CN105538855A - High performance polypropylene film and preparation method thereof - Google Patents
High performance polypropylene film and preparation method thereof Download PDFInfo
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- CN105538855A CN105538855A CN201510888580.7A CN201510888580A CN105538855A CN 105538855 A CN105538855 A CN 105538855A CN 201510888580 A CN201510888580 A CN 201510888580A CN 105538855 A CN105538855 A CN 105538855A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
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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
- 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 high performance polypropylene film and a preparation method thereof. The film comprises a top film, a core film and a lower film. The top film includes 2.0-3.0% of a nano-silica composition and 97.0-98.0% of first polypropylene, the core film includes 0.5-2.0% of a nano-silica composition and 99.5-98.0% of second polypropylene, and the lower film includes 3.5-5.0% of a nano-silica composition and 96.5-95% of third polypropylene, wherein the nano-silica composition includes 50-55% of nano-silica particles and 45-50% a resin modifier. Each layer of the film contains a specific content of nano-silica composition, so that the film has high modulus and elongation at break, low diffusion coefficient and solubility parameter to solvent small molecules, low dynamic friction coefficient, and has good comprehensive properties, thus being suitable for flexible packaging materials.
Description
Technical field
The present invention relates to polypropylene film technical field, in particular to a kind of high-performance polypropylene film and preparation method thereof.
Background technology
Polypropylene film is one of topmost packing film, usually needs it to possess good printing performance and heat sealability.But as printing element, the maximum shortcoming of polypropylene film one is that after print, solvent residual amount is high compared with the film (as PETG (PET) film) of other types.For this reason, color printing factory can only by reducing linear velocity, improving drying tunnel temperature, increasing the dissolvent residual that the methods such as curing time reduce polypropylene film.Also there is report to adopt a kind of special printing-ink in addition, solvent molecule can be made to volatilize the dissolvent residual after reducing polypropylene film print to greatest extent by the ink skinning evacuated.Along with countries in the world are to food-safety problem pay attention to day by day, more and more stricter to the restriction of residual solvent in compound flexible packaging film, this possibility be eliminated with regard to making general polypropylene film face.For this reason, the security performance improving polypropylene film is the task of top priority.
About in the study on the modification of polyolefin film, pay attention to the improvement of mechanical property and the raising of machine-shaping stability for many, and have ignored polyacrylic foodsafety.For this reason, be necessary to propose a kind of novel polypropylene film design, unified with the optimization realizing various performance.
Summary of the invention
Main purpose of the present invention is to provide a kind of high-performance polypropylene film and preparation method thereof, to solve the problem that polypropylene film of the prior art is difficult to meet multiple performance requirement simultaneously.
To achieve these goals, according to an aspect of the present invention, provide a kind of high-performance polypropylene film, it comprises: topmost thin film, by the weight percent meter of topmost thin film, topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.0 ~ 3.0% and first polypropylene of 97.0 ~ 98.0%; Core layer film, on the surface, by the weight percent meter of core layer film, core layer film comprises the nanometer titanium dioxide silicon composition of 0.5 ~ 2.0% and second polypropylene of 99.5 ~ 98.0% in the side being positioned at topmost thin film; Lower film, on the surface, by the weight percent meter of lower film, lower film comprises the nanometer titanium dioxide silicon composition of 3.5 ~ 5.0% and the tripropylene of 96.5 ~ 95% in the side away from topmost thin film being positioned at core layer film; Wherein, by the weight percent meter of nanometer titanium dioxide silicon composition, nanometer titanium dioxide silicon composition comprises the nanometer silicon dioxide particle of 50 ~ 55% and the modifier of 45 ~ 50%.
Further, by the weight percent meter of topmost thin film, topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.3 ~ 2.8% and first polypropylene of 97.2 ~ 97.7%; By the weight percent meter of core layer film, core layer film comprises the nanometer titanium dioxide silicon composition of 0.7 ~ 1.5% and second polypropylene of 98.5 ~ 99.3%; By the weight percent meter of lower film, lower film comprises the nanometer titanium dioxide silicon composition of 3.7 ~ 4.5% and the tripropylene of 95.5 ~ 96.3%.
Further, by the weight percent meter of topmost thin film, topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.6% and first polypropylene of 97.4%; By the weight percent meter of core layer film, core layer film comprises the nanometer titanium dioxide silicon composition of 1.0% and second polypropylene of 99.0%; By the weight percent meter of lower film, lower film comprises the nanometer titanium dioxide silicon composition of 4.0% and the tripropylene of 96.0%.
Further, the degree of crystallinity of high-performance polypropylene film is 30 ~ 39%; Preferably, the glass transition temperature of high-performance polypropylene film is 22.2 ~ 24.7 DEG C; Preferably, the crystal grain of high-performance polypropylene film is grenade-shaped crystal grain, and grenade-shaped crystal grain comprises Pellet Warhead and column bullet handle; Preferably, in grenade-shaped crystal grain, the particle diameter of Pellet Warhead is 0.08 ~ 0.1 μm, and 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 wherein the thickness of topmost thin film is 3 ~ 5 μm, and the thickness of lower film is 3 ~ 5 μm.
Further, the first polypropylene, the second polypropylene and tripropylene be separately selected from polypropylene F280, X37F, 2605, one or more in FC801M, F800EDF and F-603.
Further, the particle diameter of nanometer silicon dioxide particle is 5 ~ 20nm; Preferably, modifier is selected from one or more in ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic acid series copolymer, PEO and poly-PLA.
According to a further aspect in the invention, provide a kind of preparation method of high-performance polypropylene film, it comprises the following steps: nanometer titanium dioxide silicon composition is carried out melt blending with the first polypropylene, the second polypropylene and tripropylene respectively, obtains the first modified polypropene, the second modified polypropene and the 3rd modified polypropene respectively; First modified polypropene, the second modified polypropene and the 3rd modified polypropene are carried out three-layer co-extruded biaxial tension film forming, forms high-performance polypropylene film.
Further, in the process of three-layer co-extruded biaxial tension film forming, longitudinal stretching ratio is 4 ~ 5, and cross directional stretch ratio is 9 ~ 10.
Further, in the process of three-layer co-extruded biaxial tension film forming, the temperature of extrusion screw rod is 220 ~ 250 DEG C, and screw 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, comprise topmost thin film (printed layers or the composite bed with other film), core layer film and lower film (food contact layer).And the nanometer titanium dioxide silicon composition all containing certain content in each layer, this nanometer titanium dioxide silicon composition comprises nanometer silicon dioxide particle and the modifier of certain content, each layer film is made to have specific performance, specific as follows: core layer film, compared with conventional polypropylene resin film, has higher modulus and elongation at break.As the skeleton of three-decker polypropylene film, the sandwich layer of high-modulus can improve stiffness of thin film, and realize the minimizing of packaging, higher elongation at break improves the puncture resistant ability of film.Topmost thin film has lower diffusion coefficient and low solubility parameter to small solvent molecule.So just effectively reduce the residual quantity of solvent in polypropylene film in printing-ink or adhesive, improve the security of polypropylene film.Lower film then has the lower coefficient of kinetic friction, can adapt to the demand of automatically packaging, can avoid adding slipping agent in this layer and the pollution that brings to food.In a word, this film has good combination property, is suitable for food flexible packing material and uses.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the SEM photo of the polypropylene film of preparation in embodiments of the invention 1.
Detailed description of the invention
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
As described by background technology part, existing flexible package polypropylene film is difficult to meet multiple performance requirement.In order to address this problem, inventor provides a kind of high-performance polypropylene film, and it is three-decker, comprises topmost thin film, core layer film and lower film; By the weight percent meter of topmost thin film, topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.0 ~ 3.0% and first polypropylene of 97.0 ~ 98.0%; Core layer film is positioned at the side of topmost thin film on the surface, and presses the weight percent meter of core layer film, and it comprises the nanometer titanium dioxide silicon composition of 0.5 ~ 2.0% and second polypropylene of 98.0 ~ 99.5%; Lower film is positioned at the side away from topmost thin film of core layer film on the surface, and presses the weight percent meter of lower film, and it comprises the nanometer titanium dioxide silicon composition of 3.5 ~ 5.0% and the tripropylene of 95.0 ~ 96.5%; Wherein, by the weight percent meter of nanometer titanium dioxide silicon composition, nanometer titanium dioxide silicon composition comprises the nanometer silicon dioxide particle of 50 ~ 55% and the modifier of 45 ~ 50%.
In above-mentioned high-performance polypropylene film provided by the invention, there is three-decker, comprise topmost thin film (printed layers or the composite bed with other film), core layer film and lower film (food contact layer).And the nanometer titanium dioxide silicon composition all containing certain content in each layer, this nanometer titanium dioxide silicon composition comprises nanometer silicon dioxide particle and the modifier of certain content, makes each layer film have specific performance, specific as follows:
Core layer film, compared with conventional polypropylene resin film, has higher modulus and elongation at break.As the skeleton of three-decker polypropylene film, the sandwich layer of high-modulus can improve stiffness of thin film, and realize the minimizing of packaging, higher elongation at break improves the puncture resistant ability of film.
Topmost thin film has lower diffusion coefficient and low solubility parameter to small solvent molecule.In the application process of reality, when polypropylene film and other Film laminated prepare flexible package, its upper strata needs to apply adhesive, then with compounds such as aluminium foil, PET, nylon, and the compatibility of organic solvent ethyl acetate, acetone, isopropyl alcohol etc. in polypropylene and common adhesive is higher, the diffusion coefficient of these solvents in polypropylene film is large, diffusion rate is fast, saturation solubility is also large, common stoving process can not remove solvent remaining in film completely, remaining organic solvent quantity is in the film more, threatens to foodsafety.And the topmost thin film in the present invention has lower diffusion coefficient and low solubility parameter to these small solvent molecules, when carry out compound with other material films such as aluminium foils or printed time, this topmost thin film can intercept the diffusion of organic solvent molecule (solvent in adhesive or ink) to polypropylene film inside largely, so just effectively reduce the residual quantity of solvent in polypropylene film in printing-ink or adhesive, improve the security of polypropylene film.
Lower film then has the lower coefficient of kinetic friction.When preparing food packaging laminated film, polypropylene film is often used as the direct contact food of inner membrance, and therefore its lower film needs and Food Contact.Auto-filling or automatically packaging time this layer can with the mutual friction of metal parts phase, this just needs lower film to have lower coefficient of friction.But, the coefficient of kinetic friction of general polypropylene film is 0.4 ~ 0.6, in order to reduce the coefficient of kinetic friction further, usual needs add erucyl amide class slipping agent in acrylic resin, but erucyl amide Small molecular can pollute food in the precipitation of food contact layer, therefore the technique of this general reduction coefficient of friction is not best method.With it unlike, in above-mentioned high-performance polypropylene film provided by the invention, in acrylic resin, add the nanometer titanium dioxide silicon composition of certain content, make it have the lower coefficient of kinetic friction.When using this polypropylene film automatically to pack, lower film, as food contact layer, because it has the lower coefficient of kinetic friction, can adapt to the demand of automatically packaging, can avoid adding slipping agent in this layer and the pollution that brings to food.
In a word, nanometer titanium dioxide silicon composition containing certain content in each layer of this film, make the modulus of film and elongation at break is high, to the diffusion coefficient of small solvent molecule with solubility parameter is low, the coefficient of kinetic friction is low, its combination property had, and is suitable for food flexible packing material.
In above-mentioned high-performance polypropylene film, as long as the material of each layer is arranged according to aforementioned proportion scope, each layer just can be made to have specific excellent properties, whole polypropylene film has preferably combination property simultaneously.In a preferred embodiment, by the weight percent meter of topmost thin film, topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.3 ~ 2.8% and first polypropylene of 97.2 ~ 97.7%; By the weight percent meter of core layer film, core layer film comprises the nanometer titanium dioxide silicon composition of 0.7 ~ 1.5% and second polypropylene of 98.5 ~ 99.3%; By the weight percent meter of lower film, lower film comprises the nanometer titanium dioxide silicon composition of 3.7 ~ 4.5% and the tripropylene of 95.5 ~ 96.3%.The content of nanometer titanium dioxide silicon composition in each layer is controlled in above-mentioned scope, the combination property of polypropylene film can be improved further.
More preferably, by the weight percent meter of topmost thin film, topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.6% and first polypropylene of 97.4%; By the weight percent meter of core layer film, core layer film comprises the nanometer titanium dioxide silicon composition of 1.0% and second polypropylene of 99.0%; By the weight percent meter of lower film, lower film comprises the nanometer titanium dioxide silicon composition of 4.0% and the tripropylene of 96.0%.
Add the nanometer titanium dioxide silicon composition of 1%, make that the hot strength of core layer film can reach 37.6MPa, elastic modelling quantity can reach 688Mpa, elongation at break can reach 349%, respectively than not adding the hot strength of polypropylene film of nanometer titanium dioxide silicon composition, elastic modelling quantity, elongation at break improve 119%, 42% and 12%.
In acrylic resin, add the nanometer titanium dioxide silicon composition of 2.6%, the topmost thin film obtained has lower diffusion coefficient to acetone solvent Small molecular can be low to moderate D=0.97 × 10
-13m
2/ s
-2, solubility can be low to moderate S=0.035% (relative mass concentration), itself D and S value reduces by 63% and 20% respectively than the polypropylene film not adding nanometer titanium dioxide silicon composition.Organic solvent D and S in the film significantly reduces simultaneously, this solvent molecule is reduced significantly to the diffusion rate P (P=D × S) of film depths, the moment of this topmost thin film is contacted (from the time interval before entering drying tunnel to film after gluing at adhesive, lower than 1 second), almost do not have organic solvent can infiltrate through in fine and close topmost thin film, thus making the dissolvent residual numerical value in whole polypropylene film be able to significantly reduce further, the security of film is further ensured.In addition, this topmost thin film can't reduce the combined strength bination between film and other material film to the barrier of organic solvent, on the contrary because adding of nanometer titanium dioxide silicon composition, improves the polarity of topmost thin film, add the compatibility between itself and adhesive, bonding strength is improved.
In acrylic resin, add the nanometer titanium dioxide silicon composition of 4.0%, the coefficient of kinetic friction of the lower film obtained more effectively is reduced, and this nanometer titanium dioxide silicon composition can not to surface migration.Compared with not adding the polypropylene film of nanometer titanium dioxide silicon composition, not change (μ at the confficient of static friction of lower film
0about 0.45), when, its coefficient of kinetic friction can be reduced to μ
d=0.24, reduce by 44% than the coefficient of kinetic friction not adding nanometer titanium dioxide silicon composition polypropylene film.In addition, this lower film can be low to moderate D=1.1 × 10 to the diffusion coefficient of acetone
-13m
2/ s
-2, solubility can be low to moderate S=0.035%, reduces by 58% and 20% respectively than D, S of the polypropylene film not adding nanometer titanium dioxide silicon composition.The lower film of this densification reduces the adsorptivity of food flavor, is more conducive to the local flavor keeping packaged food.
In addition, the upper strata of high-performance polypropylene film, sandwich layer and lower floor, except having the performance of above excellence, mechanical property is also very excellent.Hot strength is all between 24.5 ~ 37.6MPa, and elastic modelling quantity is between 486 ~ 688MPa, and elongation at break is between 313 ~ 349%, and acetone diffusion coefficient is in the film 0.97 × 10
-13m
2/ s
-2~ 1.78 × 10
-13m
2/ s
-2between, acetone solubility is in the film between 0.035 ~ 0.041 (mass concentration), and temperature of initial decomposition is between 185.4 ~ 269 DEG C, and 50% decomposition temperature is between 448.8 ~ 450.4 DEG C, confficient of static friction is about 0.45, and the coefficient of kinetic friction is between 0.24 ~ 0.36.These performances are all much better than conventional polypropylene film.
In a preferred embodiment, the degree of crystallinity of high-performance polypropylene film is 30 ~ 39%.Preferably, the glass transition temperature of high-performance polypropylene film is 22.2 ~ 24.7 DEG C.Under this degree of crystallinity and glass transition temperature, the combination property of above-mentioned polypropylene film can be improved further.
Preferably, the crystal grain of above-mentioned high-performance polypropylene film is grenade-shaped crystal grain, and grenade-shaped crystal grain comprises Pellet Warhead and column bullet handle; More preferably, in grenade-shaped crystal grain, the particle diameter of Pellet Warhead is 0.08 ~ 0.1 μm, and 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.
Do not add in the polypropylene film of nanometer titanium dioxide silicon composition, crystalling propylene size (crystal particle volume) is 10 ~ 30 microns, for area be 1 square metre, thickness is this film of 11 microns, quality about about 10 grams, if degree of crystallinity is 35%, in this film of so 1 square meter, have 8.93 × 10
8individual particle diameter is the crystal grain (polypropylene structure cell density is 0.936g/ml) of 20 microns.And in the above-mentioned high-performance polypropylene film provided in the present invention, with the addition of the nanometer titanium dioxide silicon composition of special ratios in layers, crystallite dimension is reduced a lot, crystal grain quantity increases by 6 ~ 7 orders of magnitude, the core layer film such as obtained after the diameter of interpolation 1.0% is the nanometer titanium dioxide silicon composition of 20nm, has 5.4 × 10 in every square meter film
15individual crystal grain, and the unconventional spherocrystal of grain shape, but in " grenade " shape, warhead section is spherical in shape, diameter 0.1 microns, and handle portion is cylindricality, diameter 0.04 microns; The diameter adding 2.6% is the topmost thin film obtained after the nanometer titanium dioxide silicon composition of 20nm, and every square meter is containing 1.4 × 10
16individual crystal grain, bullet diameter about 0.1 microns of " grenade " shape crystal grain; And the diameter adding 4.0% is the lower film obtained after the silica of 20 nanometers, every square meter is containing 2.2 × 10
16individual crystal grain, crystal grain Pellet Warhead diameter about 0.08 microns, and the diameter of " grenade " shape bullet is suitable with bullet shank diameter, whole crystal grain almost presents bar-shaped.
When degree of crystallinity is identical, crystallite dimension is less, then crystalline region number is more, and the constraint of crystalline region to amorphous region strand is stronger.By the amorphous region strand that crystalline region fetters, be called as the chain that is obstructed, the ratio that the chain that is obstructed accounts for total amorphous strand is along with the reduction of crystallite dimension, the increase of number of dies and increasing, and then make (the free body integration rate of fractional free volume in amorphous region, FFV) reduce, also can have influence on the diameter R of amorphous region microchannel.In the high-performance polypropylene film that the present invention is above-mentioned, there is the crystallite district of numerous grenade shapes.These crystallite districts add the ratio of the chain that is obstructed, fetter the dispersion of the random coil shape of the chain that is obstructed, make some be obstructed chain from a crystallite district out after, the composition also do not disperse to form free water cement ratio, just participating in rapidly next crystallite district, this situation significantly can reduce amorphous region free water cement ratio quantity undoubtedly.Positron annihilation analysis shows, the polypropylene film that the nanometer titanium dioxide silicon composition adding different proportion is formed, its free water cement ratio diameter is 3.13 nanometers, little with the free water cement ratio diameter difference of unmodified polypropylene film, but number of cavities obviously reduces, the free body integration rate in the present invention in each layer of high-performance polypropylene film is finally impelled to be minimized.For these reasons, this polypropylene film in the present invention is made to have better combination property.
In the above-mentioned polypropylene film of the present invention, the thickness of each layer can adjust according to concrete performance requirement.In a preferred embodiment, the gross thickness of above-mentioned high-performance polypropylene film is 18 ~ 20 μm, and wherein the thickness of topmost thin film is 3 ~ 5 μm, and the thickness of lower film is 3 ~ 5 μm.By the THICKNESS CONTROL of layer each in three layers in above-mentioned scope, the combination property of polypropylene film can be improved further, make it have properties advantage concurrently, meet the requirements of flexible packaging industry.
In the present invention high-performance polypropylene film each layer in the acrylic resin that adopts can be the conventional acrylic resin in this area.In a preferred embodiment, above-mentioned first polypropylene, the second polypropylene and tripropylene be separately selected from polypropylene F280, X37F, 2605, one or more in FC801M, F800EDF and F-603.This several polypropylene has good processing characteristics, and wide material sources, price is lower.
The high-performance polypropylene film that the present invention is above-mentioned, in the nanometer titanium dioxide silicon composition of employing, the particle diameter of preferred nanometer silicon dioxide particle is 15 ~ 20nm; More preferably, modifier is selected from one or more in ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic acid series copolymer, PEO and PLA.Further preferably, in nanometer titanium dioxide silicon composition, the weight percentage of nanometer silicon dioxide particle is 54%.Particularly, above-mentioned nanometer titanium dioxide silicon composition can be prepared according to the preparation technology recorded in CN101724176, CN102020796 and CN103189441, not repeat them here.
According to a further aspect in the invention, additionally provide a kind of preparation method of above-mentioned high-performance polypropylene film, it comprises the following steps: nanometer titanium dioxide silicon composition is carried out melt blending with the first polypropylene, the second polypropylene and tripropylene respectively, obtains the first modified polypropene, the second modified polypropene and the 3rd modified polypropene respectively; First modified polypropene, the second modified polypropene and the 3rd modified polypropene are carried out three-layer co-extruded biaxial tension film forming, forms high-performance polypropylene film.
In above-mentioned preparation method provided by the invention, first nanometer titanium dioxide silicon composition is carried out melt blending with the first polypropylene, the second polypropylene and tripropylene respectively, recycle three-layer co-extruded biaxial tension film forming, preparation has the polypropylene film of topmost thin film (printed layers or the composite bed with other film), core layer film and lower film (food contact layer) three-decker.Due to the nanometer titanium dioxide silicon composition all containing certain content in each layer, this nanometer titanium dioxide silicon composition comprises nanometer silicon dioxide particle and the modifier of certain content, each layer film is made to have specific performance, specific as follows: core layer film, compared with conventional polypropylene resin film, has higher modulus and elongation at break.As the skeleton of three-decker polypropylene film, the sandwich layer of high-modulus can improve stiffness of thin film, and realize the minimizing of packaging, higher elongation at break improves the puncture resistant ability of film.Topmost thin film has lower diffusion coefficient and low solubility parameter to small solvent molecule.So just effectively reduce the residual quantity of solvent in polypropylene film in printing-ink or adhesive, improve the security of polypropylene film.Lower film then has the lower coefficient of kinetic friction, can adapt to the demand of automatically packaging, can avoid adding slipping agent in this layer and the pollution that brings to food.In addition, this high-performance polypropylene film is except improve foodsafety, and its mechanical property, resistance oxygen, block-water performance, heat endurance have to be improved largely, can meet the multiple performance requirement of flexible packaging industry.
Specifically, in the above-mentioned preparation method of the present invention, make use of three-layer co-extruded biaxial tension and become this polypropylene film of film preparation.Utilize heterogeneous nucleating effect and the biaxial tension effect of nano-silicon dioxide particle simultaneously, the degree of crystallinity of polypropylene film can be improved.Make its degree of crystallinity even can reach 38 ~ 39%, improve 8.5 ~ 11% than the degree of crystallinity of plain polypropylene F280 polypropylene film.Meanwhile, above-mentioned technique can also make crystallite dimension reduce, and crystal grain quantity increases, and this will make essence molecule (limonene) and solvent molecule diffusion path tortuosity in the film increase, and diffusion path is elongated, and diffusion coefficient reduces.In addition, in polypropylene film, between the strand of amorphous region, channel diameter R (D is about 3.13nm) is although change is little, and duct quantity (number of cavities) reduces, and makes fractional free volume relatively reduce 3.2 ~ 7.2%.The reduction of fractional free volume makes solvent molecule or limonene molecule solubility in the film reduce.This suitable crystal region and amorphous region microstructure for the residue of reduction solvent molecule in high performance thin film, to reduce polypropylene very important to the absorption of perfume materials.
In addition, in high-performance polypropylene film prepared by said method, the glass transition temperature (Tg) of each layer is 22.2 ~ 24.7 DEG C, improve 3.9 ~ 6.4 DEG C than common F280 trade mark polypropylene film, illustrate that nano silicon exists larger intermolecular force between amorphous region and polypropylene molecular chain.Infrared spectrum analysis demonstrates this viewpoint, 472 in polypropylene film
-1the flexural vibrations peak red shift to 463 of place Si-O
-1place, illustrates that silica and polypropylene segment attract each other and causes Si-O key die down and red shift occurs.Theoretical according to Polymer Physics, the glass transition temperature of polymer is higher, then its free body integration rate is less, and diffusion coefficient in this film of solvent or limonene Small molecular and solubility all can reduce.The glass transition temperature of polymer is higher, and deflection, the elastic modelling quantity of film are also higher, and the barrier of film to the gas of oxygen and steam is also improved.The oxygen percent of pass of high-performance polypropylene film obtained in the present invention is at 1400 ~ 1850ml/m
2.day.atm, between, 37 ~ 53% are reduced than conventional polypropylene films.High-performance polypropylene film water steam percent of pass is at 3.35 ~ 3.88g/m
2.day.95%RH, between, 34 ~ 43% are reduced than conventional polypropylene films.
In a preferred embodiment, in the process of three-layer co-extruded biaxial tension film forming, longitudinal stretching ratio is 4 ~ 5, and cross directional stretch ratio is 9 ~ 10.
High stretching ratio makes polypropylene segment height-oriented, the polypropylene segment after orientation adsorb by the nano-silicon dioxide particle in nanometer titanium dioxide silicon composition (nano particle has high surface energy).Under the extended state of orientation stress, be positioned at a little higher than degree of orientation away from nano-silicon dioxide particle place polypropylene segment of the degree of orientation of the polypropylene segment of nano-silicon dioxide particle surrounding, therefore be parallel to each other near the segment of nano-silicon dioxide particle and be attracted to the surface of particle, segment will complete crystallization in extremely short moment, forms crystallite particles one by one.
Simultaneously, nano silicon exists only in crystal region, and is not present in amorphous region, and this is the effect due to high elongation orientation, make the chain segment orientation Du Genggao around silicon dioxide granule, unavoidably mutually reset and adsorbed and crystallization by high surface energy silicon dioxide granule.Under the double action of the incorgruous nucleation of above-mentioned high power stretch processes combining nano silica, the crystal grain in high-performance polypropylene film is made to present unique grenade-shaped crystal grain.
In a word, based on the effect of above-mentioned high power stretch processes and the incorgruous nucleation of nano silicon, the polypropylene film that the above-mentioned preparation method of the present invention is obtained has unique microstructure, and then significantly improves the combination property of film.
In the preparation process of reality, preferably, the temperature 220 ~ 250 DEG C of extrusion screw rod in the process of three-layer co-extruded biaxial tension film forming, screw speed is 40 ~ 50rpm, and pressure is 40 ~ 50bar, and die temperature is 230 ~ 235 DEG C.Above-mentioned process conditions can improve the combination property of polypropylene film further.
Be described in further detail the application below in conjunction with specific embodiment, these embodiments can not be interpreted as restriction the application scope required for protection.
Film performance test method:
The test of the moisture-vapor transmission (WVTR) of film is according to " GB/T1037-88 plastic sheeting and sheet material water vapor permeability test method ", and it is 50cm that film is cut into area
2circle, adopts the model of Mocon company of the U.S. to be the test of Model3/33 water vapor permeation rate tester; According to OTR oxygen transmission rate (OTR) and the carbon dioxide percent of pass of " GB/T1038-2000 plastic sheeting and thin slice gas-premeable test method pressure differential method " testing film, tester to be Mocon company of U.S. model be 8001 OTR oxygen transmission rate tester.Utilize MOCON820 type headspace analysis instrument, test the gas concentration lwevel in crisper and oxygen concentration every day.
The Mechanics Performance Testings such as hot strength, Young's modulus, elongation at break, use Instron-5565A electronic tensile machine, test at temperature (253 ± 2) DEG C according to " GB/T1040-92 plastic tensile method for testing performance " and " GB13022-91 stretched plastic film method for testing performance ", biaxial stretching film batten size: 20mm × 150mm, gauge length 100mm, test rate 200mm/min.
Crystal property is tested, and uses DSC-200PC differential scanning calorimeter, according to " mensuration of GB/T19466.3-2004 plastics differential scanning calorimetry (DSC) the 3rd partial melting and crystallization temperature and heat content " test.Temperature is arranged: from room temperature to 210 DEG C, heating rate 20 DEG C/min, and insulation 5min, is then cooled to 50 DEG C, rate of temperature fall 10 DEG C/min, and insulation 5min, to eliminate thermal history; Then 210 DEG C are warmed up to from 50 DEG C, speed 20 DEG C/min.According to the endothermic peak area of heating curve, calculate degree of crystallinity.
FTIR spectrum (FTIR), utilize Japanese Shimadzu Corporation FTIR-8400SFTIR apparatus measures, wave-length coverage is 400 ~ 4000cm
-1, resolution ratio is 0.85cm
-1, signal to noise ratio is 20000:1.
Thermogravimetric (TG) is analyzed, and adopt Netzsch company's T G-209 thermogravimetric analyzer, measuring tempeature scope is 20 DEG C ~ 500 DEG C, and protection gas is nitrogen, heating rate 15 DEG C/min.
Positron annihilation is composed, and tester is the high-resolution positron annihilation life spectrometer of Institute of High Energy Physcis, Academia Sinica, is fast-conventional positron annihilation life spectrometer of meeting slowly, adopts
22na radioactive source is as positron source, and source strength is about 13 microcuries, and detector adopts a pair BaF
2probe, temporal resolution is about 205ps, and fitting software is LT9.0, adopts the free matching of three life-spans; Two same samples are clamped at
22the both sides of Na radioactive source, form the structure of " sandwich "; Button derived components: 385ps, 19.50%.Positron annihilation spectrum is in order to survey its free water cement ratio diameter R.
The coefficient of kinetic friction and confficient of static friction adopt Instron-5565A electronic tensile machine to measure, and measure coefficient of friction, gliding cable structure=100mm/min with reference to GB10006-88 method.
The mensuration of solubility S and diffusion coefficient D, according to the method mensuration introduced at the Research Literature " Masstransferoftoluenevaporthroughprotectivepolymergloves " of JournalofMembraneScience magazine 409-410 upper 2012 year phase (180 ~ 190 pages) of Li-HsinCheng etc.; Cut the film sample of 8cm × 8cm, flood different time in acetone, record the curve that quality in time increases, test and average for 10 times.
Dissolvent residual analysis after film print: on intaglio press, print in the side, upper strata of high-performance polypropylene film with chlorinated polypropylene ink, ordinary polypropylene film also adopts identical process conditions printing, test the dissolvent residual value after two kinds of film prints respectively: the film after print is cut into the size that specification is 3cm × 8cm, printing surface is rolled into tubular inwardly, installing to volume is in 10ml ml headspace bottle, add 1ml triacetyl glycerine (internal standard compound), utilize Agilent7890A/5975C type look-matter combined instrument to measure organic solvent residual value; Headspace sample bottle is heated to 80 DEG C, insulation duration of oscillation 45min, sample size is 0.5ml; Chromatographic condition: VOC capillary column (Agilent19091R-316), 60m × 0.32mm × 1.80 μm, carrier gas is high-purity helium, injector temperature 150 DEG C, carrier gas flux 1.0Lmin
-1, split ratio 10:1, temperature programming (initial temperature 40 DEG C, retention time 3min, rises to 80 DEG C with 2 DEG C/min, then rises to 180 DEG C with 8 DEG C/min); Mass Spectrometry Conditions: electron impact ion source (EI), electron energy 70eV, transmission line temperature 230 DEG C, ion source temperature 170 DEG C, ion trap temperature 180 DEG C, TIC pattern, quality of scanning scope m/z30 ~ 150; Analysis result uses NIST retrieval and standard substance contrast retention time to carry out component qualification.
Film is analyzed aromatic odor retentivity: by the internal layer of three-layer co-extruded for high-performance film towards inboard, makes the freshness protection package 1 of three bandings of 5cm × 15cm size, and the fresh squeezing lemon juice of filling 20ml, tests the total concentration of lemon material in freshness protection package head space for 30 days afterwards; Utilize common three-layer co-extruded polypropylene film also to make the freshness protection package 2 of formed objects, the fresh squeezing lemon juice of filling 20ml, and make freshness protection package 2 head space volume identical with freshness protection package 1, within 30 days, test the total concentration of lemon material in freshness protection package head space afterwards; Agilent7890A gas-chromatography is utilized to test each material concentration in freshness protection package head space; The total concentration of lemon material is characterized with the gross area at each peak.More containing aromatic odor content of material in head space, illustrate that the barrier of film to aroma gases (smell) is higher.
Embodiment 1
With reference to the method that patent CN101724176, CN102020796 and CN103189441 propose, prepare nanometer titanium dioxide silicon composition, wherein nano-silicon dioxide particle accounts for 54% of said composition gross mass, and concrete operation step is as follows:
Be equipped with stirring, dropping funel, thermometer capacity 50 liters reactor in add 10Kg solid content be 50% EVA emulsion. setting stir speed (S.S.) 100rpm, temperature is 50 degree, adds Powdered polyethylene oxide resin 50g and PLA 50g.Stir after 30 minutes, add the water glass solution that 25Kg dioxide-containing silica is 24%, stir 30 minutes, drip 40% sulfuric acid, until PH=5.5, then be warming up to 70 degree, drip 40% sulfuric acid until PH=7.0, continue stirring 30 minutes, then washing removing sulfate ion, press filtration, dry, pulverize and be prepared into nanometer titanium dioxide silicon composition.
By the nanometer titanium dioxide silicon composition of 1.0Kg and the F280 acrylic resin of 99.0Kg after 210 ~ 230 DEG C of melt blendings, granulating and drying, obtain sandwich layer resin raw material;
Three extruders of three-layer co-extruded biaxial tension equipment all add this sandwich layer resin, and the temperature of setting three extrusion screw rods is all 230 DEG C, and cross directional stretch ratio is 10, and longitudinal stretching ratio is 5, and screw speed is 48rpm, and pressure is 45bar, and die temperature is 230 DEG C.Obtain the polypropylene film (the Nomenclature Composition and Structure of Complexes is identical with core layer film) that thickness is the single structure of 18 μm.The SEM photo of this polypropylene film as shown in Figure 1.
Embodiment 2
Other condition, with embodiment 1, changes nano silicon composition levels.After the F280 acrylic resin melt blending of the nanometer titanium dioxide silicon composition of 2.6Kg and 97.4Kg, granulating and drying, obtain upper strata resin raw material;
Three extruders of three-layer co-extruded biaxial tension equipment all add this upper strata resin, and the temperature of setting three extrusion screw rods is all 230 DEG C, and cross directional stretch ratio is 9, and longitudinal stretching ratio is 4, and screw speed is 48rpm, and pressure is 45bar, and die temperature is 230 DEG C.Obtain the polypropylene film (the Nomenclature Composition and Structure of Complexes is identical with topmost thin film) that thickness is the single structure of 18 μm.
Embodiment 3
Other condition, with embodiment 1, changes nano silicon composition levels.After the F280 acrylic resin melt blending of the nanometer titanium dioxide silicon composition of 4.0Kg and 96.0 mass parts, granulating and drying, obtain lower-layer resin raw material;
Three extruders of three-layer co-extruded biaxial tension equipment all add this lower-layer resin, and the temperature of setting three extrusion screw rods is all 230 DEG C, and cross directional stretch ratio is 9, and longitudinal stretching ratio is 5, and screw speed is 48rpm, and pressure is 45bar, and die temperature is 230 DEG C.Obtain the polypropylene double-way stretched film (the Nomenclature Composition and Structure of Complexes is filled a prescription identical with same lower film) that thickness is the single structure of 18 μm.
Embodiment 4
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide silicon composition of different quality mark and F280 acrylic resin after 210 ~ 230 DEG C of melt blendings, granulating and drying, obtain nano silicon composition levels be 2.6% upper strata modified resin, nano silicon composition levels be 1.0% sandwich layer modified resin and nano silicon composition levels be 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, sandwich layer modified resin is added in sandwich layer extruder hopper, lower-layer modified resin is added in lower floor's extruder hopper, the temperature of setting three extrusion screw rods is all 230 DEG C, cross directional stretch ratio is 10, longitudinal stretching ratio is 5, control the upper and lower extruder screw rotating speed and be respectively 50rpm and 50rpm, pressure is 45bar, die temperature is 230 DEG C, obtaining upper thickness is 3 μm, lower thickness is 3 μm, core layer thickness be 12 μm 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 silicon composition of different quality mark and F280 acrylic resin after 210 ~ 230 DEG C of melt blendings, granulating and drying, obtain nano silicon composition levels be 2.6% upper strata modified resin, nano silicon composition levels be 1.0% sandwich layer modified resin and nano silicon composition levels be 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, sandwich layer modified resin is added in sandwich layer extruder hopper, lower-layer modified resin is added in lower floor's extruder hopper, the temperature of setting three extrusion screw rods is all 230 DEG C, cross directional stretch ratio is 10, longitudinal stretching ratio is 5, control the upper and lower extruder screw rotating speed and be respectively 50rpm and 50rpm, pressure is 45bar, die temperature is 230 DEG C, obtaining upper thickness is 5 μm, lower thickness is 5 μm, core layer thickness be 10 μm three-layer co-extruded go out bidirectional stretching polypropylene film.
Embodiment 6
Thin film preparation process is with embodiment 5, and just cross directional stretch multiplying power 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 silicon composition of different quality mark and F280 acrylic resin after 210 ~ 230 DEG C of melt blendings, granulating and drying, obtain nano silicon composition levels be 2.8% upper strata modified resin, nano silicon composition levels be 1.5% sandwich layer modified resin and nano silicon composition levels be 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, sandwich layer modified resin is added in sandwich layer extruder hopper, lower-layer modified resin is added in lower floor's extruder hopper, the temperature of setting three extrusion screw rods is all 230 DEG C, cross directional stretch ratio is 9, longitudinal stretching ratio is 4, control the upper and lower extruder screw rotating speed and be respectively 44rpm and 44rpm, pressure is 43bar, die temperature is 230 DEG C, obtaining upper thickness is 5 μm, lower thickness is 5 μm, core layer thickness be 10 μm 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 silicon composition of different quality mark and F280 acrylic resin after 210 ~ 230 DEG C of melt blendings, granulating and drying, obtain nano silicon composition levels be 2.3% upper strata modified resin, nano silicon composition levels be 0.7% sandwich layer modified resin and nano silicon composition levels be 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, sandwich layer modified resin is added in sandwich layer extruder hopper, lower-layer modified resin is added in lower floor's extruder hopper, the temperature of setting three extrusion screw rods is all 230 DEG C, cross directional stretch ratio is 8, longitudinal stretching ratio is 2, control the upper and lower extruder screw rotating speed and be respectively 40rpm and 40rpm, pressure is 45bar, die temperature is 230 DEG C, obtaining upper thickness is 5 μm, lower thickness is 5 μm, core layer thickness be 10 μm three-layer co-extruded go out bidirectional stretching polypropylene film.
Comparative example 1
Thin film preparation process, with embodiment 1, just prepares with common F280 acrylic resin the film that thickness is 18 μm.
Comparative example 2
Thin film preparation process, with embodiment 5, just prepares with common F280 acrylic resin the film that thickness is 20 μm.
Comparative example 3
The preparation process of nanometer titanium dioxide silicon composition is with embodiment 1, respectively by the nanometer titanium dioxide silicon composition of different quality mark and F280 acrylic resin after 210 ~ 230 DEG C of melt blendings, granulating and drying, obtain nano silicon composition levels be 3.5% upper strata modified resin, nano silicon composition levels be 2.5% sandwich layer modified resin and nano silicon composition levels be 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, sandwich layer modified resin is added in sandwich layer extruder hopper, lower-layer modified resin is added in lower floor's extruder hopper, the temperature of setting three extrusion screw rods is all 230 DEG C, cross directional stretch ratio is 5, longitudinal stretching ratio is 2, control the upper and lower extruder screw rotating speed and be respectively 46rpm and 46rpm, pressure is 45bar, die temperature is 230 DEG C, obtaining upper thickness is 5 μm, lower thickness is 5 μm, core layer thickness be 10 μm three-layer co-extruded go out bidirectional stretching polypropylene film.
According to aforesaid method of testing in embodiment 1 to 8 and comparative example 1 to 3 preparation polypropylene film carry out performance characterization, characterization result as shown in Table 1 and Table 2:
Table 1
Table 2
As can be seen from above data, under high magnification biaxial tension condition, the upper strata of single layer structure, middle level and core layer film, have different microstructures, highlight its some feature performance, make its microstructure be more conducive to improve the security and functional of packaging.In topmost thin film add 1.3% nano silicon, make it have the finest and close amorphous region structure, namely free body integration rate be minimum, degree of crystallinity is the highest, diffusion coefficient D and solubility S minimum.When making topmost thin film and adhesive or ink contact, solvent molecule is slack-off to the diffusion of film sandwich layer, avoid causing too much dissolvent residual, but the problem that adhesion strength is inadequate or ink adhesion is not enough can not be caused, because the effect that the modifier in nanometer titanium dioxide silicon composition and the nano-silicon dioxide particle of polarity all can play to be increased polypropylene film polarity, improve polypropylene film and layer of ink (or adhesive phase) affinity, layer of ink (or adhesive phase) is improved with the bonding strength of interlayer on polypropylene.The lower film obtained after the nano silicon of interpolation 2.0%, not only amorphous region compact structure, free body integration rate is little, D and S in film microcosmic duct is little for Small molecular, but also there is unique surface texture, make film surface have the lower coefficient of kinetic friction, be particularly suitable for the demand of packaging automatically, avoid the pollution that slipping agent brings to food.In the nano silicon situation of interpolation 0.5%, nano particle is able to better dispersion in acrylic resin, at utmost play heterogeneous nucleating effect, acrylic resin crystal region crystal grain quantity is increased, crystal size is little, this microstructure is given sandwich layer and is had higher intensity and toughness, make core layer film excellent in mechanical performance, there is higher hot strength and elongation at break (toughness), this is beneficial to the stability improving biaxial tension process, the high-modulus characteristic that sandwich layer has is beneficial to the deflection improving packaging, reduce the difficulty of bag, be beneficial to minimizing packaging.
Utilize the three-layer co-extruded polypropylene film that the internal layer with specific microstructure designed by the present invention, sandwich layer, upper strata resin-made are standby, topmost thin film and other Film laminated or printed time, solvent residual quantity in the film in ink or adhesive is little, lower floor is food contact layer, coefficient of friction is applicable to the needs of packaging automatically, there is not slipping agent to pollute, and the microstructure of this inner compact layer also can stop aromatic odor molecule to the diffusion of sandwich layer, reduce the absorption of packaging to fragrance, improve the fragrance protectiveness energy of packaging.The three-layer co-extruded film of this high-performance polypropylene is except having higher food security performance, and resistance oxygen, block-water performance, heat endurance are improved all largely, improve the defencive function to food.
Under low range pulled out condition (2 × 3), such as embodiment 6, the properties of nano modification film is all lower than high magnification pulled out condition (4 ~ 5) × (9 ~ 10), this illustrates under low range stretching condition, the degree of orientation of polypropylene segment is lower, and around nano-silicon dioxide particle, degree of orientation is inadequate, can not better be adsorbed by silica, or few by the segment quantity of adsorbing, the heterogeneous nucleating effect of silica plays insufficient.Under low range pulled out condition, the crystallite dimension of the modified polypropene crystal region prepared is comparatively large, crystal grain quantity relatively high stretching ratio time few, cause barrier properties for gases, aromatic odor barrier slightly low, but still be better than common unmodified polypropylene film.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a high-performance polypropylene film, is characterized in that, comprising:
Topmost thin film, by the weight percent meter of described topmost thin film, described topmost thin film comprises the nanometer titanium dioxide silicon composition of 2.0 ~ 3.0% and first polypropylene of 97.0 ~ 98.0%;
Core layer film, on the surface, by the weight percent meter of described core layer film, described core layer film comprises the described nanometer titanium dioxide silicon composition of 0.5 ~ 2.0% and second polypropylene of 99.5 ~ 98.0% in the side being positioned at described topmost thin film;
Lower film, be positioned at the side away from described topmost thin film of described core layer film on the surface, by the weight percent meter of described lower film, described lower film comprises the described nanometer titanium dioxide silicon composition of 3.5 ~ 5.0% and the tripropylene of 96.5 ~ 95%;
Wherein, by the weight percent meter of described nanometer titanium dioxide silicon composition, described nanometer titanium dioxide silicon composition comprises the nanometer silicon dioxide particle of 50 ~ 55% and the modifier of 45 ~ 50%.
2. high-performance polypropylene film according to claim 1, is characterized in that,
By the weight percent meter of described topmost thin film, described topmost thin film comprises the described nanometer titanium dioxide silicon composition of 2.3 ~ 2.8% and described first polypropylene of 97.2 ~ 97.7%;
By the weight percent meter of described core layer film, described core layer film comprises the described nanometer titanium dioxide silicon composition of 0.7 ~ 1.5% and described second polypropylene of 98.5 ~ 99.3%;
By the weight percent meter of described lower film, described lower film comprises the described nanometer titanium dioxide silicon composition of 3.7 ~ 4.5% and the described tripropylene of 95.5 ~ 96.3%.
3. high-performance polypropylene film according to claim 2, is characterized in that,
By the weight percent meter of described topmost thin film, described topmost thin film comprises the described nanometer titanium dioxide silicon composition of 2.6% and described first polypropylene of 97.4%;
By the weight percent meter of described core layer film, described core layer film comprises the described nanometer titanium dioxide silicon composition of 1.0% and described second polypropylene of 99.0%;
By the weight percent meter of described lower film, described lower film comprises the described nanometer titanium dioxide silicon composition of 4.0% and the described tripropylene of 96.0%.
4. high-performance polypropylene film according to any one of claim 1 to 3, is characterized in that, the degree of crystallinity of described high-performance polypropylene film is 30 ~ 39%;
Preferably, the glass transition temperature of described high-performance polypropylene film is 22.2 ~ 24.7 DEG C;
Preferably, the crystal grain of described high-performance polypropylene film is grenade-shaped crystal grain, and described grenade-shaped crystal grain comprises Pellet Warhead and column bullet handle;
Preferably, in described grenade-shaped crystal grain, the particle diameter of described Pellet Warhead is 0.08 ~ 0.1 μm, and the radial width of described column bullet handle is 0.04 ~ 0.08 μm, and the axial length of described column bullet handle is 0.8 ~ 1.6 μm.
5. high-performance polypropylene film according to any one of claim 1 to 3, it is characterized in that, the gross thickness of described high-performance polypropylene film is 18 ~ 20 μm, and the thickness of wherein said topmost thin film is 3 ~ 5 μm, and the thickness of described lower film is 3 ~ 5 μm.
6. high-performance polypropylene film according to any one of claim 1 to 3, it is characterized in that, described first polypropylene, described second polypropylene and described tripropylene be separately selected from polypropylene F280, X37F, 2605, one or more in FC801M, F800EDF and F-603.
7. high-performance polypropylene film according to any one of claim 1 to 3, is characterized in that, the particle diameter of described nanometer silicon dioxide particle is 5 ~ 20nm; Preferably, described modifier is selected from one or more in ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic acid series copolymer, PEO and poly-PLA.
8. a preparation method for the high-performance polypropylene film according to any one of claim 1 to 7, is characterized in that, comprise the following steps:
Nanometer titanium dioxide silicon composition is carried out melt blending with the first polypropylene, the second polypropylene and tripropylene respectively, obtains the first modified polypropene, the second modified polypropene and the 3rd modified polypropene respectively;
Described first modified polypropene, described second modified polypropene and described 3rd modified polypropene are carried out three-layer co-extruded biaxial tension film forming, forms described high-performance polypropylene film.
9. preparation method according to claim 8, is characterized in that, in the process of described three-layer co-extruded biaxial tension film forming, longitudinal stretching ratio is 4 ~ 5, and cross directional stretch ratio is 9 ~ 10.
10. preparation method according to claim 9, is characterized in that, in the process of described three-layer co-extruded biaxial tension film forming, the temperature of extrusion screw rod is 220 ~ 250 DEG C, screw speed is 40 ~ 50rpm, and pressure is 40 ~ 50bar, and die temperature is 230 ~ 235 DEG C.
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Cited By (2)
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| CN105926079A (en) * | 2016-06-24 | 2016-09-07 | 深圳市新纶科技股份有限公司 | Polypropylene film splitting fibers and preparation method thereof as well as air filtering material prepared from polypropylene film splitting fibers |
| CN109266233A (en) * | 2018-08-08 | 2019-01-25 | 北京众邦健业印刷有限责任公司 | Tape substrate, adhesive tape and preparation method with it |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102964683A (en) * | 2012-12-03 | 2013-03-13 | 北京印刷学院 | Polypropylene modified master batch and low-residual solvent polypropylene flexible package thin film |
-
2015
- 2015-12-01 CN CN201510888580.7A patent/CN105538855B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102964683A (en) * | 2012-12-03 | 2013-03-13 | 北京印刷学院 | Polypropylene modified master batch and low-residual solvent polypropylene flexible package thin film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105926079A (en) * | 2016-06-24 | 2016-09-07 | 深圳市新纶科技股份有限公司 | Polypropylene film splitting fibers and preparation method thereof as well as air filtering material prepared from polypropylene film splitting fibers |
| CN109266233A (en) * | 2018-08-08 | 2019-01-25 | 北京众邦健业印刷有限责任公司 | Tape substrate, adhesive tape and preparation method with it |
| CN109266233B (en) * | 2018-08-08 | 2021-02-19 | 北京众邦健业印刷有限责任公司 | Adhesive tape base material, adhesive tape with same and preparation method |
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