WO2015183385A1 - Low phosphorus low color polyamides - Google Patents
Low phosphorus low color polyamides Download PDFInfo
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- WO2015183385A1 WO2015183385A1 PCT/US2015/021562 US2015021562W WO2015183385A1 WO 2015183385 A1 WO2015183385 A1 WO 2015183385A1 US 2015021562 W US2015021562 W US 2015021562W WO 2015183385 A1 WO2015183385 A1 WO 2015183385A1
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- WIPO (PCT)
- Prior art keywords
- phosphorus
- polyamide
- polyamide according
- containing compound
- ppm
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
Definitions
- Polyamide resins and means for their preparation are well known. When manufactured according to conventional processes but in the absence of conventional pigments, these resins tend to exhibit varying degrees of undesired yellowness, with the yellowness increasing over time. Polyamide resins also generally exhibit increased yellowness when exposed to the high temperatures associated with subsequent commonly employed melt processing operations. Since many of these polyamide resins are stored for extended periods of time and in view of the potential for repeated cycles of melting during molding and extrusion, there is an incentive to provide improved polyamide resins which initially show low color and which continue to show low color over time.
- Phosphorus-containing compounds are well known catalysts for polymerization of polyamides. Notably, the use of these compounds results in polyamides having a greater degree of whiteness and color stability, presumably by reducing the degree of oxidative and thermal degradation of the polyamide. See, e.g., U.S. Patent No. 5,929,200. More particularly, hypophosphite compounds have been used as catalysts for polymerization of the polyamides, as described in, for example, U.S. Patent Nos. 3,860,558; 3,173,898; and 3,691,131.
- U.S. Patent Nos. 3,585,264 and 4,866,115 also disclose using nucleating agents for improving the rate of crystallization of polyamides.
- U.S. Patent No. 6,197,855 discloses the incorporation of nylon 2,2 and a phosphorous-containing whitening agent into the polyamide before, during or after the polycondensation step. Preferably, the phosphorous-containing whitening agent is added during the polycondensation step to result in a white polymer.
- the present invention is directed to (i) the use of low phosphorus content for the purpose of improving color, catalytic activity, and low deposit/plate out, (ii) end group configuration designed to maximize injection molding productivity; and (iii) application of a metal-containing compound to the outside of the polyamide (typically in pellet form) after polymerization, but before injection molding to reduce the catalytic activity of the phosphorus-containing compound during injection molding, while preserving the integrity of the catalytic behavior of the phosphorus-containing compound during polymerization.
- the present invention reflects the unexpected discovery that the use of phosphorus- containing compounds in amounts conventionally thought to be too low to be effective protection against yellowing are surprisingly effective in preparing low color polyamides, where the low color does not degrade over an extended period of time. These same low levels of phosphorus that provide improvement in color and polymerization rate also mitigate the negative effect of phosphate plate out in the polymerization and processing equipment.
- An aspect of the present invention is a low-color polyamide comprising 25 to 50 ppm of phosphorus, wherein the phosphorus is present as a phosphorus-containing compound.
- Another aspect of the invention is a process for preparing a low-color polyamide comprising 25 to 50 ppm of phosphorus.
- Another aspect of the invention is an article comprising a low-color polyamide comprising 25 to 50 ppm of phosphorus.
- the low-color polyamide comprises 25 to 45 ppm, such as 25 to 40 ppm, such as 25 to 35 ppm, such as 25 to 30 ppm of phosphorus.
- the phosphorus-containing compound is selected from the group consisting of hypophosphorus acid, phosphorus acid and their respective salts. Hypophosphorus acid and sodium hypophosphite (SHP) are preferred phosphorus- containing compounds.
- the low-color polyamide further comprises at least one of a metal-containing compound capable of reducing the catalytic effect of the phosphorus- containing compound, especially during injection molding.
- the low-color polyamide further comprises 1,200 to 1,800 ppm of a carboxylic acid, such as a lower carboxylic acid (e.g., acetic acid or propionic acid), phthalic acid, benzoic acid or other compound capable of rendering various end groups of the polyamide inert (i.e., non-reactive).
- a carboxylic acid such as a lower carboxylic acid (e.g., acetic acid or propionic acid), phthalic acid, benzoic acid or other compound capable of rendering various end groups of the polyamide inert (i.e., non-reactive).
- the polyamide is selected from the group consisting of nylon 6, nylon 4/6, nylon 6/6, nylon 6/10, nylon 6/12, nylon 11 and nylon 12.
- the polyamide is nylon 6/6 (also referred to herein as nylon 66 or nylon 6,6 or nylon66 or polyamide 66 or PA 66 or PA66).
- the low-color polyamide further comprises one or more additives, fillers, reinforcing agents and modifiers.
- the low-phosphorus polyamide comprises 250 to 1,500 ppm, such as 250 to 1,000 ppm, such as 250 to 750 ppm, such as 250 to 500 ppm, such as 500 to 1,500 ppm, such as 500 to 1,000 ppm, such as 500 to 750 ppm of a metal-containing compound.
- the yellow color index ranges from -3 to -9, such as -3 to -8, such as -3 to -7, such as -3 to -6, such as -4 to -9, such as -4 to -8, such as -5 to -9, such as -5 to -8.
- the metal-containing compound is applied to the external surface of a solid form of the polyamide - e.g., after the polyamide has already been processed, wherein the solid form is, for example, a pellet or a flake. Alternatively, the metal-containing compound may be applied internal to the pellet.
- the low-phosphorus polyamide (such as nylon 66) has a specific configuration of end groups, such as, for example, amine end groups, carboxylate end groups and so-called inert end groups including mono-carboxylic acids, mono amines, lower dicarboxylic acids capable of forming inert imine end groups, phthalic acids and derivatives thereof). The specific combination of all of these components provides the observed polymerization performance in the form of catalytic activity of the phosphorus- containing compound, the whiteness of the final product, low deposition during
- Figure 1 illustrates a scanning electron microscope image of a filter element containing deposits.
- Figure 2 illustrates the reduced cost of filter changes associated with reduced levels of phosphorus.
- Figure 3 illustrates a graphical representation of the rise in filter pressure versus increasing phosphorus levels.
- Figure 4 illustrates the effect of phosphorus (SHP) levels on the color (Yl) of PA66.
- Figure 5 illustrates the effect of phosphorus (SHP) levels on the color (Yl) of molded plaques.
- Figure 6 illustrates the effect of phosphorus content on RV build during SSP.
- Figure 7 illustrates the relationship between phosphorus levels and transfer line pressure.
- Figure 8 illustrates the change in RV upon injection molding of PA66 containing a phosphorus-containing compound.
- Figure 9 illustrates the change in RV upon injection molding of PA66 containing a phosphorus-containing compound and end capped with acetic acid.
- Figure 10 illustrates the average installation success rate for cable ties comprised of materials containing no phosphorus, materials containing 20 ppm phosphorus and materials containing 45 ppm phosphorus.
- relative viscosity refers to a comparison of the viscosity of a solution of polymer in formic acid with the viscosity of the formic acid itself and is measured using 90% formic acid and glass capillary Ubbelohde viscometers according to ASTM D789.
- RV relative viscosity
- low color refers to a lowering of the yellowness index by 3 to 5 units lower compared to the absence of a phosphorus-containing compound as measured by ASTM 6290. Suitable color determinations can be used as well, as described by the standard, Yellowness I ndex (Yl), CIE X, Y, 2, and Hunter L, a, b, or G E L*, a*, b*.
- End groups should be noted to be in the ranges using micro-equivalents (moles per million grams polyamide) and should cover the ranges say 5 to 40 moles per million grams, preferably 15 to 25 micromoles, and most preferably 20-33 moles per million grams of polyamide.
- the metal content should be described as moles metal per mole of phosphorus.
- the polyamide is selected from the group consisting of nylon 6, nylon 4/6, nylon 6/6, nylon 6/10, nylon 6/12, nylon 11, nylon 12, nylon MXD6, copolymer nylon (a copolymer of caprolactam with hexamethylenediamine adipate), nylon block copolymers, and copolymers comprising these nylons as main components.
- the general methods of preparation of polyamides such as nylon 6/6 are well known.
- the low- phosphorus polyamides described herein are prepared by conventional methods known in the art - such as the polycondensation of amino carboxylic acids or of mixtures of diamines and dicarboxylic acids including interpolyamides obtained by the polycondensation of different polyamide forming components. See, e.g., U.S. Patent Nos. 6,197,855; 4,981,906; 4,320,213; 4,346,200; 4,713,415; 4,031,164; 2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966; 2,512,606; and 3,393,210.
- Suitable phosphorus-containing compounds include hypophosphorus acids, phosphorus acid, and their corresponding salts.
- Preferred phosphorus-containing compounds include hypophosphorus acid and hypophosphite salts, such as lithium, sodium, potassium, strontium or zinc hypophosphite.
- M ultivalent metal-containing compounds used in the present invention serve as phosphorus catalyst deactivators, with the effect of reducing undesirable increases in the molecular weight of the polyamide during subsequent melt processing operations.
- the degree of phosphorus catalyst deactivation may be controlled by the amount of the phosphorus-containing compound and the multivalent metal-containing compound added to the polyamide.
- Suitable multivalent metal-containing compounds are well known to one skilled in the art and include halides, nitrates, and carboxylate salts (e.g., acetates, propionates, benzoates and stearates) of Group MA metals, zinc and aluminum.
- a preferred multivalent metal-containing compound is a stearate, such as, for example aluminum distearate or zinc stearate.
- Suitable carboxylic acids include acetic acid, propionic acid, benzoic acid, phthalic acid, or succinic acid.
- the low-phosphorus polyamide has a relative viscosity (RV) range between 35 and 80, such as between 40 and 80, such as between 40 and 65, such as between 40 and 50.
- RV relative viscosity
- the low-color polyamide may be mixed/blended with materials that include but are not limited to, glass fibers (e.g., fiberglass, such as in chopped or roving form), waxes (including, e.g., ethylene bis-stearamide or stearyl erucamide), minerals, carbon fibers, aramide fibers, fiber reinforcement, chain terminators, viscosity modifiers, plasticizers, heat stabilizers, UV stabilizers, colorants (such as, e.g., nigrosine or carbon black), catalysts, other polymers and impact modifiers, flame retardants, delusterants, fillers, antimicrobial agents, antistatic agents, optical brighteners, extenders, processing aids, talc, mica, gypsum, wollastonite and other commonly used additives known to those of skill in the art.
- glass fibers e.g., fiberglass, such as in chopped or roving form
- waxes including, e.g., ethylene bis-stearamide or stearyl
- additives are hydrolysis resistant chopped glass, heat stabilizers (including, e.g., copper heat stabilizers such as Cul or Kl) and nucleating agents. Additional suitable additives may be found in Plastics Additives, An A-Z reference, edited by Geoffrey Pritchard (1998).
- the optional addition of a stabilizer to the additive dispersion is present in an exemplary embodiment at between about 0.75% and about 7.5% by total dispersion weight.
- Stabilizers suitable for the additive dispersion include, but are not limited to,
- polyethoxylates such as the polyethoxylated alkyl phenol Triton X-100
- polypropoxylates block copolymeric polyethers, long chain alcohols, polyalcohols, alkyl-sulfates, alkyl- sulfonates, alkyl-benzenesulfonates, alkyl-phosphates, alkyl-phosphonates, alkyl- naphthalene sulfonates, carboxylic acids and perfluoronates.
- the material to be mixed/blended with the polyamide is added to the polyamide as itself (or a salt thereof) or is formed in situ using appropriate reactants.
- the terms "added” or “addition” without further clarification are intended to encompass either the addition of the material itself to the polymer or the in situ formation of the material in the polyamide.
- a masterbatch containing a low molecular weight carrier polymer and a high concentration of the additive material can be melt blended with the main polyamide source.
- the material(s) to be mixed/blended are added to the interior of the polyamide product (e.g., in pellet or flake form), while in another embodiment, the material(s) to be mixed/blended are added exterior to the polyamide product (e.g., in pellet or flake form).
- Examples of applications which would benefit from the improvements described herein include articles prepared by injection molding processes, profile extrusion processes, sheet extrusion processes, and other forming processes known to those skilled in the art.
- These articles may be used in electrical and electronic applications (such as, but not limited to, circuit breakers, terminal blocks, connectors and the like), automotive applications (such as, but not limited to, air handling systems, radiator end tanks, fans, shrouds, and the like), furniture and appliance parts, and wire positioning devices such as cable ties.
- electrical and electronic applications such as, but not limited to, circuit breakers, terminal blocks, connectors and the like
- automotive applications such as, but not limited to, air handling systems, radiator end tanks, fans, shrouds, and the like
- furniture and appliance parts such as cable ties.
- Phosphorus-containing compounds are used to improve color and to act as catalysts to achieve improved polymerization rates.
- FIG. 4 illustrates the effect of phosphorus (P) on color of PA66 prepared with varying phosphorus levels.
- P phosphorus
- the Yl of these materials was unexpectedly observed to change significantly between zero (0) P and about 24 ppm P, and then slightly more at about 45 ppm P and very slightly more at about 69 ppm P. These results clearly and unexpectedly show a diminishing effect of increasing phosphorus content on color at conventionally low phosphorus levels.
- PA66 produced in a continuous polymerization unit was prepared with two different phosphorus content levels using SHP as the phosphorus-containing compound. Plaques were molded from materials containing these two different phosphorus levels and the color of the materials was measured. The color of the plaques were determined weekly or so for several months. Figure 5 shows the results of the Yl measurement of these molded plaques. The difference in color between plaques prepared with 56 ppm phosphorus and plaques prepared with 45 ppm phosphorus is minor, and this difference in color does not significantly change over time. This study demonstrates that the color of PA66 is improved with the addition of SHP, but that once an effective level is reached, there is little or no improvement in color or color stability over time.
- a phosphorus-containing compound of the present invention in the manufacture of a polyamide such as PA66 is that the phosphorus- containing compound is a catalyst and higher production rates are achievable with it.
- the catalytic effectiveness at different phosphorus levels was determined using the lab autoclave samples described in Tables 1 and 2. Each sample was subjected to solid state polymerization at 175°C. Samples were retrieved at incremental times and the relative viscosity or RV was determined for each time. The results are summarized in Table 3 which shows the effect of phosphorus levels on SSP RV build, and are shown graphically in Figure 6.
- the amount of phosphorus-containing catalyst was reduced 68% (i.e., from 1.18 Ibs/min to 0.8 Ibs/min) a change from 56 ppm to approximately 40 ppm phosphorus.
- the pressure drop in the transfer line did not change over a four hour run period. This run period provides sufficient residence time for the polymer with the reduced level of phosphorus to have made it through the process. No discernible change in transfer line pressure differential was observed during this test. See Figure 7.
- the conclusion is that the product melt viscosity (and therefore the product molecular weight) had not changed due to the presence of the reduced amount of phosphorus.
- the catalytic effectiveness of the phosphorus-containing compound was not changed significantly between approximately 40 ppm P and approximately 56 ppm P.
- nylon 6,6 is the preferred polyamide and is used to prepare injection molded articles, such as, for example, cable ties, such as for electrical installation.
- the cable ties can be tested for performance using various techniques, such as those described by Underwriters Laboratory (UL) Standard No. 62275, which describes, for example, how to install a cable tie.
- UL Underwriters Laboratory
- the cable ties were injection molded from one or more nylon 6,6-containing materials, and sealed in moisture proof packaging to keep them 'dry as molded'
- the cable ties were then installed on, for example, a steel mandrel using an installation tool with an adjustable tensioning capability, set to deliver approximately 35 to 37 lbs of tension during installation before cutting the excess "tail" off of the tie. Installation of the ties is considered successful if the assembled cable tie is installed without any breakage, and remains intact after installation.
- the installation test is therefore a pass-fail type of test, wherein the success rate (i.e., the percentage of ties passing the installation test) is a measure of the toughness of the nylon 6,6-containing materials comprising the ties, as a fraction of the cable ties failed to be installed successfully.
- the success rate i.e., the percentage of ties passing the installation test
- n (items) number of items tested
- n (ties) number of cable ties tested
- the high number of specimens tested and the high probability of passing the test allows for a high degree of confidence - approximately 0.4% - which is sufficient to allow a statement that the difference in performance between the three tested materials is significant at the 95% confidence interval.
- Figure 8 shows that at lower moistures, the change in RV is greater than 20 units, whereas with the addition to the external surface of the pellet a metal- containing compound, in this case 500 ppm zinc stearate, causes the material to be less reactive and exhibit a change in RV under low moisture conditions of less than 11 RV units.
- a metal- containing compound in this case 500 ppm zinc stearate
Abstract
Description
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Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15800525.6A EP3149084A4 (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
JP2017515668A JP6817197B2 (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamide |
CN201580033313.XA CN106536633A (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
BR112016027990-5A BR112016027990B1 (en) | 2014-05-30 | 2015-03-19 | REDUCED COLOR POLYAMIDES AND LOW PHOSPHORUS CONTENT THAT PRESENT SOLID FORM |
KR1020167036443A KR102295420B1 (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
US15/314,837 US10865288B2 (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
CN202210825631.1A CN115353731A (en) | 2014-05-30 | 2015-03-19 | Low-phosphorus low-color polyamide |
CA2950405A CA2950405C (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
SG11201609952SA SG11201609952SA (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
IL249128A IL249128B (en) | 2014-05-30 | 2016-11-22 | Low phosphorus low color polyamides |
SA516380402A SA516380402B1 (en) | 2014-05-30 | 2016-11-30 | Low Phosphorus Low Color Polyamides |
HK17105727.0A HK1232245A1 (en) | 2014-05-30 | 2017-06-09 | Low phosphorus low color polyamides |
Applications Claiming Priority (2)
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US201462005813P | 2014-05-30 | 2014-05-30 | |
US62/005,813 | 2014-05-30 |
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WO2015183385A1 true WO2015183385A1 (en) | 2015-12-03 |
WO2015183385A9 WO2015183385A9 (en) | 2016-01-28 |
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PCT/US2015/021562 WO2015183385A1 (en) | 2014-05-30 | 2015-03-19 | Low phosphorus low color polyamides |
Country Status (14)
Country | Link |
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US (1) | US10865288B2 (en) |
EP (1) | EP3149084A4 (en) |
JP (2) | JP6817197B2 (en) |
KR (1) | KR102295420B1 (en) |
CN (3) | CN110951250A (en) |
AR (1) | AR100651A1 (en) |
BR (1) | BR112016027990B1 (en) |
CA (1) | CA2950405C (en) |
HK (1) | HK1232245A1 (en) |
IL (1) | IL249128B (en) |
SA (1) | SA516380402B1 (en) |
SG (1) | SG11201609952SA (en) |
TW (1) | TWI745270B (en) |
WO (1) | WO2015183385A1 (en) |
Cited By (1)
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WO2017184422A1 (en) * | 2016-04-21 | 2017-10-26 | Invista North America S.A R.L. | Resins for improved flow in injection molding |
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CN111849152B (en) * | 2020-06-29 | 2022-02-18 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
WO2024068509A1 (en) | 2022-09-27 | 2024-04-04 | Basf Se | Thermoplastic moulding compositions having an improved colour stability-1 |
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Also Published As
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US10865288B2 (en) | 2020-12-15 |
JP2017516913A (en) | 2017-06-22 |
TWI745270B (en) | 2021-11-11 |
HK1232245A1 (en) | 2018-01-05 |
IL249128A0 (en) | 2017-01-31 |
BR112016027990B1 (en) | 2022-01-18 |
AR100651A1 (en) | 2016-10-19 |
KR102295420B1 (en) | 2021-08-31 |
CA2950405C (en) | 2022-11-29 |
EP3149084A1 (en) | 2017-04-05 |
IL249128B (en) | 2020-02-27 |
CN110951250A (en) | 2020-04-03 |
JP6817197B2 (en) | 2021-01-20 |
CN115353731A (en) | 2022-11-18 |
TW201546178A (en) | 2015-12-16 |
WO2015183385A9 (en) | 2016-01-28 |
SA516380402B1 (en) | 2021-07-13 |
US20170107349A1 (en) | 2017-04-20 |
CA2950405A1 (en) | 2015-12-03 |
EP3149084A4 (en) | 2018-01-24 |
JP2020002362A (en) | 2020-01-09 |
CN106536633A (en) | 2017-03-22 |
SG11201609952SA (en) | 2016-12-29 |
JP6938578B2 (en) | 2021-09-22 |
KR20170016882A (en) | 2017-02-14 |
BR112016027990A2 (en) | 2017-08-22 |
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