CN106541661A - One kind exempts from corona Biaxially oriented polypropylene packing film and its manufacture method - Google Patents

One kind exempts from corona Biaxially oriented polypropylene packing film and its manufacture method Download PDF

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Publication number
CN106541661A
CN106541661A CN201610956767.0A CN201610956767A CN106541661A CN 106541661 A CN106541661 A CN 106541661A CN 201610956767 A CN201610956767 A CN 201610956767A CN 106541661 A CN106541661 A CN 106541661A
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corona
exempt
top layer
polypropylene
blend
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CN106541661B (en
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韦丽明
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Zhejiang Lanye Technology Co ltd
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If Shanghai Yi New Mstar Technology Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • B32B2307/70—Other properties
    • B32B2307/728—Hydrophilic
    • 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
    • B32B2307/75—Printability
    • 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
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention discloses one kind exempts from corona Biaxially oriented polypropylene (BOPP) packing film and its manufacture method, belong to Biaxially oriented polypropylene (BOPP) processing technique field, including major-minor top layer, sandwich layer, secondary auxiliary top layer；The major-minor top layer by polypropylene, tissue adhesion masterbatch, exempt from that corona is polymer-modified to be prepared from；Sandwich layer is prepared from by polypropylene, smooth master batch, antifogging master batch；Secondary auxiliary top layer by polypropylene, tissue adhesion masterbatch, exempt from that corona is polymer-modified to be prepared from；Exempt from the major-minor top layer of corona Biaxially oriented polypropylene (BOPP) packing film and secondary auxiliary top layer with the addition of that to exempt from corona polymer-modified, improve polypropylene surface polarity and keep polarity unattenuated, greatly improve bidirectional stretching polypropylene film surface hydrophilicity, antistatic behaviour, cementability, impressionability.

Description

One kind exempts from corona Biaxially oriented polypropylene packing film and its manufacture method
Technical field
The present invention relates to one kind exempts from corona Biaxially oriented polypropylene packing film and its manufacture method, belong to biaxial tension and gather Propylene
(BOPP) processing technique field.
Background technology
The newest statistical data of PIRA companies of the U.S. points out, to Plastic demand compound annual growth rate is within 2012～2017 years 7.7%.To in Flexible Package Market demand, packaging for foodstuff compound annual growth rate is 4.3% to global terminal client within 2012～2017 years, Cosmetic package compound annual growth rate is 5.5%.Biaxially oriented polypropylene (BOPP) thin film is used as a kind of packaging of function admirable Material, is widely used in the fields such as clothing, cosmetics, food, books, napkin packaging.Bao Wei expert moulds in Chinese packaging community Recent statistics data are pointed out, to 12 the end of month in 2015, Chinese Biaxially oriented polypropylene (BOPP) packing film aggregated capacity 5,200,000 Ton, was incremented by with average 10% year rate of rise in recent years.
Polypropylene (PP) is hypocrystalline non-polar material, with the poor compatibility such as polar polymer, be not surface-treated On the premise of cannot print colouring, cannot also carry out further deep processing.BOPP packing films production process generally needs to increase Plus corona treatment plant, applying high-frequency high-voltage makes its corona discharge.The various plasmas produced after air ionization are in highfield In the presence of, acceleration shock film surface, the energy of plasma particle induce polypropylene chemical bond fission and degrade, and increase surface Roughness.In corona discharge, substantial amounts of ozone can be also produced.Ozone is a kind of strong oxidizer, aoxidizes polypropylene molecule, is produced Raw carbonyl compound, per-compound etc..After above-mentioned physics and chemical modification, the wettability of frosting can be obviously improved And tack.But while sided corona treatment also brings certain negative effect.Including：Safety, increase energy consumption, the ozone of generation are drawn Play air pollution and cause operator uncomfortable.In addition, packaging field has to the outward appearance and transparency of transparent packaging film Higher requirement, thin film can not occur degraded in wrapping cycle, and degraded can make film appearance color change (deepening), transparency It is deteriorated (mist degree increase), mechanical properties decrease.Ozone makes polypropylene molecule further aoxidize (degrade), can cause thin film end face face Color sends out the outward appearance phenomenons such as (powder) is red, transparency declines.
BOPP film is crystallized after still producing after timeliness, meanwhile, after sided corona treatment, the function of thin film skin surface layer There is higher animal migration in group.So in storage more than one week, sided corona treatment effect gradually failed.Migration-type additive from inside to Surface migration, declines surface energy, affects the adhesive force such as follow-up printing, coating, this negative effect completely inhibit.Therefore BOPP film surface polarity is improved by sided corona treatment, the method for wettability has certain limitation.
The present invention is in maximum wide cut (10.4m) highest mechanical speed (550m/min) biaxial stretching polypropylene in the world at present On alkene (BOPP) production line, one kind is with the addition of in BOPP film factory formula, and to exempt from corona polymer-modified, exempts from corona modified poly- Compound improves polypropylene surface polarity and the holding surface coefficient of tension is unattenuated, greatly improves bidirectional stretching polypropylene film surface Hydrophilic, antistatic behaviour, cementability, impressionability.Exempt from the polymer-modified addition of corona by adjusting, obtain moderate and not The high-performance Biaxially oriented polypropylene packing film of decay coefficient of surface tension.
The content of the invention
The invention provides one kind exempts from corona Biaxially oriented polypropylene packing film and its manufacture method, need not change existing Production technology, need not transform existing equipment, produce the high-performance biaxial stretching polypropylene with moderate and unattenuated surface polarity Alkene packing film, function and outward appearance meet market demands.
To achieve these goals, the technical solution adopted in the present invention is：
One kind exempts from corona Biaxially oriented polypropylene (BOPP) packing film and its manufacture method, including major-minor top layer, sandwich layer, Secondary auxiliary top layer, the major-minor top layer by polypropylene, tissue adhesion masterbatch, exempt from that corona is polymer-modified to be prepared from；Sandwich layer is by poly- third Alkene, smooth master batch, antifogging master batch are prepared from；Secondary auxiliary top layer by polypropylene, tissue adhesion masterbatch, exempt from the polymer-modified preparation of corona Form；Specifically, the major-minor top layer is respectively polypropylene 43.0～94.0%, tissue adhesion masterbatch 1.0 from percentage by weight ～7.0%, the component for exempting from corona polymer-modified 5.0～50.0% is prepared from；Sandwich layer is respectively poly- from percentage by weight Propylene 94.0～100.0%, smooth master batch 0～2.0%, the component of antifogging master batch 0～4.0% are prepared from；Secondary auxiliary top layer choosing With percentage by weight be respectively polypropylene 75.0～99.0%, tissue adhesion masterbatch 1.0～5.0%, exempt from corona it is polymer-modified 0～ 20.0% component is prepared from；It is 0.8%～10% that the thickness on the major-minor top layer accounts for overall film thickness ratio, the thickness of sandwich layer It is 80～98.4% that degree accounts for overall film thickness ratio, and the thickness on secondary auxiliary top layer accounts for overall film thickness ratio for 0.8%～10%.
Wherein, the tissue adhesion masterbatch is referred to by 5%～15%SiO2Antiblock additive for main body and 85%～95% Polypropylene blending modified to be prepared from, in special blending equipment, blending extrusion is prepared from, and extrusion processing temperature is 180～250 ℃.Add to thin film top layer and can play tissue adhesion effect；The tissue adhesion masterbatch be 3 μm of spherical inorganic class tissue adhesion masterbatch, 5 μm Spherical inorganic class tissue adhesion masterbatch, 4.5 μm of irregular shape mineral-type tissue adhesion masterbatch.
The smooth master batch is erucyl amide class smooth master batch；The smooth master batch is that smooth auxiliary agent, polypropylene granules are common Mixed thing A, blend A include：1) smooth auxiliary agent is erucyl amide, and its consumption is the 0.7%～20% of blend A gross weights, Preferably, 5%～20%, it is further preferably 0.7%, 12%；2) balance of polypropylene granules composition.
The antifogging master batch is glycerol ester type nonionic surfactant, Span, octadecyldimethyl Amine oxide and polypropylene blend B.Blend B contains 1) glycerol ester type nonionic surfactant, and its consumption is blend B The 1%～6% of gross weight, it is therefore preferable to, 4%；With 2) Span, its consumption for blend B gross weights 8%～ 15%, it is therefore preferable to, 11%；With 3) octadecyl dimethyl amine oxide, its consumption is the 1%～6% of blend B gross weights, Preferably, 4%；With 4) balance of polypropylene.
The polypropylene that major-minor top layer, sandwich layer, secondary auxiliary top layer are selected is HOPP or COPP, and the copolymerization gathers The melt flow rate (MFR) scope of propylene is 5.5～8.0g/10min, and the melt flow rate (MFR) scope of the HOPP is 2.8 ～4.5g/10min.
It is described to exempt from the polymer-modified blend C high pressure polymerisations preparation being made up of main monomer, comonomer, catalyst of corona Form, in blend C, main monomer, the mol ratio of comonomer are 11.5：1, consumption is that single puts into main monomer and copolymerization list The 0.0025wt% of body total amount；Main monomer, comonomer are formed by free radical mechanism copolymerization under high pressure, by main monomer, altogether Polycondensation monomer, catalyst add high-pressure reactor, under conditions of 100～250 DEG C of temperature, 108～180MPa of pressure carry out combined polymerization Reaction, obtains that described to exempt from corona polymer-modified.Wherein, 1) comonomer is acrylic monomerss and its derivant；2) catalyst is Active oxygen amount is high, the organic peroxide with suitable decomposition temperature and initiation half-life, and its concentration is preferably single input The 0.0025wt% of main monomer and comonomer total amount；With 3) balance of vinyl monomer.
Wherein, the main monomer is vinyl monomer.
The comonomer is acrylic monomerss or derivatives thereof, in acrylic acid, acrylic acid methyl ester., ethyl acrylate One kind；
The catalyst is active oxygen amount height, the organic peroxide with suitable decomposition temperature and initiation half-life, and which is dense Degree is preferably 0.0025wt% (putting into the 0.0025wt% of main monomer and comonomer total amount for single), be potassium peroxydisulfate with Al is combined or peroxide combination (t-butylperoxy pivarate, tert-butyl hydroperoxide -2-ethylhexanoate, tert-butyl group mistake Acetic oxide ester, di-tert-butyl peroxide, to Meng's alkane hydrogen peroxide combine)；Wherein, during potassium peroxydisulfate is combined with Al, over cure The mass fraction that sour potassium accounts for both gross masses with Al is respectively 99.95%, 0.05%；In peroxide combination, t-butyl peroxy Change pivalate, tert-butyl hydroperoxide -2-ethylhexanoate, tert-butyl hydroperoxide acetass, di-tert-butyl peroxide, to Meng Alkane hydrogen peroxide each component account for five kinds of combinations of substances gross masses mass fraction be respectively 6%, 3.5%, 1.5%, 0.8%, 1.7%.
In a specific embodiment, it is described exempt from corona it is polymer-modified be main monomer, comonomer, catalyst blending Thing C' high pressure polymerisations, blend C' include：1) comonomer is acrylic acid methyl ester., and which is exempting from the polymer-modified middle copolymerization of corona Monomer rate about 20% (that is, comonomer is exempting to account for 20% during corona is polymer-modified)；2) catalyst is potassium peroxydisulfate and Al groups Close, its consumption is the 0.0025wt% that single puts into main monomer and comonomer total amount；With 3) balance of vinyl monomer.
The smooth master batch is smooth auxiliary agent, polypropylene granules blend A', and blend A' includes：1) smooth auxiliary agent is Erucyl amide, its consumption for blend A' gross weights 12%；2) balance of polypropylene granules composition.
The antifogging master batch is glycerol ester type nonionic surfactant, Span, octadecyldimethyl Amine oxide and polypropylene blend B'.Blend B' contains 1) glycerol ester type nonionic surfactant, and its consumption is blending The 4% of thing B' gross weights；With 2) Span, its consumption for blend B' gross weights 11%；With 3) octadecyl Dimethyl amine, its consumption are blend B' gross weights 4%；With 4) balance of polypropylene.
The major-minor top layer institute materials are to exempt from that corona is polymer-modified, 5 μm of spherical inorganic tissue adhesion masterbatch, polypropylene granules Blend D, blend D include：1) exempt from that corona is polymer-modified, its consumption for blend D gross weights 20%；2) 5 μm of balls The inorganic tissue adhesion masterbatch of shape, its consumption for blend D gross weights 5%；3) balance of polypropylene granules composition.
Sandwich layer institute materials are smooth master batch, polypropylene granules blend E, and blend E includes：1) smooth master batch is Erucyl amide, its consumption for blend E gross weights 0.7%；2) balance of polypropylene granules composition.
Time auxiliary top layer institute materials are to exempt from that corona is polymer-modified, 3 μm of spherical inorganic tissue adhesion masterbatch, polypropylene granules Blend F, blend F include：1) exempt from that corona is polymer-modified, its consumption for blend F gross weights 5%；2) 3 μm it is spherical Inorganic tissue adhesion masterbatch, its consumption for blend F gross weights 3%；3) balance of polypropylene granules composition.
The manufacture method for exempting from corona Biaxially oriented polypropylene packing film, in the current whole world most wide cut (10.4m) most High mechanical speed (550m/min) Biaxially oriented polypropylene packaging film production line production, comprises the steps：
(1) premix and feed intake：By the weight percent score each component on major-minor top layer, sandwich layer, secondary auxiliary top layer described above Do not put into each self-corresponding low speed and puddle glassware, premix 30 minutes.By pre- mixed major-minor top layer, sandwich layer, secondary auxiliary top layer Negative pressure is drawn in three layers of extruder barrel；
(2) extrusion plasticizing：By each component in screw extruder, the melting extrusion under 230～245 DEG C of temperature conditionss；
(3) crystallisation by cooling：Extruder melt extrusion Jing clothes hangers die head is extruded, and air knife is air-cooled, sharp cooling roll is cooled to sheet, mould Lip gap 0.5mm, at 20～30 DEG C, entery and delivery port water temperature difference is controlled at ± 2 DEG C for the water temperature control of sharp cooling roll；Bosh water Temperature control system is at 25～35 DEG C；
(4) indulge and draw preheating：Preheating temperature is controlled at 115～130 DEG C；
(5) longitudinal stretching：Twin-stage is stretched, and the control of total stretching ratio is between 4.5～5.5；
(6) it is horizontal to draw preheating：Preheating temperature is controlled at 170～180 DEG C；
(7) cross directional stretch cooling and shaping：Between cross directional stretch multiplying power 10～11；
(8) traction, corona：Sided corona treatment, it is ensured that thin film wetting tension is more than or equal to 44 dynes；
(9) wind：Thin film is rolled into semi-finished product under suitable tension；
(10) aging time：Under 25 ± 5 DEG C of temperature, temperature 60%RH temperature environment, 1～2 day is stood；
(11) line speed：480～520m/min.
The invention allows for exempting from corona Biaxially oriented polypropylene (BOPP) packing film as above is preparing packaging Application in material, is widely used in the fields such as clothing, cosmetics, food, books, napkin.
One of key technical feature of the present invention is：Under conditions of sided corona treatment is not carried out, exempt from corona polymer-modified Thin film polarity, wettability can be improved.Compared with other packing films, can exempt from that corona is polymer-modified to be added in the film by adjusting Plus ratio reaches moderate and unattenuated coefficient of surface tension, film surface hydrophilic, antistatic behaviour, cementability, printable is improved Property.In one preferred embodiment of the invention, it is 20% in major-minor top layer adding proportion to exempt from corona polymer-modified, secondary auxiliary Top layer adding proportion is 5%, and the film surface coefficient of tension does not occur substantially decay within the half a year.Exempt from the material modified propylene of corona Sour methylmethacrylate monomer comonomer rate about 20%.It is a kind of and preferable material of the PP compatibilitys to exempt from corona polymer-modified, processes bar Part is sufficiently close to PP, exempts from the polymer-modified addition of corona by adjusting, and obtains moderate and unattenuated surface polarity two-way Oriented polypropylene (BOPP) packing film.
The key technical feature of the present invention two is：Using German Bruckner (Br ü ckner Technology Co., Ltd. the whole world for) manufacturing most wide cut (10.4m) highest mechanical speed (550m/min) Biaxially oriented polypropylene packing film production Line is produced, and extruder mixing is homogeneous, stretching is steady, temperature control equilibrium advantage, using 230～245 DEG C of mixing extrusion techniques, has Disperse and be difficult thermal cracking failure beneficial to polymer-modified fully the melting in PP of corona is exempted from.
The present invention in order to avoid corona modified polymeric films are used as a kind of additive in factory formula, in existing German Brooker Receive.
Corona Biaxially oriented polypropylene (BOPP) the packing film half a year inner surface coefficient of tension of exempting from of present invention manufacture is not sent out It is raw substantially to decay.Common Biaxially oriented polypropylene (BOPP) packing film is in production offline one month or so, coefficient of surface tension 38dyne is decayed to by firm offline 44dyne, or even below 36dyne can be decayed to.
The HOPP pellet that the present invention is used is the T38F that middle scape petrochemical industry is produced；COPP is oil of SPC F800E；Shanghai Ruo Yi new materials Science and Technology Ltd. produces：Spherical tissue adhesion masterbatch model MB3005PB, MB5005PB；It is anti- Mist masterbatch model MF2002PP；Smooth master batch model MS07PP.
Description of the drawings
Fig. 1 exempts from one of corona Biaxially oriented polypropylene (BOPP) packing film key technology for the present invention：Exempt from corona to be modified The infrared spectrogram of polymer；2931cm-1、2854cm-1、1467cm-1Peak be methylene infrared absorption peak；1739cm-1Peak For C=O bond infrared absorption peak, 1377cm-1Peak be methyl infrared absorption peak.1195cm-1、1164cm-1, 1018cm-1 Peak is the peak of carbon oxygen singly-bound, 720cm-1Peak be (CH2) n infrared absorption peaks (wherein n >=4).Exempt from corona polymer-modified for second The copolymer of alkene-acrylic acid methyl ester..
Fig. 2 be the embodiment of the present invention 2 prepare to exempt from corona Biaxially oriented polypropylene (BOPP) packing film two-way with common The antifog comparison test result of oriented polypropylene (BOPP) anti-fog thin film heat；The secondary auxiliary top layer of thin film prepared by the embodiment of the present invention 2 (anti-fog layer) is designated as " 1. ", common Biaxially oriented polypropylene (BOPP) anti-fog thin film anti-fog layer and is designated as " 3. "；The embodiment of the present invention 2 The hot anti-fog effect for exempting from corona Biaxially oriented polypropylene (BOPP) packing film anti-fog layer for preparing and common biaxial stretching polypropylene The hot anti-fog effect of alkene (BOPP) thin film anti-fog layer is almost consistent.According to GB/T 31726-2015《The anti-fog properties test of plastic sheeting Method》Judge, hot anti-fog effect is up to grade 1：The best rank of anti-fog effect.
Note：GB/T 31726-2015《The anti-fog properties test method of plastic sheeting》Regulation：Anti- fog effect is the poles such as 5 altogether, Grade 1 is optimum rank, class 5 worst (without anti-fog effect).It is ordered as to worst grade by optimum：Grade 1, grade 2, grade 3rd, class 4, class 5.
Fig. 3 be the embodiment of the present invention 2 prepare to exempt from corona Biaxially oriented polypropylene (BOPP) packing film two-way with common The cold antifog comparison test data of oriented polypropylene (BOPP) anti-fog thin film, effect (excellent to difference)：1. 2. ＞ is 3. for ＞；The present invention is implemented The secondary auxiliary top layer (anti-fog layer) of thin film prepared by example 2 is designated as " 1. ", major-minor top layer (non-anti-fog layer) and is designated as " 2. ", common two-way drawing The anti-fog layer of stretched polypropylene (BOPP) anti-fog thin film is designated as " 3. "；Prepared by the embodiment of the present invention 2 exempts from corona biaxial stretching polypropylene The cold anti-fog effect of the anti-fog layer of alkene (BOPP) packing film is optimum, and the cold anti-fog effect of non-anti-fog layer takes second place, and the former two is equal It is substantially better than the cold anti-fog effect of common Biaxially oriented polypropylene (BOPP) thin film anti-fog layer.According to GB/T 31726-2015《Modeling The anti-fog properties test method of material thin film》Judge：Corona Biaxially oriented polypropylene (BOPP) of exempting from prepared by the embodiment of the present invention 2 packs thin Up to grade 2, up to grade 3, common biaxial tension gathers the cold anti-fog effect of non-anti-fog layer the cold anti-fog effect of the anti-fog layer of film The cold anti-fog effect of propylene (BOPP) thin film anti-fog layer is class 5 (without anti-fog properties).Effect (excellent to difference)：1. 2. ＞ is 3. for ＞.
Fig. 4 be the embodiment of the present invention 5 prepare to exempt from corona Biaxially oriented polypropylene (BOPP) packing film two-way with common The aluminize aluminium coated of base film of oriented polypropylene (BOPP) covers and puts forth effort comparison test data；Prepared by the embodiment of the present invention 5 exempts from The aluminize aluminium coated of base film of corona Biaxially oriented polypropylene (BOPP) packing film covers and puts forth effort to be substantially better than common two-way drawing Stretched polypropylene (BOPP) base film aluminium coated of aluminizing covers and puts forth effort.
Specific embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail.The process of the enforcement present invention, Condition, experimental technique etc., in addition to the following content for specially referring to, are the universal knowledege and common knowledge of this area, this It is bright that content is not particularly limited.
Method：
(1)BB/T 0030-2004《Packaging metallized film》Require aluminium coated attachment force detection method be aluminizer with Pressure sensitive adhesive tape paste, peeled off on tensile testing machine, observe aluminium coated the area that comes off, it is desirable to aluminium coated come off area≤ 20%.In actual production process, there are the feelings for varying with each individual in the aluminium coated size that comes off for passing judgment on same membrane sample of aluminizing Condition, is difficult Quantitative evaluation.Transnational enterprise of Amcor companies mark is used for reference herein, is sealed with aluminizer using EAA thin film, according to QB/T 2358《Plastic film packaging bag heat sealing strength test method》(ZBY 28004《Plastic sheeting heat seal strength algoscopy》) method, Parallel testing contrasts aluminium coated adhesive force.
Sample prepares：The upper envelope knife temperature of adjustment heat-sealing instrument is to 110 DEG C.Cut aluminizer, EAA films, PET film respectively to cut The wide battens of 15mm 5.Take each sample 1 neatly to be sealed by aluminium coated film face of aluminizing //EAA films //PET film is folded successively.Take 5 The arithmetic mean of instantaneous value of sample is the aluminium lamination adhesive force by sample product.
(2) according to GB/T 31726-2015《The anti-fog properties test method of plastic sheeting》Contrast cold antifog with hot anti-fog effect.
Embodiment 1：
The present invention exempts from corona Biaxially oriented polypropylene (BOPP) printing packaging thin film, and percentage by weight is selected on its major-minor top layer Respectively HOPP 80.0%, tissue adhesion masterbatch 5%MB5005PB, exempt from corona polymer-modified 15.0% component prepare Form, and the melting means scope of HOPP is 3.0～4.5g/10min.Sandwich layer is respectively homopolymerization poly- third from percentage by weight Alkene 100.0%, and the melting means scope of HOPP is 3.0～4.5g/10min.Distinguished from percentage by weight on secondary auxiliary top layer It is formulated for HOPP 92.0%, tissue adhesion masterbatch 3.0%MB3005PB components, and the melting means scope of HOPP For 3.0～4.5g/10min.The THICKNESS CONTROL on major-minor top layer is 0.8 μm, the THICKNESS CONTROL of sandwich layer is 21.4 μm, secondary auxiliary top layer THICKNESS CONTROL is 0.8 μm.It is main monomer, comonomer, catalyst, plumper blend high pressure polymerisation to exempt from corona polymer-modified, The blend includes：1) it is main monomer, comonomer, catalyst blend high pressure polymerisation, the blend includes：1) comonomer is Acrylic acid methyl ester., its comonomer rate about 20% in the copolymer；2) catalyst is combined with Al for potassium peroxydisulfate, its consumption 0.0025wt%；3) balance of vinyl monomer.
Specific manufacture method is as follows：
(1) premix and feed intake：The each component on major-minor top layer, sandwich layer, secondary auxiliary top layer is pressed into percentage by weight described above Each self-corresponding low speed is put into respectively and puddles glassware, premix 30 minutes.By pre- mixed major-minor top layer, sandwich layer, secondary auxiliary table Layer negative pressure is drawn in three layers of extruder barrel；
(2) extrusion plasticizing：By each component in screw extruder, the melting extrusion under 230～245 DEG C of temperature conditionss；
(3) crystallisation by cooling：Extruder melt extrusion Jing clothes hangers die head is extruded, and air knife is air-cooled, sharp cooling roll is cooled to sheet, mould Lip gap 0.5mm, at 20～30 DEG C, entery and delivery port water temperature difference is controlled at ± 2 DEG C for the water temperature control of sharp cooling roll；Bosh water Temperature control system is at 25～35 DEG C；
(4) indulge and draw preheating：Preheating temperature is controlled at 115～130 DEG C；
(5) longitudinal stretching：Twin-stage is stretched, and the control of total stretching ratio is between 4.5～5.5；
(6) it is horizontal to draw preheating：Preheating temperature is controlled at 170～180 DEG C；
(7) cross directional stretch cooling and shaping：Between cross directional stretch multiplying power 10～11；
(8) traction, corona：Sided corona treatment, it is ensured that thin film wetting tension is more than or equal to 44 dynes；
(9) wind：Thin film is rolled into semi-finished product under suitable tension；
(10) aging time：Under 25 ± 5 DEG C of temperature, temperature 60%RH temperature environment, 1～2 day is stood；
(11) line speed：480～520m/min.
Embodiment 2：
The present invention exempts from the antifog heat sealed package thin film of corona Biaxially oriented polypropylene (BOPP), and weight hundred is selected on its major-minor top layer Divide than respectively COPP 80.0%, tissue adhesion masterbatch 5%MB5005PB, exempt from polymer-modified by 15.0% component of corona It is formulated, and the melting means scope of COPP is 5.5～8.0g/10min.Sandwich layer is respectively homopolymerization from percentage by weight Polypropylene 97.0%, smooth master batch 0.5%MS07PP, antifogging master batch 2.5%MF2002PP are formulated, and HOPP Melting means scope is 3.0～4.5g/10min.Secondary auxiliary top layer (anti-fog layer) from percentage by weight be respectively co-polypropylene 86.0%, Tissue adhesion masterbatch 3.0%MB3005PB, antifogging master batch 1.0%MF2002PP, the component for exempting from corona polymer-modified 15.0% are matched somebody with somebody System is formed, and the melting means scope of COPP is 5.5～8.0g/10min.The THICKNESS CONTROL on major-minor top layer is 0.8 μm, sandwich layer THICKNESS CONTROL be 22.4 μm, the THICKNESS CONTROL on secondary auxiliary top layer be 0.8 μm.It is main monomer, copolymerization list to exempt from corona polymer-modified Body, catalyst, plumper blend high pressure polymerisation, the blend include：1) it is main monomer, comonomer, catalyst blend high pressure Polymerization, the blend include：1) comonomer is acrylic acid methyl ester., its comonomer rate about 20% in the copolymer；2) catalyst Combine with Al for potassium peroxydisulfate, its consumption is 0.0025wt%；3) balance of vinyl monomer.
Specific preparation method is with embodiment 1.
Embodiment 3：
The present invention exempts from the super cool sliding packing film of corona Biaxially oriented polypropylene (BOPP), and weight percent is selected on its major-minor top layer Match somebody with somebody than being respectively HOPP 86.0%, tissue adhesion masterbatch 4%MB5005PB, exempting from polymer-modified by 20.0% component of corona System is formed, and the melting means scope of HOPP is 3.0～4.5g/10min.Sandwich layer is respectively homopolymerization from percentage by weight and gathers Propylene 98.0%, smooth master batch 2%MS07PP are formulated, and the melting means scope of HOPP is 3.0～4.5g/10min. Secondary auxiliary top layer is respectively HOPP 92.0%, tissue adhesion masterbatch 3.0%MB5005PB, is exempted from corona and change from percentage by weight Property polymer 5.0% component be formulated, and the melting means scope of HOPP be 3.0～4.5g/10min.Major-minor top layer THICKNESS CONTROL be 0.8 μm, the THICKNESS CONTROL of sandwich layer be 16.4 μm, the THICKNESS CONTROL on secondary auxiliary top layer be 0.8 μm.Exempt from corona to be modified Polymer is main monomer, comonomer, catalyst, plumper blend high pressure polymerisation, and the blend includes：1) it is main monomer, is total to Polycondensation monomer, catalyst blend high pressure polymerisation, the blend include：1) comonomer is acrylic acid methyl ester., and which is in the copolymer altogether Polycondensation monomer rate about 20%；2) catalyst is combined with Al for potassium peroxydisulfate, and its consumption is 0.0025wt%；3) balance of vinyl monomer.
Specific preparation method is with embodiment 1.
Embodiment 4：
The present invention exempts from corona Biaxially oriented polypropylene (BOPP) one side heat sealed package thin film, and weight hundred is selected on its major-minor top layer Divide than COPP 77.5%, tissue adhesion masterbatch 2.5%MB5005PB respectively, exempt from polymer-modified by 20.0% component of corona It is formulated, and the melting means scope of COPP is 5.5～8.0g/10min.Sandwich layer is respectively homopolymerization from percentage by weight Polypropylene 100.0%, and the melting means scope of HOPP is 3.0～4.5g/10min.Percentage by weight is selected on secondary auxiliary top layer Respectively HOPP 97.0%, the component of tissue adhesion masterbatch 3.0%MB3005PB are formulated, and HOPP is molten How is 3.0～4.5g/10min.The THICKNESS CONTROL on major-minor top layer is 0.8 μm, the THICKNESS CONTROL of sandwich layer is 23.4 μm, secondary auxiliary The THICKNESS CONTROL on top layer is 0.8 μm.It is main monomer, comonomer, catalyst, plumper blend high pressure to exempt from corona polymer-modified Polymerization, the blend include：1) it is main monomer, comonomer, catalyst blend high pressure polymerisation, the blend includes：1) copolymerization Monomer is acrylic acid methyl ester., its comonomer rate about 20% in the copolymer；2) catalyst is combined with Al for potassium peroxydisulfate, its consumption For 0.0025wt%；3) balance of vinyl monomer.
Specific preparation method is with embodiment 1.
Embodiment 5：
The present invention exempts from corona Biaxially oriented polypropylene (BOPP) and aluminizes base film, and percentage by weight is selected on its major-minor top layer COPP 85.0%, the component for exempting from corona polymer-modified 25.0% are formulated respectively, and the melting means of COPP Scope is 5.5～8.0g/10min.Sandwich layer is respectively HOPP 100.0%, and HOPP from percentage by weight Melting means scope be 3.0～4.5g/10min.Secondary auxiliary top layer is respectively HOPP 95.0%, anti-stick from percentage by weight Even the component of masterbatch 5%MB5005PB is formulated, and the melting means scope of HOPP is 3.0～4.5g/10min.It is major-minor The THICKNESS CONTROL on top layer is 0.8 μm, the THICKNESS CONTROL of sandwich layer is 23.4 μm, the THICKNESS CONTROL on secondary auxiliary top layer is 0.8 μm.Exempt from corona Polymer-modified is main monomer, comonomer, catalyst blend high pressure polymerisation, and the blend includes：1) comonomer is propylene Sour methyl ester, its comonomer rate about 20% in the copolymer；2) catalyst is combined with Al for potassium peroxydisulfate, and its consumption is 0.0025wt%；3) balance of vinyl monomer.
Specific preparation method is with embodiment 1.
Measurement result：
Prepared by the embodiment of the present invention 1～5 exempts from the enforcement of corona Biaxially oriented polypropylene (BOPP) packing film and common double To oriented polypropylene (BOPP) packing film, the same day, one month, two months, six months coefficient of surface tension correction data such as tables 1 It is shown.
1 coefficient of surface tension of table
Note 1：Sample holding region domain is without neighbouring thermal source, depletion of YANG light direct beam, without the warehouse for directly drenching with rain.(half a year span) is deposited Put ambient temperature：10～35 DEG C；Humidity：50～75%.
Note 2：Major-minor top layer is designated as " A ", sandwich layer and is designated as " B ", secondary auxiliary top layer being designated as " C ".
Note 3：Coefficient of surface tension unit：dyne/cm
As can be seen from Table 1：Corona Biaxially oriented polypropylene (BOPP) of exempting from prepared by the embodiment of the present invention 1～5 packs thin Coefficient of surface tension of the film within half a year declines without substantially decay, common Biaxially oriented polypropylene (BOPP) the film surface coefficient of tension Subtract substantially.
The embodiment of the present invention 5 exempt from after corona Biaxially oriented polypropylene (BOPP) packing film is aluminized with common biaxial tension Polypropylene (BOPP) is aluminized after base film aluminizes, the same day, timeliness, a month coefficient of surface tension correction data, such as 2 institute of table Show.
2 coefficient of surface tension of table
Note 5：Sample holding region domain is without neighbouring thermal source, depletion of YANG light direct beam, without the warehouse for directly drenching with rain.(a month span) Storage environment temperature：25～35 DEG C；Humidity：50～75%.
Note 6：Major-minor top layer (aluminium coated) is designated as " A ".
Note 7：Coefficient of surface tension unit：dyne/cm
As can be seen from Table 2：It is thin that prepared by the embodiment of the present invention 5 exempts from corona Biaxially oriented polypropylene (BOPP) plating aluminium base Film at one month coefficient of surface tension without substantially decay, common Biaxially oriented polypropylene (BOPP) is aluminized base film surface Force coefficient decay is obvious.
The protection content of the present invention is not limited to above example.Under the spirit and scope without departing substantially from inventive concept, this Art personnel it is conceivable that change and advantage be all included in the present invention, and with appending claims as protect Shield scope.

Claims (10)

1. one kind exempts from corona Biaxially oriented polypropylene packing film, including major-minor top layer, sandwich layer, secondary auxiliary top layer, it is characterised in that： The major-minor top layer is respectively polypropylene 43.0～94.0%, tissue adhesion masterbatch 1.0～7.0%, is exempted from electricity from percentage by weight Dizzy polymer-modified 5.0～50.0% component is prepared from；Sandwich layer from percentage by weight be respectively polypropylene 94.0～ 100.0%th, smooth master batch 0～2.0%, 0～4.0% component of antifogging master batch are prepared from；Percentage by weight is selected on secondary auxiliary top layer Respectively polypropylene 75.0～99.0%, tissue adhesion masterbatch 1.0～5.0%, exempt from the component of corona polymer-modified 0～20.0% It is prepared from；It is 0.8%～10% that the thickness on the major-minor top layer accounts for overall film thickness ratio, and the thickness of sandwich layer accounts for total film thickness Degree ratio is 80～98.4%, and the thickness on secondary auxiliary top layer accounts for overall film thickness ratio for 0.8%～10%.
It is 2. according to claim 1 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：Major-minor top layer, core The polypropylene that layer, secondary auxiliary top layer are selected is HOPP or COPP；The melt flow rate (MFR) of the COPP Scope is 5.5～8.0g/10min, and the melt flow rate (MFR) scope of the HOPP is 2.8～4.5g/10min.
It is 3. according to claim 1 and 2 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：It is described to exempt from electricity It is dizzy it is polymer-modified be that main monomer, comonomer, the blend C high pressure polymerisations of catalyst composition are prepared from, in blend C, Main monomer, the mol ratio of comonomer are 11.5：1, catalyst consumption is that single puts into main monomer and comonomer total amount 0.0025wt%, it is described to exempt from the polymer-modified main monomer of corona for vinyl monomer；The comonomer be acrylic monomerss or Its derivant, selected from acrylic acid, acrylic acid methyl ester. or ethyl acrylate；It is described to exempt from the polymer-modified catalyst of corona for organic mistake Oxide, is combined with Al selected from potassium peroxydisulfate or peroxide combination.
It is 4. according to claim 1 and 2 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：It is described anti-stick Even masterbatch is by 5%～15%SiO2Antiblock additive for main body polypropylene blending modified with 85%～95% is prepared from；Institute Smooth master batch is stated for erucyl amide class smooth master batch.
It is 5. according to claim 1 and 2 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：It is described antifog Masterbatch is common for glycerol ester type nonionic surfactant, Span, octadecyl dimethyl amine oxide and polypropylene Mixed thing B.
It is 6. according to claim 1 and 2 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：It is described major-minor Top layer institute materials are to exempt from that corona is polymer-modified, 5 μm of spherical inorganic tissue adhesion masterbatch, polypropylene granules blend D, the blend D includes：1) exempt from that corona is polymer-modified, its consumption for blend D gross weights 20%；2) 5 μm of spherical inorganic tissue adhesion masterbatch, Its consumption for blend D gross weights 5%；3) balance of polypropylene granules composition.
It is 7. according to claim 1 and 2 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：The sandwich layer Institute's materials are smooth master batch, polypropylene granules blend E, and blend E includes：1) smooth auxiliary agent be erucyl amide, its consumption For the 0.7%～20% of blend E gross weights；2) balance of polypropylene granules composition.
It is 8. according to claim 1 and 2 to exempt from corona Biaxially oriented polypropylene packing film, it is characterised in that：Described time auxiliary Top layer institute materials are to exempt from that corona is polymer-modified, 3 μm of spherical inorganic tissue adhesion masterbatch, polypropylene granules blend F, the blend F includes：1) exempt from that corona is polymer-modified, its consumption for blend F gross weights 5%；2) 3 μm of spherical inorganic tissue adhesion masterbatch, Its consumption for blend F gross weights 3%；3) balance of polypropylene granules composition.
9. a kind of manufacture method for exempting from corona Biaxially oriented polypropylene packing film as claimed in claim 1, it is characterised in that：Bag Include following steps：
(1) premix and feed intake：By major-minor top layer, sandwich layer, secondary auxiliary top layer percentage by weight of each component as described in claim 1 Each self-corresponding low speed is put into respectively and puddles glassware, premix 30 minutes；By pre- mixed major-minor top layer, sandwich layer, secondary auxiliary table Layer negative pressure is drawn in three layers of extruder barrel；
(2) extrusion plasticizing：By each component in screw extruder, the melting extrusion under 230～245 DEG C of temperature conditionss；
(3) crystallisation by cooling：Extruder melt extrusion Jing clothes hangers die head is extruded, and air knife is air-cooled, sharp cooling roll is cooled to sheet, die lip seam Gap 0.5mm, at 20～30 DEG C, entery and delivery port water temperature difference is controlled at ± 2 DEG C for the water temperature control of sharp cooling roll；Bosh water temperature control System is at 25～35 DEG C；
(4) indulge and draw preheating：Preheating temperature is controlled at 115～130 DEG C；
(5) longitudinal stretching：Twin-stage is stretched, and the control of total stretching ratio is between 4.5～5.5；
(6) it is horizontal to draw preheating：Preheating temperature is controlled at 170～180 DEG C；
(7) cross directional stretch cooling and shaping：Between cross directional stretch multiplying power 10～11；
(8) traction, corona：Sided corona treatment, it is ensured that thin film wetting tension is more than or equal to 44 dynes；
(9) wind：Thin film is rolled into semi-finished product under suitable tension；
(10) aging time：Under 25 ± 5 DEG C of temperature, temperature 60%RH temperature environment, 1～2 day is stood；
(11) line speed：480～520m/min.
10. application of the corona Biaxially oriented polypropylene packing film in packaging material are prepared is exempted from as claimed in claim 1.
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