WO2011081441A2 - Procédé de préparation de fils élastiques ayant d'excellentes puissance et élongation - Google Patents
Procédé de préparation de fils élastiques ayant d'excellentes puissance et élongation Download PDFInfo
- Publication number
- WO2011081441A2 WO2011081441A2 PCT/KR2010/009493 KR2010009493W WO2011081441A2 WO 2011081441 A2 WO2011081441 A2 WO 2011081441A2 KR 2010009493 W KR2010009493 W KR 2010009493W WO 2011081441 A2 WO2011081441 A2 WO 2011081441A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- diisocyanate
- elastic yarn
- polyurethaneurea
- prepolymer
- glycol
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Definitions
- the present invention relates to a method for producing a polyurethane urea, more specifically, a glycol having a low number average molecular weight of about 500 to 1200 Daltons, and 1 to 15 mol% of 2,4'-di to the total weight of the diisocyanate
- Prepolymer was prepared using a diisocyanate mixture containing phenylmethane diisocyanate, and a chain extender was added to the prepolymer to obtain a polyurethaneurea polymer, followed by stirring to obtain a polyurethaneurea spinning stock solution. It relates to a method for producing a polyurethane urea characterized in that.
- the polyurethane urea elastic yarn is used to enable high power and light weight of the woven fabric, so that it is not embrittled by heat when thermal setting It is about technology to do.
- Polyurethane urea is a primary polymerization reaction product which generally reacts a polyol which is a high molecular weight diol compound with an excess diisocyanate compound to obtain a prepolymer having an isocyanate group at both ends of the polyol, and the prepolymer in an appropriate solvent. After dissolving, a diamine-based or diol-based chain extender is added to the solution, and a chain terminator such as monoalcohol or monoamine is reacted to form a spinning solution of polyurethaneurea fibers, and then subjected to dry and wet spinning. The polyurethaneurea elastic fiber is obtained by this.
- Polyurethane urea elastic fibers are used in various applications because of their inherent properties with excellent elasticity and elastic recovery ability, and as the range of applications thereof is expanded, new additional properties are continuously required for existing fibers.
- polyurethane urea elastic fibers are thermally embrittled by high heat in the post-processing after knitting with the other company (nylon, cotton, silk, wool, etc.), which causes problems such as lowering the power of the fabric. .
- the other company nylon, cotton, silk, wool, etc.
- problems such as lowering the power of the fabric.
- polyurethane urea elastic fiber there is an increasing demand for high power and elongation of polyurethane urea elastic fiber, especially demanding to improve the power while lightening the fabric during knitting using denier elastic yarn. Is gradually increasing.
- the present invention has been invented to solve the above problems, the present invention has an object to provide a method for producing an elastic yarn having excellent power and elongation.
- a polyurethane urea elastic yarn consisting of a polyol and a diisocyanate polymer
- 2) A prepolymer is prepared using a diisocyanate mixture containing 1 to 15 mol% of 2,4'-diphenylmethane diisocyanate relative to the total weight of the diisocyanate, and 3) a chain extender is added to the prepolymer to After obtaining the urethane urea polymer, there is provided a method for producing a high-power elastic yarn, characterized in that the polyurethane urea spinning stock solution obtained by stirring the aging.
- the fabric knitted by using the elastic yarn having excellent power and elongation as described above can improve the thermal embrittlement by the post processing after the high power of the fabric and knitting.
- the present invention is to produce a polyurethane urea elastic yarn having excellent power and elongation, to enable high power of the woven fabric using the polyurethane urea elastic yarn, it is not embrittled by heat when heat setting.
- the polyurethaneurea used in the preparation of the elastic yarn of the present invention is prepared by reacting an organic diisocyanate with a polymer diol to prepare a prepolymer, and then dissolving it in an organic solvent and then reacting with a diamine and a monoamine.
- diisocyanate used in the production of the polyurethaneurea elastic yarn used in the present invention include 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexa Methylene diisocyanate, 1,4'-cyclohexanediisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate and the like, including 4,4'-diphenylmethane diisocyanate 2,4'-diphenylmethane diisocyanate is used by mixing at least 1 type of diisocyanate, and the content of 2,4'- diphenylmethane diisocyanate is 1-15 mol%.
- 2,4'-diphenylmethane diisocyanate has a three-dimensional structure, and when added, the 2,4'-diphenylmethane diisocyanate has an intermolecular hydrogen bond or an intramolecular hydrogen bond in a hard segment because of steric hindrance.
- the bonds are formed in a coarse shape, which has substantially the same effect as an increase in the content of the soft segments rather than the hard segments. Therefore, by forming a lot of soft domains (elastic fibers) excellent in elongation can be obtained.
- the content of diphenylmethane diisocyanate is preferably in the above range.
- the polyol used in the present invention is polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymer of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol, 3-methyl-tetrahydrofuran and It may be exemplified as one or a mixture of two or more thereof in a copolymer of tetrahydrofuran and the like, but is not necessarily limited thereto.
- the molecular weight of the polyol used by this invention about 500-1200 are suitable.
- the length of the soft segment is shorter than that of the polyol having a molecular weight higher than that, thereby substantially giving the same effect as that of increasing the capping ratio, thereby obtaining a high-power elastic fiber. can do.
- the molecular weight is 500 or less, the effect of increasing the capping ratio described above is too high, so that the solubility decreases greatly during the secondary polymerization, and thus the process is not applicable.
- Diamines are used as the chain extender, and examples thereof include ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1, One kind or a mixture of two or more kinds thereof, such as 5-diaminopentane, 1, 6-hexamethylenediamine and 1,4-cyclohexanediamine, can be exemplified.
- an amine having a monofunctional group for example, diethylamine, monoethanolamine, dimethylamine and the like can be used.
- a steric hindrance phenol compound in order to prevent discoloration of the polyurethane urea and deterioration of physical properties due to ultraviolet rays, atmospheric smog, and heat treatment associated with spandex processing, a steric hindrance phenol compound, a benzofuran-one compound, and a semicarbazide Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably.
- the polyurethaneurea elastic yarn of the present invention may include additives such as titanium dioxide, magnesium stearate, and the like in addition to the above components.
- NCO% of the polymers mentioned in Examples and Comparative Examples to be described later physical properties of the polyurethane urea elastic yarn, and the power of the fabric were measured as follows.
- NCO% [100 * 2 * NCO chemical formula * (capping ratio-1)] / ⁇ (diisocyanate molecular weight * capping ratio) + polyol molecular weight ⁇
- capping ratio is the diisocyanate molar ratio / polyol molar ratio.
- Denier weight of 10 strands of sample g / 9m * 9000m / 1g
- the sample is measured by repeating 300% 5 times with a sample length of 10cm * 20 strands and a tensile speed of 100cm / min.
- the heat treatment of the yarn is 100% elongated while being exposed to the air, followed by dry heat treatment at 190 ° C. for 1 minute, cooling to room temperature, followed by wet heat treatment at 100 ° C. for 30 minutes in a relaxed state, and drying at room temperature.
- the elastic knitted fabric and nylon yarn were manufactured using a circular knitting machine having a diameter of 32 inches, a 28 gauge, and a 96 feeder. This circular knitted fabric was knitted using 70 denier of nylon yarn and 40 denier of elastic yarn prepared above, and the content of elastic yarn was 8% of the total weight of the knitted fabric. to be.
- the sample is measured by using an automatic elongation measuring device (MEL machine, Textechno). 2.5 cm in width * Sample length 20 cm, tensile rate 100 cm / min 100% repeated five times elongation is measured.
- MEL machine Textechno
- Capping ratio (CR) 1.70 polyol was used polytetramethylene ether glycol (PTMG, molecular weight 1000), 3 mol% content of 2,4'-diphenylmethane isocyanate and 97 mol of 4,4'-diphenylmethane diisocyanate Prepared in% content.
- Ethylenediamine and 1,2-diamino propane were used as the chain extender at a ratio of 80 mol% and 20 mol%, and diethylamine was used as the chain terminator.
- the ratio of the chain extender to the chain terminator was 10: 1, and the amine used was prepared at a total concentration of 7 mol%, and dimethylacetamide was used as the solvent.
- the spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning (spinning temperature: 260 ° C.) to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof are shown in Table 1 below.
- Example 2 It is the same as Example 1 except preparing with 8 mol% content of 2,4'- diphenylmethane isocyanate and 92 mol% content of 4,4'- diphenylmethane diisocyanate.
- the obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, and the physical properties are shown in Table 1 and 2.
- Example 2 It is the same as Example 1 except preparing 15 mol% of 2,4'- diphenylmethane isocyanate, and 85 mol% content of 4,4'- diphenylmethane diisocyanate.
- the obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, the physical properties are shown in Table 1 to evaluate the properties.
- Example 2 It is the same as Example 1 except not adding 2,4'- diphenylmethane isocyanate.
- the obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, the physical properties are shown in Table 1 to evaluate the properties.
- the polyol was the same as in Example 1 except that polytetramethylene ether glycol (molecular weight 1800) was used.
- the obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, and the physical properties are shown in Table 1 and 2.
- Example 1 PTMG Molecular Weight NCO% 2,4'-MDI / 4,4'-MDI [mol%] Strength [g / d] Elongation [%] 200% Modulus [g] 5'thUnload at 200% [g] Heat resistance [%] Example 1 1000 4.127 5/97 1.63 440 14.11 1.68 66 Example 2 1000 4.127 8/92 1.64 485 13.98 1.66 64 Example 3 1000 4.127 15/85 1.60 542 11.25 1.34 55 Comparative Example 1 1000 4.127 0/100 1.70 390 14.46 1.72 67 Comparative Example 2 1800 2.643 0/100 1.20 463 8.82 1.28 45
- Polyurethane urea elastic yarn prepared by using polytetramethylene ether glycol (molecular weight 1000) and mixed 2,4'-diphenylmethane isocyanate content of 5 mol% or more as shown in [Table 1] excellent power and elongation could be confirmed.
- Table 2 shows the processing conditions and power of the fabric fabricated by the circular fabric by the fabric evaluation method.
- Example 2 As shown in Table 2, the fabric produced in Example 2 when the nylon circular knitted fabric was prepared was confirmed to have superior fabric power compared to the fabric produced in Comparative Example 2 even when pre-set at 190 ° C.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
La présente invention concerne un procédé de préparation de fils élastiques à base de polyuréthaneurée, les fils élastiques ayant une puissance élevée étant préparés en préparant un prépolymère en utilisant 1) un glycol ayant un poids moléculaire moyen en nombre de 500 à 1 200 dalton et 2) un mélange de diisocyanate comprenant de 1 à 15 % en moles de 2,4'-diphénylméthane diisocyanate en se basant sur le poids total de diisocyanate ; en ajoutant 3) un allongeur de chaîne au prépolymère afin d'obtenir un polymère polyuréthaneurée ; et en agitant le polymère polyuréthaneurée afin de conditionner la solution non diluée sous agitation de polyuréthaneurée obtenue et en agitant la solution non diluée. Les fils élastiques de polyuréthaneurée préparés par le procédé ont une puissance élevée et une excellente élongation, et la détérioration thermique des produits tricotés et tissés utilisant les fils élastiques obtenus par un procédé ultérieur mis en œuvre après tricotage ou tissage peut être réduite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CN2010800600886A CN102666948A (zh) | 2009-12-30 | 2010-12-29 | 具有优异的弹力和伸长度的弹性丝的制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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KR1020090134396A KR101148583B1 (ko) | 2009-12-30 | 2009-12-30 | 우수한 파워 및 신도를 가진 탄성사의 제조 방법 |
KR10-2009-0134396 | 2009-12-30 |
Publications (2)
Publication Number | Publication Date |
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WO2011081441A2 true WO2011081441A2 (fr) | 2011-07-07 |
WO2011081441A3 WO2011081441A3 (fr) | 2011-12-01 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/KR2010/009493 WO2011081441A2 (fr) | 2009-12-30 | 2010-12-29 | Procédé de préparation de fils élastiques ayant d'excellentes puissance et élongation |
Country Status (3)
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KR (1) | KR101148583B1 (fr) |
CN (1) | CN102666948A (fr) |
WO (1) | WO2011081441A2 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140034850A (ko) * | 2011-05-27 | 2014-03-20 | 도레이 오페론텍스 가부시키가이샤 | 탄성 직물 |
WO2014210378A3 (fr) * | 2013-06-28 | 2016-11-10 | Invista Technologies S.A.R.L. | Fibre de polyuréthane-urée comprenant un mélange de glycol |
CN112127006A (zh) * | 2020-08-25 | 2020-12-25 | 烟台泰和新材料股份有限公司 | 一种易染氨纶纤维及制备方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114181373B (zh) * | 2022-01-29 | 2023-08-11 | 万华化学集团股份有限公司 | 一种舒适氨纶的制备工艺及制得的氨纶 |
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US20090253858A1 (en) * | 2006-05-18 | 2009-10-08 | Argyropoulos John N | Polyurethane-urea polymers derived from cyclohexane dimethanol |
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TW589421B (en) * | 2000-04-26 | 2004-06-01 | Du Pont | Spandex with high heat-set efficiency |
CN101247897B (zh) * | 2005-08-24 | 2013-06-12 | 贝林格尔·英格海姆国际有限公司 | 雾化器 |
KR20090106288A (ko) * | 2008-04-04 | 2009-10-08 | 주식회사 효성 | 우수한 신도 및 합착력을 갖는 폴리우레탄우레아 탄성사 및그의 제조방법 |
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2009
- 2009-12-30 KR KR1020090134396A patent/KR101148583B1/ko active IP Right Grant
-
2010
- 2010-12-29 CN CN2010800600886A patent/CN102666948A/zh active Pending
- 2010-12-29 WO PCT/KR2010/009493 patent/WO2011081441A2/fr active Application Filing
Patent Citations (4)
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KR20020052018A (ko) * | 2000-12-23 | 2002-07-02 | 유현식 | 열가소성 엘라스토머 블렌드 |
KR20050024720A (ko) * | 2003-09-01 | 2005-03-11 | 주식회사 효성 | 높은 모듈러스, 내알칼리성 및 내열성을 가진 탄성사제조방법 |
US20090253858A1 (en) * | 2006-05-18 | 2009-10-08 | Argyropoulos John N | Polyurethane-urea polymers derived from cyclohexane dimethanol |
KR20090033402A (ko) * | 2006-07-12 | 2009-04-02 | 미쓰비시 가가꾸 가부시키가이샤 | 폴리우레탄의 제조 방법 및 그것으로부터 얻어진 폴리우레탄의 용도 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140034850A (ko) * | 2011-05-27 | 2014-03-20 | 도레이 오페론텍스 가부시키가이샤 | 탄성 직물 |
EP2714975A2 (fr) * | 2011-05-27 | 2014-04-09 | Toray Opelontex Co., Ltd | Tissu élastique |
EP2714975A4 (fr) * | 2011-05-27 | 2014-11-12 | Toray Opelontex Co Ltd | Tissu élastique |
KR101972611B1 (ko) | 2011-05-27 | 2019-04-25 | 도레이 오페론텍스 가부시키가이샤 | 탄성 직물 |
WO2014210378A3 (fr) * | 2013-06-28 | 2016-11-10 | Invista Technologies S.A.R.L. | Fibre de polyuréthane-urée comprenant un mélange de glycol |
CN112127006A (zh) * | 2020-08-25 | 2020-12-25 | 烟台泰和新材料股份有限公司 | 一种易染氨纶纤维及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2011081441A3 (fr) | 2011-12-01 |
CN102666948A (zh) | 2012-09-12 |
KR101148583B1 (ko) | 2012-05-23 |
KR20110077746A (ko) | 2011-07-07 |
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