WO2017185533A1 - 一种双向拉伸聚合物薄膜及其制备方法与应用 - Google Patents

一种双向拉伸聚合物薄膜及其制备方法与应用 Download PDF

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WO2017185533A1
WO2017185533A1 PCT/CN2016/090007 CN2016090007W WO2017185533A1 WO 2017185533 A1 WO2017185533 A1 WO 2017185533A1 CN 2016090007 W CN2016090007 W CN 2016090007W WO 2017185533 A1 WO2017185533 A1 WO 2017185533A1
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polymer film
polymer
layer
film layer
film
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PCT/CN2016/090007
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English (en)
French (fr)
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董侠
王笃金
王峰
阳明书
赵莹
周勇
张建伟
张德清
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中国科学院化学研究所
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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

Definitions

  • the invention belongs to the field of polymer films, and in particular relates to a biaxially stretched polymer film and a preparation method and application thereof.
  • Biaxially oriented polypropylene (BOPP) film has the advantages of light weight, transparency, non-toxicity, moisture resistance, low gas permeability and high mechanical strength. It is widely used in the packaging of food, medicine, daily light industry, cigarettes, etc. A substrate for a composite film. Since the industrial production of polypropylene (PP) resin in 1957, the world companies competed to develop BOPP film. In 1958, Montecatini of Italy pioneered the production of BOPP film. In 1959 and 1962, Europe, America and Japan began production. The production capacity has reached 2.82 million tons, the annual output exceeds 1.55 million tons, and the output is increasing at a rate of about 15% per year.
  • PP polypropylene
  • the tube membrane method is cheap, the material is lost, the width is not wide, the production speed is low, the condition range is narrow, the longitudinal and lateral properties are balanced, the thickness uniformity is poor, the heat shrinkage rate is large, the surface is easily scratched, and it is suitable for various thermoplastics.
  • the heat shrinkable film can be made, and it is difficult to make a thick film.
  • the flat film method is divided into a two-way two-step stretching method and a two-way one-step stretching method.
  • the two-way two-step stretching method has more expensive and marginal material loss, easy to achieve high speed, high efficiency; wide range of changing conditions; uneven longitudinal and lateral properties, but uniform film thickness and good dimensional stability; To a very thick film, a high-strength film can also be produced. It is the best processing method for the most general commercialization.
  • the two-way one-step stretching method is expensive, the material loss is large, and it is difficult to achieve high speed; and the degree of freedom of stretching magnification is small, the thickness of the product is limited, and the advantage is that the vertical and horizontal properties are balanced. It has not been adopted on a large scale.
  • the two-step two-step stretching process is: raw material ⁇ extrusion ⁇ casting ⁇ longitudinal stretching ⁇ transverse stretching ⁇ trimming ⁇ corona treatment ⁇ winding ⁇ aging ⁇ slitting ⁇ finished product.
  • the BOPP film is generally a 3-5 layer co-extruded multilayer structure.
  • the step-by-step drawing production process mainly consists of the following processes: batching, compounding, extrusion, extruding thick sheets through a T-die, and slab cooling, The slab is preheated by a heating roll, slab longitudinally stretched, heat set, reheated, transversely stretched, heat set, cooled, corona treated, wound, slitted and warehousing.
  • Publication No. CN101160209A discloses a biaxially stretched laminated polypropylene film obtained by biaxially pulling a propylene-based polymer composition (A) formed by adding an inorganic compound powder (a2) to a propylene-based polymer (a1).
  • the both sides of the polypropylene film base layer (B) are provided with a surface layer and a back layer containing the propylene polymer (a1), and the surface roughness (three-dimensional center plane average roughness SRa) of the front and back layers is less than 0.08 ⁇ m.
  • the gloss (incident angle of 60 degrees) is 114% or more, and the total light transmittance of the biaxially stretched laminated polypropylene film is 20% or less and the density is in the range of 0.40 to 0.65 g/cm 3 . It is obtained that a propylene-based polymer forming a substrate layer is obtained by a co-extrusion method to obtain a multilayer sheet, and is stretched to a face ratio by a biaxial stretching film forming method such as a simultaneous biaxial stretching method or a sequential biaxial stretching method (portrait) ⁇ transverse) is obtained 45 to 65 times.
  • a biaxial stretching film forming method such as a simultaneous biaxial stretching method or a sequential biaxial stretching method (portrait) ⁇ transverse
  • the sequential biaxial stretching method can be stretched in the range of 4.5 to 7.5 times in the longitudinal direction at a temperature of 70 to 140 ° C, and then 7 to 12 times in the temperature range of 120 to 190 ° C in the transverse direction. Further, the surface magnification (longitudinal direction ⁇ transverse direction) was stretched to 45 to 65 times, and then obtained by heat setting in a temperature range of 110 to 180 °C.
  • CN102198748A discloses a BOPP film suitable for shallow web printing, which is formed into a three-layer structure having a printing surface layer, a core layer and a bottom layer by a multilayer coextrusion biaxial stretching process, wherein the printing surface layer contains a main ingredient.
  • the polypropylene resin also contains a spherical inorganic anti-blocking masterbatch having a particle diameter of 1.5 to 2 ⁇ and a spherical organic anti-joint masterbatch having a particle diameter of 2.5 to 3 ⁇ , and the weight percentage of the inorganic anti-blocking masterbatch in the printing surface layer is 1.5.
  • the invention also provides a production method suitable for the above-mentioned shallow-screen printing BOPP film, which comprises the steps of compounding, mixing, melt-extruding, casting, longitudinal stretching, transverse stretching and drawing and winding, etc. Control of the temperature of the exit die and the chill roll further increases the crystallinity of the film surface.
  • Publication No. CN105235336A discloses a low temperature resistant biaxially oriented polypropylene film which is composed of a low temperature resistant anti-adhesion layer, a low temperature resistant core layer and a low temperature resistant corona treatment layer from the outside to the inside, wherein the polypropylene film is composed of a low temperature resistant anti-adhesion layer, a low temperature resistant core layer and a low temperature resistant corona treatment layer.
  • the low temperature resistant core layer is made of 30 to 70% of homopolypropylene, 10 to 40% of thermoplastic elastomer masterbatch, and 20 to 50% of low temperature resistant masterbatch.
  • the low temperature resistant anti-adhesive layer and the low temperature resistant corona treatment layer are all
  • the copolymerized modified polypropylene is 50-70%
  • the low temperature resistant masterbatch is 25-40%
  • the silica antiblocking agent is 2-10%.
  • the preparation method of the invention is complicated, and the low temperature resistance can only reach -30 °C.
  • the above prior art BOPP film has high tensile strength and good transparency, but the low temperature resistance, tear resistance and stiffness can not meet the existing requirements, along with China's food, medicine, tobacco, electronic appliances, printing industry And the development of high-end use, the domestic demand for BOPP film will continue to increase, and at the same time, the quality of its products will also put forward higher requirements.
  • the thickness of domestic BOPP film is usually less than 50um, and the current technology is generally difficult to prepare a thick film with a thickness exceeding 50um.
  • domestic BOPP film special materials are still 80% dependent on imports, there are many special membranes still need to be imported. Looking forward to proposing new research ideas to solve the high transparency and high stiffness of BOPP film At the same time, however, it has the requirement of low temperature resistance and high tear strength.
  • the present invention has been made in view of the above reasons.
  • the present invention adopts the following technical solutions:
  • a first object of the present invention is to provide a biaxially stretched polymer film comprising a base film layer formed of an olefin polymer, a surface film layer formed of a multicomponent copolymerized polyolefin, and the base film layer being the polymer film
  • the 110 crystal plane of the ⁇ crystal of the polymer film has an orientation in two directions of the equatorial direction and the meridional direction, and the length of the lamella in the equatorial direction is 28 to 42, and the period of the crystal in the meridional direction is 37 ⁇ 46;
  • the polymer film Since the long period of the lamella in the equatorial direction of the polymer film is 28 to 42 and the period of the lamella in the meridional direction is 37 to 46, the polymer film has a high crystallinity and a small grain size, thereby exhibiting a high degree.
  • the multi-component copolymerized polyolefin of the surface film layer has a melting point lower than that of the olefin polymer of the base film layer. Since the tensile properties of the low melting point material are easy to be high melting point materials at the same temperature, the polyolefin of the lower melting point surface film layer is selected, and the thickness of the surface layer can be effectively adjusted in the production process to obtain thickness uniformity. A better polymer film.
  • the polymer film has a gloss of 93% or more at an incident angle of 60 degrees;
  • the polymer film of the present invention also has an appropriate surface roughness. Roughness affects the degree of gloss, the gloss is too low, the color is dull, and the surface is not beautiful; the roughness of the surface also affects the transfer speed of the ink. If the ink transfer is insufficient, the surface of the printed product will produce a thick image. Since the surface roughness is mainly affected by process conditions such as processing temperature, production speed, and corona strength, the present invention adjusts the surface crystallization and solidification state of the film to control the gloss of the film within a certain range. The glossiness of the present invention was measured using a hand-held gloss meter (Model: Micro Tri Gloss-BYK Gardner).
  • the thickness is 60 to 90 um; the thickness in the prior art is generally less than 50 um, and the polymer film prepared by the present invention is 60 to 90 um, and the thickness of the present invention is measured using a JIS P 8118 thickness gauge.
  • the haze is 1.30% or less; the haze in the present invention refers to the percentage of incident light transmitted through the film which is deflected or scattered more than 2.5 degrees from the incident light direction, and the haze of the film can be measured by ASTM method D1003.
  • the photometric or turbidimeter is used to determine that the haze affects the gloss and transparency of the film, especially the decrease in imageability.
  • the present invention selects a suitable haze so that the polymer film has better transparency.
  • the degree of crystallinity is from 35 to 77%; the polymer film resin of the present invention has a high degree of crystallinity and a crystallinity in the range of from 35 to 77%. Since the crystallinity of the material affects the transparency of the film, the crystallinity is high, the transparency is deteriorated, and the surface free energy of the material having high crystallinity is low, resulting in poor adhesion of the surface layer ink and the adhesive after printing. At the same time, the polymer in the high crystalline state is more irregular than the uncrystallized portion, the molecular chain is aligned, and the denseness is high, and the surface of the binder molecule is difficult to diffuse into the surface of the substrate.
  • the glass transition temperature is from -65 to -35 °C.
  • the polymer film of the invention has a lower glass transition temperature, which indicates that the polymer film structure is stable at a low temperature, maintains good flexibility, and has good low temperature resistance.
  • the olefin polymer comprises one or more of a polyhydrocarbon, a polyethylene, an ethylene propylene copolymer, an alpha olefin or an alpha olefin copolymer
  • the surface layer further comprises inorganic nanoparticles, low temperature resistant materials.
  • the inorganic nanoparticle is a fatty acid metal salt, calcium carbonate or calcined silica, preferably glass microbeads, glass micropowder, nano silica
  • the low temperature resistant material is a random copolymer, preferably butadiene. a styrene random copolymer or a vinyl chloride-vinyl acetate random copolymer.
  • the function of the inorganic nanoparticles added in the invention is to reduce the adhesion between the polymers and to appropriately increase the polarity of the surface of the polymer film. If the adhesion is relatively strong, the surface of the polymer film is rough, the processing is difficult, and the surface gloss is poor. The particles solve the surface problem and increase the production speed through anti-blocking action.
  • the low temperature resistant material for the surface layer is generally a branched polymer. When the branched polymer is grafted onto the main chain of the polymer film, the surface flatness of the film is lowered and has a certain roughness. The surface microphase of the molecular chain is separated, so that the surface microstructure of the polymer film is patterned.
  • the olefin polymer is 75 to 99% by mass
  • the inorganic nanoparticles are 1 to 12%
  • the low temperature resistant material is 0 to 8%
  • the matting agent is 0 to 7%.
  • the inventors have found through extensive experiments that the raw material olefin polymer, inorganic nanoparticles, low temperature resistant material and matting agent which form the base film layer can form a highly transparent, tear resistant and dimensionally stable polymer film within the above ratio range. .
  • the base film layer is an n layer, wherein n is 1-5, preferably 3 layers, and preferably, when the base film layer is 2 or more, the adhesive film layer is further included between the base film layers.
  • the polymer film includes a base film layer and a surface film layer, when the base film layer is larger than When it is equal to two layers, the base film layer and the base film layer are connected by an adhesive layer.
  • the olefin polymer of each of the base film layers is the same or different, and it is preferred that the olefin polymer constituting the base film layer is the same.
  • the formed polymer film has good uniformity and strong tear resistance.
  • the orientation in the equatorial direction is greater than the orientation in the meridional direction, and preferably the molecular chain of the polymer film is parallel to the equator.
  • the polymer film has orientation in two directions due to biaxial stretching, and should be tensile-induced crystallization, so that the polymer film has high crystallinity and small grain size, thereby exhibiting high transparency. Sex, high tear resistance, good tensile properties and high stiffness.
  • a second object of the present invention is to provide a method for preparing a polymer film, which comprises the following methods:
  • a T-die is formed to form a composite layer to coextrude the thick sheet, the working temperature of the die is 180-350 ° C, and the obtained slab is cooled and formed, and the cooling temperature is 20-60 ° C. ;
  • the slab obtained in the step (2) is preheated, longitudinally stretched at a temperature of 100 to 200 ° C, stretched 5 to 10 times, and transversely stretched at a temperature of 180 to 300 ° C, and stretched. 6 to 18 times;
  • the extrusion temperature of the base film layer is 150 to 350 ° C, and the extrusion temperature of the adhesive film layer is 130 to 300 ° C.
  • the polymer film obtained at this extrusion temperature has a moderate crystallinity and a better transparency.
  • the polymer film prepared by the method has a high transparency, high toughness, tear resistance, low temperature resistance, dimensional stability of the polymer multilayer composite film.
  • a third object of the present invention is to provide a biaxially stretched polymer film for use in the field of printing.
  • the present invention has the following advantages:
  • the polymer film of the present invention has a gloss of 93% or more, a haze of 1.30% or less, and a crystallinity of 35 to 77%, and the polymer film 110 has a crystal plane having two in the equatorial direction and the meridional direction.
  • the orientation of the directions is 28 to 42 in the equatorial direction and 37 to 46 in the meridian direction;
  • the polymer film of the present invention has high transparency, high toughness, tear resistance, low temperature resistance, and dimensional stability.
  • the polymer film of the present invention is higher than a conventional polyolefin biaxially oriented film (thickness less than 50 um), The thickness is between 60-90 um.
  • Figure 1 embodiment 1-7 two-dimensional WAXS diagram
  • Figure 2 is a one-dimensional WAXS graph of Embodiments 1-7;
  • Figure 3 is an azimuth angle integral curve of the crystal planes of Embodiments 1-7 (110);
  • Figure 4 is an azimuthal integral curve of the crystal planes of Embodiments 1-7 (111);
  • Figure 5 is a two-dimensional SAXS diagram of Embodiments 1-7;
  • Figure 6 is a one-dimensional SAXS graph of the equator directions of Embodiments 1 to 7;
  • Figure 7 is a one-dimensional SAXS curve in the meridian direction of Embodiments 1-7;
  • Figure 8a is a front electron micrograph of the polymer film obtained in Example 4.
  • Figure 8b is a front electron micrograph of the polymer film obtained in Example 4.
  • Figure 9a is a reverse electron micrograph of the polymer film obtained in Example 4.
  • Figure 9b is a reverse electron micrograph of the polymer film obtained in Example 4.
  • Figure 10a is a front electron micrograph of the polymer film obtained in Example 5.
  • Figure 10b is a front electron micrograph of the polymer film obtained in Example 5.
  • Figure 11a is a reverse electron micrograph of the polymer film obtained in Example 5.
  • Figure 11b is a reverse electron micrograph of the polymer film obtained in Example 5.
  • Figure 12a is a front electron micrograph of the polymer film obtained in Example 7.
  • Figure 12b is a front electron micrograph of the polymer film obtained in Example 7.
  • Figure 13a is a reverse electron micrograph of the polymer film obtained in Example 7.
  • Figure 13b is a reverse electron micrograph of the polymer film obtained in Example 7.
  • Figure 14 is a main orientation pattern of the molecular chain of the polymer film of the present invention (Machine direction corresponds to the meridional direction, and Transverse direction corresponds to the equator direction).
  • a, b, c, d, e, f, and g represent Embodiment 1, Embodiment 2, Embodiment 3, Embodiment 4, Embodiment 5, Embodiment 6, and Embodiment 7.
  • the WAXS and SAXS tests of the present invention are performed at the wide-angle station (BL14B1) and the small-angle station (BL16B1) of the Shanghai light source, respectively.
  • the wavelength of the X-ray light of the light source is
  • the exposure times of WAXS and SAXS were 60s and 150s, respectively, and the distance from the sample to the detector was 336.5mm and 2024.1mm, respectively. All images are deducted from background scatter, air scatter and light fluctuations.
  • q max corresponds to the abscissa value of the highest peak on the scattering curve.
  • the intensities in the equatorial direction and the meridian direction are integrated in the range of -45° ⁇ ⁇ ⁇ 45° and 45° ⁇ ⁇ ⁇ 135°, respectively.
  • the sampling in the following examples was performed on a larger film, and a small piece of film sample was cut along the direction of stretching indicated in FIG.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains, by mass percentage, 75% of polypropylene, 12% of silica, 8% of butadiene-styrene random copolymer, and matting agent 2 5% of silicon oxide, wherein the temperature of the extruder is 150 ° C; the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 200 ° C;
  • the temperature is 1000 ° C, longitudinal stretching, stretching 5 times, transverse stretching at a temperature of 180 ° C, stretching 6 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains 80% of polypropylene, 12% of glass microbeads, and 8% of butadiene-styrene random copolymer by mass percentage, wherein The temperature of the extruder is 180 ° C; the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 250 ° C;
  • the temperature is 150 ° C, longitudinal stretching, stretching 6 times, transverse stretching at a temperature of 200 ° C, stretching 9 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains 85% of ethylene propylene copolymer, 2% of nano silica, 8% of vinyl chloride-vinyl acetate copolymer by mass percentage, and extinction 5% silica, wherein the temperature of the extruder is 250 ° C; the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 300 ° C;
  • the temperature is 200 ° C, longitudinal stretching, stretching 8 times, transverse stretching at a temperature of 200 ° C, stretching 18 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains 96% of poly-1-butene, 3% of glass fine powder, and 1% of matting agent silica by mass percentage, wherein the extruder
  • the temperature is 300 ° C
  • the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 350 ° C;
  • the temperature is 200 ° C, longitudinal stretching, stretching 10 times, transverse stretching at a temperature of 300 ° C, stretching 15 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains 90% of polystyrene, 8% of calcium carbonate, 2% of matting agent silica, and the temperature of the extruder. 300 ° C; the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 250 ° C;
  • the temperature is 200 ° C, longitudinal stretching, stretching 6 times, transverse stretching at a temperature of 200 ° C, stretching 8 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the front electron micrograph of the obtained polymer film is shown in Fig. 10a, Fig. 10b, and the reverse electron micrograph is shown in Fig. 11a and Fig. 11b.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains, by mass percentage, 82% of polypropylene, 12% of silica, 6% of butadiene-styrene random copolymer, wherein extrusion
  • the temperature of the machine is 200 ° C
  • the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 250 ° C;
  • the temperature is 150 ° C, longitudinal stretching, stretching 6 times, transverse stretching at a temperature of 300 ° C, stretching 8 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the raw material of the base film layer is put into an extruder, wherein the raw material contains 80% of polypropylene, 10% of silica, 5% of butadiene-styrene random copolymer, and matting agent 2 by mass percentage. 5% of silicon oxide, wherein the temperature of the extruder is 200 ° C; the raw material of the adhesive layer is put into an auxiliary extruder, the extrusion temperature is 250 ° C;
  • the temperature is 160 ° C, longitudinal stretching, stretching 7 times, transverse stretching at a temperature of 260 ° C, stretching 8 times;
  • the mechanical properties and thickness tests of the obtained polymer films are shown in Table 1.
  • the half-width of the azimuthal integral of (110) and (111) and the long period in the equatorial direction and the meridian direction are shown in Table 2, and the two-dimensional WAXS is shown in the figure.
  • the one-dimensional WAXS curve is shown in Fig. 2
  • the azimuthal integral curve of the (110) crystal plane is shown in Fig. 3
  • the azimuthal integral curve of the (111) crystal plane is shown in Fig. 4
  • the two-dimensional SAXS is shown in Fig. 5
  • the one-dimensional in the equator direction The SAXS curve is shown in Figure 6.
  • the one-dimensional SAXS curve in the meridian direction is shown in Figure 7.
  • the front electron micrograph of the obtained polymer film is shown in Fig. 12a, Fig. 12b, and the reverse electron micrograph is shown in Fig. 13a, Fig. 13b.
  • the 2 ⁇ of the diffraction peak of the film-2 ⁇ was slightly shifted, and moved to a low angle by about 0.4°.
  • the diffraction patterns of the seven film samples are all diffraction gratings, that is, the orientation crystals appear.
  • the (110) crystal faces of the seven film samples showed orientations in two directions: the equatorial direction and the meridional direction, which may be related to the biaxially oriented film. However, they are more oriented in the equator, meaning that the molecular chains are predominantly parallel to the lateral direction.

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Abstract

一种双向拉伸聚合物薄膜及其制备方法，聚合物薄膜包括烯烃聚合物形成的基体膜层、多元共聚聚烯烃形成的表面膜层，基体膜层为聚合物薄膜的中间层，聚合物薄膜的α晶的110晶面具有赤道方向和子午线方向的两个方向的取向，赤道方向的片晶长周期为28～42，子午线方向的片晶长周期为37～46；优选，表面膜层的多元共聚聚烯烃的熔点小于基体膜层的烯烃聚合物。该聚合物薄膜具有较高的透明度、高刚韧性、抗撕裂、耐低温、尺寸稳定的性能。

Description

一种双向拉伸聚合物薄膜及其制备方法与应用 技术领域
本发明属于聚合物薄膜领域，特别涉及一种双向拉伸聚合物薄膜及其制备方法与应用。
背景技术
双向拉伸聚丙烯(BOPP)薄膜具有质轻、透明、无毒、防潮、透气性低、机械强度高等优点，广泛用于食品、医药、日用轻工、香烟等产品的包装，并大量用作复合膜的基材。自1957年聚丙烯(PP)树脂工业化生产后，世界各公司竞相开发BOPP薄膜，1958年意大利Montecatini公司首创BOPP薄膜生产技术，1959年和1962年欧美及日本相继开始生产，目前全世界BOPP薄膜年生产能力已达282万吨，年产量超过155万吨，而且产量每年还在以15％左右的速率递增。
目前薄膜加工方式有两种，管膜法和平膜法。管膜法设备便宜，无边料损失，难宽幅化，生产速度低；变更条件范围狭窄；纵横向性能均衡，厚度均匀性差，热收缩率大，表面易擦伤；适于各种热塑性塑料，可制热收缩膜，难制较厚的膜。
平膜法又分双向二步拉伸法和双向一步拉伸法。其中双向二步拉伸法设备贵、边料损失较多，易实现高速化，效率高；变更条件范围宽；纵横向性能有不均衡，但是薄膜厚度均匀，尺寸稳定性好；能制极薄到极厚的膜，亦可制高强度膜。是目前最为通用商业化最好的加工方式。双向一步拉伸法设备昂贵，边料损失多，难于实现高速化；且拉伸倍率变化自由度小，制品厚度受限制，优点是纵横向性能均衡。目前未被大规模采用。
其中，双向二步拉伸法的工艺流程为：原料→挤出→流延→纵向拉伸→横向拉伸→切边→电晕处理→收卷→陈化→分切→成品。
BOPP薄膜一般为3-5层的共挤出多层结构，分步拉伸生产工艺主要由以下工序组成：配料、混料、挤出、通过T型模头挤出厚片、厚片急冷、对厚片通过加热辊预热、厚片纵向拉伸、热定型、再预热、横向拉伸、热定型、冷却、电晕处理、收卷、分切和入库。
公开号CN101160209A公开了一种双向拉伸层压聚丙烯薄膜，其在由向丙烯系聚合物(a1)中添加无机化合物粉末(a2)形成的丙烯系聚合物组合物(A)得到的双向拉伸聚丙烯薄膜基材层(B)的两面，具备含有丙烯系聚合物(a1)的表面层及背面层，表、背面层的表面粗糙度(三维中心面平均粗糙度SRa)小于0.08μm，光泽度(入射角60度)为114％以上，且双向拉伸层压聚丙烯薄膜的总光线透射率为20％以下，密度为0.40～0.65g/cm3的范围，所述薄膜通过以下方法得到：将形成基材层的丙烯系聚合物通过共挤成型方法得到多层片材，采用同时双向拉伸法或顺次双向拉伸法等双向拉伸薄膜成型方法拉伸至面倍率(纵向×横向)45～65倍而得到。以采用顺次双向拉伸法为例，可通过在纵向70～140℃的温度下以4.5～7.5倍的范围拉伸后，然后在横向120～190℃的温度范围下在7～12倍下且面倍率(纵向×横向)拉伸至45～65倍后，在110～180℃的温度范围热固定而得到。
公开号CN102198748A公开了一种适合浅网印刷的BOPP薄膜，该薄膜由多层共挤出双向拉伸工艺形成具有印刷面层、芯层和底层的三层结构，其中印刷面层除含有主料聚丙烯树脂外，还含有粒径为1.5～2μ的球形无机抗粘连母料和粒径为2.5～3μ的球形有机抗连母料，无机抗粘连母料在印刷面层中的重量百分比为1.5％～2.0％，有机抗连母料在印刷面层中的重量百分比为0.5～1.0％。本发明还提供了一种上述适合浅网印刷BOPP薄膜的生产方法，该方法包括配料、混料、熔融挤出、铸片、纵向拉伸、横向拉伸和牵引收卷等工序，通过对挤出机模头和急冷辊温度的控制，进一步提高薄膜表面的结晶度。
公开号CN105235336A公开了一种耐低温的双向拉伸聚丙烯薄膜及其制作工艺，该聚丙烯薄膜由外到内由耐低温抗粘层、耐低温芯层和耐低温电晕处理层构成，其中耐低温芯层是由均聚聚丙烯30～70％、热塑性弹性母料10～40％、耐低温母料20～50％制成，耐低温抗粘层和耐低温电晕处理层均是由共聚改性聚丙烯50～70％、耐低温母料25-40％、二氧化硅抗粘连剂2～10％制成，本发明的制备方法复杂，且耐低温只能到-30℃。
以上现有技术中的BOPP薄膜的拉伸强度高、透明性好，但是耐低温性能、耐撕裂和挺度满足不了现有的要求，随着我国食品、医药、烟草、电子电器、印刷业和高端用途的发展，国内对BOPP薄膜的需求量将不断增加，同时对其产品质量也将提出更高的要求。目前国内BOPP薄膜的厚度范围通常低于50um，目前技术通常难于制备厚度超过50um的厚膜。且国内BOPP薄膜专用料仍有80％依赖进口，有许多专用膜也仍需进口。期待提出新的研究思路解决BOPP薄膜高透明性和高挺度 但同时又具有耐低温性能、高撕裂强度的需求。
鉴于以上原因，特提出本发明。
发明内容
本发明的目的在于提供一种有双取向特征的、高透明、抗撕裂、尺寸稳定的、厚度较大的聚合物薄膜，应用在印刷领域。
为达到以上本发明的目的，本发明采用如下技术方案：
本发明的第一目的是提供一种双向拉伸聚合物薄膜，包括烯烃聚合物形成的基体膜层、多元共聚聚烯烃形成的表面膜层，所述的基体膜层为所述的聚合物薄膜的中间层，所述的聚合物薄膜的α晶的110晶面具有赤道方向和子午线方向的两个方向的取向，赤道方向的片晶长周期为28～42，子午线方向的片晶长周期为37～46；
由于聚合物薄膜赤道方向的片晶长周期为28～42，子午线方向的片晶长周期为37～46，使得聚合物薄膜具有较高的结晶度和小的晶粒尺寸，从而表现出较高的透明性，耐撕裂性能高，拉伸性能好，挺度高等优点。
优选的，表面膜层的多元共聚聚烯烃的熔点小于基体膜层的烯烃聚合物。由于在相同的温度下，低熔点的材料的拉伸性能要易于高熔点的材料，选择较低熔点的表面膜层的聚烯烃，可以在生产过程中有效调整表面层的厚度，得到厚度均匀性更好的聚合物薄膜。
优选的，所述的聚合物薄膜的在入射角60度测定光泽度为93％以上；
本发明的聚合物薄膜还具有适当的表面粗糙度。粗糙度影响到光泽度的大小，光泽度过低，色泽晦暗，表面不美观；表面的粗糙程度还会影响油墨的转移速度，如果油墨转移不充分，印品的表面会产生图像浓淡斑。由于表面粗糙度主要受到加工温度、生产速度、电晕强度等工艺条件的影响，本发明调整工艺控制薄膜的表面结晶和固化状态，控制薄膜的光泽度在一定范围内。本发明的光泽度的测量用手持光泽度计(型号：Micro Tri Gloss-BYK Gardner)测得。
优选，厚度为60～90um；现有技术的中的厚度一般低于50um，而本发明制备的聚合物薄膜为60～90um，本发明的厚度采用JIS P 8118厚度计进行测定。
优选，雾度为1.30％以下；本发明中的雾度是指从入射光方向偏转或散射超过2.5度的、透射过薄膜的入射光的百分比，薄膜的雾度可以使用ASTM方法D1003、用分光光度计或浊度计来测定，雾度影响了薄膜的光泽度以及透明度，尤其是成像度下降，本发明选择合适的雾度，从而聚合物薄膜具有更好的透明度。
优选，结晶度为35～77％；本发明的聚合物薄膜树脂具有较高的结晶度，结晶度在35～77％范围。由于材料的结晶度影响薄膜的透明性，结晶度高，透明性就会变差，且结晶度高的材料的表面自由能低，导致印刷后表面层油墨和胶黏剂的附着力差。同时，高结晶状态的高分子较未结晶部分，分子链排列规整，致密性高，表面的粘合剂分子难以向基体表面内扩散。但是结晶度过低会使薄膜刚性低。因此，为了平衡薄膜的透明性、印刷性和刚度等力学性能的综合优异性能，需要控制薄膜加工过程中的结晶度和晶粒尺寸在一定范围内，同时控制双取向的程度解决纵横向力学性能不均匀的问题，调控力学性能的平衡，本发明的结晶度是通过X-射线衍射、密度或量热器测量。
优选，玻璃化转变温度为-65～-35℃。
本发明的聚合物薄膜具有较低的玻璃化转变温度，表明在低温下聚合物薄膜结构稳定，保持良好的柔韧性能，具有较好的耐低温性能。
优选的，所述的烯烃聚合物包括聚丙烃、聚乙烯、乙烯丙烯共聚物、α烯烃或α烯烃共聚物中的一种或多种，所述的表面层还包括无机纳米颗粒、耐低温材料或消光剂，所述的无机纳米颗粒为脂肪酸金属盐、碳酸钙或煅烧硅石，优选玻璃微珠、玻璃微粉、纳米二氧化硅，所述的耐低温材料为无规共聚物，优选丁二烯-苯乙烯无规共聚物、氯乙烯-醋酸乙烯无规共聚物。
本发明加入无机纳米颗粒的作用是减少聚合物之间的粘连作用，并适当提高聚合物薄膜表面的极性，如果粘连作用比较强，聚合物薄膜表面粗糙、加工困难，表面光泽度差，纳米颗粒解决表面问题，并通过防粘连作用，使得生产速度提高。表层用的耐低温材料一般为带有支链的聚合物，当带有支链的聚合物接枝到聚合物薄膜的主链上时，会使得薄膜的表面平整度降低，具有一定的粗糙度，使得分子链的表层微相分离，从而聚合物薄膜的表面微观结构图案化。
优选的，以质量百分比计所述的烯烃聚合物75～99％，无机纳米颗粒1～12％，耐低温材料0～8％，消光剂0～7％。
本发明人经过大量的试验发现，形成基体膜层的原料烯烃聚合物、无机纳米颗粒、耐低温材料、消光剂在上述的比例范围内才能形成高透明、抗撕裂、尺寸稳定的聚合物薄膜。
优选的，所述的基体膜层为n层，其中n为1-5，优选3层，优选基体膜层大于等于2时，基体膜层之间还包括胶粘膜层。
当基体膜层为1层时，聚合物薄膜包括基体膜层和表面膜层，当基体膜层大于 等于2层时，基体膜层与基体膜层之间通过胶粘膜层连接。
基体膜层大于等于2时，每层组成基体膜层的烯烃聚合物相同或不同，优选组成基体膜层的烯烃聚合物相同。
当基体膜层的烯烃聚合物相同时，形成的聚合物薄膜的均匀性较好，抗撕裂能力强。
优选的，所述的赤道方向的取向大于所述子午线方向的取向，优选所述的聚合物薄膜的分子链平行于赤道。
聚合物薄膜具有两个方向的取向是由于双向拉伸的原因，同时应为拉伸诱导结晶作用，使得聚合物薄膜具有较高的结晶度和小的晶粒尺寸，从而表现出较高的透明性，耐撕裂性能高，拉伸性能好，挺度高等优点。
本发明的第二个目的是提供一种聚合物薄膜的制备方法，所述的制备方法包括如下：
(1)将基体膜层和胶粘膜层的原料投入挤出机中挤出；
(2)上述原料挤出后，流经T型模头形成复合层共挤出厚片，模头的工作温度为180～350℃，将所得的厚片冷却成型，冷却温度为20～60℃；
(3)将步骤(2)得到的厚片预热，在温度为100～200℃下，进行纵向拉伸，拉伸5～10倍，在温度180～300℃下进行横向拉伸，拉伸6～18倍；
(4)然后经过单面或双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
优选的，步骤(1)中基体膜层的挤出温度为150～350℃，胶粘膜层的挤出温度为130～300℃。在此挤出温度下得到的聚合物薄膜的结晶度适中，具有更好的透明性。
通过本方法制备的聚合物薄膜具有较高的透明度、高刚韧性、抗撕裂、耐低温、尺寸稳定的聚合物多层复合薄膜。
本发明的第三目的是提供一种双向拉伸聚合物薄膜在印刷领域的应用。
与现有技术相比，本发明具有如下优点：
(1)本发明所述的聚合物薄膜光泽度为93％以上，雾度为1.30％以下，结晶度为35～77％，所述的聚合物薄膜110晶面具有赤道方向和子午线方向的两个方向的取向，赤道方向的长周期为28～42，子午线方向的长周期为37～46；
(2)本发明的聚合物薄膜具有较高的透明度、高刚韧性、抗撕裂、耐低温、尺寸稳定的性能。
(3)本发明的聚合物薄膜高于通常的聚烯烃双向拉伸薄膜(厚度低于50um)， 厚度在60-90um之间。
附图说明
图1实施例1～7二维WAXS图；
图2实施例1～7一维WAXS曲线图；
图3实施例1～7(110)晶面的方位角积分曲线图；
图4实施例1～7(111)晶面的方位角积分曲线图；
图5实施例1～7二维SAXS图；
图6实施例1～7赤道方向的一维SAXS曲线图；
图7实施例1～7子午线方向的一维SAXS曲线；
图8a实施例4得到的聚合物薄膜的正面电镜图；
图8b实施例4得到的聚合物薄膜的正面电镜图；
图9a实施例4得到的聚合物薄膜的反面电镜图；
图9b实施例4得到的聚合物薄膜的反面电镜图；
图10a实施例5得到的聚合物薄膜的正面电镜图；
图10b实施例5得到的聚合物薄膜的正面电镜图；
图11a实施例5得到的聚合物薄膜的反面电镜图；
图11b实施例5得到的聚合物薄膜的反面电镜图；
图12a实施例7得到的聚合物薄膜的正面电镜图；
图12b实施例7得到的聚合物薄膜的正面电镜图；
图13a实施例7得到的聚合物薄膜的反面电镜图；
图13b实施例7得到的聚合物薄膜的反面电镜图；
图14本发明的聚合物薄膜分子链主要的取向方向图(Machine direction对应子午线方向，Transverse direction对应赤道方向)。
其中，图中a，b，c，d，e，f，g代表实施例1，实施例2，实施例3，实施例4，实施例5，实施例6，实施例7。
具体实施方式
以下实施例中的实施方案可以进一步组合或者替换，且实施例仅仅是对本发明的优选实施例进行描述，并非对本发明的构思和范围进行限定，在不脱离本发明设计思想的前提下，本领域中专业技术人员对本发明的技术方案作出的各种变化和改 进，均属于本发明的保护范围。
性能的评价
本发明对WAXS与SAXS测试分别在上海光源的广角线站(BL14B1)与小角线站(BL16B1)进行。光源的X射线光波长为
Figure PCTCN2016090007-appb-000001
WAXS的探测器为MAR 225，分辨率为3072×3072像素(像素尺寸＝73×73μm2)，SAXS的探测器为MAR 165，分辨率为2048×2048像素(像素尺寸＝79×79μm2)。测试时，WAXS与SAXS的曝光时间分别为60s与150s，样品到探测器的距离分别为336.5mm与2024.1mm。所有的图像均扣除了背景散射、空气散射与光线波动的影响。通过在不同方位角Φ范围内进行积分得到二维SAXS的积分强度I(q)(q＝4πsinθ/λ)。
运用Bragg方程计算长周期(L)：
Figure PCTCN2016090007-appb-000002
qmax对应于散射曲线上最高峰的横坐标值。赤道方向与子午线方向的强度分别在-45°≤Φ≤45°与45°≤Φ≤135°范围内积分。
以下实施例中的取样都是在较大的薄膜上，沿着图14所标出的拉伸方向剪取小块薄膜样品。
实施例1
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有聚丙烯75％，硅石12％，丁二烯-苯乙烯无规共聚物8％，消光剂二氧化硅5％，其中挤出机的温度为150℃；胶粘膜层的原料投入一台辅助挤出机中，挤出温度为200℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为180℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为20℃；
(3)将上面的厚片通过加热辊预热，温度为1000℃，进行纵向拉伸，拉伸5倍，在温度180℃下进行横向拉伸，拉伸6倍；
(4)经过双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
实施例2
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有聚丙烯80％，玻璃微珠12％，丁二烯-苯乙烯无规共聚物8％，其中挤出机的温度为180℃；将胶粘膜层的原料投入一台辅助挤出机中，挤出温度为250℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为200℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为30℃；
(3)将上面的厚片通过加热辊预热，温度为150℃，进行纵向拉伸，拉伸6倍，在温度200℃下进行横向拉伸，拉伸9倍；
(4)经过单面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
实施例3
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有乙烯丙烯共聚物85％，纳米二氧化硅2％，氯乙烯-醋酸乙烯共聚物8％，消光剂二氧化硅5％，其中挤出机的温度为250℃；将胶粘膜层的原料投入一台辅助挤出机中，挤出温度为300℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为250℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为20℃；
(3)将上面的厚片通过加热辊预热，温度为200℃，进行纵向拉伸，拉伸8倍，在温度200℃下进行横向拉伸，拉伸18倍；
(4)经过单面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
实施例4
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有聚1-丁烯96％，玻璃微粉3％，消光剂二氧化硅1％，其中挤出机的温度为300℃；将胶粘膜层的原料投入一台辅助挤出机中，挤出温度为350℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为350℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为30℃；
(3)将上面的厚片通过加热辊预热，温度为200℃，进行纵向拉伸，拉伸10倍，，在温度300℃下进行横向拉伸，拉伸15倍；
(4)经过双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
得到的聚合物薄膜的正面电镜图间图8a，图8b，反面电镜图见图9a，图9b。实施例5
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有聚苯乙烯90％，碳酸钙8％，消光剂二氧化硅2％，其中挤出机的温度为300℃；将胶粘膜层的原料投入一台辅助挤出机中，挤出温度为250℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为300℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为50℃；
(3)将上面的厚片通过加热辊预热，温度为200℃，进行纵向拉伸，拉伸6倍，在温度200℃下进行横向拉伸，拉伸8倍；
(4)经过双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
得到的聚合物薄膜的正面电镜图间图10a，图10b，反面电镜图见图11a，图11b。
实施例6
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有聚丙烯82％，硅石12％，丁二烯-苯乙烯无规共聚物6％，其中挤出机的温度为200℃；将胶粘膜层的原料投入一台辅助挤出机中，挤出温度为250℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为200℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为60℃；
(3)将上面的厚片通过加热辊预热，温度为150℃，进行纵向拉伸，拉伸6倍，在温度300℃下进行横向拉伸，拉伸8倍；
(4)经过双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
实施例7
(1)将基体膜层的原料投入挤出机中，其中所述的原料以质量百分比计含有聚丙烯80％，硅石10％，丁二烯-苯乙烯无规共聚物5％，消光剂二氧化硅5％，其中挤出机的温度为200℃；将胶粘膜层的原料投入一台辅助挤出机中，挤出温度为250℃；
(2)上述原料经熔融塑化后挤出，流经T型模头形成复合层共挤出厚片，模头的工作温度为250℃，将所得的厚片经冷却辊和水槽冷却成型，冷却辊和水槽的温度为25℃；
(3)将上面的厚片通过加热辊预热，温度为160℃，进行纵向拉伸，拉伸7倍，在温度260℃下进行横向拉伸，拉伸8倍；
(4)经过双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
将得到的聚合物薄膜进行力学性能和厚度测试见表1，(110)与(111)的方位角积分的半峰宽与其在赤道方向与子午线方向的长周期见表2，二维WAXS见图1，一维WAXS曲线见图2，(110)晶面的方位角积分曲线见图3，(111)晶面的方位角积分曲线见图4，二维SAXS见图5，赤道方向的一维SAXS曲线见图6，子午线方向的一维SAXS曲线见图7。
得到的聚合物薄膜的正面电镜图见图12a，图12b，反面电镜图见图13a，图13b。
实施例1～7聚合物薄膜分子链主要的取向方向见图14。
由图2可以看出，除了实施例1的样品，其他6种薄膜样品在2θ＝11.4°，13.6°，15.0°，17.0°与17.6°都出现了5个衍射峰，分别对应于聚丙烯α晶的(110)，(040)，(130)，(111)与(-131)晶面的衍射。薄膜-2θ的衍射峰的2θ稍微有偏移，向低角度移动了大约0.4°。
由图1可以看出，这7种薄膜样品的衍射图案均为衍射弧，即出现取向晶体。另外，这7种薄膜样品的(110)晶面都出现了两个方向的取向：赤道方向与子午线方向，这可能与其是双向拉伸膜有关。不过，它们在赤道方向的取向较强，也就是说分子链主要平行于横向排列。
表1
Figure PCTCN2016090007-appb-000003
表2
Figure PCTCN2016090007-appb-000004

Claims (10)

  1. 一种双向拉伸聚合物薄膜，其特征在于，包括烯烃聚合物形成的基体膜层、多元共聚聚烯烃形成的表面膜层，所述的基体膜层为所述的聚合物薄膜的中间层，所述的聚合物薄膜的α晶的110晶面具有赤道方向和子午线方向的两个方向的取向，赤道方向的片晶长周期为28～42，子午线方向的片晶长周期为37～46；
    优选，表面膜层的多元共聚聚烯烃的熔点小于基体膜层的烯烃聚合物。
  2. 根据权利要求1所述的聚合物薄膜，其特征在于，所述的聚合物薄膜的在入射角60度测定光泽度为93％以上；优选，厚度为60～90um；优选，雾度为1.30％以下；优选，结晶度为35～77％；优选，玻璃化转变温度为-65～-35℃。
  3. 根据权利要求1所述的聚合物薄膜，其特征在于，所述的烯烃聚合物包括聚丙烃、聚乙烯、乙烯丙烯共聚物、α烯烃或α烯烃共聚物中的一种或多种，所述的表面层还包括无机纳米颗粒、耐低温材料或消光剂，所述的无机纳米颗粒为脂肪酸金属盐、碳酸钙或煅烧硅石，优选玻璃微珠、玻璃微粉、纳米二氧化硅，所述的耐低温材料为无规共聚物，优选丁二烯-苯乙烯无规共聚物、氯乙烯-醋酸乙烯无规共聚物。
  4. 根据权利要求1-3任意一项所述的聚合物薄膜，其特征在于，以质量百分比计所述的烯烃聚合物75～99％，无机纳米颗粒1～12％，耐低温材料0～8％，消光剂0～7％。
  5. 根据权利要求1所述的聚合物薄膜，其特征在于，所述的基体膜层为n层，其中n为1-5，优选3层，优选基体膜层大于等于2时，基体膜层之间还包括胶粘膜层。
  6. 根据权利要求5所述的聚合物薄膜，其特征在于，基体膜层大于等于2时，每层组成基体膜层的烯烃聚合物相同或不同，优选组成基体膜层的烯烃聚合物相同。
  7. 根据权利要求1～6任意一项所述的聚合物薄膜，其特征在于，所述的赤道方向的取向大于所述子午线方向的取向，优选所述的聚合物薄膜的分子链平行于赤道。
  8. 一种权利要求1～7任意一项所述的聚合物薄膜的制备方法，其特征在于，所述的制备方法包括如下：
    (1)分别将基体膜层和胶粘膜层的原料挤出；
    (2)上述原料挤出后，流经T型模头形成复合层共挤出厚片，模头的工作温度为180～350℃，将所得的厚片冷却成型，冷却温度为20～60℃；
    (3)将步骤(2)得到的厚片预热，在温度为100～200℃下，进行纵向拉伸，拉伸5～10倍，在温度180～300℃下进行横向拉伸，拉伸6～18倍；
    (4)然后经过单面或双面电晕处理，在收卷机出卷得到双向拉伸聚合物薄膜。
  9. 根据权利要求8所述的聚合物薄膜的制备方法，其特征在于，步骤(1)中基体膜层的挤出温度为150～350℃，胶粘膜层的挤出温度为130～300℃。
  10. 一种权利要求1～7任意一项所述的双向拉伸聚合物薄膜在印刷领域的应用。
PCT/CN2016/090007 2016-04-25 2016-07-14 一种双向拉伸聚合物薄膜及其制备方法与应用 WO2017185533A1 (zh)

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