CN104877314A - Microporous polylactic acid oriented film - Google Patents
Microporous polylactic acid oriented film Download PDFInfo
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- CN104877314A CN104877314A CN201410070430.0A CN201410070430A CN104877314A CN 104877314 A CN104877314 A CN 104877314A CN 201410070430 A CN201410070430 A CN 201410070430A CN 104877314 A CN104877314 A CN 104877314A
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Abstract
The present invention provides a microporous polylactic acid oriented film, wherein the film has surface pores with a diameter of 10-1000 nm when the film is at a temperature of less than or equal to the glass transition temperature of the polylactic acid component in the film, and the area of the pores with the diameter of 10-1000 nm is reduced by more than or equal to 50% after the film is at the temperature 30 DEG C more than or equal to the glass transition temperature for 1 h. According to the present invention, the nano-scale micro-pore microporous oriented film with characteristics of compactness, uniformity and temperature response can be prepared, the processing method has characteristics of simpleness, high speed, and green environmental protection, and does not use toxic and hazardous solvents, and the microporous oriented film can be applied in a variety of fields of health care, medicine, building, water treatment, electronic products, packaging, decoration, and the like.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of polylactic acid film with microporous structure.
Background technology
Micro-porous membrane, as moisture permeable waterproof film, battery diaphragm, separatory membrane, tissue engineering material, energy storage material etc., is widely used at multiple fields such as hygiene care, medical treatment, building, water treatment, electronic products.The preparation method of micro-porous membrane, mainly contains foaming, particle-filled-stretching, solvent etched, is separated, self-assembly etc., and the obtained micro-porous membrane of various method structurally respectively has feature.
Poly(lactic acid) is a kind of Biodegradable polyester, and the micro-porous membrane containing this polymkeric substance is referred, can be applied in the field such as hygiene care, medical treatment.
CN201310185870.6 adopts the method for particle-filled-stretching, a kind of micro-porous oriented film containing biological degradation polyalcohols such as poly(lactic acid) is provided, the area of the surface holes of diameter within the scope of 0.2 ~ 7 μm accounts for the 0.5%-15% of total surface area, and fastness to water is greater than 800mm, and Water Vapour Permeability is greater than 1000g/m
2day, firm softness is less than 40mm.Can be used as moisture permeable waterproof film for health care field.
CN201110414695.4 adopts phase detachment technique, provides the poly-lactic acid material that a kind of aperture is controlled between 5-400 μm, and the porous support that can be used as used in tissue engineering uses.
CN201080052568.8 adopts and the foam of poly(lactic acid) is formed powder through pulverizing, and described powder is adhered by melting and is bonded with each other, and obtains the continuous poriferous structure between aperture 100-2000 μm, can be used as water-absorbing material.
The aperture of micro-porous membrane that above-mentioned each technology prepares is different, but be all difficult to obtained have nanometer, submicron order other, micro-porous polylactic acid film in homogeneous aperture.
When using as semipermeability films such as moisture permeable waterproof films, sometimes need flux controlled.Such as, the water vapour permeability of the micro-porous membrane of poly(lactic acid) can be used for the humidity regulating content.Sometimes need to make the humidity of content lower at a lower temperature, now need the water vapour permeability of film better; Make the humidity of content higher at relatively high temperatures, or make content no longer continue dehydration, now need the water vapour permeability of film less.Again such as, the water vapour permeability of the micro-porous membrane of poly(lactic acid) can be used for regulating the evaporation rate with volatile fragrances content.Sometimes need to allow volatile fragrances quickly through film at a lower temperature, and allow volatile fragrances more slowly through film at relatively high temperatures.
And all do not proposed to realize above-mentioned even, the Nano grade hole that has in prior art, and aperture and hole area have the technical scheme of the micro-porous membrane of poly(lactic acid) of temperature-responsive.
Summary of the invention
Along with the range of application of micro-porous polylactic acid film constantly expands, we find in prior art, large size aperture, the uneven pore size distribution of micro-porous polylactic acid film, do not possess the defects such as temperature-responsive, limit its application at multiple fields such as hygiene care, medical treatment, building, water treatment, electronic product, packaging, decorations.In order to address the deficiencies of the prior art, the invention provides a kind of micro-porous polylactic acid orientation film, and part or all of aperture in this film and hole area has temperature-responsive.So-called oriented film, it is the known term of those skilled in the art, refer to that the former film (unorientating film) prepared through methods such as curtain coating, blowing, cast, mold pressings is through unidirectional or two-way stretch, makes polymer molecule segment, molecular chain and/or crystallization generation orientation, prepares.The formation of orientation generally gives film in useful performance and character, such as the raising of film strength, toughness, the transparency; Depending on post-treatment condition, film also can be made to have heat-shrinkable.The orientation of film can be carried out on unidirectional, two-way drawing machine, and the blow moiding method that also can be improved by double-membrane soaking method (bubble tube method) etc. is carried out.
The invention provides a kind of micro-porous polylactic acid orientation film, time below the second-order transition temperature that film is in poly(lactic acid) component in film, there is the surface holes of diameter within the scope of 10-1000nm; When film was in the temperature of more than the second-order transition temperature of poly(lactic acid) component in film more than 30 DEG C after 1 hour, such hole area reduces more than 50%.
Surface holes described in the present invention refers to and is exposed to outside, and not by the hole that polymkeric substance and/or other holes cover completely, observes this pores on the membrane surface by microscope.
Second-order transition temperature refers to the amorphous phase of polymkeric substance by vitreous state to elastomeric state or by the transition temperature of the latter to the former, is the free-moving minimum temperature of unformed macromolecular chain segment, usually represents with Tg.The Tg of poly(lactic acid), generally at about 55 DEG C, can be subject to the impact of in degree of crystallinity, orientation degree, degree of crosslinking or additive types or content etc. or several factors.The existence of crystallization, orientation or the factor such as crosslinked, plays restriction to the athletic meeting of amorphous polymer segment, thus improves Tg.Due to the existence of the additives such as softening agent or comonomer, the Tg of poly(lactic acid) can be reduced to about 15 DEG C, even lower, concrete effect depends on kind or content.
The second-order transition temperature of polymkeric substance can be measured by the change detecting volume, thermodynamic property, mechanical property or electromagnetic property.Comparatively conventional means are dsc (DSC) or Dynamic thermo-mechanical property analytical method (DMA).The second-order transition temperature that different methods records difference to some extent, the second-order transition temperature described in the present invention obtains with the testing method test in following embodiment.
Time below the second-order transition temperature that film is in poly(lactic acid) component in film, the aperture of the surface holes of the nano level of diameter within the scope of 10-1000nm or submicron order, under the prerequisite not hindering vapor permeation, can effectively hinder passing through of liquid water.When film was in the temperature of more than the second-order transition temperature of poly(lactic acid) component in film more than 30 DEG C after 1 hour, such hole area reduces more than 50%.The reduction of hole area is reduced by aperture and is caused.
Increase the hole area sum of the surface holes of diameter within the scope of 10-1000nm, be conducive to improving Water Vapour Permeability.In the present invention, preferably, such hole area sum accounts for more than 20% of described micro-porous polylactic acid orientation film total surface area.Consider and increase Water Vapour Permeability further, in the present invention, the above-mentioned area sum with the surface holes of diameter within the scope of 10-1000nm more preferably accounts for more than 35% of described film total surface area, and further preferably more than 45%.
Consider that uniform pore diameter is conducive to improving the mechanical property of film and the homogeneity of water vapour permeability.In the present invention, preferably the above-mentioned aperture with the surface holes of diameter within the scope of 10-1000nm is homogeneous, and pore size distribution is less than 2.0, is more preferably less than 1.5, is preferably less than 1.3 further.
Further, in above-mentioned micro-porous polylactic acid orientation film, time below the second-order transition temperature that film is in poly(lactic acid) component in film, also there is the internal holes of diameter within the scope of 10-1000nm.Having of internal holes is beneficial to the further rate of perviousness improving film.
Internal holes described in the present invention refers to the hole completely by polymkeric substance and/or other maskaperture masks, can observe this pores by microscope on the cross section of film.
Described internal holes can weigh the amount of this pores by section area accounting.Utilize the means such as diamond cutter or ion polishing, along longitudinal direction (MD) or horizontal (TD) direction of film, after preparing MD-normal direction (ZD) section or TD-ZD section, this section is observed with microscope (electron microscope or atomic force microscope etc.), recycling image processing techniques, can add up the per-cent (section area accounting) that the area sum of this pores on the MD-ZD section or TD-ZD section of film accounts for this cross-sectional area.After statistical computation, with cross-sectional area for 100%, in the present invention, the section area accounting of the internal holes of above-mentioned diameter within the scope of 10-1000nm is preferably more than 20%.Consider and improve Water Vapour Permeability further, in the present invention, the internal holes of above-mentioned diameter within the scope of 10-1000nm further preferably more than 35%, more further preferably more than 45%.Consider the homogeneity improving film, in the present invention, the aperture of the internal holes of preferred above-mentioned diameter within the scope of 10-1000nm is homogeneous, and pore size distribution is less than 2.0, is preferably less than 1.5 further, is more preferably less than 1.3 further.
Further, when film was in more than the second-order transition temperature of poly(lactic acid) component in film more than 30 DEG C after 1 hour, the hole section area of the internal holes of described diameter within the scope of 10-1000nm reduces more than 50%.The reduction degree of this area can be passed through to regulate following formula and drawing process state modulator, to correspond to actual needs.
Consider the water vapour permeability improving film further, in the present invention, in above-mentioned micro-porous polylactic acid orientation film, diameter can also be had and be greater than 1 μm, and be less than the internal holes within the scope of 100 μm.Can above described method add up.After statistical computation, with cross-sectional area for 100%, above-mentioned in the present invention have diameter and be greater than 1 μm, and the section area accounting being less than the internal holes within the scope of 100 μm is preferably more than 10%.
Described micro-porous polylactic acid orientation film, the component containing, for example lower parts by weight: polylactic resin A:40-99 weight part, hydrophilic organic compound B:1-60 weight part; Described hydrophilic organic compound B is selected from water soluble or can one or more in organic compound swelling in water.
From structure, described polylactic resin A is that poly(lactic acid) (polylactide) or lactic acid are with one or more in the multipolymer of other chemical structures.
The molecular structure of preferred poly(lactic acid) is, the molecular structure be made up of 80-100mol% and the respective enantiomorph 0-20mol% of L lactic acid or D lactic acid.Above-mentioned polylactic resin from one or both L lactic acid or D lactic acid as raw material, and can be obtained by dehydrating polycondensation.Preferably, from the rac-Lactide of the cyclic dimer as lactic acid, can be obtained by ring-opening polymerization.The Study of Meso-Lactide having the cyclic dimer of L lactic acid and L rac-Lactide, the cyclic dimer of D lactic acid and D rac-Lactide, D lactic acid and L lactic acid to carry out cyclic dimer and obtain in rac-Lactide and the racemic mixture of D rac-Lactide and L rac-Lactide and DL rac-Lactide.Any one rac-Lactide can be used in the present invention.But, the preferred D rac-Lactide of main raw material or L rac-Lactide.
Described lactic acid, with the multipolymer of other chemical structures, refers to one or more in random copolymers, segmented copolymer or graft copolymer that lactic acid is formed with any chemical structural units.Wherein, there is no particular limitation for the chain length of lactic acid units, but consider from the angle of the mechanical property improving micro-porous membrane, and preferred lactic acid chain length is 1-20 ten thousand weight-average molecular weight.Described lactic acid, with the multipolymer of other chemical structures, is considered from the angle improving biological degradability and environment friendly, the multipolymer of the same hydroxycarboxylic acid of preferred lactic acid, binary or polyalcohols or binary or polycarboxylic acid class.
From crystal property, described polylactic resin A can be crystalline polylactic acid resin, also can be the mixture of amorphism polylactic resin or crystalline polylactic acid resin and amorphism polylactic resin.Consider from raising processability, the mixture of preferred amorphism polylactic resin or crystalline polylactic acid resin and amorphism polylactic resin.For the mixture of crystalline polylactic acid resin and amorphism polylactic resin, consider from raising processability, preferred amorphism polylactic resin accounts for more than 30% of mixture total weight amount, and further preferably more than 50%.
About the molecular weight of polylactic resin A, there is no particular limitation, but consider from the angle improving molding processibility and mechanical property, preferable weight-average molecular weight 50,000 ~ 500,000, and further preferably 80,000-30 ten thousand.
Above described water-soluble organic compound refers to: when a certain temperature of 4-100 DEG C, and this organic compound can dissolve more than 1g in 100g water.
Organic compound that can be swelling in water refers to: when a certain temperature of 4-100 DEG C, and the volumetric expansion of more than 10% occurs this organic compound of 1g in 100g water.
Described hydrophilic organic compound B can be small molecular organic compounds, also can be macromolecular organic compound and/or polymkeric substance.
Specifically, described hydrophilic organic compound B is selected from ethylene glycol, glycol ether, glycerine, or the alcohols micromolecular compound such as propylene glycol, succinic acid, or the carboxylic-acid micromolecular compound such as lactic acid, rac-Lactide, caprolactone, lactate, citrate, glyceryl ester, or the ester micromolecular compound such as Coronex, polyoxyethylene glycol, polyoxyethylene, polypropylene glycol, the polyether-based polymers such as polyethylene glycol-propylene glycol copolymers, or polyethers-polyolefin copolymer, polyether-polyester copolymer, polyether(poly)urethane, polyvinyl alcohol, polymine, polyvinylpyrrolidone, polyacrylamide, polymaleic acid, diallyl quaternary ammonium polymkeric substance, poly aspartic acid, poly-epoxy succinic acid, Carboxymethylinulin, starch or derivatives thereof, ether of cellulose, chitin, xanthan gum, or one or more in vegetable jelly.
From the ready availability consideration of raw material, described hydrophilic organic compound B is preferably ethylene glycol, glycerine, succinic acid, lactic acid, rac-Lactide, lactate, tributyl citrate, triethyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, vanay, Coronex, polyoxyethylene glycol, polyoxyethylene, polypropylene glycol, polyethylene glycol-propylene glycol copolymers, PLGA-PEG-PLGA, polypropylene glycol-copolymer of poly lactic acid, polyethylene glycol-propylene glycol-copolymer of poly lactic acid, polyvinyl alcohol, polymine, polyvinylpyrrolidone, starch, polymaleic acid, or one or more in poly aspartic acid.
From amount and the pore homogeneity of the surface holes of diameter within the scope of 10-1000nm described in improving and/or internal holes, preferred same polylactic resin A has the hydrophilic organic compound B of better consistency further.Specifically, can be one or more in ethylene glycol, glycerine, succinic acid, lactic acid, rac-Lactide, lactate, tributyl citrate, triethyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, vanay, Coronex, polyoxyethylene glycol, polyoxyethylene, polypropylene glycol, polyethylene glycol-propylene glycol copolymers, PLGA-PEG-PLGA, polypropylene glycol-copolymer of poly lactic acid or polyethylene glycol-propylene glycol-copolymer of poly lactic acid.
The present invention for the molecular weight of described hydrophilic organic compound B, special requirement, but from the mechanical property of film, preferred number average molecular weight is less than 100,000, and further preferred number average molecular weight is less than 50,000.
By regulating the proportioning of polylactic resin A and hydrophilic organic compound B, amount and the aperture of the surface holes of described diameter within the scope of 10-1000nm and/or internal holes can be regulated and controled.Improve the content of hydrophilic organic compound B, be conducive to amount and the aperture of improving described hole.
If above-mentioned film also has diameter be greater than 1 μm, and when being less than the internal holes within the scope of 100 μm, the water vapour permeability of film can be improved further.Contriver finds, described micro-porous polylactic acid orientation film, be 100 parts by weight with polylactic resin A and hydrophilic organic compound B, can also containing the hydrophobicity within 400 parts by weight during incompatible component C, described diameter can be formed in film and be greater than 1 μm, and be less than the internal holes within the scope of 100 μm.The incompatible component C of described hydrophobicity is selected from except described hydrophilic organic compound B, and can form heterogeneous structure with poly(lactic acid) when 40-100 DEG C, material in one or more.Describedly can form heterogeneous structure with poly(lactic acid) when 40-100 DEG C, when referring to the arbitrary temperature in the temperature range of 40-100 DEG C, heterogeneous structure can be formed with poly(lactic acid).
So-called heterogeneous structure is the term that polymer association area is general, refers at a certain temperature, there is two-phase or the above system of two-phase between polymkeric substance and polymkeric substance, between polymkeric substance and micromolecular compound or between polymkeric substance and inorganics.Heterogeneous structure directly can judge with microscopic methods such as opticmicroscope, electron microscope, atomic force microscope, and the indirect method such as differential scanning calorimeter, Dynamic Mechanical Analysis instrument also can be used to judge.
The incompatible component C of described hydrophobicity can be organism, also can be inorganics, or the mixture of organism and inorganics.Specifically, the incompatible component C of described hydrophobicity is selected from except described hydrophilic organic compound B, one or more in following substances: the alkane that carbonatoms is less than 100, alkene, the micromolecular compounds such as aromatic series, polyolefine, urethane, polyester except poly(lactic acid), polymeric amide, polyimide, polycarbonate, polythioether, polyethers, fluoropolymer, unsaturated polyester, epoxy resin, acrylic resin, or the polymkeric substance such as polystyrene, wood powder, Mierocrystalline cellulose, sisal fibers, or the vegetative fiber such as bamboo fibers, the animal fibers such as wool fiber, Kevlar, or the organic synthetic fibers such as aromatic polyester fibres, glass fibre, fibrous magnesium silicate, carbon fiber, graphite fibre, steel fiber, potassium titanate crystal whisker, aluminium borate whisker, magnesium system whisker, silicon system whisker, wollastonite, sepiolite, asbestos, slag fibre, xonotlite, ellestadite, gypsum fiber, silica fiber, silica/alumina fiber, Zirconium oxide fibre, boron nitride fibre, silicon nitride fiber or boron fibre, glass flake, non-bloating tendency mica, bloating tendency mica, graphite, tinsel, ceramic beads, talcum, clay, mica, sericite, zeolite, wilkinite, vermiculite, polynite, rhombspar, kaolin, micro mist silicic acid, Feldspar Powder, potassium titanate, fine hollow glass ball, calcium carbonate, magnesiumcarbonate, calcium sulfate, titanium dioxide, boehmite alumina, silicon oxide, gypsum, novaculite, the inorganics such as dawsonite or carclazyte.
The incompatible component C of above-mentioned hydrophobicity also can carry out surface modification or the Interfacial compatibilization of arbitrary form, to strengthen it with the interfacial adhesion between polylactic resin.
From the biodegradability consideration keeping or improve material, the preferred biological degradation polyalcohol of the incompatible component C of described hydrophobicity or mineral filler.
The incompatible component C of described hydrophobicity more preferably poly butyric ester, PHBV, polyhydroxybutyrate capronate, poly butylene succinate, poly-succinic tetramethylene adipate, polycaprolactone, poly terephthalic acid tetramethylene adipate, poly terephthalic acid hexanodioic acid propylene glycol ester, poly terephthalic acid succinic acid-butanediol ester, poly-ethylene carbonate, polypropylene carbonate, polymerized thylene carbonate cyclohexyl, calcium carbonate, talcum powder, mica powder, zeolite, vermiculite, titanium dioxide, silicon-dioxide, one or more in calcium sulfate or polynite.
In micro-porous polylactic acid orientation film of the present invention, not hindering in the scope realizing object of the present invention, can be added one or more in the additives such as softening agent, expanding material, end-capping reagent, fire retardant, nucleator, antioxidant, lubricant, static inhibitor, antifogging agent, photostabilizer, UV light absorber, pigment, mould inhibitor, antiseptic-germicide or whipping agent.In described hydrophilic organic compound B component C incompatible with hydrophobicity, part also can be used as the additives such as softening agent, nucleator, weighting agent, lubricant, pigment or dyestuff and use.
Described micro-porous polylactic acid orientation film, flood 10min in the water of 25 DEG C after, the water content of this film is the 1-50% of total film mass.
In described micro-porous polylactic acid orientation film, the weight-average molecular weight of polylactic resin is 5-50 ten thousand, in order to the mechanical characteristics of satisfied practicality, is preferably 8-40 ten thousand, more preferably 10-30 ten thousand.
Further, when film was in more than the second-order transition temperature of poly(lactic acid) component in film 30 DEG C or the temperature more than it after 1 hour, due to the internal holes of diameter within the scope of 10-1000nm and/or the reduction of surface holes aperture and the total area, may occur that the transmittance of film increases, the trend that mist degree reduces.In some technical scheme, when film was in more than the second-order transition temperature of poly(lactic acid) component in film 30 DEG C or the temperature more than it after 1 hour, transmittance can be obtained and be greater than 90%, the film that mist degree is less than 10%.The change of transparency makes this film can use as packaging film, decorating film.
The present invention utilizes the wetting ability of hydrophilic organic compound, preferably uses the micro-porous polylactic acid orientation film described in following various method preparation.
Method one
Described oriented film, is prepared through unidirectional or two-way stretch by unorientating film while heating by water vapour.
Method two
Described oriented film, is prepared through unidirectional or two-way stretch by unorientating film while liquid body heats; Described liquid is selected from water or is greater than the mixing liquid of 10 weight parts with mixing liquid 100 parts by weight water content.Described mixing liquid is including but not limited to the mixed solution (water-content is greater than 10%) of one or more liquid in water, ethanol, ethylene glycol or glycerine.From the concept of price and environmental protection, preferably water.Clean level for water quality or water does not have particular requirement, considers from the angle of product cleaning, is good with comparatively pure water, such as tap water, deionized water or distilled water.
Method three
Oriented film soaks rear taking-up in a liquid by unorientating film, while heated air heating, prepares through unidirectional or two-way stretch; Described liquid is selected from water or is greater than the mixing liquid of 10 weight parts with mixing liquid 100 parts by weight water content.Described mixing liquid is including but not limited to the mixed solution (water-content is greater than 10%) of one or more liquid in water, ethanol, ethylene glycol or glycerine.From the concept of price and environmental protection, preferably water.Clean level for water quality or water does not have particular requirement, considers from the angle of product cleaning, is good with comparatively pure water.Such as tap water, deionized water or distilled water.For the time of liquid infiltration, there is no special requirement, if fluid temperature is lower, longer dipping time can be selected, if fluid temperature is higher, in order to prevent the hydrolysis of poly(lactic acid), shorter dipping time can be selected, be generally 4s-10h.
In above-mentioned three kinds of methods, described unorientating film is before being stretched, and its water content does not specially require.But experiment shows, when water content is the 0.1-30% of total mass, is conducive to the homogeneity of described microporous structure.
In above-mentioned three kinds of methods, the temperature of described stretching is 40-100 DEG C.Consider from the angle improving processing stability, preferred draft temperature is 60-97 DEG C.
Can by regulating the drawing process parameters such as formula and stretching ratio, the aperture of control surface (and inner) hole, the number average in the aperture in the hole of described diameter within the scope of 10-1000nm is generally 100-800nm(and is accurate to 10nm).Stretching ratio is larger, and aperture is larger.
Based on the above method, described micro-porous polylactic acid orientation film can be prepared by general filming technologies such as additional heat setting types again.
The invention has the advantages that nanometer level microporous micro-porous oriented film that can obtain and possess intensive, all even temperature-responsive feature, and working method simply, at a high speed, need not use poisonous and harmful solvent, environmental protection.This micro-porous oriented film can be applied in the multiple fields such as hygiene care, medical treatment, building, water treatment, electronic product, packaging, decoration.
Embodiment
By following examples, the present invention is described in more detail, but described embodiment is not construed as limiting the invention.
The testing method used in embodiment and comparative example is as follows:
Thickness: use instrument company 7050 of Sanyo type thickness gauge to measure, get the mean value of 9 data.
Weight-average molecular weight and number-average molecular weight: use gel permeation chromatography, take tetrahydrofuran (THF) as moving phase, measure 3 times, average.
The second-order transition temperature (Tg) of poly(lactic acid) component: use differential scanning calorimeter (DSC) by the temperature rise rate of 10 DEG C/min, in the first time of film, heating curve obtains.
Rate of perviousness: based on JIS Z0208:1976, temperature 25 DEG C, humidity 90%.Measure 3 times, average.
The transparency: transmittance and mist degree press GB/T2410-2008, measure with photoelectricity haze meter.
Water content: by sample at 25 DEG C after vacuum-drying 24h, weigh m
1, be immersed in 10min in 25 DEG C of water, after taking-up, wipe surface water away, weigh m
2, calculate water content by formula (1),
< surface topography measures >
Aperture d: film surface is observed by scanning electronic microscope (SEM), 5, the photo of random shooting different positions enlargement ratio 10000 times, after ticking hole profile with pen, the area S of each surface holes is calculated with image processing software ImageJ1.46r, the aperture d(mono-kind in each hole diameter of equal value is calculated again, namely equal with hole area circular diameter by formula (2)):
Mean pore size (nano grade pore) d
n: by the aperture averaging value in the hole of formula (3) calculated diameter within the scope of 10-1000nm,
Wherein, ∑ d be adding of the aperture d in the hole of aperture within the scope of 10-1000nm and, n is the number in hole within the scope of the 10-1000nm that participates in calculating.
Pore size distribution (nano grade pore) SD: first calculate volume averaging aperture d by formula (4-1)
v, then by formula (4-2) calculated hole diameters distribution SD,
Wherein, ∑ d
4for the aperture d in the hole of aperture within the scope of 10-1000nm 4 powers add and; ∑ d
3for the aperture d in the hole of aperture within the scope of 10-1000nm 3 powers add and.
Area ratio (nano grade pore) S%: the area of the surface holes of diameter within the scope of 10-1000nm accounts for the per-cent of total surface area.Calculate by formula (5):
Wherein, ∑ S
mfor above-mentioned SEM observes area sum.
< internal morphology measures >
The means such as diamond cutter or ion polishing prepare smooth MD-ZD section, observe this section with SEM,
Aperture d: by statistics and the method for calculation in aforementioned surfaces aperture, calculates the aperture of internal holes.
Mean pore size (nano grade pore) d
n: by the aperture averaging value in the hole of formula (3) calculated diameter within the scope of 10-1000nm.Wherein, ∑ d be the aperture d in the hole of aperture within the scope of 10-1000nm adding and.
Pore size distribution (nano grade pore) SD: first calculate volume averaging aperture d by formula (4-1)
v, then by formula (4-2) calculated hole diameters distribution SD.
Area ratio (nano grade pore) S%: the area of the surface holes of diameter within the scope of 10-1000nm accounts for the per-cent of total surface area.Calculate by formula (5).
Mean pore size (micrometer grade hole) d '
m: the aperture averaging value representing the hole of diameter within the scope of 1-100 μm, calculates by formula (6).
Wherein, the aperture d that ∑ d ' is the hole of aperture within the scope of 1-100 μm add and, m is the number in hole within the scope of 1-100 μm that participates in calculating.
The raw material used in embodiment and comparative example is as follows:
< polylactic resin > (A)
A-1: poly(lactic acid), 4032D, Natureworks company of the U.S..Weight-average molecular weight 230,000.
A-2: poly(lactic acid), 4060D, Natureworks company of the U.S..Weight-average molecular weight 230,000.
< hydrophilic organic compound > (B)
B-1: polyoxyethylene glycol, number-average molecular weight 600, Chinese traditional Chinese medicines group.
B-2: PLA-PEG-PLA triblock copolymer, manufactures according to the embodiment 1 of CN200810018621.7.Number-average molecular weight 2.5 ten thousand.
The incompatible component > of < hydrophobicity (C)
C-1: poly butylene succinate, Bionolle1020, Japanese Showa polymer company.
C-2: poly terephthalic acid tetramethylene adipate, Ecoflex C1200, BASF Corp. of Germany.
C-3: calcium carbonate, particle diameter 3.6-5.0 μm, fine powder Co., Ltd. altogether of Japan three.
Embodiment 1 ~ 3, comparative example 1
By the proportioning that table 1 is listed, use twin screw extruder extruding pelletization, extrusion temperature 175-200 DEG C.Then, by single screw extrusion machine blowing, the unorientating film that thickness is 90 μm is prepared.Blow temperatures 180-200 DEG C.And then in the water vapour of 85 DEG C, two-way stretch while carrying out 3 × 3 times to unorientating film, then, carries out the test of various performance to the film of gained.Then, film is placed more than poly(lactic acid) component second-order transition temperature 30 DEG C in the film, after 1 hour, then carry out the mensuration of various performance.The results are shown in Table 1.
Embodiment 4 ~ 6, comparative example 2
By the proportioning that table 1 is listed, use twin screw extruder extruding pelletization, extrusion temperature 175-200 DEG C.Then, by single screw extrusion machine blowing, the unorientating film that thickness is 90 μm is prepared.Blow temperatures 180-200 DEG C.And then in the water of 85 DEG C, two-way stretch while carrying out 3 × 3 times to unorientating film, then, carries out the test of various performance to the film of gained.Then, film is placed more than poly(lactic acid) component second-order transition temperature 30 DEG C in the film, after 1 hour, then carry out the mensuration of various performance.The results are shown in Table 1.
Embodiment 7 ~ 9, comparative example 3
By the proportioning that table 1 is listed, use twin screw extruder extruding pelletization, extrusion temperature 175-200 DEG C.Then, by Single screw extrusion curtain coating, casting temperature 180-220 DEG C, prepares the unorientating film that thickness is 90 μm.And then unorientating film first soaks after 10 minutes in the water of 85 DEG C, then two-way stretch carry out 3 × 3 times under 85 DEG C of warm air beating while.Then, the film of gained is carried out to the test of various performance, the results are shown in Table 1.Then, film is placed more than poly(lactic acid) component second-order transition temperature 30 DEG C in the film, after 1 hour, then carry out the mensuration of various performance.The results are shown in Table 1.
Table 1 (unit: weight part)
Table 1(continues) (unit: weight part)
Claims (15)
1. a micro-porous polylactic acid orientation film, is characterized in that: time below the second-order transition temperature that film is in poly(lactic acid) component in film, has the surface holes of diameter within the scope of 10-1000nm; When film was in the temperature of more than this second-order transition temperature more than 30 DEG C after 1 hour, such hole area reduces more than 50%.
2. micro-porous polylactic acid orientation film according to claim 1, is characterized in that: the surface holes of described diameter within the scope of 10-1000nm, and such hole area sum accounts for more than 20% of described micro-porous polylactic acid orientation film total surface area.
3. micro-porous polylactic acid orientation film according to claim 1, is characterized in that: the pore size distribution of the surface holes of described diameter within the scope of 10-1000nm is less than 2.0.
4. the micro-porous polylactic acid orientation film according to any one of claim 1-3, is characterized in that: time below the second-order transition temperature that film is in poly(lactic acid) component in film, also has the internal holes of diameter within the scope of 10-1000nm.
5. micro-porous polylactic acid orientation film according to claim 4, is characterized in that: the pore size distribution of the internal holes of described diameter within the scope of 10-1000nm is less than 2.0.
6. micro-porous polylactic acid orientation film according to claim 4, it is characterized in that: when film was in the temperature of more than the second-order transition temperature of poly(lactic acid) component in film more than 30 DEG C after 1 hour, the section area of the internal holes of described diameter within the scope of 10-1000nm reduces more than 50%.
7. micro-porous polylactic acid orientation film according to claim 4, is characterized in that: also have diameter and be greater than 1 μm, and be less than the internal holes within the scope of 100 μm.
8. micro-porous polylactic acid orientation film according to claim 1, it is characterized in that: containing, for example the component of lower parts by weight in described micro-porous polylactic acid orientation film: polylactic resin A:40-99 weight part, hydrophilic organic compound B:1-60 weight part; Described hydrophilic organic compound B is selected from water soluble or can one or more in organic compound swelling in water.
9. micro-porous polylactic acid orientation film according to claim 8, is characterized in that: described polylactic resin A is the mixture of amorphism polylactic resin or crystalline polylactic acid resin and amorphism polylactic resin.
10. micro-porous polylactic acid orientation film according to claim 8, it is characterized in that: described hydrophilic organic compound B is selected from ethylene glycol, glycerine, succinic acid, lactic acid, rac-Lactide, lactate, tributyl citrate, triethyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, vanay, Coronex, polyoxyethylene glycol, polyoxyethylene, polypropylene glycol, polyethylene glycol-propylene glycol copolymers, PLGA-PEG-PLGA, polypropylene glycol-copolymer of poly lactic acid, polyethylene glycol-propylene glycol-copolymer of poly lactic acid, polyvinyl alcohol, polymine, polyvinylpyrrolidone, starch, polymaleic acid, or one or more in poly aspartic acid.
11. micro-porous polylactic acid orientation films according to Claim 8 according to any one of-10, is characterized in that: be 100 parts by weight with polylactic resin A and hydrophilic organic compound B, also containing the incompatible component C of hydrophobicity within 400 parts by weight; The incompatible component C of described hydrophobicity is selected from except described hydrophilic organic compound B, and when 40-100 DEG C, can with poly(lactic acid) formed in the material of heterogeneous structure one or more.
12. micro-porous polylactic acid orientation films according to claim 11, it is characterized in that: the incompatible component C of described hydrophobicity is selected from poly butyric ester, PHBV, polyhydroxybutyrate capronate, poly butylene succinate, poly-succinic tetramethylene adipate, polycaprolactone, poly terephthalic acid tetramethylene adipate, poly terephthalic acid hexanodioic acid propylene glycol ester, poly terephthalic acid succinic acid-butanediol ester, poly-ethylene carbonate, polypropylene carbonate, polymerized thylene carbonate cyclohexyl, talcum powder, mica powder, zeolite, vermiculite, calcium carbonate, titanium dioxide, silicon-dioxide, one or more in calcium sulfate or polynite.
13., according to the micro-porous polylactic acid orientation film described in claim 1, is characterized in that: flood after 10 minutes in the water of 25 DEG C, the water content of this film is the 1-50% of total film mass.
14., according to the micro-porous polylactic acid orientation film described in claim 1, is characterized in that: in described film, and the weight-average molecular weight of polylactic resin is 5-50 ten thousand.
15., according to the micro-porous polylactic acid orientation film described in claim 1, is characterized in that: when film was in the temperature of more than the second-order transition temperature of poly(lactic acid) component in film more than 30 DEG C after 1 hour, transmittance is greater than 90%, and mist degree is less than 10%.
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| CN201410070430.0A CN104877314A (en) | 2014-02-28 | 2014-02-28 | Microporous polylactic acid oriented film |
| JP2016526147A JP6302060B2 (en) | 2013-10-23 | 2014-10-15 | Microporous polylactic acid oriented film and its application |
| PCT/CN2014/088612 WO2015058638A1 (en) | 2013-10-23 | 2014-10-15 | Microporous polylactic acid oriented film and uses thereof |
| CN201480058315.XA CN105683288B (en) | 2013-10-23 | 2014-10-15 | Micro- porous polylactic acid orientation film and its application |
| TW103136430A TW201520241A (en) | 2013-10-23 | 2014-10-22 | Micro-porous polylactic-acid oriented film and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348761A (en) * | 2015-12-11 | 2016-02-24 | 河南工程学院 | Polylactic acid material for fused deposition molding and preparation method of polylactic acid material |
| CN106147160A (en) * | 2015-04-14 | 2016-11-23 | 东丽先端材料研究开发（中国）有限公司 | Micro-porous polylactic acid orientation thin film |
| CN106947228A (en) * | 2017-05-05 | 2017-07-14 | 四川大学 | Multistage porous poly-lactic acid material and preparation method thereof |
-
2014
- 2014-02-28 CN CN201410070430.0A patent/CN104877314A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106147160A (en) * | 2015-04-14 | 2016-11-23 | 东丽先端材料研究开发（中国）有限公司 | Micro-porous polylactic acid orientation thin film |
| CN105348761A (en) * | 2015-12-11 | 2016-02-24 | 河南工程学院 | Polylactic acid material for fused deposition molding and preparation method of polylactic acid material |
| CN106947228A (en) * | 2017-05-05 | 2017-07-14 | 四川大学 | Multistage porous poly-lactic acid material and preparation method thereof |
| CN106947228B (en) * | 2017-05-05 | 2021-11-05 | 四川大学 | Multistage porous polylactic acid material and preparation method thereof |
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