CN114714723B - Polypropylene type recyclable packaging film and preparation method thereof - Google Patents

Polypropylene type recyclable packaging film and preparation method thereof Download PDF

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Publication number
CN114714723B
CN114714723B CN202210385040.7A CN202210385040A CN114714723B CN 114714723 B CN114714723 B CN 114714723B CN 202210385040 A CN202210385040 A CN 202210385040A CN 114714723 B CN114714723 B CN 114714723B
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film
polypropylene
powder
mopp
carbon black
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CN114714723A (en
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卓友敬
杨浩文
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Huizhou Logos Packaging Material Co ltd
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Huizhou Logos Packaging Material Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the field of packaging films, and particularly discloses a polypropylene type recyclable packaging film and a preparation method thereof. The polypropylene type recyclable packaging film consists of a CPP film inner layer, an MOPP film middle layer and a BOPP film surface layer which are sequentially connected; the CPP film inner layer is prepared from the following components: binary copolymerized polypropylene, ternary copolymerized polypropylene and an opening agent; the MOPP film middle layer is prepared from the following components: binary copolymerized polypropylene; terpolymer polypropylene; the BOPP film surface layer is prepared from the following components: polypropylene; modified carbon black powder; modifying zinc oxide powder; the preparation method of the polypropylene recyclable packaging film comprises the following steps: preparing a CPP film inner layer, preparing a MOPP film intermediate layer, preparing a BOPP film surface layer, laminating the MOPP film intermediate layer and the BOPP film surface layer to form a composite film, laminating the CPP film inner layer and the composite film to form the polypropylene type recyclable packaging film. The packaging film disclosed by the invention has the advantages of convenience in recycling, and strong aging resistance.

Description

Polypropylene type recyclable packaging film and preparation method thereof
Technical Field
The invention relates to the field of packaging films, in particular to a polypropylene type recyclable packaging film and a preparation method thereof.
Background
Along with the increasing living standard of people, the environmental protection consciousness of people is stronger and stronger, and the environmental protection requirement on the packaging film is higher and higher, so the recyclable packaging film gradually becomes the mainstream product of the market.
In order to better satisfy the performance of the packaging film such as barrier property, flexibility and the like, the packaging film is generally formed by compounding multiple films, and the multiple films are generally different small types of films of the same type for recycling the packaging film. Among them, PP-based films are most common.
However, the PP-based film has poor light aging resistance, and when the packaging film is used for producing a bagged laundry detergent packaging bag, the bagged laundry detergent may be placed on the floor of a balcony and may be irradiated by sunlight, so that the aging of the laundry detergent packaging bag is easily accelerated, the service life of the packaging bag is shortened, and even the macromolecular structure of the packaging bag is likely to be changed, the components of the laundry detergent in the packaging bag are also changed, and the cleaning effect of the laundry detergent is affected. Thus, there is still room for improvement.
Disclosure of Invention
In order to improve the aging resistance of the packaging film, the application provides a polypropylene type recyclable packaging film and a preparation method thereof.
In a first aspect, the present application provides a polypropylene type recyclable packaging film, which adopts the following technical scheme:
a polypropylene type recyclable packaging film comprises a CPP film inner layer, an MOPP film middle layer and a BOPP film surface layer which are sequentially connected;
the CPP film inner layer is prepared from the following components in parts by mass: 55-60 parts of binary copolymer polypropylene, 80-85 parts of ternary copolymer polypropylene and 3-5 parts of a cracking agent;
the MOPP film interlayer is prepared from the following components in parts by mass: 70-80 parts of binary copolymer polypropylene; 15-20 parts of ternary copolymer polypropylene;
the BOPP film surface layer is prepared from the following components in parts by mass: 80-90 parts of polypropylene; 0.5-1 part of modified carbon black powder; 1-2 parts of modified zinc oxide powder;
the preparation method of the modified carbon black powder comprises the following steps: adding carbon black into a hydrochloric acid solution with the mass percentage concentration of 10% -15% to be soaked for 2-3 hours, filtering and drying, then soaking the carbon black in hydrogen peroxide with the mass percentage concentration of 15% -20% for 4-5 hours, dispersing for 5-10 minutes by ultrasonic waves, placing a suspension of the carbon black and the hydrogen peroxide in a constant-temperature water bath with the temperature of 75-80 ℃ to stand for 5-6 hours, filtering and drying, finally placing the carbon black in a sodium hexadecyl benzene sulfonate solution to be soaked for 1-1.5 hours, filtering, washing the filtered carbon black 1-2 times by using water or ethanol, and drying to obtain modified carbon black powder;
the preparation method of the modified zinc oxide powder comprises the following steps: calcining zinc oxide powder at 700-800 ℃ for 2-3 hours, adding the zinc oxide powder and nano alumina into hydroxy silicone oil according to the mass ratio of 5-8:1, uniformly stirring, dispersing for 3-5min by using ultrasonic waves, filtering, adding vanillic acid methyl ester and ethanol into the filtered powder, wherein the mass ratio of vanillic acid methyl ester to ethanol is 1:4-6, stirring for 3-5min at the rotating speed of 1000-1200r/min, filtering, washing the filtered powder for 1-2 times by using water or ethanol, and drying to obtain the modified zinc oxide powder.
Through utilizing CPP MOPP/BOPP three-layer material complex to form the packaging film for the multilayer material of packaging film is single PP material, thereby makes the packaging film be convenient for recovery processing and utilization, is favorable to reducing the pollution to the environment, still is favorable to the energy saving.
Meanwhile, the CPP film inner layer and the MOPP film intermediate layer both adopt the same binary copolymer polypropylene and the same ternary copolymer polypropylene as main raw materials of the film, so that the compatibility between two layers of films can be improved better, the adhesive force between the CPP film inner layer and the MOPP film intermediate layer can be improved better, and the inner layer peel strength between the inner layer and the intermediate layer is higher.
Meanwhile, the modified carbon black powder and the modified zinc oxide powder are added into the surface layer of the BOPP film for synergistic compounding, so that the aging resistance of the packaging film is favorably improved, and when the packaging film is used for manufacturing a laundry detergent packaging bag, the laundry detergent is placed on a balcony for solarization, so that the packaging bag and the quality of the laundry detergent in the packaging bag are not easy to cause problems.
The carbon black powder modified by the method is beneficial to better improving the ultraviolet resistance of the carbon black, so that when the carbon black is scattered in polypropylene, oxygen-containing functional groups such as hydroxyl on the surface of the carbon black are easier to react with groups generated after the polypropylene is decomposed by ultraviolet irradiation, thereby playing a role in clearing the groups, preventing the polypropylene from being further decomposed, and further being beneficial to better improving the aging resistance of the packaging film; meanwhile, the modified carbon black powder also has stronger light-absorbing capacity, so that after ultraviolet rays irradiate the packaging bag, the carbon black aggregates scattered in the polypropylene can cause the scattering of the ultraviolet rays, and the scattered light of the ultraviolet rays is more easily absorbed by the carbon black aggregates, so that the ultraviolet rays absorbed by the polypropylene are less, and the aging resistance of the packaging film is better improved.
The zinc oxide modified by the method is beneficial to better improving the capability of the zinc oxide for absorbing scattered light of scattered ultraviolet rays, thereby being beneficial to reducing the ultraviolet rays absorbed by polypropylene and being beneficial to better improving the aging resistance of the packaging film.
Preferably, the MOPP film intermediate layer is prepared from the following components in parts by mass:
1-2 parts of modified calcium carbonate powder;
the preparation method of the modified calcium carbonate powder comprises the following steps: calcining calcium carbonate at 500-600 ℃ for 4-5 hours, grinding into powder with the particle size of 300-400 meshes, adding the ground calcium carbonate powder into a mixed solution of epoxidized soybean oil and tetraphenyl silicate, wherein the mass ratio of the epoxidized soybean oil to the tetraphenyl silicate is 1:3-4, uniformly stirring, dispersing for 5-10min by using ultrasonic waves, soaking for 5-7 hours, stirring for 5-10min at the rotating speed of 1200-1500r/min after soaking is finished, filtering, washing the filtered powder for 1-2 times by using water or ethanol, and drying to obtain the modified calcium carbonate powder.
The calcium carbonate powder modified by the method is beneficial to better improving the bonding performance of the MOPP film intermediate layer, the BOPP film surface layer and the CPP film inner layer, so that the inner layer peel strength between the MOPP film intermediate layer and the BOPP film surface layer and between the MOPP film intermediate layer and the CPP film inner layer is higher, and the packaging film is favorably pressed and molded better.
Preferably, the opening agent comprises one or more of talcum powder, diatomite and silicon dioxide.
By using one or more substances as the opening agent, the tensile strength of the packaging film is favorably and better improved, so that the packaging film is less prone to cracking, the packaging film is favorably used for better protecting the laundry detergent inside, and the packaging bag is less prone to leakage.
Preferably, the opening agent is prepared by mixing diatomite and silicon dioxide in a mass ratio of 1:3-5.
By adopting the synergistic compounding of the diatomite and the silicon dioxide in a specific proportion, the tensile strength of the packaging film is favorably improved, so that the packaging film is favorably protected from the laundry detergent inside, and the condition of liquid leakage of the packaging bag is more difficult to occur; meanwhile, the adhesive property between the CPP film inner layer and the MOPP film middle layer is favorably and better improved, so that the peeling strength between the CPP film inner layer and the MOPP film middle layer is higher, and the packaging is favorably pressed and molded better.
Preferably, the polypropylene of the surface layer of the BOPP film has an isotacticity of 95-97%.
By controlling the isotacticity of the polypropylene on the surface layer of the BOPP film, the crystallinity and the crystallization speed can be better controlled, so that the stiffness of the surface layer of the BOPP film is improved, the stiffness of the packaging bag is improved, the packaging bag can stand, and the laundry detergent can be conveniently placed.
Preferably, the polypropylene of the surface layer of the BOPP film has an average molecular weight of 8000-8600 and a molecular weight distribution coefficient of 4-4.5.
The film forming property of the BOPP film surface layer is favorably improved and the tensile strength of a packaging film is favorably improved by controlling the average molecular weight and the molecular weight distribution coefficient of the polypropylene of the BOPP film surface layer, so that the packaging bag is favorably used for better protecting the laundry detergent inside, and the situation of liquid leakage of the packaging bag is more difficultly caused.
In a second aspect, the present application provides a method for preparing a polypropylene type recyclable packaging film, which adopts the following technical scheme:
a preparation method of a polypropylene type recyclable packaging film comprises the following steps:
step 1, mixing all components of the CPP film inner layer, and carrying out casting molding to obtain the CPP film inner layer;
step 2, mixing the components of the MOPP film intermediate layer, carrying out melt extrusion, cooling to form a casting sheet, and carrying out longitudinal stretching, cooling and traction on the casting sheet to obtain the MOPP film intermediate layer;
step 3, mixing the components of the BOPP film surface layer, carrying out melt extrusion, cooling to form a casting sheet, longitudinally stretching and transversely stretching the casting sheet to the thickness of 20-30 mu m, carrying out heat preservation and shaping at 120-130 ℃, and carrying out cooling and traction to obtain the BOPP film surface layer;
step 4, coating glue on one side of the surface layer of the BOPP film, adhering the middle layer of the MOPP film, drying and pressing to obtain a BOPP/MOPP composite film;
and 5, coating glue on one side of the MOPP film middle layer, which is far away from the BOPP film surface layer, adhering the CPP film inner layer, drying and pressing to obtain the polypropylene type recyclable packaging film.
The polypropylene type recyclable packaging film can be obtained by independently preparing each layer of film and then laminating and molding each layer of film, is simple and convenient to prepare, and is beneficial to industrial production of the polypropylene type recyclable packaging film.
Preferably, in the step 2, the longitudinal stretching temperature of the MOPP film middle layer is 95-100 ℃, and the longitudinal stretching multiple is 6-8 times.
Preferably, in the step 3, the longitudinal stretching temperature of the surface layer of the BOPP film is 95-100 ℃, and the longitudinal stretching multiple is 4-6.
Preferably, in the step 3, the transverse stretching temperature of the surface layer of the BOPP film is 130-140 ℃, and the transverse stretching multiple is 7-9 times.
By controlling the stretching temperature and stretching multiple of longitudinal stretching and transverse stretching of the MOPP film middle layer and the BOPP film surface layer, the viscosity and relaxation time of polypropylene can be better controlled, so that the stretching strength of the formed packaging film can be better improved, the packaging film can better protect the laundry detergent inside, and the packaging film is less prone to leakage.
In summary, the present application has the following beneficial effects:
1. the modified carbon black powder and the modified zinc oxide powder are added into the surface layer of the BOPP film, so that the aging resistance of the surface layer of the BOPP film is favorably improved, and the condition that the quality of a packaging bag or the laundry detergent inside the packaging bag is changed when the laundry detergent is placed on a balcony for solarization is avoided; meanwhile, each layer of the packaging film is formed by compounding single PP materials, so that the packaging film is favorable for recycling, processing and utilization, the pollution to the environment is reduced, and the energy is saved.
2. By adding the modified calcium carbonate into the middle layer of the MOPP film and adopting the diatomite and the silicon dioxide in a specific proportion to be cooperatively compounded as the opening agent, the bonding performance of different layers of the packaging film can be better improved, and the peeling strength of the inner layer between the different layers can be improved.
3. The polypropylene type recyclable packaging film can be obtained by separately preparing each layer of material and then pressing each layer of material, and the preparation process is simple and convenient and is beneficial to industrial production.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
The source of the raw materials for the following examples is detailed in table 1.
TABLE 1
Figure BDA0003594611470000081
Example 1
The embodiment discloses a polypropylene type recyclable packaging film, which consists of a CPP film inner layer, an MOPP film middle layer and a BOPP film surface layer which are sequentially connected.
The CPP film inner layer is prepared from the following components in parts by mass: 55kg of binary copolymer polypropylene; 80kg of ternary copolymer polypropylene; 3kg of the opening agent.
In this example, the opening agent is oleamide.
The MOPP film interlayer is prepared from the following components in parts by mass: 70kg of binary copolymerized polypropylene; 15kg of ternary copolymer polypropylene.
The BOPP film surface layer is prepared from the following components in parts by mass: 70kg of polypropylene; 0.5kg of modified carbon black powder; 1kg of modified zinc oxide powder.
In this example, the polypropylene had an isotacticity of 95%, an average molecular weight of 8000, and a molecular weight distribution coefficient of 4.
The preparation method of the modified carbon black powder comprises the following steps: adding carbon black powder into a hydrochloric acid solution with the mass percentage concentration of 10% for soaking for 3 hours, filtering a suspension of the carbon black and the hydrochloric acid solution through a funnel, taking the carbon black powder, putting the carbon black powder into an oven for drying, wherein the drying temperature is 95 ℃, the drying time is 15min, after the drying is finished, soaking the carbon black powder in hydrogen peroxide with the mass percentage concentration of 15% for 5 hours, after the soaking is finished, dispersing the carbon black powder for 5 minutes by using ultrasonic waves, after the dispersing is finished, placing the suspension of the carbon black and the hydrogen peroxide into a 75 ℃ constant-temperature water bath for standing for 6 hours, then filtering the suspension through the funnel, putting the filtered carbon black powder into the oven for drying, wherein the drying temperature is 95 ℃, the drying time is 15min, after the drying is finished, placing the carbon black into a 90% hexadecyl sodium alkyl benzene sulfonate solution for soaking for 1.5 hours, after the soaking is finished, filtering the suspension of the carbon black and the hexadecyl sodium alkyl benzene sulfonate solution through the funnel, washing the carbon black powder obtained by 2 times of filtration through water, after the washing is finished, placing the carbon black powder into the oven for drying, wherein the drying temperature is 95 ℃, the drying time is 35min, and the modified carbon black powder is obtained.
The preparation method of the modified zinc oxide powder comprises the following steps: calcining zinc oxide powder at 700 ℃ for 3 hours, and then mixing the zinc oxide powder with nano alumina in a ratio of 5:1, adding mixed powder obtained by mixing into hydroxyl silicone oil, uniformly stirring at a rotating speed of 120r/min, dispersing for 5min by using ultrasonic waves, filtering suspension of the mixed powder and the hydroxyl silicone oil by using a funnel, taking the filtered mixed powder, adding a mixed solution of vanillic acid methyl ester and ethanol into the mixed powder, wherein the mass ratio of the vanillic acid methyl ester to the ethanol is 1: and 4, stirring at the rotation speed of 1000r/min for 5min, filtering the mixed powder, the methyl vanillic acid and the suspension of ethanol by using a funnel, washing the filtered powder for 2 times by using water, drying the mixed powder in an oven at the drying temperature of 95 ℃ for 40min after the washing is finished, and obtaining the modified zinc oxide powder after the drying is finished.
The embodiment also discloses a preparation method of the polypropylene type recyclable packaging film, which comprises the following steps:
step 1, weighing binary copolymer polypropylene, ternary copolymer polypropylene and oleamide according to the mass, uniformly mixing, adding the uniformly mixed mixture into an extruder, carrying out melt extrusion, wherein the feeding temperature is 65 ℃, the melting temperature is 230 ℃, the die head temperature is 235 ℃, casting the melt-extruded polypropylene onto a cooling roller, cooling and shaping, the casting and traction speed is 100m/min, the cooling roller temperature is set to be 30 ℃, and finally carrying out edge cutting, traction and rolling on the cooled and shaped CPP film to obtain the CPP film inner layer.
And 2, weighing binary copolymer polypropylene and ternary copolymer polypropylene according to the mass, uniformly mixing, adding the uniformly mixed mixture into an extruder, and carrying out melt extrusion, wherein the temperature of a conveying section of the extruder is set to be 200 ℃, the temperature of a melt plasticizing section is set to be 230 ℃, the temperature of a homogenizing section is set to be 250 ℃, and the temperature of a filter screen is set to be 265 ℃. And then casting the melt-extruded polypropylene onto a cooling roller to be cooled into a cast sheet, setting the temperature of the cooling roller to be 35 ℃, then drawing the cast sheet to a drawing area to carry out longitudinal drawing, controlling the drawing temperature to be 90 ℃ and the drawing multiple to be 5 times, drawing the MOPP film into a shaping area after drawing is finished, carrying out heat preservation and shaping, controlling the heat preservation temperature to be 55 ℃, finally cooling to room temperature through the cooling roller with the set temperature of 20 ℃, drawing and rolling to obtain the MOPP film intermediate layer.
And 3, weighing the polypropylene, the modified carbon black powder and the modified zinc oxide powder according to the mass, uniformly mixing, adding the uniformly mixed mixture into an extruder, and carrying out melt extrusion, wherein the feeding temperature is 60 ℃, the melting temperature is 235 ℃, and the die head temperature is 245 ℃. Then casting the melt-extruded polypropylene on a cooling roller to be cooled into a cast sheet, setting the temperature of the cooling roller to be 35 ℃, then drawing the cast sheet to a drawing area, firstly drawing longitudinally, then drawing transversely, controlling the temperature of longitudinal drawing to be 90 ℃, the multiple of longitudinal drawing to be 3 times, the temperature of transverse drawing to be 125 ℃, the multiple of transverse drawing to be 6 times, and simultaneously controlling the thickness of the cast sheet after longitudinal drawing and transverse drawing to be 30 mu m. And after the stretching is finished, drawing the BOPP film into a shaping area, carrying out heat preservation and shaping, controlling the heat preservation temperature to be 120 ℃, finally cooling to room temperature through a cooling roller with the set temperature of 25 ℃, drawing and rolling to obtain the surface layer of the BOPP film.
And 4, passing the BOPP film surface layer through a rubber pressing roller to uniformly coat glue on one side of the BOPP film surface layer, then feeding the BOPP film surface layer coated with the glue into a drying tunnel, setting the temperature of the drying tunnel to be 70 ℃, drawing and attaching the MOPP film intermediate layer to the side, coated with the glue, of the BOPP film surface layer by using an attaching roller, feeding a composite film formed by the BOPP film surface layer and the MOPP film intermediate layer into a curing chamber after laminating, controlling the curing temperature to be 40 ℃, and curing for 26 hours to obtain the BOPP/MOPP composite film.
And 5, passing the BOPP/MOPP composite film through a rubber pressing roller to uniformly coat glue on one side of the MOPP film middle layer, which is far away from the BOPP film surface layer, feeding the BOPP/MOPP composite film coated with the glue into a drying tunnel, setting the temperature of the drying tunnel to be 70 ℃, drawing and attaching the CPP film inner layer to one side of the MOPP film middle layer coated with the glue by using an attaching roller, feeding the composite film formed by the BOPP/MOPP composite film and the CPP film inner layer into a curing chamber after laminating, controlling the curing temperature to be 40 ℃, and curing for 26 hours to obtain the polypropylene type recyclable packaging film.
Example 2
The difference from example 1 is that:
the CPP film inner layer has different usage amounts of the following components: 60kg of binary copolymer polypropylene; 85kg of ternary copolymer polypropylene; 5kg of opening agent.
The MOPP film interlayer has different use amounts of the following components: 80kg of binary copolymerized polypropylene; 20kg of ternary copolymer polypropylene.
The BOPP film surface layer has different composition dosage, which is as follows: 90kg of polypropylene; 1kg of modified carbon black powder; 2kg of modified zinc oxide powder.
In this example, the polypropylene had an isotacticity of 97%, an average molecular weight of 8600 and a molecular weight distribution coefficient of 4.5.
Meanwhile, the preparation parameters of the modified carbon black powder and the modified zinc oxide powder are different, and specifically, the preparation parameters are as follows:
the preparation method of the modified carbon black powder comprises the following steps: adding carbon black powder into a hydrochloric acid solution with the mass percentage concentration of 15% for soaking for 2 hours, filtering a suspension of the carbon black and the hydrochloric acid solution through a funnel, taking the carbon black powder, placing the carbon black powder into a drying oven for drying, wherein the drying temperature is 90 ℃, the drying time is 20min, after the drying is finished, soaking the carbon black powder into hydrogen peroxide with the mass percentage concentration of 20% for 4 hours, after the soaking is finished, dispersing the carbon black powder for 10 minutes by using ultrasonic waves, after the dispersing is finished, placing the suspension of the carbon black and the hydrogen peroxide into a constant-temperature water bath with the temperature of 80 ℃ for standing for 5 hours, then filtering the suspension through the funnel, placing the filtered carbon black powder into the drying oven for drying, wherein the drying temperature is 90 ℃, the drying time is 45min, after the drying is finished, placing the carbon black powder into the drying oven for drying, and washing the carbon black powder obtained by filtering the carbon black powder for 1 time by using water, and after the washing is finished, placing the carbon black powder into the drying oven for drying, wherein the drying temperature is 90 ℃, and the drying time is 45 min.
The preparation method of the modified zinc oxide powder comprises the following steps: the zinc oxide powder was calcined at 800 ℃ for 2 hours and then mixed with nano-alumina at a ratio of 8:1, adding mixed powder obtained by mixing into hydroxyl silicone oil, uniformly stirring at a rotating speed of 120r/min, dispersing for 3min by using ultrasonic waves, filtering suspension of the mixed powder and the hydroxyl silicone oil by using a funnel, taking the filtered mixed powder, adding a mixed solution of vanillic acid methyl ester and ethanol into the mixed powder, wherein the mass ratio of the vanillic acid methyl ester to the ethanol is 1: and 6, stirring at the rotating speed of 1200r/min for 3min, filtering the mixed powder and suspension of the methyl vanillic acid and the ethanol by using a funnel, washing the filtered powder for 1 time by using water, drying the mixed powder in an oven at the drying temperature of 90 ℃ for 50min after the washing is finished, and obtaining the modified zinc oxide powder after the drying is finished.
The parameters of the preparation method of the polypropylene type recyclable packaging film are different, and the preparation method specifically comprises the following steps:
in step 1, the feeding temperature is 60 ℃, the melting temperature is 235 ℃, the die head temperature is 240 ℃, the casting pulling speed is 120m/min, and the temperature of a cooling roller is set to be 25 ℃.
In the step 2, the temperature of the conveying section of the extruder is set to be 220 ℃, the temperature of the melting and plasticizing section is set to be 260 ℃, the temperature of the homogenizing section is set to be 265 ℃, the temperature of the filter screen is set to be 270 ℃, the temperature of the cooling roller is set to be 25 ℃, the stretching temperature is 105 ℃, the stretching multiple is 9 times, the temperature of the heat preservation and shaping is set to be 60 ℃, and the temperature of the cooling roller is set to be 30 ℃.
In the step 3, the feeding temperature is 65 ℃, the melting temperature is 230 ℃, the die head temperature is 240 ℃, the temperature of a cooling roller is set to be 30 ℃, the longitudinal stretching temperature is 105 ℃, the longitudinal stretching multiple is 7 times, the transverse stretching temperature is 145 ℃, the transverse stretching multiple is 10 times, the thickness of the cast sheet after longitudinal stretching and transverse stretching is 20 μm, the temperature for heat preservation and shaping is set to be 130 ℃, and the temperature of the cooling roller is set to be 30 ℃.
In the step 4, the drying tunnel temperature is set to be 80 ℃, the curing temperature is 45 ℃, and the curing time is 24 hours.
In the step 5, the drying tunnel temperature is set to 80 ℃, the curing temperature is 45 ℃, and the curing time is 24 hours.
Example 3
The difference from example 1 is that:
the CPP film inner layer has different use amounts of the following components: 58kg of binary copolymerized polypropylene; 82kg of ternary copolymer polypropylene; 4kg of the opening agent.
The MOPP film interlayer has different use amounts of the following components: 75kg of binary copolymer polypropylene; 18kg of terpolymer polypropylene.
The BOPP film surface layer has different composition dosage, which is as follows: 85kg of polypropylene; 0.8kg of modified carbon black powder; 1.5kg of modified zinc oxide powder.
In this example, the polypropylene had an isotacticity of 96%, an average molecular weight of 8300 and a molecular weight distribution coefficient of 4.3.
Meanwhile, the preparation parameters of the modified carbon black powder and the modified zinc oxide powder are different, and specifically, the preparation parameters are as follows:
the preparation method of the modified carbon black powder comprises the following steps: adding carbon black powder into a hydrochloric acid solution with the mass percentage concentration of 12% for soaking for 2.5 hours, filtering a suspension of the carbon black and the hydrochloric acid solution through a funnel, taking the carbon black powder, putting the carbon black powder into an oven for drying, wherein the drying temperature is 93 ℃, the drying time is 18min, after the drying is finished, soaking the carbon black powder in hydrogen peroxide with the mass percentage concentration of 18% for 4.5 hours, after the soaking is finished, dispersing the carbon black powder for 8 minutes by using ultrasonic waves, after the dispersion is finished, putting the suspension of the carbon black and the hydrogen peroxide into a constant-temperature water bath with the temperature of 78 ℃, standing for 5.5 hours, then filtering through the funnel, putting the filtered carbon black powder into the oven for drying, wherein the drying temperature is 93 ℃, the drying time is 18min, after the drying is finished, putting the carbon black into a sodium hexadecylbenzene sulfonate solution with the mass percentage concentration of 93%, soaking for 1.5 hours, after the soaking is finished, filtering the suspension of the carbon black powder and the sodium hexadecylbenzene sulfonate solution through the funnel, washing with ethanol for 1 time, and after the washing, putting the carbon black powder into the oven for drying, obtaining the modified carbon black powder.
The preparation method of the modified zinc oxide powder comprises the following steps: the zinc oxide powder was calcined at a temperature of 750 ℃ for 2.5 hours and then mixed with nano alumina in a ratio of 7:1, adding mixed powder obtained by mixing into hydroxyl silicone oil, uniformly stirring at a rotating speed of 120r/min, dispersing for 4min by using ultrasonic waves, filtering suspension of the mixed powder and the hydroxyl silicone oil by using a funnel, taking the filtered mixed powder, adding a mixed solution of vanillic acid methyl ester and ethanol into the mixed powder, wherein the mass ratio of the vanillic acid methyl ester to the ethanol is 1: and 5, stirring at the rotating speed of 1100r/min for 4min, filtering the mixed powder, methyl vanillic acid and ethanol suspension by using a funnel, washing the filtered powder for 1 time by using ethanol, drying the mixed powder in an oven at the drying temperature of 93 ℃ for 45min after the washing is finished, and obtaining the modified zinc oxide powder after the drying is finished.
The parameters of the preparation method of the polypropylene type recyclable packaging film are different, and specifically comprise the following steps:
in step 1, the feeding temperature is 63 ℃, the melting temperature is 233 ℃, the die head temperature is 238 ℃, the casting pulling speed is 110m/min, and the temperature of the cooling roll is set to be 28 ℃.
In the step 2, the temperature of the conveying section of the extruder is set to 210 ℃, the temperature of the melting and plasticizing section is set to 245 ℃, the temperature of the homogenizing section is set to 260 ℃, the temperature of the filter screen is set to 268 ℃, the temperature of the cooling roller is set to 30 ℃, the stretching temperature is 103 ℃, the stretching multiple is 9 times, the temperature of the heat preservation and shaping is set to 58 ℃, and the temperature of the cooling roller is set to 25 ℃.
In the step 3, the feeding temperature is 63 ℃, the melting temperature is 233 ℃, the die head temperature is 243 ℃, the temperature of a cooling roller is 32 ℃, the longitudinal stretching temperature is 102 ℃, the longitudinal stretching multiple is 7 times, the transverse stretching temperature is 142 ℃, the transverse stretching multiple is 10 times, the thickness of the cast sheet after longitudinal stretching and transverse stretching is 25 μm, the temperature for heat preservation and shaping is 125 ℃, and the temperature of the cooling roller is 28 ℃.
In the step 4, the drying tunnel temperature is set to be 75 ℃, the curing temperature is 43 ℃, and the curing time is 25 hours.
In the step 5, the drying tunnel temperature is set to be 75 ℃, the curing temperature is 43 ℃, and the curing time is 25 hours.
Example 4
The difference from example 3 is that:
the MOPP film interlayer also comprises 1kg of modified calcium carbonate powder as a raw material, and the modified calcium carbonate powder is mixed with the binary copolymer polypropylene and the ternary copolymer polypropylene during preparation.
The preparation method of the modified calcium carbonate powder comprises the following steps: calcining calcium carbonate at 500 ℃ for 5 hours, grinding the calcined calcium carbonate into powder with the particle size of 300 meshes by a ball mill, adding the ground calcium carbonate powder into a mixed solution of epoxidized soybean oil and tetraphenyl silicate, wherein the mass ratio of the epoxidized soybean oil to the tetraphenyl silicate is 1:3, uniformly stirring at the rotating speed of 100r/min, dispersing for 5 minutes by using ultrasonic waves, standing and soaking for 7 hours, stirring at the rotating speed of 1200r/min for 10 minutes after soaking is finished, filtering suspension of the calcium carbonate powder, the epoxy soybean and the tetraphenyl silicate by using a funnel, washing the filtered calcium carbonate powder for 2 times by using water, drying the calcium carbonate powder in an oven at the drying temperature of 80 ℃ for 45 minutes after washing is finished, and obtaining the modified calcium carbonate powder after drying is finished.
Example 5
The difference from example 4 is that:
the addition amount of the modified calcium carbonate powder is 2kg.
The preparation method of the modified calcium carbonate powder has different parameters, and specifically comprises the following steps: calcining calcium carbonate at 600 ℃ for 4 hours, grinding the calcined calcium carbonate into powder with the particle size of 400 meshes by a ball mill, adding the ground calcium carbonate powder into a mixed solution of epoxidized soybean oil and tetraphenyl silicate, wherein the mass ratio of the epoxidized soybean oil to the tetraphenyl silicate is 1:4, uniformly stirring at the rotating speed of 100r/min, dispersing for 10min by using ultrasonic waves, standing and soaking for 5 hours, stirring at the rotating speed of 1500r/min for 5min after soaking is finished, filtering suspension of the calcium carbonate powder, the epoxy soybean and the tetraphenyl silicate by using a funnel, cleaning the filtered calcium carbonate powder for 1 time by using ethanol, drying the calcium carbonate powder in an oven at the drying temperature of 85 ℃ for 40min after cleaning is finished, and obtaining the modified calcium carbonate powder.
Example 6
The difference from example 3 is that:
the MOPP film interlayer also comprises 2kg of calcium carbonate powder in the preparation raw materials, wherein the calcium carbonate powder is directly obtained by grinding calcium carbonate through a ball mill, and the particle size of the ground calcium carbonate powder is 400 meshes. And the calcium carbonate powder is mixed with binary co-polypropylene and ternary co-polypropylene in the preparation process.
Example 7
The differences from example 5 are: the opening agent is a mixture of diatomite and silicon dioxide, and the mixing mass ratio of the diatomite to the silicon dioxide is 1:3.
example 8
The difference from example 5 is that: the opening agent is a mixture of diatomite and silicon dioxide, and the mixing mass ratio of the diatomite to the silicon dioxide is 1:5.
example 9
The differences from example 8 are: equal amounts of talc were substituted for the diatomaceous earth.
Example 10
The difference from example 8 is that: the silica was replaced by an equal amount of talc.
Example 11
The difference from example 3 is that: the opening agent is a mixture of diatomite and silicon dioxide, and the mixing mass ratio of the diatomite to the silicon dioxide is 1:5.
example 12
The difference from example 3 is that:
the polypropylene recyclable packaging film has different preparation parameters, specifically as follows:
in the step 2, the longitudinal stretching temperature of the MOPP film middle layer is 95 ℃, and the longitudinal stretching multiple is 6 times;
in the step 3, the longitudinal stretching temperature of the surface layer of the BOPP film is 95 ℃, the longitudinal stretching multiple is 4 times, the transverse stretching temperature is 130 ℃, and the transverse stretching multiple is 7 times.
Example 13
The difference from example 3 is that:
the polypropylene type recyclable packaging film has different preparation parameters, specifically as follows:
in the step 2, the longitudinal stretching temperature of the MOPP film middle layer is 100 ℃, and the longitudinal stretching multiple is 8 times;
in the step 3, the longitudinal stretching temperature of the surface layer of the BOPP film is 100 ℃, the longitudinal stretching multiple is 6 times, the transverse stretching temperature is 140 ℃, and the transverse stretching multiple is 9 times.
Example 14
The differences from example 5 are:
the opening agent is a mixture of diatomite and silicon dioxide, and the mixing mass ratio of the diatomite to the silicon dioxide is 1:4.
the polypropylene type recyclable packaging film has different preparation parameters, specifically as follows:
in the step 2, the longitudinal stretching temperature of the middle layer of the MOPP film is 98 ℃, and the longitudinal stretching multiple is 7 times;
in the step 3, the longitudinal stretching temperature of the surface layer of the BOPP film is 97 ℃, the longitudinal stretching multiple is 5 times, the transverse stretching temperature is 135 ℃, and the transverse stretching multiple is 8 times
Comparative example 1
The polypropylene type recyclable packaging film is used for a bagged laundry detergent packaging bag in the market.
Comparative example 2
The difference from example 3 is that: the carbon black powder and the zinc oxide powder added were all commercially available unmodified powders.
Comparative example 3
The difference from example 3 is that: the carbon black powder added is a commercially available unmodified powder.
Comparative example 4
The difference from example 3 is that: the zinc oxide powder added is a commercially available unmodified powder.
Experiment 1
The tensile strength (MPa) of the packaging films prepared in the above examples and comparative examples was measured according to GB/T13022-1991, test method for tensile Properties of Plastic films.
Experiment 2
According to GB/T16422.3-2004 Plastic laboratory light Source Exposure test method part 3: the method A in the fluorescent ultraviolet lamp test method A is used for carrying out aging treatment on the packaging films prepared in the above examples and comparative examples, after the aging treatment is finished, the tensile strength (MPa) of the packaging films subjected to the aging treatment is respectively detected according to GB/T13022-1991 Plastic film tensile property test method, and the change rate (%) of the tensile strength of the packaging films before and after the aging treatment is calculated. Wherein the content of the first and second substances,
Figure BDA0003594611470000201
experiment 3
The CPP film inner layer and BOPP/MOPP composite film 15mm and the BOPP film surface layer and MOPP film intermediate layer 15mm in the packaging film prepared in the above examples and comparative examples were peeled off according to method a in GB 8808-88 "peel test method for soft composite plastic material", and the inner layer peel strength (N) of the CPP film inner layer and MOPP film intermediate layer and the inner layer peel strength (N) of the BOPP film surface layer and MOPP film intermediate layer were examined and recorded.
The data from the above experiments are detailed in table 2.
TABLE 2
Figure BDA0003594611470000211
Figure BDA0003594611470000221
According to the comparison of the data of the example 3 and the comparative example 1 in the table 2, the polypropylene recyclable packaging film is beneficial to better improving the aging resistance of the packaging film, so that the quality of the packaging film and the laundry detergent inside the packaging film are not easily affected by sunlight exposure.
According to the comparison of the data of example 3 and comparative examples 2-4 in table 2, the aging resistance of the BOPP film surface layer can be better improved only by adding the modified carbon black powder and the modified zinc oxide powder to the BOPP film surface layer, so that the tensile strength of the packaging film is less susceptible to the influence of ultraviolet irradiation, and one of the materials is not modified and is likely to have great influence on the aging resistance of the packaging film.
According to the comparison of the data of the examples 3-6 in the table 2, the modified calcium carbonate powder can only be added into the preparation raw material of the MOPP film middle layer to improve the bonding performance of the MOPP film middle layer and other two layers, so that the inner layer peeling strength between the layers is higher, and if the calcium carbonate powder is not modified, the effect can not be realized.
According to comparison of data of the embodiment 3 and the embodiments 7 to 11 in the table 2, the adhesion performance of the CPP film inner layer and the MOPP film intermediate layer can be better improved only by adopting the diatomite and the silicon dioxide in a specific proportion to be cooperatively compounded to form the opening agent and compounding the opening agent with the modified calcium carbonate, so that the peeling strength of the CPP film inner layer and the MOPP film intermediate layer is higher, the influence of the opening agent on the adhesion performance of the CPP film inner layer and the MOPP film intermediate layer is favorably reduced, and the influence of any substance on the peeling strength of the CPP film inner layer and the MOPP film intermediate layer is changed.
According to the comparison of the data of the example 3 and the examples 12-13 in the table 2, the longitudinal tensile strength and the longitudinal stretching multiple of the middle layer of the MOPP film are controlled, and the longitudinal stretching time, the longitudinal stretching multiple, the transverse stretching time and the transverse stretching multiple of the surface layer of the BOPP film are controlled, so that the tensile strength of the packaging film is better improved, and the packaging film is less prone to cracking.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.

Claims (8)

1. A polypropylene type recyclable packaging film characterized in that: the CPP film consists of a CPP film inner layer, an MOPP film middle layer and a BOPP film surface layer which are sequentially connected;
the CPP film inner layer is prepared from the following components in parts by mass: 55-60 parts of binary copolymer polypropylene, 80-85 parts of ternary copolymer polypropylene and 3-5 parts of a cracking agent;
the MOPP film interlayer is prepared from the following components in parts by mass: 70-80 parts of binary copolymer polypropylene; 15-20 parts of ternary copolymer polypropylene;
the BOPP film surface layer is prepared from the following components in parts by mass: 80-90 parts of polypropylene; 0.5-1 part of modified carbon black powder; 1-2 parts of modified zinc oxide powder;
the preparation method of the modified carbon black powder comprises the following steps: adding carbon black into a hydrochloric acid solution with the mass percent concentration of 10% -15% to be soaked for 2-3 hours, filtering and drying, then soaking the carbon black into hydrogen peroxide with the mass percent concentration of 15% -20% for 4-5 hours, dispersing for 5-10min by ultrasonic waves, placing a suspension of the carbon black and the hydrogen peroxide into a constant-temperature water bath with the temperature of 75-80 ℃, standing for 5-6 hours, filtering and drying, finally placing the carbon black into a sodium hexadecylbenzene sulfonate solution to be soaked for 1-1.5 hours, filtering, washing the filtered carbon black with water or ethanol for 1-2 times, and drying to obtain modified carbon black powder;
the preparation method of the modified zinc oxide powder comprises the following steps: calcining zinc oxide powder at 700-800 ℃ for 2-3 hours, adding the zinc oxide powder and nano alumina into hydroxy silicone oil according to the mass ratio of 5-8:1, uniformly stirring, dispersing for 3-5min by using ultrasonic waves, filtering, adding vanillic acid methyl ester and ethanol into the filtered powder, wherein the mass ratio of vanillic acid methyl ester to ethanol is 1:4-6, stirring for 3-5min at the rotating speed of 1000-1200r/min, filtering, washing the filtered powder for 1-2 times by using water or ethanol, and drying to obtain modified zinc oxide powder;
the MOPP film interlayer is prepared from the following components in parts by mass:
1-2 parts of modified calcium carbonate powder;
the preparation method of the modified calcium carbonate powder comprises the following steps: calcining calcium carbonate at 500-600 ℃ for 4-5 hours, grinding into powder with the particle size of 300-400 meshes, adding the ground calcium carbonate powder into a mixed solution of epoxidized soybean oil and tetraphenyl silicate, wherein the mass ratio of the epoxidized soybean oil to the tetraphenyl silicate is 1:3-4, uniformly stirring, dispersing for 5-10min by using ultrasonic waves, soaking for 5-7 hours, stirring for 5-10min at the rotating speed of 1200-1500r/min after soaking is finished, filtering, washing the filtered powder for 1-2 times by using water or ethanol, and drying to obtain the modified calcium carbonate powder.
2. The polypropylene-based recyclable packaging film as defined in claim 1, wherein: the opening agent comprises one or more of talcum powder, diatomite and silicon dioxide.
3. The polypropylene-based recyclable packaging film as defined in claim 2, wherein: the opening agent is prepared by mixing diatomite and silicon dioxide in a mass ratio of 1:3-5.
4. A polypropylene based recyclable packaging film according to any of claims 1 to 3, wherein: the polypropylene of the BOPP film surface layer has an isotacticity of 95-97%.
5. A process for the preparation of a recyclable packaging film of the polypropylene type as defined in any of claims 1 to 4, characterized in that: the method comprises the following steps:
step 1, mixing all components of the CPP film inner layer, and carrying out casting molding to obtain the CPP film inner layer;
step 2, mixing the components of the MOPP film intermediate layer, carrying out melt extrusion, cooling to form a casting sheet, and carrying out longitudinal stretching, cooling and traction on the casting sheet to obtain the MOPP film intermediate layer;
step 3, mixing the components of the BOPP film surface layer, carrying out melt extrusion, cooling to form a casting sheet, longitudinally stretching and transversely stretching the casting sheet to the thickness of 20-30 mu m, carrying out heat preservation and shaping at 120-130 ℃, cooling and drawing to obtain the BOPP film surface layer;
step 4, coating glue on one side of the surface layer of the BOPP film, adhering the middle layer of the MOPP film, drying and pressing to obtain a BOPP/MOPP composite film;
and 5, coating glue on one side of the MOPP film middle layer, which is far away from the BOPP film surface layer, adhering the CPP film inner layer, drying and pressing to obtain the polypropylene type recyclable packaging film.
6. The method of claim 5, wherein the polypropylene-based recyclable packaging film comprises: in the step 2, the longitudinal stretching temperature of the MOPP film middle layer is 95-100 ℃, and the longitudinal stretching multiple is 6-8 times.
7. The process for the preparation of a recyclable packaging film of the polypropylene type according to any of claims 5 to 6, characterized in that: in the step 3, the longitudinal stretching temperature of the surface layer of the BOPP film is 95-100 ℃, and the longitudinal stretching multiple is 4-6 times.
8. The method of claim 7, wherein the polypropylene-based recyclable packaging film comprises: in the step 3, the transverse stretching temperature of the surface layer of the BOPP film is 130-140 ℃, and the transverse stretching multiple is 7-9 times.
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CN111171410A (en) * 2018-11-12 2020-05-19 台州太阳风橡胶有限公司 Modified white carbon black reinforced rubber tire material and preparation method thereof

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CN111171410A (en) * 2018-11-12 2020-05-19 台州太阳风橡胶有限公司 Modified white carbon black reinforced rubber tire material and preparation method thereof
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