CN105339155A - Process for manufacturing polylactic acid-based resin film - Google Patents
Process for manufacturing polylactic acid-based resin film Download PDFInfo
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- CN105339155A CN105339155A CN201480037098.6A CN201480037098A CN105339155A CN 105339155 A CN105339155 A CN 105339155A CN 201480037098 A CN201480037098 A CN 201480037098A CN 105339155 A CN105339155 A CN 105339155A
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- film
- polylactic acid
- inflation
- plasticising
- based resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/28—Storing of extruded material, e.g. by winding up or stacking
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/007—Using fluid under pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0019—Combinations of extrusion moulding with other shaping operations combined with shaping by flattening, folding or bending
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
- B29C48/147—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle
- B29C48/1472—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle at the die nozzle exit zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2467/00—Use of polyesters or derivatives thereof as filler
- B29K2467/04—Polyesters derived from hydroxycarboxylic acids
- B29K2467/046—PLA, i.e. polylactic acid or polylactide
-
- 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The present invention addresses the problem of providing: a plasticized polylactic acid-based resin film which is produced by an inflation molding method and which does not cause problematic tight winding; and a process for manufacturing the same. A process for manufacturing a plasticized polylactic acid-based resin film by inflation-molding a polylactic acid -based resin composition which comprises 100 parts by weight of polylactic acid and 10 to 30 parts by weight of a plasticizer, characterized by including a heat treatment step subsequent to the step for ejecting the polylactic acid-based resin composition through an orifice for inflation molding.
Description
Technical field
The present invention relates to the method manufacturing and utilize the plasticizer in addition plasticising film of the soft polylactic acid based resin changed.More specifically, the manufacture method of the plasticising film of the polylactic acid based resin that relate to after utilizing inflation shaping to form, also can not be out of shape in room temperature keeping.
Background technology
In recent years, based on the raising of environmental consciousness, receive publicity for the soil contamination problem caused by plastic products discarded and by the greenhouse effects of the earth problem of burning caused by the rise of carbon dioxide that causes.As for the former countermeasure, study energetically, develop various Biodegradable resin, as the countermeasure for the latter, even if study, develop the resin be made up of living beings (plant origin raw material) of the load burning the carbon dioxide that also can not provide new in air energetically.
As the resin solving this kind of problem, the research of PLA, exploitation are particularly carried out energetically.PLA is meeting 100% biodegradation within some months was by 1 year in the body of animal, starts degraded in addition, disappeared about 1 year to several years time under environment moistening as in soil or seawater when a few week.In addition, also there is the characteristic that its catabolite is harmless lactic acid, carbon dioxide and water.
PLA in recent years due to can utilize fermentation method in a large number and manufacture at an easy rate fast as the Pfansteihl of raw material, degradation speed in compost, for the resistance of mould, the excellent feature such as odor profiles or coloring resistance is held for food, thus it utilizes the expansion in field to be expected.
But, because the rigidity of PLA is high, be therefore the resin of the soft film purposes being suitable for the special requirement flexibilities such as Farm mulch, food packaging bag, refuse bag hardly.
Generally speaking, as the technology making resin softening, there will be a known mixing soft polymer or add the methods such as plasticizer.
But in the method for mixing soft polymer, if consider biological degradability, then mixed resin is restricted to the Biodegradable resin with flexibility.As this kind of resin, such as, can enumerate poly butylene succinate, polyethylene glycol succinate, polycaprolactone etc.But, in the method, enough flexibilities (such as elastic modelling quantity is below 1000MPa) to be given to PLA, just need to add soft polymer in a large number.Such as, poly butylene succinate needs to add more than 60 % by weight of entirety, consequently, can damage the speciality of aforesaid PLA.And percentage elongation during stretching also can diminish, not too practical as soft film.
On the other hand, the film that will add plasticizer and softness is generally called plasticising film, even and if the method for this interpolation plasticizer can give enough flexibilities to resin combination, the melt viscosity of resin combination also can reduce, consequently, cannot carry out inflation shaping etc., thus film forming method is restricted.In addition, in the method for adding plasticizer, the problem that plasticizer oozes out can be produced, therefore will must solve a lot of problem by practical for the method.
Manufacturing process as plasticising film can enumerate inflation shaping, T die head formula film extrusion molding, extruding layer pressing formation etc.Wherein inflation forming process is compared with other forming processes, and can carry out with compact device, the productivity ratio of a small amount of multi items is excellent, and cost is low.In addition, the film shape due to gained is tubular (without gap-like), is therefore suitable for use in the manufacture of the bag or bag etc. of packaging for foodstuff.
The method being utilized by polylactic acid based resin inflation shaping to carry out membranization is such as disclosed in patent document 1 ~ 3 (WO1999/45067 publication, Japan Patent No. 3510218 publication, Japanese Unexamined Patent Publication 11-116788 publication).But in the method recorded in these documents, using the fusions (ア ロ イ) of PLA and other aliphatic esters, is not the membranization of the resin of independent PLA, therefore have the problem of the characteristic of infringement PLA.
Thus in patent document 4 (Japanese Unexamined Patent Publication 2008-260895 publication), disclose use utilize plasticizer in addition soft changed PLA, utilize inflation to be shaped to manufacture the method for the plasticising film having practical intensity and flexibility concurrently.But, in the method recorded in the publication, also because of the distortion when near room temperature is taken care of after forming, and can have and cannot extract the problems such as core out from the reel of winding.
Prior art document
Patent document
Patent document 1:WO1999/45067 publication
Patent document 2: Japan Patent No. 3510218 publication
Patent document 3: Japanese Unexamined Patent Publication 11-116788 publication
Patent document 4: Japanese Unexamined Patent Publication 2008-260895 publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, provide and utilize inflation forming process to be shaped and polylactic acid based resin plasticising film and the manufacture method thereof that can not roll tightly (volume Parties ま り) (being difficult to the state of being extracted out from reel by core).More specifically, there is provided a kind of manufacturing process of polylactic acid based resin plasticising film, by after utilizing the plasticising film inflation forming machine of the plasticizer in addition soft polylactic acid based resin changed to be shaped, even if near room temperature with drum keeping, also can not extract core out, can produce efficiently.
For the method for dealing with problems
The present inventors conducts in-depth research to solve the problem, result obtains following opinion, namely, the phenomenon rolled tightly results from, (on the vertical Chi Ga り) stress that partly (part resin being expanded because of the air after tube head ejection) produces that erects be shaped at inflation still remains after film winding, and therefore in keeping, As time goes on film deforms.Find in addition, by before film keeping (film be shaped in or after being shaped) heat-treat, the distortion in film keeping can be suppressed, thus complete the present invention.
Said, according to the present invention, following method can be provided.
The manufacture method of (item 1) a kind of polylactic acid based resin plasticising film, the polylactic acid based resin composition containing plasticizer 10 ~ 30 weight portion relative to PLA 100 weight portion utilized inflation forming process to be shaped and manufacture the method for polylactic acid based resin plasticising film, it is characterized in that, the operation after the tube head ejection that inflation is shaped comprises the operation carrying out heating.
(item 2), according to the manufacture method recorded in item 1, wherein, described plasticizer is benzalkonium diethylene glycol adipate.
(item 3) according to the manufacture method recorded in item 1 or 2, wherein, described heating be the film that makes to be shaped with higher than 40 DEG C and be the medium contact method of 2 ~ 300 seconds of less than 100 DEG C.
(item 4) according to the manufacture method recorded in item 1 or 2, wherein, described heating be the film that makes to be shaped with higher than 40 DEG C and be the method that the heating surface of less than 100 DEG C contacts 2 ~ 300 seconds.
The manufacture method that (item 5) is recorded any one of item 1 ~ 4, wherein, carries out described heating after the tube head ejection be shaped from inflation in the operation of the initial winding of described plasticising film.
The manufacture method that (item 6) is recorded any one of item 1 ~ 5, is characterized in that, after inflation is shaped, carries out described heating after temporarily being reeled by described plasticising film.
The manufacture method that (item 7) is recorded any one of item 1 ~ 6, is characterized in that, even if described plasticising film is maintained the plasticising film that drum also can not roll tightly at 20 ~ 40 DEG C.
The manufacture method that (item 8) is recorded any one of item 1 ~ 7, is characterized in that, even if described plasticising film is maintained drum also can not produce the generation of fold and/or the plasticising film of adhesion at 20 ~ 40 DEG C.
(item 9) a kind of prevents the rolling tightly of polylactic acid based resin plasticising film, the generation of fold and/or the method for adhesion, it is characterized in that, utilizing inflation shaping legal system to make in the method for polylactic acid based resin plasticising film, the operation after the tube head ejection that inflation is shaped comprises the operation carrying out heating.
(item 10) a kind of polylactic acid based resin plasticising film utilizing inflation forming process to be shaped, is characterized in that, can not roll tightly.
Invention effect
According to the present invention, can provide and utilize inflation forming process to be shaped the manufacture method of the polylactic acid based resin plasticising film that can not roll tightly and the polylactic acid based resin plasticising film that can not roll tightly.More specifically, after the plasticising film utilizing inflation shaping legal system to make with the plasticizer in addition soft polylactic acid based resin changed, even if keep reel state near room temperature (about 20 DEG C ~ about 40 DEG C) keeping, the situation (generation rolled tightly) cannot extracting core out also can not occur unchangeably, can operate efficiently at the scene.In addition, according to the present invention, though by plasticising film with reel state about 20 DEG C ~ about 40 DEG C keepings, also can prevent the generation of the fold of plasticising film, adhesion, the reduction of product property can be prevented.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of inflation forming process.
Fig. 2 is the schematic diagram of the keeping flow process in the past representing inflation forming process and film.
Fig. 3 is the schematic diagram of hot-rolling used in the heating of embodiment 13 ~ 23 and comparative example 7.
Detailed description of the invention
Below Details of the present invention is described.
In the present invention, so-called " rolling tightly ", comprises following state, that is, making drum being twisted on core by the film after being shaped, when maintaining reel state, being difficult to the core being wound with film to be extracted out from reel.Such as, because film contraction, film are wound on more tightly on core and make the core of reel be difficult to also be contained in " rolling tightly " with the state of the UF membrane of drum.
< film >
(plasticising film)
First, plasticising film of the present invention is described.
In preferred mode of the present invention, so-called plasticising film is the film utilizing inflation to be shaped the polylactic acid based resin composition utilizing plasticizer that PLA softness has been changed and obtain.The tensile modulus of elasticity of described plasticising film is preferably about 100 ~ 1500MPa from the viewpoint of practical, is more preferably about 100 ~ 1000MPa, more preferably about 110 ~ 800MPa.In addition, during the fracture of described plasticising film, percentage elongation is preferably about 20 ~ 400% from the viewpoint of practical, is more preferably about 100 ~ 375%, and more preferably about 150 ~ 350%.If tensile modulus of elasticity is above-mentioned scope, then film has enough flexibilities, if the scope of percentage elongation during above-mentioned fracture, then can become the film with practical enough frees degree, and can obtain the shape stability of practical film.The thickness of film is different according to purposes, but usually can be set to about 5 ~ 500 μm.
(tensile modulus of elasticity)
The tensile modulus of elasticity of described film uses universal testing machine (Autograph based on JIS standard (JISK7127); SIMADZU AG-1) with the value of the draw speed of 200mm/ minute stretching, mensuration.
(during fracture percentage elongation)
During the fracture of described film, percentage elongation uses universal testing machine (Autograph based on JIS standard (JISK7127); SIMADZU Inc. AG-1) with the value of the draw speed of 200mm/ minute stretching, mensuration.
< polylactic acid based resin composition >
Next, described polylactic acid based resin composition is described.
(PLA)
For described PLA used in the present invention, starting monomer is not particularly limited, and can enumerate Pfansteihl, D-ALPHA-Hydroxypropionic acid, DL-LACTIC ACID, their mixture and the known monomer such as lactide as the cyclic dimer of lactic acid.Described PLA can be the material making single monomer polymerization and obtain, and also can be material various of monomer being polymerized and obtaining, be that required physical property can suitably be selected in order to make the plasticising film of gained.Lactic acid can be obtained by the resource fermentation that granulated sugar, starch etc. can be regenerated, and consider from this point, be also useful raw material in the middle of biodegradable fatty mylar.
In a mode of the present invention, the weight average molecular weight of PLA is not particularly limited, but considers from the viewpoint such as physical property of processability and/or the film after being shaped, and is preferably 10,000 ~ about 1,000,000, more preferably 30,000 ~ about 600,000, further preferably 50,000 ~ about 400,000.Weight average molecular weight is that the mechanical strength of the PLA of aforementioned range is abundant, and excellent processability, therefore can preferably use.It should be noted that, in the present invention, weight average molecular weight is the value utilizing gel permeation chromatography.Specifically, gel permeation chromatography uses Tosoh Co., Ltd. HLC-8120GPC, chromatographic column is TSKgelG4000Hxl × 1 using the said firm, analysis uses the GPC-8020modelII of the said firm to carry out under the condition of flow velocity 1ml/ minute, uses the known polystyrene of molecular weight to measure as standard specimen.
(plasticizer)
As long as described plasticizer used in the present invention is just not particularly limited for the plasticizer of PLA, the various plasticizer (such as the fatty acid ester of citrate, glycerine, the fatty acid ester of dihydroxylic alcohols or fatty group dibasic acid etc.) usually used in this field also can be used.Described plasticizer is such as from the viewpoint of making the melt viscosity of polylactic acid based resin composition be appropriate value, and preferred aliphat dibasic acid ester, particularly preferably uses the adipate ester system plasticizer comprising benzalkonium diethylene glycol adipate.The alkyl of described benzalkonium diethylene glycol adipate can be any one of straight-chain or branched, but preferred straight-chain.In addition, the carbon number of alkyl is preferably 1 ~ 20, is more preferably 1 ~ 8, and more preferably 1 ~ 4.Particularly preferably there are the benzyl methyl diethylene glycol adipate of the alkyl of the carbon number 1 ~ 4 of straight-chain, benzyl ethyl diethylene glycol adipate, benzyl n-pro-pyl diethylene glycol adipate and benzyl normal-butyl diethylene glycol adipate etc.
In a mode of the present invention, about the content of described plasticizer is preferably 10 ~ 30 weight portions relative to polylactic resin 100 weight portion, about being more preferably 12 ~ 28 weight portions, more preferably about 15 ~ 26 weight portions.If above-mentioned scope, then can obtain the film with practical sufficient flexibility, and the resin combination being suitable for the intensity that inflation is shaped can be obtained.
(hydrolysis-resisting agent)
Though polylactic acid resin composition of the present invention is nonessential, still hydrolysis-resisting agent can be contained.
As described hydrolysis-resisting agent, the hydrolysis-resisting agent of mylar can be used as ad lib and known compound.As this kind of hydrolysis-resisting agent, such as, can enumerate carbodiimide compound, oxazoline based compound and isocyanate compound etc.Especially preferred is carbodiimide compound.
There is cross-linking reaction preferably by the terminal carboxylic with polylactic acid based resin in described carbodiimide compound, and demonstrates the effect of the hydrolysis suppressing polylactic acid based resin.As carbodiimide compound, as long as have the carbodiimide-based of more than 1 in molecule, be just not particularly limited, according to known method, such as, can use the compound synthesized through decarboxylic reaction by isocyanate compound.In addition, also commercially available compound can be used.
In a mode of the present invention, described carbodiimide compound has the basic structure of following general formula (1).
-(N＝C＝N-R-)
n-(1)
In above-mentioned formula (1), n represents the integer of more than 1.In addition, R represents to have substituent aliphatic (alkane, olefine, alkynes etc. of such as straight or branched), the organic system bonding units such as alicyclic (such as the cycloalkane, volution etc. of monocycle, two rings or many rings) or aromatic series (BTX aromatic of such as monocycle or many rings, furans, thiophene, the heteroaromatic etc. such as pyrroles or imidazoles).
More specifically, as single carbodiimide compound (in above-mentioned formula (1), n is the compound of 1) in molecule with 1 carbodiimide-based, the aromatic series list such as the aliphatic such as Diisopropylcarbodiimide, dicyclohexyl carbodiimide, dioctyl carbodiimides or alicyclic single carbodiimides, diphenyl carbodiimides carbodiimides etc. can be exemplified.
In addition, as have in molecule more than 2 carbodiimide-based polycarbodiimide synthesis in isocyanate compound (above-mentioned formula (1) in n be the compound of more than 2), can 1 be exemplified, 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 4, the aromatic diisocyanates such as 4 '-diphenyldimethyhnethane vulcabond; 1,4-cyclohexane diisocyanate, 1-methyl-2, aliphatic or the alicyclic diisocyanates etc. such as 4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, IPDI, HMDI, HDI.Polycarbodiimide can be the whole of the NCO remaining in end or a part by the material of end-blocking, as this end-capping reagent, the monoisocyanate compound such as cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate can be exemplified; There is the compound etc. of hydroxyl, amino isoreactivity hydrogen.
In above-mentioned carbodiimide compound, from the viewpoint of the hydrolytic resistance improvement of the formed products that the resin combination by gained is shaped, preferably there is the polycarbodiimide of the carbodiimide-based of more than 2 in molecule, in addition, from the viewpoint of the intermiscibility with polylactic acid based resin and the stability to hydrolysis resistance of formed products that is shaped by obtained resin combination, preferred aliphat or alicyclic carbodiimides, the polycarbodiimide obtained by aliphatic or alicyclic diisocyanate.Concrete example as this kind of polycarbodiimide compound can enumerate Misshin Spinning Co., Ltd CarbodiliteLA-1, HMV-15CA etc.
Hydrolysis-resisting agent can be used alone a kind, or used in combination multiple.
In a mode of the present invention, about the content of hydrolysis-resisting agent is preferably 0.1 ~ 5 weight portion relative to polylactic resin 100 weight portion, about being more preferably 0.5 ~ 3 weight portion, more preferably about 1 ~ 2 weight portion.If the addition of hydrolysis-resisting agent is above-mentioned scope, then can prevents the viscosity caused by the reduction of molecular weight from reducing, inflation shaping can be carried out swimmingly.In addition, can prevent the viscosity caused by excessive cross-linking reaction from increasing, thus inflation shaping can be carried out swimmingly.
(other additive)
In polylactic acid based resin composition of the present invention, as required, other the composition usually added in Biodegradable resin composition can be added in the scope not damaging effect of the present invention.As this kind of composition, such as, can enumerate nucleator, modifier, spices, antiseptic, pigment, dyestuff, heat-resistant agent, antioxidant, weather resisting agent, lubricant, antistatic agent, stabilizing agent, filler, hardening agent, antiblocking agent, fire retardant, wood powder, starch etc.
The manufacture method > of < plasticising film
Below, the manufacture method of described plasticising film of the present invention is specifically described.
(mixing)
By mentioned component with after the mixing of required ratio, as long as used at the temperature about about 130 ~ 250 DEG C, preferably 140 ~ 200 DEG C by this mixture, biaxial extruder is mixing makes moulding material.For the spray volume of biaxial extruder, if small Twin-shaft extruder, be then set to 1 ~ 20kg/ hours, be preferably set to 2 ~ 10kg/ hours.
(shaping)
The moulding material utilizing said method to make is suitable for utilizing inflation forming process to be configured as film.In preferred mode of the present invention, inflation forming process is utilized to be configured as film above-mentioned moulding material.Inflation forming process is suitable for the manufacture of a small amount of multi items, in addition owing to can obtain with tubular, therefore has and easily film can be made the advantages such as bag-shaped.
The method that inflation is shaped can be carried out according to known method, known method itself or the method with reference to them.Specifically, as inflation forming process, the moulding material melting in an extruder normally will added from hopper, material by this melting is from annular die head (リ Application グ ダ イ), circular die (サ ー キ ュ ラ ー ダ イ), or extrude in the tube head (1 of Fig. 1) of the inflation die for forming such as ring shape die head (ball type ダ イ), after utilizing air stream to make it expansion (2 of Fig. 1), make it flat with the guide plate (3 of Fig. 1) of the shape being configured to people's shape, with drum winding (5 of Fig. 1), just can manufacture the formed body (film) of tubular thus.As long as the temperature that the temperature of polylactic acid resin composition when inflation is shaped makes it melting is just not particularly limited, but is usually set to about 140 ~ 200 DEG C, more preferably about 150 ~ 180 DEG C.
(expansion ratio)
As long as normally used ratio during the expansion ratio film that inflation of the present invention is shaped is shaped, is preferably 1.2 ~ 5, is more preferably 1.5 ~ 4, is particularly preferably 1.8 ~ 3.Expansion ratio can be controlled by the temperature and the air amount of being blown into adjusting the resin blowing unit of forming machine.
Expansion ratio utilizes following formula to obtain.
The bore of the width/die head of the film of expansion ratio (BUR)=reeled
(heating)
In preferred mode of the present invention, the operation after tube head (1 of Fig. 1) ejection that the manufacture method of described plasticising film is shaped at inflation comprises the operation heated plasticising film.
Described heating can be carried out in any one or both in inflation is shaped or after being shaped.During so-called inflation is shaped, refer to after the tube head ejection of forming machine to (2 ~ 5 of Fig. 1) during initial winding film.In addition, after so-called inflation is shaped, refer to after initial winding film to during moving to site of storage.Specifically, reel pull-out film from initial winding is referred to and during being wound into second reel (7 of Fig. 2) or during directly being extracted out by the film of the drum reeled at first and being transported to site of storage (by 5 of Fig. 2 and the 9 direct arrows linked).
As the method heated, as long as can heat fully film, be just not particularly limited.Specifically, such as can contact special time by the medium or heating surface making film and specific temperature range to contact to carry out.As the temperature of described medium or heating surface, from the viewpoint rolled tightly of the plasticising film prevented keeping and the consideration such as viewpoint manufacturing efficiency, be preferably higher than 40 DEG C and be less than 100 DEG C, be more preferably 50 ~ 90 DEG C, be particularly preferably 60 ~ 85 DEG C.For the time making film contact with medium or heating surface, from the viewpoint rolled tightly of the plasticising film prevented keeping and the consideration such as viewpoint manufacturing efficiency, be preferably 2 ~ 300 seconds, be more preferably 5 ~ 120 seconds, be particularly preferably 10 seconds ~ 90 seconds.The number of times that film is contacted with medium or heating surface is not particularly limited.Both can be 1 time, and also can be repeatedly.When repeatedly, as long as in the scope being aggregated in the above-mentioned time of time of contact.
If in above-mentioned scope, then can reduce fully film be just shaped after residual stress, do not have the film situation about deforming near room temperature is preserved.
As the heating means of medium or heating surface, as long as the method that steam, electricity, induction heating, infrared ray etc. are generally used, be just not particularly limited.As long as consider the scale of device and security and suitably select.
(medium)
As long as film can heat by medium fully used in heating of the present invention, be just not particularly limited, various medium can be used.Specifically, air, inactive gas (nitrogen, helium, neon, argon gas etc.) and water etc. can such as be enumerated.From the viewpoint of the efficiency of heating surface and cost, be preferably air and/or water.
(heating surface)
So-called heating surface used in heating of the present invention is the object remaining on specific temperature range, have certain area.Heating surface can be any one of plane or curved surface.It should be noted that, so-called certain area, as long as film can be heated fully, is just not particularly limited.In addition, from the viewpoint of the efficiency of heating surface, the surface that heating surface preferably contacts with film is by smoothing.
For the material of heating surface, be just not particularly limited as long as film can be heated fully, various material can be used.Specifically, such as the alloys such as the metals such as iron, copper, titanium or nickel, stainless steel, carbon steel, pottery, resin, rubber and glass etc. can be enumerated.From the viewpoint of the efficiency of heating surface and cost etc., be preferably copper or carbon steel.
In a mode of the present invention, heating surface is not particularly limited, but specifically such as can enumerate metallic plate (comprising alloy sheets), ceramic wafer, resin plate, metal roller (comprising alloy roller), ceramic roller, resin roller, rubber coated pressure bowl etc.
In another mode of the present invention, use metal roller as heating surface.As the material of metal roller, as long as material generally used is just not particularly limited, the nickel etc. copper, carbon steel, stainless steel, titanium can enumerated or utilize electrocasting to manufacture.In addition, the surface of metal roller can be implemented the surface treatments such as plating hard chromium, nickel plating, plating amorphous chromium etc. or ceramic spraying.
It should be noted that, after above-mentioned heating of the present invention, the operation of described plasticising film cooling being with or without can.In a mode of the present invention, the temperature of the described plasticising film at 8 places of 5 or Fig. 2 of Fig. 2 is about less than 50 DEG C, from the viewpoint of the quality maintaining film, is preferably about less than 40 DEG C, is more preferably less than 30 DEG C.
Particularly preferred mode of the present invention relates to a kind of manufacture method of polylactic resin plasticising film, be the manufacture method polylactic acid based resin composition containing PLA 100 weight portion and plasticizer 10 ~ 30 weight portion being utilized the shaping of inflation forming process, manufacture polylactic resin plasticising film, in the operation after the tube head ejection that inflation is shaped, comprise heating treatment step.For PLA, plasticizer and heating treatment method, can be described above.In which, by comprising heating in a manufacturing method, even if the polylactic resin plasticising film of gained is constant about 20 DEG C ~ about 40 DEG C maintenance reel states, the generation, adhesion etc. of the rolling tightly of described plasticising film, fold also can be suppressed.Be not particularly limited during being maintained reel state, such as, be generally more than 1 month, from the viewpoint of maintenance quality, can be half a year more than, be more preferably more than 1 year.
In addition, another preferred mode of the present invention relates to a kind of method, at the polylactic acid based resin plasticising film that will inflation forming process utilized to be shaped when about 20 DEG C ~ about 40 DEG C with drum keeping, prevents the rolling tightly of described plasticising film, the generation of fold and/or adhesion.Specifically, before keeping, described plasticising film is heated.Polylactic acid based resin plasticising film and the implementation method heated can be same as described above.
Embodiment
Below, the present invention will be described in more detail to provide embodiment, but the present invention does not limit by them.
(1) material
PLA: IngeoBiopolymer4043D
(NatureWorksLLC Inc.; L body 95.75 % by weight: D body 4.25 % by weight)
Plasticizer: DAIFATTY-101
(Daihachi Chemical Industry Co., Ltd.'s system; Adipate ester composition containing benzalkonium diethylene glycol adipate)
Nucleator: ECOPROMOTE (Nissan Chemical Ind Ltd's system; Phenyl-phosphonic acid zinc)
Hydrolysis-resisting agent: CarbodiliteHMV-15CA (Nisshinbo knits chemical company's system)
(2) film extracts the evaluation method of easness (with or without rolling tightly)
At external diameter 8cm and the film of 50m that the core columned made of paper of long 34cm reels, make the reel of film.Under the state not extracting this reel, at 30 ~ 35 DEG C, keeping, after 24 hours, utilizes following benchmark to evaluate to extraction easness when being extracted from reel by core made of paper.
Zero keeps the shape invariance ground of winding easily to extract core from reel
× the shape of not destroying reel just cannot extract core
(3) resin combination is mixing
With the ratio shown in following table 1, in PLA, mix each composition, use biaxial extruder (Toshiba Machinery Co., Ltd. TEM-37BS) that melting temperature is set as 150 DEG C, carry out mixing, obtain moulding material.
[table 1]
(4) shaping of film
(embodiment 1)
By moulding material A inflation forming machine (Ji Jing ironworker Co., Ltd. system, YEI-S45-60-R) melting under the condition of barrels set temperature 160 DEG C, with expansion ratio (BUR) 2 be shaped thick 50 μm and flatten time width be the film of the tubular of 30cm, in the warm water of 80 DEG C, utilize above-mentioned evaluation method to evaluate by the film of 60 seconds to as the 4d part heated at Fig. 2.The results are shown in table 2.
(comparative example 1)
Except heating, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 2)
Except changing to except B by moulding material A, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(comparative example 2)
Except heating, the operation identical with embodiment 2 and evaluation are carried out.The results are shown in table 2.
(embodiment 3)
Except changing to except C by moulding material A, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(comparative example 3)
Except heating, the operation identical with embodiment 3 and evaluation are carried out.The results are shown in table 2.
(embodiment 4)
Except changing to except D by moulding material A, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(comparative example 4)
Except heating, the operation identical with embodiment 4 and evaluation are carried out.The results are shown in table 2.
(embodiment 5)
Except changing to except 5 seconds by the time making film pass through in warm water from 60 seconds, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 6)
Except changing to except 10 seconds by the time making film pass through in warm water from 60 seconds, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 7)
Except changing to except 30 seconds by the time making film pass through in warm water from 60 seconds, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 8)
Except changing to except 90 seconds by the time making film pass through in warm water from 60 seconds, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 9)
Except the temperature of warm water is become 60 DEG C and became except 30 seconds by the time making film pass through warm water from 60 seconds from 80 DEG C, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 10)
Except becoming except 60 seconds by the time making film pass through in warm water from 30 seconds, the operation identical with embodiment 9 and evaluation are carried out.The results are shown in table 2.
(embodiment 11)
Except the temperature of warm water is become 70 DEG C and became except 30 seconds by the time making film pass through warm water from 60 seconds from 80 DEG C, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(embodiment 12)
Except becoming except 60 seconds by the time making film pass through in warm water from 30 seconds, the operation identical with embodiment 11 and evaluation are carried out.The results are shown in table 2.
(embodiment 13)
Except as heating from making film warm water by except becoming and making it to contact with the multiple hot-rollings shown in Fig. 3, carried out the operation identical with embodiment 1 and evaluation.The results are shown in table 2.
The temperature of the roller 10 ~ 19 of Fig. 3 utilized induction heating to be adjusted to 60 DEG C, film passes through with the speed of 5m/ minute.Heating in this situation is set to carries out 60 seconds at 60 DEG C.
It should be noted that, the roller of Fig. 3 used in the present embodiment employs first ~ the tenth roller from casting device side in the longitudinal stretching machine of the multilayer extrusion casting and stretching testing arrangement being arranged at M Co., Ltd. usashino-Kikai.
(embodiment 14)
Except the temperature of roller is become 80 DEG C and became except 10m/ minute by the speed making film pass through from 5m/ minute from 60 DEG C, the operation identical with embodiment 13 and evaluation are carried out.The results are shown in table 2.
(embodiment 15)
Except becoming except 80 DEG C by the temperature of roller from 60 DEG C, the operation identical with embodiment 13 and evaluation are carried out.The results are shown in table 2.
(embodiment 16)
Except the temperature of roller is become 90 DEG C and became except 10m/ minute by the speed making film pass through from 5m/ minute from 60 DEG C, the operation identical with embodiment 13 and evaluation are carried out.The results are shown in table 2.
(embodiment 17)
Except becoming except 90 DEG C by the temperature of roller from 60 DEG C, the operation identical with embodiment 13 and evaluation are carried out.The results are shown in table 2.
(embodiment 18)
Except changing to except D from moulding material A, the operation identical with embodiment 13 and evaluation are carried out.The results are shown in table 2.
(embodiment 19)
Except the temperature of roller is become 80 DEG C and became except 10m/ minute by the speed making film pass through from 5m/ minute from 60 DEG C, the operation identical with embodiment 18 and evaluation are carried out.The results are shown in table 2.
(embodiment 20)
Except becoming except 80 DEG C by the temperature of roller from 60 DEG C, the operation identical with embodiment 18 and evaluation are carried out.The results are shown in table 2.
(embodiment 21)
Except changing to E from moulding material A, becoming except 80 DEG C by the temperature of roller from 60 DEG C, the operation identical with embodiment 13 and evaluation are carried out.The results are shown in table 2.
(embodiment 22)
Except the temperature of roller is become 90 DEG C and became except 10m/ minute by the speed making film pass through from 5m/ minute from 80 DEG C, the operation identical with embodiment 21 and evaluation are carried out.The results are shown in table 2.
(embodiment 23)
Except becoming except 90 DEG C by the temperature of roller from 80 DEG C, the operation identical with embodiment 21 and evaluation are carried out.The results are shown in table 2.
(comparative example 5)
Except changing to except E from moulding material A, the operation identical with comparative example 1 and evaluation are carried out.The results are shown in table 2.
(comparative example 6)
Except the temperature of warm water is become 40 DEG C and became except 120 seconds by the time making film pass through warm water from 60 seconds from 80 DEG C, the operation identical with embodiment 1 and evaluation are carried out.The results are shown in table 2.
(comparative example 7)
Except the temperature of roller is become 40 DEG C and became except 1.66m/ minute by the speed making film pass through from 5m/ minute from 60 DEG C, the operation identical with embodiment 18 and evaluation are carried out.The results are shown in table 2.
[table 2]
Confirmed with comparing of comparative example 1 ~ 5 by embodiment 1 ~ 23, utilize and heat, the phenomenon rolled tightly caused by room temperature keeping can be prevented.In addition, confirmed by embodiment 1 ~ 23, heating is the contact of film and thermal medium or all effective with any one of the contact of heating surface.
Utilizability in industry
The present invention can utilize to be blown into that describing changes places manufactures the method for poly lactic acid series plasticising film efficiently, and the film utilizing the present invention to manufacture can be suitable as Farm mulch, food packaging bag, refuse bag etc.
The explanation of symbol
Tube head during 1 inflation is shaped
Dilated plasticising film during 2 inflations are shaped
3 guide plates
The plasticising film that 4a is stretched
The plasticising film that 4b is stretched
The plasticising film that 4c is stretched
The plasticising film that 4d is stretched
The plasticising film of 5 drums be wound
The plasticising film of 6 drums
The 7 plasticising films be stretched in reeling again
8 by the plasticising film of drum reeled again
The plasticising film of 9 drums taken care of in warehouse
Claims (10)
1. the manufacture method of a polylactic acid based resin plasticising film, the polylactic acid based resin composition containing plasticizer 10 ~ 30 weight portion relative to PLA 100 weight portion utilized inflation forming process to be shaped and manufacture the method for polylactic acid based resin plasticising film, it is characterized in that, the operation after the tube head ejection that inflation is shaped comprises the operation carrying out heating.
2. manufacture method according to claim 1, wherein, described plasticizer is benzalkonium diethylene glycol adipate.
3. manufacture method according to claim 1 and 2, wherein, described heating be the film that makes to be shaped with higher than 40 DEG C and be the medium contact method of 2 ~ 300 seconds of less than 100 DEG C.
4. manufacture method according to claim 1 and 2, wherein, described heating be the film that makes to be shaped with higher than 40 DEG C and be the method that the heating surface of less than 100 DEG C contacts 2 ~ 300 seconds.
5. the manufacture method according to any one of Claims 1 to 4, wherein, carries out described heating after the tube head ejection be shaped from inflation in the operation of the initial winding of described plasticising film.
6. the manufacture method according to any one of Claims 1 to 5, is characterized in that, after inflation is shaped, carries out described heating after temporarily being reeled by described plasticising film.
7. the manufacture method according to any one of claim 1 ~ 6, is characterized in that, even if described plasticising film is maintained the plasticising film that drum also can not roll tightly at 20 ~ 40 DEG C.
8. the manufacture method according to any one of claim 1 ~ 7, is characterized in that, even if described plasticising film is maintained drum also can not produce the generation of fold and/or the plasticising film of adhesion at 20 ~ 40 DEG C.
9. the rolling tightly of a polylactic acid based resin plasticising film, the generation of fold and/or the prevention method of adhesion, it is characterized in that, utilizing inflation shaping legal system to make in the method for polylactic acid based resin plasticising film, the operation after the tube head ejection that inflation is shaped comprises the operation carrying out heating.
10. the polylactic acid based resin plasticising film utilizing inflation forming process to be shaped, is characterized in that, can not roll tightly.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-135100 | 2013-06-27 | ||
| JP2013135100 | 2013-06-27 | ||
| PCT/JP2014/066037 WO2014208403A1 (en) | 2013-06-27 | 2014-06-17 | Process for manufacturing polylactic acid-based resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105339155A true CN105339155A (en) | 2016-02-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480037098.6A Pending CN105339155A (en) | 2013-06-27 | 2014-06-17 | Process for manufacturing polylactic acid-based resin film |
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| Country | Link |
|---|---|
| JP (1) | JPWO2014208403A1 (en) |
| CN (1) | CN105339155A (en) |
| TW (1) | TW201510006A (en) |
| WO (1) | WO2014208403A1 (en) |
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| CN113561604B (en) * | 2021-08-16 | 2023-03-31 | 中国科学院长春应用化学研究所 | Polylactic acid-based multifunctional multilayer composite agricultural mulching film and preparation method thereof |
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| EP1816164A1 (en) * | 2003-11-25 | 2007-08-08 | Asahi Kasei Life & Living Corporation | Matte film |
| JP2008120865A (en) * | 2006-11-09 | 2008-05-29 | Toray Ind Inc | Manufacturing method of polylactic acid resin film |
| JP2008260895A (en) * | 2007-04-13 | 2008-10-30 | Osaka City | Polylactic acid-based resin film and method for producing the same |
| CN101722654A (en) * | 2008-10-28 | 2010-06-09 | 上海华义化工科技有限公司 | Method for preparing polylactic acid-based resin film by liquid phase medium heat conduction double-membrane soaking method |
| CN101767465A (en) * | 2008-12-29 | 2010-07-07 | 佛山塑料集团股份有限公司 | Method for preparing thermoplastic resin film |
| CN101802057A (en) * | 2007-09-10 | 2010-08-11 | 帝人株式会社 | Film |
| CN102171278A (en) * | 2008-10-02 | 2011-08-31 | 日东电工株式会社 | Polylactic acid-based film or sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263931A (en) * | 2004-03-17 | 2005-09-29 | Asahi Kasei Life & Living Corp | Inorganic filler-loaded matte film |
-
2014
- 2014-06-17 WO PCT/JP2014/066037 patent/WO2014208403A1/en active Application Filing
- 2014-06-17 JP JP2015523995A patent/JPWO2014208403A1/en active Pending
- 2014-06-17 CN CN201480037098.6A patent/CN105339155A/en active Pending
- 2014-06-27 TW TW103122388A patent/TW201510006A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1816164A1 (en) * | 2003-11-25 | 2007-08-08 | Asahi Kasei Life & Living Corporation | Matte film |
| JP2008120865A (en) * | 2006-11-09 | 2008-05-29 | Toray Ind Inc | Manufacturing method of polylactic acid resin film |
| JP2008260895A (en) * | 2007-04-13 | 2008-10-30 | Osaka City | Polylactic acid-based resin film and method for producing the same |
| CN101802057A (en) * | 2007-09-10 | 2010-08-11 | 帝人株式会社 | Film |
| CN102171278A (en) * | 2008-10-02 | 2011-08-31 | 日东电工株式会社 | Polylactic acid-based film or sheet |
| CN101722654A (en) * | 2008-10-28 | 2010-06-09 | 上海华义化工科技有限公司 | Method for preparing polylactic acid-based resin film by liquid phase medium heat conduction double-membrane soaking method |
| CN101767465A (en) * | 2008-12-29 | 2010-07-07 | 佛山塑料集团股份有限公司 | Method for preparing thermoplastic resin film |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201510006A (en) | 2015-03-16 |
| JPWO2014208403A1 (en) | 2017-02-23 |
| WO2014208403A1 (en) | 2014-12-31 |
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