TW201704432A - 用於黏性熱熔黏合劑之外殼材料 - Google Patents
用於黏性熱熔黏合劑之外殼材料 Download PDFInfo
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- TW201704432A TW201704432A TW105105875A TW105105875A TW201704432A TW 201704432 A TW201704432 A TW 201704432A TW 105105875 A TW105105875 A TW 105105875A TW 105105875 A TW105105875 A TW 105105875A TW 201704432 A TW201704432 A TW 201704432A
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- weight
- melt adhesive
- hot
- polymer composition
- polyolefin
- Prior art date
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 81
- 239000011257 shell material Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 64
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- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
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- 239000004014 plasticizer Substances 0.000 claims description 14
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- 239000003963 antioxidant agent Substances 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 239000008240 homogeneous mixture Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims 2
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- 239000011162 core material Substances 0.000 description 23
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- 238000012360 testing method Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
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- XPVIQPQOGTVMSU-UHFFFAOYSA-N (4-acetamidophenyl)arsenic Chemical compound CC(=O)NC1=CC=C([As])C=C1 XPVIQPQOGTVMSU-UHFFFAOYSA-N 0.000 description 1
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LUNMJRJMSXZSLC-UHFFFAOYSA-N 2-cyclopropylethanol Chemical compound OCCC1CC1 LUNMJRJMSXZSLC-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004348 Glyceryl diacetate Substances 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- KBAYQFWFCOOCIC-GNVSMLMZSA-N [(1s,4ar,4bs,7s,8ar,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthren-1-yl]methanol Chemical compound OC[C@@]1(C)CCC[C@]2(C)[C@H]3CC[C@H](C(C)C)C[C@H]3CC[C@H]21 KBAYQFWFCOOCIC-GNVSMLMZSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- B29C48/04—Particle-shaped
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0097—Glues or adhesives, e.g. hot melts or thermofusible adhesives
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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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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Abstract
本發明係有關非黏性薄膜形成聚合物組合物(外殼材料)及其所覆蓋之丸粒形式黏性熱熔黏合劑,並可藉共擠壓熱熔黏合劑及外殼材料製造。該薄膜形成組合物包含5至40重量%之至少一費托蠟,其熔點係>95℃及30至70重量%之至少一茂金屬催化之聚烯烴,其軟化點係>95℃且熔流指數(MFI)(230℃,2.16kg)係□1000且□300g/10分鐘。此外,本發明係有關此類熱熔黏合劑之適當應用、其用途之方法、及含彼等黏合劑之產物。
Description
本發明係有關丸粒形式之熱熔黏合劑,其具黏性熱熔黏合劑核心,且丸粒係封入特殊之聚合物薄膜非黏性外殼材料,及可藉共擠壓熱熔黏合劑核心與外殼材料產生。所得熱熔黏合劑丸粒適於終端使用者之自動化配料系統,係因其小尺寸且輕微及/或不存在之表面黏性,且其特徵亦在於外殼材料對所得熱熔黏合劑性質,具體而言其加工性,不具負面影響,同時對於熱熔黏合劑核心之低分子成分具良好阻隔性質,且係根據核可終端使用之原料,例如,核可用於食品包裝。此外,本發明係闡述此類熱熔黏合劑之合適用途、應用方法、及含此類黏合劑之產物。
封入非黏性薄膜形成材料(外殼材料)之熱熔黏合劑係習知,例如,美國專利號2013/0143997 A1。此類丸粒形式之熱熔黏合劑之優勢為,表面塗層於生產、運輸、及儲存期間能防止個別熱熔黏合劑丸粒之黏著,其中丸粒形式始能簡易配料及處理。
然而,習知之外殼材料之缺點為,其對所得熱熔黏合劑丸粒之加工性具一定影響,例如,改變流變性質,使得通過噴嘴系統(噴塗性)加工熱熔黏合劑需要比無外殼材料之黏合劑更高之溫度,典型而言溫度約20K以上。
因此,本發明之目的係提供改進之聚合物組合物,使其適合作為外殼材料,其一方面,容許顆粒形式之黏性熱熔黏合劑之生產、運
輸、及儲存,以使其可自動化配料,且另一方面,於熔融時與熱熔黏合劑核心均勻混溶,且對其加工性質不具負面影響。此類聚合物組合物從而優勢地具下列性質:
- 輕微及/或無黏性表面。
- 對欲封入外殼之熱熔黏合劑具耐受性(包括均勻之混溶性)。
- 對熱熔黏合劑之加工性具輕微或無負面影響。
- 對於熱熔黏合劑之低分子成分,如塑化劑油類,具良好阻隔性質。
- 以終端應用,如食品包裝領域,所核可之原料為主。
本發明達成此目標,係藉提供兼容於烯烴系黏合劑之聚合物組合物,且符合前述所有性質。具體而言,其容許通過噴嘴系統(亦即,噴塗法)加工熱熔黏合劑丸粒,且對於無相對應外殼材料之熱熔黏合劑無侷限及調整。
在第一態樣,本發明因此關於一聚合物組合物,基於其總重量,包含a)5至40重量%,具體而言為10至20重量%,之至少一費托蠟(Fischer-Tropsch wax),其熔點係>95℃;b)30至70重量%,具體而言為40至65重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>95℃且熔流指數(MFI)(230℃,2.16kg)係1000且300g/10分鐘;c)0至65重量%,具體而言為20至40重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>85℃且熔流指數(MFI)(230℃,2.16kg)係>1000g/10分鐘;d)0至40重量%之至少一茂金屬催化之聚烯烴,具體而言為聚丙
烯,其軟化點係>115℃且熔流指數(MFI)(230℃,2.16kg)係<300g/10分鐘;e)0至60重量%之至少一聚烯烴,具體而言為茂金屬催化之聚烯烴,其係不同於b)至d),其分子量Mn係<140,000g/mol;以及f)0至20重量%之添加劑及輔助物質,其係選自於抗氧化劑、安定劑、塑化劑、其他聚合物或其組合。
在另一態樣,本發明係有關於一種丸粒形式之熱熔黏合劑,其包含:(1)一熱熔黏合劑核心,其軟化點係65℃至140℃,其含有至少一聚烯烴及至少一膠黏樹脂;以及(2)根據本發明之一聚合物組合物薄膜,其基本上完全密封該核心且較佳地於20℃至60℃之溫度下係非黏性。
本發明之其他態樣係有關以本文所述之熱熔黏合劑丸粒作為黏合劑之用途,例如,用於黏接薄膜型基材與非織物,及以熱熔黏合劑裝載熔融裝置之方法,包括藉輸送帶裝置,具體而言真空輸送帶裝置,將一或多個本文所述之熱熔黏合劑丸粒餵料至熔融裝置。
除非另有指明,本文給定之分子量係指數均分子量(Mn)。除非另有指明,所有分子量數據係根據凝膠滲透層析術(gel permeation chromatography;GPC)取得之數值。聚苯乙烯係作為參考體。
使用於此,「至少一」意指一或多個,亦即1、2、3、4、
5、6、7、8、9、或以上。以一成分為基礎,此資訊係有關成分類型而非分子絕對數目。因此,例如,「至少一聚合物」意指至少一類型之聚合物,亦即可使用一類型之聚合物或數種不同聚合物之混合物。連同重量資訊,此資訊係有關經指明含於組合物/混合物之類型之所有化合物,亦即,超出所述量之相對應化合物之外,組合物不含任何其他此類化合物。
本發明使用之「基本上」乙詞相當於97%,較佳地98%,更佳地99%,最佳地100%,之其所指之相應值。舉例而言,「基本上完全封入外殼」係理解為意指至少97%之黏性熱熔黏合劑製成之核心係封入本發明之聚合物組合物薄膜。
除非另有指明,結合本文所述組合物給定之所有百分比量係有關重量%,其係始終以個別混合物為基準。
「大約」或「約」,於本文中結合數值使用,係有關數值±10%,較佳地±5%。
本文使用之熔點可藉DSC(動態差示熱量測定法,EN差示掃描熱量測定法)確定,其係根據ISO 11357-3:2011。除非另有指明,本文所述數值係指藉此方法決定之數值。
本文使用之軟化點可藉環球法(ring and ball method)決定,其係根據ISO 4625-1:2004。除非另有指明,本文所述數值係指藉此方法決定之數值。
本文使用之熔流指數(EN melt flow index,MFI)可藉DIN EN ISO 1133及/或ASTM D1238之方法決定,其中測試溫度係230℃且測試重量係2.16kg。除非另有指明,本文所述數值係指藉此方法決定之數值。
本文使用之「丸粒」乙詞包括小體型之熱熔黏合劑,其具
對稱或不對稱形狀且重量至多15g,較佳地至多10g,更佳地至多5g。丸粒尺寸最大係25mm,較佳地所有方位至多20mm,較佳地係最大程度且至少1mm,較佳地最小程度方位係3mm。丸粒形狀可變,其取決於生產過程。舉例而言,丸粒可為枕形,例如,其維度約15mm×5mm×5mm;近似球形,例如,球形,任意地直徑係10至20mm;或者圓柱形,例如,其中高度係25mm且直徑係2至10mm。形狀毋須一致,以便球形,例如,可經壓縮或拉伸。丸粒可為不同形狀丸粒之混合物,但其最佳係具近似相同形狀。較小丸粒典型上具較佳流動性質。
本發明之聚合物組合物及熱熔黏合劑丸粒之表面不具黏性,其中「不具黏性」係根據本發明定義為於20℃至60℃之溫度下「自由流動(free flowing)」。「自由流動」意指於所述溫度下(20℃至60℃),較大量之熱熔黏合劑丸粒或聚合物組合物(亦以丸粒形式)將於重力影響下流過直徑10cm且長度50cm之直立管路,而管路未觀察到任何黏著、結塊、或阻塞。此性質應保留,即使於高溫下長期儲存後。其係以下列方式測試:以金屬或塑料製成之直徑10cm管路係以丸粒(較佳地各自大小係15mm×5mm×5mm)填充至多高度10cm。隨後,將500g重量之平板置於丸粒上,並將測試裝置放置於60℃及/或20℃爐中7天。於此時間後,視需求將丸粒冷卻至20℃,並藉上述方法測試其流動性質(將整體物質澆注至直徑10cm及長度50cm之直立管路)。
本發明薄膜形成非黏性聚合物組合物,其亦稱作「外殼材料」、「薄膜形成聚合物組合物」、或「薄膜形成組合物」,含有至少一蠟,且此蠟可為費托蠟(Fischer-Tropsch wax),其中熔點大於95℃。本文使用之彼等費托蠟係合成蠟,其係由費雪-闕布希法製成且組成自烴類。於各具體實施例,蠟係合成石蠟。對比於源自礦物油之產物,此類產物主要源
自非支鏈正烷類。
用於聚合物組合物之蠟之量係5至40重量%,較佳地為10至20重量%,尤其較佳地為13至17重量%,更佳地約為15重量%,各係以組合物之總重量為基準。
此外,薄膜形成組合物含有至少一聚烯烴,其可藉茂金屬催化之聚合反應取得。用於產生聚烯烴之單體具體而言係聚丙烯,亦即,於各具體實施例,聚烯烴係聚丙烯。或者,亦可使用可與乙烯或丙烯共聚合之乙烯或習知C4至C20烯烴單體。可共聚合之單體係具體而言直鏈或支鏈C4至C20烯烴,其亦定為α-烯烴,如丁烯、己烯、甲基戊烯、辛烯、環不飽和化合物如降冰片烯或降冰片二烯;對稱或不對稱經取代乙烯衍生物,其中C1至C12烷基係適於作為取代基;以及任意地不飽和羧酸或羧酸酐。一般而言,本發明使用之聚烯烴可為同元聚合物、共聚合物、或三元聚合物,其亦可含額外單體。然而,同元聚合物,具體而言聚丙烯同元聚合物係較佳。
用於外殼材料之聚烯烴之重要性質係其黏度。由於彼等係可熔性組合物,其作為熔融體,其黏度以MFI測定。本發明使用之聚烯烴之軟化點係>95℃(ISO 4625)且MFI介於300與1000g/10min之間(根據ISO 1133,其於溫度230℃下測定,且測試重量係2.16kg)。於較佳具體實施例,MFI係介於350與1000g/10min之間或介於400與1000g/10min之間。彼等聚烯烴之分子量通常小於100,000g/mol,具體而言小於90,000g/mol,尤其最佳地小於80,000g/mol。下限係50,000g/mol(數均分子量如GPC之測定)。彼等聚合物之特徵為,其具較窄之分子量分佈。此類聚合物係文獻中習知,且可購自各製造商。舉例而言,適用之聚合物可取自品名L-ModuTM S600(Idemitsu Kosan Co.,Ltd.)。此聚烯烴之MFI係
350、分子量係70,000g/mol、及軟化點係100℃。
以軟化點>95℃之聚烯烴用於聚合物組合物,其量係30至70重量%,較佳地為40至65重量%,更佳地為55至65重量%。
除了上述聚烯烴之外,亦可使用其他聚烯烴,其係取自茂金屬催化。「茂金屬催化」或「茂金屬催化之聚合反應」於此可替換使用,意指烯烴之聚合反應係以使用茂金屬作為催化劑而催化。舉例而言,以此方式可產生嚴格同排聚丙烯(strictly isotactic polypropylenes)。
於較佳具體實施例,除了上述聚烯烴之外,舉例而言,可使用藉茂金屬催化取得之聚烯烴,其軟化點係>85℃且熔流指數(MFI)(230℃,2.16kg)係>1000g/10min。聚烯烴可如前面之定義,但較佳地係聚丙烯。彼等聚烯烴之分子量通常小於50,000g/mol(數均分子量如GPC之測定)。彼等聚烯烴之較佳用量係0至65重量%,更佳地為20至40重量%,尤其較佳地為22至27重量%,最佳地約為25重量%,各係以聚合物組合物為基準。適用之聚烯烴係取自,例如,商品名L-ModuTM S400(Idemitsu Kosan Co.,Ltd.)。此聚烯烴之MFI係約2000、分子量係45,000g/mol、及軟化點係90℃。
於較佳具體實施例,除了上述聚烯烴之外,舉例而言,可使用藉茂金屬催化取得之聚烯烴,其軟化點係>115℃且熔流指數(MFI)(230℃,2.16kg)係<300g/10min。聚烯烴可如前面之定義,但較佳地係聚丙烯。彼等聚烯烴之分子量通常大於100,000g/mol但小於200,000g/mol(數均分子量如GPC之測定)。彼等聚烯烴之較佳用量係0至40重量%,其係以聚合物組合物為基準。適用之聚烯烴係,例如,L-ModuTM S901(Idemitsu Kosan Co.,Ltd.)。此聚烯烴之MFI係約50、分子量係120,000g/mol、及軟化點係120℃。
其他可用於薄膜形成聚合物組合物之聚合物包括其他聚烯烴,例如,至少一茂金屬催化之聚烯烴,其分子量Mn係<140,000g/mol。彼等可用於外殼材料之量係0至60重量%,係以其總重量為基準。
作為本發明外殼材料之薄膜形成組合物,亦可含有0至20重量%之添加劑及輔助物質,其係如先前技術習知。具體而言,此類添加劑及輔助物質係選自於抗氧化劑、安定劑、塑化劑、其他聚合物、或其組合。
適用之塑化劑說明如下,且包括具體而言,烴油如石蠟油、環烷油、及/或礦物油,及聚(異)丁烯。塑化劑可有助於取得薄膜形成聚合物組合物與熔融態熱熔黏合劑核心之均質混合物及使用熱熔黏合劑丸粒。
於各具體實施例,該薄膜形成組合物含有:a)10至20重量%,具體而言為13至17重量%,之至少一費托蠟,其熔點係>95℃;b)40至65重量%,具體而言為55至65重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>95℃且熔流指數(MFI)(230℃,2.16kg)係1000且300g/10分鐘;c)20至40重量%,具體而言為22至27重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>85℃且熔流指數(MFI)(230℃,2.16kg)係>1000g/10分鐘;d)0至2重量%,具體而言為0.5重量%,之一抗氧化劑。
於本發明之較佳具體實施例,薄膜形成材料之熔點係<130℃。
核心材料係詳盡說明如下。
本發明熱熔黏合劑之核心材料含有至少一熱塑性聚合物,具體而言至少一聚烯烴及至少一膠黏樹脂。所使用之聚合物較佳地係不具反應性。藉使用膠黏樹脂,獲得25℃下具有表面黏合強度之熱熔黏合劑。
適用之聚合物之實例包括但不侷限於,聚乙烯、聚丙烯、及其共聚合物,以及非晶形聚-α-烯烴(APAO)。
於本發明之各具體實施例,熱熔黏合劑組合物之基礎聚合物(核心材料)係選自於聚烯烴、聚烯烴共聚合物、或聚烯烴/α-烯烴之互聚物,以及非晶形聚-α-烯烴如雜排(atactic)丙烯及與乙烯、丁烯、己烯與辛烷之丙烯共聚合物、或乙烯及/或丙烯同元聚合物、或前述之共聚合物及摻合物。
前述聚合物係可由商業上購得多樣之組合物及分子量,以用於黏著熱熔黏合劑。本領域之彼等技術人員可易於選擇適用之熱塑性聚合物,其取決於所需之用途領域,諸如熔點、黏度、黏合力等。
習知之聚合物係配製成黏性熱熔黏合劑,並連同至少一膠黏樹脂,且任意地亦具一塑化劑。
預期黏著基礎聚合物之樹脂之一般用量係10至60重量%,具體而言為20至60重量%,各係以黏性熱熔黏合劑組合物為基準,亦即,根據本發明熱熔黏合劑之核心材料。
原則上可使用習知之樹脂,如芳族、脂族、或環脂族烴樹脂,舉例而言,每一者係完全或部分氫化形式,以及改質或氫化之天然樹脂。用於本發明範疇內之適用樹脂包括但不侷限於,萜烯樹脂如萜烯之三元聚合物或共聚合物;以松香或松油樹脂為主之天然樹脂,包括其衍生
物,如其季戊四醇(pentaerythritol)或甘油酯;其他改質之天然樹脂如源自香脂(balsamic)樹脂、松油樹脂、或木樹脂之樹脂酸,任意地尚有氫松酯醇(hydroabietyl alcohol)及其酯類;丙烯酸共聚合物如苯乙烯-丙烯酸共聚合物或乙烯、丙烯酸酯、及馬來酸酐之共聚合物;或者以功能性烴樹脂為主之樹脂。彼等可部分地亦作為添加劑或作為附加試劑。
至少一膠黏樹脂可為單一樹脂或較佳地一樹脂混合物。
於各具體實施例,樹脂包含完全或部分氫化之烴樹脂及/或至少一天然樹脂,其係以松香或松油樹脂或季戊四醇或其甘油酯為主。至少一完全或部分氫化之烴樹脂可為,具體而言,芳族改質樹脂、聚萜烯、萜烯酚樹脂、1,3-戊二烯樹脂、環戊二烯樹脂、2-甲基-2-丁烯共聚合物、或上述彼等之衍生物。
較佳之膠黏樹脂之軟化點係約80℃至150℃(環球法;ISO 4625及/或ASTM E28-58)。
另一可存在於核心之熱熔黏合劑之成分係塑化劑,其可選自於礦物油、聚(異)丁烯、液態或糊狀氫化烴、及低分子聚烯烴。適用之塑化劑包括但不侷限於,藥用白油、環烷礦物油、聚丙烯、聚丁烯、聚異戊二烯寡聚物、氫化聚異戊二烯及/或聚丁二烯寡聚物、苯甲酸酯、酞酸酯、己二酸酯、植物油或動物油、及其衍生物。氫化塑化劑係選自於如石蠟烴油之群組。聚丙二醇及聚丁二醇,以及聚甲二醇(polymethylene glycol)亦適用。聚烯烴二醇或聚丁烯寡聚物之分子量較佳地應為200至6000g/mol之範圍,而聚烯烴之分子量至多應為約2000g/mol,具體而言至多1000g/mol。
亦可以酯類作為塑化劑,例如,液態聚酯類及甘油酯類,如甘油二乙酸酯、甘油三乙酸酯、新戊基甘油二苯甲酸酯、甘油三苯甲酸
酯、新戊四醇四苯甲酸酯、及1,4-環己烷二甲醇二苯甲酸酯。亦可使用芳族二羧酸酯類,例如,酞酸、異酞酸、或對酞酸酯類。磺酸酯類或脂肪酸亦可作為塑化劑。
具體而言,可使用白油、礦物油、聚(異)丁烯、及液態或糊狀氫化烴。
塑化劑於黏性熱熔黏合劑中之量應介於0與25重量%之間,具體而言為5至20重量%。若塑化劑之量太大,其造成黏合劑之內聚性質(cohesive properties)下降。
視需要,核心熱熔黏合劑亦可添加0至20重量%之蠟。該量應使得,於一方面,黏度降至所需範圍,但另一方面,對黏合不具負面影響。蠟可為天然形式或任意地亦可為化學改質形式或合成源。本文使用之天然蠟包括植物蠟、動物蠟、或礦物蠟或石化蠟。可用之化學改質蠟包括硬蠟,如褐煤酯蠟、沙索蠟(Sasol waxes)等。可用之合成蠟包括聚亞烷基蠟及聚乙二醇蠟。石化蠟較佳係使用如液態石蠟脂、石蠟、微晶質蠟、及合成蠟。石蠟及/或微晶質蠟及/或其氫化型態係尤其較佳,具體而言聚丙烯或聚乙烯蠟,其中根據ASTM D-3954,其落點(drop point)溫度為130℃至170℃。
除了前述成分之外,本發明之核心熱熔黏合劑可含其他成分以作為添加劑,其係常規上用於熱熔黏合劑。彼等包括,例如,安定劑、黏合促進劑、抗氧化劑、填料、顏料、或其組合。因此,可影響黏合劑之特定性質,如黏著力、安定性、黏著性、或強度。添加劑之量較佳可為0至3重量%,典型上0.1至2重量%。尤其較佳之添加劑包括安定劑,以防止熱裂解及氧化裂解及紫外光照射時裂解。
本領域之彼等技術人員應熟習添加劑如安定劑或黏合促
進劑。彼等係商品,且本領域之彼等技術人員可根據所需性質擇取。需留意,以確保彼等產品兼容於聚合物摻合物。
熱熔黏合劑係藉習知方法產生,係藉由混合熔融體。所有組分可作為起始材料,加熱且之後均質化,或首先可加入較低熔融組分以作為起始材料,混合且之後可加入其他樹脂成分。亦可能,且較佳地於擠壓機中持續產生熱熔黏合劑。適用之熱熔黏合劑係固體,且除了雜質之外,基本上無溶劑。
核心熱熔黏合劑較佳地軟化點(環球法,ASTM E 28)係65℃至140℃,較佳地為至多130℃,具體而言為小於120℃。
熱熔黏合劑丸粒係詳盡說明如下。
於各具體實施例,薄膜形成聚合物組合物形成一基本上連續薄膜,其基本上完全覆蓋熱熔黏合劑核心。此可藉加熱薄膜形成組合物至高於其熔點以應用,且之後於熔化態時施加。該施加較佳地係以共擠壓方式完成。外殼與核心二材料較佳地係兼容,以便於熔融時,形成安定、均質之摻合物。於本發明之一具體實施例,外殼材料之熔點等同於或低於核心材料之熔點。
上述定義之薄膜形成聚合物組合物形成一塗層或薄膜,其較佳地於溫度20℃至60℃下係非黏性,且保護黏合劑核心免於周圍環境之影響。於本發明丸粒形式熱熔黏合劑之應用,其係經熔融、形成外殼材料與核心材料之均質混合物。此過程可藉混合設備加速,如靜態或動態混合機或經由泵。所得熔融體係均質之熱熔黏合劑,且以此熔化形式使用/施加。
聚合物薄膜之典型上厚度範圍係2至200μm,具體而言為10至100μm,尤其最佳地為約20μm。然而,薄膜厚度亦取決於丸粒
尺寸。因此,丸粒形式之熱熔黏合劑之聚合物薄膜量通常至多12重量%,較佳地為1至10重量%,甚而更佳地為3至8重量%,尤其較佳地為5至7重量%,其係以熱熔黏合劑丸粒之總重量為基準。
如前面之進一步闡釋,本發明之丸粒形熱熔黏合劑較佳地係藉共擠壓產生。於共擠壓過程中,熱熔黏合劑及/或其成分係於混合裝置中熔融,及均質化且之後通過擠壓機孔口或噴嘴擠出。噴嘴可具任何常規形狀,但典型上具一槽形或圓形孔口,其用來泵送組合物。擠壓機噴嘴之溫度通常維持在高於材料之熔點,其溫度範圍常為80℃至150℃。於共擠壓時,薄膜形成聚合物組合物同時由擠壓機噴嘴擠出,亦即該方式使得其基本上封入欲封入核心以作為一連續薄膜,因此基本上封入熱熔黏合劑。此類共擠壓方法及其使用設備係先前技術習知。
於較佳具體實施例,於冷卻水中以壓輪(pinch roller)模製丸粒以完成生產,其中熱熔黏合劑與聚合物薄膜係共擠出。隨後,以乾式離心機將個別丸粒彼此分開。此方法係本領域之技術人員熟習。
於冷卻後,可將丸粒包裝於容器、箱、或袋以運送。容器可由機械安定性材料製成,以便盡可能運送及處理大量丸粒。
丸粒較佳地於20℃至60℃溫度下係非黏性,從而可儲存及運送而不黏著。
本文所述之熱熔黏合劑丸粒係適於,具體而言作為黏合劑丸粒(PSA,壓力敏感性黏合劑)且適於本發明之目的。使用領域包括,例如,黏合薄膜彼此或其他基材如織物或非織物,例如,用於製造衛生用品,具體而言嬰兒尿布。以本發明熱熔黏合劑黏接之產物係從而亦為本發明之構件。
本發明之熱熔黏合劑丸粒亦常於大型容器中操作,並於第
一步驟即送至輸送帶裝置,其之後將丸粒運送至熔融裝置。此輸送帶裝置可由螺旋輸送機、輸送帶、或其類似物組成,但較佳地丸粒係藉氣流輸送,例如,壓縮空氣或減壓(真空)。由於此一輸送方式造成顆粒表面間之機械摩擦,因此,塗層可防止於輸送帶裝置內黏著及凝集。本發明從而亦有關將熱熔黏合劑裝載於熔融裝置之方法,其包含藉一輸送帶裝置,具體而言真空輸送帶裝置,將複數個本發明熱熔黏合劑丸粒餵料至熔融裝置。於熔融裝置中熔融丸粒後,熔融體隨即輸送至適用之分配裝置,如噴嘴或輥,通常經泵輸送,且亦應用於所需接合之基材。
本文所述之熱熔黏合劑丸粒可用於自動化流程,以施用來自於熱熔黏合劑丸粒之熱熔黏合劑。
由於丸粒可具相對較小體積,例如,其容許於輸送帶裝置內簡易及標靶性分配。因此,可減少一時間內黏合劑於熔融裝置內之量,因此可防止長熔融時間、配料過剩、或於熔融裝置內之長靜置時間可能導致之黏合劑成分降解。
下列實例之呈現,旨在闡述本發明,但本發明不侷限於此。
實施例
實施例1:黏合劑配方
以組合物(重量%)為基準,產生含下列成分之薄膜形成組合物:
E=根據本發明
合成石蠟:Sasolwax® H1(Sasol)
茂金屬催化之PP,MFI 2000:L-ModuTM S400(Idemitsu Kosan Co.,Ltd.),軟化點90℃,Mn 45,000
茂金屬催化之PP,MFI 350:L-ModuTM S600(Idemitsu Kosan Co.,Ltd.),軟化點100℃,Mn 70,000
茂金屬催化之PP,MFI 50:L-ModuTM S901(Idemitsu Kosan Co.,Ltd.),軟化點120℃,Mn 120,000
實施例2:流變測試
隨後,以實施例1之本發明配方E3(定為DM 2900+6%本發明保護劑(protector),如圖1)之流變性質相較於實施例1之彼等常規配方(定為DM 2900+6%舊有保護劑,如圖1)。就此目的,將6重量%之薄膜形成組合物加入常規熱熔黏合劑(Technomelt® DM2900,Henkel AG),並以記憶模數(memory module;G')及/或損耗模數(黏性模數)與記憶模數(彈性模數)之比確定損耗因數(loss factor;tan △)。
彼等測定結果顯示於圖1。彼等結果清楚顯示,以本發明
之薄膜形成組合物相較於過往使用之塗層材料,對熱熔黏合劑之加工性不具任何負面影響。具體而言,當省略薄膜形成組合物時,熱熔黏合劑於相同溫度下仍可加工(噴塗),而於習知之塗層配方,溫度必須提高約20℃以確保噴塗性。
流變測試係以實際測試確認。實際測試亦確認,新穎外殼材料對任何其他重要黏合劑參數,具體而言黏合劑性質,不具任何負面影響。
Claims (12)
- 一種聚合物組合物,其特徵為該聚合物組合物基於其總重量,包含:a)5至40重量%,具體而言為10至20重量%,之至少一費托蠟(Fischer-Tropsch wax),其熔點係>95℃;b)30至70重量%,具體而言為40至65重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>95℃且熔流指數(MFI)(230℃,2.16kg)係1000且300g/10分鐘;c)0至65重量%,具體而言為20至40重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>85℃且熔流指數(MFI)(230℃,2.16kg)係>1000g/10分鐘;d)0至40重量%之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>115℃且熔流指數(MFI)(230℃,2.16kg)係<300g/10分鐘;e)0至60重量%之至少一聚烯烴,具體而言為茂金屬催化之聚烯烴,其係不同於b)至d),其分子量Mn係<140,000g/mol;以及f)0至20重量%之添加劑及摻合物,其係選自於抗氧化劑、安定劑、塑化劑及/或其他聚合物, 其中該聚合物組合物較佳地於20℃至60℃之溫度下係非黏性。
- 如申請專利範圍第1項所述之聚合物組合物,其特徵為該費托蠟係合成石蠟。
- 如申請專利範圍第1項或第2項所述之聚合物組合物,其特徵為該塑化劑係選自於烴油,具體而言為石蠟油、環烷油、及/或礦物油,以及聚(異)丁烯。
- 如申請專利範圍第1項至第3項中任一項所述之聚合物組合物,其特徵為該聚合物組合物之熔點係130℃。
- 如申請專利範圍第1項至第4項中任一項所述之聚合物組合物,其特徵為該聚合物組合物基於其總重量,包含:a)10至20重量%,具體而言為13至17重量%,之至少一費托蠟,其熔點係>95℃;b)40至65重量%,具體而言為55至65重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>95℃且熔流指數(MFI)(230℃,2.16kg)係1000且300g/10分鐘;c)20至40重量%,具體而言為22至27重量%,之至少一茂金屬催化之聚烯烴,具體而言為聚丙烯,其軟化點係>85℃且熔流指數(MFI)(230℃,2.16kg)係>1000g/10分鐘;以及d)0至2重量%,具體而言為0.5重量%,之一抗氧化劑。
- 一種丸粒形式之熱熔黏合劑,其包含:(1)一熱熔黏合劑核心,其軟化點係65至140℃,其含有至少一聚烯烴及至少一膠黏樹脂;以及(2)一如申請專利範圍第1項至第5項中任一項所述之聚合物組合物薄膜,其基本上完全包覆該核心且較佳地於20℃至60℃之溫度下係非黏性。
- 如申請專利範圍第6項所述之熱熔黏合劑,其特徵為該丸粒(1)各具小於15g之重量及/或(2)各維度之直徑小於25mm及/或(3)具圓柱形、球形、或墊形之形狀及/或(4)係藉共擠壓該核心及該聚合物組合物薄膜而產生。
- 如申請專利範圍第6項或第7項所述之熱熔黏合劑,其特徵為(a)該聚合物組合物薄膜之厚度係2至200μm,較佳地為2至20μm及/或(b)該熱熔黏合劑含有小於12重量%,較佳地為1至10重量%,更佳地為3至8重量%之量之外殼材料,其係以該熱熔黏合劑之總重量為基準。
- 如申請專利範圍第6項至第8項中任一項所述之熱熔黏合劑,其特徵為該至少一膠黏樹脂係樹脂或樹脂混合物,其 包含至少一完全或部分氫化之烴樹脂及/或至少一天然樹脂,其係以松香或松油樹脂或新戊四醇或其甘油酯為主。
- 如申請專利範圍第5項至第9項中任一項所述之熱熔黏合劑,其特徵為(a)該丸粒於20至60℃之溫度範圍下係非黏性;及/或(b)該丸粒於熔化態下形成均質混合物。
- 一種以如申請專利範圍第5項至第10項中任一項所述之丸粒形式之熱熔黏合劑作為黏性黏合劑之用途。
- 一種以熱熔黏合劑進料熔融裝置之方法,其包含藉輸送帶裝置,具體而言為真空輸送帶裝置,將一或多個如申請專利範圍第5項至第10項中任一項所述之熱熔黏合劑丸粒餵料至該熔融裝置。
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DE102015204468.8 | 2015-03-12 | ||
DE102015204468.8A DE102015204468A1 (de) | 2015-03-12 | 2015-03-12 | Hüllenmaterial für haftklebrige Schmelzklebstoffe |
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US (1) | US10544295B2 (zh) |
EP (2) | EP3268428B1 (zh) |
JP (1) | JP6807858B2 (zh) |
KR (1) | KR102584659B1 (zh) |
CN (1) | CN107405792B (zh) |
AR (1) | AR103909A1 (zh) |
BR (1) | BR112017018997B1 (zh) |
CA (1) | CA2979124A1 (zh) |
DE (1) | DE102015204468A1 (zh) |
HU (1) | HUE056619T2 (zh) |
MX (1) | MX2017011420A (zh) |
RU (1) | RU2700513C2 (zh) |
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EP3847221B1 (en) * | 2018-09-03 | 2023-01-18 | Sasol South Africa Limited | Hot melt adhesive compositions |
JP2020117606A (ja) * | 2019-01-23 | 2020-08-06 | ヘンケルジャパン株式会社 | ホットメルト組成物 |
EP4269529A1 (en) | 2023-02-24 | 2023-11-01 | Colquimica-Indústria Nacional de Colas, S.A. | Sprayable hot melt adhesive in the form of pellets for manufacturing disposable hygiene articles |
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2015
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- 2016-03-09 KR KR1020177028842A patent/KR102584659B1/ko active IP Right Grant
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- 2016-03-09 HU HUE16710124A patent/HUE056619T2/hu unknown
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JP6807858B2 (ja) | 2021-01-06 |
KR102584659B1 (ko) | 2023-10-04 |
KR20170127542A (ko) | 2017-11-21 |
EP3268428A1 (de) | 2018-01-17 |
US10544295B2 (en) | 2020-01-28 |
BR112017018997A2 (pt) | 2018-04-17 |
JP2018513234A (ja) | 2018-05-24 |
HUE056619T2 (hu) | 2022-02-28 |
WO2016142422A1 (de) | 2016-09-15 |
RU2017134121A (ru) | 2019-04-03 |
US20170369690A1 (en) | 2017-12-28 |
MX2017011420A (es) | 2018-01-25 |
DE102015204468A1 (de) | 2016-09-15 |
EP3978565A1 (de) | 2022-04-06 |
CA2979124A1 (en) | 2016-09-15 |
CN107405792A (zh) | 2017-11-28 |
BR112017018997B1 (pt) | 2021-11-23 |
EP3268428B1 (de) | 2021-08-25 |
CN107405792B (zh) | 2021-02-09 |
RU2700513C2 (ru) | 2019-09-17 |
RU2017134121A3 (zh) | 2019-04-24 |
AR103909A1 (es) | 2017-06-14 |
TWI691575B (zh) | 2020-04-21 |
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