CN114228286A - Anti-penetration PVC (polyvinyl chloride) winding film - Google Patents

Anti-penetration PVC (polyvinyl chloride) winding film Download PDF

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Publication number
CN114228286A
CN114228286A CN202111570662.9A CN202111570662A CN114228286A CN 114228286 A CN114228286 A CN 114228286A CN 202111570662 A CN202111570662 A CN 202111570662A CN 114228286 A CN114228286 A CN 114228286A
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film
pvc
parts
penetration
improved
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庞晓峰
徐宏华
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Ningbo Dahua Packaging Material Technology Co ltd
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Ningbo Dahua Packaging Material Technology 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • 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
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    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • 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
    • B32B2307/536—Hardness
    • 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
    • B32B2307/54—Yield strength; Tensile 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
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    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/10—Homopolymers or copolymers of unsaturated ethers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2497/00—Characterised by the use of lignin-containing materials
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    • 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
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Abstract

The invention provides an anti-penetration PVC (polyvinyl chloride) wound film, which takes a PVC base film as a substrate, and a hard elastic film is compounded on the surface of the PVC base film through an adhesive, wherein the PVC base film is prepared from the following raw materials in parts by mass: 100 parts of PVC resin, 2-4 parts of plasticizer, 1-10 parts of acetylated cellulose nanocrystal, 0-20 parts of polyethylene glycol methacrylate, 0-10 parts of trifluoroethyl methacrylate, 1.5-2.5 parts of zinc oxide and 0.1-0.3 part of lignin; the PVC winding film with the penetration resistance provided by the invention is high in rebound rate and penetration resistance through compounding of the PVC base film and the hard elastic film, the plasticizer is a mixture of dioctyl terephthalate, phthalic acid ester and polyallyl glycidyl ether, and the polyallyl glycidyl ether is added, so that the thermal stability is improved, the toughness of the PVC winding film can be obviously improved while the strength of the PVC is not lost, the surface resistivity of the PVC winding film is reduced, and the antistatic and penetration resistance of the PVC winding film with the penetration resistance are improved.

Description

Anti-penetration PVC (polyvinyl chloride) winding film
Technical Field
The invention relates to the technical field of wound films, in particular to an anti-penetration PVC wound film.
Background
The PVC winding film is a special winding film, is commonly used for winding special-shaped product packages such as electric wires and cables, various finish machining rollers, mechanical equipment, hardware fittings, rubber tubes, steel tubes, furniture, building decoration materials, sneakers, non-woven fabrics and the like, is applied to the field of packaging by the self-adhesion of the PVC winding film, and does not produce secondary pollution to the packaged products.
After the PVC winding film commonly used in the market is stretched once or for many times, the rebound effect of the film is poor, the toughness and strength reduction rate of the film are high, the film is easy to shrink and deform, and the film is easy to penetrate and puncture, so that the packaged product is easy to pollute, and the packaging and using effects of the PVC winding film are influenced.
Disclosure of Invention
In order to make up for the defects, the invention provides an anti-penetration PVC winding film and a preparation method thereof, aiming at solving the problems that the PVC winding film has poor rebound effect after being stretched for use, high reduction rate of toughness and strength, and easy shrinkage and deformation of the film, which cause easy penetration and puncture.
The invention is realized by the following steps:
the invention provides an anti-penetration PVC (polyvinyl chloride) wound film, which takes a PVC base film as a substrate, and a hard elastic film is compounded on the surface of the PVC base film through an adhesive, wherein the PVC base film is prepared from the following raw materials in parts by mass: 100 parts of PVC resin, 2-4 parts of plasticizer, 1-10 parts of acetylated cellulose nanocrystal, 0-20 parts of polyethylene glycol methacrylate, 0-10 parts of trifluoroethyl methacrylate, 1.5-2.5 parts of zinc oxide and 0.1-0.3 part of lignin;
the hard elastic film is a hard PP elastic film, the plasticizer is a mixture of dioctyl terephthalate, phthalic acid ester and polyallyl glycidyl ether, the dioctyl terephthalate accounts for 0.05 wt% -0.1 wt% of the total amount, and the phthalic acid ester accounts for 0.05 wt% -0.1 wt% of the total amount.
Compared with an unmodified PVC winding film, the zinc oxide and the lignin are added, the characteristics of the PVC winding film are further modified, the pore structure and the performance of the PVC winding film can be promoted, the specific surface area of the film is increased, the thermal decomposition process can be inhibited, the adsorption performance of the film is improved, and the pollution resistance and the stability of the film are further improved.
The hard PP elastic film has high elasticity, in the deformation of the microstructure of the film, as the stress is increased, the lamella linearity is increased and is not influenced by the temperature, a nano cavity appears in intergranular cracks, and when the film is circularly stretched, the lamella generates the periodic separation and recovery phenomenon, less deformation occurs in the lamella, the lamella continues to be kept stable, and the PVC winding film formed by compounding the hard PP elastic film and the PVC base film not only has the characteristic of winding the film, but also further improves the penetration resistance and the tensile strength of the film and reduces the deformation rate.
The penetration-resistant PVC winding film provided by the invention is compounded by the PVC base film and the hard elastic film, after the prepared PVC winding film is stretched by first stress, in the room temperature environment, the initial rebound rate is kept above 96 percent, the initial rebound rate after the second stretching can be kept above 90 percent, the prepared winding film has strong rebound rate and penetration resistance, the plasticizer is a mixture of dioctyl terephthalate, phthalate and polyallyl glycidyl ether, the conventional dioctyl phthalate and phthalate plasticizers are referred, and the polyallyl glycidyl ether is added to improve the thermal stability, the toughness of the PVC winding film can be obviously improved while the strength of the PVC is not lost, the surface resistivity of the PVC winding film is reduced, a certain antistatic effect is generated, and the antistatic and anti-penetration capabilities of the anti-penetration PVC winding film are improved.
Preferably, the amount of the polyethylene glycol methacrylate is 10-20 parts.
Preferably, the trifluoroethyl methacrylate is used in an amount of 5 to 10 parts.
Preferably, the adhesive is any two or more of epoxy modified polyurethane, polyurethane prepolymer, methyl triethoxysilane and silane coupling agent.
The tensile strength and elongation at break of the film are affected by the curing time, the longer the curing time, the lower the performance, and the stability of the adhesive directly affects the strength and toughness of the composite film.
The epoxy modified polyurethane can shorten the curing time and improve the stability of the film, the polyurethane prepolymer can be subjected to polymerization reaction with moisture in the air or moisture of a composite bonded matrix, the bonding stability is improved, the elasticity and the penetration resistance are improved, the methyl triethoxysilane serving as a cross-linking agent and a silane coupling agent can enhance the stability of the adhesive, and the stability of the adhesive serving as a glue layer connection of the composite film is improved.
Preferably, the raw material of the PVC base film also comprises polystyrene, and the mass ratio of the polystyrene is 5-10 parts.
The addition of the polystyrene enhances the rigidity of the prepared PVC base film, and the prepared PVC base film has good shrinkage characteristics, so that the shrinkage deformation phenomenon is relieved, and the deformation characteristics of the traditional PVC winding film are further reduced.
Preferably, the thickness of the hard elastic film is 10 to 20 μm.
Preferably, the polyallyl glycidyl ether takes allyl glycidyl as a monomer, and an intermediate product of the polyallyl glycidyl ether is prepared by using AROP; taking PAGE as a precursor, and introducing flexible alkyl into a side chain of the PAGE by virtue of a mercapto-alkene click reaction to obtain a target product.
Preferably, the raw material of the PVC base film also comprises modified boron nitride, and the mass ratio of the modified boron nitride is 0.5-1.5. Chemically modifying the hexagonal boron nitride by adopting dioctyl pyrophosphate acyl-oxy to obtain modified boron nitride; the modified boron nitride is added into the raw materials by a physical blending mode to prepare the PVC basement membrane.
In the specific application process of the PVC winding film, the PVC winding film not only needs to bear the influence of stretching and puncturing, but also has certain examination on pollution resistance and corrosion resistance due to the application of the PVC winding film in the field of packaging.
After the modified boron nitride is added into the film material, the alkali resistance of the film is 59.69mJ/m2Down to 52.64mJ/m2And then, the compatibility with PVC resin is improved, the bonding force between the PVC resin and the PVC resin is improved, a compact labyrinth structure is formed in the PVC base film in a stacking manner, the corrosion of an alkaline medium to the PVC film material is effectively prevented, the tensile strain retention rate is improved from 72.13% to 95.74%, and the tensile strain force and the penetration resistance are further improved.
Preferably, the raw material of the PVC base film further comprises ionic liquid copolymer, and the mass ratio of the ionic liquid copolymer is 0.2-0.3 parts, such as but not limited to 0.2 part, 0.21 part, 0.22 part, 0.23 part, 0.24 part, 0.25 part, 0.26 part, 0.27 part, 0.28 part, 0.29 part, 0.3 part; the ionic liquid copolymer is prepared from 1-butyl-3-vinyl imidazole tetrafluoroborate, a PVC base film is used as a polymer matrix, and the 1-butyl-3-vinyl imidazole tetrafluoroborate is added into the PVC base film to prepare the composite base film by an immersion precipitation phase conversion method.
The addition of the 1-butyl-3-vinyl imidazole tetrafluoroborate improves the porosity of the surface of the film, the contact angle of the original film is reduced from 82.3 degrees to 52.8 degrees, the mechanical property of the film is improved, and the flux recovery rate can reach 83.2 percent, so that the film has good pollution resistance and flux recovery rate.
In some embodiments of the present invention, a nano metal layer is formed on the surface of the hard elastic membrane, the nano metal layer is any one of a nano calcium carbonate and nano montmorillonite composite material and nano inorganic particles, and the thickness of the nano metal layer is 2-3 μm.
The hard elastic film is modified by adding the nano metal layer, so that the toughness and strength of the compounded PVC winding film are enhanced, wherein when the filling amount of the nano calcium carbonate in the hard elastic film is 2.69%, the tensile strength, the impact strength and the elongation at break of the nano calcium carbonate are respectively improved by 5.7%, 11.3% and 33.7%, when the content of the nano montmorillonite composite material in the hard elastic film is less than 3.0%, the tensile strength, the impact strength and the elongation at break of the film are obviously improved, when the content of the nano inorganic particles in the hard elastic film is 0.5%, the impact strength is improved by 56%, the tensile strength is improved by 3MPa, the penetration resistance strength and the tensile strength of the hard elastic film are improved, and the performance of the penetration resistance PVC winding film after compound molding is improved.
In addition, the invention also provides a preparation method of the penetration-resistant PVC winding film, which comprises the following steps:
step 1: mixing the plasticizer in a high-speed mixer at a low speed for 1-1.5 min;
step 2: adding PVC resin, acetylated cellulose nanocrystal, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting a high-speed gear in a high-speed mixer, mixing for 3-5min, then adding zinc oxide and lignin, mixing at the temperature of 80-100 ℃ in the high-speed mixer, and continuously mixing for 1-2 min;
and step 3: heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, and calendering, cooling and rolling to obtain a PVC base membrane;
and 4, step 4: uniformly coating an adhesive on the surfaces of the PVC basement membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
It is understood that the low gear speed of the high-speed mixer is 50-100r/min, and the high gear speed of the high-speed mixer is 200-400 r/min.
The invention also provides the application of the penetration-resistant PVC winding film as a packaging film.
Compared with the prior art, the invention has the beneficial effects that:
1. the penetration-resistant PVC wound film provided by the invention is compounded by the PVC base film and the hard elastic film, after the prepared PVC wound film is stretched by first stress, in the room temperature environment, the initial rebound rate is kept above 96 percent, the initial rebound rate after the second stretching can be kept above 90 percent, the prepared winding film has strong rebound rate and penetration resistance, the plasticizer is a mixture of dioctyl terephthalate, phthalate and polyallyl glycidyl ether, the conventional dioctyl phthalate and phthalate plasticizers are referred, and the polyallyl glycidyl ether is added to improve the thermal stability, the toughness of the PVC winding film can be obviously improved while the strength of the PVC is not lost, the surface resistivity of the PVC winding film is reduced, a certain antistatic effect is generated, and the antistatic and anti-penetration capabilities of the anti-penetration PVC winding film are improved.
The addition of zinc oxide and lignin further modifies the characteristics of the PVC winding film, can promote the pore structure and performance of the PVC winding film, improves the specific surface area of the film, can inhibit the thermal decomposition process, improves the adsorption performance of the film, and further improves the pollution resistance and stability of the film.
The hard PP elastic film has high elasticity, in the deformation of the microstructure of the film, as the stress is increased, the lamella linearity is increased and is not influenced by the temperature, a nano cavity appears in intergranular cracks, and when the film is circularly stretched, the lamella generates the periodic separation and recovery phenomenon, less deformation occurs in the lamella, the lamella continues to be kept stable, and the PVC winding film formed by compounding the hard PP elastic film and the PVC base film not only has the characteristic of winding the film, but also further improves the penetration resistance and the tensile strength of the film and reduces the deformation rate.
2. The rigidity of the prepared PVC base film is enhanced due to the addition of the polystyrene, the prepared PVC base film has good shrinkage characteristics, the shrinkage deformation phenomenon is relieved, and the deformation characteristics of the traditional PVC winding film are further reduced.
3. After the modified boron nitride is added into the film material, the alkali resistance of the film is from 59.69mJ/m2Down to 52.64mJ/m2And then, the compatibility with PVC resin is improved, the bonding force between the PVC resin and the PVC resin is improved, a compact labyrinth structure is formed in the PVC base film in a stacking manner, the corrosion of an alkaline medium to the PVC film material is effectively prevented, the tensile strain retention rate is improved from 72.13% to 95.74%, and the tensile strain force and the penetration resistance are further improved.
4. The addition of the 1-butyl-3-vinyl imidazole tetrafluoroborate improves the porosity of the surface of the film, the contact angle of the original film is reduced from 82.3 degrees to 52.8 degrees, the mechanical property of the film is improved, and the flux recovery rate can reach 83.2 percent, so that the film has good pollution resistance and flux recovery rate.
5. The hard elastic film is modified by adding the nano metal layer, so that the toughness and strength of the compounded PVC winding film are enhanced, wherein when the filling amount of the nano calcium carbonate in the hard elastic film is 2.69%, the tensile strength, the impact strength and the elongation at break of the nano calcium carbonate are respectively improved by 5.7%, 11.3% and 33.7%, when the content of the nano montmorillonite composite material in the hard elastic film is less than 3.0%, the tensile strength, the impact strength and the elongation at break of the film are obviously improved, when the content of the nano inorganic particles in the hard elastic film is 0.5%, the impact strength is improved by 56%, the tensile strength is improved by 3MPa, the penetration resistance and the tensile strength of the hard elastic film are improved, and the penetration resistance PVC winding film after compound molding is improved in performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph of three stretches versus initial spring back for a penetration resistant PVC wound film provided by an embodiment of the present invention;
FIG. 2 is a graph of rate of change of rigid elastomeric film with stress change in a penetration resistant PVC wound film provided in accordance with an embodiment of the present invention;
fig. 3 is a graph showing the relationship between the polystyrene content in the raw material of the PVC base film and the shrinkage ratio of the film according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1-3, the present invention provides an anti-penetration PVC wound film, which is prepared by using a PVC base film as a substrate and compounding a hard elastic film on the surface of the PVC base film by using an adhesive, wherein the PVC base film is prepared from the following raw materials by mass:
100 parts of PVC resin;
2-4 parts of plasticizer, such as but not limited to 2 parts, 3 parts, 4 parts;
1-10 parts of acetylated cellulose nanocrystals, such as but not limited to 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts;
0-20 parts of polyethylene glycol methacrylate, such as but not limited to 0 part, 1 part, 0.22 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts;
0-10 parts of trifluoroethyl methacrylate, such as but not limited to 0 part, 1 part, 0.22 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts;
1.5-2.5 parts of zinc oxide, such as but not limited to 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts;
0.1-0.3 parts of lignin, such as but not limited to 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts;
wherein the rigid elastic film is a rigid PP elastic film, the plasticizer is a mixture of dioctyl terephthalate, phthalate and polyallyl glycidyl ether, the dioctyl terephthalate accounts for 0.05 wt% to 0.1 wt% of the total amount, such as but not limited to 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, and the phthalate accounts for 0.05 wt% to 0.1 wt% of the total amount, such as but not limited to 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%.
Compared with an unmodified PVC winding film, the zinc oxide and the lignin are added, the characteristics of the PVC winding film are further modified, the pore structure and the performance of the PVC winding film can be promoted, the specific surface area of the film is increased, the thermal decomposition process can be inhibited, the adsorption performance of the film is improved, and the pollution resistance and the stability of the film are further improved.
Referring to fig. 2, the hard PP elastic film has high elasticity, and in the deformation of the microstructure thereof, as the stress increases, the lamella linearity increases, and is not affected by the temperature, a nano cavity appears in an intergranular crack, and when the film is circularly stretched, the lamella generates a periodic separation and recovery phenomenon, so that less deformation occurs in the lamella, the lamella continues to be stable, and the PVC winding film formed by compounding the hard PP elastic film and the PVC base film has the characteristics of a winding film, and meanwhile, the penetration resistance and the tensile strength of the film are further improved, and the deformation rate is reduced.
Referring to fig. 1, the penetration-resistant PVC wound film provided by the present invention is prepared by compounding a PVC base film and a rigid elastic film, and after the PVC wound film is stretched by a first stress, in the room temperature environment, the initial rebound rate is kept above 96 percent, the initial rebound rate after the second stretching can be kept above 90 percent, the prepared winding film has strong rebound rate and penetration resistance, the plasticizer is a mixture of dioctyl terephthalate, phthalate and polyallyl glycidyl ether, the conventional dioctyl phthalate and phthalate plasticizers are referred, and the polyallyl glycidyl ether is added to improve the thermal stability, the toughness of the PVC winding film can be obviously improved while the strength of the PVC is not lost, the surface resistivity of the PVC winding film is reduced, a certain antistatic effect is generated, and the antistatic and anti-penetration capabilities of the anti-penetration PVC winding film are improved.
Table 1 below is a comparison of the elastic recovery of PVC wound films at different recovery temperatures before and after addition of polyallyl glycidyl ether:
Figure BDA0003423253310000111
as can be seen from Table 1, the addition of polyallyl glycidyl ether results in a film with high elastic recovery, high thermal stability, reduced dielectric constant, reduced surface resistivity, and a certain antistatic effect.
In some embodiments of the invention, the polyethylene glycol methacrylate is used in an amount of 10-20 parts, such as, but not limited to, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts.
In some embodiments of the invention, the trifluoroethyl methacrylate is used in an amount of 5 to 10 parts, such as but not limited to 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.
It is understood that the adhesive is any two or more of epoxy modified polyurethane, polyurethane prepolymer, methyl triethoxysilane and silane coupling agent.
The tensile strength and elongation at break of the film are affected by the curing time, the longer the curing time, the lower the performance, and the stability of the adhesive directly affects the strength and toughness of the composite film.
The epoxy modified polyurethane can shorten the curing time and improve the stability of the film, the polyurethane prepolymer can be subjected to polymerization reaction with moisture in the air or moisture of a composite bonded matrix, the bonding stability is improved, the elasticity and the penetration resistance are improved, the methyl triethoxysilane serving as a cross-linking agent and a silane coupling agent can enhance the stability of the adhesive, and the stability of the adhesive serving as a glue layer connection of the composite film is improved.
Referring to fig. 3, in some embodiments of the present invention, the raw material of the PVC base film further includes polystyrene, and the mass ratio of the polystyrene is 5 to 10 parts, such as but not limited to 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts.
The addition of the polystyrene enhances the rigidity of the prepared PVC base film, and the prepared PVC base film has good shrinkage characteristics, so that the shrinkage deformation phenomenon is relieved, and the deformation characteristics of the traditional PVC winding film are further reduced.
In some embodiments of the invention, the hard elastic film has a thickness of 10-20 μm, such as, but not limited to, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm.
It is understood that the polyallyl glycidyl ether is prepared by taking allyl glycidyl as a monomer and utilizing AROP to prepare a polyallyl glycidyl ether intermediate product; taking PAGE as a precursor, and introducing flexible alkyl into a side chain of the PAGE by virtue of a mercapto-alkene click reaction to obtain a target product.
In addition, the invention also provides a preparation method of the penetration-resistant PVC winding film, which comprises the following steps:
step 1: mixing the plasticizer in a high speed mixer at a low speed for 1-1.5min, such as but not limited to 1min, 1.5 min;
step 2: adding PVC resin, acetylated cellulose nanocrystal, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting high-speed mixing in a high-speed mixer for 3-5min, such as but not limited to 3min, 4min and 5min, then adding zinc oxide and lignin, wherein the mixing temperature in the high-speed mixer is 80-100 ℃, such as but not limited to 80 ℃, 90 ℃ and 100 ℃, and continuing mixing for 1-2min, such as but not limited to 1min, 1.5min and 2 min;
and step 3: heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, and calendering, cooling and rolling to obtain a PVC base membrane;
and 4, step 4: uniformly coating an adhesive on the surfaces of the PVC basement membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
It is understood that the low gear speed of the high speed mixer is 50-100r/min, such as but not limited to 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, and the high gear speed of the high speed mixer is 200-400r/min, such as but not limited to 200r/min, 250r/min, 300r/min, 350r/min, 400 r/min.
The invention also provides the application of the penetration-resistant PVC winding film as a packaging film.
It is to be understood that the raw material of the PVC base film further comprises modified boron nitride, and the mass ratio of the modified boron nitride is 0.5-1.5 parts, such as but not limited to 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, 1.1 part, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts. Chemically modifying the hexagonal boron nitride by adopting dioctyl pyrophosphate acyl-oxy to obtain modified boron nitride; the modified boron nitride is added into the raw materials by a physical blending mode to prepare the PVC basement membrane.
In the specific application process of the PVC winding film, the PVC winding film not only needs to bear the influence of stretching and puncturing, but also has certain examination on pollution resistance and corrosion resistance due to the application of the PVC winding film in the field of packaging.
After the modified boron nitride is added into the film material, the alkali resistance of the film is 59.69mJ/m2Down to 52.64mJ/m2The compatibility with PVC resin is improved, the bonding force with the PVC resin is improved, and the PVC resin is stacked in a PVC basement membrane to formThe dense labyrinth structure can effectively prevent the corrosion of an alkaline medium to the PVC film material, the tensile strain retention rate is improved from 72.13% to 95.74%, and the tensile strain force and the penetration resistance are further improved.
In some embodiments of the present invention, the raw material of the PVC base film further comprises an ionic liquid copolymer, and the mass ratio of the ionic liquid copolymer is 0.2-0.3 parts, such as but not limited to 0.2 part, 0.21 part, 0.22 part, 0.23 part, 0.24 part, 0.25 part, 0.26 part, 0.27 part, 0.28 part, 0.29 part, 0.3 part; the ionic liquid copolymer is prepared from 1-butyl-3-vinyl imidazole tetrafluoroborate, a PVC base film is used as a polymer matrix, and the 1-butyl-3-vinyl imidazole tetrafluoroborate is added into the PVC base film to prepare the composite base film by an immersion precipitation phase conversion method.
The addition of the 1-butyl-3-vinyl imidazole tetrafluoroborate improves the porosity of the surface of the film, the contact angle of the original film is reduced from 82.3 degrees to 52.8 degrees, the mechanical property of the film is improved, and the flux recovery rate can reach 83.2 percent, so that the film has good pollution resistance and flux recovery rate.
In some embodiments of the present invention, the hard elastic film is formed with a nano metal layer on the surface, the nano metal layer is any one of nano calcium carbonate and nano montmorillonite composite material and nano inorganic particles, and the thickness of the nano metal layer is 2-3 μm, such as but not limited to 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3 μm.
Table 2 below shows the lifting change ratios of the tensile strength, impact strength and elongation at break of the three nano-metal materials compared with the conventional hard elastic film as follows:
material Tensile Strength (MPa) Impact Strength (MPa) Elongation at Break (%)
Nano calcium carbonate +5.7％ +11.3％ +33.7％
Nano montmorillonite composite material +3.5％ +21.5％ +17.4％
Inorganic nanoparticles 3MPa 56％ +25.5％
According to table 2, the hard elastic film is modified by adding the nano metal layer, so that the toughness and strength of the compounded PVC winding film are enhanced, wherein when the filling amount of the hard elastic film is 2.69%, the tensile strength, the impact strength and the elongation at break of the nano calcium carbonate are respectively increased by 5.7%, 11.3% and 33.7%, when the content of the nano montmorillonite composite material in the hard elastic film is less than 3.0%, the tensile strength, the impact strength and the elongation at break of the film are obviously increased, when the content of the nano inorganic particles in the hard elastic film is 0.5%, the impact strength is increased by 56%, the tensile strength is increased by 3MPa, the penetration resistance and the tensile strength of the hard elastic film are improved, and the performance of the penetration-resistant PVC winding film after compound molding is improved.
Example 1
A preparation method of a penetration-resistant PVC winding film comprises the following steps:
mixing the plasticizer in a high-speed mixer at a low speed for 1 min; adding PVC resin, acetylated cellulose nanocrystal, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting a high-speed gear in a high-speed mixer, mixing for 3min, then adding zinc oxide and lignin, and mixing at 80 ℃ in the high-speed mixer; heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, calendering, cooling and rolling to obtain a PVC base membrane, uniformly coating an adhesive on the surfaces of the PVC base membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
Example 2
A preparation method of a penetration-resistant PVC winding film comprises the following steps:
mixing the plasticizer in a high-speed mixer at a low speed for 1.5 min; adding PVC resin, acetylated cellulose nanocrystal, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting a high-speed mixer to mix for 4min, then adding zinc oxide and lignin, and mixing at 90 ℃ in the high-speed mixer; heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, calendering, cooling and rolling to obtain a PVC base membrane, uniformly coating an adhesive on the surfaces of the PVC base membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
Example 3
A preparation method of a penetration-resistant PVC winding film comprises the following steps:
mixing the plasticizer in a high-speed mixer at a low speed for 1.5 min; adding PVC resin, acetylated cellulose nanocrystalline, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting a high-speed gear in a high-speed mixer to mix for 5min, then adding zinc oxide and lignin, and mixing the mixture in the high-speed mixer at 100 ℃; heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, calendering, cooling and rolling to obtain a PVC base membrane, uniformly coating an adhesive on the surfaces of the PVC base membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
Example 4
A method for preparing penetration resistant PVC wrapping film, except adding polystyrene in the raw material of PVC base film, the other operation conditions are the same as those of examples 1-3.
Example 5
A preparation method of a penetration-resistant PVC winding film comprises the following steps:
mixing the plasticizer in a high-speed mixer at a low speed for 1.5 min; adding PVC resin, acetylated cellulose nanocrystalline, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting a high-speed gear in a high-speed mixer to mix for 5min, and then adding zinc oxide, lignin and modified boron nitride, wherein the mixing temperature in the high-speed mixer is 100 ℃; heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, calendering, cooling and rolling to obtain a PVC base membrane, uniformly coating an adhesive on the surfaces of the PVC base membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
Example 6
A penetration-resistant PVC wrapping film is prepared by adding ionic liquid copolymer to the raw material of PVC base film under the same operation conditions as those in example 5.
Example 7
A method for preparing a penetration-resistant PVC wrap film, except that a nano metal layer is formed on the surface of a hard elastic film, the other operating conditions are the same as those of example 6.
The penetration resistant PVC wrapping films prepared in examples 1-7 above were tested to obtain the following properties shown in Table 3 below:
Figure BDA0003423253310000181
Figure BDA0003423253310000191
as shown in Table 3, the alkali resistance of the PVC wrapping film prepared in example 7 is 52.64mJ/m2The tensile strain retention rate is improved to 95.74 percent, and the contact angle of the original film is 52.8 degrees, the mechanical property of the film is improved, the flux recovery rate can reach 83.2 percent, and the penetration resistance of the PVC winding film is obviously improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The anti-penetration PVC winding film is characterized in that a PVC base film is used as a substrate, and a hard elastic film is compounded on the surface of the PVC base film through an adhesive, wherein the PVC base film is prepared from the following raw materials in parts by mass:
Figure FDA0003423253300000011
the hard elastic film is a hard PP elastic film, the plasticizer is a mixture of dioctyl terephthalate, phthalic acid ester and polyallyl glycidyl ether, the dioctyl terephthalate accounts for 0.05 wt% -0.1 wt% of the total amount, and the phthalic acid ester accounts for 0.05 wt% -0.1 wt% of the total amount.
2. The penetration resistant PVC wrap film of claim 1, wherein said polyethylene glycol methacrylate is used in an amount of 10-20 parts.
3. The penetration resistant PVC wrap film of claim 1, wherein said trifluoroethyl methacrylate is used in an amount of 5 to 10 parts.
4. The penetration-resistant PVC wrapping film according to claim 1, wherein the adhesive is any two or more of epoxy modified polyurethane, polyurethane prepolymer, methyl triethoxysilane, and silane coupling agent.
5. The penetration-resistant PVC wound film according to claim 1, wherein the raw material of the PVC base film further comprises polystyrene, and the mass ratio of the polystyrene is 5-10 parts.
6. The penetration resistant PVC wound film of claim 1, wherein the thickness of said rigid elastic film is 10-20 μm.
7. The penetration resistant PVC wrap film of claim 1, wherein the polyallyl glycidyl ether is prepared by using AROP with allyl glycidyl as a monomer to prepare an intermediate polyallyl glycidyl ether product;
taking PAGE as a precursor, and introducing flexible alkyl into a side chain of the PAGE by virtue of a mercapto-alkene click reaction to obtain a target product.
8. A method for preparing the penetration-resistant PVC wrapping film according to any one of claims 1-7, comprising the steps of:
step 1: mixing the plasticizer in a high-speed mixer at a low speed for 1-1.5 min;
step 2: adding PVC resin, acetylated cellulose nanocrystal, polyethylene glycol methacrylate and trifluoroethyl methacrylate, starting a high-speed gear in a high-speed mixer, mixing for 3-5min, then adding zinc oxide and lignin, continuously mixing for 1-2min, wherein the mixing temperature in the high-speed mixer is 80-100 ℃;
and step 3: heating the raw materials to a molten state, extruding the raw materials by an extruder, feeding the raw materials to a calender, and calendering, cooling and rolling to obtain a PVC base membrane;
and 4, step 4: uniformly coating an adhesive on the surfaces of the PVC basement membrane and the hard elastic membrane, and carrying out hot pressing, cooling and curing molding.
9. The method as claimed in claim 8, wherein the low gear speed of the high speed mixer is 50-100r/min, and the high gear speed of the high speed mixer is 200-400 r/min.
10. Use of the penetration-resistant PVC wrapping film according to at least one of claims 1 to 7 as a packaging film.
CN202111570662.9A 2021-12-21 2021-12-21 Anti-penetration PVC (polyvinyl chloride) winding film Pending CN114228286A (en)

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CN112271405A (en) * 2020-10-16 2021-01-26 欣旺达电动汽车电池有限公司 Lithium-supplementing composite diaphragm and preparation method thereof
CN113214571A (en) * 2021-04-01 2021-08-06 浙江理工大学 Alkali-corrosion-resistant high-strength flexible polyvinyl chloride film material and preparation method thereof
CN113214468A (en) * 2021-06-07 2021-08-06 陕西科技大学 Polyvinyl chloride plasticizing antistatic agent and preparation method thereof
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CN103395153A (en) * 2013-07-26 2013-11-20 常州大学 Method for preparing hard elastic polypropylene cast film at low temperature
CN106729975A (en) * 2015-11-19 2017-05-31 爱博诺德（北京）医疗科技有限公司 For the material of manufacture of intraocular crystal
CN206719929U (en) * 2017-04-01 2017-12-08 吴江市好运包装材料有限公司 Wind film
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