Patent Application
20230076268
The present disclosure relates to a foamed sheet, a manufacture, and a method for producing a foamed sheet.
Plastic products are widely distributed after processed into various shapes such as a bag and a container. Those plastic products, however, have such properties that are not easily degradable in the natural world. This raises a problem with how to dispose of the plastic products after use. Under such circumstances, developments on materials for the plastic products have actively been made to replace non-degradable plastics, which are not easily degradable in the natural world, with biodegradable plastics which are degradable in the natural world.
As plastics having biodegradability, aliphatic polyesters having biodegradability have attracted attention.
In order to widely use the aliphatic polyesters, foamed sheets have been proposed in which the aliphatic polyesters are foamed to reduce the amounts of the aliphatic polyesters (see, for example, PTLs 1 to 4).
[PTL 1]
JP-2007-46019-A
[PTL 2]
JP-5207277-B
[PTL 3]
JP-5454137-B
[PTL 4]
JP-2006-328225-A
The present disclosure has an object to provide a foamed sheet that is excellent in strength.
According to one aspect of the present disclosure, a foamed sheet includes an aliphatic polyester resin and a filler. A degree of hydrophobization of the filler is 50% by mass or more. pH of the filler is 6.5 or lower.
The present disclosure can provide a foamed sheet that is excellent in strength.
The accompanying drawings are intended to depict example embodiments of the present invention and should not be interpreted to limit the scope thereof. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted. Also, identical or similar reference numerals designate identical or similar components throughout the several views.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In describing embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this specification is not intended to be limited to the specific terminology so selected and it is to be understood that each specific element includes all technical equivalents that have a similar function, operate in a similar manner, and achieve a similar result.
(Foamed Sheet)
A foamed sheet of the present disclosure includes an aliphatic polyester resin (hereinafter also referred to as “aliphatic polyester”) and a filler, and if necessary further includes other ingredients.
It is generally known that aliphatic polyesters including polylactic acid are difficult to mold. In view of this, JP-2007-46019-A proposes to mix polylactic acid with other resins to perform reforming of polylactic acid and a polylactic acid sheet. However, the above proposal to mix polylactic acid with other resins produces a resin that is not easily biodegradable as a whole, because the other resins are not easily biodegradable.
A foamed sheet obtained by foaming a resin is preferable in terms of being able to reduce the amount of the resin to reduce the weight. In order to achieve both sufficient strength and sufficient flexibility in the foamed sheet, there is a need to disperse foams uniformly and finely in terms of the diameters of the foams.
The finely foamed body disclosed in JP-5207277-B is produced using carbon dioxide in the supercritical state as a foaming agent and has a foam diameter of 1 micrometer or less. The carbon dioxide in the supercritical state has a structure similar to the backbone of an aliphatic polyester. Thus, the carbon dioxide in the supercritical state has a high affinity to the aliphatic polyester resin and is considered to be suitable as a foaming agent. In this proposal, however, the foamed body can only be produced in a batch-type apparatus, and cannot be mass-produced on an industrial scale through a continuous process.
It is generally known that once an aliphatic polyester resin having crystallinity has melted, the viscosity of the aliphatic polyester resin drastically decreases. This is likely to cause, for example, breakage of foams and coalescence of foams. As a result, it is difficult to make the foam diameter fine and uniform in the first place.
The present inventors conducted studies to obtain a polylactic acid foamed sheet that can solve the above problems; i.e., a polylactic acid foamed sheet that has fine and uniform foams and can be mass-produced on an industrial scale. As a result, the present inventors have found that by using a filler having appropriate degree of hydrophobization and pH, it is possible to produce a foamed sheet containing a large amount of the aliphatic polyester resin having uniform and fine foams. On the basis of this finding, the present invention has been completed.
<Aliphatic Polyester Resin>
The aliphatic polyester resin is biodegraded by microorganisms (a biodegradable resin) and has attracted attention as an environmentally-friendly, low-environmental-load polymer material (see “Structure, physical properties, and biodegradability of aliphatic polyester”, KOBUNSHI (High Polymers, Japan), 2001, Vol. 50, No. 6, pp. 374-377″). Examples of the aliphatic polyester resin include, but are not limited to, polylactic acid, polyglycolic acid, poly(3-hydroxybutylate), poly(3-hydroxybutylate-3-hydroxyhexanoate), poly(3-hydroxybutylate-3-hydroxyvalerate), polycaprolactone, polybutylene succinate, and poly(butylene succinate-adipate). One of these may be used alone or two or more of these may be used in combination. Among them, preference is given to polylactic acid that is a carbon-neutral material and is relatively inexpensive.
Examples of the polylactic acid include, but are not limited to, a copolymer between D-lactic acid and L-lactic acid, a homopolymer of D-lactic acid (D body) or L-lactic acid (L body), and ring-opening polymers of one or more lactides selected from the group consisting of D-lactide (D body), L-lactide (L body), and DL-lactide. One of these may be used alone or two or more of these may be used in combination.
When a copolymer between D-lactic acid and L-lactic acid is used as the polylactic acid, the ratio between D-lactic acid and L-lactic acid is not particularly limited and may be appropriately selected depending on the intended purpose. The copolymer between D-lactic acid and L-lactic acid, as the optical isomer of a smaller amount decreases, tends to increase in crystallinity to have an increased melting point or glass transition temperature. Meanwhile, as the optical isomer of a smaller amount increases, the copolymer tends to decrease in crystallinity to be non-crystalline eventually. Crystallinity is a contributing factor of heat resistance of a foamed sheet and a forming temperature for foaming. Thus, crystallinity may be determined depending on applications and is not particularly limited. As used herein, “crystallinity” expresses a degree of crystallization, a speed of crystallization, or both. High crystallinity means a high degree of crystallization, a high speed of crystallization, or both. The polylactic acid used may be an appropriately synthesized product or a commercially available product.
In terms of biodegradability, the proportion of the aliphatic polyester resin is preferably 80% by mass or more, more preferably 99% by mass or more, relative to the total amount of organic substances in the foamed sheet.
<Measuring Method of the Proportion of the Aliphatic Polyester Resin>
The proportion of the aliphatic polyester resin can be calculated from the relative amounts of materials to be charged. When the material ratio is unknown, for example, the following GCMS analysis can be performed to identify the ingredient through comparison using a known aliphatic polyester resin as a standard sample. If necessary, the area ratio of spectra by NMR measurement or other analysis methods can be used in combination with the GCMS analysis for calculation.
Measurement by GCMS analysis
GCMS: QP2010 available from Shimadzu Corporation, with Frontier Lab Py3030D as auxiliary equipment
Separation column: Frontier Lab Ultra ALLOY UA5-30M-0.25F
Heating temperature of sample: 300 degrees Celsius
Column oven temperature: increasing from 50 degrees Celsius (retained for 1 minute) at 15 degrees Celsius/min to 320 degrees Celsius (6 minutes)
Ionization method: Electron Ionization (E.I) method
Detection mass range: 25 to 700 (m/z)
<Filler>
The filler (hereinafter also referred to as “foam nucleating agent”) is contained to adjust, for example, the foamed state of the foamed sheet (the size, amount, and arrangement of the foams).
Examples of the filler include, but are not limited to, inorganic fillers and organic fillers. One of these may be used alone or two or more of these may be used in combination.
Examples of the inorganic fillers include, but are not limited to, talc, kaolin, calcium carbonate, layered silicate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, glass fibers, and carbon fibers.
Examples of the organic fillers include, but are not limited to, naturally occurring polymers such as starch, cellulose particles, wood powder, soybean curd residue (okara), chaff, and bran, modified products thereof, sorbitol compounds, benzoic acid, metal salts of benzoic acid compounds, metal salts of phosphate esters, and rosin compounds.
Among them, silica, which is an inorganic nucleating agent, is preferable in terms of its high affinity to the below-described compressive fluid. Also, when other fillers than silica are used as a base, those fillers are preferably surface-treated with silica.
Silica is a substance containing silicon dioxide represented by SiO2 as a main ingredient. Depending on the production method of silica particles, it is roughly classified into fumed silica and wet silica. In the present disclosure, any of fumed silica and wet silica can be used.
If necessary, the silica is subjected to a surface treatment with a reactive compound such as a silane coupling agent, a titanate coupling agent, or organosiloxane.
In particular, a silane coupling agent can be suitably used for the surface treatment of silica particles. Specific examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, and gamma-mercaptopropyltriethoxysilane.
The proportion of the silica is preferably 50% by mass or more, more preferably 60% by mass or more, relative to the total amount of inorganic substances in the foamed sheet, both when a filler surface-treated with silica is used and when silica is used in combination with other fillers than silica. When the proportion of the silica is 50% by mass or more, foams become uniform and fine.
The number average particle diameter of the filler is preferably from 5 nm (0.005 micrometers) through 100 nm (0.1 micrometers), more preferably from 0.01 micrometers through 0.08 micrometers. When the number average particle diameter of the filler is less than 5 nm (0.005 micrometers), dispersibility becomes poor in the case of silica, and the resultant foamed sheet may be degraded in physical properties as sheets such as impact resistance. When the number average particle diameter of the filler is more than 100 nm (0.1 micrometers), the resultant foamed sheet may be degraded in surface appearance.
The number average particle diameter of the filler may be expressed with a BET specific surface area by conveniently assuming the filler as a true sphere. In this case, the BET specific surface area is from 23 m2/g through 230 m2/g.
(BET specific surface area (m2/g)=the specific surface area of one particle/the weight of one particle=3/(average diameter/2)×true specific gravity=3/(average diameter/2)/(true specific gravity×106)
Weight of one particle: (average diameter/2)3×4/3×3.14×true specific gravity (2.65)×106 (g/particle)
Specific surface area of one particle (average diameter/2)2×4'33.14
The standard deviation (σ) of the number average particle diameter of the filler is preferably three or less times the number average particle diameter and more preferably twice or less the number average particle diameter. The standard deviation (σ) falling within the above ranges indicates uniform foams of the foamed sheet.
Incidentally, there is a correlation between the standard deviation of the filler and the standard deviation of the foams. In other words, the standard deviation of the filler falling within the above ranges can mean uniform foams.
The proportion of coarse particles of the filler having particle diameters of 10 micrometers or more is preferably 100 or less particles per 1 g of the foamed sheet, more preferably 40 or less particles per 1 g of the foamed sheet. When the number of the coarse particles is 100 or less, the foam diameter is fine, and physical properties such as appearance and strength are favorable.
The proportion of the coarse particles can be measured in the following manner. Specifically, 50 mg of the foamed sheet is allowed to melt to form a thin film of 10 micrometers. The thin film is observed under an optical microscope (available from NIKON CORPORATION, FX-21, at a magnitude of ×100) to count the number of the coarse particles formed from the filler having particle diameters of 10 micrometers or more.
The degree of hydrophobization of the filler is 50 wt % (% by mass) or more and preferably 60 wt % or more. As used herein, the degree of hydrophobization refers to a degree of methanol hydrophobization. The degree of hydrophobization of less than 50 wt % is not preferable because not only the increased hygroscopicity causes aggregation of the filler in the aliphatic polyester but also adverse side effects occur such as hydrolysis of the aliphatic polyester due to water when introducing the filler into the aliphatic polyester.
The degree of hydrophobization can be measured in the following manner. Specifically, methanol is dropped in a state, under stirring, where 1 g of the filler is floating in the surface of 50 ml of pure water. The amount of methanol necessary for suspending the total amount of the filler in the pure water is determined in % by weight.
The pH of the filler is 6.5 or lower, and preferably from 3.5 through 6, more preferably from 4 through 6. As used herein, the pH of the filler refers to pH in the surface of the filler determined in a 4% dispersion liquid (watermethano1=1:1) of the filler. When the pH is higher than 6, the fillers may aggregate together. When the pH is lower than 3.5, the aliphatic polyester may degrade.
The reason why the pH of the filler is in the above range is as follows. Specifically, when carbon dioxide is used as the foaming agent and is considered as a dispersion medium for the filler, particles are believed to tend to aggregate at an isoelectric point of the dispersion liquid of the filler. CO2 is intrinsically electrophilic as presented by the following values of carbon dioxide; i.e., the ionization potential of 13.7 eV and the electron affinity of 3.8 eV. Thus, it is believed that there is a surface state of the filler optimum for dispersion.
The pH can be obtained by preparing a 4% dispersion liquid (watermethano1=1:1 vol/vol) of the filler and measuring the prepared suspension for pH.
Evaluation of the filler for, for example, the above degree of hydrophobization and pH can be performed even after the production of the foamed sheet. In a specific possible manner, the foamed sheet is dissolved with a solvent to separate the aliphatic polyester resin ingredients through filtration and take out the filler, which is then analyzed.
When evaluation is performed on the filler of the obtained foamed sheet, the foamed sheet may be subjected to a pre-treatment of burning it in, for example, an electronic furnace to take it out as ash.
The amount of the filler contained may be appropriately selected depending on the intended purpose as long as physical properties of the resultant foamed sheet are not degraded. It is preferably from 0.1% by mass through 10% by mass, more preferably from 0.5% by mass through 5% by mass, relative to the entirety of the foamed sheet. When the amount of the filler is from 0.1% by mass through 10% by mass, it is possible to prevent occurrence of an unfavorable phenomenon where the fillers aggregate together.
<Other Ingredients>
The other ingredients are not particularly limited and may be appropriately selected depending on the intended purpose as long as they are usually contained in the foamed sheet. Examples of the other ingredients include, but are not limited to, a crosslinking agent.
The crosslinking agent is preferably a (meth)acrylic acid ester compound containing two or more (meth)acrylic groups in a molecule thereof or a (meth)acrylic acid ester compound containing one or more (meth)acrylic groups and one or more glycidyl groups or vinyl groups in a molecule thereof. This is because such a (meth)acrylic acid ester compound has high reactivity with a polylactic acid resin to leave a small amount of the monomer, and colors the resin to a small extent.
Specific examples of the (meth)acrylic acid ester compound include, but are not limited to, glycidyl methacrylate, glycidyl acrylate, glycerol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, allyloxypolyethylene glycol monoacrylate, allyloxypolyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, and polytetramethylene glycol dimethacrylate. It may be a copolymer of alkylenes in which the alkylene glycol moieties in the above-listed compounds have various lengths. Further examples include butanediol methacrylate and butanediol acrylate.
Incorporation of the crosslinking agent can impart melt tension to adjust the expansion ratio of a foamed polylactic acid sheet. A method of imparting melt tension is, for example, a method of dispersing a filler such as layered silicate at a nano level, a method of crosslinking a resin composition using, for example, a crosslinking agent or a crosslinking aid, a method of crosslinking a resin composition with, for example, electron beams, or a method of adding another resin composition having a high melt tension. In addition to the above, the other ingredients include additives such as a thermal stabilizer, an antioxidant, and a plasticizer. One of these may be used alone or two or more of these may be used in combination.
In terms of recycle performance, the proportion of the other ingredients is preferably 20% by mass or less, more preferably 10% by mass or less, relative to the total amount of organic substances in the foamed sheet.
<Physical Properties of the Foamed Sheet>
The average foam diameter of the foamed sheet of the present disclosure is preferably 15 micrometers or less, more preferably 7 micrometers or less. The average foam diameter is preferably 0.1 micrometers or more.
When the average foam diameter is more than 15 micrometers, the strength of the resultant foamed sheet may be lowered.
A method of measuring the average foam diameter of the foamed sheet is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the average foam diameter of the foamed sheet can be measured by subjecting the foamed sheet to cross-section processing with an ion milling device and observing the resultant cross section with a SEM.
Using software of Image-Pro Premier (available from mediacy Co.) for the obtained cross-section SEM image (at a magnification of ×3,000), the gray components representing the foams (pores) and the resin components (white) are binarized. In an area of 35 micrometers×20 micrometers, the average particle diameter (Feret diameter) is determined. The gray components (foams) having Feret diameters of 0.5 micrometers or more are calculated for the average foam diameter.
The bulk density of the foamed sheet is preferably from 0.1 g/cm3 or more but 0.9 g/cm3 or less, more preferably 0.7 g/cm3 or less, further preferably 0.5 g/cm3 or less. When the bulk density of the foamed sheet is within this range, the resultant foamed sheet can have an excellent balance between strength and lightness in weight
The bulk density of the foamed sheet can be measured in the following manner, for example. Specifically, after left for 24 hours or longer in an environment of 23 degrees Celsius in temperature and 50% in relative humidity, the foamed sheet is measured for bulk volume from outer dimensions. Then, the weight (g) of this foamed sheet is precisely measured. The weight of the foamed sheet is divided by the bulk volume to determine the bulk density.
The foamed sheet of the present disclosure may be used as the below-described manufacture. For example, printing may be performed before use on the sheet without any pre-treatment. Alternatively, a mold may be used to process the foamed sheet to obtain a product.
A method of processing the sheet using a mold is not particularly limited and may be a hitherto known method for thermoplastic resins. Examples of the method include, but are not limited to, vacuum molding, air pressure molding, vacuum air pressure molding, and press molding.
(Manufacture)
A manufacture of the present disclosure includes the foamed sheet of the present disclosure and if necessary further includes other ingredients.
The other ingredients are not particularly limited and may be appropriately selected depending on the intended purpose as long as they are usually used in resin products.
Examples of the manufacture (which may be referred to as a “consumption material”) include, but are not limited to, livingware such as a bag, a packaging container, a tray, dishware, cutlery, and stationery, and a cushioning material. The concept of this manufacture includes not only an original fabric obtained by forming the sheet into a roll as an intermediate product to be processed into the manufacture and a manufacture alone as a single product, but also parts formed of the manufacture such as a handle of the tray and products provided with manufactures such as a tray with a handle.
Examples of the bag include, but are not limited to, a plastic bag, a shopping bag, and a garbage bag.
Examples of the stationery include, but are not limited to, a file folder and a badge.
Existing foamed sheets have problems with physical properties as sheets such as sheet strength and flexibility because foam diameters and variation therein are large.
The manufacture molded using the foamed sheet of the present disclosure has excellent physical properties, and thus can also be used in other applications than those as the above livingware, for example, in a wide variety of applications such as sheets for industrial materials, agriculture, foods, pharmaceuticals, and cosmetics; and packaging materials.
The foamed sheet of the present disclosure is useful in applications requiring biodegradability of the foamed sheet, especially as a packaging material used for foods and a medical-use sheet for, for example, cosmetics and pharmaceuticals. For example, thinning the foamed sheet can be expected for the resultant foamed sheet to have improved performances.
(Method for Producing the Foamed Sheet)
A method for producing the foamed sheet of the present disclosure includes a kneading step and a foaming step and if necessary further includes other steps.
The kneading step and the foaming step may be performed at the same time or as separate steps.
<Kneading Step>
The kneading step is a step of kneading the aliphatic polyester resin and the filler in the presence of a compressive fluid at a temperature lower than the melting point of the aliphatic polyester resin.
In the kneading step, for more efficient foaming, a foaming agent may be added besides the aliphatic polyester resin and the filler.
Incidentally, a mixture of the aliphatic polyester resin, the filler, and the foaming agent before foaming may be referred to as a polylactic acid composition or a masterbatch.
<<Foaming Agent>>
In terms of the ability to easily produce a polylactic acid-based resin foamed sheet having a high expansion ratio, examples of the foaming agent include: but are not limited to, hydrocarbons including lower alkanes such as propane, normal butane, iso butane, normal pentane, iso pentane, and hexane; ethers such as dimethyl ether; halogenated hydrocarbons such as methyl chloride and ethyl chloride; and physical foaming agents such as compressive gases of, for example, carbon dioxide and nitrogen.
Among them, use of compressive gases of, for example, carbon dioxide and nitrogen is preferable from the viewpoints of being odorless, able to be handled safely, and low in environmental load.
The aliphatic polyester has such a property that its melt viscosity drastically decreases after the melting point. Thus, in kneading the filler and other materials, the filler easily aggregates. This phenomenon is significant when the size of the filler is small.
In the present disclosure, in order to uniformly disperse the filler in polylactic acid having such a property, a compressive fluid is used for the kneading. Incidentally, when the compressive fluid is the same as the foaming agent, kneading of the filler and foaming can be performed as a single process, which is more preferable as the form of production from the viewpoint of reduction in environmental load.
Description will be given to the reason why use of a compressive fluid is preferable in kneading the fine filler and the aliphatic polyester resin.
It is generally known that the compressive fluid plasticizes a resin to decrease a melt viscosity of the resin (see “Latest application technique of supercritical fluid”, NTS). A decrease in the melt viscosity and an improvement in the kneading performance seem to be contradictory. Actually, a pressure may be applied without using the compressive fluid for kneading general filler, but this decreases the free volume of the resin to aim at an increase in interaction between the resins (increase in viscosity), which is opposite to plasticization of the resin (see “k. Yang. R. Ozisik R. Polymer, 47. 2849 (2006)”).
Hitherto, it is known that a compressive fluid has such a property as to plasticize (soften) a resin, and the resin behaves like a liquid in the compressive fluid at an increased temperature. Dispersing the filler in the resin in such a state is like dispersing the filler in a liquid. As a result, the filler aggregates in the liquid to be unable to obtain a highly dispersed resin composition. In other words, the resin cannot have a suitable viscosity for kneading in the presence of the compressive fluid, and thus it had been considered difficult to use the compressive fluid for kneading the resin and the filler.
Under such circumstances, the present inventors intensively studied whether the compressive fluid can be used for kneading between the aliphatic polyester resin and the filler, and have found that the aliphatic polyester resin has a suitable viscosity for kneading at a temperature lower than the melting point of the aliphatic polyester resin, resulting in being able to knead the filler. In particular, the aliphatic polyester resin, the melt viscosity of which drastically decreases at a temperature equal to or higher than the melting point, enabled kneading only in the state of low melt viscosity. In the present disclosure, meanwhile, the filler can be kneaded in the state of high viscosity, and also the compressive fluid can be used as the foaming agent as is, which is more suitable.
<<Compressive Fluid>>
Examples of a substance that can be used in the state of the compressive fluid include, but are not limited to, carbon monoxide, carbon dioxide, dinitrogen monoxide, nitrogen, methane, ethane, propane, 2,3-dimethylbutane, ethylene, and dimethyl ether. Among them, carbon dioxide is preferable because the critical pressure and critical temperature of carbon dioxide are about 7.4 MPa and about 31 degrees Celsius, respectively, and thus a supercritical state of carbon dioxide is easily generated. In addition, carbon dioxide is non-flammable and easily handled. One of these compressive fluids may be used alone or two or more of these compressive fluids may be used in combination.
Referring now to
In such regions, the substance is known to have extremely high density and show different behaviors from those observed at normal temperature and normal pressure. Incidentally, the substance in the region (1) is a supercritical fluid. The supercritical fluid is a fluid that exists as a non-condensable high-density fluid at temperature and pressure exceeding limits (critical points) at which a gas and a liquid can coexist and that does not condense even when it is compressed. The substance in the region (2) turns into a liquid but represents a liquefied gas obtained by compressing a substance existing as a gas at normal temperature (25 degrees Celsius) and normal pressure (1 atm). The substance is in the region (3) is in the state of a gas but represents a high-pressure gas of which pressure is ½ or higher of the critical pressure (Pc), i.e. ½ Pc or higher.
Solubility of the compressive fluid varies depending on the combination of the kind of the resin and the compressive fluid and temperature and pressure. Thus, there is a need to appropriately adjust the amount of the compressive fluid supplied.
For example, in the combination of polylactic acid and carbon dioxide, the amount of the carbon dioxide supplied is preferably 2% by mass or more but 30% by mass or less. When the amount of the carbon dioxide supplied is 2% by mass or more, it is possible to prevent an unfavorable phenomenon where an obtainable plasticizing effect is limitative. When the amount of the carbon dioxide supplied is 30% by mass or less, it is possible to prevent an unfavorable phenomenon where the carbon dioxide and the polylactic acid are phase-separated to be unable to obtain the foamed sheet having a uniform thickness.
<Kneading Apparatus>
As a kneading apparatus used for producing the aliphatic polyester resin composition, a continuous process may be employed or a batch process may be employed. Preferably, a reaction process is appropriately selected by considering, for example, efficiency of an apparatus, characteristics of a product, and quality.
In terms of the ability to achieve the viscosity suitable for kneading, the kneading apparatus usable is, for example, a single screw extruder, a twin screw extruder, a kneader, a screw-less basket-shaped stirring vessel, BIVOLAK (available from Sumitomo Heavy Industries, Ltd.), N-SCR (available from Mitsubishi Heavy Industries, Ltd.), or a tube-shaped polymerization vessel equipped with a spectacle-shaped blade (available from Hitachi, Ltd.), lattice-blade or Kenix-type, or Sulzer-type SMLX-type static mixer. In terms of color tone, the kneading apparatus usable is a finisher that is a self-cleaning-type polymerization apparatus, N-SCR, or a twin-screw extruder. Among them, a finisher and N-SCR are preferable in terms of production efficiency, color tone of a resin, stability, and heat resistance.
As illustrated in
<<Raw Material Mixing and Melting Area>>
In the raw material mixing and melting area, the resin pellets and the filler are mixed and heated. The heating temperature is set to a temperature that is equal to or higher than the melting temperature of the resin, which makes it possible to uniformly mix the mixture with a compressive fluid in a subsequent area where the compressive fluid is to be supplied.
<<Compressive Fluid Supplying Area>>
The resin pellets become melted through warming, and the compressive fluid is supplied in the state that the filler is wetted, to thereby plasticize the melted resin.
<<Kneading Area>>
The temperature in the kneading area is set so that the viscosity suitable for kneading the filler is achieved. The setting temperature is not particularly limited because it varies depending on, for example, the specification of a reaction apparatus, the kind of a resin, and the structure and molecular weight of the resin. However, for commercially available polylactic acid having a weight average molecular weight (Mw) of about 200,000, the kneading is usually performed at the melting point of polylactic acid plus 10 degrees Celsius through 20 degrees Celsius. Meanwhile, the present disclosure has the feature that the kneading is performed at a temperature lower than the melting point of polylactic acid. In the present disclosure, it is possible to perform the kneading at a relatively high viscosity at the temperature lower than the melting point of polylactic acid. Specifically, the temperature for the kneading is the melting point of polylactic acid minus 20 degrees Celsius through 80 degrees Celsius, more preferably the melting point of polylactic acid minus 30 degrees Celsius through 60 degrees Celsius. Conveniently, the temperature may be set by referring to, for example, the current values of stirring power of the apparatus. However, it can be said that these setting values are usually unreachable ranges except in the present disclosure.
<Foaming Step>
The foaming step is a step of removing the compressive fluid and foaming the polylactic acid composition.
The compressive fluid can be removed by releasing the pressure.
The temperature in the foaming step is preferably equal to or higher than the melting point of the polylactic acid resin.
In the foaming step, in response to treatments to change solubility of the compressive fluid such as pressure reduction and heating, the compressive fluid dissolved in the polylactic acid composition vaporizes at the interface with the filler and precipitates, to thereby cause foaming. The foaming starts from the filler. Thus, only when the filler is uniformly dispersed in polylactic acid, the foamed sheet containing uniform and fine foams can be produced.
<Other Steps>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose as long as they are steps that are usually performed in the production of a foamed sheet. Examples of the other steps include a molding step of processing into a sheet.
Examples of the molding step include, but are not limited to, vacuum molding, air pressure molding, and press molding. The molding step produces a molded product in the form of sheet.
The present disclosure will be described by way of Examples, which however should not be construed as limiting the present disclosure thereto in any way.
<Production of Foamed Sheet>
<<Preparation of Masterbatch>>
The continuous kneading apparatus 100 illustrated in
The temperatures of the respective zones were set as follows: the raw material mixing and melting area a and the compressive fluid supplying area b: 190 degrees Celsius; the kneading area c: 150 degrees Celsius; the compressive fluid removing area d: 190 degrees Celsius; and the molding processing area e: 190 degrees Celsius. With the pressures of the respective zones being set as follows: from the compressive fluid supplying area b to the kneading area c: 7.0 MPa; and the compressive fluid removing area d: 0.5 MPa, the composition was extruded as a strand. After cooled in a water bath, the strand was pelletized with a strand cutter to obtain a masterbatch containing the filler by 3% by mass.
<<Production of the Foamed Sheet>>
The continuous foamed sheet forming apparatus 110 illustrated in
The kneaded product was discharged at 10 kg/h from a circular mold having a slit diameter of 70 mm attached to the tip of the second extruder, and cooled to 167 degrees Celsius as the resin temperature. The compressive fluid was removed from the aliphatic polyester resin composition kneaded in the second extruder heating area d for extrusion foaming. The cylindrical foamed sheet after the extrusion from the mold slit was allowed to contour on a mandrel being cooled, and the outer surface thereof was sprayed with air from an air ring for cold molding. The resultant was cut with a cutter into a flat sheet to thereby obtain the foamed sheet.
The temperatures of the respective zones were set as follows: the first extruder: the raw material mixing and melting area a and the compressive fluid supplying area b: 190 degrees Celsius and the kneading area c: 150 degrees Celsius; and the second extruder heating area d: 167 degrees Celsius. The pressures of the respective zones were set as follows: from the compressive fluid supplying area b to the kneading area c and the second extruder heating area d: 7.0 MPa.
In the same manner as in Example 1 except that the kind of silica as the filler was changed to each of the following, foamed sheets of Examples 2 and 3, Examples 11, 12, and 15, and Comparative Examples 1 and 2 were produced.
Example 2: AEROSIL R816 (obtained from NIPPON AEROSIL Co., Ltd.)
Example 3: AEROSIL NY50 (obtained from NIPPON AEROSIL Co., Ltd.)
Example 11: Mixture of AEROSIL R220 (obtained from NIPPON AEROSIL Co., Ltd.) and SG-2000 (obtained from NIPPON TALC CO., LTD.) (50:50 by weight)
Example 12: Mixture of AEROSIL R220 (obtained from NIPPON AEROSIL Co., Ltd.) and SG-2000 (obtained from NIPPON TALC CO., LTD.) (80:20 by weight)
Example 15 QSG-100 (obtained from Shin-Etsu Chemical Co., Ltd.)
Comparative Example 1 HDK-2000H (obtained from Clariant Co., Ltd.)
Comparative Example 2 AEROSIL MOX170 (obtained from NIPPON AEROSIL Co., Ltd.)
In the same manner as in Example 1 except that the amount of the filler was changed as presented in Table 1, foamed sheets of Examples 4 and 5 were produced.
In the same manner as in Example 1 except that the aliphatic polyester resin was changed to polylactic acid (REVODE190, obtained from HISUN Co., melting point: 175 degrees Celsius) and the compressive fluid was changed to carbon dioxide at 0.78 kg/h (equivalent to 8% by mass relative to the polylactic acid) and dimethyl ether 0.19 kg/h (equivalent to 2% by mass relative to the polylactic acid), a foamed sheet of Example 6 was produced.
In the same manner as in Example 1 except that the aliphatic polyester resin was changed to polylactic acid (REVODE101, obtained from HISUN Co., melting point: 150 degrees Celsius), a foamed sheet of Example 7 was produced.
In the same manner as in Example 1 except that the aliphatic polyester resin was changed to polybutylene succinate (obtained from PTT MCC Biochem Co., melting point: 115 degrees Celsius), a foamed sheet of Example 8 was produced.
A foamed sheet of Example 9 was produced in the same manner as in Example 1 except that the aliphatic polyester resin was changed to polyglycolic acid (PGA) (obtained from KUREHA Co., Ltd., kuredux100E35, melting point: 220 degrees Celsius), the compressive fluid used for the preparation of the masterbatch and the production of the foamed sheet were changed to carbon dioxide supplied at 0.25 kg/h as the first compressive fluid and dimethyl ether supplied at 0.25 kg/h as the second compressive fluid, and the temperatures of the raw material mixing and melting area a and the compressive fluid supplying area b were changed to 230 degrees Celsius.
A foamed sheet of Example 10 was produced in the same manner as in Example 1 except that the aliphatic polyester resin was changed to a resin containing, at a ratio of 99:1, polylactic acid (REVODE110, obtained from HISUN Co., melting point: 160 degrees Celsius) which is an aliphatic polyester and JONCRYL (obtained from BASF Co.) as a styrene acrylic crosslinking agent which is not an aliphatic polyester.
A foamed sheet of Example 13 was produced in the same manner as in Example 1 except that the aliphatic polyester resin was changed to a resin containing, at a ratio of 80:20, polylactic acid (REVODE110, obtained from HISUN Co., melting point: 160 degrees Celsius) which is an aliphatic polyester and polystyrene (obtained from PS Japan Corporation, HF77) which is not an aliphatic polyester.
A foamed sheet of Example 14 was produced in the same manner as in Example 1 except that the aliphatic polyester resin was changed to a resin containing, at a ratio of 50:50, polylactic acid (REVODE110, obtained from HISUN Co., melting point: 160 degrees Celsius) which is an aliphatic polyester and polystyrene (obtained from PS Japan Corporation, HF77) which is not an aliphatic polyester.
The filler in each of the obtained foamed sheets was measured for number average particle diameter, degree of hydrophobization, and pH by analyzing the filler taken out as ash from each foamed sheet. The ash is defined as the residue when the foamed sheet is burnt at 600 degrees Celsius for 4 hours.
The ash was measured in the following manner.
Specifically, a 100 mL-crucible was precisely weighed to four decimal places with a precision balance. About 3 g of the foamed sheet sample was measured and placed in the crucible. The total weight of the crucible and the sample was precisely measured.
The crucible was placed in muffle furnace FP-310 obtained from Yamato Scientific Co., Ltd. for burning at 600 degrees Celsius for 4 hours to burn organic components. Then, the crucible was cooled in a desiccator for 1 hour. The weight of the crucible was precisely measured again to measure the total weight of the crucible and ash. The amount of the ash (i.e., the amount of the filler) and the total amount of the organic substances are calculated from the following formulae.
Amount of the filler [%] (i.e., amount of the ash [%])=(the total weight of the crucible and the sample after the burning and cooling [g]−the weight of the crucible [g])/(the total weight of the crucible and the sample before the burning [g]−the weight of the crucible [g])×100
Total amount of the organic substances [%]=100−the amount of the ash [%]
The above measurement was performed with n=2, and the average value was a reported value.
The foamed sheet was measured for bulk density, average foam diameter, number of coarse particles, and standard deviation. Measurement results are presented in Table 1 to Table 4. Also, the obtained foamed sheet was evaluated for strength and flexibility in the following manners. Evaluation results are presented in Table 1 to Table 4.
<Number Average Particle Diameter and Standard Deviation (σ) of the Filler>
The foamed sheet was subjected to cross-section processing with an ion milling device, and the cross section was observed with a SEM.
Using software of Image-Pro Premier (obtained from mediacy Co.) for the obtained cross-section SEM image (at a magnification of ×10,000), the white components representing the filler and the polylactic acid components were binarized. In an area of 10 micrometers×7 micrometers, the particle diameter (Feret diameter) was determined. The white components (filler) having Feret diameters of 0.005 micrometers or more were calculated for number average particle diameter and standard deviation (σ).
<Degree of Hydrophobization>
One gram of the filler was weighed and allowed to float on the surface of 50 mL of pure water. Methanol was dropped to the resultant under stirring to determine the amount of methanol (% by mass) necessary for suspending the total amount of the filler in the pure water.
<pH>
The filler was used to prepare a 4% suspension (watermethano1=1:1 vol/vol) of the filler. This prepared suspension was measured for pH with a pH meter (obtained from DKK-TOA CORPORATION).
<Number of Coarse Particles of the Filler>
The foamed sheet (50 mg) was allowed to melt to form a thin film of 10 micrometers. The thin film was observed under an optical microscope (obtained from NIKON CORPORATION, FX-21, at a magnitude of ×100) to count the number of the coarse particles formed from the filler having particle diameters of 10 micrometers or more.
This operation was repeated for five different samples of the foamed sheet, and the average value of the counted numbers was defined as the number of the coarse particles of the filler.
<Bulk Density>
After left for 24 hours or longer in an environment of 23 degrees Celsius in temperature and 50% in relative humidity, the foamed sheet was measured for bulk volume from outer dimensions. Then, the weight (g) of this foamed sheet was precisely measured. The weight of the foamed sheet was divided by the bulk volume to determine the bulk density.
<Average Foam Diameter>
The average foam diameter of the foamed sheet was measured by subjecting the foamed sheet to cross-section processing with an ion milling device and observing the resultant cross section with a SEM.
Using software of Image-Pro Premier (obtained from mediacy Co.) for the obtained cross-section SEM image (at a magnification of ×3,000), the gray components representing the foams (pores) and the resin components (white) were binarized. In an area of 35 micrometers×20 micrometers, the average particle diameter (Feret diameter) was determined. The gray components (foams) having Feret diameters of 0.5 micrometers or more were calculated for the average foam diameter.
Incidentally, the average foam diameter was a value obtained from the above foams in three locations.
<Strength>
The obtained foamed sheet was measured for tensile strength according to JISK6767. The strength was evaluated based on the following evaluation criteria; i.e., the extent of the strength of the foamed sheet relative to the strength of a non-foamed sheet (polylactic acid sheet). Incidentally, the measurement result of the non-foamed sheet was found to be 55 MPa.
—Evaluation Criteria—
A: The tensile strength was 60% or higher relative to that of the non-foamed sheet.
B: The tensile strength was 40% or higher but lower than 60% relative to that of the non-foamed sheet.
C: The tensile strength was lower than 40% relative to that of the non-foamed sheet.
Incidentally, the references for the aliphatic polyester resin in the table have the following meanings.
PLA(a): Polylactic acid (REVODE110, obtained from HISUN Co., melting point: 160 degrees Celsius)
PLA(b): Polylactic acid (REVODE190, obtained from HISUN Co., melting point: 175 degrees Celsius)
PLA(c): Polylactic acid (REVODE101, obtained from HISUN Co., melting point: 150 degrees Celsius)
PBS: Polybutylene succinate
PGA: Polyglycolic acid (PGA)
Aspects of the present disclosure are as follows, for example.
<1> A foamed sheet including:
an aliphatic polyester resin; and
a filler,
wherein a degree of hydrophobization of the filler is 50% by mass or more, and wherein pH of the filler is 6.5 or lower.
<2> The foamed sheet according to <1>, wherein a number average particle diameter of the filler is from 5 nm through 100 nm.
<3> The foamed sheet according to <1> or <2>, wherein the pH of the filler is 3.5 or higher but 6.5 or lower.
<4> The foamed sheet according to any one of <1> to <3>, wherein number of coarse particles of the filler which have particle diameters of 10 micrometers is 100 particles or less/mm2.
<5> The foamed sheet according to any one of <1> to <4>, wherein a proportion of the aliphatic polyester resin is 80% by mass or more relative to a total amount of organic substances in the foamed sheet.
<6> The foamed sheet according to any one of <1> to <5>, wherein a bulk density is 0.9 g/cm3 or less.
<7> The foamed sheet according to any one of <1> to <6>, wherein the filler is silica.
<8> The foamed sheet according to <7>, wherein a proportion of the silica is 50% by mass or more relative to a total amount of inorganic substances in the foamed sheet.
<9> The foamed sheet according to any one of <1> to <8>, wherein the aliphatic polyester resin is at least one kind selected from the group consisting of polylactic acid, polybutylene succinate, and polyglycolic acid.
<10> A manufacture including
the foamed sheet according to any one of <1> to <9>.
<11> The manufacture according to <10>, wherein the manufacture is at least one kind selected from the group consisting of a bag, a packaging container, dishware, cutlery, stationery, and a cushioning material.
<12> A method for producing a foamed sheet, the method including:
kneading an aliphatic polyester resin and a filler in presence of a compressive fluid at a temperature lower than a melting point of the aliphatic polyester resin, to obtain an aliphatic polyester resin composition; and
removing the compressive fluid from the aliphatic polyester resin composition to foam the aliphatic polyester resin composition.
<13> The method according to <12>, wherein the foamed sheet is the foamed sheet according to any one of <1> to <9>.
<14> The method according to <12> or <13>, wherein the compressive fluid is carbon dioxide.
<15> A method for producing a manufacture, the method including
molding the foamed sheet according to any one of claims <1> to <9> through at least one selected from the group consisting of vacuum molding, air pressure molding, and press molding, to obtain the manufacture.
The foamed sheet according to any one of <1> to <9> above, the manufacture according to <10> or <11> above, the method according to any one of <12> to <14> above, and the method according to <15> above can solve the various existing problems and achieve the object of the present disclosure.
The above-described embodiments are illustrative and do not limit the present invention. Thus, numerous additional modifications and variations are possible in light of the above teachings. For example, elements and/or features of different illustrative embodiments may be combined with each other and/or substituted for each other within the scope of the present invention.
This patent application is based on and claims priority to Japanese Patent Application No. 2020-011076, filed on Jan. 27, 2020 and Japanese Patent Application No. 2020-193309, filed on Nov. 20, 2020, in the Japan Patent Office, the entire disclosure of each of which is hereby incorporated by reference herein.
1 Resin pellets supply tank
2 Calcium carbonate supply tank
3 Compressive fluid supply tank
4 T die
100 Continuous kneading apparatus
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-011076 | Jan 2020 | JP | national |
| 2020-193309 | Nov 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2020/062368 | 12/23/2020 | WO |
