EP4183918A1 - Procédé de fabrication d'une structure formée tridimensionnelle dans les textiles polyamides - Google Patents

Procédé de fabrication d'une structure formée tridimensionnelle dans les textiles polyamides Download PDF

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Publication number
EP4183918A1
EP4183918A1 EP21209577.2A EP21209577A EP4183918A1 EP 4183918 A1 EP4183918 A1 EP 4183918A1 EP 21209577 A EP21209577 A EP 21209577A EP 4183918 A1 EP4183918 A1 EP 4183918A1
Authority
EP
European Patent Office
Prior art keywords
textile fabric
etoh
polyamide
treatment solution
fabric
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.)
Pending
Application number
EP21209577.2A
Other languages
German (de)
English (en)
Inventor
Barbara Rietzler
Tung Pham
Thomas Bechtold
Barbara Paul
Orhan Arslan
Andreas Röhrich
Mario Hartmann
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.)
Universitaet Innsbruck
Wolford AG
Original Assignee
Universitaet Innsbruck
Wolford AG
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
Application filed by Universitaet Innsbruck, Wolford AG filed Critical Universitaet Innsbruck
Priority to EP21209577.2A priority Critical patent/EP4183918A1/fr
Publication of EP4183918A1 publication Critical patent/EP4183918A1/fr
Pending legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
    • D06M23/18—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment for the chemical treatment of borders of fabrics or knittings; for the thermal or chemical fixation of cuttings, seams or fibre ends
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/08—Decorating textiles by fixation of mechanical effects, e.g. calendering, embossing or Chintz effects, using chemical means
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C23/00—Making patterns or designs on fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

Definitions

  • the present invention relates to a method for manufacturing a three-dimensional formed structure. Furthermore, the invention relates to an article comprising a three-dimensional formed structure.
  • Polyamide 66 (or PA 66 or PA 6.6) is one of the most widely spread polymers in the textile industry. It has excellent mechanical properties and is inert towards most organic solvents. Known solvents require toxic and harsh conditions such as formic acid, cresol and phenol. Furthermore, polyamide 66 exhibits a low surface energy, which impedes the application in products requiring interfacial adhesion, such as textile composites. Surface treatments such as plasma treatment, grafting and surface roughening with solvents are used. The interaction of the carbonyl group of polyamide 66 and Lewis acids enables Lewis acid-base complexation and dissolution of polyamide 66 in solutions containing GaCl 3 , AlCl 3 , CaCl 2 , BF 3 , or BCl 3 .
  • the inventors of the present invention have now found that treatment of textile fabric comprising polyamide with CaCl 2 /H 2 O/EtOH mixtures in a defined concentration range, for a defined exposure time and a defined temperature yields modified polyamide with specific properties, in particular, it was found that textile fabrics treated under such conditions allow the formation of articles with a three-dimensional structure. Furthermore, the invention allows to form three-dimensional structures having soft and hard segments without any additional joining steps.
  • the invention relates to a method for manufacturing a three-dimensional formed structure from a textile fabric, comprising the steps of
  • the treatment of a flowing fabric comprising polyamide with a mixture of CaCl 2 /EtOH/H 2 O as described above allows forming the fabric into a three dimensionally shaped article.
  • the stability of the formed textile fabric is surprising in view of the prior art such as EP 3 378 988 A1 which describes surface modification lowering the overall stability of the polyamide.
  • the present invention now shows that a treatment solution with a mixture of CaCl 2 /EtOH/H 2 O under well-defined conditions results in a three-dimensional stable article.
  • a combination of soft segments and hard three dimensionally shaped structures can be formed without any additional joining steps between those segments.
  • the textile fabric is a knitted fabric or woven fabric, comprising interlacing threads or a nonwoven.
  • the basis weight of the textile fabric is preferably in the range between 10 and 220 g/m 2 , more preferably 30 and 180 g/m 2 .
  • Such a textile fabric has no dimensional stability before treatment.
  • the basis weight remains the same (preferably in the range between 10 and 220 g/m 2 , more preferably 30 and 180 g/m 2 ) but it has dimensional stability.
  • the contacting step of the fabric sample in a treatment solution of CaCl 2 /EtOH/H 2 O is carried out for at least 10 s and at most 60 minutes.
  • the contacting step of the fabric sample in a treatment solution of CaCl 2 /EtOH/H 2 O is carried out and immediately followed by squeezing and consolidating.
  • the spraying time is preferably at least 5 s and at most 2.5 minutes immediately followed by squeezing and consolidating steps.
  • the molar ratio between CaCl 2 : EtOH : H 2 O is approximately 1 : 1.5 : 5.5.
  • the contacting step of the of the fabric in the treatment solution can be immersion with a squeezer, spraying, dipping, pressing etc.
  • the contacting step of the fabric sample in the treatment solution of CaCl 2 /EtOH/H 2 O is carried out for approximately 2 minutes.
  • step (c) During squeezing of the treatment solution (step (c)) from the fabrics to adjust the solvent content in the fabrics also pressure can be applied to pre-form the shape of the textile fabric.
  • the temperature in step (d) is between 10 °C to 120 °C with the provision that the temperature is at least 100 °C below the melting point of the polyamide and can involve heating and/or cooling depending on the conditions.
  • Obtaining the formed textile fabric in step (f) can involve isolating of the formed fabric.
  • One preferred way of forming includes applying a pressure of between 0.1 bar and 100 bar, preferably 2 to 12 bar to the textile fabric.
  • the polyamide (PA) is an AB polymer, an AA/BB polymer or a mixture thereof, wherein the AB polymer comprises the following structure units -[NH-(CH 2 ) x -CO] n - and the AA/BB polymer comprises the following structure units -[NH-(CH 2 ) x -NH-CO-(CH 2 ) y -CO] n -.
  • PA are usually categorized as AB polymers and AA/BB polymers.
  • PA of the AB polymer type comprise the following structure units -[NH-(CH 2 ) x -CO] n -.
  • PA type PA 6, because the repetitive unit has 6 carbon atoms.
  • PA of the AA/BB polymer type comprise the following structure units. -[NH-(CH 2 ) x -NH-CO-(CH 2 ) y -CO] n -.
  • PA 6 PA 6
  • PA 6.6 PA 6.6
  • PA 6.6. has a melting point T m of 264 °C.
  • the invention further relates to a textile fabric comprising a three-dimensional formed structure obtainable by a method as described above.
  • the invention relates to an article, comprising at least
  • the textile fabric is a woven fabric comprising interlacing threads.
  • the basis weight of the textile fabric in the first area is preferably in the range between 10 and 220 g/m 2 , more preferably 30 and 180 g/m 2 and the basis weight in the second area is preferably in the range between 10 and 220 g/m 2 , more preferably 30 and 180 g/m 2 .
  • the basis weight of the textile fabric in the first area is essentially the same as the basis weight of the textile fabric in the second area.
  • the ratio of the bending stiffness of the second area and the second area may be at least 1.4.
  • PA polyamide
  • Treatment with CaCl 2 /EtOH/H 2 O enables not only physical surface properties like roughness, sorption behavior and also changes of the fiber diameter but according to the invention the modification of the hardness and shape.
  • the contact time of the treatment solvent on the fabrics is varied between 1 and 60 min before forming (consolidating) step.
  • Bending stiffness was determined following the cantilever method (ASTM D5732-95, 2001). Stripes of approx. 2 cm width and 10 cm length were tested using a fabric stiffness tester Model 112 (Taber Industries, New York, USA). The fabric stripe slowly is pushed over a sharp edge and the stripe starts to bend due to its own weight. When the stripe has reached a bending angle of 41.5 ° the length of the bent fabric stripe is recorded. The length of the bent stripe then is a measure for the stiffness of the sample. Bending was measured for both sides of the fabric (two repetitions each) and the mean value of these four results was calculated.
  • Example 11 on-site production of anchor fitting (see Fig.2)
  • Fig. 1a to 1c shows an article according to the invention in plain view, comprising a first area 10, consisting of a textile fabric comprising polyamide (PA) and a second area 20, consisting of a formed textile fabric comprising polyamide.
  • the basis weight of the textile fabric in the first area is 110 g/m 2 and the basis weight in the second area is identical with 110 g/m 2 .
  • the bending stiffness of the first area is 15 mm and the bending stiffness of the second area is 26 mm determined according to ASTM D5732-95(2001).
  • the ratio of the bending stiffness of the second area and the second area is 1,73.
  • the first area is flowing and has no dimensional stability
  • the second area is three dimensional stable.
  • the second area is formed by embossing the letters "TEXT". This may e.g. be used to integrate stable structures in a fabric.
  • Fig. 2 shows the manufacturing steps of a dowel according to the invention.
  • a textile fabric comprising polyamide (PA) is provided and inserted into a wall.
  • step (b) the textile fabric is treated with the treatment solution according to example 11, according to which the treatment solution is a mixture of CaCl 2 , EtOH and H 2 O, wherein the CaCl 2 content is 12.5 mol%, the EtOH content is 18.75 mol%, the molar ratio between CaCl 2 : EtOH : H 2 O is 1 : 1.5 : 5.5 and the H 2 O/EtOH molar ratio is 3.67.
  • the treatment solution is sprayed onto the fabric for ca. 5 s.
  • step (c) the treatment solution is squeezed from the fabric by a screw to adjust the solvent content in the fabric.
  • step (d) is performed by consolidating the textile fabric for 10 minutes while the textile fabric is still containing the treatment solution by adjusting the temperature of the textile fabric to a temperature of 25 °C with thereby forming the textile fabric in the desired three-dimensional structure.
  • step (e) the treatment solution is quenched while the formed textile fabric still contains treatment solution by adding water, followed by air dying at ambient temperature.
  • the formed textile fabric is obtained by unscrewing the screw followed by washing and drying (step (f)).

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP21209577.2A 2021-11-22 2021-11-22 Procédé de fabrication d'une structure formée tridimensionnelle dans les textiles polyamides Pending EP4183918A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21209577.2A EP4183918A1 (fr) 2021-11-22 2021-11-22 Procédé de fabrication d'une structure formée tridimensionnelle dans les textiles polyamides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21209577.2A EP4183918A1 (fr) 2021-11-22 2021-11-22 Procédé de fabrication d'une structure formée tridimensionnelle dans les textiles polyamides

Publications (1)

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EP4183918A1 true EP4183918A1 (fr) 2023-05-24

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Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB555490A (en) * 1942-02-20 1943-08-25 Ronald George Bartlett Stiffened synthetic linear polyamide woven fabrics
GB708815A (en) * 1951-02-01 1954-05-12 British Nylon Spinners Ltd Improvements in or relating to setting and stiffening fabrics
US2738566A (en) * 1955-05-17 1956-03-20 Carter William Co Puckered knit fabric and method of producing same
GB764088A (en) * 1953-06-30 1956-12-19 Bradford Dyers Ass Ltd Textile finishing
GB813289A (en) * 1955-09-26 1959-05-13 Heberlein & Co Ag Improvements in or relating to the treatment of textile fabrics
GB1243076A (en) * 1967-12-06 1971-08-18 Freudenberg Carl Non-woven fabrics
JPS5118482B1 (fr) * 1971-08-04 1976-06-10
JPS52117348A (en) * 1976-03-26 1977-10-01 Sekaicho Rubber Binder components
DE2650038A1 (de) * 1976-10-30 1978-05-03 Bayer Ag Wickelduebel
JPS5795489A (en) * 1980-12-05 1982-06-14 Asahi Chem Ind Co Ltd Preparation of basic cloth for ink ribbon
DE3225051A1 (de) * 1982-07-05 1984-01-05 Hilti AG, 9494 Schaan Duebel fuer hohlraeume aufweisende aufnahmematerialien
DD239015A1 (de) * 1985-07-01 1986-09-10 Reichsbahn Reichsbahnbaudirekt Duebel
US4861663A (en) * 1986-07-25 1989-08-29 Bayer Aktiengesellschaft Process for antistatic treatment or pretreatment of polyamides, polyimides, antistatically treated or pretreated materials, and the use thereof
JPH02154074A (ja) * 1988-11-29 1990-06-13 Dynic Corp 印刷用シート材
CN1059002A (zh) * 1990-09-25 1992-02-26 尹龙华 微孔膜涂层织物的制造方法
WO2001051697A1 (fr) * 2000-01-07 2001-07-19 Milliken & Company Sac destine au nettoyage a sec domestique
EP1782768A1 (fr) * 2004-07-14 2007-05-09 Mycoal Products Corporation Élément chauffant
EP3378988A1 (fr) 2017-03-22 2018-09-26 Universität Innsbruck Fibre de polyamide

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB555490A (en) * 1942-02-20 1943-08-25 Ronald George Bartlett Stiffened synthetic linear polyamide woven fabrics
GB708815A (en) * 1951-02-01 1954-05-12 British Nylon Spinners Ltd Improvements in or relating to setting and stiffening fabrics
GB764088A (en) * 1953-06-30 1956-12-19 Bradford Dyers Ass Ltd Textile finishing
US2738566A (en) * 1955-05-17 1956-03-20 Carter William Co Puckered knit fabric and method of producing same
GB813289A (en) * 1955-09-26 1959-05-13 Heberlein & Co Ag Improvements in or relating to the treatment of textile fabrics
GB1243076A (en) * 1967-12-06 1971-08-18 Freudenberg Carl Non-woven fabrics
JPS5118482B1 (fr) * 1971-08-04 1976-06-10
JPS52117348A (en) * 1976-03-26 1977-10-01 Sekaicho Rubber Binder components
DE2650038A1 (de) * 1976-10-30 1978-05-03 Bayer Ag Wickelduebel
JPS5795489A (en) * 1980-12-05 1982-06-14 Asahi Chem Ind Co Ltd Preparation of basic cloth for ink ribbon
DE3225051A1 (de) * 1982-07-05 1984-01-05 Hilti AG, 9494 Schaan Duebel fuer hohlraeume aufweisende aufnahmematerialien
DD239015A1 (de) * 1985-07-01 1986-09-10 Reichsbahn Reichsbahnbaudirekt Duebel
US4861663A (en) * 1986-07-25 1989-08-29 Bayer Aktiengesellschaft Process for antistatic treatment or pretreatment of polyamides, polyimides, antistatically treated or pretreated materials, and the use thereof
JPH02154074A (ja) * 1988-11-29 1990-06-13 Dynic Corp 印刷用シート材
CN1059002A (zh) * 1990-09-25 1992-02-26 尹龙华 微孔膜涂层织物的制造方法
WO2001051697A1 (fr) * 2000-01-07 2001-07-19 Milliken & Company Sac destine au nettoyage a sec domestique
EP1782768A1 (fr) * 2004-07-14 2007-05-09 Mycoal Products Corporation Élément chauffant
EP3378988A1 (fr) 2017-03-22 2018-09-26 Universität Innsbruck Fibre de polyamide

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
BARBARA RIETZLER ET AL: "Investigation of the decomplexation of polyamide/CaCl2 complex toward a green, nondestructive recovery of polyamide from textile waste", JOURNAL OF APPLIED POLYMER SCIENCE, JOHN WILEY & SONS, INC, US, vol. 138, no. 40, 20 May 2021 (2021-05-20), pages n/a, XP071309791, ISSN: 0021-8995, DOI: 10.1002/APP.51170 *
DATABASE WPI Week 197628, 1976 Derwent World Patents Index; AN 1976-53351X, XP002806219 *
DATABASE WPI Week 197745, 1977 Derwent World Patents Index; AN 1977-80548Y, XP002806218 *
LI ET AL.: "Effect of Calcium Chloride on the Surface Properties of Kevlar Fiber", J. APPL. POLYM. SCI, 2015
RIETZLER BARBARA ET AL: "Controlled Surface Modification of Polyamide 6.6 Fibres Using CaCl2/H2O/EtOH Solutions", POLYMERS, vol. 10, no. 2, 21 February 2018 (2018-02-21), CH, pages 1 - 14, XP055847660, ISSN: 2073-4360, DOI: 10.3390/polym10020207 *
RIETZLER, B.T. BECHTOLDT. PHAM: "Spatial structure investigation of porous shell layer formed by swelling of PA66 fibres in CaCb/FbO/EtOFI mixtures", LANGMUIR, vol. 35, no. 14, 2019, pages 4902 - 4908
SUN ET AL.: "Study on the mechanism of nylon 66 dissolving process using CaCb/MeOFI as the solvent", CHIN. J. POLYM. SCI., 1994
YAMAMOTO HIDEKI ET AL: "Development of a Regeneration Process for Nylon-6 and Nylon-6,6 from Felt Wastes", KAGAKU KOGAKU RONBUNSHU, 20 May 2013 (2013-05-20), pages 238 - 243, XP055912732, Retrieved from the Internet <URL:...> [retrieved on 20220413], DOI: 10.1252/kakoronbunshu.39.238 *

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