CN104356610B - A kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film and preparation method thereof - Google Patents
A kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film and preparation method thereof, its raw material comprises 1 ~ 50 part, nanometer flaxen fiber, polyester 50 ~ 95 parts, additive level at 0.1 ~ 5 part, and the content of interface coupling agent is at 0.1 ~ 5 part; Described interface coupling agent is one or more in silane coupling agent, titanate coupling agent, isocyanates coupling agent, aluminate coupling agent; Described polyester is polyethylene glycol 2，6-naphthalene dicarboxylate and/or PET.It is good that the high temperature resistant oriented transparent nanometer flaxen fiber polyester film prepared has the transparency, glossy, there is low, the good chemical proofing of excellent mechanical property, tensile strength and resistance to impact shock, dimensional stabilizing, coefficient of linear expansion and oil-proofness, can be widely used on the products such as packaging, electronics, photoelectricity, thin film switch, panel and Flexible Displays base material.
Description
Technical field
The present invention relates to a kind of oriented transparent nanometer flaxen fiber polyester film and preparation method thereof, more specifically, the present invention relates to a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film and preparation method thereof, this film at high temperature has dimensional stability, for having in the temperature variation of use temperature scope that excellent dimensional stability, coefficient of linear expansion are low, the transparency and flatness.
Background technology
Living environment worsens, resource shortage and energy dilemma make human knowledge arrive protection of the environment and efficent use of resources to the importance and the urgency that realize society and sustained economic development, and people more and more pay attention to employing renewable biological source and manufacture novel material.But along with the requirement of Environmental Ecological Balance to forest coverage is more and more higher, the scarcity of timber resources and people are increasingly sharpened to the contradiction between timber resources demand, the fresh target that the raw material utilizing growth cycle short is studied to replace timber resources to become again people.So people start sight to be turned to the hemp resources such as flax, sisal hemp, bluish dogbane and source agricultural fibre widely as non-woods such as stalks, alternative wood producing matrix material is carried out, to effectively solving the contradiction excessively using timber resources with them.From the current study, the matrix material that the mechanical property of the especially flaxen fiber reinforced composite of the natural plant fibre except timber can strengthen with glass fibre etc. compares favourably.Its flaxen fiber readily biodegradable, reusable edible, it has high temperature resistant, acid and alkali-resistance, rapid heat dissipation and without the unique advantage such as electrostatic, specific tenacity and specific modulus are all higher.
Polyester film, particularly polyethylene terephthalate (PET) and PEN (PEN) biaxially oriented film are the comprehensive films of a class Performance comparision, and its transparency is good, glossy; There is excellent resistance to air loss, mechanical property, heat-resisting, winter hardiness and chemical proofing, be widely used on the products such as electronic component, circuit card, signal equipment and flexible display device.
Flaxen fiber element is a kind of hydrophilic natural high molecular compound of strong polarity, and general high molecular polymer is hydrophobic nature, and this bi-material can not well combine.When the material that two kinds of polarity spectrum are larger meets; usually two-phase phase tolerance can be caused; make flaxen fiber that physical action can only be relied on to be coated in polyester matrix; two-phase interface bonding force is little; thus cause the physical and mechanical property of matrix material lower; such as modulus, elongation at break reduction, appearance poor, limit application.Improve the consistency at composite wood interface, make between the upper layer of flaxen fiber and the upper layer of polyester matrix, to reach molecular level to merge, therefore, need the third material adopting a kind of character between this bi-material to reach compatible to make them, coupling agent just plays this effect.
In addition, if wish such film to be applied to flexible display, so, the dimensional stability of plastic base makes key.For TFT-LCD processing procedure, in whole manufacturing processed, substrate needs the high temperature process facing 300-400 DEG C, so per pass processing procedure is a test for plastic base, develops the key that resistant to elevated temperatures plastic base is exploitation flexible display.The superior dimensional stability of plastic basis material also needs lower coefficient of linear expansion.
Summary of the invention
The first object of the present invention is, utilizes natural nano flaxen fiber to provide a kind of oriented transparent nanometer flaxen fiber polyester film, makes it have at high temperature dimensional stability and have excellent dimensional stability in the temperature variation of use temperature scope.
The second object of the present invention is, provides a kind of oriented transparent nanometer flaxen fiber polyester film, except having at high temperature except dimensional stability, also has both lower coefficient of linear expansion, the transparency, good surface smoothness and the resistance oxygen characteristic that blocks water.
For reaching above-mentioned purpose, the invention provides a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film, its raw material comprises nanometer flaxen fiber, polyester, additive and interface coupling agent.
Wherein, the content of nanometer flaxen fiber material, at 1 ~ 50 part, is preferably 1 ~ 40 part, is more preferably 1 ~ 30 part.When nanometer flaxen fiber adds more than 50%, moulding product performance is not good, and the tensile strength of film, modulus, shock strength all decline; When nanometer flaxen fiber adds lower than 1%, moulding product mechanics, thermal property are not good, and thermostability is general.
Nanometer flaxen fiber is chosen as one or more nanometer flaxen fibers in kenaf, hemp fibre, flax fiber, bastose, jute fibre and sisal fibers etc.
The substrate layer of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is polyester, and it is PEN and/or PET, and its amount of polyester is at 50 ~ 95 parts, be preferably 60 ~ 95 parts, be more preferably 70 ~ 95 parts, polyester is preferably polyethylene glycol 2，6-naphthalene dicarboxylate (PEN).
The limiting viscosity of polyethylene glycol 2，6-naphthalene dicarboxylate of the present invention, in ortho chloro phenol, the two 35 DEG C be preferably more than 0.4dl/g, be more preferably 0.40 ~ 0.90dl/g.When limiting viscosity is lower than below 0.4dl/g, often can there is process interruption, when limiting viscosity is higher than below 0.9dl/g, because melt viscosity is high thus cause being difficult to melt extrude.
Additive level, at 0.1 ~ 5 part, is preferably 0.1 ~ 3 part, is more preferably 0.1 ~ 2 part.Described additive, can be such as one or more mixtures of the organic particle such as the inorganic nano-particles such as silicon-dioxide, calcium carbonate, barium sulfate, kaolin, magnesiumcarbonate, calcium oxide, zinc oxide, water glass, weisspiessglanz, titanium oxide and acrylic acid or the like cross-linked polymer, erucicamide, stearic amide, the roughness on film surface microcosmic can be increased, during minimizing rolling, open ended air between film, prevents film blocking.
The content of interface coupling agent, at 0.1 ~ 5 part, is preferably 0.1 ~ 3 part, is more preferably 0.1 ~ 2 part.It can be one or more coupling agents in silane coupling agent, titanate coupling agent, isocyanates coupling agent (as polymethylene polyphenyl isocyanate, n-butyl isocyanate and vinylbenzene isocyanic ester etc.), aluminate coupling agent etc., the intermixing ability between flaxen fiber and polyester macromolecule material can be improved, improve the transparency of film, mist degree and mechanical mechanics property.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention analyzes from by nanometer sight matter interaction power and quantum mechanics, solid nano material is dispersed in high-viscosity polyester polymer with extensional flow hybrid mode, thus make high temperature resistant orientation nano flaxen fiber polyester film transparent, and there is the premium properties of flaxen fiber and polyester material.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is the polyester film using carrying out stretch orientation at least one direction as substrate layer containing polyethylene glycol 2，6-naphthalene dicarboxylate material.High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention preferably carries out the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film stretched at biaxially oriented.
The temperature expansion coefficient α T of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention at 30 ~ 100 DEG C of temperature in the direction in length and breadth of film all at 0 ~ 10ppm/ DEG C.The upper limit of temperature expansion coefficient of the present invention is preferably less than 10ppm/ DEG C, is more preferably less than 8ppm/ DEG C.The lower limit of temperature expansion coefficient of the present invention is preferably more than 1ppm/ DEG C, is more preferably more than 3ppm/ DEG C.
In order to reach the said temperature coefficient of expansion, preferred stretching ratio in MD direction, TD direction is all the scope of 3.5 ~ 5.0 times.Draft temperature is preferably 120 ~ 150 DEG C, and heat setting temperature is preferably greater than 180 DEG C ~ 230 DEG C.In order to percent thermal shrinkage is lower, preferably carry out heat-relaxing treatment, preferably carry out heat-relaxing treatment at the temperature of 120 ~ 160 DEG C.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is all be preferably less than 0.15% at the percent thermal shrinkage of 100 DEG C × 10min in the longitudinal and transverse direction of film, is more preferably less than 0.1%, is particularly preferably less than 0.05%.If percent thermal shrinkage is excessive, when for display applications, easy heat tracing and affect the change of pattern, causes figure that small mismatch occurs.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is all be preferably less than 1.0% at the percent thermal shrinkage of 150 DEG C × 30min in the longitudinal and transverse direction of film, is more preferably less than 0.7%, is particularly preferably less than 0.5%.
The total light transmittance of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is preferably more than 85%, is more preferably more than 87%, is particularly preferably more than 90%.When total light transmittance is prescribed a time limit lower than lower, the transparency of film is deteriorated, and during for electronic product, attractive in appearance or brightness can decline, thus affects the normal use of product.
The turbidity of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is preferably less than 1.5%, is more preferably less than 1.0%, is particularly preferably less than 0.5%.When turbidity exceedes in limited time, the transparency is deteriorated, and during for Flexible Displays or screen protecting film, brightness reduces, and affects the normal use of product.
Obtain the high temperature resistant oriented transparent nanometer flaxen fiber polyester film of thickness 12-250 μm, its natural ramie fiber nano-scale will have good homogeneity, and natural ramie fiber nanometer diameter is between 50-300nm, and length is at below 1000nm.
Present invention also offers a kind of preparation method of high temperature resistant oriented transparent nanometer flaxen fiber polyester film:
1) by natural nano flaxen fiber at 160-220 DEG C of heat drying, controlling dried nanometer flaxen fiber water content is less than 0.1%;
2) by mixing machine by the nanometer natural fiber material under solid state and powdery interface coupling agent Homogeneous phase mixing;
3) by PEN (PEN) pellet at 180-190 DEG C of heat drying, controlling dried water content is less than 0.1%;
4) by dried PEN pellet pulverize, then mix with the nanometer natural ramie fiber homogenize material of band interface coupling agent;
5) by forcing machine melting polyester mixture, again by dispersion mixing equipment by nanometer natural ramie fiber material and polyester mixture in the molten state, nanoscale mixes, makes nanometer natural ramie fiber homogenize material be dispersed in high-viscosity polyester macromolecular material;
The runner formed between the major parts of this mixing equipment produces extensional flow.Extensional flow can be axisymmetric (circle) or plane.Polymer composite is at least stretched dispersion three times in stretching runner.Spacing between tensile part can regulate, and can be 0 ~ 5mm spacing.According to differing materials and processing requirement, the shape of stretching runner also can change.
6) this mixing equipment has at least three grades to disperse mixing section, and every one-level can reduce, by the agglomerate size of disperse phase 10 times, after 3 grades, can reduce 1000 times.Like this, the nanofiber of reuniting together just can remain on nanoscale and be disperseed.
7) by extrusion equipment, the films/sheets extruded is stretched at least in one direction, thus make film have higher physical mechanical mechanical property.Described extrusion equipment mould used is slit coat hanger die.
8) under the draft temperature of 120-180 DEG C (preferred 150-180 DEG C), carry out biaxial stretch-formed with the multiplying power of 3.5 ~ 5.0 times respectively along longitudinal direction, transverse direction, and at the temperature heat setting type 1-100s of 160 to 250 DEG C, obtain product film.
Heat setting temperature preferably 180 DEG C ~ 230 DEG C, and carry out heat-relaxing treatment at the temperature of 120 ~ 160 DEG C.
The present invention relates to a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film, using polyethylene glycol 2，6-naphthalene dicarboxylate material as the main component of substrate layer, its film thickness at 12-250 μm, wherein:
1) the temperature expansion coefficient α t at 30-100 DEG C of temperature is 0-5ppm/ DEG C in the direction in length and breadth of film;
2) the percent thermal shrinkage of 100 DEG C × 10min in the longitudinal and transverse direction of film all below 0.2%.
3) the full light transmittance of film is more than 85%, turbidity is below 1.5%.
High temperature resistant its water-intake rate of oriented transparent nanometer flaxen fiber polyester film of the present invention controls at <0.1g/m
2day, air barrier rate controls at <0.05g/m
2day.
In the present invention, we adopt interface coupling agent to carry out modification, reduce the hydroxyl of fiber surface, thus reduce the water-intake rate of natural fiber, the binding ability of fortifying fibre and resin matrix.Meanwhile, modified flaxen fiber and polyester matrix produce cross-linked network structure, avoid fiber generation Swelling.Secondly, another Chief amongst is exactly nanometer flaxen fiber and polyester combined technology in the present invention, its nanometer flaxen fiber (yardstick is less than visible wavelength 380-780nm) can be evenly dispersed in polyester base material, do not reunite, thus obtain higher physical and mechanical properties, make biaxial stretch-formed after film there is the transparency.
In the present invention according to the thermo-dynamic principle of high molecule nano composite material, when nanometer natural fiber is evenly dispersed in plastic basis material one by one, polymer base material in the scope of the surrounding 10-15 times nanofiber diameter of each root nanofiber will together with nanofiber " solidification ", and namely these macromolecular materials will present the physical property of the nano-fiber material that it is wrapped in.Different types of flaxen fiber coefficient of linear expansion is different, and its numerical value is at about 1-3ppm/ DEG C.Thickness is the coefficient of linear expansion of 125mm polyethylene terephthalate (PET) film is 15ppm/ DEG C, the coefficient of linear expansion of PEN (PEN) film of same thickness is 13ppm/ DEG C, when nanometer natural ramie fiber and polyester material Homogeneous phase mixing on nanoscale, the film of production just can obtain lower coefficient of linear expansion.
It is good that high temperature resistant oriented transparent nanometer flaxen fiber polyester film prepared by the present invention has the transparency, glossy, there is excellent mechanical property, tensile strength and resistance to impact shock, dimensional stabilizing, good chemical proofing and oil-proofness, can be widely used on the products such as packaging, electronics, photoelectricity, thin film switch, panel and Flexible Displays base material.
Accompanying drawing explanation
Fig. 1 is mixing equipment principle of work schematic diagram of the present invention.
Embodiment
Embodiment is below adopted to illustrate one of the present invention high temperature resistant oriented transparent nanometer flaxen fiber polyester film and preparation method thereof.
Nanometer flaxen fiber material in a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, its diameter is between 50 ~ 300nm, and between preferred nano-scale 50 ~ 100nm, length is at below 1000nm.Its nano-scale range is unsuitable excessive, and nano-scale is too small or excessive, and easily cause reunion when the later stage stretches diffusion slab, thus film easily produces brilliant point, mechanics mechanical property declines, and transmittance declines, and turbidity is bigger than normal; Nano-scale width range is excessive, and nanometer is disperseed uneven in the material, and material each several part physicals has larger difference.
The content of the nanometer flaxen fiber material in a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, at 1 ~ 50 part, is preferably 1 ~ 40 part, is more preferably 1 ~ 30 part.When nanometer flaxen fiber adds more than 50%, moulding product performance is not good, and the tensile strength of film, modulus, shock strength all decline; When nanometer flaxen fiber adds lower than 1%, moulding product mechanics, thermal property are not good, and thermostability is general.
In nanometer flaxen fiber material in a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, nanometer flaxen fiber is chosen as one or more nanometer flaxen fibers in kenaf, hemp fibre, flax fiber, bastose, jute fibre and sisal fibers etc.
The substrate layer of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, main component is polyethylene glycol 2，6-naphthalene dicarboxylate, and its amount of polyester, at 50 ~ 95 parts, is preferably 60 ~ 95 parts, is more preferably 70 ~ 95 parts.
The limiting viscosity of polyethylene glycol 2，6-naphthalene dicarboxylate of the present invention, in ortho chloro phenol, the two 35 DEG C be preferably more than 0.4dl/g, be more preferably 0.40 ~ 0.90dl/g.When limiting viscosity is lower than below 0.4dl/g, often can there is process interruption, when limiting viscosity is higher than below 0.9dl/g, because melt viscosity is high thus cause being difficult to melt extrude.
Additive level in high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, at 0.1 ~ 5 part, is preferably 0.1 ~ 3 part, is more preferably 0.1 ~ 2 part.Described additive, can be such as one or more mixtures of the organic particle such as the inorganic nano-particles such as silicon-dioxide, calcium carbonate, barium sulfate, kaolin, magnesiumcarbonate, calcium oxide, zinc oxide, water glass, weisspiessglanz, titanium oxide and acrylic acid or the like cross-linked polymer, erucicamide, stearic amide, the roughness on film surface microcosmic can be increased, during minimizing rolling, open ended air between film, prevents film blocking.
The content of the interface coupling agent in high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, at 0.1 ~ 5 part, is preferably 0.1 ~ 3 part, is more preferably 0.1 ~ 2 part.It can be one or more coupling agents in silane coupling agent, titanate coupling agent, isocyanates coupling agent (as polymethylene polyphenyl isocyanate, n-butyl isocyanate and vinylbenzene isocyanic ester etc.), aluminate coupling agent etc., the intermixing ability between flaxen fiber and polyester macromolecule material can be improved, improve the transparency of film, mist degree and mechanical mechanics property.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention analyzes from by nanometer sight matter interaction power and quantum mechanics, nano material is dispersed in high-viscosity polyester polymer in extensional flow mode, thus make high temperature resistant orientation nano flaxen fiber polyester film transparent, and there is the premium properties of flaxen fiber and polyester material.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is the polyester film using carrying out stretch orientation at least one direction as substrate layer containing polyethylene glycol 2，6-naphthalene dicarboxylate material.High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention preferably carries out the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film stretched at biaxially oriented.
The temperature expansion coefficient α T of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention at 30 ~ 100 DEG C of temperature in the direction in length and breadth of film all at 0 ~ 10ppm/ DEG C.The upper limit of temperature expansion coefficient of the present invention is preferably less than 10ppm/ DEG C, is more preferably less than 8ppm/ DEG C.The lower limit of temperature expansion coefficient of the present invention is preferably more than 1ppm/ DEG C, is more preferably more than 3ppm/ DEG C.
In order to reach the said temperature coefficient of expansion, preferred stretching ratio in MD direction, TD direction is all the scope of 3.5 ~ 5.0 times.Draft temperature is preferably 120 ~ 150 DEG C, and heat setting temperature is preferably greater than 180 DEG C ~ 230 DEG C.In order to percent thermal shrinkage is lower, preferably carry out heat-relaxing treatment, preferably carry out heat-relaxing treatment at the temperature of 120 ~ 160 DEG C.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is all be preferably less than 0.15% at the percent thermal shrinkage of 100 DEG C × 10min in the longitudinal and transverse direction of film, is more preferably less than 0.1%, is particularly preferably less than 0.05%.If percent thermal shrinkage is excessive, when for display applications, easy heat tracing and affect the change of pattern, causes figure that small mismatch occurs.
High temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is all be preferably less than 1.0% at the percent thermal shrinkage of 150 DEG C × 30min in the longitudinal and transverse direction of film, is more preferably less than 0.7%, is particularly preferably less than 0.5%.
The total light transmittance of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is preferably more than 85%, is more preferably more than 87%, is particularly preferably more than 90%.When total light transmittance is prescribed a time limit lower than lower, the transparency of film is deteriorated, and during for electronic product, attractive in appearance or brightness can decline, thus affects the normal use of product.
The turbidity of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention is preferably less than 1.5%, is more preferably less than 1.0%, is particularly preferably less than 0.5%.When turbidity exceedes in limited time, the transparency is deteriorated, and during for Flexible Displays or screen protecting film, brightness reduces, and affects the normal use of product.
The preparation method of a kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention, it is as described below:
1) by nanometer flaxen fiber at 160 ~ 220 DEG C of heat dryings, controlling dried nanometer flaxen fiber water content is 0.05% ~ 0.1%;
2) by mixing equipment by the nanometer natural fiber material under solid state and powdery coupling agent Homogeneous phase mixing;
3) by PEN pellet at 160-190 DEG C of heat drying, controlling dried water content is less than 0.1%;
4) by dried PEN pellet pulverize, then mix with the nanometer natural ramie fiber homogenize material of band coupling agent;
5) mixed powder is sent in the hopper of forcing machine of customization, through conveying, heating, melting at 290 DEG C, by the dispersion mixing equipment of customization, the mixture of nanometer natural ramie fiber material and polyester material is mixed in the molten state again, make nanometer natural ramie fiber homogenize material be dispersed in high-viscosity polyester macromolecular material;
6) this mixing equipment has three grades to disperse mixing section, and every one-level can reduce, by the agglomerate size of disperse phase 10 times, after 3 grades, can reduce 1000 times.Like this, the nanofiber of reuniting together just can remain on nanoscale and be disperseed.See the major parts 1 and 2 of the mixing equipment in Fig. 1, Fig. 1, the runner formed therebetween produces extensional flow, and parts 1 and 2 can be axisymmetric (circle) or plane.Polymer composite narrows at A, B, C point/face place runner, then broadens, i.e. three grades of dispersion mixing section A, B and C.Imaginary material block F, through B point, is drawn as G, and components different in matrix material is disperseed.Spacing between parts 1 and 2 to regulate, adjustable interval 0 ~ 5mm.According to differing materials and processing requirement, the shape of stretching runner E is also change.
7) by slit coat hanger die and extrusion equipment, the nanometer natural ramie fiber polyester material film-like extruded is made;
8) with casting drum, its film type cooling is solidified, obtain unstretching film;
9) this unstretching film is at the draft temperature of Tg ~ (Tg+30) DEG C, the draft temperature being preferably 150-180 DEG C carries out biaxial stretch-formed with the multiplying power of 3.5 ~ 5.0 times along longitudinal direction, transverse direction respectively, and at (Tg+5) ~ (Tg+100) DEG C, be preferably greater than the temperature heat setting type 1-100s of less than 160 to 250 DEG C, obtain desired film.
10) in order to obtain the higher film of dimensional stability, and there is foregoing temperature expansion coefficient with percent thermal shrinkage, need carry out heat-relaxing treatment to film, preferable temperature at 100-160 DEG C, with obtaining high temperature resistant oriented transparent nanometer flaxen fiber polyester film of the present invention.
Embodiment 1
By 15 parts of nanometer jute fibres, 85 parts poly-2, 6-(ethylene naphthalate) is respectively at 170 DEG C of heat dryings after 6 hours, and 2 parts of mixing coupling agent (silane coupling agent: titanate coupling agent=2:1) and 2 parts of mixed additives (silicon-dioxide: barium sulfate=2:1) were 110 DEG C of heat dryings 6 hours, dried nanometer natural ramie fiber material and powdery coupling agent and additive Homogeneous phase mixing, mix with powdery PEN again, the forcing machine hopper that supply is corresponding, melting at 290 DEG C of temperature, with the stainless steel filament net filtration of average open cell 14 μm, in the slit-shaped mould of 3mm, melt films is extruded into after being mixed by mixing equipment, film is chilling on the rotation cooling stick cylinder of surface temperature 50 DEG C, namely non-stretched film is obtained.By the unstretching film that obtains 120 DEG C of preheatings, again between the rod of low speed, high speed, IR heating in below apart from film 20mm place with 900 DEG C, and stretch 4.5 times along longitudinal direction, 4.5 times are transversely stretched again afterwards under temperature is 145 DEG C of environment, the high temperature resistant oriented transparent nanometer flaxen fiber polyester film obtained is carried out at the temperature of 200 DEG C the heat setting type of 40 seconds, carry out 20 seconds heat-relaxing treatment at the temperature of 140 DEG C, namely obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of the film obtained is listed in table 1.
Embodiment 2
The content of nanometer jute fibre, polyethylene glycol 2，6-naphthalene dicarboxylate is become respectively 10 parts, 90 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 1.
Embodiment 3
The content of nanometer jute fibre, polyethylene glycol 2，6-naphthalene dicarboxylate is become respectively 20 parts, 80 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 1.
Embodiment 4
The content of nanometer jute fibre, polyethylene glycol 2，6-naphthalene dicarboxylate is become respectively 25 parts, 75 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 1.
Embodiment 5
Nanometer jute fibre is substituted with nanometer sisal fibers, its content is 15 parts, and the content of polyethylene glycol 2，6-naphthalene dicarboxylate becomes 85%, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 1.
Embodiment 6
Nanometer flaxen fiber and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts, 85 parts, but its flaxen fiber is the mixing flaxen fiber of jute and sisal hemp, its ratio is 1:2, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 1.
Embodiment 7
Nanometer jute fibre is substituted with natural nano xylon, its content is 15 parts, and the content of polyethylene glycol 2，6-naphthalene dicarboxylate becomes 85%, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 1, and its percent thermal shrinkage is obviously greater than the percent thermal shrinkage of its flaxen fiber polyester film, and in like manner the coefficient of linear expansion of its xylon polyester film is also larger than its flaxen fiber polyester film.
Table 1
Note: (1) air barrier rate: ◎ is lower than 0.05g/m
2my god; Zero 0.05g/m
2more than it, be less than 0.1g/m
2my god; △ 0.1g/m
2more than it, be less than 0.5g/m
2my god; × 0.5g/m
2more than it.
(2) film flatness: zero lower than the amount of warpage of 10mm; The amount of warpage of × more than 10mm
(3) roughness: zero is good; △ is bad a little; × bad.
(4) comprehensive evaluation: ◎ is very good; Zero is good; △ is bad a little; × bad.
Embodiment 8
Nanometer jute fibre and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but its coupling agent is become single coupling agent silane coupling agent, content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.
Embodiment 9
Nanometer jute fibre and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but its coupling agent is become single coupling agent aluminate coupling agent, content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.
Embodiment 10
Nanometer jute fibre and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but mixed coupling agent and become aluminate coupling agent: silane coupling agent=1:2, content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.
Embodiment 11
Nanometer jute fibre and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but its mixed additive is become silicon-dioxide: kaolin=2:1, content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.
Embodiment 12
Nanometer jute fibre and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but its mixed additive is become silicon-dioxide: calcium carbonate=2:1, content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.
Embodiment 12
Nanometer flaxen fiber and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but its mixed additive is become silicon-dioxide: stearic amide=2:1, content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.
Embodiment 13
Nanometer flaxen fiber and poly-2, the content of 6-(ethylene naphthalate) is respectively 15 parts and 85 parts, but do not add its interface coupling agent, only add mixed additive, its content is 2 parts, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 2.Though can two-way stretch owing to not adding interface coupling agent plastics film, but the physicalies such as its surfaceness, transparency, mist degree, thermal property all obviously reduce, do not embody nanometer natural ramie fiber, with the film after polyester material mixture manufacturing, there is lower coefficient of linear expansion.
Table 2
Note: (1) air barrier rate: ◎ is lower than 0.05g/m
2my god; Zero 0.05g/m
2more than it, be less than 0.1g/m
2my god; △ 0.1g/m
2more than it, be less than 0.5g/m
2my god; × 0.5g/m
2more than it.
(2) film flatness: zero lower than the amount of warpage of 10mm; The amount of warpage of × more than 10mm
(3) roughness: zero is good; △ is bad a little; × bad.
(4) comprehensive evaluation: ◎ is very good; Zero is good; △ is bad a little; × bad.
Embodiment 14
Except stretching ratio longitudinal direction be 3.5 times, transverse direction is 3.5 times, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 3.
Embodiment 15
Change polyethylene glycol 2，6-naphthalene dicarboxylate into polyethylene terephthalate, melt temperature is 290 DEG C, and chilling on the rotation cooling stick cylinder of 20 DEG C, obtains unstretching film.This unstretching film stretches 4.5 times at 90 DEG C along longitudinal direction, and transversely stretch 4.5 times at 110 DEG C, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 3.
Embodiment 16
Except stretching ratio longitudinal direction be 3.5 times, transverse direction is 3.5 times, heat setting temperature is except 220 DEG C, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 3.
Embodiment 17
Except stretching ratio longitudinal direction be 3.5 times, transverse direction is 4.8 times, heat setting temperature is except 230 DEG C, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 3.
Embodiment 18
Except stretching ratio longitudinal direction be 3.5 times, transverse direction is 4.8 times, all the other operational conditions are all identical with embodiment 1, obtain the twin shaft high temperature resistant oriented transparent nanometer flaxen fiber polyester film of 150 μm.The characteristic of its film lists in table 3.
Comparative example 19
Directly melt extrude without this mixing equipment, all the other operational conditions are all identical with embodiment 1, obtain the partially transparent nanometer of 150 μm, flaxen fiber polyester film.Because film has brilliant point, and uneven, film carries out two-way stretch rupture of membranes often.This film is except surface difference, and the transparency is also poor, and water-intake rate is also high.The characteristic of its film lists in table 3.
Table 3
Note: (1) air barrier rate: ◎ is lower than 0.05g/m
2my god; Zero 0.05g/m
2more than it, be less than 0.1g/m
2my god; △ 0.1g/m
2more than it, be less than 0.5g/m
2my god; × 0.5g/m
2more than it.
(2) film flatness: zero lower than the amount of warpage of 10mm; The amount of warpage of × more than 10mm
(3) roughness: zero is good; △ is bad a little; × bad.
(4) comprehensive evaluation: ◎ is very good; Zero is good; △ is bad a little; × bad.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a high temperature resistant oriented transparent nanometer flaxen fiber polyester film, is characterized in that: its raw material comprises 1 ~ 50 part, nanometer flaxen fiber, polyester 50 ~ 95 parts, additive level at 0.1 ~ 5 part, and the content of interface coupling agent is at 0.1 ~ 5 part;
Described interface coupling agent is one or more in silane coupling agent, titanate coupling agent, isocyanates coupling agent, aluminate coupling agent;
Described polyester is polyethylene glycol 2，6-naphthalene dicarboxylate and/or PET;
Described additive is one or more mixing of silicon-dioxide, calcium carbonate, barium sulfate, kaolin, magnesiumcarbonate, calcium oxide, zinc oxide, water glass, weisspiessglanz, titanium oxide, acrylic acid or the like cross-linked polymer, erucicamide, stearic amide;
Described nanometer flaxen fiber is one or more in kenaf, hemp fibre, flax fiber, bastose, jute fibre and sisal fibers; Its diameter is between 50 ~ 300nm, and length is at below 1000nm.
2. high temperature resistant oriented transparent nanometer flaxen fiber polyester film according to claim 1, it is characterized in that: the limiting viscosity of described polyethylene glycol 2，6-naphthalene dicarboxylate, in ortho chloro phenol, is more than 0.4dl/g at 35 DEG C.
3. high temperature resistant oriented transparent nanometer flaxen fiber polyester film according to claim 1, is characterized in that: 1 ~ 30 part, nanometer flaxen fiber, polyester 70 ~ 95 parts, additive level are at 0.1 ~ 2 part, and the content of interface coupling agent is at 0.1 ~ 2 part.
4. high temperature resistant oriented transparent nanometer flaxen fiber polyester film according to claim 1, it is characterized in that: described interface coupling agent is silane coupling agent: the mixture of titanate coupling agent=2:1, or be aluminate coupling agent: the mixture of silane coupling agent=1:2;
Described additive is silicon-dioxide: the mixture of barium sulfate=2:1, or silicon-dioxide: the mixture of kaolin=2:1, or is silicon-dioxide: the mixture of calcium carbonate=2:1, or is silicon-dioxide: the mixture of stearic amide=2:1.
5. the method for the high temperature resistant oriented transparent nanometer flaxen fiber polyester film of preparation as described in one of claim 1-4, it is characterized in that, described method comprises the steps:
By nanometer flaxen fiber at 160-220 DEG C of heat drying, controlling dried nanometer flaxen fiber water content is less than 0.1%;
By mixing machine by the nanometer flaxen fiber material under solid state and powdery interface coupling agent Homogeneous phase mixing;
By polyester granules at 180-190 DEG C of heat drying, controlling dried water content is less than 0.1%;
By dried polyester granules pulverize, then mix with the nanometer flaxen fiber homogenize material of band interface coupling agent;
Mixed powder is sent in the hopper of forcing machine, through conveying, heating, melting at 290 DEG C;
Mixed in the molten state by the mixture of dispersion mixing equipment by nanometer flaxen fiber material and polyester material, make nanometer flaxen fiber homogenize material be dispersed in high-viscosity polyester macromolecular material;
By extrusion die, make the nanometer flaxen fiber polyester material film-like extruded;
Under the draft temperature of 150-180 DEG C, carry out biaxial stretch-formed with the multiplying power of 3.5 ~ 5.0 times respectively along longitudinal direction, transverse direction, and at the temperature heat setting type 1-100s of 160 to 250 DEG C, obtain product film.
6. the method for preparation according to claim 5 high temperature resistant oriented transparent nanometer flaxen fiber polyester film, it is characterized in that, the runner that formed between the major parts of described dispersion mixing equipment produces extensional flow, and extensional flow field is axisymmetric or for plane; Polymer composite flows and narrows from the width in this flow field, then is broadened by narrow, at least three times repeatedly; Spacing between tensile part can regulate, and adjustable distance is 0 ~ 5mm; Described extrusion die is slit coat hanger die.
7. the method for preparation according to claim 5 high temperature resistant oriented transparent nanometer flaxen fiber polyester film, is characterized in that, heat setting temperature 180 DEG C ~ 230 DEG C, and carries out heat-relaxing treatment at the temperature of 120 ~ 160 DEG C.
8. the method for preparation according to claim 5 high temperature resistant oriented transparent nanometer flaxen fiber polyester film, is characterized in that, the thickness of stretched film is 12 ~ 250 μm.
9. the method for preparation according to claim 5 high temperature resistant oriented transparent nanometer flaxen fiber polyester film, is characterized in that, the coefficient of expansion of described film at 30 ~ 150 DEG C is less than or equal to 10ppm/ DEG C, is more than or equal to 1ppm/ DEG C.
10. the method for preparation according to claim 5 high temperature resistant oriented transparent nanometer flaxen fiber polyester film, it is characterized in that, the total light transmittance of described film is more than or equal to 85%.
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