WO2015058638A1 - Microporous polylactic acid oriented film and uses thereof - Google Patents
Microporous polylactic acid oriented film and uses thereof Download PDFInfo
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- WO2015058638A1 WO2015058638A1 PCT/CN2014/088612 CN2014088612W WO2015058638A1 WO 2015058638 A1 WO2015058638 A1 WO 2015058638A1 CN 2014088612 W CN2014088612 W CN 2014088612W WO 2015058638 A1 WO2015058638 A1 WO 2015058638A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Definitions
- the invention belongs to the field of polymer materials and relates to a polylactic acid film having a microporous structure.
- microporous membranes are widely used in various fields such as health care, medical treatment, construction, water treatment, agriculture, electronic products, and decoration.
- the preparation method of the microporous film mainly includes foaming, particle filling-stretching, solvent etching, phase separation, self-assembly, etc., and the microporous film obtained by various methods has various structural characteristics.
- Polylactic acid is a biodegradable polyester, and a microporous film containing the polymer has been mentioned, and can be applied in fields such as sanitary care and medical treatment.
- a microporous oriented film containing a biodegradable polymer such as polylactic acid is provided by a particle filling-stretching method, and the surface pore area having a diameter in the range of 0.2 to 7 ⁇ m accounts for 0.5% to 15% of the total surface area.
- the water resistance is greater than 800 mm, the moisture permeability is greater than 1000 g/m 2 ⁇ day, and the softness is less than 40 mm. It can be used as a moisture permeable waterproof film in the field of health care.
- phase separation technology to provide a polylactic acid material with a pore diameter of between 5 and 400 ⁇ m can be used as a porous support for tissue engineering.
- CN201080052568.8 is a method in which a foam of polylactic acid is pulverized to form a powder, and the powders are joined to each other by fusion bonding to obtain a continuous porous structure having a pore diameter of 100 to 2000 ⁇ m, which can be used as a water absorbing material.
- microporous film prepared by the above various techniques has different pore diameters, but it is difficult to obtain a microporous polylactic acid film having a nanometer, submicron order and uniform pore diameter.
- the moisture permeability of a polylactic acid microporous film can be used to adjust the humidity of the contents. Sometimes it is necessary to lower the humidity of the contents at a lower temperature, in which case the film is required to have better moisture permeability; at higher temperatures, the humidity of the contents is higher, or the contents are no longer dehydrated. The film is required to have less moisture permeability. As another example, the moisture permeability of the polylactic acid microporous film can be used to adjust the rate of volatilization of the contents of the volatile aromatic component. It is sometimes desirable to have the volatile aromatic component pass through the film faster at lower temperatures and to allow the volatile aromatic component to pass through the film more slowly at higher temperatures.
- transparency is sometimes required to vary with temperature. For example, at lower temperatures, the film is less transparent; at higher temperatures, the film is more transparent.
- microporous polylactic acid film has large pore size, uneven pore size distribution and the like in the prior art, which limits its health care, medical treatment, construction, water treatment, Applications in various fields such as agriculture, electronics, packaging, and decoration. In addition, in some cases, temperature responsiveness is also required.
- the present invention provides a microporous polylactic acid oriented film.
- the so-called oriented film is a term well known to those skilled in the art and refers to casting, blow molding,
- the original film (unoriented film) prepared by casting, molding or the like is prepared by uniaxially or biaxially stretching to orient the polymer molecular segments, molecular chains and/or crystals.
- the formation of orientation generally imparts beneficial properties and properties to the film, such as increased film strength, toughness, and transparency; and depending on post-treatment conditions, the film can also be heat shrinkable.
- the orientation of the film can be carried out on a one-way or two-way stretching machine, or by an improved blow molding method such as a double bubble method (bubble method).
- a method of detecting whether or not the film is oriented is a well-known technique, and conventionally, there are an X-ray diffraction method, a birefringence method, a Raman spectroscopy method, an infrared method, an ultrasonic method, and the like.
- the present invention provides a microporous polylactic acid oriented film having a surface pore having a diameter in the range of 10 to 1000 nm when the film is below the glass transition temperature of the polylactic acid component in the film, and the sum of the pore areas occupies the film More than 20% of the total surface area.
- the oriented polylactic acid film has better strength and storage stability than the unoriented polylactic acid film.
- the surface pores described in the present invention refer to pores which are exposed to the outside and are not completely shielded by the polymer and/or other pores, and such pores can be observed on the surface of the film by a microscope.
- the area of the hole refers to the projected area of the hole on the horizontal surface when the film is horizontally placed.
- the total surface area of the film refers to the projected area of the film on the horizontal surface when the film is horizontally placed.
- nano-scale and sub-micron pore diameters in the range of 10-1000 nm can effectively hinder the passage of liquid water without hindering water vapor permeation.
- the glass transition temperature refers to the transition temperature of the amorphous phase of the polymer from the glassy state to the high elastic state or from the former to the lowest temperature of the free movement of the amorphous macromolecular segment, which is usually expressed by Tg.
- the Tg of polylactic acid is generally around 55 ° C, and is affected by one or several factors such as crystallinity, degree of orientation, degree of crosslinking, or type or content of additives. The presence of factors such as crystallization, orientation, or crosslinking can limit the movement of the amorphous polymer segments, thereby increasing the Tg. Due to the presence of additives such as plasticizers or comonomers, the Tg of polylactic acid can be lowered to about 15 ° C or even lower. The specific effect depends on the type or content.
- the glass transition temperature of the polymer can be determined by measuring changes in volume, thermodynamic properties, mechanical properties, or electromagnetic properties. The more common means are differential scanning calorimetry (DSC) or dynamic thermomechanical performance analysis (DMA). The glass transition temperatures measured by the different methods are different, and the glass transition temperature described in the present invention is tested by the test method in the following specific embodiment.
- the pore size of the nano- or sub-micron surface pores having a diameter in the range of 10 to 1000 nm can effectively hinder the liquid without hindering the vapor permeation.
- the passage of water The passage of water.
- the sum of the pore areas of the surface pores having a diameter in the range of 10 to 1000 nm is advantageous for increasing the moisture permeability.
- the sum of the pore areas of the pores accounts for 20% or more of the total surface area of the microporous polylactic acid oriented film.
- the sum of the areas of the surface pores having a diameter in the range of 10 to 1000 nm is more preferably 35% or more, and still more preferably 45% or more of the total surface area of the film.
- the upper limit of the area of the surface pores is not particularly limited, and may be, for example, 70% or less.
- Uniform pore size is beneficial to improve the mechanical properties of the film and the uniformity of moisture permeability.
- the above-mentioned pores having surface pores having a diameter in the range of 10 to 1000 nm have a uniform pore diameter, and the pore diameter distribution is preferably less than 2.0, more preferably less than 1.5, still more preferably less than 1.3.
- the lower limit of the pore size distribution is not particularly limited, and may be, for example, 1.05 or more.
- the film when the film is below the glass transition temperature of the polylactic acid component in the film, it also has internal pores having a diameter in the range of 10 to 1000 nm. The presence of the internal pores is advantageous for further increasing the moisture permeability of the film.
- the internal pores described in the present invention refer to pores that are completely obscured by the polymer and/or other pores, which can be observed by a microscope on the cross section of the film.
- the internal bore can measure the amount of such pores by the ratio of the cross-sectional area.
- Prepare the MD-normal (ZD) section or the TD-ZD section along the longitudinal (MD) or transverse (TD) direction of the film by means of a diamond knife or ion polishing, using a microscope (electron microscope or atomic force microscope, etc.) Observing the section, and using image processing techniques, the sum of the areas of the pores on the MD-ZD section or the TD-ZD section of the film as a percentage of the area of the section (the ratio of the cross-sectional area) can be counted.
- the cross-sectional area of the inner diameter in the range of 10 to 1000 nm in the present invention is preferably 20% or more in the cross-sectional area of 100%.
- the internal pores having a diameter in the range of 10 to 1000 nm are more preferably 35% or more, still more preferably 45% or more.
- the upper limit of the cross-sectional area ratio of the internal pores is not particularly limited, and may be, for example, 70% or less.
- the inner pores having a diameter in the range of 10 to 1000 nm have a uniform pore diameter, and the pore diameter distribution is preferably less than 2.0, further preferably less than 1.5, still more preferably less than 1.3.
- the lower limit of the aforementioned pore size distribution is not particularly limited, and may be, for example, 1.1 or more.
- the microporous polylactic acid oriented film of the present invention can be made temperature sensitive by changing the formulation and process.
- the film is at a temperature higher than the glass transition temperature of the polylactic acid component in the film by 30 ° C or more for 1 hour, the sum of the pore areas of the surface pores having a diameter in the range of 10 to 1000 nm is reduced by 50% or more.
- the reduction in the area of the hole is caused by the reduction in the aperture.
- the film when the film is at a temperature higher than the glass transition temperature of the polylactic acid component in the film by more than 30 ° C for 1 hour, the sum of the pore cross-sectional areas of the internal pores having a diameter in the range of 10 to 1000 nm is reduced by 50%. the above.
- the extent of this reduction can be controlled by adjusting the formulation and stretching process parameters described below to meet actual needs.
- the film when the film is at a temperature 30 ° C higher or higher than the glass transition temperature of the polylactic acid component in the film for 1 hour, A decrease in the pore size and total area of the internal pores and/or surface pores in the range of 10-1000 nm may increase the transmittance of the film and decrease the haze.
- a film having a light transmittance of more than 90% and a haze of less than 10% can be obtained. .
- the internal pore and/or surface pore diameter and total area are reduced due to the diameter in the range of 10 to 1000 nm.
- the moisture permeability of the film may decrease.
- a film having a moisture permeability reduction of 40% or more can be obtained. The change in transparency and moisture permeability allows the film to be used as a packaging film or a decorative film.
- the microporous polylactic acid oriented film of the present invention can be made to have no temperature sensitivity or weak temperature sensitivity by changing the formulation and the process. That is, after the film is at a temperature 30 ° C higher than the glass transition temperature of the polylactic acid component in the film for 1 hour, the sum of the pore areas of the surface pores having a diameter in the range of 10 to 1000 nm is reduced by 50% or less (excluding 50%).
- the film when the film is at a temperature 30 ° C higher than the glass transition temperature of the polylactic acid component in the film, the sum of the pore cross-sectional areas of the internal pores having a diameter in the range of 10 to 1000 nm is reduced by 50%.
- the microporous polylactic acid oriented film may further have internal pores having a diameter of more than 1 ⁇ m and less than 100 ⁇ m. Statistics can be performed as described above. After the statistical calculation, the cross-sectional area is 100%, and in the present invention, the cross-sectional area ratio of the inner pores having a diameter of more than 1 ⁇ m and less than 100 ⁇ m is preferably 10% or more. The lower limit of the cross-sectional area ratio is not particularly limited, and may be, for example, 30% or less.
- the microporous polylactic acid oriented film contains the following components by weight: polylactic acid resin A: 40-99 parts by weight, hydrophilic organic compound B: 0.1-60 parts by weight; said hydrophilic organic Compound B is one or more selected from the group consisting of organic compounds which are soluble in water or swellable in water.
- the polylactic acid resin A may be any polylactic acid resin, and further, may be one or more of polylactic acid (polylactide), or a copolymer of lactic acid and other chemical structures.
- the molecular structure of the preferred polylactic acid is a molecular structure consisting of 80 to 100 mol% of L lactic acid or D lactic acid and 0 to 20 mol% of the respective enantiomers.
- the polylactic acid resin can be obtained by dehydrating polycondensation from one or both of L lactic acid or D lactic acid. Preferably, it can be obtained by ring-opening polymerization from lactide which is a cyclic dimer of lactic acid.
- lactide which is a cyclic dimer of L lactic acid
- D-lactide which is a cyclic dimer of D lactic acid
- D-lactide of D lactic acid and L lactic acid are subjected to cyclic dimerization.
- the main raw material is preferably D lactide or L lactide.
- the copolymer of lactic acid and other chemical structures refers to one or more of a random copolymer, a block copolymer or a graft copolymer formed of lactic acid and any chemical structural unit.
- the length of the segment of the lactic acid unit is not particularly limited, but from the viewpoint of improving the mechanical properties of the microporous film, the lactic acid segment length is preferably from 1 to 200,000 weight average molecular weight.
- the copolymer of lactic acid and other chemical structures is preferably lactic acid with a hydroxycarboxylic acid, a dihydric or polyhydric alcohol, or a binary or polycarboxylic acid, from the viewpoint of improving biodegradability and environmental friendliness. Copolymer.
- the polylactic acid resin A may be a crystalline polylactic acid resin or an amorphous polylactic acid resin, or may be a mixture of a crystalline polylactic acid resin and an amorphous polylactic acid resin. From the viewpoint of improving the moldability, a mixture of an amorphous polylactic acid resin or a crystalline polylactic acid resin and an amorphous polylactic acid resin is preferred.
- the mixture of the crystalline polylactic acid resin and the non-crystalline polylactic acid resin preferably has a non-crystalline polylactic acid resin of 30% or more, and more preferably 50% or more, based on the total weight of the mixture, from the viewpoint of improving the moldability.
- DSC differential scanning calorimetry
- the molecular weight of the polylactic acid resin A is not particularly limited, but from the viewpoint of improving moldability and mechanical properties, the weight average molecular weight is preferably 50,000 to 500,000, and more preferably 80,000 to 300,000.
- the water-soluble organic compound described above means that the organic compound can dissolve 1 g or more in 100 g of water at a certain temperature of 4-100 °C.
- the organic compound which can swell in water means that 1 g of the organic compound undergoes volume expansion of 10% or more in 100 g of water at a certain temperature of 4-100 °C.
- the hydrophilic organic compound B may be a small molecule organic compound or a macromolecular organic compound and/or a polymer.
- the hydrophilic organic compound B may be selected from small alcoholic compounds such as ethylene glycol, diethylene glycol, glycerin, or propylene glycol, small carboxylic acids such as succinic acid or lactic acid.
- small alcoholic compounds such as ethylene glycol, diethylene glycol, glycerin, or propylene glycol
- small carboxylic acids such as succinic acid or lactic acid.
- Molecular compound, lactide, caprolactone, lactate, citrate, glyceride, or isosorbide ester compound polyethylene glycol, polyethylene oxide, polypropylene glycol, polyethylene glycol - a polyether polymer such as a polypropylene glycol copolymer, or a polyether-polyolefin copolymer, a polyether-polyester copolymer, a polyether polyurethane, a polyvinyl alcohol, a polyethyleneimine, a polyvinylpyrrolidone, a polyacrylamide
- the hydrophilic organic compound B is preferably ethylene glycol, glycerin, succinic acid, lactic acid, lactide, lactate, tributyl citrate or triethyl citrate from the viewpoint of availability of the raw material. , acetyl triethyl citrate, acetyl tributyl citrate, triacetin, isosorbide, polyethylene glycol, poly Ethylene oxide, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol-polylactic acid copolymer, polypropylene glycol-polylactic acid copolymer, polyethylene glycol-polypropylene glycol-polylactic acid copolymer, polyvinyl alcohol One or more of polyethyleneimine, polyvinylpyrrolidone, starch, polymaleic acid, or polyaspartic acid.
- the hydrophilic organic compound B having better compatibility with the polylactic acid resin A is more preferable.
- it may be ethylene glycol, glycerin, succinic acid, lactic acid, lactide, lactate, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tributyl Ester, triacetin, isosorbide, polyethylene glycol, polyethylene oxide, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol-polylactic acid copolymer, polypropylene glycol-polylactic acid copolymerization Or one or more of polyethylene glycol-polypropylene glycol-polylactic acid copolymer.
- the present invention has no particular requirement for the molecular weight of the hydrophilic organic compound B.
- the number average molecular weight is preferably less than 100,000, and more preferably the number average molecular weight is less than 50,000.
- the lower limit of the number average molecular weight is not particularly limited, and may be, for example, 55 or more.
- the microporous polylactic acid oriented film has a hydrophobic incompatible component C of 400 parts by weight or less based on 100 parts by weight of the polylactic acid resin A and the hydrophilic organic compound B. Internal pores having a diameter greater than 1 ⁇ m and less than 100 ⁇ m are formed in the film.
- the hydrophobic incompatible component C is selected from one or more of the substances other than the hydrophilic organic compound B and which can form a multiphase structure with polylactic acid at 40-100 ° C. .
- the formation of a multi-phase structure with polylactic acid at 40-100 ° C means that a polyphase structure can be formed with polylactic acid at any temperature in the temperature range of 40-100 ° C.
- the so-called multiphase structure is a general term in the field of polymer related, which means that it is concentrated at a certain temperature.
- a system of two-phase system or more is present between the compound and the polymer, between the polymer and the small molecule compound, or between the polymer and the inorganic substance.
- the multiphase structure can be directly judged by microscopic methods such as optical microscopy, electron microscopy, atomic force microscopy, etc., or can be judged by indirect methods such as differential scanning calorimetry and dynamic mechanical performance analyzer.
- the hydrophobic incompatible component C may be an organic substance, an inorganic substance, or a mixture of an organic substance and an inorganic substance.
- the hydrophobic incompatible component C is selected from one or more of the following substances other than the hydrophilic organic compound B: an alkane or an olefin having a carbon number of less than 100 , small aromatic compounds such as aromatics, polyolefins, polyurethanes, polyesters other than polylactic acid, polyamides, polyimides, polycarbonates, polythioethers, polyethers, fluoropolymers, unsaturated resins, rings
- Polymers such as oxygen resin, acrylic resin, or polystyrene, vegetable powder such as wood flour, cellulose, sisal fiber, or bamboo fiber, animal fiber such as wool fiber, aramid fiber, or aromatic polyester
- Organic synthetic fibers such as fibers, glass fibers, asbestos fibers, carbon fibers, graphite fibers, metal fibers, potassium titanate whiskers, aluminum borate whiskers, magnesium whiskers
- the above hydrophobic incompatible component C can also be subjected to any form of surface modification or interfacial compatibilization to enhance its interfacial adhesion to the polylactic acid resin.
- the hydrophobic incompatible component C is preferably a biodegradable polymer or an inorganic filler from the viewpoint of maintaining or enhancing the biodegradability of the material.
- the hydrophobic incompatible component C is further preferably polyhydroxybutyrate, polyhydroxybutyrate valerate, polyhydroxybutyrate caproate, polybutylene succinate, polybutylene succinate Butylene glycol ester, polycaprolactone, polybutylene terephthalate, propylene terephthalate, polybutylene succinate, polyethylene
- One or more of carbonate, polypropylene carbonate, polycyclohexylene carbonate, calcium carbonate, talc, mica powder, zeolite, vermiculite, titanium dioxide, silica, calcium sulfate or montmorillonite is further preferably polyhydroxybutyrate, polyhydroxybutyrate valerate, polyhydroxybutyrate caproate, polybutylene succinate, polybutylene succinate Butylene glycol ester, polycaprolactone, polybutylene terephthalate, propylene terephthalate, polybutylene succinate, polyethylene
- a plasticizer, a compatibilizer, a terminal blocking agent, a flame retardant, a nucleating agent, an antioxidant, and a lubricant may be added to the extent that the object of the present invention is not hindered from being achieved.
- additives such as an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, an antifungal agent, an antibacterial agent, or a foaming agent.
- Some of the hydrophilic organic compound B and the hydrophobic incompatible component C may also be used as an additive such as a plasticizer, a nucleating agent, a filler, a lubricant, a pigment, or a dye.
- the microporous polylactic acid oriented film has good hydrophilicity, and after immersing in water at 25 ° C for 10 minutes, the water content of the film is 1-50% of the total mass of the film.
- the polylactic acid resin has a weight average molecular weight of 50,000 to 50,000, and is preferably from 8 to 400,000, more preferably from 100,000 to 300,000, in order to satisfy practical mechanical properties.
- the present invention utilizes the hydrophilicity of the hydrophilic organic compound, and it is preferred to prepare the microporous polylactic acid oriented film by the following method.
- Step 1 The raw materials are blended by extrusion, mixing or opening.
- Step 2 The unoriented film is obtained by casting, blow molding, calendering, molding, extruding, and casting the blend obtained in the first step.
- Step 3 Prepare an oriented film by any of the following methods:
- the oriented film is prepared by unidirectional or biaxial stretching of the unoriented film while being heated by steam.
- the oriented film is prepared by unidirectional or biaxial stretching while the liquid is heated by the unoriented film; the liquid is selected from water or a mixed liquid having a water content of more than 10 parts by weight based on 100 parts by weight of the mixed liquid.
- the mixed liquid includes, but is not limited to, a mixture of one or more of water, ethanol, ethylene glycol, or glycerin (water content greater than 10%). From the concept of price and environmental protection, water is preferred. There is no special requirement for the cleanliness of water or water. From the perspective of product cleanliness, it is better to use pure water, such as tap water, deionized water, or distilled water.
- the oriented film is taken out after immersing in the liquid in the unoriented film, and is prepared by unidirectional or biaxial stretching while being heated by the heated air; the liquid is selected from water or the water content is more than 10 in 100 parts by weight of the mixed liquid. Parts by weight of the mixed liquid.
- the mixed liquid includes, but is not limited to, a mixture of one or more of water, ethanol, ethylene glycol, or glycerin (water content greater than 10%). From the concept of price and environmental protection, water is preferred. There is no special requirement for the cleanliness of water quality or water. From the perspective of product cleanliness, it is better to use pure water. Such as tap water, deionized water, or distilled water. There is no special requirement for the time of liquid immersion. If the liquid temperature is low, a longer immersion time can be selected. If the liquid temperature is high, in order to prevent hydrolysis of polylactic acid, a shorter immersion time can be selected, generally 4 s - 10h.
- the water content of the unoriented film before the stretching is not particularly required.
- the water content is from 0.1 to 30% of the total mass, which is advantageous for the uniformity of the microporous structure.
- the stretching temperature is 40 to 100 °C. From the corner of improving processing stability
- the preferred stretching temperature is 60-97 ° C.
- the pore size of the surface (and internal) pores can be controlled by adjusting the stretching process parameters such as formulation and draw ratio, and the average number of pores of the pores having a diameter in the range of 10-1000 nm is generally 100-800 nm (accurately 10nm). The larger the draw ratio, the larger the pore size.
- the microporous polylactic acid oriented film can be further prepared by a general film forming process such as heat setting.
- step four a microporous polylactic acid oriented film which is not temperature sensitive or has low temperature sensitivity can be obtained.
- Step 4 The oriented film is post-treated, and the post-treatment may be any one or more of the following methods, but is not limited to the following methods:
- Method 1 using a liquid to soak the oriented film, the liquid used is selected from water or a mixed liquid having a water content of more than 10 parts by weight based on 100 parts by weight of the mixed liquid, and the temperature of the liquid is selected from 40 ° C to 99 ° C, preferably 60 ° C -
- the post-treatment time is from 90 s C to 1 s to 180 min, preferably from 2 s to 120 min.
- Method 2 Apply a layer of high heat resistance material to the surface of the film, and apply a solution or a suspension-dispersed heat-resistant material to the surface of the mesh of the film.
- the coating material is any one or more of epoxy resin, polyurethane, and acrylic resin.
- the coating method is any one or more of dipping, roll coating, and spray coating.
- Method 3 Coating the surface of the film.
- the coating material is: gold, platinum, aluminum, silver, nickel, molybdenum, copper, tin, antimony, zinc, tungsten, titanium, chromium, zirconium, silicon, graphite, aluminum oxide, indium oxide, titanium oxide, magnesium oxide.
- the coating method is one or more of vacuum sputtering coating, vacuum ion plating, ion beam deposition, ion beam assisted deposition, optical coating, chemical vapor deposition, and vacuum evaporation coating.
- Method 4 A crosslinking agent is added in the step of film preparation, and crosslinking is carried out in this step.
- the cross-linking agent refers to: polyfunctional polyester acrylate, triallyl isocyanurate, epoxy-acrylic resin, polyether acrylate, multifunctional alcohol or ethylene glycol acrylate, urethane acrylic acid One or more of ester, epoxy-cation, benzophenone, aziridine, amine, thioxanthone.
- the crosslinking method is one or more of gamma ray radiation crosslinking, electron beam radiation crosslinking, microwave radiation crosslinking, and ultraviolet light crosslinking.
- the invention has the advantages that a microporous oriented film with nano-scale micropores with dense, uniform and temperature responsive characteristics can be obtained, and the processing method is simple and high-speed, and no toxic and harmful solvent is needed, and the environment is green.
- the microporous oriented film can be used in various fields such as sanitary care, medical treatment, construction, water treatment, agriculture, electronic products, packaging, decoration, and the like.
- test methods used in the examples and comparative examples are as follows. For all tests, if the test temperature is not clearly stated, the test is carried out at 25 ° C:
- Thickness Measured using a Sanyo Instruments 7050 thickness gauge and averaged 9 data.
- Weight average molecular weight and number average molecular weight measured by gel permeation chromatography, using tetrahydrofuran as a mobile phase, measured three times, and averaged.
- the glass transition temperature (Tg) of the polylactic acid component was obtained on a first heating curve of the film using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C/min.
- Moisture permeability based on JIS Z0208: 1976, humidity 90%. It was measured 3 times and averaged.
- Transparency Transmittance and haze are determined by photoelectric haze according to GB/T 2410-2008.
- Water content After drying the sample under vacuum at 25 ° C for 24 h, weigh m 1 and immerse it in water for 10 min. After taking out, wipe off the surface water, weigh m 2 , calculate the water content according to formula (1).
- the surface topography was observed at 25 °C.
- Aperture d The surface of the film was observed by scanning electron microscope (SEM), and 5 photographs with magnifications of 10,000 times at different positions were randomly taken. After the contour of the hole was extracted with a pen, the area of each surface hole was calculated by image processing software ImageJ 1.46r. S, then calculate the aperture d of each hole according to the formula (2) (an equivalent diameter, that is, the diameter of a circle equal to the hole area):
- Average pore diameter (nanoscale pore) d n Calculate the average pore diameter of a pore having a diameter in the range of 10 to 1000 nm according to the formula (3),
- ⁇ d is the sum of the pore diameters d of the pores having a pore diameter in the range of 10 to 1000 nm, and n is the number of pores in the range of 10-1000 nm participating in the calculation.
- Pore size distribution (nano-scale pores) SD First calculate the volume average pore diameter d v according to formula (4-1), and then calculate the pore size distribution SD according to formula (4-2).
- Area ratio (nanoscale pores) S% The area of the surface pores in the range of 10 to 1000 nm in diameter as a percentage of the total surface area. Calculated according to formula (5):
- ⁇ S m is the sum of the above-mentioned SEM observation areas.
- the surface topography was observed at 25 °C.
- a flat MD-ZD section was prepared by means of a diamond knife or ion polishing, and the section was observed by SEM.
- Aperture d The pore diameter of the internal pore is calculated according to the statistical and calculation method of the aforementioned surface pore diameter.
- Average pore diameter (nanoscale pore) d n The average value of the pore diameter of the pore having a diameter in the range of 10 to 1000 nm is calculated according to the formula (3). Wherein ⁇ d is the sum of the pore diameters d of the pores having a pore diameter in the range of 10 to 1000 nm.
- Pore size distribution (nano-scale pores) SD First, the volume average pore diameter d v is calculated according to the formula (4-1), and the pore size distribution SD is calculated according to the formula (4-2).
- Area ratio (nanoscale pores) S% The area of the surface pores in the range of 10 to 1000 nm in diameter as a percentage of the total surface area. Calculated according to equation (5).
- Average pore diameter (micron-sized pore) d' m represents the average value of the pore diameter of the pore having a diameter in the range of 1-100 ⁇ m, which is calculated according to the formula (6).
- ⁇ d' is the sum of the pore diameters d of the pores having a pore diameter in the range of 1-100 ⁇ m, and m is the number of pores in the range of 1-100 ⁇ m participating in the calculation.
- A-1 Polylactic acid, 4032D, American Natureworks. The weight average molecular weight is 230,000.
- A-2 Polylactic acid, 4060D, American Natureworks. The weight average molecular weight is 230,000.
- B-1 polyethylene glycol, number average molecular weight 600, China National Pharmaceutical Group.
- B-2 Polylactic acid-polyethylene glycol-polylactic acid triblock copolymer, which was produced in accordance with Example 1 of CN200810018621.7.
- the number average molecular weight is 20,000.
- C-1 polybutylene succinate, Bionolle 1020, Japan Showa Polymer Co., Ltd.
- C-3 Calcium carbonate, particle size 1.2-3.5 ⁇ m, Japan Sankyo Fine Powder Co., Ltd.
- the raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C.
- a non-oriented film having a thickness of 100 ⁇ m was prepared by blow molding by a single screw extruder.
- the blow molding temperature is 180-200 °C.
- the unoriented film was subjected to simultaneous biaxial stretching at 3 ⁇ 3 times in water vapor at 85 ° C to obtain an oriented film.
- Table 1 lists the composition of the film. The properties of each film were measured at 25 ° C and are listed in Table 1.
- the raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C.
- a non-oriented film having a thickness of 100 ⁇ m was prepared by blow molding by a single screw extruder.
- the blow molding temperature is 180-200 °C.
- the unoriented film was subjected to simultaneous biaxial stretching at 3 ⁇ 3 times in hot air at 85 ° C to obtain an oriented film.
- Table 1 lists the composition of the film. The properties of each film were measured at 25 ° C and are listed in Table 1.
- the raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C.
- casting was carried out by a single-screw extruder at a casting temperature of 180 to 200 ° C to prepare a non-oriented film having a thickness of 120 ⁇ m.
- the unoriented film was stretched in water at 80 ° C according to the stretching method listed in Table 2 to obtain an oriented film.
- Table 2 lists the film composition. The properties of each film were measured at 25 ° C and are listed in Table 2.
- the raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C.
- casting was carried out by a single-screw extruder at a casting temperature of 180 to 200 ° C to prepare a non-oriented film having a thickness of 120 ⁇ m. Further, it was immersed in water at 80 ° C for 30 minutes. Further, the unoriented film was stretched in air at 90 ° C according to the stretching method listed in Table 3 to obtain an oriented film.
- Table 3 lists the film composition. The properties of each film were measured at 25 ° C and are listed in Table 3.
- the surface of the oriented film described in Example 12 is evaporated with a layer of aluminum oxide having a thickness of 40 nm;
- the surface of the oriented film described in Example 13 was evaporated to a thickness of 40 nm;
- the surface of the oriented film described in Example 14 was coated with an epoxy resin having a thickness of 20 nm.
- each film was placed at a temperature higher than the glass transition temperature of the polylactic acid component in the film by 30 ° C, and after 1 hour, various properties were measured. The results are shown in Table 5.
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Abstract
The present invention provides a microporous polylactic acid oriented film, wherein, when the film is at a temperature below the glass transition temperature of the polylactic acid component in the film, it has surface pores with a diameter in the range of 10-1000 nm, and the sum of the areas of the pores is no less than 20% of the total surface area of the film. The advantage of the present invention is that a microporous oriented film having dense and uniform nanoscale micropores with thermal stability can be prepared, and the processing method is simple and fast, and the product of the present invention can be partly or even completely biodegraded. The microporous oriented film can be used in the fields of health care, medical treatment, construction, water treatment, agriculture, electronics, packaging, decoration, and so an.
Description
本发明属于高分子材料领域,涉及一种具有微多孔结构的聚乳酸薄膜。The invention belongs to the field of polymer materials and relates to a polylactic acid film having a microporous structure.
微多孔薄膜作为透湿防水薄膜、电池隔膜、分离膜、组织工程材料、储能材料等,在卫生护理、医疗、建筑、水处理、农业、电子产品、装饰等多种领域有广泛的应用。微多孔薄膜的制备方法,主要有发泡、粒子填充-拉伸、溶剂刻蚀、相分离、自组装等,各种方法制得的微多孔薄膜在结构上各有特点。As a moisture-permeable waterproof film, battery separator, separation membrane, tissue engineering material, energy storage material, etc., microporous membranes are widely used in various fields such as health care, medical treatment, construction, water treatment, agriculture, electronic products, and decoration. The preparation method of the microporous film mainly includes foaming, particle filling-stretching, solvent etching, phase separation, self-assembly, etc., and the microporous film obtained by various methods has various structural characteristics.
聚乳酸是一种生物降解聚酯,含该聚合物的微多孔薄膜已被提到,可以在卫生护理、医疗等领域中得到应用。Polylactic acid is a biodegradable polyester, and a microporous film containing the polymer has been mentioned, and can be applied in fields such as sanitary care and medical treatment.
CN201310185870.6采用粒子填充-拉伸的方法,提供一种含聚乳酸等生物降解聚合物的微多孔取向薄膜,直径在0.2~7μm范围内的表面孔的面积占总表面积的0.5%-15%,耐水度大于800mm,透湿度大于1000g/m2·day,刚软度小于40mm。可作为透湿防水薄膜用于卫生护理领域。CN201310185870.6 A microporous oriented film containing a biodegradable polymer such as polylactic acid is provided by a particle filling-stretching method, and the surface pore area having a diameter in the range of 0.2 to 7 μm accounts for 0.5% to 15% of the total surface area. The water resistance is greater than 800 mm, the moisture permeability is greater than 1000 g/m 2 ·day, and the softness is less than 40 mm. It can be used as a moisture permeable waterproof film in the field of health care.
CN 201110414695.4采用相分离技术,提供一种孔径在5-400μm之间可控的聚乳酸材料,可作为组织工程用的多孔支架使用。CN 201110414695.4 The use of phase separation technology to provide a polylactic acid material with a pore diameter of between 5 and 400 μm can be used as a porous support for tissue engineering.
CN201080052568.8采用将聚乳酸的发泡体经粉碎形成粉体,所述粉体再通过熔融粘着而相互接合,得到孔径100-2000μm之间的连续多孔构造,可用做吸水材料。
CN201080052568.8 is a method in which a foam of polylactic acid is pulverized to form a powder, and the powders are joined to each other by fusion bonding to obtain a continuous porous structure having a pore diameter of 100 to 2000 μm, which can be used as a water absorbing material.
上述各技术制备得到的微多孔薄膜的孔径不同,但都难以制得具有纳米、亚微米级别的、且孔径均匀的微多孔聚乳酸薄膜。The microporous film prepared by the above various techniques has different pore diameters, but it is difficult to obtain a microporous polylactic acid film having a nanometer, submicron order and uniform pore diameter.
另外,当作为透湿防水薄膜等半透性薄膜使用时,有时对于温度敏感性有特别要求。Further, when used as a semipermeable film such as a moisture-permeable waterproof film, there are cases where temperature sensitivity is particularly required.
比如,有时需要通量随温度变化。比如,聚乳酸微多孔薄膜的透湿性可用于调节内容物的湿度。有时需要在较低温度下使内容物的湿度较低,此时需要薄膜的透湿性较好;在较高温度下使内容物的湿度较高,或使内容物不再继续失水,此时需要薄膜的透湿性较小。又比如,聚乳酸微多孔薄膜的透湿性可用于调节具有挥发性芳香组分内容物的挥发速度。有时需要在较低温度下让挥发性芳香组分较快地透过薄膜,而在较高温度下让挥发性芳香组分较慢地透过薄膜。For example, sometimes flux needs to change with temperature. For example, the moisture permeability of a polylactic acid microporous film can be used to adjust the humidity of the contents. Sometimes it is necessary to lower the humidity of the contents at a lower temperature, in which case the film is required to have better moisture permeability; at higher temperatures, the humidity of the contents is higher, or the contents are no longer dehydrated. The film is required to have less moisture permeability. As another example, the moisture permeability of the polylactic acid microporous film can be used to adjust the rate of volatilization of the contents of the volatile aromatic component. It is sometimes desirable to have the volatile aromatic component pass through the film faster at lower temperatures and to allow the volatile aromatic component to pass through the film more slowly at higher temperatures.
又比如,有时需要透明性随温度变化。如在较低温度下,薄膜透明性较差;在较高温度下,薄膜透明性较好。As another example, transparency is sometimes required to vary with temperature. For example, at lower temperatures, the film is less transparent; at higher temperatures, the film is more transparent.
而现有技术中都未曾提出过实现上述具有均匀、纳米级别孔,且孔径和孔面积具有温度敏感性的聚乳酸微多孔薄膜的技术方案。However, the prior art has not proposed a technical solution for realizing the above-mentioned polylactic acid microporous film having uniform, nanometer-scale pores and having pore size and pore area temperature sensitivity.
发明内容Summary of the invention
随着微多孔薄膜的应用范围不断扩大,我们发现现有技术中,微多孔聚乳酸薄膜的大尺寸孔径、不均匀的孔径分布等缺陷,限制了其在卫生护理、医疗、建筑、水处理、农业、电子产品、包装、装饰等多种领域的应用。此外,在某些场合下,还需要具备温度响应性。As the application range of microporous films continues to expand, we have found that the microporous polylactic acid film has large pore size, uneven pore size distribution and the like in the prior art, which limits its health care, medical treatment, construction, water treatment, Applications in various fields such as agriculture, electronics, packaging, and decoration. In addition, in some cases, temperature responsiveness is also required.
为了解决现有技术的缺陷,本发明提供一种微多孔聚乳酸取向薄膜。In order to solve the drawbacks of the prior art, the present invention provides a microporous polylactic acid oriented film.
所谓的取向薄膜,是本专业技术人员公知的术语,是指经流延、吹塑、
浇注、模压等方法制备的原膜(未取向薄膜)经单向或双向拉伸,使聚合物分子链段、分子链和/或结晶发生取向,而制备得到的。取向的形成一般赋予薄膜于有益的性能和性质,诸如薄膜强度、韧性、透明性的提高;视后处理条件,也可使薄膜具有热收缩性。薄膜的取向可以在单向、双向的拉伸机上进行,也可以通过双膜泡法(泡管法)等改进的吹塑方法进行。检测薄膜是否取向的方法是公知技术,常规的有X射线衍射法、双折射法、拉曼光谱法、红外法、超声法等。The so-called oriented film is a term well known to those skilled in the art and refers to casting, blow molding,
The original film (unoriented film) prepared by casting, molding or the like is prepared by uniaxially or biaxially stretching to orient the polymer molecular segments, molecular chains and/or crystals. The formation of orientation generally imparts beneficial properties and properties to the film, such as increased film strength, toughness, and transparency; and depending on post-treatment conditions, the film can also be heat shrinkable. The orientation of the film can be carried out on a one-way or two-way stretching machine, or by an improved blow molding method such as a double bubble method (bubble method). A method of detecting whether or not the film is oriented is a well-known technique, and conventionally, there are an X-ray diffraction method, a birefringence method, a Raman spectroscopy method, an infrared method, an ultrasonic method, and the like.
本发明提供一种微多孔聚乳酸取向薄膜,当薄膜处于薄膜中聚乳酸组分的玻璃化温度以下时,具有直径在10-1000nm范围内的表面孔,该类孔面积之和占所述薄膜总表面积的20%以上。相对于未取向的聚乳酸薄膜,取向的聚乳酸薄膜具有更好的强度和储存稳定性。The present invention provides a microporous polylactic acid oriented film having a surface pore having a diameter in the range of 10 to 1000 nm when the film is below the glass transition temperature of the polylactic acid component in the film, and the sum of the pore areas occupies the film More than 20% of the total surface area. The oriented polylactic acid film has better strength and storage stability than the unoriented polylactic acid film.
本发明中所述的表面孔是指暴露在外部,且未被聚合物和/或其他孔完全遮蔽的孔,可通过显微镜在薄膜表面上观察到该类孔。The surface pores described in the present invention refer to pores which are exposed to the outside and are not completely shielded by the polymer and/or other pores, and such pores can be observed on the surface of the film by a microscope.
所述的孔的面积是指,薄膜水平放置时,孔在水平面上的投影面积。所述的薄膜总表面积是指,薄膜水平放置时,薄膜在水平面上的投影面积。The area of the hole refers to the projected area of the hole on the horizontal surface when the film is horizontally placed. The total surface area of the film refers to the projected area of the film on the horizontal surface when the film is horizontally placed.
直径在10-1000nm范围内的纳米级和亚微米级的孔径在不阻碍水蒸气渗透的前提下,能够有效的阻碍液体水的通过。The nano-scale and sub-micron pore diameters in the range of 10-1000 nm can effectively hinder the passage of liquid water without hindering water vapor permeation.
玻璃化温度指聚合物的无定形相由玻璃态向高弹态或者由后者向前者的转变温度,是无定型大分子链段自由运动的最低温度,通常用Tg表示。聚乳酸的Tg一般在55℃左右,会受到结晶度、取向度、交联度、或添加剂种类或含量等中的一项或几项因素的影响。结晶、取向、或交联等因素的存在,对无定型聚合物链段的运动会起到限制作用,从而提高Tg。由于增塑剂等添加剂或共聚单体的存在,可以将聚乳酸的Tg降低至15℃左右,甚至更低,
具体的效果取决于种类或含量。The glass transition temperature refers to the transition temperature of the amorphous phase of the polymer from the glassy state to the high elastic state or from the former to the lowest temperature of the free movement of the amorphous macromolecular segment, which is usually expressed by Tg. The Tg of polylactic acid is generally around 55 ° C, and is affected by one or several factors such as crystallinity, degree of orientation, degree of crosslinking, or type or content of additives. The presence of factors such as crystallization, orientation, or crosslinking can limit the movement of the amorphous polymer segments, thereby increasing the Tg. Due to the presence of additives such as plasticizers or comonomers, the Tg of polylactic acid can be lowered to about 15 ° C or even lower.
The specific effect depends on the type or content.
聚合物的玻璃化温度可以通过检测体积、热力学性质、力学性质、或电磁性质的变化来测定。较常用的手段为差示扫描量热法(DSC)或动态热机械性能分析法(DMA)。不同方法测得的玻璃化温度有所差异,本发明中所述的玻璃化温度以下述具体实施方式中的测试方法测试得到。The glass transition temperature of the polymer can be determined by measuring changes in volume, thermodynamic properties, mechanical properties, or electromagnetic properties. The more common means are differential scanning calorimetry (DSC) or dynamic thermomechanical performance analysis (DMA). The glass transition temperatures measured by the different methods are different, and the glass transition temperature described in the present invention is tested by the test method in the following specific embodiment.
当薄膜处于薄膜中聚乳酸组分的玻璃化温度以下时,直径在10-1000nm范围内的纳米级或亚微米级的表面孔的孔径在不阻碍水蒸气渗透的前提下,能够有效的阻碍液体水的通过。When the film is below the glass transition temperature of the polylactic acid component in the film, the pore size of the nano- or sub-micron surface pores having a diameter in the range of 10 to 1000 nm can effectively hinder the liquid without hindering the vapor permeation. The passage of water.
增加直径在10-1000nm范围内的表面孔的孔面积之和,有利于提高透湿度。本发明中,优选,该类孔面积之和占所述微多孔聚乳酸取向薄膜总表面积的20%以上。考虑到进一步增大透湿度,本发明中,上述具有直径在10-1000nm范围内的表面孔的面积之和进一步优选为占所述薄膜总表面积的35%以上,更进一步优选45%以上。前述表面孔的面积的上限没有特别限定,其例如可以在70%以下。Increasing the sum of the pore areas of the surface pores having a diameter in the range of 10 to 1000 nm is advantageous for increasing the moisture permeability. In the present invention, it is preferable that the sum of the pore areas of the pores accounts for 20% or more of the total surface area of the microporous polylactic acid oriented film. In view of further increasing the moisture permeability, in the present invention, the sum of the areas of the surface pores having a diameter in the range of 10 to 1000 nm is more preferably 35% or more, and still more preferably 45% or more of the total surface area of the film. The upper limit of the area of the surface pores is not particularly limited, and may be, for example, 70% or less.
孔径均匀有利于提高薄膜的机械性能、透湿性能的均匀性。本发明中,上述具有直径在10-1000nm范围内的表面孔的孔径均匀,孔径分布优选小于2.0,更优选小于1.5,进一步优选小于1.3。孔径分布的下限没有特别限定,其例如可以在1.05以上。Uniform pore size is beneficial to improve the mechanical properties of the film and the uniformity of moisture permeability. In the present invention, the above-mentioned pores having surface pores having a diameter in the range of 10 to 1000 nm have a uniform pore diameter, and the pore diameter distribution is preferably less than 2.0, more preferably less than 1.5, still more preferably less than 1.3. The lower limit of the pore size distribution is not particularly limited, and may be, for example, 1.05 or more.
进一步的,上述微多孔聚乳酸取向薄膜中,当薄膜处于薄膜中聚乳酸组分的玻璃化温度以下时,还具有直径在10-1000nm范围内的内部孔。内部孔的存在有利于进一步提高薄膜的透湿率。Further, in the above microporous polylactic acid oriented film, when the film is below the glass transition temperature of the polylactic acid component in the film, it also has internal pores having a diameter in the range of 10 to 1000 nm. The presence of the internal pores is advantageous for further increasing the moisture permeability of the film.
本发明中所述的内部孔是指完全被聚合物和/或其他孔遮蔽的孔,可以通过显微镜在薄膜的截面上观察到该类孔。
The internal pores described in the present invention refer to pores that are completely obscured by the polymer and/or other pores, which can be observed by a microscope on the cross section of the film.
所述内部孔可以通过截面面积占比来衡量该类孔的量。利用钻石刀或离子抛光等手段,沿薄膜的纵向(MD)或横向(TD)方向,制备出MD-法向(ZD)断面或TD-ZD断面后,用显微镜(电子显微镜或原子力显微镜等)观察该断面,再利用图像处理技术,可以统计该类孔在薄膜的MD-ZD断面或TD-ZD断面上的面积之和占该断面面积的百分比(截面面积占比)。经统计计算后,以断面面积为100%,本发明中上述直径在10-1000nm范围内的内部孔的截面面积占比优选为20%以上。考虑到进一步提高透湿度,本发明中,上述直径在10-1000nm范围内的内部孔进一步优选35%以上,再进一步优选45%以上。前述内部孔的截面面积占比的上限没有特别限定,其例如可以在70%以下。考虑到提高薄膜的均匀性,本发明中,上述直径在10-1000nm范围内的内部孔的孔径均匀,孔径分布优选小于2.0,进一步优选小于1.5,再进一步优选小于1.3。前述孔径分布的下限没有特别限定,其例如可以在1.1以上。The internal bore can measure the amount of such pores by the ratio of the cross-sectional area. Prepare the MD-normal (ZD) section or the TD-ZD section along the longitudinal (MD) or transverse (TD) direction of the film by means of a diamond knife or ion polishing, using a microscope (electron microscope or atomic force microscope, etc.) Observing the section, and using image processing techniques, the sum of the areas of the pores on the MD-ZD section or the TD-ZD section of the film as a percentage of the area of the section (the ratio of the cross-sectional area) can be counted. After the statistical calculation, the cross-sectional area of the inner diameter in the range of 10 to 1000 nm in the present invention is preferably 20% or more in the cross-sectional area of 100%. In view of further increasing the moisture permeability, in the present invention, the internal pores having a diameter in the range of 10 to 1000 nm are more preferably 35% or more, still more preferably 45% or more. The upper limit of the cross-sectional area ratio of the internal pores is not particularly limited, and may be, for example, 70% or less. In view of improving the uniformity of the film, in the present invention, the inner pores having a diameter in the range of 10 to 1000 nm have a uniform pore diameter, and the pore diameter distribution is preferably less than 2.0, further preferably less than 1.5, still more preferably less than 1.3. The lower limit of the aforementioned pore size distribution is not particularly limited, and may be, for example, 1.1 or more.
本发明的微多孔聚乳酸取向薄膜,可以通过改变配方和工艺,使其具有温度敏感性。当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃以上的温度1小时后,所述的直径在10-1000nm范围内的表面孔的孔面积之和减小50%以上。孔面积的减小是由孔径缩小造成的。The microporous polylactic acid oriented film of the present invention can be made temperature sensitive by changing the formulation and process. When the film is at a temperature higher than the glass transition temperature of the polylactic acid component in the film by 30 ° C or more for 1 hour, the sum of the pore areas of the surface pores having a diameter in the range of 10 to 1000 nm is reduced by 50% or more. The reduction in the area of the hole is caused by the reduction in the aperture.
进一步的,当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃以上的温度1小时后,所述的直径在10-1000nm范围内的内部孔的孔截面面积之和减小50%以上。该面积的减小程度可以通过调节下述的配方和拉伸过程参数控制,以符合实际需要。Further, when the film is at a temperature higher than the glass transition temperature of the polylactic acid component in the film by more than 30 ° C for 1 hour, the sum of the pore cross-sectional areas of the internal pores having a diameter in the range of 10 to 1000 nm is reduced by 50%. the above. The extent of this reduction can be controlled by adjusting the formulation and stretching process parameters described below to meet actual needs.
对于所述的具有温度敏感性的微多孔聚乳酸取向薄膜,当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃或高更多的温度1小时后,由于直径在
10-1000nm范围内的内部孔和/或表面孔孔径和总面积的减小,可能出现薄膜的透光率增大,雾度减小的趋势。在某些技术方案中,当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃或高更多的温度1小时后,可以得到透光率大于90%,雾度小于10%的薄膜。当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃或高更多的温度1小时后,由于直径在10-1000nm范围内的内部孔和/或表面孔孔径和总面积的减小,还可能出现薄膜的透湿度降低的趋势。在某些技术方案中,当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃或高更多的温度1小时后,可以得到透湿度降低40%以上的薄膜。透明度和透湿度的变化使该薄膜可以作为包装薄膜、装饰薄膜使用。For the temperature-sensitive microporous polylactic acid oriented film, when the film is at a temperature 30 ° C higher or higher than the glass transition temperature of the polylactic acid component in the film for 1 hour,
A decrease in the pore size and total area of the internal pores and/or surface pores in the range of 10-1000 nm may increase the transmittance of the film and decrease the haze. In some embodiments, when the film is at a temperature 30 ° C higher or higher than the glass transition temperature of the polylactic acid component in the film for 1 hour, a film having a light transmittance of more than 90% and a haze of less than 10% can be obtained. . When the film is at a temperature 30 ° C higher or higher than the glass transition temperature of the polylactic acid component in the film for 1 hour, the internal pore and/or surface pore diameter and total area are reduced due to the diameter in the range of 10 to 1000 nm. There may also be a tendency for the moisture permeability of the film to decrease. In some embodiments, when the film is at a temperature 30 ° C higher or higher than the glass transition temperature of the polylactic acid component in the film for 1 hour, a film having a moisture permeability reduction of 40% or more can be obtained. The change in transparency and moisture permeability allows the film to be used as a packaging film or a decorative film.
同时,本发明的微多孔聚乳酸取向薄膜,可以通过改变配方和工艺,使其不具有温度敏感性,或温度敏感性较弱。即,薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃的温度1小时后,所述的直径在10-1000nm范围内的表面孔的孔面积之和减小50%以下(不含50%)。Meanwhile, the microporous polylactic acid oriented film of the present invention can be made to have no temperature sensitivity or weak temperature sensitivity by changing the formulation and the process. That is, after the film is at a temperature 30 ° C higher than the glass transition temperature of the polylactic acid component in the film for 1 hour, the sum of the pore areas of the surface pores having a diameter in the range of 10 to 1000 nm is reduced by 50% or less (excluding 50%).
进一步的,当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃的温度下1小时后,所述的直径在10-1000nm范围内的内部孔的孔截面面积之和减小50%以下(不含50%)。Further, when the film is at a temperature 30 ° C higher than the glass transition temperature of the polylactic acid component in the film, the sum of the pore cross-sectional areas of the internal pores having a diameter in the range of 10 to 1000 nm is reduced by 50%. The following (excluding 50%).
考虑到进一步提高薄膜的透湿性,本发明中,上述微多孔聚乳酸取向薄膜中,还可以具有直径大于1μm,且小于100μm范围内的内部孔。可以上文中所述方法进行统计。经统计计算后,以断面面积为100%,本发明中上述具有直径大于1μm,小于100μm范围内的内部孔的截面面积占比优选为10%以上。上述截面面积占比的下限没有特别限定,其例如可以为30%以下。In view of further improving the moisture permeability of the film, in the present invention, the microporous polylactic acid oriented film may further have internal pores having a diameter of more than 1 μm and less than 100 μm. Statistics can be performed as described above. After the statistical calculation, the cross-sectional area is 100%, and in the present invention, the cross-sectional area ratio of the inner pores having a diameter of more than 1 μm and less than 100 μm is preferably 10% or more. The lower limit of the cross-sectional area ratio is not particularly limited, and may be, for example, 30% or less.
所述的微多孔聚乳酸取向薄膜,含有如下重量份数的组分:聚乳酸树脂A:40-99重量份,亲水性有机化合物B:0.1-60重量份;所述的亲水性有机
化合物B是选自于可溶于水或可在水中溶胀的有机化合物中的一种或几种。The microporous polylactic acid oriented film contains the following components by weight: polylactic acid resin A: 40-99 parts by weight, hydrophilic organic compound B: 0.1-60 parts by weight; said hydrophilic organic
Compound B is one or more selected from the group consisting of organic compounds which are soluble in water or swellable in water.
从结构上看,所述的聚乳酸树脂A可以是任何聚乳酸树脂,进一步地,可以是聚乳酸(聚丙交酯)、或乳酸同其他化学结构的共聚物中的一种或几种。Structurally, the polylactic acid resin A may be any polylactic acid resin, and further, may be one or more of polylactic acid (polylactide), or a copolymer of lactic acid and other chemical structures.
优选的聚乳酸的分子结构是,由L乳酸或D乳酸的80-100mol%和各自的对映体0-20mol%构成的分子结构。上述聚乳酸树脂可以从L乳酸或D乳酸中的一种或两种作为原料,并通过脱水缩聚而得到。优选的是,可以从作为乳酸的环状二聚物的丙交酯,通过开环聚合而得到。丙交酯中有L乳酸的环状二聚物即L丙交酯、D乳酸的环状二聚物即D丙交酯、D乳酸与L乳酸进行环状二聚化而得到的内消旋丙交酯、以及D丙交酯和L丙交酯的外消旋混合物即DL丙交酯。本发明中可以使用任何一种丙交酯。不过,主原料优选D丙交酯或L丙交酯。The molecular structure of the preferred polylactic acid is a molecular structure consisting of 80 to 100 mol% of L lactic acid or D lactic acid and 0 to 20 mol% of the respective enantiomers. The polylactic acid resin can be obtained by dehydrating polycondensation from one or both of L lactic acid or D lactic acid. Preferably, it can be obtained by ring-opening polymerization from lactide which is a cyclic dimer of lactic acid. Among the lactide, L-lactide which is a cyclic dimer of L lactic acid, D-lactide which is a cyclic dimer of D lactic acid, and D-lactide of D lactic acid and L lactic acid are subjected to cyclic dimerization. Lactide, and a racemic mixture of D-lactide and L-lactide, DL lactide. Any of the lactides can be used in the present invention. However, the main raw material is preferably D lactide or L lactide.
所述的乳酸同其他化学结构的共聚物,是指乳酸同任意化学结构单元形成的无规共聚物、嵌段共聚物或接枝共聚物中的一种或几种。其中,乳酸单元的链段长度没有特别的限定,但从提高微多孔薄膜的力学性能的角度上考虑,优选乳酸链段长度为1-20万重均分子量。所述的乳酸同其他化学结构的共聚物,从提高生物降解性和环境友好性的角度上考虑,优选乳酸同羟基羧酸类、二元或多元醇类、或二元或多元羧酸类的共聚物。The copolymer of lactic acid and other chemical structures refers to one or more of a random copolymer, a block copolymer or a graft copolymer formed of lactic acid and any chemical structural unit. The length of the segment of the lactic acid unit is not particularly limited, but from the viewpoint of improving the mechanical properties of the microporous film, the lactic acid segment length is preferably from 1 to 200,000 weight average molecular weight. The copolymer of lactic acid and other chemical structures is preferably lactic acid with a hydroxycarboxylic acid, a dihydric or polyhydric alcohol, or a binary or polycarboxylic acid, from the viewpoint of improving biodegradability and environmental friendliness. Copolymer.
从结晶性能上看,所述的聚乳酸树脂A可以是结晶性聚乳酸树脂,也可以是非晶性聚乳酸树脂,或可以是结晶性聚乳酸树脂和非结晶性聚乳酸树脂的混合物。从提高成型性能考虑,优选非晶性聚乳酸树脂、或结晶性聚乳酸树脂和非结晶性聚乳酸树脂的混合物。对于结晶性聚乳酸树脂和非结晶性聚乳酸树脂的混合物,从提高成型性能考虑,优选非结晶性聚乳酸树脂占混合物总重量的30%以上,进一步优选50%以上。
The polylactic acid resin A may be a crystalline polylactic acid resin or an amorphous polylactic acid resin, or may be a mixture of a crystalline polylactic acid resin and an amorphous polylactic acid resin. From the viewpoint of improving the moldability, a mixture of an amorphous polylactic acid resin or a crystalline polylactic acid resin and an amorphous polylactic acid resin is preferred. The mixture of the crystalline polylactic acid resin and the non-crystalline polylactic acid resin preferably has a non-crystalline polylactic acid resin of 30% or more, and more preferably 50% or more, based on the total weight of the mixture, from the viewpoint of improving the moldability.
有多种方法可以判定薄膜中结晶性聚乳酸树脂和非结晶性聚乳酸树脂的比例。方法之一是,通过差示扫描量热分析(DSC)。对薄膜样品进行组分分离,分离出聚乳酸组分后,进行DSC测试,通过计算熔融焓的大小可以判定结晶性聚乳酸树脂和非结晶性聚乳酸树脂的比例。There are various methods for determining the ratio of the crystalline polylactic acid resin to the non-crystalline polylactic acid resin in the film. One of the methods is by differential scanning calorimetry (DSC). The film sample was subjected to component separation, and after separating the polylactic acid component, a DSC test was performed, and the ratio of the crystalline polylactic acid resin to the non-crystalline polylactic acid resin was determined by calculating the size of the molten ruthenium.
关于聚乳酸树脂A的分子量,没有特别的限定,但从提高成型加工性和力学性能的角度上考虑,优选重均分子量5万~50万,进一步优选8万-30万。The molecular weight of the polylactic acid resin A is not particularly limited, but from the viewpoint of improving moldability and mechanical properties, the weight average molecular weight is preferably 50,000 to 500,000, and more preferably 80,000 to 300,000.
上文中所述的可溶于水的有机化合物是指:在4-100℃的某一温度时,该有机化合物在100g水中的可以溶解1g以上。The water-soluble organic compound described above means that the organic compound can dissolve 1 g or more in 100 g of water at a certain temperature of 4-100 °C.
可在水中溶胀的有机化合物是指:在4-100℃的某一温度时,1g该有机化合物在100g水中发生10%以上的体积膨胀。The organic compound which can swell in water means that 1 g of the organic compound undergoes volume expansion of 10% or more in 100 g of water at a certain temperature of 4-100 °C.
所述的亲水性有机化合物B可以是小分子有机化合物,也可以是大分子有机化合物和/或聚合物。The hydrophilic organic compound B may be a small molecule organic compound or a macromolecular organic compound and/or a polymer.
具体而言,所述的亲水性有机化合物B可以选自于乙二醇、一缩二乙二醇、甘油、或丙二醇等醇类小分子化合物、丁二酸、或乳酸等羧酸类小分子化合物、丙交酯、己内酯、乳酸酯、柠檬酸酯、甘油酯、或异山梨醇酯等酯类小分子化合物、聚乙二醇、聚氧化乙烯、聚丙二醇、聚乙二醇-聚丙二醇共聚物等聚醚类聚合物、或聚醚-聚烯烃共聚物、聚醚-聚酯共聚物、聚醚型聚氨酯、聚乙烯醇、聚乙烯亚胺、聚乙烯吡咯烷酮、聚丙烯酰胺、聚马来酸、二烯丙基季铵盐聚合物、聚天冬氨酸、聚环氧琥珀酸、羧甲基菊粉、淀粉或其衍生物、纤维素醚、甲壳质、黄原胶、或植物胶中的一种或几种。Specifically, the hydrophilic organic compound B may be selected from small alcoholic compounds such as ethylene glycol, diethylene glycol, glycerin, or propylene glycol, small carboxylic acids such as succinic acid or lactic acid. Molecular compound, lactide, caprolactone, lactate, citrate, glyceride, or isosorbide ester compound, polyethylene glycol, polyethylene oxide, polypropylene glycol, polyethylene glycol - a polyether polymer such as a polypropylene glycol copolymer, or a polyether-polyolefin copolymer, a polyether-polyester copolymer, a polyether polyurethane, a polyvinyl alcohol, a polyethyleneimine, a polyvinylpyrrolidone, a polyacrylamide , polymaleic acid, diallyl quaternary ammonium salt polymer, polyaspartic acid, polyepoxysuccinic acid, carboxymethyl inulin, starch or its derivatives, cellulose ether, chitin, xanthan gum Or one or more of the vegetable gums.
从原料的易得性考虑,所述的亲水性有机化合物B优选为乙二醇、甘油、丁二酸、乳酸、丙交酯、乳酸酯、柠檬酸三丁酯、柠檬酸三乙酯、乙酰柠檬酸三乙酯、乙酰柠檬酸三丁酯、三乙酸甘油酯、异山梨醇酯、聚乙二醇、聚
氧化乙烯、聚丙二醇、聚乙二醇-聚丙二醇共聚物、聚乙二醇-聚乳酸共聚物、聚丙二醇-聚乳酸共聚物、聚乙二醇-聚丙二醇-聚乳酸共聚物、聚乙烯醇、聚乙烯亚胺、聚乙烯吡咯烷酮、淀粉、聚马来酸、或聚天冬氨酸中的一种或几种。The hydrophilic organic compound B is preferably ethylene glycol, glycerin, succinic acid, lactic acid, lactide, lactate, tributyl citrate or triethyl citrate from the viewpoint of availability of the raw material. , acetyl triethyl citrate, acetyl tributyl citrate, triacetin, isosorbide, polyethylene glycol, poly
Ethylene oxide, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol-polylactic acid copolymer, polypropylene glycol-polylactic acid copolymer, polyethylene glycol-polypropylene glycol-polylactic acid copolymer, polyvinyl alcohol One or more of polyethyleneimine, polyvinylpyrrolidone, starch, polymaleic acid, or polyaspartic acid.
从提高所述的直径在10-1000nm范围内的表面孔和/或内部孔的量和孔径均匀性出发,进一步优选同聚乳酸树脂A具有较好相容性的亲水性有机化合物B。具体而言,可以是乙二醇、甘油、丁二酸、乳酸、丙交酯、乳酸酯、柠檬酸三丁酯、柠檬酸三乙酯、乙酰柠檬酸三乙酯、乙酰柠檬酸三丁酯、三乙酸甘油酯、异山梨醇酯、聚乙二醇、聚氧化乙烯、聚丙二醇、聚乙二醇-聚丙二醇共聚物、聚乙二醇-聚乳酸共聚物、聚丙二醇-聚乳酸共聚物、或聚乙二醇-聚丙二醇-聚乳酸共聚物中的一种或几种。From the viewpoint of increasing the amount of the surface pores and/or the internal pores and the pore diameter uniformity in the range of 10 to 1000 nm in diameter, the hydrophilic organic compound B having better compatibility with the polylactic acid resin A is more preferable. Specifically, it may be ethylene glycol, glycerin, succinic acid, lactic acid, lactide, lactate, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tributyl Ester, triacetin, isosorbide, polyethylene glycol, polyethylene oxide, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol-polylactic acid copolymer, polypropylene glycol-polylactic acid copolymerization Or one or more of polyethylene glycol-polypropylene glycol-polylactic acid copolymer.
本发明对于所述的亲水性有机化合物B的分子量,没有特别的要求,但从薄膜的力学性能出发,优选数均分子量小于10万,进一步优选数均分子量小于5万。数均分子量的下限没有特别限定,例如可以为55以上。The present invention has no particular requirement for the molecular weight of the hydrophilic organic compound B. However, from the viewpoint of mechanical properties of the film, the number average molecular weight is preferably less than 100,000, and more preferably the number average molecular weight is less than 50,000. The lower limit of the number average molecular weight is not particularly limited, and may be, for example, 55 or more.
上述薄膜若还具有直径大于1μm,且小于100μm范围内的内部孔时,能进一步提高薄膜的透湿性。发明人发现,所述的微多孔聚乳酸取向薄膜,以聚乳酸树脂A和亲水性有机化合物B为100重量份计,还含有400重量份数以内的疏水性不相容组分C时,薄膜中会形成所述的直径大于1μm,且小于100μm范围内的内部孔。所述疏水性不相容组分C选自于除所述的亲水性有机化合物B以外的,且在40-100℃时可与聚乳酸形成多相结构的物质中的一种或几种。所述在40-100℃时可与聚乳酸形成多相结构,是指在40-100℃的温度范围内的任一温度时,可与聚乳酸形成多相结构。When the above film further has internal pores having a diameter of more than 1 μm and less than 100 μm, the moisture permeability of the film can be further improved. The inventors have found that the microporous polylactic acid oriented film has a hydrophobic incompatible component C of 400 parts by weight or less based on 100 parts by weight of the polylactic acid resin A and the hydrophilic organic compound B. Internal pores having a diameter greater than 1 μm and less than 100 μm are formed in the film. The hydrophobic incompatible component C is selected from one or more of the substances other than the hydrophilic organic compound B and which can form a multiphase structure with polylactic acid at 40-100 ° C. . The formation of a multi-phase structure with polylactic acid at 40-100 ° C means that a polyphase structure can be formed with polylactic acid at any temperature in the temperature range of 40-100 ° C.
所谓的多相结构,是高分子相关领域通用的术语,指在一定温度下,聚
合物和聚合物之间、聚合物和小分子化合物之间、或聚合物和无机物之间存在两相体系或更多相的体系。多相结构可以用光学显微镜、电子显微镜、原子力显微镜等显微方法直接判断,也可以用差示扫描量热仪、动态机械性能分析仪等间接方法判断。The so-called multiphase structure is a general term in the field of polymer related, which means that it is concentrated at a certain temperature.
A system of two-phase system or more is present between the compound and the polymer, between the polymer and the small molecule compound, or between the polymer and the inorganic substance. The multiphase structure can be directly judged by microscopic methods such as optical microscopy, electron microscopy, atomic force microscopy, etc., or can be judged by indirect methods such as differential scanning calorimetry and dynamic mechanical performance analyzer.
所述疏水性不相容组分C,可以是有机物,也可以是无机物,或有机物和无机物的混合物。具体而言,所述疏水性不相容组分C选自于除所述的亲水性有机化合物B以外的,下述物质中的一种或多种:碳原子数小于100的烷烃、烯烃、芳香族等小分子化合物、聚烯烃、聚氨酯、除聚乳酸以外的聚酯、聚酰胺、聚酰亚胺、聚碳酸酯、聚硫醚、聚醚、含氟聚合物、不饱和树脂、环氧树脂、丙烯酸树脂、或聚苯乙烯等聚合物、木粉、纤维素、剑麻纤维、或竹纤维等植物性纤维、羊毛纤维等动物性纤维、芳族聚酰胺纤维、或芳族聚酯纤维等有机合成纤维、玻璃纤维、石棉纤维、碳纤维、石墨纤维、金属纤维、钛酸钾晶须、硼酸铝晶须、镁系晶须、硅系晶须、硅灰石、海泡石、石棉、矿渣纤维、硬硅钙石、硅磷灰石、石膏纤维、二氧化硅纤维、二氧化硅/氧化铝纤维、氧化锆纤维、氮化硼纤维、氮化硅纤维或硼纤维、玻璃薄片、非膨润性云母、膨润性云母、石墨、金属箔、陶瓷珠粒、滑石、粘土、云母、绢云母、沸石、膨润土、蛭石、蒙脱土、白云石、高岭土、微粉硅酸、长石粉、钛酸钾、微细中空玻璃球、碳酸钙、碳酸镁、硫酸钙、二氧化钛、勃姆石氧化铝、氧化硅、石膏、均密石英岩、片钠铝石或白土等无机物。The hydrophobic incompatible component C may be an organic substance, an inorganic substance, or a mixture of an organic substance and an inorganic substance. Specifically, the hydrophobic incompatible component C is selected from one or more of the following substances other than the hydrophilic organic compound B: an alkane or an olefin having a carbon number of less than 100 , small aromatic compounds such as aromatics, polyolefins, polyurethanes, polyesters other than polylactic acid, polyamides, polyimides, polycarbonates, polythioethers, polyethers, fluoropolymers, unsaturated resins, rings Polymers such as oxygen resin, acrylic resin, or polystyrene, vegetable powder such as wood flour, cellulose, sisal fiber, or bamboo fiber, animal fiber such as wool fiber, aramid fiber, or aromatic polyester Organic synthetic fibers such as fibers, glass fibers, asbestos fibers, carbon fibers, graphite fibers, metal fibers, potassium titanate whiskers, aluminum borate whiskers, magnesium whiskers, silicon whiskers, wollastonite, sepiolite, asbestos , slag fiber, xonotlite, silica apatite, gypsum fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber or boron fiber, glass flake, Non-swelling mica, swellable cloud , graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, vermiculite, montmorillonite, dolomite, kaolin, micronized silicic acid, feldspar powder, potassium titanate, fine hollow glass sphere Inorganic materials such as calcium carbonate, magnesium carbonate, calcium sulfate, titanium dioxide, boehmite alumina, silica, gypsum, uniform quartzite, dawsonite or clay.
上述疏水性不相容组分C也可以进行任意形式的表面改性、或界面增容,以增强其同聚乳酸树脂之间的界面黏附性。The above hydrophobic incompatible component C can also be subjected to any form of surface modification or interfacial compatibilization to enhance its interfacial adhesion to the polylactic acid resin.
从保持或提高材料的生物降解性能考虑,所述的疏水性不相容组分C优选生物降解聚合物或无机填料。
The hydrophobic incompatible component C is preferably a biodegradable polymer or an inorganic filler from the viewpoint of maintaining or enhancing the biodegradability of the material.
所述疏水性不相容组分C进一步优选为聚羟基丁酸酯、聚羟基丁酸戊酸酯、聚羟基丁酸己酸酯、聚丁二酸丁二醇酯、聚丁二酸己二酸丁二醇酯、聚己内酯、聚对苯二甲酸己二酸丁二醇酯、聚对苯二甲酸己二酸丙二醇酯、聚对苯二甲酸丁二酸丁二醇酯、聚乙撑碳酸酯、聚丙撑碳酸酯、聚碳酸亚环己酯、碳酸钙、滑石粉、云母粉、沸石、蛭石、钛白粉、二氧化硅、硫酸钙或蒙脱土中的一种或几种。The hydrophobic incompatible component C is further preferably polyhydroxybutyrate, polyhydroxybutyrate valerate, polyhydroxybutyrate caproate, polybutylene succinate, polybutylene succinate Butylene glycol ester, polycaprolactone, polybutylene terephthalate, propylene terephthalate, polybutylene succinate, polyethylene One or more of carbonate, polypropylene carbonate, polycyclohexylene carbonate, calcium carbonate, talc, mica powder, zeolite, vermiculite, titanium dioxide, silica, calcium sulfate or montmorillonite .
本发明的微多孔聚乳酸取向薄膜中,可以在不妨碍实现本发明的目的的范围内,添加增塑剂、增容剂、封端剂、阻燃剂、成核剂、抗氧化剂、润滑剂、抗静电剂、防雾剂、光稳定剂、紫外线吸收剂、颜料、防霉剂、抗菌剂、或发泡剂等添加剂中的一种或几种。所述的亲水性有机化合物B和疏水性不相容组分C中,部分也可以用作增塑剂、成核剂、填充剂、润滑剂、颜料、或染料等添加剂使用。In the microporous polylactic acid oriented film of the present invention, a plasticizer, a compatibilizer, a terminal blocking agent, a flame retardant, a nucleating agent, an antioxidant, and a lubricant may be added to the extent that the object of the present invention is not hindered from being achieved. One or more of additives such as an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, an antifungal agent, an antibacterial agent, or a foaming agent. Some of the hydrophilic organic compound B and the hydrophobic incompatible component C may also be used as an additive such as a plasticizer, a nucleating agent, a filler, a lubricant, a pigment, or a dye.
所述的微多孔聚乳酸取向薄膜,具有较好的亲水性,在25℃的水中浸渍10min后,该薄膜的含水量为薄膜总质量的1-50%。The microporous polylactic acid oriented film has good hydrophilicity, and after immersing in water at 25 ° C for 10 minutes, the water content of the film is 1-50% of the total mass of the film.
所述的微多孔聚乳酸取向薄膜中,聚乳酸树脂的重均分子量为5-50万,为了满足实用的机械特性,优选为8-40万,进一步优选为10-30万。In the microporous polylactic acid oriented film, the polylactic acid resin has a weight average molecular weight of 50,000 to 50,000, and is preferably from 8 to 400,000, more preferably from 100,000 to 300,000, in order to satisfy practical mechanical properties.
本发明利用亲水性有机化合物的亲水性,优选使用下述方法制备所述的微多孔聚乳酸取向薄膜。The present invention utilizes the hydrophilicity of the hydrophilic organic compound, and it is preferred to prepare the microporous polylactic acid oriented film by the following method.
步骤一:将各原料通过挤出、密炼或开炼等方法进行共混。Step 1: The raw materials are blended by extrusion, mixing or opening.
步骤二:将以步骤一得到的共混物,通过流延、吹塑、压延、模压、挤出、浇注成型制得未取向薄膜。Step 2: The unoriented film is obtained by casting, blow molding, calendering, molding, extruding, and casting the blend obtained in the first step.
步骤三:由以下方法中的任意一种制备取向薄膜:Step 3: Prepare an oriented film by any of the following methods:
方法一
method one
所述取向薄膜由未取向薄膜在受水蒸气加热的同时,经过单向或双向拉伸制备得到。The oriented film is prepared by unidirectional or biaxial stretching of the unoriented film while being heated by steam.
方法二Method Two
所述取向薄膜由未取向薄膜在受液体加热的同时,经过单向或双向拉伸制备得到;所述的液体选自于水或以混合液体100重量份计含水量大于10重量份的混合液体。所述的混合液体包含但不限于:水、乙醇、乙二醇、或甘油中的一种或更多种液体的混合液(水含量大于10%)。从价格和绿色环保的概念出发,优选水。对于水质或水的洁净程度没有特殊要求,从产品洁净的角度考虑,以较为纯净的水为佳,比如自来水、去离子水、或蒸馏水。The oriented film is prepared by unidirectional or biaxial stretching while the liquid is heated by the unoriented film; the liquid is selected from water or a mixed liquid having a water content of more than 10 parts by weight based on 100 parts by weight of the mixed liquid. . The mixed liquid includes, but is not limited to, a mixture of one or more of water, ethanol, ethylene glycol, or glycerin (water content greater than 10%). From the concept of price and environmental protection, water is preferred. There is no special requirement for the cleanliness of water or water. From the perspective of product cleanliness, it is better to use pure water, such as tap water, deionized water, or distilled water.
方法三Method three
取向薄膜由未取向薄膜在液体中浸泡后取出,在受热空气加热的同时,经过单向或双向拉伸制备得到;所述的液体选自于水或以混合液体100重量份计含水量大于10重量份的混合液体。所述的混合液体包含但不限于:水、乙醇、乙二醇、或甘油中的一种或更多种液体的混合液(水含量大于10%)。从价格和绿色环保的概念出发,优选水。对于水质或水的洁净程度没有特殊要求,从产品洁净的角度考虑,以较为纯净的水为佳。比如自来水、去离子水、或蒸馏水。对于液体浸渍的时间,没有特殊的要求,如果液体温度较低,可以选择较长的浸渍时间,如果液体温度较高,为了防止聚乳酸的水解,可以选择较短的浸渍时间,一般为4s-10h。The oriented film is taken out after immersing in the liquid in the unoriented film, and is prepared by unidirectional or biaxial stretching while being heated by the heated air; the liquid is selected from water or the water content is more than 10 in 100 parts by weight of the mixed liquid. Parts by weight of the mixed liquid. The mixed liquid includes, but is not limited to, a mixture of one or more of water, ethanol, ethylene glycol, or glycerin (water content greater than 10%). From the concept of price and environmental protection, water is preferred. There is no special requirement for the cleanliness of water quality or water. From the perspective of product cleanliness, it is better to use pure water. Such as tap water, deionized water, or distilled water. There is no special requirement for the time of liquid immersion. If the liquid temperature is low, a longer immersion time can be selected. If the liquid temperature is high, in order to prevent hydrolysis of polylactic acid, a shorter immersion time can be selected, generally 4 s - 10h.
上述三种方法中,所述未取向薄膜在受到拉伸前,其含水量没有特别要求。但实验表明,含水量为总质量的0.1-30%时,有利于所述的微多孔结构的均匀性。In the above three methods, the water content of the unoriented film before the stretching is not particularly required. However, experiments have shown that the water content is from 0.1 to 30% of the total mass, which is advantageous for the uniformity of the microporous structure.
上述三种方法中,所述拉伸的温度为40-100℃。从提高加工稳定性的角
度上考虑,优选的拉伸温度为60-97℃。In the above three methods, the stretching temperature is 40 to 100 °C. From the corner of improving processing stability
The preferred stretching temperature is 60-97 ° C.
可以通过调节配方和拉伸倍率等拉伸过程参数,控制表面(及内部)孔洞的孔径,所述的直径在10-1000nm范围内的孔的孔径的数量平均值一般为100-800nm(精确到10nm)。拉伸倍率越大,孔径越大。The pore size of the surface (and internal) pores can be controlled by adjusting the stretching process parameters such as formulation and draw ratio, and the average number of pores of the pores having a diameter in the range of 10-1000 nm is generally 100-800 nm (accurately 10nm). The larger the draw ratio, the larger the pore size.
在上述方法的基础上,还可以再通过追加热定型等通用的制膜工艺来制备所述的微多孔聚乳酸取向薄膜。On the basis of the above method, the microporous polylactic acid oriented film can be further prepared by a general film forming process such as heat setting.
进一步的,追加步骤四,可以制得不具有温度敏感性,或温度敏感性低的微多孔聚乳酸取向薄膜。Further, by adding step four, a microporous polylactic acid oriented film which is not temperature sensitive or has low temperature sensitivity can be obtained.
步骤四:将取向薄膜进行后处理,所述的后处理可以是以下方法中的任意一种或更多种,但不局限于以下方法:Step 4: The oriented film is post-treated, and the post-treatment may be any one or more of the following methods, but is not limited to the following methods:
方法一:使用液体浸泡取向薄膜,所用的液体选自于水或以混合液体100重量份计含水量大于10重量份的混合液体,液体的温度选自40℃-99℃,优选为60℃-90℃,后处理时间为1s-180min,优选为2s-120min。Method 1: using a liquid to soak the oriented film, the liquid used is selected from water or a mixed liquid having a water content of more than 10 parts by weight based on 100 parts by weight of the mixed liquid, and the temperature of the liquid is selected from 40 ° C to 99 ° C, preferably 60 ° C - The post-treatment time is from 90 s C to 1 s to 180 min, preferably from 2 s to 120 min.
方法二:在薄膜表面涂覆一层高耐热性的材料,将溶液或者悬浮分散的耐热材料涂覆在薄膜的网孔表面。Method 2: Apply a layer of high heat resistance material to the surface of the film, and apply a solution or a suspension-dispersed heat-resistant material to the surface of the mesh of the film.
所述的涂覆材料是:环氧树脂、聚氨酯、丙烯酸树脂中的任意一种或多种。The coating material is any one or more of epoxy resin, polyurethane, and acrylic resin.
涂覆方法是:浸渍、辊涂、喷涂中的任意一种或多种。The coating method is any one or more of dipping, roll coating, and spray coating.
方法三:在薄膜表面镀膜。Method 3: Coating the surface of the film.
所述的镀膜材料是:金、铂、铝、银、镍、钼、铜、锡、铌、锌、钨、钛、铬、锆、硅、石墨、氧化铝、氧化铟、氧化钛、氧化镁、氧化钙、三氧化二锑、氧化铋、氧化钆、氧化钨、二氧化钛、二氧化硅、二氧化铈、氧化钇、五氧化二铌、氧化钪、二氧化锆、五氧化二钽、氧化锌、二氧化硅、氟
化钨、氟化钡、氟化铅、氟化铈、氟化镧、氮化铝、氮化钛、氮化硅中的一种或多种。The coating material is: gold, platinum, aluminum, silver, nickel, molybdenum, copper, tin, antimony, zinc, tungsten, titanium, chromium, zirconium, silicon, graphite, aluminum oxide, indium oxide, titanium oxide, magnesium oxide. , calcium oxide, antimony trioxide, antimony oxide, antimony oxide, antimony oxide, tungsten oxide, titanium dioxide, silicon dioxide, hafnium oxide, antimony oxide, antimony pentoxide, antimony oxide, zirconium dioxide, antimony pentoxide, zinc oxide , silica, fluorine
One or more of tungsten, barium fluoride, lead fluoride, barium fluoride, barium fluoride, aluminum nitride, titanium nitride, and silicon nitride.
镀膜方法是:真空溅射镀膜、真空离子镀膜、离子束沉积、离子束辅助沉积、光学镀膜、化学气相沉积、真空蒸发镀膜中的一种或多种。The coating method is one or more of vacuum sputtering coating, vacuum ion plating, ion beam deposition, ion beam assisted deposition, optical coating, chemical vapor deposition, and vacuum evaporation coating.
方法四:在薄膜制备的步骤中添加交联剂,在本步骤中进行交联。Method 4: A crosslinking agent is added in the step of film preparation, and crosslinking is carried out in this step.
所述的交联剂是指:多官能团聚酯丙烯酸酯、三烯丙基异氰脲酸酯、环氧-丙烯酸树脂、聚醚丙烯酸酯、多功能醇或乙二醇的丙烯酸酯、聚氨酯丙烯酸酯、环氧树脂-阳离子、苯甲酮、氮丙啶、胺类、噻吨酮中的一种或多种。The cross-linking agent refers to: polyfunctional polyester acrylate, triallyl isocyanurate, epoxy-acrylic resin, polyether acrylate, multifunctional alcohol or ethylene glycol acrylate, urethane acrylic acid One or more of ester, epoxy-cation, benzophenone, aziridine, amine, thioxanthone.
交联方法为:伽玛射线辐射交联、电子束辐射交联、微波辐射交联、紫外光交联中的一种或多种。The crosslinking method is one or more of gamma ray radiation crosslinking, electron beam radiation crosslinking, microwave radiation crosslinking, and ultraviolet light crosslinking.
本发明的优点在于可以制得具备密集、均匀和温度响应性特点的纳米级微孔的微多孔取向薄膜,且加工方法简单、高速,无须使用有毒有害溶剂,绿色环保。该微多孔取向薄膜可以应用在卫生护理、医疗、建筑、水处理、农业、电子产品、包装、装饰等多种领域。The invention has the advantages that a microporous oriented film with nano-scale micropores with dense, uniform and temperature responsive characteristics can be obtained, and the processing method is simple and high-speed, and no toxic and harmful solvent is needed, and the environment is green. The microporous oriented film can be used in various fields such as sanitary care, medical treatment, construction, water treatment, agriculture, electronic products, packaging, decoration, and the like.
通过以下实施例对本发明做更详细的描述,但所述实施例不构成对本发明的限制。The invention is described in more detail by the following examples, which are not intended to limit the invention.
实施例与对比例中使用的测试方法如下,对于所有测试,如果没有明确说明测试温度,则在25℃下测试:The test methods used in the examples and comparative examples are as follows. For all tests, if the test temperature is not clearly stated, the test is carried out at 25 ° C:
厚度:使用三洋仪器公司7050型厚度计测定,取9个数据的平均值。Thickness: Measured using a Sanyo Instruments 7050 thickness gauge and averaged 9 data.
重均分子量和数均分子量:使用凝胶渗透色谱测定,以四氢呋喃为流动相,测定3次,取平均值。
Weight average molecular weight and number average molecular weight: measured by gel permeation chromatography, using tetrahydrofuran as a mobile phase, measured three times, and averaged.
聚乳酸组分的玻璃化温度(Tg):使用差示扫描量热仪(DSC)按10℃/min的升温速率,在薄膜的第一次升温曲线上得到。The glass transition temperature (Tg) of the polylactic acid component was obtained on a first heating curve of the film using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C/min.
透湿率:基于JIS Z0208:1976,湿度90%。测定3次,取平均值。Moisture permeability: based on JIS Z0208: 1976, humidity 90%. It was measured 3 times and averaged.
透明性:透光率和雾度按GB/T 2410-2008,用光电雾度计测定。Transparency: Transmittance and haze are determined by photoelectric haze according to GB/T 2410-2008.
含水量:将试样在25℃下真空干燥24h后,称重m1,浸渍在水中10min,取出后,拭去表面水,称重m2,按式(1)计算含水量,Water content: After drying the sample under vacuum at 25 ° C for 24 h, weigh m 1 and immerse it in water for 10 min. After taking out, wipe off the surface water, weigh m 2 , calculate the water content according to formula (1).
<表面形貌测定><Measurement of surface topography>
表面形貌观察在25℃下进行。The surface topography was observed at 25 °C.
孔径d:用扫描电子显微镜(SEM)对薄膜表面进行观察,随机拍摄不同位置放大倍率10000倍的照片5张,用笔勾出孔洞轮廓后,用图像处理软件ImageJ 1.46r计算各表面孔的面积S,再按式(2)计算各孔的孔径d(一种等价的直径,即与孔面积相等的圆的直径):Aperture d: The surface of the film was observed by scanning electron microscope (SEM), and 5 photographs with magnifications of 10,000 times at different positions were randomly taken. After the contour of the hole was extracted with a pen, the area of each surface hole was calculated by image processing software ImageJ 1.46r. S, then calculate the aperture d of each hole according to the formula (2) (an equivalent diameter, that is, the diameter of a circle equal to the hole area):
平均孔径(纳米级孔)dn:按式(3)计算直径在10-1000nm范围内的孔的孔径平均值,Average pore diameter (nanoscale pore) d n : Calculate the average pore diameter of a pore having a diameter in the range of 10 to 1000 nm according to the formula (3),
其中,∑d为孔径在10-1000nm范围内的孔的孔径d的加和,n为参与计算的10-1000nm范围内的孔的个数。Wherein ∑d is the sum of the pore diameters d of the pores having a pore diameter in the range of 10 to 1000 nm, and n is the number of pores in the range of 10-1000 nm participating in the calculation.
孔径分布(纳米级孔)SD:先按式(4-1)计算体积平均孔径dv,再按式(4-2)计算孔径分布SD,
Pore size distribution (nano-scale pores) SD: First calculate the volume average pore diameter d v according to formula (4-1), and then calculate the pore size distribution SD according to formula (4-2).
其中,∑d4为孔径在10-1000nm范围内的孔的孔径d的4次方的加和;∑d3为孔径在10-1000nm范围内的孔的孔径d的3次方的加和。Wherein ∑d 4 is the sum of the fourth power of the pore diameter d of the pores having a pore diameter in the range of 10 to 1000 nm; ∑d 3 is the sum of the third power of the pore diameter d of the pores having a pore diameter in the range of 10 to 1000 nm.
面积比(纳米级孔)S%:直径在10-1000nm范围内的表面孔的面积占总表面积的百分比。按式(5)计算:Area ratio (nanoscale pores) S%: The area of the surface pores in the range of 10 to 1000 nm in diameter as a percentage of the total surface area. Calculated according to formula (5):
其中,∑Sm为上述SEM观测面积之和。Where ∑S m is the sum of the above-mentioned SEM observation areas.
<内部形貌测定><Internal topography measurement>
表面形貌观察在25℃下进行。The surface topography was observed at 25 °C.
钻石刀或离子抛光等手段制备出平整的MD-ZD断面,用SEM对该断面进行观察,A flat MD-ZD section was prepared by means of a diamond knife or ion polishing, and the section was observed by SEM.
孔径d:按前述表面孔径的统计和计算方法,计算内部孔的孔径。Aperture d: The pore diameter of the internal pore is calculated according to the statistical and calculation method of the aforementioned surface pore diameter.
平均孔径(纳米级孔)dn:按式(3)计算直径在10-1000nm范围内的孔的孔径平均值。其中,∑d为孔径在10-1000nm范围内的孔的孔径d的加和。Average pore diameter (nanoscale pore) d n : The average value of the pore diameter of the pore having a diameter in the range of 10 to 1000 nm is calculated according to the formula (3). Wherein ∑d is the sum of the pore diameters d of the pores having a pore diameter in the range of 10 to 1000 nm.
孔径分布(纳米级孔)SD:先按式(4-1)计算体积平均孔径dv,再按式(4-2)计算孔径分布SD。Pore size distribution (nano-scale pores) SD: First, the volume average pore diameter d v is calculated according to the formula (4-1), and the pore size distribution SD is calculated according to the formula (4-2).
面积比(纳米级孔)S%:直径在10-1000nm范围内的表面孔的面积占总表面积的百分比。按式(5)计算。Area ratio (nanoscale pores) S%: The area of the surface pores in the range of 10 to 1000 nm in diameter as a percentage of the total surface area. Calculated according to equation (5).
平均孔径(微米级孔)d’m:表示直径在1-100μm范围内的孔的孔径平均值,按式(6)计算。
Average pore diameter (micron-sized pore) d' m : represents the average value of the pore diameter of the pore having a diameter in the range of 1-100 μm, which is calculated according to the formula (6).
其中,∑d’为孔径在1-100μm范围内的孔的孔径d的加和,m为参与计算的1-100μm范围内的孔的个数。Wherein ∑d' is the sum of the pore diameters d of the pores having a pore diameter in the range of 1-100 μm, and m is the number of pores in the range of 1-100 μm participating in the calculation.
实施例与对比例中使用的原料如下:The materials used in the examples and comparative examples are as follows:
<聚乳酸树脂>(A)<Polylactic acid resin> (A)
A-1:聚乳酸,4032D,美国Natureworks公司。重均分子量23万。A-1: Polylactic acid, 4032D, American Natureworks. The weight average molecular weight is 230,000.
A-2:聚乳酸,4060D,美国Natureworks公司。重均分子量23万。A-2: Polylactic acid, 4060D, American Natureworks. The weight average molecular weight is 230,000.
<亲水性有机化合物>(B)<Hydrophilic Organic Compound> (B)
B-1:聚乙二醇,数均分子量600,中国国药集团。B-1: polyethylene glycol, number average molecular weight 600, China National Pharmaceutical Group.
B-2:聚乳酸-聚乙二醇-聚乳酸三嵌段共聚物,按照CN200810018621.7的实施例1进行制造。数均分子量2万。B-2: Polylactic acid-polyethylene glycol-polylactic acid triblock copolymer, which was produced in accordance with Example 1 of CN200810018621.7. The number average molecular weight is 20,000.
<疏水性不相容组分>(C)<Hydrophobic incompatible components> (C)
C-1:聚丁二酸丁二醇酯,Bionolle 1020,日本昭和高分子公司。C-1: polybutylene succinate, Bionolle 1020, Japan Showa Polymer Co., Ltd.
C-2:聚对苯二甲酸己二酸丁二醇酯,Ecoflex C1200,德国BASF公司。C-2: polybutylene terephthalate, Ecoflex C1200, BASF, Germany.
C-3:碳酸钙,粒径1.2-3.5μm,日本三共精粉株式会社。C-3: Calcium carbonate, particle size 1.2-3.5 μm, Japan Sankyo Fine Powder Co., Ltd.
实施例1~7Examples 1 to 7
将原料按一定的配比用双螺杆挤出机挤出造粒,挤出温度175-200℃。接着,通过单螺杆挤出机吹塑,制备厚度为100μm的未取向薄膜。吹塑温度180-200℃。进而,在85℃的水蒸气中,对未取向薄膜进行3×3倍的同时双向拉伸,得到取向薄膜。表1列出了该薄膜组成。在25℃下,测定了各薄膜的性能,列于表1。
The raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C. Next, a non-oriented film having a thickness of 100 μm was prepared by blow molding by a single screw extruder. The blow molding temperature is 180-200 °C. Further, the unoriented film was subjected to simultaneous biaxial stretching at 3 × 3 times in water vapor at 85 ° C to obtain an oriented film. Table 1 lists the composition of the film. The properties of each film were measured at 25 ° C and are listed in Table 1.
对比例1~3Comparative Examples 1 to 3
将原料按一定的配比用双螺杆挤出机挤出造粒,挤出温度175-200℃。接着,通过单螺杆挤出机吹塑,制备厚度为100μm的未取向薄膜。吹塑温度180-200℃。进而,在85℃的热空气中,对未取向薄膜进行3×3倍的同时双向拉伸,得到取向薄膜。表1列出了该薄膜组成。在25℃下,测定了各薄膜的性能,列于表1。The raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C. Next, a non-oriented film having a thickness of 100 μm was prepared by blow molding by a single screw extruder. The blow molding temperature is 180-200 °C. Further, the unoriented film was subjected to simultaneous biaxial stretching at 3 × 3 times in hot air at 85 ° C to obtain an oriented film. Table 1 lists the composition of the film. The properties of each film were measured at 25 ° C and are listed in Table 1.
实施例8~14、对比例4Examples 8 to 14, Comparative Example 4
将原料按一定的配比用双螺杆挤出机挤出造粒,挤出温度175-200℃。接着,通过单螺杆挤出机流延,流延温度180-200℃,制备厚度为120μm的未取向薄膜。进而,在80℃的水中,按表2所列的拉伸方法对未取向薄膜进行拉伸,得到取向薄膜。表2列出了该薄膜组成。在25℃下,测定了各薄膜的性能,列于表2。The raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C. Next, casting was carried out by a single-screw extruder at a casting temperature of 180 to 200 ° C to prepare a non-oriented film having a thickness of 120 μm. Further, the unoriented film was stretched in water at 80 ° C according to the stretching method listed in Table 2 to obtain an oriented film. Table 2 lists the film composition. The properties of each film were measured at 25 ° C and are listed in Table 2.
实施例15~18Examples 15-18
将原料按一定的配比用双螺杆挤出机挤出造粒,挤出温度175-200℃。接着,通过单螺杆挤出机流延,流延温度180-200℃,制备厚度为120μm的未取向薄膜。进而,在80℃的水中,浸泡30min。再在90℃的空气中,按表3所列的拉伸方法对未取向薄膜进行拉伸,得到取向薄膜。表3列出了该薄膜组成。在25℃下,测定了各薄膜的性能,列于表3。The raw materials were extruded and granulated by a twin-screw extruder at a certain ratio, and the extrusion temperature was 175-200 °C. Next, casting was carried out by a single-screw extruder at a casting temperature of 180 to 200 ° C to prepare a non-oriented film having a thickness of 120 μm. Further, it was immersed in water at 80 ° C for 30 minutes. Further, the unoriented film was stretched in air at 90 ° C according to the stretching method listed in Table 3 to obtain an oriented film. Table 3 lists the film composition. The properties of each film were measured at 25 ° C and are listed in Table 3.
实施例19~25
Examples 19-25
分别将实施例8~14所述的取向薄膜放置在比薄膜中聚乳酸组分玻璃化温度高30℃的温度条件下,1小时后,再进行各种性能的测定。结果列于表4中。The oriented films described in Examples 8 to 14 were placed at a temperature higher than the glass transition temperature of the polylactic acid component by 30 ° C in the film, and after 1 hour, various properties were measured. The results are shown in Table 4.
实施例26~32Examples 26 to 32
分别对实施例8~14所述的取向薄膜进行以下处理。The oriented films described in Examples 8 to 14 were subjected to the following treatments.
热处理方法:Heat treatment method:
将实施例8和9所述的取向薄膜在80℃水中浸泡0.5h;The oriented films described in Examples 8 and 9 were immersed in water at 80 ° C for 0.5 h;
将实施例10和11所述的取向薄膜在80℃水中浸泡2h;The oriented films described in Examples 10 and 11 were immersed in water at 80 ° C for 2 h;
将实施例12所述的取向薄膜的表面蒸镀一层三氧化二铝,厚度为40nm;The surface of the oriented film described in Example 12 is evaporated with a layer of aluminum oxide having a thickness of 40 nm;
将实施例13所述的取向薄膜的表面蒸镀一层氧化硅,厚度为40nm;The surface of the oriented film described in Example 13 was evaporated to a thickness of 40 nm;
将实施例14所述的取向薄膜的表面涂覆一层厚度为20nm的环氧树脂。The surface of the oriented film described in Example 14 was coated with an epoxy resin having a thickness of 20 nm.
继而,将各薄膜放置在比薄膜中聚乳酸组分玻璃化温度高30℃的温度条件下,1小时后,再进行各种性能的测定。结果列于表5中。Then, each film was placed at a temperature higher than the glass transition temperature of the polylactic acid component in the film by 30 ° C, and after 1 hour, various properties were measured. The results are shown in Table 5.
对以上实施例进行GPC测试,测得聚乳酸组分的重均分子量为11-20万。
表1The GPC test was carried out on the above examples, and the weight average molecular weight of the polylactic acid component was measured to be 1 to 200,000.
Table 1
表1(续)Table 1 (continued)
表2Table 2
表2(续)Table 2 (continued)
备注:逐次双向为先MD方向拉伸,再TD方向拉伸
Remarks: successive two-way stretching in the first MD direction, then stretching in the TD direction
表3table 3
表4Table 4
表5table 5
本说明书中提到的所有专利文献、非专利文献均通过引用的方式并入本文。本说明书中提到的“多种”包含大于一种的所有情况,即,“一种或多种”包括一种、两种、三种、……等等。本说明书中针对某数值范围分别记载上限和下限时,或者以上限和下限组合的方式记载某数值范围时,其中记载的各上限和各下限可任意组合为新的数值范围,这与直接明确记载组合而成的数值范围的记载形式应被视为是相同的。在不偏离本发明主旨的情况下,本领域技术人员可对本发明进行改变和改良,这些也包括在本发明的范围内。
All patent documents and non-patent documents mentioned in the specification are herein incorporated by reference. The term "a plurality" as used in the specification includes all cases of more than one, that is, "one or more" includes one, two, three, ..., and the like. In the present specification, when the upper limit and the lower limit are respectively described for a certain numerical range, or when a certain numerical range is described in combination of the upper limit and the lower limit, each of the upper limit and the lower limit described in the above may be arbitrarily combined into a new numerical range, which is directly and clearly described. The combined description of the numerical ranges should be considered identical. Variations and modifications of the invention may be made by those skilled in the art without departing from the scope of the invention, which is also included in the scope of the invention.
Claims (21)
- 一种微多孔聚乳酸取向薄膜,其特征在于:当薄膜处于薄膜中聚乳酸组分的玻璃化温度以下时,具有直径在10-1000nm范围内的表面孔,该类孔面积之和占所述薄膜总表面积的20%以上。A microporous polylactic acid oriented film characterized by having a surface pore having a diameter in the range of 10 to 1000 nm when the film is below the glass transition temperature of the polylactic acid component in the film, and the sum of the pore areas More than 20% of the total surface area of the film.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:所述的直径在10-1000nm范围内的表面孔的孔径分布小于2.0。The microporous polylactic acid oriented film according to claim 1, wherein the surface pores having a diameter in the range of 10 to 1000 nm have a pore size distribution of less than 2.0.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:所述的直径在10-1000nm范围内的表面孔的孔径分布小于1.5。The microporous polylactic acid oriented film according to claim 1, wherein the surface pores having a diameter in the range of 10 to 1000 nm have a pore size distribution of less than 1.5.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:具有直径在10-1000nm范围内的内部孔。The microporous polylactic acid oriented film according to claim 1, which has an internal pore having a diameter in the range of 10 to 1000 nm.
- 根据权利要求4所述的微多孔聚乳酸取向薄膜,其特征在于:所述的直径在10-1000nm范围内的内部孔的孔径分布小于2.0。The microporous polylactic acid oriented film according to claim 4, wherein the internal pores having a diameter in the range of 10 to 1000 nm have a pore size distribution of less than 2.0.
- 根据权利要求4所述的微多孔聚乳酸取向薄膜,其特征在于:所述的直径在10-1000nm范围内的内部孔的孔径分布小于1.5。The microporous polylactic acid oriented film according to claim 4, wherein the internal pores having a diameter in the range of 10 to 1000 nm have a pore size distribution of less than 1.5.
- 根据权利要求4所述的微多孔聚乳酸取向薄膜,其特征在于:所述的直径在10-1000nm范围内的内部孔的截面面积占比为20%以上。The microporous polylactic acid oriented film according to claim 4, wherein the cross-sectional area of the internal pores having a diameter in the range of 10 to 1000 nm is 20% or more.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃以上的温度1小时后,所述的直径在10-1000nm范围内的表面孔的孔面积之和减小50%以上。The microporous polylactic acid oriented film according to claim 1, wherein the film has a diameter of from 10 to 1000 nm after the film is at a temperature higher than a glass transition temperature of the polylactic acid component in the film by at least 30 ° C for 1 hour. The sum of the pore areas of the surface pores in the range is reduced by more than 50%.
- 根据权利要求3所述的微多孔聚乳酸取向薄膜,其特征在于:当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃以上的温度1小时后,所述的直径在10-1000nm范围内的内部孔的截面面积之和减小50%以上。 The microporous polylactic acid oriented film according to claim 3, wherein the film has a diameter of 10 to 1000 nm after the film is at a temperature higher than a glass transition temperature of the polylactic acid component in the film by 30 ° C or more for 1 hour. The sum of the cross-sectional areas of the internal holes in the range is reduced by more than 50%.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:当薄膜处于薄膜中聚乳酸组分的玻璃化温度高30℃的温度1小时后,所述的直径在10-1000nm范围内的表面孔的孔面积之和减小50%以下(不含50%)。The microporous polylactic acid oriented film according to claim 1, wherein when the film is at a temperature at which the glass transition temperature of the polylactic acid component in the film is 30 ° C for 1 hour, the diameter is in the range of 10 to 1000 nm. The sum of the pore areas of the surface pores is reduced by 50% or less (excluding 50%).
- 根据权利要求3所述的微多孔聚乳酸取向薄膜,其特征在于:当薄膜比处于薄膜中聚乳酸组分的玻璃化温度高30℃的温度1小时后,所述的直径在10-1000nm范围内的内部孔的截面面积之和减小50%以下(不含50%)。The microporous polylactic acid oriented film according to claim 3, wherein the film has a diameter in the range of 10 to 1000 nm after the film is at a temperature 30 ° C higher than the glass transition temperature of the polylactic acid component in the film for 1 hour. The sum of the cross-sectional areas of the inner holes inside is reduced by 50% or less (excluding 50%).
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:具有直径大于1μm,且小于100μm范围内的内部孔。The microporous polylactic acid oriented film according to claim 1, which has an inner pore having a diameter of more than 1 μm and less than 100 μm.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:含有如下重量份数的组分:聚乳酸树脂A:40-99.9重量份,亲水性有机化合物B:0.1-60重量份;所述的亲水性有机化合物B选自于可溶于水或可在水中溶胀的有机化合物中的一种或几种。The microporous polylactic acid oriented film according to claim 1, which comprises the following components by weight: polylactic acid resin A: 40-99.9 parts by weight, hydrophilic organic compound B: 0.1-60 parts by weight The hydrophilic organic compound B is selected from one or more of organic compounds which are soluble in water or swellable in water.
- 根据权利要求13所述的微多孔聚乳酸取向薄膜,其特征在于:所述的聚乳酸树脂A为非晶性聚乳酸树脂、或为结晶性聚乳酸树脂和非晶性聚乳酸树脂的混合物。The microporous polylactic acid oriented film according to claim 13, wherein the polylactic acid resin A is an amorphous polylactic acid resin or a mixture of a crystalline polylactic acid resin and an amorphous polylactic acid resin.
- 根据权利要求13所述的微多孔聚乳酸取向薄膜,其特征在于:所述的亲水性有机化合物B选自于乙二醇、甘油、丁二酸、乳酸、丙交酯、乳酸酯、柠檬酸三丁酯、柠檬酸三乙酯、乙酰柠檬酸三乙酯、乙酰柠檬酸三丁酯、三乙酸甘油酯、异山梨醇酯、聚乙二醇、聚氧化乙烯、聚丙二醇、聚乙二醇-聚丙二醇共聚物、聚乙二醇-聚乳酸共聚物、聚丙二醇-聚乳酸共聚物、聚乙二醇-聚丙二醇-聚乳酸共聚物、聚乙烯醇、聚乙烯亚胺、聚乙烯吡咯烷酮、淀粉、聚马来酸、或聚天冬氨酸中的一种或几种。The microporous polylactic acid oriented film according to claim 13, wherein the hydrophilic organic compound B is selected from the group consisting of ethylene glycol, glycerin, succinic acid, lactic acid, lactide, and lactate. Tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, triacetin, isosorbide, polyethylene glycol, polyethylene oxide, polypropylene glycol, polyethyl b Glycol-polypropylene glycol copolymer, polyethylene glycol-polylactic acid copolymer, polypropylene glycol-polylactic acid copolymer, polyethylene glycol-polypropylene glycol-polylactic acid copolymer, polyvinyl alcohol, polyethyleneimine, polyethylene One or more of pyrrolidone, starch, polymaleic acid, or polyaspartic acid.
- 根据权利要求13所述的微多孔聚乳酸取向薄膜,其特征在于:以聚乳 酸树脂A和亲水性有机化合物B为100重量份计,还含有400重量份数以内的疏水性不相容组分C;所述疏水性不相容组分C选自于除所述的亲水性有机化合物B以外的,且在40-100℃时,可与聚乳酸形成多相结构的物质中的一种或几种。The microporous polylactic acid oriented film according to claim 13, wherein the polylactic acid oriented film is characterized in that: The acid resin A and the hydrophilic organic compound B are 100 parts by weight, and further contain 400 parts by weight or less of the hydrophobic incompatible component C; the hydrophobic incompatible component C is selected from the group consisting of One or more of substances other than the hydrophilic organic compound B which form a multiphase structure with polylactic acid at 40 to 100 °C.
- 根据权利要求16所述的微多孔聚乳酸取向薄膜,其特征在于:所述疏水性不相容组分C选自于聚羟基丁酸酯、聚羟基丁酸戊酸酯、聚羟基丁酸己酸酯、聚丁二酸丁二醇酯、聚丁二酸己二酸丁二醇酯、聚己内酯、聚对苯二甲酸己二酸丁二醇酯、聚对苯二甲酸己二酸丙二醇酯、聚对苯二甲酸丁二酸丁二醇酯、聚乙撑碳酸酯、聚丙撑碳酸酯、聚碳酸亚环己酯、滑石粉、云母粉、沸石、蛭石、碳酸钙、钛白粉、二氧化硅、硫酸钙或蒙脱土中的一种或几种。The microporous polylactic acid oriented film according to claim 16, wherein the hydrophobic incompatible component C is selected from the group consisting of polyhydroxybutyrate, polyhydroxybutyrate valerate, polyhydroxybutyrate Acid ester, polybutylene succinate, polybutylene succinate, polycaprolactone, polybutylene terephthalate, polybutylene terephthalate Propylene glycol ester, polybutylene terephthalate, polyethylene carbonate, polypropylene carbonate, polycyclohexylene carbonate, talc, mica powder, zeolite, vermiculite, calcium carbonate, titanium dioxide One or more of silica, calcium sulfate or montmorillonite.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:在25℃的水中浸渍10分钟后,该薄膜的含水量为薄膜总质量的1-50%。The microporous polylactic acid oriented film according to claim 1, wherein the film has a water content of 1 to 50% of the total mass of the film after being immersed in water at 25 ° C for 10 minutes.
- 根据权利要求1所述的微多孔聚乳酸取向薄膜,其特征在于:所述的取向薄膜中,聚乳酸树脂的重均分子量为5-50万。The microporous polylactic acid oriented film according to claim 1, wherein the polylactic acid resin has a weight average molecular weight of from 50,000 to 500,000.
- 根据权利要求8或9中所述的微多孔聚乳酸取向薄膜,其特征在于:当薄膜处于比薄膜中聚乳酸组分的玻璃化温度高30℃以上的温度1小时后,透光率大于90%,雾度小于10%。The microporous polylactic acid oriented film according to claim 8 or 9, wherein the film has a light transmittance of more than 90 when the film is at a temperature higher than 30 ° C higher than a glass transition temperature of the polylactic acid component in the film. %, the haze is less than 10%.
- 权利要求1-20中任一项所述的微多孔聚乳酸取向薄膜在卫生护理、医疗、建筑、水处理、农业、电子产品、包装、装饰领域的应用。 Use of the microporous polylactic acid oriented film according to any one of claims 1 to 20 in the fields of health care, medical treatment, construction, water treatment, agriculture, electronic products, packaging, and decoration.
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CN105670249A (en) * | 2016-01-25 | 2016-06-15 | 中国科学院长春应用化学研究所 | Polylactic acid porous material and preparation method thereof |
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 |
CN106800754A (en) * | 2015-11-26 | 2017-06-06 | 东丽先端材料研究开发(中国)有限公司 | A kind of micro- porous membrane |
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CN109265941B (en) * | 2018-08-09 | 2021-07-23 | 束建军 | Semitransparent heat-resistant polylactic acid composite material and preparation method thereof |
CN113493599A (en) * | 2020-03-19 | 2021-10-12 | 东丽先端材料研究开发(中国)有限公司 | Oriented film and multilayer film containing same |
CN112662145B (en) * | 2020-12-21 | 2023-03-28 | 内蒙古农业大学 | Bacteriostatic degradable respiratory membrane with self-contraction performance, preparation method and application |
CN112793250A (en) * | 2020-12-30 | 2021-05-14 | 重庆和泰润佳股份有限公司 | Multilayer co-extrusion biodegradable breathable film, preparation method thereof and sanitary towel |
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