CN106166882A - A kind of biaxial tension thin polymer film and preparation method and application - Google Patents

A kind of biaxial tension thin polymer film and preparation method and application Download PDF

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Publication number
CN106166882A
CN106166882A CN201610262621.6A CN201610262621A CN106166882A CN 106166882 A CN106166882 A CN 106166882A CN 201610262621 A CN201610262621 A CN 201610262621A CN 106166882 A CN106166882 A CN 106166882A
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thin polymer
film
polymer film
film layer
layer
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CN106166882B (en
Inventor
董侠
王笃金
王峰
阳明书
赵莹
周勇
张建伟
张德清
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Guangdong Zhongke Huatong New Mstar Technology Ltd
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Institute of Chemistry CAS
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Priority to PCT/CN2016/090007 priority patent/WO2017185533A1/en
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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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

A kind of biaxial tension thin polymer film, base film layer, the superficial film of multi-component copolymer polyolefin formation including olefin polymer formation, the described intermediate layer that base film layer is described thin polymer film, 110 brilliant for the α of described thin polymer film crystal faces have the orientation of the both direction of equatorial direction and meridian direction, the platelet long period of equatorial direction is 28～42, and the platelet long period of meridian direction is 37～46；Preferably, the polyolefinic fusing point of the multi-component copolymer of superficial film is less than the olefin polymer of base film layer.The invention also discloses the preparation method of this thin polymer film, this thin polymer film has higher transparency, high strong and unyielding property, anti tear, low temperature resistant, the performance of dimensionally stable.

Description

A kind of biaxial tension thin polymer film and preparation method and application
Technical field
The invention belongs to thin polymer film field, particularly to a kind of biaxial tension thin polymer film and preparation method thereof with Application.
Background technology
Biaxially oriented polypropylene (BOPP) thin film has light weight, transparent, nontoxic, moistureproof, breathability is low, mechanical strength is high Advantage, is widely used in the packaging of the products such as food, medicine, daily light industry, medicated cigarette, and is used as the base material of composite membrane in a large number.From Nineteen fifty-seven polypropylene (PP) Resin Industry metaplasia puerperal, each company of the world competitively develops BOPP thin film, Italy in 1958 Montecatini company initiates BOPP thin film fabrication techniques, and nineteen fifty-nine and 1962 are American-European and Japan starts to produce, at present in succession BOPP thin film yearly productive capacity in the whole world has reached 2,820,000 tons, and annual production is more than 1,550,000 tons, and yield is annual also with 15% The increasing rate of left and right.
Current thin film processing mode has two kinds, periosteum method peace embrane method.Periosteum method equipment is cheap, loses without rim charge, difficult wide Width, speed of production is low；Change condition and range is narrow；Vertically and horizontally balancing performance, thickness evenness is poor, and percent thermal shrinkage is big, surface Easily scratch；Be suitable to various thermoplastic, shrink film, the film that difficult system is thicker can be heated.
Flat embrane method divides again two-way two step pulling methods and two-way once step stretching method.The most two-way two step pulling method equipment are expensive, limit Material loss is more, easily realizes high speed, and efficiency is high；Change condition and range width；Vertically and horizontally performance has unbalanced, but film thickness Uniformly, good stability of the dimension；Can make very thin to extremely thick film, also can high-strength membrane processed.It is presently the most common commercialization best Processing mode.Two-way once step stretching method apparatus expensive, rim charge loss is many, it is difficult to realize high speed；And stretching ratio change is certainly Little by degree, products thickness is restricted, and advantage is vertically and horizontally balancing performance.Do not used on a large scale at present.
Wherein, the technological process of two-way two step pulling methods is: raw material → extrusion → curtain coating → longitudinal stretching → cross directional stretch → trimming → sided corona treatment → rolling → be aged → cut → finished product.
BOPP thin film is generally the coextruded multilayer structure of 3-5 layer, and step drawing production technology is mainly by following operation group Become: dispensing, batch mixing, extrude, by T-shaped die head extrusion sheet, sheet chilling, sheet is preheated by heating roller, sheet longitudinally Stretching, thermal finalization, preheat again, cross directional stretch, thermal finalization, cooling, sided corona treatment, rolling, cut and put in storage.
Publication number CN101160209A discloses a kind of Biaxially stretched multilayer polypropylene film, and it is being polymerized by propylene The Biaxially oriented polypropylene that the propylene polymer composition (A) that in thing (a1), interpolation inorganic compound powder (a2) is formed obtains The two sides of film substrate layer (B), possesses the surface layer containing acrylic polymer (a1) and back layer, table, the surface of back layer Roughness (three-dimensional center face mean roughness SRa) is less than 0.08 μm, and glossiness (angle of incidence 60 degree) is more than 114%, and double Total light transmittance to stretching multilayer polypropylene film is less than 20%, and density is 0.40～0.65g/cm3Scope, described Thin film obtains by the following method: by coextrusion mold method, the acrylic polymer forming substrate layer is obtained multi-layer sheet, The simultaneously bi-directionally biaxially oriented film forming method such as pulling method or sequentially biaxial tension method is used to be stretched to face multiplying power (longitudinally × horizontal stroke To) 45～65 times and obtain.As a example by using sequentially biaxial tension method, can pass through at a temperature of longitudinally 70～140 DEG C with 4.5 ～after the scope stretching of 7.5 times, then under the temperature range of horizontal 120～190 DEG C under 7～12 times and face multiplying power (longitudinally × laterally) be stretched to 45～65 times after, obtain at the temperature range heat fixation of 110～180 DEG C.
Publication number CN102198748A discloses the BOPP thin film of a kind of applicable shallow reticulated printing, and this thin film is by multi-layer co-extruded Stretch processes forms the three-decker with printing face layer, sandwich layer and bottom, and wherein printing face layer is except containing major ingredient poly-third Outside olefine resin, possibly together with the inorganic spherical tissue adhesion masterbatch that particle diameter is 1.5～2 μ and spherical organic anti-company that particle diameter is 2.5～3 μ Masterbatch, inorganic tissue adhesion masterbatch percentage by weight in printing face layer is 1.5%～2.0%, and organic anti-even masterbatch is in printing Percentage by weight in surface layer is 0.5～1.0%.Present invention also offers the life of a kind of above-mentioned applicable shallow reticulated printing BOPP thin film Product method, the method include dispensing, batch mixing, melt extrude, the operation such as slab, longitudinal stretching, cross directional stretch and traction rolling, logical Cross extruder die head and the control of chilling roll temperature, improve the degree of crystallinity of film surface further.
Publication number CN105235336A discloses a kind of low temperature resistant bidirectional stretching polypropylene film and processing technology thereof, should Polypropylene film is made up of low temperature resistant anti-sticking layer, low temperature resistant sandwich layer and low temperature resistant corona processing layer from outside to inside, the most low temperature resistant Sandwich layer is made up of HOPP 30～70%, thermoplastic elastic masterbatch 10～40%, low temperature resistant masterbatch 20～50%, resistance to low Temperature anti-sticking layer and low temperature resistant corona processing layer be all by modification by copolymerization polypropylene 50～70%, low temperature resistant masterbatch 25-40%, dioxy SiClx antiblocking agent 2～10% is made, and the preparation method of the present invention is complicated, and low temperature resistant can only arrive-30 DEG C.
The hot strength of BOPP thin film the most of the prior art is high, the transparency is good, but resistance to low temperature, tear-resistant and Deflection can not meet existing requirement, along with sending out of China's food, medicine, Nicotiana tabacum L., electronic apparatus, press and high-end purposes Exhibition, the domestic demand to BOPP thin film will be continuously increased, and its product quality also will propose higher requirement simultaneously.State at present The thickness range of interior BOPP thin film is usually less than 50um, and current technology is typically difficult to the thick film preparing thickness more than 50um.And state Interior BOPP thin film PP Pipe Compound still has 80% dependence on import, has many dedicated films also to still need to import.Expect to propose new Research Thinking Solve BOPP thin film high transparent and high-stiffness but there is again the demand of resistance to low temperature, high-tear strength simultaneously.
For these reasons, the special proposition present invention.
Summary of the invention
It is an object of the invention to provide a kind of have double orientation feature, high transparency, anti tear, dimensionally stable, thickness Bigger thin polymer film, applies at print field.
For reaching the above purpose of the present invention, the present invention adopts the following technical scheme that
The first object of the present invention is to provide a kind of biaxial tension thin polymer film, the matrix formed including olefin polymer The superficial film that film layer, multi-component copolymer polyolefin are formed, the described intermediate layer that base film layer is described thin polymer film, institute 110 brilliant for the α of the thin polymer film stated crystal faces have the orientation of the both direction of equatorial direction and meridian direction, equatorial direction Platelet long period be 28～42, the platelet long period of meridian direction is 37～46；
Preferably, the polyolefinic fusing point of the multi-component copolymer of superficial film is less than the olefin polymer of base film layer.
Owing at that same temperature, the tensile property of the material of low melting point to be prone to dystectic material, select relatively low The polyolefin of the superficial film of fusing point, can the most effectively adjust the thickness of surface layer, obtain thickness evenness more Good thin polymer film.
Preferably, described thin polymer film is more than 93% in angle of incidence 60 degree mensuration glossiness；
The thin polymer film of the present invention also has suitable surface roughness.Roughness has influence on the size of glossiness, light Pool is spent low, and color and luster is dark and gloomy, and surface is unsightly；The degree of roughness on surface also can affect ink transfer velocity and, if ink Shifting insufficient, the surface of printing can produce the deep or light speckle of image.Mainly it is subject to processing temperature due to surface roughness, produces speed The impact of the process conditions such as degree, corona intensity, adjusting process of the present invention controls surface crystallization and the solid state of thin film, controls thin The glossiness of film is within the specific limits.
Preferably, thickness is 60～90um；Thickness in prior art is generally below 50um, and polymerization prepared by the present invention Thing thin film is 60～90um.
Preferably, mist degree is less than 1.30%；Mist degree have impact under glossiness and the transparency of thin film, especially imaging degree Fall, the present invention selects suitable mist degree, thus thin polymer film has more preferable transparency.
Preferably, degree of crystallinity is 35～77%；The polymer thin film resin of the present invention has higher degree of crystallinity, and degree of crystallinity exists 35～77% scope.Owing to the degree of crystallinity of material affects the transparency of thin film, degree of crystallinity is high, and the transparency will be deteriorated, and crystallization The surface free energy spending high material is low, causes printing rear surface layer ink and the poor adhesive force of adhesive.Meanwhile, highly crystalline shape The more non-crystalline portion of macromolecule of state, strand arrangement is regular, and compactness is high, and the binder molecule on surface is difficult to matrix surface Internal diffusion.But the too low meeting of degree of crystallinity makes Film stiffness low.Therefore, for the transparency, printing and the rigidity etc. of Balanced films The comprehensive excellent properties of mechanical property, needs the degree of crystallinity in control film manufacturing process and crystallite dimension within the specific limits, The degree simultaneously controlling double orientation solves the problem of vertically and horizontally mechanical heterogeneity, the balance of regulation and control mechanical property.
Preferably, glass transition temperature is-65～-35 DEG C.
The thin polymer film of the present invention has relatively low glass transition temperature, surface structured polymer film at low temperatures Stable, keep good flexility, there is preferable resistance to low temperature.
Preferably, described olefin polymer includes poly-third hydrocarbon, polyethylene, ethylene propylene copolymer, alhpa olefin or alhpa olefin One or more in copolymer, described surface layer also includes inorganic nanoparticles, low temperature material or delustering agent, described Inorganic nanoparticles is fatty acid metal salts, calcium carbonate or calcined silica, preferably glass microballoon, glass micropowder, nanometer titanium dioxide Silicon, described low temperature material is random copolymer, preferably butadiene-styrene random copolymer, vinyl chloride-vinyl acetate without Rule copolymer.
It is to reduce the adhesion effect between polymer that the present invention adds the effect of inorganic nanoparticles, and properly increases polymerization The polarity of thing film surface, if adhesion effect is stronger, polymeric film surface is coarse, processing difficulties, and surface gloss is poor, Nano-particle solves cosmetic issue, and by anti effect so that speed of production improves.The low temperature material on top layer is general For the polymer with side chain, when the polymer with side chain is grafted on the main chain of thin polymer film, thin film can be made Surface smoothness reduces, and has certain roughness so that the top layer microphase-separated of strand, thus the surface of thin polymer film Microstructured patterns.
Preferably, olefin polymer 75～99% described by percentage to the quality, inorganic nanoparticles 1～12%, resistance to Cryogenic material 0～8%, delustering agent 0～7%.
The present inventor through substantial amounts of test find, formed the raw material olefin polymer of base film layer, inorganic nanoparticles, Low temperature material, delustering agent could form the polymer thin of high transparency, anti tear, dimensionally stable in above-mentioned proportion Film.
Preferably, described base film layer is n-layer, and wherein n is 1-5, preferably 3 layers, and preferred substrate film layer is more than or equal to 2 Time, also include tacky film layer between base film layer.
When base film layer is 1 layer, thin polymer film includes base film layer and superficial film, when base film layer is more than or equal to When 2 layers, it is connected by tacky film layer between base film layer with base film layer.
When base film layer is more than or equal to 2, the olefin polymer of every layer of composition base film layer is identical or different, preferably constitutes base The olefin polymer of body film layer is identical.
When the olefin polymer of base film layer is identical, the uniformity of the thin polymer film of formation is preferable, lear energy By force.
Preferably, the orientation of described equatorial direction is more than the orientation of described meridian direction, preferably described polymer The strand of thin film is parallel to equator.
It is due to biaxial tension that thin polymer film has the orientation of both direction, should be stretching induction crystallization simultaneously Effect so that thin polymer film has higher degree of crystallinity and little crystallite dimension, thus shows the higher transparency, resistance to tears Fragility can be high, and tensile property is good, deflection advantages of higher.
Second object of the present invention is to provide the preparation method of a kind of thin polymer film, described preparation method include as Under:
(1) raw material of base film layer and tacky film layer is put into extrusion in extruder；
(2) after above-mentioned raw materials extrusion, flowing through T-shaped die head and form composite bed coextrusion sheet, the operating temperature of die head is 180 ～350 DEG C, the sheet of gained is cooled down molding, chilling temperature is 20～60 DEG C；
(3) sheet preheating step (2) obtained, at temperature is 100～200 DEG C, carries out longitudinal stretching, stretching 5～ 10 times, at temperature 180～300 DEG C, carry out cross directional stretch, stretch 6～18 times；
(4) being then passed through single or double sided corona treatment, making the test at winder obtains biaxial tension thin polymer film.
Preferably, in step (1), the extrusion temperature of base film layer is 150～350 DEG C, and the extrusion temperature of tacky film layer is 130～300 DEG C.The degree of crystallinity of the thin polymer film obtained under this extrusion temperature is moderate, has the more preferable transparency.
The thin polymer film prepared by this method has higher transparency, high strong and unyielding property, anti tear, low temperature resistant, chi Very little stable polymer multi-layer laminated film.
The third object of the present invention is to provide the application at print field of a kind of biaxial tension thin polymer film.
Compared with prior art, present invention have the advantage that
(1) thin polymer film glossiness of the present invention is more than 93%, and mist degree is less than 1.30%, and degree of crystallinity is 35 ～77%, described thin polymer film 110 crystal face has the orientation of the both direction of equatorial direction and meridian direction, equator side To long period be 28～42, the long period of meridian direction is 37～46；
(2) thin polymer film of the present invention has higher transparency, high strong and unyielding property, anti tear, low temperature resistant, dimensionally stable Performance.
(3) thin polymer film of the present invention is higher than common polyolefin biaxially oriented film (thickness is less than 50um), thickness Between 60-90um.
Accompanying drawing explanation
Fig. 1 embodiment 1～7 two dimension WAXS figure；
The one-dimensional WAXS curve chart of Fig. 2 embodiment 1～7；
The azimuth integral curve figure of Fig. 3 embodiment 1～7 (110) crystal face；
The azimuth integral curve figure of Fig. 4 embodiment 1～7 (111) crystal face；
Fig. 5 embodiment 1～7 two dimension SAXS figure；
The one-dimensional SAXS curve chart of Fig. 6 embodiment 1～7 equatorial direction；
The one-dimensional SAXS curve of Fig. 7 embodiment 1～7 meridian direction；
The front Electronic Speculum figure of the thin polymer film that Fig. 8 a embodiment 4 obtains；
The front Electronic Speculum figure of the thin polymer film that Fig. 8 b embodiment 4 obtains；
The reverse side Electronic Speculum figure of the thin polymer film that Fig. 9 a embodiment 4 obtains；
The reverse side Electronic Speculum figure of the thin polymer film that Fig. 9 b embodiment 4 obtains；
The front Electronic Speculum figure of the thin polymer film that Figure 10 a embodiment 5 obtains；
The front Electronic Speculum figure of the thin polymer film that Figure 10 b embodiment 5 obtains；
The reverse side Electronic Speculum figure of the thin polymer film that Figure 11 a embodiment 5 obtains；
The reverse side Electronic Speculum figure of the thin polymer film that Figure 11 b embodiment 5 obtains；
The front Electronic Speculum figure of the thin polymer film that Figure 12 a embodiment 7 obtains；
The front Electronic Speculum figure of the thin polymer film that Figure 12 b embodiment 7 obtains；
The reverse side Electronic Speculum figure of the thin polymer film that Figure 13 a embodiment 7 obtains；
The reverse side Electronic Speculum figure of the thin polymer film that Figure 13 b embodiment 7 obtains；
Differently-oriented directivity figure (Machine direction correspondence that the thin polymer film strand of Figure 14 present invention is main Noon line direction, Transverse direction correspondence equatorial direction).
Wherein, a in figure, b, c, d, e, f, g represent embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, reality Execute example 6, embodiment 7.
Detailed description of the invention
Embodiment in following example can be further combined or replace, and embodiment is only to the present invention's Preferred embodiment is described, and is not defined the spirit and scope of the present invention, without departing from design philosophy of the present invention Under premise, the various changes and modifications that in this area, technical scheme is made by professional and technical personnel, belong to this Bright protection domain.
The evaluation of performance
WAXS Yu SAXS is tested respectively at the Radix Rumicis line station (BL14B1) of SSRF and little linea angulata station by the present invention (BL16B1) carry out.The X-ray light wave of light source is a length ofThe detector of WAXS is MAR 225, resolution is 3072 × 3072 pixels (Pixel Dimensions=73 × 73 μm 2), the detector of SAXS is MAR 165, resolution be 2048 × 2048 pixels (as Element size=79 × 79 μm 2).During test, the time of exposure of WAXS Yu SAXS is respectively 60s and 150s, and sample is to detector Distance respectively 336.5mm and 2024.1mm.All of image has all deducted backscatter, air scattering and light fluctuation Impact.By being integrated obtaining integrated intensity I (q) (q=4 π sin θ/λ) of two dimension SAXS in the range of different orientations Φ.
Utilization Bragg Equation for Calculating long period (L):
qmaxCorresponding to the abscissa value of summit on scattering curve.The intensity of equatorial direction and meridian direction respectively- Integration in the range of 45 °≤Φ≤45 ° and 45 °≤Φ≤135 °.
Sampling in following example is all on bigger thin film, the draw direction clip fritter marked along Figure 14 Film sample.
Embodiment 1
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains poly-third by percentage to the quality Alkene 75%, Silicon stone 12%, butadiene-styrene random copolymer 8%, delustering agent silicon dioxide 5%, the wherein temperature of extruder It it is 150 DEG C；The raw material of tacky film layer puts in a subsidiary extruder, and extrusion temperature is 200 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 180 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 20 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 1000 DEG C, carries out longitudinal stretching, stretches 5 times, in temperature Carry out cross directional stretch at spending 180 DEG C, stretch 6 times；
(4) through two-sided sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
Embodiment 2
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains poly-third by percentage to the quality Alkene 80%, glass microballoon 12%, butadiene-styrene random copolymer 8%, wherein the temperature of extruder is 180 DEG C；By gluing The raw material of film layer puts in a subsidiary extruder, and extrusion temperature is 250 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 200 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 30 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 150 DEG C, carries out longitudinal stretching, stretches 6 times, in temperature Carry out cross directional stretch at spending 200 DEG C, stretch 9 times；
(4) through one side sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
Embodiment 3
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains ethylene by percentage to the quality Propylene copolymer 85%, nano silicon 2%, vinyl chloride-vinyl acetate copolymer 8%, delustering agent silicon dioxide 5%, its The temperature of middle extruder is 250 DEG C；Being put in a subsidiary extruder by the raw material of tacky film layer, extrusion temperature is 300 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 250 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 20 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 200 DEG C, carries out longitudinal stretching, stretches 8 times, in temperature Carry out cross directional stretch at 200 DEG C, stretch 18 times；
(4) through one side sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
Embodiment 4
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains poly-1-by percentage to the quality Butylene 96%, glass micropowder 3%, delustering agent silica 1 %, wherein the temperature of extruder is 300 DEG C；Former by tacky film layer Material puts in a subsidiary extruder, and extrusion temperature is 350 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 350 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 30 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 200 DEG C, carries out longitudinal stretching, stretches 10 times, Carry out cross directional stretch at temperature 300 DEG C, stretch 15 times；
(4) through two-sided sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
Fig. 8 a between the front Electronic Speculum figure of the thin polymer film obtained, Fig. 8 b, reverse side Electronic Speculum figure is shown in Fig. 9 a, Fig. 9 b.
Embodiment 5
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains polyphenyl by percentage to the quality Ethylene 90%, calcium carbonate 8%, delustering agent silicon dioxide 2%, wherein the temperature of extruder is 300 DEG C；Raw material by tacky film layer Putting in a subsidiary extruder, extrusion temperature is 250 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 300 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 50 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 200 DEG C, carries out longitudinal stretching, stretches 6 times, in temperature Carry out cross directional stretch at 200 DEG C, stretch 8 times；
(4) through two-sided sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
Figure 10 a between the front Electronic Speculum figure of the thin polymer film obtained, Figure 10 b, reverse side Electronic Speculum figure is shown in Figure 11 a, Figure 11 b.
Embodiment 6
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains poly-third by percentage to the quality Alkene 82%, Silicon stone 12%, butadiene-styrene random copolymer 6%, wherein the temperature of extruder is 200 DEG C；By tacky film layer Raw material put in a subsidiary extruder, extrusion temperature is 250 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 200 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 60 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 150 DEG C, carries out longitudinal stretching, stretches 6 times, in temperature Carry out cross directional stretch at 300 DEG C, stretch 8 times；
(4) through two-sided sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
Embodiment 7
(1) being put in extruder by the raw material of base film layer, wherein said raw material contains poly-third by percentage to the quality Alkene 80%, Silicon stone 10%, butadiene-styrene random copolymer 5%, delustering agent silicon dioxide 5%, the wherein temperature of extruder It it is 200 DEG C；Being put in a subsidiary extruder by the raw material of tacky film layer, extrusion temperature is 250 DEG C；
(2) above-mentioned raw materials is extruded after fusion plastification, flows through T-shaped die head and forms composite bed coextrusion sheet, the work of die head Being 250 DEG C as temperature, cooled for the sheet of gained roller and tank are cooled down molding, the temperature of chill roll and tank is 25 DEG C；
(3) being preheated by heating roller by sheet above, temperature is 160 DEG C, carries out longitudinal stretching, stretches 7 times, in temperature Carry out cross directional stretch at 260 DEG C, stretch 8 times；
(4) through two-sided sided corona treatment, make the test at winder and obtain biaxial tension thin polymer film.
The thin polymer film obtained being carried out mechanical property and thickness measuring is shown in Table 1, (110) are long-pending with the azimuth of (111) Point the long period of half-peak breadth and its direction and meridian direction under the line be shown in Table 2, two dimension WAXS is shown in Fig. 1, one-dimensional WAXS curve Seeing Fig. 2, the azimuth integral curve of (110) crystal face is shown in Fig. 3, and the azimuth integral curve of (111) crystal face is shown in Fig. 4, two dimension SAXS Seeing Fig. 5, the one-dimensional SAXS curve of equatorial direction is shown in Fig. 6, and the one-dimensional SAXS curve of meridian direction is shown in Fig. 7.
The front Electronic Speculum figure of the thin polymer film obtained is shown in that Figure 12 a, Figure 12 b, reverse side Electronic Speculum figure are shown in Figure 13 a, Figure 13 b.
The main differently-oriented directivity of embodiment 1～7 thin polymer film strand is shown in Figure 14.
As seen from Figure 2, except the sample of embodiment 1, other 6 kinds of film samples in 2 θ=11.4 °, 13.6 °, 15.0 °, 17.0 ° all occur in that 5 diffraction maximums with 17.6 °, correspond respectively to (110) of polypropylene α crystalline substance, (040), (130), (111) with the diffraction of (-131) crystal face.2 θ of the diffraction maximum of thin film-2 θ somewhat offset, and move about 0.4 ° to low angle.
As seen from Figure 1, the diffraction pattern of these 7 kinds of film samples is diffraction arc, oriented crystal i.e. occurs.It addition, (110) crystal face of these 7 kinds of film samples all occurs in that the orientation of both direction: equatorial direction and meridian direction, and this may be with It is that biaxial stretching film is relevant.But, the orientation in they directions under the line is stronger, say, that strand is predominantly parallel to laterally Arrangement.
Table 1
Table 2

Claims (10)

1. a biaxial tension thin polymer film, it is characterised in that include base film layer, multi-component copolymer that olefin polymer formed The superficial film that polyolefin is formed, the described intermediate layer that base film layer is described thin polymer film, described polymer thin 110 brilliant for the α of film crystal faces have the orientation of the both direction of equatorial direction and meridian direction, the platelet long period of equatorial direction Being 28～42, the platelet long period of meridian direction is 37～46；
Preferably, the polyolefinic fusing point of the multi-component copolymer of superficial film is less than the olefin polymer of base film layer.
Thin polymer film the most according to claim 1, it is characterised in that described thin polymer film angle of incidence 60 degree Measuring glossiness is more than 93%；Preferably, thickness is 60～90um；Preferably, mist degree is less than 1.30%；Preferably, degree of crystallinity is 35～77%；Preferably, glass transition temperature is-65～-35 DEG C.
Thin polymer film the most according to claim 1, it is characterised in that described olefin polymer includes poly-third hydrocarbon, gathers One or more in ethylene, ethylene propylene copolymer, alhpa olefin or alpha olefin copolymer, described surface layer also includes inorganic receiving Rice grain, low temperature material or delustering agent, described inorganic nanoparticles is fatty acid metal salts, calcium carbonate or calcined silica, Preferably glass microballoon, glass micropowder, nano silicon, described low temperature material is random copolymer, preferably butadiene-benzene Ethylene atactic copolymer, vinyl chloride-vinyl acetate random copolymer.
4. according to the thin polymer film described in claim 1-3 any one, it is characterised in that described in by percentage to the quality Olefin polymer 75～99%, inorganic nanoparticles 1～12%, low temperature material 0～8%, delustering agent 0～7%.
Thin polymer film the most according to claim 1, it is characterised in that described base film layer is n-layer, wherein n is 1- 5, preferably 3 layers, when preferred substrate film layer is more than or equal to 2, between base film layer, also include tacky film layer.
Thin polymer film the most according to claim 5, it is characterised in that when base film layer is more than or equal to 2, every layer of composition base The olefin polymer of body film layer is identical or different, and the olefin polymer preferably constituting base film layer is identical.
7. according to the thin polymer film described in claim 1～6 any one, it is characterised in that taking of described equatorial direction To the orientation more than described meridian direction, the strand of preferably described thin polymer film is parallel to equator.
8. the preparation method of the thin polymer film described in claim 1～7 any one, it is characterised in that described system Preparation Method includes the following:
(1) respectively the raw material of base film layer and tacky film layer is extruded；
(2) above-mentioned raw materials extrusion after, flow through T-shaped die head formed composite bed coextrusion sheet, the operating temperature of die head be 180～ 350 DEG C, the sheet of gained being cooled down molding, chilling temperature is 20～60 DEG C；
(3) sheet preheating step (2) obtained, at temperature is 100～200 DEG C, carries out longitudinal stretching, stretches 5～10 times, At temperature 180～300 DEG C, carry out cross directional stretch, stretch 6～18 times；
(4) being then passed through single or double sided corona treatment, making the test at winder obtains biaxial tension thin polymer film.
The preparation method of thin polymer film the most according to claim 8, it is characterised in that base film layer in step (1) Extrusion temperature is 150～350 DEG C, and the extrusion temperature of tacky film layer is 130～300 DEG C.
10. the biaxial tension thin polymer film described in claim 1～7 any one is in the application of print field.
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