CN110328947A - A kind of preparation method of environment-protecting and non-poisonous beer plastic bag material - Google Patents

A kind of preparation method of environment-protecting and non-poisonous beer plastic bag material Download PDF

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Publication number
CN110328947A
CN110328947A CN201910744509.XA CN201910744509A CN110328947A CN 110328947 A CN110328947 A CN 110328947A CN 201910744509 A CN201910744509 A CN 201910744509A CN 110328947 A CN110328947 A CN 110328947A
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beer
poisonous
protecting
environment
plastic bag
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郭坤
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Maanshan Zhuofan New Material Technology Co Ltd
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Maanshan Zhuofan New 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
    • B32B27/06—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
    • B32B27/30—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Packages (AREA)
  • Wrappers (AREA)

Abstract

The invention discloses a kind of preparation methods of environment-protecting and non-poisonous beer plastic bag material, and the invention belongs to technical field of polymer materials, beer prepared by the present invention polybag good barrier property, oxygen infiltration rate is low, and light-proofness is good, can extend the shelf-life of beer on tap；Heat resistance is good, meets that beer bag is filling, 30min requirement at 60 DEG C of pasteurize；Light, not quick-fried bag, mechanical strength is high, meet the requirement of transport, storage, consumption, reclaimed materials can blend recovery and reusing and recycling in any proportion, institute's reclaimed materials is when the downstreams such as melt spinning, sheet material extrusion molding utilize, it has no adverse effects to processing technology, product and production process are environmentally friendly, and the market competitiveness is strong.

Description

A kind of preparation method of environment-protecting and non-poisonous beer plastic bag material
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of system of environment-protecting and non-poisonous beer plastic bag material Preparation Method.
Background technique
Draught beer wine is the ideal beverage of appetizing of recovering from fatigue of relieving summer heat summer.Beer on tap is also with from last century China's beer It is gradually esthetically acceptable to the consumers and likes in the process of industrial boom development, more ground such as China Harbin, Qingdao, thus remove packed tank It fills outside beer, has also sold young beer in bulk, the draught beer wine of sale is popular.Currently, more and more consumers How many beer in bulk selection stamps on the way home on and off duty, and beer on tap is just becoming most important beer consumption pattern One of, now, beer has become the daily beverage of common people, in recent years, used in the market when selling draft beer in bulk The inadequate specification of metering device, uniformly, most common is with " bundle " metering.And " bundle " volume size is chaotic, when the interests of consumer It is normal thus impaired.In order to specification beer metering, State Bureau of Technical Supervision, Ministry of Internal Trade and commission of light industry issue jointly " about Reinforce the notice of beer measuring cup supervision and management ".The notice request should use China's legal unit of measurement when selling beer on tap " liter " marked price and clearing, and polybag makees container and avoids the accurate problem of metering sale just, the fresh beer just to have dispatched from the factory is orange Juice it is general white Pao Droplets, and, compared to packed, tinned, and it is more and more welcomed by the people to dissipate beer (fresh beer).Not By the fresh beer of high-temperature sterilization process, viable yeast equal size is higher, therefore gives out fresh hops fragrance.And it uses dedicated Polybag is light easy to carry, low in cost, and fill operations are simple, substantially reduce the packaging purchase of production cost and consumer at This, be significantly reduced because of the violent conflict that wine bag, wine tank occurred in food and drink during a possibility that and what consumer used Polybag installs fresh beer, heartily while, the presence of a large amount of viable yeasts and but existing polybag because existing for alcohol Extraction, small molecule organic matter, which exists, takes in intracorporal risk, and existing plastic bag material intensity is low, poor mechanical property, pole Cracky, and transparency is low, and non-refractory, the probability of bacterial infection virus is very high, and and be not easy to recycle, and this Field technical staff, it would be highly desirable to exploitation is used as a kind of Novel plastic bag material of beer on tap, to meet higher requirement, into And meet market to the widespread demand of such material.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of preparation of environment-protecting and non-poisonous beer plastic bag material is provided Method.
The invention is realized by the following technical scheme:
A kind of preparation method of environment-protecting and non-poisonous beer plastic bag material, comprising the following steps: (1) by ethylene vinyl alcohol copolymer 100 ~ 110 parts and 10 ~ 15 parts of sericite in powder of object stir in blender, obtain mixture, mixture is put into and is squeezed out In machine, effect of the material in barrel by temperature and shearing force is melted, and pushes head to by screw rod, and double bubbles is taken to squeeze out work Skill, while polyvinylidene chloride film is squeezed out by another extruder through co-extrusion die head, the coated place of polyvinylidene chloride film Reason, and the melt compound extruded of extrusion and is quenched with cold water, and membrane tube is made in cooling stretch；(2) by membrane tube reheating, inflation, Cooling, stretching is cut through cooling and shaping, tension force, thickness measuring, sided corona treatment, deburring, is wound to get film；(3) quality is pressed Aluminium powder is added in 100 ~ 110 parts of dilute hydrochloric acid of mass fraction 8 ~ 10% by the ratio than 2 ~ 3:6 ~ 7.5, adds 120 ~ 125 parts Acidic silicasol both makes to be sufficiently mixed dissolution under the conditions of 95 ~ 102 DEG C, obtained sial mixed sols, weigh mass fraction 30 ~ 15 ~ 21 parts of hexamethylenetetramine solution of 35% are added into sial mixed sols, then move to polytetrafluoroethylene (PTFE) autoclave, 130 ~ 140 DEG C of 2 ~ 4h of hydro-thermal reaction, 60 ~ 80 DEG C of deionized water filtering and washings remove soluble impurity, by deposit in 70 ~ 80 DEG C of oven dryings 1 ~ 2h, 810 ~ 900 DEG C of 2 ~ 4h of roasting are cooled to room temperature to obtain silica alumina doped and compounded material, then By film by pre-processing, it is fixed on the top of vapor deposition vacuum chamber, using silica alumina doped and compounded material as target, It is put in crucible, under nitrogen atmosphere, film substrate is baked to 130 ~ 140 DEG C, electron source is opened, after preheated, sends out filament The electron beam of injection is radiated on the target in crucible through overshoot and focusing, under the thermal energy effect of high-power electron beam, target Evaporation rapidly, vapor deposition is simultaneously attached on film, and after plated film, manufactured sample is remaining by 50 ~ 60 DEG C of annealing removals Stress is cooled to room temperature taking-up to get environment-protecting and non-poisonous beer plastic bag material.
Further, the environment-protecting and non-poisonous beer plastic bag material has two layers, and one layer is barrier layer, to gather inclined dichloro The extruded film of ethylene, the second layer are oxygen barrier layer, ethylene-vinyl alcohol copolymer barrier resins described in step (1), Ethylene vinyl The moisture of the ethylene contents 30 ~ 36% of alcohol copolymer barrier resins, ethylene-vinyl alcohol copolymer barrier resins pellet is controlled 0.1 ~ 0.3%, 230 DEG C of ethylene-vinyl alcohol copolymer, loading 2.16kg melt index is 1.3 ~ 1.9g/10min.
Further, step (1) the coating processing liquid is by the way of coating by a strata urethane adhesive layer Layer is uniformly coated on the outside of membrane tube, and 24 ~ 48h forms adhesive layer after spontaneously drying, adhesive for polyurethane be selected from PU-502B, One of which in 503H is coated using smooth roll, and the solid content of solution is 5 ~ 10%, and coated weight is 0.03 ~ 0.3g/m2, in the first floor Ethylene-vinyl alcohol copolymer barrier resins oxygen barrier layer is squeezed out on barrier layer by the way of melting extrusion.
Further, it is 0.003 ~ 0.02Pa that electron beam evaporation parameter, which is gas pressure in vacuum, evaporation time 5 ~ 10min, 200 ~ 400W of power, line is in 30 ~ 70mA, acceleration voltage in 6 ~ 8kV.
Further, step (2) extrusion process, extruder: draw ratio L/D is that 35 ~ 40, ε is 3.0 ~ 4.0；Head 2 sections of connector temperature point, is 180 ~ 230 DEG C, and 5 sections of head die lip temperature point is followed successively by, 180 ~ 210 DEG C, 210 ~ 220 DEG C, 190 ~ 210 DEG C, 180 ~ 210 DEG C, 185 ~ 220 DEG C, the i.e. temperature of fused materials control between 180 ~ 220 DEG C, and drying temperature is 50 ~ 80 DEG C, chill-roll temperature is 12 ~ 18 DEG C, blow-up ratio 1 ~ 2.5, draw ratio 2 ~ 6,120 ~ 130 DEG C of reheating temperature, corona Processing voltage is 8 ~ 30kV, and frequency is 10 ~ 25kHz.
Further, the preparation method of the step (1) acidic silicasol is that alkali is added to adjust silica aqueous solution pH It is 9.0 ~ 11.5, then acid adding makes colloidal sol polycondensation become SiO2Hydrogel, at 70 ~ 90 DEG C of temperature be aged 0 ~ for 24 hours, it is described Alkali is NaOH, Na2CO3, KOH, sodium silicate solution solution at least one, use SiO2The deionized water that 8 ~ 9 times of hydrogel, step (1) described then first to allow hydrogel by cation exchange column pH3 ~ 4, then exchanged by anion-exchange column to it is molten to obtain silicon Glue dilution, pH value be 4.5 ~ 5.8 to get.
Beneficial effects of the present invention:
In a kind of preparation process of polybag provided by the invention, metallocene PE contamination resistance is strong, and sealing effect is good, uses In the PVDC film layer of film, heat seal effect is mainly played, guarantees that packaging does not reveal liquid, sericite in powder plays increasing ethylene-second The effect of the heat seal effect of enol copolymer;The function of playing auxiliary production enables film bubble to stablize blowout, improves molding Property.Its bonding effect of coating processing liquid is good, PVDC film layer and PEVOH film layer can be well bonded to a use temperature range Extensively, it can be resistant to from -60 DEG C~200 DEG C, the higher sterilising temp of beer can be resistant to, also can tolerate lower refrigeration temperature Degree has preferable tensile strength, and puncture resistance, oxygen resistance is preferable, and there is better oxygen-barrier property to have to gas Fabulous barrier property, and processability is fabulous.But ethylene-vinyl alcohol copolymer resin to most polymers adhesive force very Difference need to use special adhering resin, and the glass transition temperature of ethylene-vinyl alcohol copolymer is high, adapts to processing and forming, Ke Yigai The shortcomings that being also easy to produce modification when kind heating, so, by the change of formula composition, there is high barrier in inventive formulation Performance effectively extends the shelf-life of beer packing content；Secondly heat sealability is excellent, and contamination resistance is strong, has extraordinary Heat seal strength, wipes that coefficient is moderate, and when cutting will not generate adhesion and be not in skid, and is very suitable to the installation of beer on tap.
The present invention has the advantage that compared with prior art
A kind of preparation method of environment-protecting and non-poisonous beer plastic bag material provided by the invention can prevent explosion of beer bottle and hurt sb.'s feelings thing Therefore when can be effectively prevented explosion of beer bottle cullet splashing casualty accident generation, substantially increase production efficiency, simultaneously Production cost is also reduced, and is conducive to control the quality of membrane tube, it is resistance to crack, is wear-resistant, being not easy to be layered.It will not be because of time mistake Degrade long, will not reduce effective shelf lives, and this oxygen barrier film be easy in the removal process of bottle by Remove, will not Pollution Cycle use production line again, made of nonpoisonous plastic material, the section of bottle is in kidney-shaped, in order to take Band, production technology is more convenient, and product cost is cheaper, meanwhile, it is easy to seal, use is safe, it is easy recycling, processing, this A little advantages are that existing beer installs not available for material.
Specific embodiment
Illustrate the present invention with specific embodiment below, but is not limitation of the present invention.
Embodiment 1
A kind of preparation method of environment-protecting and non-poisonous beer plastic bag material, comprising the following steps: (1) by ethylene vinyl alcohol copolymer 110 parts and 15 parts of sericite in powder of object stir in blender, obtain mixture, mixture are put into extruder, object Expect that the effect in barrel by temperature and shearing force is melted, and head is pushed to by screw rod, takes double bubble extrusion processes, simultaneously Polyvinylidene chloride film is squeezed out by another extruder through co-extrusion die head, the coated processing of polyvinylidene chloride film, with squeeze Melt compound extruded out is simultaneously quenched with cold water, and membrane tube is made in cooling stretch；(2) by membrane tube reheating, inflation, cooling, drawing It stretches, cuts, wound to get film through cooling and shaping, tension force, thickness measuring, sided corona treatment, deburring；(3) 3:7.5 in mass ratio Ratio aluminium powder is added in 1110 parts of dilute hydrochloric acid of mass fraction 10%, add 125 parts of acidic silicasols in 102 DEG C of items So that the two is sufficiently mixed dissolution under part, sial mixed sols is made, weighs 21 parts of hexamethylenetetramine solution of mass fraction 35% It is added into sial mixed sols, then moves to polytetrafluoroethylene (PTFE) autoclave, 140 DEG C of hydro-thermal reaction 4h, 80 DEG C of deionized waters Filtering and washing, remove soluble impurity, by deposit in 80 DEG C of oven dryings 2h, 900 DEG C of roasting 4h, be cooled to room temperature two Silica alumina doped and compounded material, then film is fixed on the top of vapor deposition vacuum chamber, by silica by pre-processing Alumina doped composite material is put in crucible as target, under nitrogen atmosphere, film substrate is baked to 140 DEG C, is opened Electron source, after preheated, the electron beam for launching filament is radiated on the target in crucible, through overshoot and focusing in height Can electron beam thermal energy effect under, target evaporate rapidly (, vapor deposition is simultaneously attached on film, after plated film, manufactured sample Product remove residual stress by 60 DEG C of annealing, are cooled to room temperature taking-up to get environment-protecting and non-poisonous beer plastic bag material.
Further, the environment-protecting and non-poisonous beer plastic bag material has two layers, and one layer is barrier layer, to gather inclined dichloro The extruded film of ethylene, the second layer are oxygen barrier layer, ethylene-vinyl alcohol copolymer barrier resins described in step (1), Ethylene vinyl The ethylene contents 36% of alcohol copolymer barrier resins, the moisture control of ethylene-vinyl alcohol copolymer barrier resins pellet 0.3%, 230 DEG C of ethylene-vinyl alcohol copolymer, loading 2.16kg melt index is 1.9g/10min.
Further, step (1) the coating processing liquid is by the way of coating by a strata urethane adhesive layer Layer is uniformly coated on the outside of membrane tube, and 48h forms adhesive layer after spontaneously drying, adhesive for polyurethane is selected from PU-502B, using light Roll coating, the solid content of solution are 10%, coated weight 0.3g/m2, squeezed by the way of melting extrusion on first floor barrier layer Ethylene-vinyl alcohol copolymer barrier resins oxygen barrier layer out.
Further, it is 0.02Pa, evaporation time 10min, power that electron beam evaporation parameter, which is gas pressure in vacuum, 2400W, line is in 70mA, acceleration voltage in 8kV.
Further, step (2) extrusion process, extruder: draw ratio L/D is 35, ε 3.0；Head connector temperature 2 sections of degree point, is 180 DEG C, and 5 sections of head die lip temperature point is followed successively by, 180 DEG C, 210 DEG C, 190 DEG C, 180 DEG C, 185 DEG C, i.e., molten Melt the temperature of material, control between 180 ~ 210 DEG C, drying temperature is 80 DEG C, and chill-roll temperature is 18 DEG C, and blow-up ratio 2.5 is led It stretches than 2,120 DEG C of reheating temperature, sided corona treatment voltage is 30kV, frequency 25kHz.
Further, the preparation method of the step (1) acidic silicasol is that alkali is added to adjust silica aqueous solution pH It is 9.0, then acid adding makes colloidal sol polycondensation become SiO2Hydrogel is aged for 24 hours under temperature 70 C, the alkali be NaOH, Na2CO3, KOH, sodium silicate solution solution at least one, use SiO2The deionized water that 9 times of hydrogel, step (1) are described then It first allows hydrogel by cation exchange column pH3, then is exchanged by anion-exchange column to obtaining silica solution dilution, pH Value for 4.5 to get.
Embodiment 2
Further, the environment-protecting and non-poisonous beer plastic bag material has two layers, and one layer is barrier layer, is polyvinylidene chloride Extruded film, the second layer is oxygen barrier layer, a kind of step (1) preparation method of environment-protecting and non-poisonous beer plastic bag material, The following steps are included: (1) stirs 110 parts and 15 parts of sericite in powder of ethylene-vinyl alcohol copolymer in blender, Mixture is obtained, mixture is put into extruder, effect of the material in barrel by temperature and shearing force is melted, and by spiral shell Bar pushes head to, takes double bubble extrusion processes, while polyvinylidene chloride film is squeezed out by another extruder through co-extrusion die head, The coated processing of polyvinylidene chloride film, and the melt compound extruded of extrusion and is quenched with cold water, and membrane tube is made in cooling stretch； (2) it by membrane tube reheating, inflation, cooling, stretching, is cut through cooling and shaping, tension force, thickness measuring, sided corona treatment, deburring, Winding is to get film；(3) aluminium powder is added in 110 parts of dilute hydrochloric acid of mass fraction 8% by the ratio of 2:7.5 in mass ratio, then 120 parts of acidic silicasols are added makes the two be sufficiently mixed dissolution under the conditions of 102 DEG C, and sial mixed sols is made, weighs quality 21 parts of hexamethylenetetramine solution of score 30% are added into sial mixed sols, then move to polytetrafluoroethylene (PTFE) autoclave, 130 DEG C of hydro-thermal reaction 2h, 60 DEG C of deionized water filtering and washings remove soluble impurity, by deposit in 70 DEG C of oven dryings 1h, 810 DEG C of roasting 2h are cooled to room temperature to obtain silica alumina doped and compounded material, then by film by pre-processing, fixed It is put in crucible on the top of vapor deposition vacuum chamber using silica alumina doped and compounded material as target, nitrogen atmosphere Under, film substrate is baked to 130 DEG C, opens electron source, after preheated, the electron beam for launching filament is through overshoot and gathers Coke is radiated on the target in crucible, and under the thermal energy effect of high-power electron beam, target evaporates rapidly, and vapor deposition simultaneously adheres to On film, after plated film, manufactured sample removes residual stress by 5060 DEG C of annealing, be cooled to room temperature take out to get Environment-protecting and non-poisonous beer plastic bag material.
Ethylene-vinyl alcohol copolymer barrier resins, the ethylene contents 30% of ethylene-vinyl alcohol copolymer barrier resins, second The moisture control of alkene ethenol copolymer barrier resins pellet is 0.1%, 230 DEG C of ethylene-vinyl alcohol copolymer, loading 2.16kg Melt index is 1.3g/10min.
Further, step (1) the coating processing liquid is by the way of coating by a strata urethane adhesive layer Layer is uniformly coated on the outside of membrane tube, and adhesive layer is formed after spontaneously drying for 24 hours, and adhesive for polyurethane selects PU-502B using smooth roll Coating, the solid content of solution are 10%, coated weight 0.03g/m2, squeezed by the way of melting extrusion on first floor barrier layer Ethylene-vinyl alcohol copolymer barrier resins oxygen barrier layer out.
Further, it is 0.02Pa, evaporation time 10min, power that electron beam evaporation parameter, which is gas pressure in vacuum, 400W, line is in 70mA, acceleration voltage in 8kV.
Further, step (2) extrusion process, extruder: draw ratio L/D is 40, ε 3.0；Head connector temperature 2 sections of degree point, is 200 DEG C, and 5 sections of head die lip temperature point is followed successively by, 180 DEG C, 220 DEG C, 210 DEG C, 210 DEG C, 1220 DEG C, i.e., The temperature of fused materials controls between 180220 DEG C, and drying temperature is 80 DEG C, and chill-roll temperature is 12 DEG C, blow-up ratio 2.5, Draw ratio 2,130 DEG C of reheating temperature, sided corona treatment voltage is 30kV, frequency 25kHz.
Further, the preparation method of the step (1) acidic silicasol is that alkali is added to adjust silica aqueous solution pH It is 11.5, then acid adding makes colloidal sol polycondensation become SiO2Hydrogel is aged for 24 hours at 90 DEG C of temperature, the alkali be NaOH, Na2CO3, KOH, sodium silicate solution solution at least one, use SiO2The deionized water that 9 times of hydrogel, step (1) are described then First allow hydrogel by cation exchange column pH value be 4, then by anion-exchange column exchange to, obtain silica solution dilution, Its pH value be 5.8 to get.
Comparative example 1
This comparative example compared with Example 2, in step (1), saves de-fatted soybean dregs ingredient, method and step in addition to this is homogeneous Together.
Comparative example 2
This comparative example compared with Example 2, saves step (3), and method and step in addition to this is all the same.
Comparative example 3
This comparative example compared with Example 2, in step (1), saves sericite in powder ingredient, method and step in addition to this is homogeneous Together.
Comparative example 4
This comparative example compared with Example 2, in step (1), saves hexamethylenetetramine solution composition, method step in addition to this It is rapid all the same.
Comparative example 5
This comparative example compared with Example 2, in step (1), saves acidic silicasol ingredient, method and step in addition to this is homogeneous Together.
Comparative example 6
This comparative example compared with Example 2, in step (1), saves coating processing, method and step in addition to this is all the same.
The mechanical property of polybag prepared by each embodiment and comparative example of table 1
Note: the standard environment of GB/T2918-2018 plastic sample status adjustment and test；Sanitation performance refers to GB/4806.6- Plastic resin is used in the contact of 2016 national food safety standard food；GB/T4806.7-2016 national food safety standard food connects Touching plastic material and product；GB/T9685-2016 food containers, packaging material use sanitary standard with additive；GB/ The measurement of T31604.2-2016 national food safety standard food contact material and product potassium permanganate consumption；GB/ T31604.7-2016 national food safety standard food contact material and product Decolorant Test；GB/T31604.8-2016 food The measurement of safe national standard food contact material and product gross migration；GB/T31604.9-2016 national food safety standard The measurement of heavy metal in food contact material and product food simulants, 60 DEG C≤10mg/kg of potassium permanganate consumption water, a huge sum of money Belong to 4% acetic acid, 60 DEG C of 2h≤1mg/L, decolorization experiment ethyl alcohol, buffet oil, soak are all that negative object benzene kind solvent, dissolvent residual are total Amount≤3mg/m2It is full coliform must not to be detected；GB/T2358-1998 plastic film packaging bag heat sealing strength test method；GB/T The 10004-2008 composite membrane of resistance to boiling, bag；The test piece that diameter is 100mm is mounted on sample film clamping ring, diameter is then used The steel needle for being 0.5mm for 10mm, spherical tips radius goes to top to pierce with the speed of (50 ± 5) mm/min, reads steel needle and penetrates test piece Peak load；Gas permeability GB/T1038-2000 plastic film and diaphragm gas-premeable test method pressure differential method surface tension GB/T4216-1993 plastic foil and piece wetting tension test method；Water imbibition QB/T1034-2008 plastic ink absorption test side Method；Shock resistance GB/T1038-2000 plastic film and diaphragm gas-premeable test method pressure differential method；GB/T 1040.3- The measurement third portion of 2006 plastic tensile performances: the experimental condition of film and thin slice；Thickness G B/T 6672-2001 plastics are thin Film and Foil thickness measurement mechanical measurement method；The test of heat sealing strength QB/T 2358-1998 plastic film packaging bag heat sealing strength Method.

Claims (6)

1. a kind of preparation method of environment-protecting and non-poisonous beer plastic bag material, which comprises the following steps: (1) by second 100 ~ 110 parts and 10 ~ 15 parts of sericite in powder of alkene-ethenol copolymer stir in blender, obtain mixture, will mix It closes in material investment extruder, effect of the material in barrel by temperature and shearing force is melted, and pushes head to by screw rod, is adopted Double bubble extrusion processes are taken, while polyvinylidene chloride film is squeezed out by another extruder through co-extrusion die head, polyvinylidene chloride The coated processing of film, and the melt compound extruded of extrusion and is quenched with cold water, and membrane tube is made in cooling stretch；(2) by membrane tube two Secondary heating, inflation, cooling, stretching are cut through cooling and shaping, tension force, thickness measuring, sided corona treatment, deburring, are wound to get thin Film；(3) aluminium powder is added in 100 ~ 110 parts of dilute hydrochloric acid of mass fraction 8 ~ 10% by the ratio of 2 ~ 3:6 ~ 7.5 in mass ratio, then 120 ~ 125 parts of acidic silicasols are added makes the two be sufficiently mixed dissolution under the conditions of 95 ~ 102 DEG C, and sial mixed sols is made, and claims It takes 15 ~ 21 parts of hexamethylenetetramine solution of mass fraction 30 ~ 35% to be added into sial mixed sols, then moves to polytetrafluoroethyl-ne Alkene autoclave, 130 ~ 140 DEG C of 2 ~ 4h of hydro-thermal reaction, 60 ~ 80 DEG C of deionized water filtering and washings remove soluble impurity, will Deposit in 70 ~ 80 DEG C of oven dryings 1 ~ 2h, 810 ~ 900 DEG C of 2 ~ 4h of roasting, be cooled to room temperature silica alumina is mixed Miscellaneous composite material, then film is fixed on the top of vapor deposition vacuum chamber, by silica alumina doped and compounded by pre-processing Material is put in crucible as target, under nitrogen atmosphere, film substrate is baked to 130 ~ 140 DEG C, electron source is opened, through pre- After heat, the electron beam for launching filament is radiated on the target in crucible through overshoot and focusing, in the heat of high-power electron beam Under capable of acting on, target evaporates rapidly, and vapor deposition is simultaneously attached on film, and after plated film, manufactured sample passes through 50 ~ 60 DEG C Annealing removal residual stress, is cooled to room temperature taking-up to get environment-protecting and non-poisonous beer plastic bag material.
2. the preparation method of environment-protecting and non-poisonous beer plastic bag material according to claim 1, which is characterized in that described Environment-protecting and non-poisonous beer plastic bag material has two layers, and one layer is barrier layer, is the extruded film of polyvinylidene chloride, the second layer is oxygen Barrier layer, ethylene-vinyl alcohol copolymer barrier resins described in step (1), the ethylene of ethylene-vinyl alcohol copolymer barrier resins Content 30 ~ 36%, the moisture control of ethylene-vinyl alcohol copolymer barrier resins pellet is 0.1 ~ 0.3%, ethylene vinyl alcohol copolymer 230 DEG C of object, loading 2.16kg melt index is 1.3 ~ 1.9g/10min.
3. the preparation method of environment-protecting and non-poisonous beer plastic bag material described in accordance with the claim 1, which is characterized in that the step Suddenly (1) described coating processing liquid is uniformly to be coated in a strata urethane gluing on the outside of membrane tube layer by layer by the way of coating, 24 ~ 48h forms adhesive layer after spontaneously drying, one of which of the adhesive for polyurethane in PU-502B, 503H is applied using smooth roll It covers, the solid content of solution is 5 ~ 10%, and coated weight is 0.03 ~ 0.3g/m2, the side of melting extrusion is used on first floor barrier layer Formula squeezes out ethylene-vinyl alcohol copolymer barrier resins oxygen barrier layer.
4. a kind of preparation method of environment-protecting and non-poisonous beer plastic bag material described in accordance with the claim 1, which is characterized in that electricity Beamlet evaporation process parameter is that gas pressure in vacuum is 0.003 ~ 0.02Pa, 5 ~ 10min of evaporation time, 200 ~ 400W of power, line In 30 ~ 70mA, acceleration voltage in 6 ~ 8kV.
5. the preparation method of environment-protecting and non-poisonous beer plastic bag material described in accordance with the claim 1, which is characterized in that the step Suddenly (2) extrusion process, extruder: draw ratio L/D is that 35 ~ 40, ε is 3.0 ~ 4.0；Head connector temperature points 2 sections are 180 ~ 230 DEG C, 5 sections of head die lip temperature point is followed successively by, 180 ~ 210 DEG C, 210 ~ 220 DEG C, 190 ~ 210 DEG C, 180 ~ 210 DEG C, 185 ~ 220 DEG C, the i.e. temperature of fused materials, control between 180 ~ 220 DEG C, drying temperature be 50 ~ 80 DEG C, chill-roll temperature be 12 ~ 18 DEG C, blow-up ratio 1 ~ 2.5, draw ratio 2 ~ 6,120 ~ 130 DEG C of reheating temperature, sided corona treatment voltage is 8 ~ 30kV, and frequency is 10~25kHz。
6. the preparation method of environment-protecting and non-poisonous beer plastic bag material described in accordance with the claim 1, which is characterized in that the acid Property silica solution preparation method be add alkali adjust silica aqueous solution pH be 9.0 ~ 11.5, then acid adding becomes colloidal sol polycondensation SiO2Hydrogel, at 70 ~ 90 DEG C of temperature be aged 0 ~ for 24 hours, the alkali be NaOH, Na2CO3, KOH, sodium silicate solution solution At least one, use SiO2The deionized water that 8 ~ 9 times of hydrogel, then step (1) is described first to allow hydrogel to be handed over by cation Change column pH3 ~ 4, then by anion-exchange column exchange to, obtain silica solution dilution, pH value be 4.5 ~ 5.8 to get.
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