1.7 to 2.3g/10min at 230 ℃ under a 2.16kg load and a density of 0.905 to 0.91g/cm3The isotactic index is 95-97%, and the tensile elastic modulus is 1000-; preferably, the high melt strength polypropylene has a melt flow rate of 1.7 to 2.2g/10min at 230 ℃ under a 2.16kg load and a density of 0.905 to 0.91g/cm3The isotacticity was 96% and the tensile elastic modulus was 1450 MPa. In the present invention, the high melt strength polypropylene is commercially available from Zhenhai chemical division, Inc., of petrochemical Co., Ltd., China, for example, HMS20Z and E02ES, wherein HMS20Z has a melt flow rate of 2.2g/10min at 230 ℃ under a 2.16kg load and a density of 0.905g/cm3The refractive index is 1.49, the isotacticity is 96.6%, and the tensile elastic modulus is 1410 MPa; e02ES had a melt flow rate of 1.7g/10min at 230 ℃ under a load of 2.16kg and a density of 0.905g/cm3The refractive index was 1.50 and the tensile modulus was 1020 MPa.
According to the invention, the content of the auxiliary agent is 5-20 wt% and the content of the high melt strength polypropylene is 80-95 wt% based on the total weight of the blend A.
According to the invention, the first extrusion layer material contains high melt strength polypropylene, non-migration inorganic slipping agent and homo-polypropylene or co-polypropylene, and the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or co-polypropylene is 0-50 wt%; preferably, the first extruded layer contains a high melt strength polypropylene and a non-migrating inorganic slip agent, and the high melt strength polypropylene is present in an amount of 20 to 99.5 wt% and the non-migrating inorganic slip agent is present in an amount of 0.5 to 80 wt%, based on the total weight of the first extruded layer; more preferably, the high melt strength polypropylene is present in an amount of from 20 to 97.5 wt% and the non-migrating inorganic slip agent is present in an amount of from 2.5 to 80 wt%, based on the total weight of the first extruded layer.
The second extrusion layer material contains high melt strength polypropylene and homo-polypropylene or co-polypropylene, or does not contain homo-polypropylene or co-polypropylene, and the total weight of the second extrusion layer material is taken as a reference, the content of the high melt strength polypropylene is 50-100 wt%, and the content of the homo-polypropylene or co-polypropylene is 0-50 wt%.
The third extrusion layer material contains high melt strength polypropylene, non-migration inorganic slipping agent and homo-polypropylene or co-polypropylene, wherein the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or co-polypropylene is 0-50 wt%; preferably, the third extruded layer contains a high melt strength polypropylene and a non-migrating inorganic slip agent, and the high melt strength polypropylene is present in an amount of 20 to 97.5 wt% and the non-migrating inorganic slip agent is present in an amount of 2.5 to 30 wt%, based on the total weight of the third extruded layer.
According to the invention, the inventor of the invention finds out through a large number of scientific experiments that: a non-migrating inorganic slip agent is added, and the bonding force between the activated glass sphere and polypropylene contained in the non-migrating inorganic slip agent is good, so that the surface of the sphere provides proper slip, the friction coefficient of the film can be reduced under the condition of a proper film production process, the film is not easy to fall off, and the packaged object is not polluted; the activated glass spheres have a refractive index close to that of polypropylene, and the film has high transparency and low haze.
According to the invention, the inventor of the invention finds out through a large number of scientific experiments that: the non-migrating inorganic slip agent is added, and the hexafluoro carbon polymer contained in the slip agent exists in the form of small droplets incompatible with the matrix in the polypropylene matrix, and the neck mold and the metal mouth mold wall have stronger affinity and low surface energy, so that a dynamic coating is formed to reduce the flow damping of the polypropylene melt, improve the film glossiness and reduce the haze.
The second aspect of the present invention provides a polypropylene film of the composition, wherein the polypropylene film comprises a first extruded layer, a second extruded layer and a third extruded layer, which are sequentially stacked, wherein the first extruded layer is obtained by extruding the first extruded layer material, the second extruded layer is obtained by extruding the second extruded layer material, and the third extruded layer is obtained by extruding the third extruded layer material.
According to the invention, the thickness of the first extruded layer is 0.5 to 45 μm, the thickness of the second extruded layer is 8 to 60 μm and the thickness of the third extruded layer is 0.5 to 45 μm.
Preferably, the polypropylene film has a thickness of 9 to 100. mu.m, preferably 12 to 85 μm, more preferably 25 to 60 μm.
According to the invention, the polypropylene film is produced by coextrusion as well as by biaxial stretching, blown tube or casting.
Biaxial stretching method
In the present invention, the method for preparing the high melt strength polypropylene film by biaxial stretching method can refer to the preparation flow diagram shown in fig. 7:
preparing materials:
based on the total weight of the first extrusion layer material, the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%;
based on the total weight of the second extrusion layer material, the content of the high melt strength polypropylene is 50-100 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%;
based on the total weight of the third extrusion layer material, the content of the high melt strength polypropylene is 20-100 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%.
Preparing ingredients: respectively putting the components of the first extrusion layer, the second extrusion layer and the third extrusion layer into respective corresponding low-speed mixers according to the weight percentage, and premixing for 30 minutes;
feeding: and (3) sucking the premixed first extrusion layer material, second extrusion layer material and third extrusion layer material into a charging barrel of a three-layer extruder under negative pressure, wherein the thicknesses of the first extrusion layer material, the second extrusion layer material and the third extrusion layer material are determined according to the dosage of the fed first extrusion layer material, second extrusion layer material and third extrusion layer material.
Plasticating and extruding: adopt many extruders to extrude the resin on first extrusion layer, second extrusion layer, third extrusion layer respectively, the reasonable layering of fused resin through the distributor, wherein:
the components of the first extrusion layer and the third extrusion layer are melt-extruded in a single-screw extruder, and the components of the second extrusion layer are melt-extruded in a double-screw extruder at the temperature of 210-245 ℃;
and (3) flaw-resistant melt filtration: the wave-shaped filter screens with the mesh numbers of 80, 150, 300, 150 and 80 are sequentially overlapped and arranged in a column shape, and the melt extrudes the filter screen at the outermost layer from the middle core rod;
cooling crystallization and sheet setting: extruding a melt extruded by an extruder through a clothes hanger die head, cooling by air knives, cooling by chilling rollers and cooling by water bath of a water tank to form a thick sheet with fine microsphere crystals, wherein a gap of a die lip is 0.5mm, the water temperature of the chilling rollers is controlled to be 15-35 ℃, and the water temperature difference between a water inlet and a water outlet is controlled to be +/-2 ℃; controlling the water temperature of the cooling water tank to be 25-35 ℃;
longitudinal stretching and shaping: double-stage stretching, wherein the total stretching ratio is controlled to be 4.0-5.0; and (3) longitudinal stretching and shaping zone: the temperature is controlled at 120-150 ℃;
transverse stretching and shaping: the transverse stretching magnification is between 7 and 11; transverse stretching and shaping area: the temperature is controlled at 190 ℃ of 170-;
traction and thickness measurement: the total thickness of the polypropylene film was measured.
Corona and winding: corona treatment may or may not be selected depending on the film application. Carrying out corona treatment on the film by a high-frequency electronic discharger, wherein the surface tension value of the lower wire is 40 mN/m; and (5) winding the film after shaping. The winding device is automatically controlled by a winding surface tension control device so as to achieve the optimal winding effect; production line speed: 200 to 500 m/min.
Aging, slitting and rolling: standing for 1-2 days at 25 + -5 deg.C and 60% RH to further stabilize size and performance; and cutting out corresponding finished product width specifications.
(II) Process for blow-moulding of a tubular foam
In the present invention, the method for preparing the high melt strength polypropylene film by using the blown tube bubble method can refer to the preparation flow diagram shown in fig. 8:
preparing materials:
based on the total weight of the first extrusion layer material, the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%;
based on the total weight of the second extrusion layer material, the content of the high melt strength polypropylene is 50-100 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%;
based on the total weight of the third extrusion layer material, the content of the high melt strength polypropylene is 20-100 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%.
Preparing ingredients: respectively putting the components of the first extrusion layer, the second extrusion layer and the third extrusion layer into respective corresponding low-speed mixers according to the weight percentage, and premixing for 30 minutes;
feeding: and (3) sucking the premixed first extrusion layer material, second extrusion layer material and third extrusion layer material into a charging barrel of a three-layer extruder under negative pressure, wherein the thicknesses of the first extrusion layer material, the second extrusion layer material and the third extrusion layer material are determined according to the dosage of the fed first extrusion layer material, second extrusion layer material and third extrusion layer material.
Plasticating and extruding: adopt many extruders to extrude the resin on first extrusion layer, second extrusion layer, third extrusion layer respectively, the reasonable layering of independent runner in the mould intracavity of fused resin, wherein:
melting and extruding the components of the first extrusion layer, the second extrusion layer and the third extrusion layer in a single-screw extruder at the temperature of 160-230 ℃;
and (3) flaw-resistant melt filtration: the mesh numbers of 100, 150 and 80 are sequentially overlapped, a porous plate type filter is adopted, and the melt extrudes an outermost filter screen from the inner layer;
and (3) transverse inflation and stretching: the transverse stretching multiplying power is between 1.2 and 3.5; transverse stretching and shaping area: the temperature is controlled at 160-230 ℃;
cooling crystallization and sheet setting: extruding the extruded melt by an extruder through a die head, and introducing cold air into an air cooling or air cooling ring for cooling and shaping. The temperature of cold air introduced into the air cooling ring is controlled to be 20 +/-1 ℃;
longitudinal traction and stretching: the traction speed is 8-40 m/min;
thickness measurement and corona: the total thickness of the polypropylene film was measured. Corona treatment may or may not be selected depending on the film application. Carrying out corona treatment on the film by a high-frequency electronic discharger, wherein the surface tension value of the lower wire is 40 mN/m;
shaping and rolling: and (5) winding the film after shaping. The winding device is automatically controlled by a winding surface tension control device so as to achieve the optimal winding effect; production line speed: 50-150 m/min.
Aging, slitting and rolling: standing for 1-2 days at 25 + -5 deg.C and 60% RH to further stabilize size and performance; and cutting out corresponding finished product width specifications.
(III) casting method
In the present invention, the method for preparing the high melt strength polypropylene film by using the casting method can refer to the preparation flow diagram shown in fig. 9:
preparing materials:
based on the total weight of the first extrusion layer material, the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%;
based on the total weight of the second extrusion layer material, the content of the high melt strength polypropylene is 50-100 wt%, and the content of the homo-polypropylene or the co-polypropylene is 0-50 wt%;
the third extrusion layer material contains high melt strength polypropylene and non-migration inorganic slipping agent, and the total weight of the third extrusion layer material is taken as a reference, the content of the high melt strength polypropylene is 20-100 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of homo-polypropylene or co-polypropylene is 0-50 wt%.
Preparing ingredients: respectively putting the components of the first extrusion layer, the second extrusion layer and the third extrusion layer into respective corresponding low-speed mixers according to the weight percentage, and premixing for 30 minutes;
feeding: and (3) sucking the premixed first extrusion layer material, second extrusion layer material and third extrusion layer material into a charging barrel of a three-layer extruder under negative pressure, wherein the thicknesses of the first extrusion layer material, the second extrusion layer material and the third extrusion layer material are determined according to the dosage of the fed first extrusion layer material, second extrusion layer material and third extrusion layer material.
Plasticating and extruding: adopt many extruders to extrude the resin on first extrusion layer, second extrusion layer, third extrusion layer respectively, the reasonable layering of fused resin through the distributor, wherein:
melting and extruding the components of the first extrusion layer, the second extrusion layer and the third extrusion layer in a single-screw extruder at the temperature of 195-260 ℃;
and (3) flaw-resistant melt filtration: the wave-shaped filter screens with the mesh numbers of 80, 150, 300, 150 and 80 are sequentially overlapped and arranged in a column shape, and the melt extrudes the filter screen at the outermost layer from the middle core rod;
cooling crystallization and sheet setting: extruding a melt extruded by an extruder through a clothes hanger die head or a T-shaped die head, cooling by air knife and a chill roll into a thick sheet with fine microsphere crystals, wherein the gap of a die lip is 0.5mm, the water temperature of the chill roll is controlled at 15-35 ℃, and the water temperature difference between a water inlet and a water outlet is controlled at +/-2 ℃;
measuring the thickness: the total thickness of the polypropylene film was measured.
Heating and setting, and corona: setting with hot water roller, controlling water temperature at 35-55 deg.C, and controlling water temperature difference at water inlet and outlet at + -2 deg.C; corona treatment may or may not be selected depending on the film application. Carrying out corona treatment on the film by a high-frequency electronic discharger, wherein the surface tension value of the lower wire is 40 mN/m;
cooling and shaping: cooling and shaping by a cold water roller, controlling the water temperature at 20-35 ℃, and controlling the water temperature difference between the water inlet and the water outlet at +/-2 ℃;
winding: and (5) winding the film after shaping. The winding device is automatically controlled by a winding surface tension control device so as to achieve the optimal winding effect; production line speed: 25-250 m/min.
Aging, slitting and rolling: standing for 1-2 days at 25 + -5 deg.C and 60% RH to further stabilize size and performance; and cutting out corresponding finished product width specifications.
The third aspect of the invention provides an application of the polypropylene film in the fields of electronic protection, flexible package batteries, printing and compounding, plating, coating or advertising decoration.
Among them, coating may also be referred to as gumming.
The inventors of the present invention have surprisingly found that: the high melt strength polypropylene is added in the processing technology of the biaxial stretching film, the blow molding bubble film and the casting film, so that the film has high temperature resistance, ultralow heat deformation rate and few appearance flaw points under specific technological conditions; the non-migration inorganic slip agent is added, the bonding force between the activated glass sphere and polypropylene contained in the non-migration inorganic slip agent is good, the surface of the sphere provides proper slip, the friction coefficient of the film can be reduced under the condition of a proper film production process, the non-migration inorganic slip agent is not easy to fall off, and the packaged object is not polluted; the activated glass sphere has a refractive index close to that of polypropylene, and the film has high transparency and low haze; a non-migrating inorganic slip agent is added, a hexafluoro carbon polymer contained in the slip agent exists in a polypropylene matrix in the form of small droplets incompatible with the matrix, and has stronger affinity and low surface energy with a metal die wall, so that a dynamic coating is formed to reduce the flow damping of a polypropylene melt, and simultaneously, the glossiness of a film is improved, and the haze is reduced.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) testing the thermal shrinkage rate: the standard environment of sample state regulation and test is performed according to GB/T2918, and the test environment condition is that the temperature is 23 ℃ + -2 ℃, the relative humidity is 50% + -1%, and the sample is pre-placed for 8hr under the condition; the heat shrinkage of the film at 80 ℃, 120 ℃ and 135 ℃ was compared according to the 5.7-bar oven test of GB/T10003 biaxially oriented Polypropylene (BOPP) film for general use. The specific method comprises the following steps: a square sample of 100mm × 100mm was placed flat on a stainless steel plate in a constant temperature oven at a specific temperature ℃. + -. 3 ℃ for 2min, the sample was taken out, cooled to a test ambient temperature, and changes in the longitudinal and transverse dimensions and the dimensions before heating were measured.
(2) Testing the coefficient of friction of heat slipping: the data of the coefficient of friction of the hot slipping at 80 ℃ are compared according to GB/T10006 'measuring method of coefficient of friction of plastic films and sheets'. The specific method comprises the following steps: the metal fixed plate of the friction coefficient instrument is heated to be constant temperature of 80 ℃, the film is placed on the instrument, the friction coefficient between the film and the heated metal is tested, and the state that the film slides smoothly on the guide roller after the high-speed packaging machine generates heat through friction is simulated.
(3) Testing the degree of grinding of the film: the degree of film graining was compared according to GB/T31727 "test method for degree of graining of transparent film". The degree of graining was evaluated in this test according to 4.2 "method A-Observation" in the Standard. The specific method comprises the following steps: adjusting the state of the friction tester: the Rockwell hardness of the silicone rubber pad is 20, the grinding block speed is 85 times/minute, and the grinding block hardness is 4Ib (1.8 KG); taking 7 film samples, removing the upper and lower film samples, rubbing the film surface by a rubbing block for parallel testing for 5 times, and observing the surface quality of the samples subjected to the rubbing test along the samples under a 40W fluorescent lamp. The degree of graining of the sample, which was the highest grade among the 5 sample evaluation results, is shown in Table 1.
TABLE 1
Degree of graining grade Appearance of the product
s0 No scratching was observed
s1 Very little scratching was observed
s2 A small amount of scratching was observed
s3 More scratching, but no hazy scratching, was observed
s4 More scratching and hazy scratching were observed
s5 Dense hazy scratches were observed
Example 1
This example illustrates the preparation of a high melt strength polypropylene film using a biaxial stretching process.
The film was prepared according to the schematic flow chart of the biaxial stretching method high melt strength polypropylene film preparation shown in FIG. 7.
Preparing materials (weight percentage):
first extrusion layer material: 97.5 wt% HMS20Z, 2.5 wt% non-migrating inorganic slip agent MB3050 PB;
second extrusion layer material: 100% by weight of HMS 20Z;
third extrusion layer material: 98 wt% HMS20Z, 2 wt% non-migrating inorganic slip agent MB3050 PB.
Preparing ingredients: respectively putting the components of the first extrusion layer, the second extrusion layer and the third extrusion layer into respective corresponding low-speed mixers according to the weight percentage, and premixing for 30 minutes;
feeding: and (3) sucking the premixed first extrusion layer material, second extrusion layer material and third extrusion layer material into a charging barrel of a three-layer extruder under negative pressure, wherein the thicknesses of the first extrusion layer material, the second extrusion layer material and the third extrusion layer material are determined according to the dosage of the fed first extrusion layer material, second extrusion layer material and third extrusion layer material.
Plasticating and extruding: adopt many extruders to extrude the resin on first extrusion layer, second extrusion layer, third extrusion layer respectively, the reasonable layering of fused resin through the distributor, wherein:
the components of the first extrusion layer and the third extrusion layer are melt-extruded in a single-screw extruder, and the components of the second extrusion layer are melt-extruded in a double-screw extruder at 235 ℃;
and (3) flaw-resistant melt filtration: the wave-shaped filter screens with the mesh numbers of 80, 150, 300, 150 and 80 are sequentially overlapped and arranged in a column shape, and the melt extrudes the filter screen at the outermost layer from the middle core rod;
cooling crystallization and sheet setting: extruding a melt extruded by an extruder through a clothes hanger die head, cooling by air knives, cooling by chilling rollers and cooling by water bath of a water tank to form a thick sheet with fine microsphere crystals, wherein a gap of a die lip is 0.5mm, the water temperature of the chilling rollers is controlled at 25 ℃, and the water temperature difference between a water inlet and a water outlet is controlled at +/-2 ℃; controlling the water temperature of the cooling water tank at 25 ℃;
longitudinal stretching and shaping: performing two-stage stretching, wherein the total stretching ratio is controlled to be 4.8; and (3) longitudinal stretching and shaping zone: controlling the temperature at 148 ℃;
transverse stretching and shaping: the transverse stretching magnification is 10; transverse stretching and shaping area: controlling the temperature at 190 ℃;
traction and thickness measurement: the total thickness of the polypropylene film was measured.
Corona and winding: corona treatment may or may not be selected depending on the film application. Carrying out corona treatment on the film by a high-frequency electronic discharger, wherein the surface tension value of the lower wire is 40 mN/m; and (5) winding the film after shaping. The winding device is automatically controlled by a winding surface tension control device so as to achieve the optimal winding effect; production line speed: 480 m/min.
Aging, slitting and rolling: standing for 2 days at the temperature of 25 +/-5 ℃ and the temperature of 60% RH, and further stabilizing the size and the performance; and cutting out corresponding finished product width specifications.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 48 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 46 μm, and the thickness of the third extruded layer was 1 μm;
the prepared biaxial stretching method high melt strength polypropylene film is subjected to a grinding degree test, and the result is shown in figure 1; wherein, fig. 1 is an SEM photograph of the surface of the film after rubbing the film prepared in example 1 of the present invention, and it can be seen from fig. 1 that: on the S3 scale, more scratches but no haze scratches were observed, and the falling point of the activated glass spheres contained in the non-migrating inorganic slip agent was < 2 points/50 cm2(remarks: the mass of a load block of the friction tester is 1800 +/-1 g by adopting a friction tester or according to the standard of GB/T31727-2015 appendix A, and mutual back-and-forth friction is respectively carried out on the film along the longitudinal direction and the transverse direction at a certain time and a certain speed according to a specified friction condition, and if the binding force of an auxiliary agent and organic resin is poor, the auxiliary agent is easy to fall off from the film surface, which is also called powder falling); in addition, fig. 4 is SEM photographs of the first extruded layer and the third extruded layer used for preparing the thin film in example 1 of the present invention, in which the first extruded layer: no agglomeration point and no crystal point; third extruded layer: no agglomeration point and no crystal point.
Example 2
A biaxially oriented high melt strength polypropylene film was produced in the same manner as in example 1 except that: stock preparation was different, i.e. HMS20Z was replaced by E02ES, specifically:
first extrusion layer material: 97.5 wt% E02ES, 2.5 wt% non-migrating inorganic slip agent MB3050 PB;
second extrusion layer material: 100% by weight of E02 ES;
third extrusion layer material: 98% by weight of E02ES, 2% by weight of non-migrating inorganic slip agent MB3050 PB.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 48 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 46 μm, and the thickness of the third extruded layer was 1 μm;
the prepared biaxially oriented polypropylene film was subjected to a degree of graining test, and the results are shown in fig. 2; wherein, fig. 2 is an SEM photograph of the surface of the film after rubbing the film prepared in example 2 of the present invention, and it can be seen from fig. 2 that: stage S2: more and foggy scratches can be observed, and the falling point of the hollow glass spheres contained in the non-migrating inorganic slipping agent is less than 1 point/50 cm2(ii) a In addition, fig. 5 is SEM photographs of the first extruded layer and the third extruded layer used for preparing the thin film in example 2 of the present invention, in which the first extruded layer: few agglomeration points and no crystal points; third extruded layer: no agglomeration point and no crystal point.
Example 3
A biaxially oriented high melt strength polypropylene film was produced in the same manner as in example 1 except that: preparing materials differently; specifically, the method comprises the following steps:
first extrusion layer material: 99.5 wt% HMS20Z, 0.5 wt% non-migrating inorganic slip agent MB3050 PB;
second extrusion layer material: 100% by weight of HMS 20Z;
third extrusion layer material: 99.5% by weight of HMS20Z, 0.5% by weight of a non-migrating inorganic slip agent MB3050 PB.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 48 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 46 μm, and the thickness of the third extruded layer was 1 μm.
Example 4
A biaxially oriented high melt strength polypropylene film was produced in the same manner as in example 1 except that: the stock preparation is different. Specifically, the method comprises the following steps:
first extrusion layer material: 97.5 wt% HMS20Z, 2.5 wt% non-migrating inorganic slip agent MB3050 PB;
second extrusion layer material: 100% by weight of HMS 20Z;
third extrusion layer material: 98 wt% HMS20Z, 2 wt% non-migrating inorganic slip agent MB3050 PB.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 80 μm, and the thickness of the first extruded layer was 0.8 μm, the thickness of the second extruded layer was 78.4 μm, and the thickness of the third extruded layer was 0.8 μm.
Example 5
A biaxially oriented high melt strength polypropylene film was produced in the same manner as in example 1 except that: preparing materials differently; specifically, the method comprises the following steps:
first extrusion layer material: 97.5 wt% E02ES, 2.5 wt% non-migrating inorganic slip agent MB3050 PB;
second extrusion layer material: 100% by weight of E02 ES;
third extrusion layer material: 98% by weight of E02ES, 2% by weight of non-migrating inorganic slip agent MB3050 PB.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 80 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 78.4 μm, and the thickness of the third extruded layer was 1 μm.
Examples 6 to 10
Polypropylene films were prepared according to the same formulations as in examples 1-5, respectively, except that: the preparation method comprises the steps of (1) preparing by a blow molding tube bubble method; wherein, the thickness proportion respectively is: the thickness of the first extrusion layer accounts for 20% of the total thickness; the thickness of the second extrusion layer accounts for 60% of the total thickness; the thickness of the third extruded layer was 20% of the total thickness.
Examples 11 to 15
Polypropylene films were prepared according to the same formulations as in examples 1-5, respectively, except that: preparing by adopting a tape casting method; wherein, the thickness proportion respectively is: the thickness of the first extrusion layer accounts for 20% of the total thickness; the thickness of the second extrusion layer accounts for 60% of the total thickness; the thickness of the third extruded layer was 20% of the total thickness.
Comparative example 1
A general biaxially oriented polypropylene film was produced in the same manner as in example 1 except that: the stock preparation is different. Specifically, the method comprises the following steps:
first extrusion layer material: 97.5 wt% of ordinary homopolypropylene T30S, 2.5 wt% of amorphous silica anti-stick masterbatch;
second extrusion layer material: 100% by weight of conventional homopolypropylene T30S;
third extrusion layer material: 98 wt.% T30S, 2 wt.% amorphous silica anti-tack masterbatch.
The total thickness of the common biaxially oriented polypropylene film was 48 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 1 μm, and the thickness of the third extruded layer was 46 μm;
the ordinary biaxially oriented polypropylene film was subjected to a degree of graining test, and the results are shown in FIG. 3; wherein, fig. 3 is an SEM photograph of the surface of the film after rubbing of the film prepared in comparative example 1 of the present invention, and it can be seen from fig. 3 that: stage S4: more and foggy scratches can be observed, and the dropping point of the anti-sticking master batch is less than 5 points/50 cm2(ii) a In addition, fig. 6 is SEM photographs of the first extruded layer and the third extruded layer used for preparing the thin film in comparative example 1 of the present invention, in which the first extruded layer: no agglomeration point and large crystal point; third extruded layer: a small amount of agglomeration points and no crystal points.
Comparative example 2
A biaxially oriented high melt strength polypropylene film was produced in the same manner as in example 1 except that: the stock preparation is different. Specifically, the method comprises the following steps:
first extrusion layer material: 97.5 wt% E02ES, 2.5 wt% amorphous silica anti-tack masterbatch;
second extrusion layer material: 100% by weight of E02 ES;
third extrusion layer material: 98% by weight of E02ES, 2% by weight of an amorphous silica antistick masterbatch.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 48 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 46 μm, and the thickness of the third extruded layer was 1 μm.
Comparative example 3
A biaxially oriented high melt strength polypropylene film was produced in the same manner as in example 1 except that: the stock preparation is different. Specifically, the method comprises the following steps:
first extrusion layer material: 100% by weight of E02ES, 0.5% by weight of a non-migrating inorganic slip agent MB3050 PB;
second extrusion layer material: 100% by weight of E02 ES;
third extrusion layer 100 wt% E02ES, 0 wt% non-migrating inorganic slip agent MB3050 PB.
The total thickness of the resulting biaxially oriented high melt strength polypropylene film was 48 μm, and the thickness of the first extruded layer was 1 μm, the thickness of the second extruded layer was 46 μm, and the thickness of the third extruded layer was 1 μm.
Test example 1
The high temperature resistant ultra-low thermal deformation polypropylene films prepared in examples 1-5, 6-10 and 11-15 of the invention and the common biaxially oriented polypropylene films in comparative examples 1-3 were offline for 48 hours, and the thermal smooth friction coefficient data at 80 ℃ are shown in Table 2.
TABLE 2
Figure BDA0001845661540000201
Figure BDA0001845661540000211
Remarks 1: the standard environment for sample condition regulation and test is specified in GB/T2918, and the test environment conditions are 23 deg.C + -2 deg.C, relative humidity 50% + -1%, and the sample is pre-treated for 8hr under the conditions.
As can be seen from table 2: examples 1,2, 4, 5, 6, 7, 9, 10, 11, 12, 14 and 15 had a high proportion of non-migrating inorganic slip agent MB3050PB and a low coefficient of friction when hot and slippery at 80 ℃; compared with the comparative examples 1 and 2, the addition of the amorphous silica anti-sticking master batch has high thermal smooth friction coefficient at 80 ℃, and belongs to a waste product in actual production; and the proportion of the non-migration inorganic slip agent MB3050PB added in the embodiments 3, 8 and 13 is low, the thermal slipping friction coefficient is higher at 80 ℃, and the non-migration inorganic slip agent is applied to product varieties with high friction coefficient requirements in actual production; and the proportion of adding the non-migration inorganic slipping agent MB3050PB in the proportion 3 is very low, the coefficient of friction of the non-migration inorganic slipping agent is high when the non-migration inorganic slipping agent is hot and slippery at 80 ℃, and the non-migration inorganic slipping agent belongs to a waste product in actual production; and examples 1,2, 4, 5, 6, 7, 9, 10, 11, 12, 14 and 15 show that polypropylene films having excellent properties can be produced by the biaxial stretching method, the blown tube method or the casting method.
Test example 2
The high melt strength polypropylene (BOPP) prepared by the high temperature resistant ultralow thermal deformation biaxial stretching method in the embodiments 1 to 5 and the comparative examples 2 and 3 and the common biaxial stretching polypropylene (BOPP) film prepared by the comparative example 1 are off-line for 48 hours, and the thermal shrinkage rate test is shown in Table 3.
TABLE 3
Figure BDA0001845661540000221
Remarks 2: the standard environment for sample condition regulation and test is specified in GB/T2918, and the test environment conditions are 23 deg.C + -2 deg.C, relative humidity 50% + -1%, and the sample is pre-treated for 8hr under the conditions.
As can be seen from table 3: examples 1, 3 and 4, in which high melt strength polypropylene HMS20Z was added and the proportions of the added HMS20Z and the non-migrating inorganic slip agent MB3050PB were within the range defined by the present invention, the heat shrinkage (heat distortion) was the lowest in the machine direction and the transverse direction at 80 ℃, 120 ℃ and 135 ℃, wherein the heat shrinkage (heat distortion) in the transverse direction was lower than that in the machine direction; example 4 has a greater thickness, higher temperature resistance and lower heat distortion rate than example 1 and other examples using HMS20Z (example 3) relative to example 1.
Examples 2, 5, 2 and 3, the high melt strength polypropylene E02ES added thereto had low longitudinal and transverse heat shrinkage (heat distortion) at 80 ℃ and low transverse heat shrinkage (heat distortion) at 120 ℃ and 135 ℃ respectively, and the longitudinal heat shrinkage (heat distortion) was gradually increased; example 5 is thick, high temperature resistance and lower in heat distortion rate than the other E02 ES.
While comparative example 1 has high longitudinal and transverse heat shrinkage rates (heat distortion) at 80 ℃, 120 ℃ and 135 ℃.
As is clear from Table 3, the heat resistance, heat shrinkage ratio, and heat distortion rate in the longitudinal and transverse directions of examples 1 to 5 were low, and the film was less likely to warp, and particularly, the heat resistance, heat shrinkage ratio (heat distortion rate) was the lowest, and heat distortion rate in the longitudinal and transverse directions was the most balanced, and the film was less likely to warp, in example 4.
Test example 3
The high melt strength polypropylene films prepared by the blown tube bubble method of examples 6-10 of the present invention and the high melt strength polypropylene (CPP) films prepared by the casting method of examples 11-15 were drawn off for 48 hours and the heat shrinkage test was as shown in Table 4.
TABLE 4
Figure BDA0001845661540000231
Figure BDA0001845661540000241
As can be seen from table 4: the heat shrinkage rates of the high melt strength polypropylene films prepared in examples 6 to 10 of the present invention by the blown tube bubble method and the high melt strength polypropylene (CPP) films prepared in examples 11 to 15 by the casting method were slightly lower than those of the high melt strength polypropylene (BOPP) prepared in examples 1 to 5 by the biaxial stretching method, but the heat shrinkage rate was better than that of comparative example 1.
Test example 4
The high temperature resistant ultralow thermal deformation polypropylene films prepared in the embodiments 1 to 15 and the comparative examples 2 and 3 of the invention and the common biaxially oriented polypropylene (BOPP) film in the comparative example 1 are offline for 48 hours, and the haze test is shown in Table 5.
TABLE 5
Figure BDA0001845661540000242
Figure BDA0001845661540000251
Remarks 3: the standard environment for sample condition regulation and test is specified in GB/T2918, and the test environment conditions are 23 deg.C + -2 deg.C, relative humidity 50% + -1%, and the sample is pre-treated for 8hr under the conditions.
From table 5, the following test rules can be derived:
1. the thicker the film thickness, the greater the haze.
2. Under the condition of the same kind of polypropylene, the more the additive is added, the higher the haze is.
3. By comparing the examples and comparative examples, it can be seen that: the haze of the film added with the amorphous silica anti-blocking agent is higher than that of the film added with the non-migrating inorganic slipping agent under the condition of the same adding proportion of the auxiliary agent.
4. Under the condition of the same addition proportion, the haze of the auxiliary agent is sequentially changed from small to big as follows: the high melt strength polypropylene HMS20Z film is less than the high melt strength polypropylene E02ES film is less than the common polypropylene film.
The film with the same HMS20Z added has the following haze values in sequence from small to big: example 3 < example 1 < example 4.
The film with the same addition of E02ES has the following haze values in order from small to large: example 2 < example 5.
The haze of the HMS 20Z-added film, the E02 ES-added film and the T30S-added common biaxially oriented film is sequentially as follows from small to big: example 1 < example 2 < comparative example 1.
5. And from examples 1 to 5, 6 to 10, and 11 to 15, it can be seen that a polypropylene film excellent in properties can be produced by the biaxial stretching method, the blown tube method, or the casting method.
In summary, in the present invention: adding a high melt strength polypropylene in a processing technology of a polypropylene film prepared by a biaxial stretching, blow molding tube bubble method or tape casting method, and enabling the polypropylene (BOPP) film to have high temperature resistance, ultralow heat deformation rate and few appearance flaw points under specific technological conditions; the non-migration inorganic slip agent is added, the bonding force between the activated glass sphere and polypropylene contained in the non-migration inorganic slip agent is good, the surface of the sphere provides proper slip, the friction coefficient of the film can be reduced under the condition of a proper film production process, the non-migration inorganic slip agent is not easy to fall off, and the packaged object is not polluted; the activated glass sphere has a refractive index close to that of polypropylene, and the film has high transparency and low haze; in addition, the added non-migration inorganic slip agent contains a hexafluoro carbon polymer which exists in a polypropylene matrix in the form of small droplets incompatible with the matrix, has stronger affinity with the wall of a metal die and low surface energy, forms a dynamic coating to reduce the flow damping of a polypropylene melt, and simultaneously improves the glossiness of a film and reduces the haze.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention. Including each of the specific features, are combined in any suitable manner. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.

Claims (10)

1. The high melt strength polypropylene film composition is characterized by comprising a first extrusion layer material, a second extrusion layer material and a third extrusion layer material, wherein at least the first extrusion layer material or the third extrusion layer material contains a non-migration inorganic slipping agent, the non-migration inorganic slipping agent is a product prepared by blending and modifying a blend A, the blend A contains high melt strength polypropylene and an auxiliary agent, the auxiliary agent contains an activated glass sphere, and the activated glass sphere is a glass solid sphere obtained by surface treatment of a silane coupling agent and a hexafluoro carbon polymer;
based on the total weight of the blend A, the content of the auxiliary agent is 5-20 wt%, and the content of the high melt strength polypropylene is 80-95 wt%;
wherein the first extrusion layer material contains high melt strength polypropylene, non-migration inorganic slipping agent and homo-polypropylene or co-polypropylene, and the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or co-polypropylene is 0-50 wt%;
the second extrusion layer material contains high melt strength polypropylene and homo-polypropylene or co-polypropylene, or does not contain homo-polypropylene or co-polypropylene, and the total weight of the second extrusion layer material is taken as a reference, the content of the high melt strength polypropylene is 50-100 wt%, and the content of the homo-polypropylene or co-polypropylene is 0-50 wt%;
the third extrusion layer material contains high melt strength polypropylene, non-migration inorganic slipping agent and homo-polypropylene or co-polypropylene, wherein the content of the high melt strength polypropylene is 20-99.5 wt%, the content of the non-migration inorganic slipping agent is 0.5-30 wt%, and the content of the homo-polypropylene or co-polypropylene is 0-50 wt% based on the total weight of the third extrusion layer material.
2. The composition of claim 1, wherein the first extruded layer and the third extruded layer each contain a non-migrating inorganic slip agent;
wherein the average particle size of the activated glass spheres is 2.5-3.5 μm;
wherein the hexafluoro-carbon polymer is a 1,1,2,3,3, 3-hexafluoro-1-propene polymer;
wherein the silane coupling agent is 3-aminopropyltriethoxysilane.
3. The composition of claim 1 or 2, wherein the weight ratio of the activated glass spheres to the hexafluorocarbon polymer to the silane coupling agent is 1: (0.1-0.5): (0.01-0.5).
4. According to claim1, wherein the high melt strength polypropylene has a melt flow rate of 1.7 to 2.5g/10min at 230 ℃ under a 2.16kg load and a density of 0.9 to 0.915g/cm3The isotactic index is greater than or equal to 95 percent, and the tensile elastic modulus is greater than or equal to 1000 MPa.
5. The composition of claim 4 wherein the high melt strength polypropylene has a melt flow rate of 1.7 to 2.2g/10min at 230 ℃ under a 2.16kg load and a density of 0.905 to 0.91g/cm3The isotactic index is 95-97%, and the tensile elastic modulus is 1000-1500 MPa.
6. A polypropylene film comprising the composition according to any one of claims 1 to 5, wherein the polypropylene film comprises a first extruded layer, a second extruded layer and a third extruded layer stacked in this order, wherein the first extruded layer is obtained by extruding the first extruded layer material, the second extruded layer is obtained by extruding the second extruded layer material, and the third extruded layer is obtained by extruding the third extruded layer material.
7. The polypropylene film according to claim 6, wherein the thickness of the first extruded layer is 0.5-45 μm, the thickness of the second extruded layer is 8-60 μm and the thickness of the third extruded layer is 0.5-45 μm.
8. The polypropylene film according to claim 7, wherein the polypropylene film has a thickness of 9 to 150 μm.
9. Polypropylene film according to claim 6 or 8, wherein the polypropylene film is produced by coextrusion and biaxial stretching, blown tube bubble or casting.
10. Use of the polypropylene film according to any one of claims 6 to 9 in the field of electronic protection, flexible packaging batteries, print compounding, coating or advertising decoration.
CN201811269458.1A 2018-10-29 2018-10-29 High melt strength polypropylene film compositions and films and uses thereof Active CN109280273B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201811269458.1A CN109280273B (en) 2018-10-29 2018-10-29 High melt strength polypropylene film compositions and films and uses thereof
PCT/CN2019/079473 WO2020087849A1 (en) 2018-10-29 2019-03-25 High melt strength polypropylene thin film composition, thin film and use thereof
MYPI2021002368A MY197918A (en) 2018-10-29 2019-03-25 High melt strength polypropylene thin film composition, thin film and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811269458.1A CN109280273B (en) 2018-10-29 2018-10-29 High melt strength polypropylene film compositions and films and uses thereof

Publications (2)

Publication Number Publication Date
CN109280273A CN109280273A (en) 2019-01-29
CN109280273B true CN109280273B (en) 2020-03-27

Family

ID=65178290

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811269458.1A Active CN109280273B (en) 2018-10-29 2018-10-29 High melt strength polypropylene film compositions and films and uses thereof

Country Status (3)

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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109280273B (en) * 2018-10-29 2020-03-27 上海若祎新材料科技有限公司 High melt strength polypropylene film compositions and films and uses thereof
CN114552081B (en) * 2021-12-14 2023-08-15 万向一二三股份公司 High-safety soft-package aluminum-plastic film for lithium battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101791889A (en) * 2010-01-29 2010-08-04 浙江凯利包装材料有限公司 Heat-resisting isolated biaxially oriented polypropylene film and manufacturing method thereof
CN102321301A (en) * 2011-08-19 2012-01-18 刘文敏 Lubricated antiseized masterbatch of a kind of die orifice and production technique thereof
CN102602106A (en) * 2012-03-16 2012-07-25 浙江绍兴华东包装有限公司 Process for producing ultra-transparent biaxially oriented polypropylene film
CN103331974A (en) * 2013-07-11 2013-10-02 中山百能思塑料科技有限公司 Aging-stable, high-gloss, low-haze and ultra-smooth BOPP film
CN103435911A (en) * 2013-08-28 2013-12-11 余小双 Anti-adhesion BOPP (Biaxially-oriented Polypropylene) master batch and preparation method thereof
CN105348624A (en) * 2015-08-31 2016-02-24 无锡市嘉邦电力管道厂 Thermoplastic anti-cracking low-smoke halogen-free and flame-retardant polyolefin cable jacket material and preparation method therefor

Family Cites Families (8)

* 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
CN102806735A (en) * 2012-08-30 2012-12-05 江苏奔多新材料有限公司 High-fastness aluminum plating polypropylene (PP) film and production process thereof
CN103029396B (en) * 2012-12-25 2015-05-06 海南赛诺实业有限公司 Biaxially oriented polypropylene shrink film for cigarette packages and manufacturing method and application of shrink film
CN103895298B (en) * 2014-04-12 2015-09-09 广东威孚包装材料有限公司 Complete biodegradable salivation polypropylene film and manufacture method thereof
CN104986437A (en) * 2015-05-29 2015-10-21 桐城市福润包装材料有限公司 Production method for UV resistant unstretched polypropylene metalized film
CN105172284A (en) * 2015-07-30 2015-12-23 中山火炬职业技术学院 BOPP film with endurable and smoothness characteristics and preparation method therefor
CN106541661B (en) * 2016-10-27 2018-07-17 上海若祎新材料科技有限公司 One kind exempting from corona Biaxially oriented polypropylene packing film and its manufacturing method
CN109280273B (en) * 2018-10-29 2020-03-27 上海若祎新材料科技有限公司 High melt strength polypropylene film compositions and films and uses thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101791889A (en) * 2010-01-29 2010-08-04 浙江凯利包装材料有限公司 Heat-resisting isolated biaxially oriented polypropylene film and manufacturing method thereof
CN102321301A (en) * 2011-08-19 2012-01-18 刘文敏 Lubricated antiseized masterbatch of a kind of die orifice and production technique thereof
CN102602106A (en) * 2012-03-16 2012-07-25 浙江绍兴华东包装有限公司 Process for producing ultra-transparent biaxially oriented polypropylene film
CN103331974A (en) * 2013-07-11 2013-10-02 中山百能思塑料科技有限公司 Aging-stable, high-gloss, low-haze and ultra-smooth BOPP film
CN103435911A (en) * 2013-08-28 2013-12-11 余小双 Anti-adhesion BOPP (Biaxially-oriented Polypropylene) master batch and preparation method thereof
CN105348624A (en) * 2015-08-31 2016-02-24 无锡市嘉邦电力管道厂 Thermoplastic anti-cracking low-smoke halogen-free and flame-retardant polyolefin cable jacket material and preparation method therefor

Also Published As

Publication number Publication date
MY197918A (en) 2023-07-25
CN109280273A (en) 2019-01-29
WO2020087849A1 (en) 2020-05-07

Similar Documents

Publication Publication Date Title
KR101577394B1 (en) Method for producing inorganic substance powder highly-oriented thin film sheet
EP1754588B1 (en) Polyamide resin film roll
EP1118452A1 (en) A process for producing a three layers co-extrusion biaxially oriented polypropylene synthetic paper of thickness 25-250 My m
CN106315009B (en) Wear-resistant patterned cigarette film and preparation method thereof
TWI404750B (en) Polyamide-based mixed resin film roll and its manufacturing method
CN114161799B (en) Uniformly-delustered stretched polypropylene film and preparation method thereof
CN109280273B (en) High melt strength polypropylene film compositions and films and uses thereof
KR101268217B1 (en) Thermo-shrinkable polyester mono-layer film
CN109532179B (en) Bottom-coating-agent-free biaxially oriented polyethylene glycol terephthalate film and preparation method thereof
CN111423647B (en) Biaxially oriented polyethylene soft surface matte film composition, film and application thereof
CN112622380B (en) High-barrier polylactic acid film and preparation method thereof
CN112724499A (en) Special functional PE-based laminating material and preparation method and application thereof
CN110303748B (en) Thinner polyolefin shrink film and production process thereof
JP3696056B2 (en) Improved production method of biaxially stretched polypropylene (BOPP) par gloss synthetic paper having a thickness of 25 to 250 μm obtained by a three-layer coextrusion method using a single screw extruder
JP3623681B2 (en) Method for producing 25-250 micron biaxially oriented polypropylene (BOPP) pearl gloss synthetic paper obtained by three-layer coextrusion method
CN115648771B (en) BOPP (biaxially-oriented polypropylene) matt film capable of being heat-sealed at low temperature and preparation method thereof
CN110920188A (en) Bio-based PTT/PLA heat-shrinkable label film and preparation method thereof
CN103112229B (en) Ultrathin biaxially-oriented polypropylene film for packaging coil paper and manufacturing method thereof
CN115674838A (en) Stiffness-enhanced temperature-resistant polyethylene film and preparation method and application thereof
CN115534464A (en) High-gloss and high-transparency BOPP film and preparation method and application thereof
CN112936899B (en) Production method of multifunctional high-haze transfer film
CN114806151B (en) Pearlescent master batch and preparation method thereof, core layer, polyamide film and preparation method thereof
CN114454581A (en) Environment-friendly mail-order express delivery film and preparation method thereof
JPH0966564A (en) Preparation of synthetic paper and product thereof
CN102848569B (en) Production method of two-way stretched thin film made of 3-hydroxybutyrate-4-hydroxybutyrate copolymer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: Wei Liming

Inventor after: Liang Yanyang

Inventor before: Wei Liming

CB03 Change of inventor or designer information
GR01 Patent grant
GR01 Patent grant
CP02 Change in the address of a patent holder

Address after: 611, T2 / F, wankeshi District, Lane 168, Taihong Road, Minhang District, Shanghai, 201107

Patentee after: SHANGHAI RUOYI NEW MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 201803 1401, room 328, Lane 328, Huajiang Road, Jiangqiao, Jiading District, Shanghai.

Patentee before: SHANGHAI RUOYI NEW MATERIAL TECHNOLOGY Co.,Ltd.

CP02 Change in the address of a patent holder