[go: up one dir, main page]

WO2011040072A1 - Composition de résine - Google Patents

Composition de résine Download PDF

Info

Publication number
WO2011040072A1
WO2011040072A1 PCT/JP2010/055892 JP2010055892W WO2011040072A1 WO 2011040072 A1 WO2011040072 A1 WO 2011040072A1 JP 2010055892 W JP2010055892 W JP 2010055892W WO 2011040072 A1 WO2011040072 A1 WO 2011040072A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
component
resin
composition according
inorganic filler
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/055892
Other languages
English (en)
Japanese (ja)
Inventor
俊 香山
実 富田
有希子 清水
輝充 小谷
圭 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Sony Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009228099A external-priority patent/JP2010106269A/ja
Application filed by Showa Denko KK, Sony Corp filed Critical Showa Denko KK
Priority to US13/130,828 priority Critical patent/US20120178866A1/en
Priority to CN2010800033575A priority patent/CN102227476A/zh
Publication of WO2011040072A1 publication Critical patent/WO2011040072A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to a resin composition capable of giving a molded article excellent in hydrolysis resistance, mechanical properties and dimensional stability.
  • Petroleum-based resins are excellent in mechanical properties, dimensional stability, processability, and other properties, and are therefore used as resin materials for covers and cases for various applications and housings for electrical appliances.
  • biodegradable resins that can be decomposed in the natural environment instead of conventional petroleum resins.
  • biodegradable resins are generally inferior in mechanical properties such as tensile strength and tensile elastic modulus than petroleum-based resins, and cause a decrease in strength due to hydrolysis degradation, so their uses are extremely limited.
  • the molded product obtained from the resin composition described in Patent Document 1 has a relatively good mechanical property, but is a precision component that requires a high degree of dimensional accuracy because of its poor dimensional stability. There was a problem that it could not be used. Therefore, the present invention has been made to solve the above-described problems, and a molding in which a biodegradable resin is blended as a main resin component and is excellent in hydrolysis resistance, mechanical properties, and dimensional stability. It aims at providing the resin composition which can give a body.
  • the present inventors have found that a biodegradable resin, an inorganic filler having a specific shape or an organic filler having water repellency, and a bifunctional or higher functional isocyanate.
  • the present inventors have found that a resin composition containing a group-containing compound or resin solves the above problems, and has completed the present invention. That is, the present invention provides at least one inorganic filler selected from (A) a biodegradable resin and (B) a fibrous inorganic filler, a plate-like inorganic filler, a rod-like inorganic filler, and a granular inorganic filler. Or it is the resin composition characterized by including the organic filler which has water repellency, and (C) the compound or resin which has an isocyanate group more than bifunctional.
  • Component (B) is preferably at least one selected from crushed shell, mica, basalt fiber, glass fiber, carbon fiber and calcium carbonate, or an organic filler having water repellency.
  • an organic filler having water repellency an organic filler having a cuticle layer such as mammalian hair, insect exoskeleton, mollusk shell, egg, rice husk, etc. is preferable. It is particularly preferable in terms of sex.
  • Component (B) is blended in an amount of 20% to 80% by mass with respect to the total of component (A) and component (B), and component (C) is added to the sum of component (A) and component (C). It is preferable that 0.1% by mass to 5% by mass is blended.
  • Component (A) is at least one selected from biodegradable aliphatic polyester, biodegradable aliphatic-aromatic copolymer polyester, polylactic acid, and a copolymer of ⁇ -hydroxybutyric acid and ⁇ -hydroxyvaleric acid. It is preferable that It is preferable that the resin composition of the present invention further contains at least one selected from acid-modified polyolefin and ethylene vinyl acetate copolymer.
  • the resin composition of the present invention may further contain at least one thermoplastic resin selected from polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyethylene, and thermoplastic elastomer.
  • a resin composition suitable for injection molding can be obtained.
  • a resin composition suitable for extrusion molding or foam molding can be obtained.
  • the present invention it is possible to provide a resin composition capable of giving a molded article excellent in hydrolysis resistance, mechanical properties and dimensional stability.
  • the molded body obtained from the resin composition according to the present invention can be applied to precision parts that require high dimensional accuracy.
  • biodegradable resin used in the present invention includes biodegradable aliphatic polyester, biodegradable aliphatic-aromatic copolymer polyester, polylactic acid, ⁇ -hydroxybutyric acid and ⁇ -hydroxykichi Examples thereof include copolymers with herbic acid, and these may be used alone or in combination of two or more.
  • biodegradable resins include polybutylene succinate, polycaprolactone, polylactic acid, polybutylene succinate adipate, polyethylene succinate, a copolymer of ⁇ -hydroxybutyric acid and ⁇ -hydroxyvaleric acid, Examples thereof include a copolymer of terephthalic acid, butanediol, and adipic acid, poly (ethylene terephthalate / succinate), polyvinyl alcohol, poly (caprolactone / butylene succinate), and the like.
  • polybutylene succinate is preferable in terms of physical properties and availability.
  • a branched aliphatic polyester is preferred.
  • the MFR of the biodegradable resin (measured under a load of 190 ° C. and 2.16 kg) is preferably 5 to 300 g / 10 min.
  • the MFR (190 ° C.) of the biodegradable resin is preferably 0.1 to 20 g / 10 min.
  • the melting point and number average molecular weight of the biodegradable resin are not particularly limited, but in terms of moldability, the melting point is 90 ° C. to 120 ° C., and the number average molecular weight is 40,000 to 88,000. It is preferable that
  • the inorganic filler used in the present invention is at least one selected from a fibrous inorganic filler, a plate-like inorganic filler, a rod-like inorganic filler, and a granular inorganic filler.
  • Fibrous, plate-like, and rod-like shapes are often apparent from the observation of the shape of the inorganic filler, but the difference from the indefinite shape is that the aspect ratio is 3 or more is fibrous, plate-like, or rod-like. It can be said. More specific examples of such inorganic fillers include crushed shells, mica, basalt fibers, glass fibers, carbon fibers, granular calcium carbonate, etc., and these may be used alone.
  • the granular calcium carbonate is surface-treated with a silane coupling agent, a fatty acid, paraffin wax or the like.
  • the silane coupling agent include silane coupling agents having a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, and the like.
  • fatty acids include stearic acid, oleic acid, linoleic acid, and the like.
  • crushed shells are preferable in that the balance between the resin composition characteristics such as dimensional stability and the cost is good.
  • Shell pulverized products are scallops, oysters, clams, clams, sea cucumbers, and other shells that have been crushed with a hammer mill, roller mill, ball mill, jet mill, etc., with a preferred average particle size of 1 ⁇ m to 100 ⁇ m. It is. More preferably, it is 5 ⁇ m to 50 ⁇ m, and most preferably 5 ⁇ m to 10 ⁇ m.
  • the organic filler used in the present invention has water repellency. Examples of the organic filler having water repellency include organic fillers having a cuticle layer. Specifically, mammalian hair, insect exoskeletons, mollusk shells, eggs, rice husks, etc. are crushed to a predetermined particle size.
  • the above-mentioned component (B) is preferably blended in an amount of 20% by mass to 80% by mass with respect to the total of the component (A) and the component (B), and 30% by mass to 60% by mass. % Is more preferable. When the blending amount of the component (B) is within the above range, the balance between rigidity and workability can be further improved.
  • (C) Compound or resin having a bifunctional or higher functional isocyanate group The compound or resin having a bifunctional or higher functional isocyanate group used in the present invention has two or more isocyanate groups in one molecule. , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl diisocyanate, tolidine diisocyanate, 1,4-diisocyanatobutane, hexa Methylene diisocyanate, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4-trimethyl-1,6-diisocyanatohexane, 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, , 3-diisocyanatocyclohex
  • the component (C) described above is preferably blended in an amount of 0.1% by mass to 5% by mass with respect to the total of the component (A) and the component (C). More preferably, it is blended in an amount of 2 to 2% by mass. When the blending amount of the component (C) is within the above range, the strength and hydrolysis resistance of the molded product can be further improved.
  • the resin composition of the present invention may contain at least one selected from acid-modified polyolefin and ethylene vinyl acetate copolymer for the purpose of further improving the strength of the molded product.
  • acid-modified polyolefin include those obtained by graft polymerization of a polyolefin such as polyethylene and polypropylene and a polymerizable carboxylic acid compound, and those obtained by copolymerizing a resin raw material monomer and a polymerizable carboxylic acid compound.
  • the polymerizable carboxylic acid compound include maleic anhydride, itaconic anhydride, acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like. These may be used alone or in combination of two or more.
  • maleic anhydride is preferred for graft polymerization, and acrylic acid, methacrylic acid and maleic anhydride are preferred for copolymerization.
  • the graft ratio (or copolymerization ratio) of the polymerizable carboxylic acid compound in the acid-modified polyolefin is preferably 1% by mass to 30% by mass.
  • the ethylene vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate. From the viewpoint of the strength of the molded product, the vinyl acetate content is preferably 65% by mass or more, more preferably acetic acid.
  • the ethylene vinyl acetate copolymer having such a vinyl acetate content include a powdered one obtained by spray-drying an ethylene vinyl acetate copolymer emulsion using polyvinyl alcohol as a protective colloid.
  • the products include Loan Fix 3000 manufactured by Showa Polymer Co., Ltd., and KBE-68A and KBE-68B manufactured by Kuraray Co., Ltd.
  • the blending amount is 1% by mass to 20% by mass with respect to the entire resin composition. It is preferable.
  • the surfactant examples include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among them, nonionic surfactants that are solid at room temperature are preferable. Examples of such commercially available surfactants include polyoxyethylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acid esters manufactured by Kao Corporation. When a surfactant is blended, the blending amount is preferably 0.1% by mass to 5% by mass with respect to the entire resin composition.
  • known additives can be added to the resin composition of the present invention within a range that does not impair the effects of the present invention.
  • additives include surfactants, antioxidants, scratch inhibitors, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, colorants (dyes and pigments), foaming agents, and fragrances.
  • the resin composition of the present invention includes known polypropylene (PP), polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyethylene, thermoplastic elastomer, etc., as long as the effects of the present invention are not impaired. These thermoplastic resins may be blended.
  • thermoplastic elastomer examples include styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, urethane thermoplastic elastomer, nitrile thermoplastic elastomer, fluorine thermoplastic elastomer, Examples thereof include polybutadiene-based thermoplastic elastomers and silicone-based thermoplastic elastomers.
  • the resin composition of the present invention can be obtained by uniformly melting and mixing the above-described components using a mixing apparatus known in the technical field such as an extruder.
  • the mixing temperature is preferably about 10 to 100 ° C. higher than the melting point of the resin.
  • the resin composition of the present invention may be formed by injection molding, blow molding, stretch blow molding, or the like, or may be formed by foamed sheet molding, board molding, or the like, or water-cooled inflation molding or air-cooled inflation molding.
  • a film product may be obtained by extrusion molding using a T-die, extrusion lamination molding, or the like.
  • Example 1 Polybutylene succinate as biodegradable resin (Bionor # 1010, Showa Polymer Co., Ltd., melting point 110 ° C., number average molecular weight 68,000, MFR 10 g / 10 min) 50 parts by mass, scallop shell pulverized product as inorganic filler (Those that passed through a 100 mesh sieve) 50 parts by mass and 0.5 parts by mass of Aquanate 105 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a compound having a bifunctional or higher isocyanate group were melt-kneaded and pellets of the resin composition Got. A test piece having a length of 30 mm, a width of 15 mm and a thickness of 2 mm was molded from the pellet using an injection molding machine.
  • Example 2 A test piece was molded in the same manner as in Example 1 except that a crushed rice husk (passed through a 100 mesh sieve) was used instead of the scallop shell crushed material.
  • Example 3 A test piece was molded in the same manner as in Example 1 except that granular calcium carbonate (surface treated with stearic acid and passed through a 100 mesh sieve) was used instead of the scallop shell pulverized product.
  • Example 4 70 parts by mass of polybutylene succinate (Bionore # 1050, Showa Polymer Co., Ltd., melting point 110 ° C., number average molecular weight 50,000, MFR 50 g / 10 min), scallop shell crushed material (passed through 100 mesh sieve) 30 mass Part, 0.5 parts by mass of Clerant VPLS 2256 (manufactured by Bayer) and 1 part by mass of maleic anhydride-modified polypropylene (Yumex (registered trademark) 1010 by Sanyo Chemical Industries) were melt-kneaded to obtain pellets of the resin composition. .
  • a test piece having a length of 30 mm, a width of 15 mm and a thickness of 2 mm was molded from the pellet using an injection molding machine.
  • Example 5 Polybutylene succinate as biodegradable resin (Bionor # 1010, Showa Polymer Co., Ltd., melting point 110 ° C., number average molecular weight 68,000, MFR 10 g / 10 min) 50 parts by mass, scallop shell pulverized product as inorganic filler (Those that passed through a 100 mesh sieve) 30 parts by mass Aquanate 105 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a compound having a difunctional or higher functional isocyanate group 0.5 parts by mass and ABS (Toyolac Co., Ltd., registered) (Trademark) 700 314 B1) 20 parts by mass was melt-kneaded to obtain pellets of a resin composition. A test piece having a length of 30 mm, a width of 15 mm and a thickness of 2 mm was molded from the pellet using an injection molding machine.
  • Example 1 A test piece was molded in the same manner as in Example 1 except that corn starch (manufactured by Nippon Corn Starch Co., Ltd.) was used instead of the scallop shell pulverized product.
  • corn starch manufactured by Nippon Corn Starch Co., Ltd.
  • Example 2 A test piece was molded in the same manner as in Example 2 except that bamboo powder was used in place of the scallop shell pulverized product.
  • elongation rate is the value which carried out arithmetic average of the measured value of 3 times.
  • Examples 1 to 5 not only have excellent mechanical properties and hydrolysis resistance, but also have an elongation of 23%, 41%, 37%, 26% and 25%. It is extremely excellent in dimensional stability.
  • Comparative Examples 1 and 2 (corresponding to the composite material of Patent Document 1) cannot be used for precision parts that require high dimensional accuracy because the elongation exceeds 50%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La composition de résine ci-décrite est caractérisée en ce qu'elle comprend (A) une résine biodégradable, (B) soit au moins une charge inorganique choisie parmi les charges inorganiques fibreuses, les charges inorganiques en forme de plaque, les charges inorganiques en forme de bâtonnets, et les charges inorganiques particulaires, soit une charge organique hydrophobe, et (C) un composé ou une résine qui contient au moins deux groupes isocyanate. Bien que la composition de résine selon l'invention contienne une résine biodégradable à titre de composant de résine principal, elle permet d'obtenir des articles moulés ayant d'excellentes résistance à l'hydrolyse, caractéristiques mécaniques, et stabilité dimensionnelle.
PCT/JP2010/055892 2008-10-01 2010-03-31 Composition de résine Ceased WO2011040072A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/130,828 US20120178866A1 (en) 2008-10-01 2010-03-31 Resin composition
CN2010800033575A CN102227476A (zh) 2009-09-30 2010-03-31 树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009228099A JP2010106269A (ja) 2008-10-01 2009-09-30 樹脂組成物
JP2009-228099 2009-09-30

Publications (1)

Publication Number Publication Date
WO2011040072A1 true WO2011040072A1 (fr) 2011-04-07

Family

ID=43827070

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/055892 Ceased WO2011040072A1 (fr) 2008-10-01 2010-03-31 Composition de résine

Country Status (2)

Country Link
CN (1) CN102227476A (fr)
WO (1) WO2011040072A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825960A (zh) * 2020-06-12 2020-10-27 彤程化学（中国）有限公司 一种可生物降解农膜及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177796B (zh) * 2014-08-27 2017-11-24 贵州一当科技有限公司 高性能可生物降解高分子材料及其制备方法
CN106496981A (zh) * 2016-11-15 2017-03-15 扬州大学 一种聚己内酯/玄武岩纤维复合材料的制备方法
CN110776694A (zh) * 2019-11-30 2020-02-11 苏州和塑美科技有限公司 一种环境友好型水净化功能母粒及其制备方法
CN111040393A (zh) * 2019-12-30 2020-04-21 淄博天成电子科技有限公司 一种环保绝缘型电源电路总成外壳及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005085346A1 (fr) * 2004-03-04 2005-09-15 Unitika Ltd. Composition de résine polyester biodégradable, procédé pour la fabrication de celle-ci, et mousse et moulage obtenus à partir de celle-ci
WO2008102919A1 (fr) * 2007-02-23 2008-08-28 Teijin Limited Composition d'acide polylactique
JP2008255349A (ja) * 2000-08-23 2008-10-23 E Khashoggi Industries Llc 積層被覆物としての使用に適した生分解性ポリマーフィルムおよびシートならびにラップその他のパッケージング材料
JP2009040949A (ja) * 2007-08-10 2009-02-26 Nippon Zeon Co Ltd 熱可塑性樹脂組成物および成形品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008255349A (ja) * 2000-08-23 2008-10-23 E Khashoggi Industries Llc 積層被覆物としての使用に適した生分解性ポリマーフィルムおよびシートならびにラップその他のパッケージング材料
WO2005085346A1 (fr) * 2004-03-04 2005-09-15 Unitika Ltd. Composition de résine polyester biodégradable, procédé pour la fabrication de celle-ci, et mousse et moulage obtenus à partir de celle-ci
WO2008102919A1 (fr) * 2007-02-23 2008-08-28 Teijin Limited Composition d'acide polylactique
JP2009040949A (ja) * 2007-08-10 2009-02-26 Nippon Zeon Co Ltd 熱可塑性樹脂組成物および成形品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825960A (zh) * 2020-06-12 2020-10-27 彤程化学（中国）有限公司 一种可生物降解农膜及其制备方法和应用

Also Published As

Publication number Publication date
CN102227476A (zh) 2011-10-26

Similar Documents

Publication Publication Date Title
WO2011040073A1 (fr) Composition de résine et article obtenu par moulage par expansion
JP2010106270A (ja) 樹脂組成物及び発泡成形体
JP2010106269A (ja) 樹脂組成物
CN111801385B (zh) 成形体、片材及容器，以及管状体、吸管、棉签及气球用杆
JP5246645B2 (ja) 樹脂組成物の製造方法
JP4703402B2 (ja) 脂肪族ポリエステル樹脂組成物、その製造方法、前記樹脂組成物からなる成形体及び発泡体
CN101787189B (zh) 耐候抗菌的聚碳酸酯工程塑料及其制备方法
CN108047658B (zh) 一种生物降解聚酯农用地膜
CN113631657A (zh) 聚羟基烷酸酯系树脂组合物、其成型体及膜或片
CN108342046A (zh) 机械强化的透明抗生物污损热塑性树脂组合物和其制造方法
CN1145674C (zh) 树脂组合物及其成型品
WO2011040072A1 (fr) Composition de résine
JPWO2007094477A1 (ja) ポリ乳酸系樹脂組成物及び成形体
US9023918B1 (en) Biodegradable plastic resin
Kocaman et al. Characterization of biocomposites based on mussel shell wastes
JP2009079215A (ja) 樹脂組成物およびそれを用いた成形体
CN102408689A (zh) 一种pha/pla共混合金及其制备方法
WO2006033229A1 (fr) Composition de resine et moulage de celle-ci
JP2010144084A (ja) 難燃性樹脂組成物およびそれを成形してなる成形体
JP7552198B2 (ja) フィルム
WO2009110171A1 (fr) Composition de résine de polyester biodégradable et corps moulé composé de celle-ci
JP2013249341A (ja) 繊維複合材料およびその製造方法
JP7706318B2 (ja) ポリ乳酸樹脂組成物
JP5277567B2 (ja) ポリ３−ヒドロキシブチレート系重合体樹脂組成物
JP4953597B2 (ja) ポリブチレンサクシネート樹脂組成物、その製造方法、それからなる成形体

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080003357.5

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10820192

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13130828

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1120100038724

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10820192

Country of ref document: EP

Kind code of ref document: A1