CN105538855B - High-performance polypropylene film and preparation method thereof - Google Patents

High-performance polypropylene film and preparation method thereof Download PDF

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Publication number
CN105538855B
CN105538855B CN201510888580.7A CN201510888580A CN105538855B CN 105538855 B CN105538855 B CN 105538855B CN 201510888580 A CN201510888580 A CN 201510888580A CN 105538855 B CN105538855 B CN 105538855B
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film
polypropylene
performance
titanium dioxide
silicon composition
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CN105538855A (en
Inventor
许文才
李东立
尤圣隆
刘枝
付亚波
石佳子
廖瑞娟
王雅珺
何晓辉
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Anhui Jintian High Tech Ltd By Share Ltd
Beijing Institute of Graphic Communication
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Anhui Jintian High Tech Ltd By Share Ltd
Beijing Institute of Graphic Communication
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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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • 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
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention provides a kind of high-performance polypropylene film and preparation method thereof.The film includes：Topmost thin film, core layer film and lower film；Topmost thin film includes 2.0~3.0% nanometer titanium dioxide silicon composition and 97.0~98.0% the first polypropylene；Core layer film includes 0.5~2.0% nanometer titanium dioxide silicon composition and 99.5~98.0% the second polypropylene；Lower film includes 3.5~5.0% nanometer titanium dioxide silicon composition and 96.5~95% tripropylene；Wherein, nanometer titanium dioxide silicon composition includes 50~55% nanometer silicon dioxide particle and 45~50% modifier.Nanometer titanium dioxide silicon composition containing certain content in each layer of the film, so that the modulus and elongation at break of film are high, low to the diffusion coefficient and solubility parameter of small solvent molecule, the coefficient of kinetic friction is low, its combination property having had, it is suitable for flexible packing material.

Description

High-performance polypropylene film and preparation method thereof
Technical field
The present invention relates to polypropylene film technical field, in particular to a kind of high-performance polypropylene film and its system Preparation Method.
Background technology
Polypropylene film is one of most important packing film, it usually needs it possesses good printing performance and heat sealability Energy.It is the more other kinds of film of solvent residual amount after print the shortcomings that one maximum of polypropylene film however, as printing element (such as polyethylene terephthalate (PET) film) is high.Therefore, color printing factory can only be by reducing linear velocity, improving drying tunnel temperature The methods of degree, increase curing time, reduces the dissolvent residual of polypropylene film.Also have been reported that in addition using a kind of special print Brush ink, by the ink skinning of evacuation solvent molecule can be made to volatilize to greatest extent to reduce the solvent after polypropylene film print Residual.With the food-safe problem pay attention to day by day in countries in the world, the limitation to residual solvent in compound flexible packaging film is more next Stricter, this just makes general polypropylene film face the possibility being eliminated.Therefore, improving the security performance of polypropylene film is The task of top priority.
About in the study on the modification to polyolefin film, the more improvement for paying attention to mechanical property and machine-shaping are stable The raising of property, and have ignored polyacrylic foodsafety.For this reason, it is necessary to propose a kind of new polypropylene film design side Case, to realize that the optimization of various performances is unified.
The content of the invention
It is a primary object of the present invention to provide a kind of high-performance polypropylene film and preparation method thereof, to solve existing skill The problem of polypropylene film in art is difficult to meet multiple performance requirement simultaneously.
To achieve these goals, according to an aspect of the invention, there is provided a kind of high-performance polypropylene film, it is wrapped Include：Topmost thin film, based on the percentage by weight of topmost thin film, the nano silicon that topmost thin film includes 2.0~3.0% combines Thing and 97.0~98.0% the first polypropylene；Core layer film, on a side surface of topmost thin film, by the weight of core layer film Percentages are measured, core layer film includes 0.5~2.0% nanometer titanium dioxide silicon composition and the second of 99.5~98.0% poly- third Alkene；Lower film, on a side surface of the remote topmost thin film of core layer film, based on the percentage by weight of lower film, Lower film includes 3.5~5.0% nanometer titanium dioxide silicon composition and 96.5~95% tripropylene；Wherein, by receiving The percentage by weight meter of rice silicon dioxide compositions, nanometer titanium dioxide silicon composition include 50~55% nano silicon Grain and 45~50% modifier.
Further, based on the percentage by weight of topmost thin film, topmost thin film includes 2.3~2.8% nanometer titanium dioxide Silicon composition and 97.2~97.7% the first polypropylene；Based on the percentage by weight of core layer film, core layer film include 0.7~ 1.5% nanometer titanium dioxide silicon composition and 98.5~99.3% the second polypropylene；Based on the percentage by weight of lower film, Lower film includes 3.7~4.5% nanometer titanium dioxide silicon composition and 95.5~96.3% tripropylene.
Further, based on the percentage by weight of topmost thin film, the nano silicon that topmost thin film includes 2.6% combines Thing and 97.4% the first polypropylene；Based on the percentage by weight of core layer film, core layer film includes 1.0% nanometer titanium dioxide Silicon composition and 99.0% the second polypropylene；Based on the percentage by weight of lower film, lower film includes 4.0% nanometer Silicon dioxide compositions and 96.0% tripropylene.
Further, the crystallinity of high-performance polypropylene film is 30~39%；Preferably, high-performance polypropylene film Glass transition temperature is 22.2~24.7 DEG C；Preferably, the crystal grain of high-performance polypropylene film is grenade-shaped crystal grain, hand pomegranate Playing shape crystal grain includes Pellet Warhead and column bullet handle；Preferably, in grenade-shaped crystal grain, the particle diameter of Pellet Warhead for 0.08~ 0.1 μm, the radial width of column bullet handle is 0.04~0.08 μm, and the axial length of column bullet handle is 0.8~1.6 μm.
Further, the gross thickness of high-performance polypropylene film is 18~20 μm, and the wherein thickness of topmost thin film is 3~5 μ M, the thickness of lower film is 3~5 μm.
Further, the first polypropylene, the second polypropylene and tripropylene separately selected from polypropylene F280, One or more in X37F, 2605, FC801M, F800EDF and F-603.
Further, the particle diameter of nanometer silicon dioxide particle is 5~20nm；Preferably, modifier is selected from ethene-vinegar One or more in vinyl acetate copolymer, polyvinyl alcohol, acrylic acid series copolymer, PEO and poly- PLA.
According to another aspect of the present invention, there is provided a kind of preparation method of high-performance polypropylene film, it includes following Step：Nanometer titanium dioxide silicon composition is subjected to melt blending with the first polypropylene, the second polypropylene and tripropylene respectively, Respectively obtain the first modified polypropene, the second modified polypropene and the 3rd modified polypropene；First modified polypropene, second are changed Property polypropylene and the 3rd modified polypropene carry out three-layer co-extruded biaxial tension film forming, form high-performance polypropylene film.
Further, during three-layer co-extruded biaxial tension film forming, longitudinal stretching ratio is 4~5, and cross directional stretch ratio is 9~10.
Further, during three-layer co-extruded biaxial tension film forming, the temperature of extrusion screw rod is 220~250 DEG C, spiral shell Bar rotating speed is 40~50rpm, and pressure is 40~50bar, and die temperature is 230~235 DEG C.
In above-mentioned high-performance polypropylene film provided by the invention, there is three-decker, including topmost thin film (printing layer or With the composite bed of other films), core layer film and lower film (food contact layer).And equal receiving containing certain content in each layer Rice silicon dioxide compositions, the nanometer titanium dioxide silicon composition include the nanometer silicon dioxide particle and resin modified of certain content Agent so that each layer film has specific performance, specific as follows：Core layer film has compared with conventional polypropylene resin film Higher modulus and elongation at break.As the skeleton of three-decker polypropylene film, the sandwich layer of high-modulus can improve film Deflection, realizes the minimizing of packaging, and higher elongation at break improves the puncture resistant ability of film.Topmost thin film is small to solvent Molecule has relatively low diffusion coefficient and low solubility parameter.Thus effectively reduce the solvent in printing-ink or adhesive Residual quantity in polypropylene film, improve the security of polypropylene film.Lower film then has relatively low dynamic friction system Number, can adapt to the demand packed automatically, can avoid the pollution added slipping agent in this layer and brought to food.In a word, The film has preferable combination property, is suitable for food flexible packing material use.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing a further understanding of the present invention, and of the invention shows Meaning property embodiment and its illustrate be used for explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the SEM photograph of the polypropylene film prepared in embodiments of the invention 1.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase Mutually combination.The present invention is described in detail below in conjunction with embodiment.
As described by background section, existing flexible package is difficult to meet that multiple performance will with polypropylene film Ask.In order to solve this problem, inventor provides a kind of high-performance polypropylene film, and it is three-decker, including Topmost thin film, core layer film and lower film；Based on the percentage by weight of topmost thin film, topmost thin film includes 2.0~3.0% Nanometer titanium dioxide silicon composition and 97.0~98.0% the first polypropylene；Core layer film is located at a side surface of topmost thin film On, and based on the percentage by weight of core layer film, it include 0.5~2.0% nanometer titanium dioxide silicon composition and 98.0~ 99.5% the second polypropylene；Lower film is located on a side surface of the remote topmost thin film of core layer film, and thin by lower floor The percentage by weight meter of film, it includes 3.5~5.0% nanometer titanium dioxide silicon composition and 95.0~96.5% trimerization third Alkene；Wherein, based on the percentage by weight of nanometer titanium dioxide silicon composition, nanometer titanium dioxide silicon composition includes 50~55% and received Rice silica dioxide granule and 45~50% modifier.
In above-mentioned high-performance polypropylene film provided by the invention, there is three-decker, including topmost thin film (printing layer or With the composite bed of other films), core layer film and lower film (food contact layer).And equal receiving containing certain content in each layer Rice silicon dioxide compositions, the nanometer titanium dioxide silicon composition include the nanometer silicon dioxide particle and resin modified of certain content Agent so that each layer film has specific performance, specific as follows：
Core layer film has higher modulus and elongation at break compared with conventional polypropylene resin film.As three layers The skeleton of structure polypropylene film, the sandwich layer of high-modulus can improve stiffness of thin film, realize the minimizing of packaging, higher fracture Elongation improves the puncture resistant ability of film.
Topmost thin film has relatively low diffusion coefficient and low solubility parameter to small solvent molecule.In the application process of reality In, when polypropylene film and other Film laminateds prepare flexible package, its upper strata needs to apply adhesive, then with aluminium foil, PET, Nylon etc. is compound, and the compatibility of organic solvent ethyl acetate, acetone, isopropanol in polypropylene and common adhesive etc. compared with Height, diffusion coefficient of these solvents in polypropylene film is big, and diffusion rate is fast, and saturation solubility is also big, common drying work Skill can not remove solvent remaining in film completely, and remaining organic solvent quantity in the film is more, and food-safe property is made Into threat.And the topmost thin film in the present invention has relatively low diffusion coefficient and low solubility parameter to these small solvent molecules, When material films other with aluminium foil etc. carry out compound or printed, the topmost thin film can largely obstruct organic solvent Molecule (solvent in adhesive or ink) thus effectively reduces printing-ink or viscous to the diffusion inside polypropylene film Residual quantity of the solvent in polypropylene film in mixture, improve the security of polypropylene film.
Lower film then has the relatively low coefficient of kinetic friction.When preparing food packaging laminated film, polypropylene film It is often used as inner membrance and directly contacts food, therefore its lower film needs to contact with food.In auto-filling or when packing automatically The layer can be with metal parts phase mutual friction, and this just needs lower film to have relatively low coefficient of friction.However, general polypropylene is thin The coefficient of kinetic friction of film is 0.4~0.6, in order to further reduce the coefficient of kinetic friction, it usually needs added into acrylic resin Erucyl amide class slipping agent, but erucyl amide small molecule can pollute in the precipitation of food contact layer to food, therefore it is this The technique of general reduction coefficient of friction is not optimal method.It is different, above-mentioned high-performance provided by the invention In polypropylene film, the nanometer titanium dioxide silicon composition of certain content is added in acrylic resin, is made it have relatively low The coefficient of kinetic friction.When being packed automatically using the polypropylene film, lower film as food contact layer, because its have compared with The low coefficient of kinetic friction, the demand packed automatically is can adapt to, can avoid adding slipping agent in this layer and bringing to food Pollution.
In a word, the nanometer titanium dioxide silicon composition containing certain content in each layer of the film so that the modulus of film and disconnected Split that elongation is high, low to the diffusion coefficient and solubility parameter of small solvent molecule, the coefficient of kinetic friction is low, it has had comprehensive Can, it is suitable for food flexible packing material.
In above-mentioned high-performance polypropylene film, as long as the material of each layer is configured according to aforementioned proportion scope, it becomes possible to Make each layer that there are specific excellent properties, while whole polypropylene film has preferable combination property.A kind of preferable real Apply in mode, based on the percentage by weight of topmost thin film, topmost thin film includes 2.3~2.8% nanometer titanium dioxide silicon composition And 97.2~97.7% the first polypropylene；Based on the percentage by weight of core layer film, core layer film includes 0.7~1.5% Nanometer titanium dioxide silicon composition and 98.5~99.3% the second polypropylene；Based on the percentage by weight of lower film, lower floor is thin Film includes 3.7~4.5% nanometer titanium dioxide silicon composition and 95.5~96.3% tripropylene.By nanometer two in each layer The content control of silica compositions within the above range, can further improve the combination property of polypropylene film.
It is highly preferred that based on the percentage by weight of topmost thin film, the nano silicon that topmost thin film includes 2.6% combines Thing and 97.4% the first polypropylene；Based on the percentage by weight of core layer film, core layer film includes 1.0% nanometer titanium dioxide Silicon composition and 99.0% the second polypropylene；Based on the percentage by weight of lower film, lower film includes 4.0% nanometer Silicon dioxide compositions and 96.0% tripropylene.
Add 1% nanometer titanium dioxide silicon composition so that the tensile strength of core layer film can reach 37.6MPa, bullet Property modulus, which can reach 688Mpa, elongation at break, can reach 349%, respectively than being not added with nanometer titanium dioxide silicon composition The tensile strength of polypropylene film, modulus of elasticity, elongation at break improve 119%, 42% and 12%.
The nanometer titanium dioxide silicon composition of addition 2.6% in acrylic resin, obtained topmost thin film is to acetone solvent Small molecule has relatively low diffusion coefficient being capable of as little as D=0.97 × 10-13m2/s-2, solubility being capable of as little as S=0.035% (relative mass concentration), itself D and S value reduce by 63% He respectively than being not added with the polypropylene film of nanometer titanium dioxide silicon composition 20%.Organic solvent D in the film and S are greatly reduced simultaneously so that diffusion rate P (P of the solvent molecule to film depths =D × S) significantly reduced, the moment that the topmost thin film is contacted in adhesive (after gluing enters drying tunnel to film In time interval before, less than 1 second), almost no organic solvent can be infiltrated through in the topmost thin film of densification, so that whole Dissolvent residual numerical value in individual polypropylene film is further greatly lowered, and the security of film is further protected Barrier.In addition, the topmost thin film can't reduce the combined strength bination between film and other material films to the barrier of organic solvent, On the contrary because the addition of nanometer titanium dioxide silicon composition, improves the polarity of topmost thin film, add its parent between adhesive And property so that bonding strength is improved.
The nanometer titanium dioxide silicon composition of addition 4.0%, the dynamic friction system of obtained lower film in acrylic resin Number is more effectively reduced, and the nanometer titanium dioxide silicon composition will not be to surface migration.With being not added with nano silicon The polypropylene film of composition is compared, and is not changed (μ in the confficient of static friction of lower film0About 0.45) in the case of, its The coefficient of kinetic friction can be reduced to μd=0.24, than the coefficient of kinetic friction for being not added with nanometer titanium dioxide silicon composition polypropylene film Reduce by 44%.In addition, the lower film being capable of as little as D=1.1 × 10 to the diffusion coefficient of acetone-13m2/s-2, solubility can As little as S=0.035%, 58% and 20% are reduced respectively than being not added with D, S of polypropylene film of nanometer titanium dioxide silicon composition. This fine and close lower film reduces to the adsorptivity of food flavor, more conducively keeps the flavor of packaged food.
In addition, the upper strata of high-performance polypropylene film, sandwich layer and lower floor, in addition to excellent performance with more than, mechanics Performance is also very excellent.Tensile strength is between 24.5~37.6MPa, and modulus of elasticity between 486~688MPa, stretch by fracture Long rate is between 313~349%, and the diffusion coefficient of acetone in the film is 0.97 × 10-13m2/s-2~1.78 × 10-13m2/s-2 Between, the solubility of acetone in the film between 0.035~0.041 (mass concentration), temperature of initial decomposition 185.4~ Between 269 DEG C, 50% decomposition temperature is between 448.8~450.4 DEG C, and 0.45 or so, the coefficient of kinetic friction exists confficient of static friction Between 0.24~0.36.These performances are much better than conventional polypropylene film.
In a preferred embodiment, the crystallinity of high-performance polypropylene film is 30~39%.Preferably, Gao Xing The glass transition temperature of energy polypropylene film is 22.2~24.7 DEG C.Under the crystallinity and glass transition temperature, Neng Goujin One step improves the combination property of above-mentioned polypropylene film.
Preferably, the crystal grain of above-mentioned high-performance polypropylene film is grenade-shaped crystal grain, and grenade-shaped crystal grain includes spherical Bullet and column bullet handle；It is highly preferred that in grenade-shaped crystal grain, the particle diameter of Pellet Warhead is 0.08~0.1 μm, column bullet handle Radial width is 0.04~0.08 μm, and the axial length of column bullet handle is 0.8~1.6 μm.
In the polypropylene film for not adding nanometer titanium dioxide silicon composition, crystalling propylene size (crystal particle volume) is 10 ~30 microns, for this film that area is 1 square metre, thickness is 11 microns, about 10 grams or so of quality, if crystallinity is 35%, then have 8.93 × 10 in this film of 1 square meter8(polypropylene structure cell density is the crystal grain that individual particle diameter is 20 microns 0.936g/ml).And in the above-mentioned high-performance polypropylene film provided in the present invention, receiving for special ratios is with the addition of in layers Rice silicon dioxide compositions so that crystallite dimension reduces a lot, crystal grain quantity 6~7 orders of magnitude of increase, such as is adding The core layer film obtained after 1.0% a diameter of 20nm nanometer titanium dioxide silicon composition, often have 5.4 × 10 in square meter film15 Individual crystal grain, and the unconventional spherocrystal of grain shape, but be in " grenade " shape, warhead section is spherical in shape, 0.1 micron of left side of diameter The right side, and handle portion is cylindrical, the microns of diameter 0.04；A diameter of 20nm of addition 2.6% nano silicon combination The topmost thin film obtained after thing, 1.4 × 10 are contained per square meter16Individual crystal grain, about 0.1 micron of left side of bullet diameter of " grenade " shape crystal grain It is right；And the lower film obtained after 4.0% a diameter of 20 nanometers of silica is added, 2.2 × 10 are contained per square meter16Individual crystalline substance Grain, the microns of crystal grain Pellet Warhead diameter about 0.08, and the diameter of " grenade " shape bullet are suitable with playing shank diameter, whole brilliant Grain almost presents bar-shaped.
In the case of crystallinity identical, crystallite dimension is smaller, then crystalline region number is more, and crystalline region is to amorphous region strand Constraint it is stronger.The amorphous region strand fettered by crystalline region, is referred to as the chain that is obstructed, and the chain that is obstructed accounts for the ratio of total amorphous strand Example increases with the reduction of crystallite dimension, the increase of number of dies, and then make it that fractional free volume is (freely in amorphous region Volume fraction, FFV) reduce, also influence whether the diameter R of amorphous region microchannel.The above-mentioned high-performance polypropylene of the present invention is thin In film, there is the crystallite area of numerous grenade shapes.These crystallite areas add the ratio for the chain that is obstructed, and have fettered the chain that is obstructed Random coil shape it is scattered so that after some chains that are obstructed come out from a crystallite area, also without it is scattered formed free water cement ratio, The composition in next crystallite area is just participated in rapidly, and amorphous region free water cement ratio quantity can be undoubtedly greatly decreased in such case. Positron annihilation analysis shows, add the polypropylene film that the nanometer titanium dioxide silicon composition of different proportion is formed, its free body Product void diameter is 3.13 nanometers, little with the free water cement ratio diameter difference of unmodified polypropylene film, but number of cavities Significantly reduce, finally promote the free body integration rate in the present invention in each layer of high-performance polypropylene film to be minimized.Based on upper State reason so that the polypropylene film has more preferably combination property in the present invention.
In the above-mentioned polypropylene film of the present invention, the thickness of each layer can be adjusted according to specific performance requirement.One In kind preferred embodiment, the gross thickness of above-mentioned high-performance polypropylene film is 18~20 μm, the wherein thickness of topmost thin film For 3~5 μm, the thickness of lower film is 3~5 μm.By the thickness control of each layer in three layers within the above range, can be further The combination property of polypropylene film is improved, it is had properties advantage concurrently, meets the requirements of flexible packaging industry.
The acrylic resin used in the present invention in each layer of high-performance polypropylene film can be commonly used in the art gathers Allyl resin.In a preferred embodiment, above-mentioned first polypropylene, the second polypropylene and tripropylene be independently One or more of the ground in polypropylene F280, X37F, 2605, FC801M, F800EDF and F-603.This several polypropylene tool There is preferable processing characteristics, and wide material sources, price are relatively low.
The above-mentioned high-performance polypropylene film of the present invention, in the nanometer titanium dioxide silicon composition of use, preferred nano-silica The particle diameter of silicon carbide particle is 15~20nm；It is highly preferred that modifier is selected from ethylene-vinyl acetate copolymer, polyethylene One or more in alcohol, acrylic acid series copolymer, PEO and PLA.It is further preferred that nano silicon The weight percentage of nanometer silicon dioxide particle is 54% in composition.Specifically, can according to CN101724176, Preparation technology described in CN102020796 and CN103189441 prepares above-mentioned nanometer titanium dioxide silicon composition, no longer superfluous herein State.
According to another aspect of the present invention, a kind of preparation method of above-mentioned high-performance polypropylene film is additionally provided, it is wrapped Include following steps：Nanometer titanium dioxide silicon composition is melted with the first polypropylene, the second polypropylene and tripropylene respectively Melt blending, respectively obtain the first modified polypropene, the second modified polypropene and the 3rd modified polypropene；Poly- third is modified by first Alkene, the second modified polypropene and the 3rd modified polypropene carry out three-layer co-extruded biaxial tension film forming, and it is thin to form high-performance polypropylene Film.
In above-mentioned preparation method provided by the invention, first by nanometer titanium dioxide silicon composition respectively with the first polypropylene, Propylene dimer and tripropylene carry out melt blending, recycle three-layer co-extruded biaxial tension film forming, and preparation has topmost thin film The polypropylene of (printing layer or the composite bed with other films), core layer film and lower film (food contact layer) three-decker is thin Film.Due to the nanometer titanium dioxide silicon composition in each layer containing certain content, the nanometer titanium dioxide silicon composition includes specific The nanometer silicon dioxide particle and modifier of content so that each layer film has specific performance, specific as follows：Sandwich layer is thin Film has higher modulus and elongation at break compared with conventional polypropylene resin film.As three-decker polypropylene film Skeleton, the sandwich layer of high-modulus can improve stiffness of thin film, realize the minimizing of packaging, and higher elongation at break improves thin The puncture resistant ability of film.Topmost thin film has relatively low diffusion coefficient and low solubility parameter to small solvent molecule.Thus have Effect reduces residual quantity of the solvent in polypropylene film in printing-ink or adhesive, improves the safety of polypropylene film Property.Lower film then has the relatively low coefficient of kinetic friction, can adapt to the demand packed automatically, can avoid adding in this layer Slipping agent and the pollution brought to food.In addition, the high-performance polypropylene film is in addition to improving foodsafety, its power Learn performance, resistance oxygen, block-water performance, heat endurance have and largely improved, disclosure satisfy that the multiple performance of flexible packaging industry will Ask.
Specifically, in the above-mentioned preparation method of the present invention, make use of three-layer co-extruded biaxial tension into film preparation this poly- third Alkene film.The heterogeneous nucleating effect of nano-silicon dioxide particle and biaxial tension effect are utilized simultaneously, it is possible to increase polypropylene is thin The crystallinity of film.Make its crystallinity or even 38~39% can be reached, than the crystallinity of plain polypropylene F280 polypropylene films Improve 8.5~11%.Meanwhile above-mentioned technique can also reduce crystallite dimension, the increase of crystal grain quantity, this will make essence molecule The diffusion path tortuosity increase of (limonene) and solvent molecule in the film, diffusion path is elongated, and diffusion coefficient reduces.This Outside, for amorphous region molecule interchain channel diameter R (D about 3.13nm) although change is little, duct quantity is (empty in polypropylene film Cave quantity) reduce so that fractional free volume is relative to reduce 3.2~7.2%.The reduction of fractional free volume causes solvent molecule Or the solubility of limonene molecule in the film reduces.This suitable crystal region and amorphous region microstructure are for reducing Residue, reduction polypropylene absorption to perfume materials of the solvent molecule in high performance thin film is particularly significant.
In addition, in high-performance polypropylene film prepared by the above method glass transition temperature (Tg) of each layer for 22.2~ 24.7 DEG C, 3.9~6.4 DEG C are improved than common F280 trades mark polypropylene film, illustrates nano silicon in amorphous region with gathering Larger intermolecular force between propylene molecules chain be present.Infrared spectrum analysis demonstrates this viewpoint, in polypropylene film 472-1Locate Si-O flexural vibrations peak red shift to 463-1Place, illustrating that silica attracts each other with polypropylene segment causes Si- O keys die down and red shift occur.Theoretical according to Polymer Physics, the glass transition temperature of polymer is higher, then its free volume Point rate is smaller, and the diffusion coefficient and solubility of solvent or limonene small molecule in the film can all reduce.The glass of polymer Glass transition temperature is higher, and the deflection of film, modulus of elasticity are also higher, and film is to oxygen and the barrier of the gas of vapor It is improved.The oxygen percent of pass of obtained high-performance polypropylene film is in 1400~1850ml/m in the present invention2.day.atm Between, reduce by 37~53% than conventional polypropylene films.High-performance polypropylene film vapor percent of pass is in 3.35~3.88g/ m2.day.95%RH between, 34~43% are reduced than conventional polypropylene films.
In a preferred embodiment, during three-layer co-extruded biaxial tension film forming, longitudinal stretching ratio be 4~ 5, cross directional stretch ratio is 9~10.
High stretching ratio make it that polypropylene segment is height-oriented, and the polypropylene segment after orientation is by nano silicon Nano-silicon dioxide particle in composition adsorbs (nano-particle has high surface energy).In the extended state of orientation stress Under, gather at a little higher than remote nano-silicon dioxide particle of the degree of orientation of the polypropylene segment of nano-silicon dioxide particle surrounding The degree of orientation of polypropylene segments, therefore the segment of close nano-silicon dioxide particle is parallel to each other and is attracted to the surface of particle, chain Section will be completed to crystallize in extremely short moment, form crystallite particles one by one.
Meanwhile nano silicon exists only in crystal region, and amorphous region is not present in, this is due to that high elongation takes To effect so that the chain segment orientation Du Genggao around silicon dioxide granule, it is inevitable mutually to reset and by high surface energy two Silicon oxide particle is adsorbed and crystallized.The double action of the incorgruous nucleation of above-mentioned high power stretch processes combination nano silicon Under so that unique grenade-shaped crystal grain is presented in the crystal grain in high-performance polypropylene film.
In a word, the effect based on above-mentioned high power stretch processes and the incorgruous nucleation of nano silicon so that the present invention Polypropylene film made from above-mentioned preparation method has unique microstructure, and then significantly improves the combination property of film.
In the preparation process of reality, it is preferable that the temperature of extrusion screw rod during three-layer co-extruded biaxial tension film forming 220~250 DEG C of degree, screw speed are 40~50rpm, and pressure is 40~50bar, and die temperature is 230~235 DEG C.Above-mentioned work Skill condition can further improve the combination property of polypropylene film.
The application is described in further detail below in conjunction with specific embodiment, these embodiments are it is not intended that limit this Apply for scope claimed.
Film performance test method：
The test of the moisture-vapor transmission (WVTR) of film according to《GB/T 1037-88 plastic sheetings and sheet material moisture vapor permeable Property test method》, it is 50cm that film, which is cut into area,2Circle, using the water of model Model 3/33 of Mocon companies of the U.S. Vapor transmission rates tester is tested；According to《GB/T 1038-2000 plastic sheetings and thin slice gas-premeable test method pressure difference Method》The OTR oxygen transmission rate (OTR) and carbon dioxide percent of pass of testing film, tester are Mocon companies of U.S. model 8001 OTR oxygen transmission rate tester.Using the type headspace analysis instruments of MOCON 820, the dense carbon dioxide tested daily in crisper Degree and oxygen concentration.
The Mechanics Performance Testings such as tensile strength, Young's modulus, elongation at break, with Instron-5565A electronic tensile machines, Foundation《GB/T 1040-92 plastic tensile method for testing performances》With《GB 13022-91 stretched plastic film method for testing performances》 Tested at temperature (253 ± 2) DEG C, biaxial stretching film batten size：20mm × 150mm, gauge length 100mm, test rate 200mm/min。
Crystal property is tested, with DSC-200PC differential scanning calorimeters, foundation《GB/T 19466.3-2004 plastics differentials The measure of scanning calorimetry (DSC) third portion temperature and enthalpy of melting and crystallization》Test.Temperature setting：From room temperature to 210 DEG C, 20 DEG C/min of heating rate, 5min is incubated, is then cooled to 50 DEG C, 10 DEG C/min of rate of temperature fall, 5min is incubated, to disappear Except thermal history；Then 210 DEG C are warming up to from 50 DEG C, 20 DEG C/min of speed.According to the heat absorption peak area of heating curve, crystallization is calculated Degree.
FTIR spectrum (FTIR), utilize Japanese Shimadzu Corporation FTIR-8400S FTIR apparatus measures, wave-length coverage It is 400~4000cm-1, resolution ratio 0.85cm-1, signal to noise ratio 20000:1.
Thermogravimetric (TG) is analyzed, and using Netzsch company's T G-209 thermogravimetric analyzers, measurement temperature scope is 20 DEG C~500 DEG C, protection gas is nitrogen, 15 DEG C/min of heating rate.
Positron annihilation is composed, and tester is the high-resolution positron annihilation life of Institute of High Energy Physcis, Academia Sinica Spectrometer, the conventional positron annihilation life spectrometer met for fast-slow, use22For Na radioactive sources as positron source, source strength is about 13 Microcurie, detector use a pair of BaF2Probe, temporal resolution about 205ps, fitting software LT9.0 are free using three life-spans Fitting；Two same samples are clamped at22The both sides of Na radioactive sources, form the structure of one " sandwich "；Detain derived components： 385ps, 19.50%.Positron annihilation is composed to survey its free water cement ratio diameter R.
The coefficient of kinetic friction and confficient of static friction are measured using Instron-5565A electronic tensile machines, with reference to GB10006-88 Method determines coefficient of friction, gliding cable structure=100mm/min.
Solubility S and diffusion coefficient D measure, according to Li-Hsin Cheng etc. in Journal of Membrane Research Literature " the Mass transfer of toluene of 409-410 phases in 2012 (page 180~190) on Science magazines The method measure that vapor through protective polymer gloves " are introduced；Cut 8cm × 8cm film sample Product, different time in acetone is impregnated, record with the increased curve of temporal quality, test 10 times and average.
Dissolvent residual is analyzed after film print：It is thin in high-performance polypropylene with chlorinated polypropylene ink on intaglio press The upper strata side printing of film, ordinary polypropylene film are also printed using identical process conditions, after testing two kinds of film prints respectively Dissolvent residual value：Film after print is cut into the size that specification is 3cm × 8cm, printing surface is rolled into tubular, is attached to volume inwardly In 10ml ml headspace bottles, to add 1ml triacetyl glycerines (internal standard compound), it is combined using Agilent7890A/5975C types color-matter Instrument determines organic solvent residual value；Headspace sample bottle is heated to 80 DEG C, is incubated duration of oscillation 45min, sample size 0.5ml； Chromatographic condition：VOC capillary columns (Agilent 19091R-316), 60m × 0.32mm × 1.80 μm, carrier gas is high-purity helium, 150 DEG C of injector temperature, carrier gas flux 1.0Lmin-1, split ratio 10:1, temperature programming (40 DEG C of initial temperature, retention time 3min, 80 DEG C are risen to 2 DEG C/min, then 180 DEG C are risen to 8 DEG C/min)；Mass Spectrometry Conditions：Electron impact ion source (EI), electronics Energy 70eV, 230 DEG C of transmission line temperature, 170 DEG C of ion source temperature, 180 DEG C of ion trap temperature, TIC patterns, quality of scanning scope M/z 30~150；Analysis result carries out component identification with NIST retrievals and standard substance contrast retention time.
Film is analyzed aromatic odor retentivity：By the internal layer of the three-layer co-extruded film of high-performance towards inboard, be made 5cm × The freshness protection package 1 of three bandings of 15cm sizes, the fresh squeezing lemon juices of 20ml are loaded, lemon thing in freshness protection package head space is tested after 30 days The total concentration of matter；The freshness protection package 2 of formed objects is also made using common three-layer co-extruded polypropylene film, loads the fresh squeezing lemons of 20ml Juice, and make the head space volume of freshness protection package 2 identical with freshness protection package 1, the total dense of lemon material in freshness protection package head space is tested after 30 days Degree；Each material concentration in freshness protection package head space is tested using Agilent7890A gas-chromatographies；Characterized with the gross area at each peak The total concentration of lemon material.It is more containing aromatic odor content of material in head space, illustrate film to aroma gases (smell) Barrier it is higher.
Embodiment 1
The method proposed with reference to patent CN101724176, CN102020796 and CN103189441, prepares nano-silica SiClx composition, wherein nano-silicon dioxide particle account for the 54% of said composition gross mass, and concrete operation step is as follows：
Equipped with stirring, dropping funel, thermometer 50 liters of capacity reactor in add 10Kg solid content be 50% EVA emulsions setting stir speed (S.S.) 100rpm, temperature be 50 degree, add powdered polyethylene oxide resin 50g and PLA 50g.After stirring 30 minutes, the water glass solution that 25Kg dioxide-containing silicas are 24% is added, is stirred 30 minutes, 40% sulphur is added dropwise Acid, until PH=5.5, then heats to 70 degree, 40% sulfuric acid is added dropwise until PH=7.0, continues stirring 30 minutes, be washed out Sulfate ion is removed, press filtration, dry, pulverize and be prepared into nanometer titanium dioxide silicon composition.
1.0Kg nanometer titanium dioxide silicon composition and 99.0Kg F280 acrylic resins is common in 210~230 DEG C of meltings After mixed, granulating and drying, sandwich layer resin raw material is obtained；
The sandwich layer resin is all added on three extruders of three-layer co-extruded biaxial tension equipment, sets three extrusion screw rods Temperature all be 230 DEG C, cross directional stretch ratio 10, longitudinal stretching ratio be 5, screw speed 48rpm, pressure 45bar, die orifice Temperature is 230 DEG C.Obtain the polypropylene film for the single structure that thickness is 18 μm (the Nomenclature Composition and Structure of Complexes is identical with core layer film).Should The SEM photograph of polypropylene film is as shown in Figure 1.
Embodiment 2
Other conditions change nano silicon composition levels with embodiment 1.By 2.6Kg nano silicon group After compound and 97.4Kg F280 acrylic resins melt blending, granulating and drying, upper strata resin raw material is obtained；
The upper strata resin is all added on three extruders of three-layer co-extruded biaxial tension equipment, sets three extrusion screw rods Temperature all be 230 DEG C, cross directional stretch ratio 9, longitudinal stretching ratio be 4, screw speed 48rpm, pressure 45bar, die orifice Temperature is 230 DEG C.Obtain the polypropylene film for the single structure that thickness is 18 μm (the Nomenclature Composition and Structure of Complexes is identical with topmost thin film).
Embodiment 3
Other conditions change nano silicon composition levels with embodiment 1.By 4.0Kg nano silicon group After compound and the F280 acrylic resins melt blending of 96.0 mass parts, granulating and drying, lower-layer resin raw material is obtained；
The lower-layer resin is all added on three extruders of three-layer co-extruded biaxial tension equipment, sets three extrusion screw rods Temperature all be 230 DEG C, cross directional stretch ratio 9, longitudinal stretching ratio be 5, screw speed 48rpm, pressure 45bar, die orifice Temperature is 230 DEG C.Obtaining the polypropylene double-way stretched film of single structure that thickness is 18 μm, (the Nomenclature Composition and Structure of Complexes and same lower floor are thin Film formulation is identical).
Embodiment 4
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide of different quality containing Silicon composition after 210~230 DEG C of melt blendings, granulating and dryings, obtains nano silicon combination with F280 acrylic resins The sandwich layer modified resin and nanometer that upper strata modified resin that thing content is 2.6%, nano silicon composition levels are 1.0% Silicon dioxide compositions content is 4.0% lower-layer modified resin；
Upper strata modified resin is added in the upper strata extruder hopper of three-layer co-extruded biaxial tension equipment, in sandwich layer extruder Sandwich layer modified resin is added in hopper, lower-layer modified resin is added in lower floor's extruder hopper, three extrusion screw rods of setting Temperature is all 230 DEG C, and cross directional stretch ratio 10, longitudinal stretching ratio is 5, and control the upper and lower extruder screw rotating speed is respectively 50rpm and 50rpm, pressure 45bar, die temperature be 230 DEG C, obtain upper thickness be 3 μm, lower thickness be 3 μm, sandwich layer Thickness be 12 μm it is three-layer co-extruded go out bidirectional stretching polypropylene film.
Embodiment 5
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide of different quality containing Silicon composition after 210~230 DEG C of melt blendings, granulating and dryings, obtains nano silicon combination with F280 acrylic resins The sandwich layer modified resin and nanometer that upper strata modified resin that thing content is 2.6%, nano silicon composition levels are 1.0% Silicon dioxide compositions content is 4.0% lower-layer modified resin；
Upper strata modified resin is added in the upper strata extruder hopper of three-layer co-extruded biaxial tension equipment, in sandwich layer extruder Sandwich layer modified resin is added in hopper, lower-layer modified resin is added in lower floor's extruder hopper, three extrusion screw rods of setting Temperature is all 230 DEG C, and cross directional stretch ratio 10, longitudinal stretching ratio is 5, and control the upper and lower extruder screw rotating speed is respectively 50rpm and 50rpm, pressure 45bar, die temperature be 230 DEG C, obtain upper thickness be 5 μm, lower thickness be 5 μm, sandwich layer Thickness be 10 μm it is three-layer co-extruded go out bidirectional stretching polypropylene film.
Embodiment 6
For thin film preparation process with embodiment 5, merely lateral stretching ratio is 3, and longitudinal stretching multiplying power is 2.
Embodiment 7
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide of different quality containing Silicon composition after 210~230 DEG C of melt blendings, granulating and dryings, obtains nano silicon combination with F280 acrylic resins The sandwich layer modified resin and nanometer that upper strata modified resin that thing content is 2.8%, nano silicon composition levels are 1.5% Silicon dioxide compositions content is 4.5% lower-layer modified resin；
Upper strata modified resin is added in the upper strata extruder hopper of three-layer co-extruded biaxial tension equipment, in sandwich layer extruder Sandwich layer modified resin is added in hopper, lower-layer modified resin is added in lower floor's extruder hopper, three extrusion screw rods of setting Temperature is all 230 DEG C, and cross directional stretch ratio 9, longitudinal stretching ratio is 4, and control the upper and lower extruder screw rotating speed is respectively 44rpm and 44rpm, pressure 43bar, die temperature be 230 DEG C, obtain upper thickness be 5 μm, lower thickness be 5 μm, sandwich layer Thickness be 10 μm it is three-layer co-extruded go out bidirectional stretching polypropylene film.
Embodiment 8
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide of different quality containing Silicon composition after 210~230 DEG C of melt blendings, granulating and dryings, obtains nano silicon combination with F280 acrylic resins The sandwich layer modified resin and nanometer that upper strata modified resin that thing content is 2.3%, nano silicon composition levels are 0.7% Silicon dioxide compositions content is 3.7% lower-layer modified resin；
Upper strata modified resin is added in the upper strata extruder hopper of three-layer co-extruded biaxial tension equipment, in sandwich layer extruder Sandwich layer modified resin is added in hopper, lower-layer modified resin is added in lower floor's extruder hopper, three extrusion screw rods of setting Temperature is all 230 DEG C, and cross directional stretch ratio 8, longitudinal stretching ratio is 2, and control the upper and lower extruder screw rotating speed is respectively 40rpm and 40rpm, pressure 45bar, die temperature be 230 DEG C, obtain upper thickness be 5 μm, lower thickness be 5 μm, sandwich layer Thickness be 10 μm it is three-layer co-extruded go out bidirectional stretching polypropylene film.
Comparative example 1
Thin film preparation process simply prepares the film that thickness is 18 μm with embodiment 1 with common F280 acrylic resins.
Comparative example 2
Thin film preparation process simply prepares the film that thickness is 20 μm with embodiment 5 with common F280 acrylic resins.
Comparative example 3
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide of different quality containing Silicon composition after 210~230 DEG C of melt blendings, granulating and dryings, obtains nano silicon combination with F280 acrylic resins The sandwich layer modified resin and nanometer that upper strata modified resin that thing content is 3.5%, nano silicon composition levels are 2.5% Silicon dioxide compositions content is 5.5% lower-layer modified resin；
Upper strata modified resin is added in the upper strata extruder hopper of three-layer co-extruded biaxial tension equipment, in sandwich layer extruder Sandwich layer modified resin is added in hopper, lower-layer modified resin is added in lower floor's extruder hopper, three extrusion screw rods of setting Temperature is all 230 DEG C, and cross directional stretch ratio 5, longitudinal stretching ratio is 2, and control the upper and lower extruder screw rotating speed is respectively 46rpm and 46rpm, pressure 45bar, die temperature be 230 DEG C, obtain upper thickness be 5 μm, lower thickness be 5 μm, sandwich layer Thickness be 10 μm it is three-layer co-extruded go out bidirectional stretching polypropylene film.
Performance is carried out to the polypropylene film prepared in embodiment 1 to 8 and comparative example 1 to 3 according to foregoing method of testing Characterize, characterization result is as shown in Table 1 and Table 2：
Table 1
Table 2
In data more than as can be seen that under the conditions of high magnification biaxial tension, upper strata, middle level and the core of single layer structure Layer film, there is different microstructures, highlight its some feature performance, its microstructure is more conducive to improve the peace of packaging Full property and feature.The nano silicon of addition 1.3%, makes it have most fine and close amorphous region structure in topmost thin film, I.e. free body integration rate is minimum, crystallinity highest, diffusion coefficient D and solubility S are minimum.Make topmost thin film and adhesive or ink During contact, diffusion of the solvent molecule to film sandwich layer is slack-off, avoids causing excessive dissolvent residual, but will not cause and bond by force The problem of spending inadequate or ink adhesion deficiency, because the nanometer of the modifier and polarity in nanometer titanium dioxide silicon composition Silicon dioxide granule can all play increase polypropylene film polarity, improve polypropylene film and layer of ink (or adhesive phase) affinity Effect so that the bonding strength of interlayer improves on layer of ink (or adhesive phase) and polypropylene.In the nano-silica of addition 2.0% The lower film obtained after SiClx, not only amorphous region compact structure, free body integration rate is small, and small molecule is in the microcosmic duct of film Interior D and S is small, but also has unique surface texture, film surface is had the relatively low coefficient of kinetic friction, particularly suitable for Automatically the demand packed, the pollution that slipping agent is brought to food is avoided.In the case of the nano silicon of addition 0.5%, Nano-particle is able to preferably disperse in acrylic resin, at utmost plays heterogeneous nucleating effect, crystallizes acrylic resin Area's crystal grain quantity increase, crystal size are small, and this microstructure, which assigns sandwich layer, has higher intensity and toughness so that sandwich layer is thin Film dynamic performance is excellent, has higher tensile strength and elongation at break (toughness), and it is processed that this is beneficial to raising biaxial tension The stability of journey, the high-modulus characteristic that sandwich layer has are beneficial to the deflection for improving packaging, the difficulty of bag are reduced, beneficial to minimizing bag Dress.
Utilize standby three-layer co-extruded of the internal layer with specific microstructure designed by the present invention, sandwich layer, upper strata resin-made Polypropylene film, topmost thin film and other Film laminateds or it is printed when, solvent in ink or adhesive in the film residual Allowance is seldom, and lower floor is food contact layer, and coefficient of friction is adapted to the needs packed automatically, polluted in the absence of slipping agent, and this is interior The fine and close microstructure of layer can also prevent diffusion of the aromatic odor molecule to sandwich layer, reduce absorption of the packaging to fragrance, improve bag The fragrance protectiveness energy of dress.The three-layer co-extruded film of the high-performance polypropylene resistance oxygen, blocks water in addition to higher food security performance Performance, heat endurance all largely improve, and improve the defencive function to food.
Under low range pulled out condition (2 × 3), such as embodiment 6, the properties of nano modification film are below high power Rate pulled out condition (4~5) × (9~10), for this explanation under low range stretching condition, the degree of orientation of polypropylene segment is relatively low, Degree of orientation is inadequate around nano-silicon dioxide particle, it is impossible to preferably adsorbed by silica, or adsorbed chain hop count Amount is few, and the heterogeneous nucleating effect performance of silica is insufficient.Under low range pulled out condition, the modified polypropene that is prepared The crystallite dimension of crystal region is larger, crystal grain quantity relatively high stretching ratio when it is few, cause to barrier properties for gases, aromatic odor barrier Property is slightly lower, but still better than common unmodified polypropylene film.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies Change, equivalent substitution, improvement etc., should be included in the scope of the protection.

Claims (12)

  1. A kind of 1. high-performance polypropylene film, it is characterised in that including：
    Topmost thin film, based on the percentage by weight of the topmost thin film, the topmost thin film includes 2.0~3.0% nanometer two Silica compositions and 97.0~98.0% the first polypropylene；
    Core layer film, on a side surface of the topmost thin film, based on the percentage by weight of the core layer film, the core Layer film includes 0.5~2.0% nanometer titanium dioxide silicon composition and 99.5~98.0% the second polypropylene；
    Lower film, on a side surface of the remote topmost thin film of the core layer film, by the lower film Percentage by weight meter, the lower film include 3.5~5.0% nanometer titanium dioxide silicon composition and 96.5~95% Tripropylene；
    Wherein, based on the percentage by weight of the nanometer titanium dioxide silicon composition, the nanometer titanium dioxide silicon composition includes 50 ~55% nanometer silicon dioxide particle and 45~50% modifier；The crystallinity of the high-performance polypropylene film is 30~39%, the crystal grain of the high-performance polypropylene film is grenade-shaped crystal grain, and the grenade-shaped crystal grain includes spherical bullet Head and column bullet handle.
  2. 2. high-performance polypropylene film according to claim 1, it is characterised in that
    Based on the percentage by weight of the topmost thin film, the topmost thin film includes 2.3~2.8% nano silicon Composition and 97.2~97.7% first polypropylene；
    Based on the percentage by weight of the core layer film, the core layer film includes 0.7~1.5% nano silicon Composition and 98.5~99.3% second polypropylene；
    Based on the percentage by weight of the lower film, the lower film includes 3.7~4.5% nano silicon Composition and 95.5~96.3% tripropylene.
  3. 3. high-performance polypropylene film according to claim 2, it is characterised in that
    Based on the percentage by weight of the topmost thin film, the nano silicon that the topmost thin film includes 2.6% combines Thing and 97.4% first polypropylene；
    Based on the percentage by weight of the core layer film, the nano silicon that the core layer film includes 1.0% combines Thing and 99.0% second polypropylene；
    Based on the percentage by weight of the lower film, the nano silicon that the lower film includes 4.0% combines Thing and 96.0% tripropylene.
  4. 4. high-performance polypropylene film according to any one of claim 1 to 3, it is characterised in that the high-performance is gathered The glass transition temperature of Polypropylene film is 22.2~24.7 DEG C.
  5. 5. high-performance polypropylene film according to claim 1, it is characterised in that described in the grenade-shaped crystal grain The particle diameter of Pellet Warhead is 0.08~0.1 μm, and the radial width of the column bullet handle is 0.04~0.08 μm, the column bullet handle Axial length be 0.8~1.6 μm.
  6. 6. high-performance polypropylene film according to any one of claim 1 to 3, it is characterised in that the high-performance is gathered The gross thickness of Polypropylene film is 18~20 μm, wherein the thickness of the topmost thin film is 3~5 μm, the thickness of the lower film For 3~5 μm.
  7. 7. high-performance polypropylene film according to any one of claim 1 to 3, it is characterised in that described first poly- third Alkene, second polypropylene and the tripropylene separately selected from polypropylene F280, X37F, 2605, FC801M, One or more in F800EDF and F-603.
  8. 8. high-performance polypropylene film according to any one of claim 1 to 3, it is characterised in that the nano-silica The particle diameter of silicon carbide particle is 5~20nm.
  9. 9. high-performance polypropylene film according to claim 8, it is characterised in that the modifier be selected from ethene- One or more in vinyl acetate co-polymer, polyvinyl alcohol, acrylic acid series copolymer, PEO and PLA.
  10. A kind of 10. preparation method of the high-performance polypropylene film any one of claim 1 to 9, it is characterised in that bag Include following steps：
    Nanometer titanium dioxide silicon composition is subjected to melt blending with the first polypropylene, the second polypropylene and tripropylene respectively, Respectively obtain the first modified polypropene, the second modified polypropene and the 3rd modified polypropene；
    First modified polypropene, second modified polypropene and the 3rd modified polypropene are carried out three-layer co-extruded double To stretching film forming, the high-performance polypropylene film is formed.
  11. 11. preparation method according to claim 10, it is characterised in that in the mistake of the three-layer co-extruded biaxial tension film forming Cheng Zhong, longitudinal stretching ratio are 4~5, and cross directional stretch ratio is 9~10.
  12. 12. preparation method according to claim 11, it is characterised in that in the mistake of the three-layer co-extruded biaxial tension film forming Cheng Zhong, the temperature of extrusion screw rod are 220~250 DEG C, and screw speed is 40~50rpm, and pressure is 40~50bar, die temperature For 230~235 DEG C.
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CN105926079B (en) * 2016-06-24 2018-01-23 深圳市新纶科技股份有限公司 Polypropylene film-fibre and preparation method and air filting material prepared therefrom
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CN101724176A (en) * 2008-10-27 2010-06-09 北京印刷学院 Processing aid of polyolefine for food flexible packing, preparation method and application thereof, and modified polyolefine adopting processing aid
CN102020796A (en) * 2009-09-18 2011-04-20 北京印刷学院 Nano-modified polypropylene soft packaging material
WO2012139292A1 (en) * 2011-04-14 2012-10-18 北京印刷学院 Modifier composition for polyolefin, polyolefin for packaging and soft package film
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CN102020796A (en) * 2009-09-18 2011-04-20 北京印刷学院 Nano-modified polypropylene soft packaging material
WO2012139292A1 (en) * 2011-04-14 2012-10-18 北京印刷学院 Modifier composition for polyolefin, polyolefin for packaging and soft package film
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