CN116787891A - Stretch wrap film and method of making the same - Google Patents

Stretch wrap film and method of making the same Download PDF

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Publication number
CN116787891A
CN116787891A CN202310742612.7A CN202310742612A CN116787891A CN 116787891 A CN116787891 A CN 116787891A CN 202310742612 A CN202310742612 A CN 202310742612A CN 116787891 A CN116787891 A CN 116787891A
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parts
lldpe
mlldpe
stretch
film
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CN116787891B (en
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刘世平
滕忻超
李泽进
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Qingdao Taibo Polymer Label Co ltd
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Qingdao Taibo Polymer Label Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24—Calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • B32B2250/03—3 layers
    • 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
    • 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
    • B32B2307/554—Wear resistance
    • 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
    • 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
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Abstract

The application relates to the field of packaging materials, and particularly discloses a stretch wrapping film and a preparation method thereof. The stretch-wrap film sequentially comprises an outer layer, a middle layer and an inner layer, wherein the outer layer comprises the following raw materials in parts by weight: 60-90 parts of MLLDPE and 200-250 parts of LLDPE; the middle layer comprises the following raw materials in parts by weight: 130-170 parts of MLLDPE and 430-470 parts of LLDPE; the inner layer comprises the following raw materials in parts by weight: 60-90 parts of MLLDPE, 200-250 parts of LLDPE and 6-10 parts of tackifying master batch. The stretch-wrap film has the advantages of thin thickness, high transparency, strong tear resistance and puncture resistance, good antifogging effect and strong antibacterial capability.

Description

Stretch wrap film and method of making the same
Technical Field
The application relates to the technical field of packaging materials, in particular to a stretch wrap film and a preparation method thereof.
Background
The packaging material is used for manufacturing packaging containers, packaging decoration, packaging printing, packaging transportation and the like, and meets the product packaging requirements, and the packaging film is an industrial film-filling product, has the advantages of high tensile strength, high elongation, good self-adhesion, high transparency and the like, can be used for manually packaging films, can also be used for machine packaging films, is widely used for centralized packaging of summarized goods, is used for packaging the goods stacked on a supporting plate, ensures that the packages are more stable and tidier, has super-strong waterproof effect, and is widely used in industries such as foreign trade export, papermaking, hardware, plastic chemical industry, building materials, medical foods and the like.
In the prior art, a low-density polyethylene is adopted to prepare a winding film through a tape casting or film blowing process, and the Chinese patent document with the application number of CN2009102421875 discloses a preparation method of a special material for a transparent winding film, which comprises the following steps: mixing polyisobutylene and LLDPE powder in a mixer according to the weight ratio of 1:10; mixing and extruding the mixture in an extruder to obtain a viscous master batch; mixing the antioxidant, the nucleating agent and the viscosity master batch in a mixer to coat the antioxidant and the nucleating agent on the viscosity master batch; mixing the coated adhesive master batch with LLDPE powder, and carrying out mixing granulation by an extruder. In the above technology, the wrapping film made of the wrapping film special material is used for meeting the use requirement of transparency, the thickness of the film is reduced, and the wrapping film meets the use requirement of high transparency, but simultaneously reduces the puncture resistance and tear resistance of the wrapping film.
Disclosure of Invention
In order to enable the winding film to have better tearing resistance and puncture resistance under the premise of having lower thickness and higher transparency, the application provides a stretching winding film and a preparation method thereof.
In a first aspect, the present application provides a stretch-wrap film, which adopts the following technical scheme:
the stretch-wrapping film sequentially comprises an outer layer, a middle layer and an inner layer, wherein the outer layer comprises the following raw materials in parts by weight: 60-90 parts of MLLDPE and 200-250 parts of LLDPE;
the middle layer comprises the following raw materials in parts by weight: 130-170 parts of MLLDPE and 430-470 parts of LLDPE;
the inner layer comprises the following raw materials in parts by weight: 60-90 parts of MLLDPE, 200-250 parts of LLDPE and 6-10 parts of tackifying master batch.
By adopting the technical scheme, LLDPE and MLLDPE are used in the inner layer, the outer layer and the middle layer, the LLDPE has higher tensile strength, puncture resistance, tear resistance and elongation, but the glossiness is poor, so that the MLLDPE with high transparency, high definition and high smoothness is used in combination with the LLDPE, the transparency of the winding film is improved, the raw materials are low-density materials, the thickness of the winding film can be reduced, the MLLDPE has higher mechanical strength and puncture resistance, and the puncture resistance and tear resistance of the winding film can be enhanced after the MLLDPE is used in combination with the LLDPE.
Optionally, the outer layer comprises the following raw materials in parts by weight: 70-80 parts of MLLDPE and 210-240 parts of LLDPE; the middle layer comprises the following raw materials in parts by weight: 140-160 parts of MLLDPE and 440-460 parts of LLDPE;
the inner layer comprises the following raw materials in parts by weight: 70-80 parts of MLLDPE, 210-240 parts of LLDPE and 7-9 parts of tackifying master batch.
By adopting the technical scheme, the consumption of each raw material is more accurate, so that the manufactured winding film has better puncture resistance and tearing resistance effects.
Optionally, the amount of MLLDPE in the middle layer is equal to the amount of MLLDPE in the inner layer, and the amount of MLLDPE in the outer layer is equal to 1:0.46-0.53:0.46-0.53;
the amount of LLDPE in the middle layer is equal to the amount of LLDPE in the inner layer, and the amount of LLDPE in the outer layer is equal to 1:0.46-0.53:0.46-0.53.
By adopting the technical scheme, the winding film with excellent puncture resistance and stretching resistance can be obtained by controlling the dosage of MLLDPE and LLDPE in the middle layer, the inner layer and the outer layer in the proportion.
Optionally, the MLLDPE has a melt index of 1-1.2g/10min and a density of 0.918-0.92g/cm 3 。
Through adopting above-mentioned technical scheme, using the MLLDPE of above-mentioned density, can make puncture resistance, stretch-proofing strong winding membrane, make the tackifying masterbatch precipitate in the inlayer more easily moreover, obtain better bonding effect.
Optionally, the LLDPE has a melt index of 1.9-2g/10min and a density of 0.9188-0.92g/cm 3 。
By adopting the technical scheme, the LLDPE with the density can be prepared into a winding film with good puncture resistance and tensile strength, and the tackifying master batch is easier to separate out in the inner layer, so that a good bonding effect is obtained.
Optionally, the tackifying master batch comprises the following raw materials in parts by weight: 1 to 2 parts of LDPE, 1.2 to 2.4 parts of polyisobutene, 0.2 to 0.4 part of antifogging agent and 0.08 to 0.16 part of antibacterial agent.
The articles such as food, vegetables and fruits are packaged by the stretch wrapping film and then put into a refrigerated cabinet, because the air sealed in the package is cooled, the water vapor in the air cannot be in a gas phase state, namely, the air is saturated by the water vapor, the water vapor is condensed into small dispersed water drops on the surface of the film, so that water mist is formed on the surface of the film, the transparency of the wrapping film is affected, the packaged food cannot be clearly observed, the aesthetic degree of the package is affected, the sales is reduced, and the water drops gathered on the surface of the film can drop into the food, so that bacteria proliferate quickly and the food is easy to deteriorate or even rot; by adopting the technical scheme, LDPE is adopted as a base material of the tackifying master batch, the base material is good in compatibility with the raw materials in the inner layer, an inner layer film with stable performance and high mechanical strength is easy to form, polyisobutylene is colorless and transparent viscous liquid and is incompatible with LLDPE and MLLDPE, so that the polyisobutylene gradually migrates and precipitates to the surface of the film, the film generates viscosity, and an antifogging agent is added into the tackifying master batch of the inner layer, and can migrate to the surface of the film due to different polarities, so that certain polarity is given to the surface of the film, the surface tension of water drops can be reduced, the gap between the film and the water surface can be reduced, the antifogging effect is achieved, the antifogging agent is added into the tackifying master batch in an internal doping mode, and can be continuously precipitated to the surface of the film, and the antifogging agent lost by the film is supplemented until the antifogging agent in the film is completely migrated to the surface of the film, and the long-acting antifogging effect is achieved; the antibacterial agent can prevent water drops from losing attractive force with the surface of the film after paving the inner surface for a long time, and the water drops drop on the package to cause bacterial growth.
Optionally, the antifogging agent is prepared by mixing, melting, extruding and granulating hydrophilic modified PVDF and hollow silica nanoparticles in a mass ratio of 1:1.3-1.6.
By adopting the technical scheme, the anti-fog agent is prepared by extruding the hydrophilic modified PVDF and the hollow silica nanoparticles, the hydrophilic modified PVDF has good compatibility with the hollow silica nanoparticles, the dosage of the hydrophilic modified PVDF is less than that of the hollow silica nanoparticles, the hydrophilic modified PVDF is taken as a carrier, the surface of the hollow silica nanoparticles can be thinly coated with a layer, when the anti-fog agent is added into the inner layer, the surface of the inner layer has obvious granular sensation, a plurality of exposed nanoparticles are exposed, and when more nanoparticles are stacked on the surface of the inner layer, a micro-nano structure is formed on the surface of the inner layer, and water drops can be rapidly spread on the surface of a film by the structure, so that the super-hydrophilicity is realized, and the anti-fog effect is realized; the hollow silica nano particles can reduce the refractive index of the film, reduce the reflection of incident light at a specific wavelength, increase light transmittance, reduce haze and improve transparency, so that the transparency of a winding film is prevented from being reduced due to the addition of an antifogging agent and an antibacterial agent in the tackifying master batch.
Optionally, the preparation method of the hydrophilic modified PVDF comprises the following steps:
14-16 parts of PVDF and 3.5-4 parts of polyvinyl alcohol are dissolved into 84-86 parts of dimethyl sulfoxide, and 1.4-1.6 parts of glutaraldehyde solution is added to adjust the pH value to 5-6 to prepare a modified liquid;
the modified liquid is evenly sprayed on 150-200 parts of nano titanium dioxide and dried for 50-60s at the temperature of 40-50 ℃.
According to the technical scheme, polyvinyl alcohol and glutaraldehyde are subjected to an acetal reaction under an acidic condition, after modified liquid formed by PVDF and other components is sprayed on nano titanium dioxide, PVDF forms a PVDF film on the surface of the nano titanium dioxide, after the polyvinyl alcohol and glutaraldehyde are subjected to the acetal reaction, the PVDF film is subjected to hydrophilic modification, and the modified liquid is solidified on the nano titanium dioxide by using a spraying mode, so that the hydrophilic modified PVDF is added into a tackifying master batch in a solid mode, and the phenomenon that liquid hydrophilic modified PVDF and hollow silicon dioxide nanoparticles are unevenly dispersed or leak is prevented; the nano titanium dioxide particles have the advantages of stable chemical property, good catalytic performance, no toxicity, low price and the like, when the titanium dioxide is irradiated by ultraviolet rays, valence electrons are excited, so that paired electrons and holes are generated, corresponding hydroxyl or peroxy ions are generated, and the oxygen vacancies adsorb dissociated water in the air, so that the surface hydrophilization is realized, the good hydrophilization and antifogging effects are realized, microorganisms can be inhibited and killed, and the effects of deodorization, mildew prevention and disinfection are realized, so that bacteria breeding can be prevented after moisture is paved on the surface of the film.
Optionally, the antimicrobial agent is selected from an organic transparent antimicrobial agent or an inorganic transparent antimicrobial agent.
By adopting the technical scheme, the organic transparent antibacterial agent or the inorganic transparent antibacterial agent is added in the tackifying master batch, when the tackifying master batch in the inner layer is continuously separated out, the inner layer has continuous antibacterial property, and the transparent antibacterial agent has little influence on the light transmittance of the winding film.
Optionally, the organic transparent antibacterial agent is KEPUYIN-J160 antibacterial agent of KEPUYIN, and the inorganic transparent antibacterial agent is KEPUYIN-J182 nanometer antibacterial agent of KEPUYIN.
In a second aspect, the present application provides a method for producing a stretch-wrap film, which adopts the following technical scheme:
a method of making a stretch wrap film comprising the steps of:
according to the proportion of the raw materials, the inner layer, the outer layer and the middle layer are respectively and uniformly mixed to prepare an inner layer material, an outer layer material and a middle layer material;
and carrying out three-layer coextrusion on the inner layer material, the outer layer material and the middle layer material, then casting, cooling and shaping, and then cutting and rolling.
Through adopting above-mentioned technical scheme, mix each layer raw materials back respectively, adopt the curtain coating mode film formation for the membrane has lower crystallinity and more amorphous regions owing to the refrigerated effect for the film transparency is good, and the tackifying master batch is separated out more easily, and the tackifying effect is better.
In summary, the application has the following beneficial effects:
1. the application adopts the raw materials of the inner layer, the outer layer and the middle layer with specific dosage, so that the prepared stretch-wound film has the advantages of thin thickness, good transparency, strong tearing resistance and puncture resistance, reduced use cost, higher softening temperature and melting temperature, high strength, good toughness, high rigidity, good environmental stress cracking resistance, good impact resistance, good tearing resistance and the like, and the inner layer, the outer layer and the middle layer all use Linear Low Density Polyethylene (LLDPE) as the main material of the stretch-wound film; the MLLDPE is added into the film, so that the tensile strength, the puncture resistance and the tear resistance of the stretch-wrap film can be obviously improved; the tackifying master batch is also added into the inner layer material, so that the winding film has a certain viscosity effect and has a better packaging and protecting effect on goods.
2. The application preferably adopts LDPE, polyisobutene, antifogging agent and antibacterial agent to prepare tackifying master batch, as the antifogging agent can be continuously separated out from the inner layer to achieve lasting antifogging effect, the transparency of the wrapping film is maintained, the aesthetic degree of the wrapping film is not affected, the antibacterial agent can improve the fresh-keeping capability of the wrapping film on the package, the shelf life is prolonged, even if moisture is condensed and dropped on the package, the wrapping film can also achieve antibacterial effect due to the contact of the wrapping package and the surface of the wrapping film.
3. According to the application, the hydrophilic modified PVDF and the hollow silica nanoparticles are preferably adopted as the antifogging agent, after the hydrophilic modified PVDF and the hollow silica nanoparticles are mixed and granulated, the surface of the hollow silica nanoparticles is coated with a layer, so that the surface of the hydrophilic modified PVDF presents a granular feel, the hot melting temperature of the hydrophilic modified PVDF is high and can reach 205-260 ℃, the prepared antifogging agent is not easy to melt when preparing a tackifying master batch, the hollow silica particles are coated with the hydrophilic modified PVDF in the tackifying master batch, the melting temperature is lower than the melting temperature of the PVDF when preparing an inner layer film by the tackifying master batch, and the antifogging agent is still coated with the hollow silica particles by the hydrophilic modified PVDF, so that a micro-nano structure is formed on the surface of the inner layer in a granular form, and the antifogging effect of the inner layer is improved.
Detailed Description
Preparation example of antifogging agent
Preparation example 1: 1kg of hydrophilic modified PVDF and 1.6kg of hollow silica nanoparticles are mixed, extruded and granulated at 220 ℃ to prepare the antifogging agent with the particle size of 2 mu m, and the hydrophilic modified PVDF is prepared by the following method: dissolving 16g PVDF and 4g polyvinyl alcohol into 86g dimethyl sulfoxide, adding 1.6g glutaraldehyde solution with concentration of 2wt%, and regulating pH to 6 with concentrated sulfuric acid to obtain modified solution, wherein the particle size of the hollow silica nano particles is 180nm, and the model is Raschi biological R-ZK18005K; the prepared modified liquid is evenly sprayed on 200g of nano titanium dioxide and dried for 50s at 50 ℃.
Preparation example 2: 1kg of hydrophilic modified PVDF and 1.3kg of hollow silica nanoparticles are mixed, extruded and granulated at 220 ℃ to prepare the antifogging agent with the particle size of 3 mu m, and the hydrophilic modified PVDF is prepared by the following method: 14g of PVDF and 3.5g of polyvinyl alcohol are dissolved in 84g of dimethyl sulfoxide, 1.4g of glutaraldehyde solution with the concentration of 2wt% is added, and the pH value is adjusted to 5 by concentrated sulfuric acid to prepare a modified solution;
the prepared modified liquid is evenly sprayed on 150g of nano titanium dioxide and dried for 60s at 40 ℃.
Preparation example 3: the difference from preparation example 1 is that 1kg of hydrophilically modified PVDF and 1.3kg of hollow silica nanoparticles were mixed, dried, and made into an antifogging agent having a particle diameter of 2 μm, the hydrophilically modified PVDF being made by the following method: 14g of PVDF and 3.5g of polyvinyl alcohol are dissolved in 84g of dimethyl sulfoxide, 1.4g of glutaraldehyde solution having a concentration of 2% by weight are added, and the pH is adjusted to 5 with concentrated sulfuric acid.
Preparation example 4: the difference from preparation 1 is that an equivalent amount of non-hydrophilically modified PVDF is used instead of hydrophilically modified PVDF.
Preparation example 5: the difference from preparation example 1 is that instead of hollow silica nanoparticles, solid silica nanoparticles having an equivalent particle diameter of 200nm were used.
Examples
Example 1: a stretch-wrap film comprising, in order, an outer layer, a middle layer and an inner layer, wherein the thickness ratio of the outer layer, the middle layer and the inner layer is 1:2:1, the raw material amounts of the layers are shown in Table 1, the MLLDPE has a melt index of 1g/10min and a density of 0.918g/cm 3 Selected from the group consisting of Exxon 2012MA, LLDPE having a melt index of 1.9g/10min and a density of 0.9188g/cm 3 A viscosity increasing masterbatch selected from Lanzhou petrochemical DFDA7042N is prepared by mixing 2kg LDPE, 2.4kg polyisobutylene, 0.4kg antifog agent and 0.16kg antibacterial agent, and melt extruding at 180deg.C to obtain LDPE with density of 0.919g/cm 3 The melt index is 7g/10min, the antifogging agent is prepared from preparation example 1, the antibacterial agent is an organic transparent antibacterial agent, the model is KEPUYIN-J160 antibacterial agent of KEPUYIN, and the molecular weight of polyisobutene is 1300.
The preparation method of the stretch-wrap film comprises the following steps:
s1, respectively and uniformly mixing an inner layer, an outer layer and a middle layer according to the proportion of raw materials to prepare an inner layer material, an outer layer material and a middle layer material;
s2, adding the inner layer material, the outer layer material and the middle layer material into a three-layer coextrusion casting machine for three-layer coextrusion casting, and then stretching by casting, cooling, shaping, cutting and rolling after corona treatment, wherein the extrusion temperature is 190 ℃, the cooling temperature of a cooling roller is 18 ℃, the power of corona treatment is 10KW, and the traction force of a rolling roller is 30N/m 2 。
TABLE 1 raw material amounts of stretch wrap films in examples 1-5
Example 2: a stretch wrap film was distinguished from example 1 in that the raw material amounts are shown in Table 1, the adhesion promoting masterbatch was prepared by mixing 1kg of LDPE, 1.2kg of polyisobutylene, 0.2kg of antifogging agent and 0.08kg of antibacterial agent, and then melt extruding the mixture, the density of the LDPE was 0.919g/cm 3 The antifogging agent with melt index of 7g/10min is prepared from preparation 2, and the antibacterial agent is inorganic transparent antibacterial agent with model number of KeThe antibacterial agent of the Pu' er Kepuyin-J182 nanometer.
Examples 3 to 5: a stretch wrap film differs from example 1 in that the raw material amounts are shown in Table 1.
Example 6: a stretch wrap film differs from example 1 in that an antifogging agent was made from preparation 3.
Example 7: a stretch wrap film was distinguished from example 1 in that an antifogging agent was prepared from preparation 4.
Example 8: a stretch wrap film was distinguished from example 1 in that an antifogging agent was prepared from preparation example 5.
Example 9: a stretch wrap film differs from example 1 in that no antifogging agent is added to the tackifying master batch.
Example 10: a stretch wrap film differs from example 1 in that the antifogging agent is glycerol ester.
Example 11: a stretch wrap film differs from example 1 in that an equivalent amount of iHeir-PSZ104 silver ion antimicrobial agent is used in place of the organic clear antimicrobial agent in the adhesion promoting masterbatch.
Example 12: a stretch wrap film differs from example 1 in that the tackifying masterbatch is selected from the group consisting of commercially available products, model number Tianjin zeheng package ZH-60.
Comparative example
Comparative example 1: a stretch wrap film was distinguished from example 1 in that a melt index of 3.5g/10min and a density of 0.959g/cm was used in the inner layer 3 The HB0035 type HDPE of the formula (I) is equivalent to replace LLDPE.
Comparative example 2: a stretch wrap film was distinguished from example 1 in that equal amounts of melt index 1.9g/10min, density 0.9188g/cm were used in the outer, inner and middle layers 3 Instead of MLLDPE, the LLDPE is selected from the group consisting of lanzhou petrochemical DFDA7042N.
Comparative example 3: a stretch wrap film was distinguished from example 1 in that the melt index was 1g/10min and the density was 0.918g/cm in each of the outer layer, inner layer and middle layer 3 MLLDPE of (c), the MLLDPE being selected from the group consisting of elkson 2012MA.
Comparative example 4: a stretch-wrap film comprising a film having a first surface,the difference from example 1 is that LDPE is used instead of LLDPE in the outer layer, the inner layer and the middle layer, the LDPE is of the type Exxon LD100AC and has the density of 0.9225g/cm 3 The melt index was 2g/10min.
Comparative example 5: a stretch wrap film is distinguished from example 1 in that LDPE is used in place of MLLDPE in the outer, inner and middle layers, the LDPE is of the type Exxon LD100AC and has a density of 0.9225g/cm 3 The melt index was 2g/10min.
Comparative example 6: a transparent winding film is prepared as follows: and heating the film blowing machine to 190 ℃, keeping the temperature for 1.5 hours, and blowing the film by using a special material for the transparent winding film. The preparation method of the special material for the transparent winding film comprises the following steps: LLDPE powder (DGM-1820) is weighed, polyisobutene with the molecular weight of 1300 is mixed in a mixer for 3 minutes according to the weight of 10:1, a twin-screw extruder is heated to 170 ℃, the temperature is kept for 1.5 hours, the mixed material is added into the twin-screw extruder, and after melting and mixing, the mixture is cooled and granulated, so that the needed adhesive master batch is prepared. Mixing the viscosity master batch, the antioxidant and the silicon dioxide with the particle size of 50 mu m in a mixer according to the weight ratio of 100:5:1 for 2 minutes, then mixing with LLDPE powder (DGM-1820), and preparing the special material by melting and mixing in a double screw extruder, cooling and granulating.
Performance test
Wound films were prepared according to the methods in examples and comparative examples, and properties of the wound films were measured with reference to the following methods, and the measurement results are recorded in table 2.
1. Thickness: the detection was carried out according to GB/T6672-2001 mechanical measurement method for measuring thickness of Plastic film and sheet.
2. Longitudinal tensile force and longitudinal elongation at break: determination of the tensile Properties of plastics according to GB/T1040.3-2006 section 3: film and sheet assays.
3. Puncture resistance: the detection is carried out according to GB/T10004-2008 method for testing puncture strength of packaging Plastic composite film.
4. Haze: the detection is carried out according to GB/T2410-1980 Standard for transparent Plastic transmittance and five toxicity test method.
5. Inner layer antibacterial rate: the strain used was Staphylococcus aureus (ATCC 6538) according to QB/T2591-2003 test method for antibacterial Property and antibacterial Effect of antibacterial plastics.
6. Water contact angle of inner layer: the water contact angle of the inner layer surface was measured by an optical contact angle measuring instrument (OCA 40, data physics, germany) and the average value of the water contact angle was obtained by selecting 5 positions of the inner layer surface at 25 ℃ with a drop volume of 0.4 μl by the hanging drop method.
TABLE 2 results of measurement of the properties of stretch wrap films
In combination with the data in examples 1-5 and Table 2, the anti-fog agents prepared in preparation examples 1 and 2 are adopted in the tackifying master batches in examples 1-2 respectively, and the obtained winding film has the advantages of thin thickness, strong puncture resistance, high stretching resistance, low haze and high transparency, and the inner layer has high antibacterial rate, water drops are easy to pave, water mist is not easy to generate, and the anti-fog effect is good. The raw materials used in examples 3-5 are different from those used in example 1, and the prepared wound film has low haze, high transparency, high puncture resistance and difficult generation of water mist in the inner layer.
The antifogging agent in example 6 was prepared in preparation example 3, in which nano titanium dioxide was not used, and the hydrophilic modified PVDF was mixed with hollow silica nanoparticles in a liquid form, and the puncture resistance of the wound film prepared in example 6 was slightly reduced, the antibacterial rate of the inner layer was reduced, and the contact angle of the inner layer with water was increased, indicating that the use of nano titanium dioxide can improve the antibacterial and antifogging effects of the inner layer of the wound film.
Example 7 compared with example 1, the antifogging agent was prepared in preparation example 4, in which PVDF which was not hydrophilically modified was used in preparation example 4, and the remaining properties of the wound film prepared in example 7 were not much different from those of example 1, but the contact angle of the inner layer with water was increased, the spreading speed of water drops on the inner layer was fast, water mist was easily generated on the inner layer, and the antifogging effect was deteriorated.
The antifoggant of example 8 was prepared from preparation 5, and the solid nanosilica used in preparation 5, and the data in table 2 show that the haze of the wound film of example 8 was significantly reduced, the light transmittance was reduced, and the transparency was reduced.
Example 9 shows in table 2 that the puncture resistance of the wound film prepared in example 9 is slightly reduced, and the haze is increased, the light transmittance is reduced, the transparency is reduced, and the inner layer antibacterial effect is reduced, as compared with example 1, without adding an antifogging agent to the tackifying master batch.
In example 10, the antifogging agent was glycerol ester, and the contact angle between the inner layer of the wound film produced in example 10 and water was reduced and the antifogging effect was improved as compared with example 9, but the antifogging effect was still inferior to that of example 1, and although the antifogging effect of the inner layer of the wound film was improved by adding the antifogging agent, the antibacterial property and haze of the wound film produced in example 10 were also inferior to those of example 1, indicating that the antibacterial effect and light transmittance of the wound film could not be improved at the same time by adding only glycerol ester as the antifogging agent.
Example 11 shows in table 2 that the wound film prepared in example 11 has reduced haze and reduced transparency compared to example 1, indicating that the use of the organic transparent antimicrobial agent not only improves the antimicrobial rate but also does not affect the transparency of the wound film.
In example 12, the adhesion promoting masterbatch is a commercial product, and compared with example 1, the wound film prepared in example 12 has the advantages of increased haze, reduced transparency, reduced antibacterial rate of the inner layer, and reduced antifogging effect of the inner layer.
Comparative example 1 shows in table 2 that the wrapping film of comparative example 1, although having an increased thickness, has a reduced breaking force and elongation at break, reduced puncture resistance, increased haze, reduced transparency, and a reduced contact angle of the inner layer with water, indicating that the HDPE having an increased density is detrimental to the precipitation of the tackifying master batch and the antifogging agent, as compared with example 1, using HDPE having a higher density in the inner layer instead of LLDPE.
Comparative example 2 and comparative example 3 LLDPE was used for the inner layer, the outer layer and the middle layer in comparative example 2, and MLLDPE was used for comparative example 3, respectively, in comparison with example 1, the puncture resistance was decreased and the stretch resistance was decreased in the wound films prepared in comparative example 2 and comparative example 3.
Comparative example 4 and comparative example 5 the inner layer, middle layer and outer layer of comparative example 4 each use LDPE instead of LLDPE, and in comparative example 5 the inner layer, middle layer and outer layer each use LDPE instead of MLLDPE, and it is shown in Table 2 that the stretch resistance, puncture resistance and transparency of the wound films prepared in comparative example 4 and comparative example 5 are reduced and the antifogging effect of the inner layer is deteriorated.
Comparative example 6 a film was made by blowing a film from the material for transparent wrapping film prepared in the prior art, which had a thin thickness, high transparency, but poor puncture strength, low tensile strength, and a large contact angle between the inner side and water, which resulted in water mist generation and poor antifogging effect.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (10)

1. The stretch-wrapping film is characterized by sequentially comprising an outer layer, a middle layer and an inner layer, wherein the outer layer comprises the following raw materials in parts by weight: 60-90 parts of MLLDPE and 200-250 parts of LLDPE;
the middle layer comprises the following raw materials in parts by weight: 130-170 parts of MLLDPE and 430-470 parts of LLDPE;
the inner layer comprises the following raw materials in parts by weight: 60-90 parts of MLLDPE, 200-250 parts of LLDPE and 6-10 parts of tackifying master batch.
2. The stretch-wrap film of claim 1, wherein: the outer layer comprises the following raw materials in parts by weight: 70-80 parts of MLLDPE and 210-240 parts of LLDPE;
the middle layer comprises the following raw materials in parts by weight: 140-160 parts of MLLDPE and 440-460 parts of LLDPE;
the inner layer comprises the following raw materials in parts by weight: 70-80 parts of MLLDPE, 210-240 parts of LLDPE and 7-9 parts of tackifying master batch.
3. The stretch-wrap film of claim 1, wherein the amount of MLLDPE in the middle layer is the amount of MLLDPE in the inner layer is the amount of MLLDPE in the outer layer = 1:0.46-0.53:0.46-0.53;
the amount of LLDPE in the middle layer is equal to the amount of LLDPE in the inner layer, and the amount of LLDPE in the outer layer is equal to 1:0.46-0.53:0.46-0.53.
4. The stretch-wrap film of claim 1 wherein the MLLDPE has a melt index of 1 to 1.2g/10min and a density of 0.918 to 0.92g/cm 3 。
5. The stretch-wrap film of claim 1 wherein the LLDPE has a melt index of 1.9 to 2g/10min and a density of 0.9188 to 0.92g/cm 3 。
6. The stretch-wrap film of claim 1, wherein the tackifying master batch comprises the following raw materials in parts by weight: 1 to 2 parts of LDPE, 1.2 to 2.4 parts of polyisobutene, 0.2 to 0.4 part of antifogging agent and 0.08 to 0.16 part of antibacterial agent.
7. The stretch-wrap film of claim 6 wherein the antifogging agent is made from a mixture, melt, extrusion granulation of hydrophilically modified PVDF and hollow silica nanoparticles in a mass ratio of 1:1.3-1.6.
8. The stretch-wrap film of claim 7, wherein the hydrophilically-modified PVDF is prepared by:
14-16 parts of PVDF and 3.5-4 parts of polyvinyl alcohol are dissolved into 84-86 parts of dimethyl sulfoxide, and 1.4-1.6 parts of glutaraldehyde solution is added to adjust the pH value to 5-6 to prepare a modified liquid;
the modified liquid is evenly sprayed on 150-200 parts of nano titanium dioxide and dried for 50-60s at the temperature of 40-50 ℃.
9. The stretch wrap film of claim 1, wherein the antimicrobial agent is selected from the group consisting of an organic transparent antimicrobial agent or an inorganic transparent antimicrobial agent.
10. A method of producing a stretch-wrap film according to any one of claims 1 to 9, comprising the steps of:
according to the proportion of the raw materials, the inner layer, the outer layer and the middle layer are respectively and uniformly mixed to prepare an inner layer material, an outer layer material and a middle layer material;
and carrying out three-layer coextrusion on the inner layer material, the outer layer material and the middle layer material, then casting, cooling and shaping, and then cutting and rolling.
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