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EP3999126A1 - Fibres coaxiales contenant un liquide - Google Patents

Fibres coaxiales contenant un liquide

Info

Publication number
EP3999126A1
EP3999126A1 EP19740547.5A EP19740547A EP3999126A1 EP 3999126 A1 EP3999126 A1 EP 3999126A1 EP 19740547 A EP19740547 A EP 19740547A EP 3999126 A1 EP3999126 A1 EP 3999126A1
Authority
EP
European Patent Office
Prior art keywords
hollow fiber
oil
fiber
hollow fibers
liquid
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
EP19740547.5A
Other languages
German (de)
English (en)
Inventor
Patrick Ott
Ralf Wyrwa
Matthias Schnabelrauch
Cindy Altmann
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.)
Symrise AG
Original Assignee
Symrise 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 Symrise AG filed Critical Symrise AG
Publication of EP3999126A1 publication Critical patent/EP3999126A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor

Definitions

  • the present invention relates to hollow fibers filled with a liquid, in particular with a liquid aromatic substance, the outer fiber diameter having a value of 100 nm to 4,000 nm.
  • the present invention also relates to a fiber fleece comprising or consisting of hollow fibers according to the invention and products comprising hollow fibers according to the invention.
  • the invention also relates to a method for releasing the liquid and a method for producing a hollow fiber according to the invention.
  • the present invention also relates to the use of a hollow fiber according to the invention in various products such as textiles, cosmetic products, adhesives and detergents. Different strategies are pursued for the encapsulation of fragrances in order to optimally adapt them to the respective application. In particular, release and stability under various conditions play an essential role.
  • Fragrances are often not chemically inert, ie they can react with other components of the formulation or are decomposed by light and oxygen. It is therefore desirable to enclose them in an inert capsule so that an undesirable reaction can be prevented and the fragrance content remains constant even after prolonged storage or at higher temperatures.
  • the fragrances should, if possible, only be released at the place of use, which requires suitable storage stability in the formulation. This means that the encapsulated fragrances are not already in the surrounding medium such as a liquid or a gel. Furthermore, the encapsulation must prevent premature release of the fragrance during the application process under the given process conditions.
  • Fragrances are often microencapsulated and used, for example, in detergents, care products or in fragrance marketing or in fragrance varnishes. However, there are also numerous other possible uses. Depending on the wall and, above all, core materials used, there are many possible uses. Further examples of core materials and areas of application for microcapsules are in the areas of dyes, e.g. B.
  • WO2017148504A1 describes a method for producing fragrance capsules with improved surfactant stability. It is described that fragrance mixtures with an acid number of at most 5 mg KOH / g form particularly stable fragrance capsules, since saponification of esters contained in the fragrance mixture is prevented.
  • the capsules described in the prior art are usually spherical aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell.
  • the substances enclosed therein in particular active substances, perfume oils or fragrances, can be encapsulated by coating materials and as macrocapsules with a diameter of about 0.1 up to about 5 mm or microcapsules with diameters of about 0.0001 to about 0.1 mm.
  • a disadvantage of the spherical macro- or microcapsules described in the prior art is that they adhere poorly to surfaces or textiles. If, for example, microencapsulated fragrances are added to detergents or fabric softeners, only some of the capsules remain on the washed textiles and can therefore later release the trapped fragrance at the desired time, e.g. while the textiles are being worn. A large part of the capsules is rinsed out of the washing machine after the washing process and thus ends up in the sewage system completely unused.
  • the primary object of the present invention was therefore to develop a novel release system with which it is possible to encapsulate active ingredients or substances so that they have a high storage stability of at least 8 weeks and at the same time at the desired time, ie controlled For example, in the event of mechanical stress, the active ingredients or substances are released.
  • the adhesion of the encapsulated active ingredients or substances to surfaces or textiles should be improved.
  • a further object of the present invention was to enable variable loading and also a high loading of active ingredients so that the release systems can be used as widely as possible, ie the shell materials can contain active ingredients from different areas such as detergents and cleaning agents, adhesives, coating compositions, Agrochemicals, but also cosmetic and pharmaceutical areas, and can be incorporated into a wide variety of products.
  • the production of the release system should be as simple as possible from a technical point of view and should exclude the use - or intermediate formation - of harmful compounds, such as formaldehyde.
  • filled hollow fibers comprising or consisting of a core and a sheath surrounding the core, the core being filled with a liquid and the sheath consisting of a polymer and the average, outer fiber diameter having a value of 100 nm to 4,000 nm. It has surprisingly been found that filled hollow fibers with an average outer fiber diameter in the range from 100 nm to 4,000 nm, so-called nanofibers, can encapsulate active ingredients or substances in such a way that they can be stored stably over a long period of time. This is surprising to the extent that it has hitherto been assumed that the active ingredients or substances diffuse out or leak out at the ends of the hollow fibers. Surprisingly, however, it has been shown that this effect is only very weak, if at all.
  • filled hollow fibers according to the invention can release the active ingredients or substances after mechanical stress. It is particularly advantageous here that a filled hollow fiber can be broken at several points by mechanical stress. As a result, if the hollow fiber is broken by appropriate pressure at different points, the simultaneous release of the active ingredients or substances can be increased. Or it is possible to mechanically break a hollow fiber several times at time intervals and to enable the active ingredients or substances to be released again each time. While a microcapsule can only be broken once with the release of the active ingredient, this is possible several times with filled hollow fibers according to the invention.
  • the fibers according to the invention can be used to produce nonwovens that can be incorporated into textiles (or other materials). It is also possible to work the individual fibers into textiles (or other materials).
  • Hollow fibers are preferred according to the invention, the inner fiber diameter deviating along the longitudinal axis of the hollow fiber by a maximum of 40%, preferably a maximum of 20%, particularly preferably a maximum of 10%, from the average, outer fiber diameter of this hollow fiber.
  • Hollow fibers are preferred according to the invention, the average outer fiber diameter having a value of 200 to 4000 nm, preferably a value of 300 to 3000 nm.
  • Hollow fibers are particularly preferred according to the invention, the average outer fiber diameter having a value of 300 to 4000 nm and the wall thickness of the hollow fiber being 50 to 1740 nm, preferably 100 to 1500 nm, particularly preferably 200 to 1250 nm.
  • Hollow fibers are particularly preferred according to the invention, the inner diameter being 10 to 1500 nm.
  • Hollow fibers according to the invention are preferably produced by means of electrospinning. Here it is possible to produce very thin fibers from polymer solutions by treatment in an electric field. Here, a polymer solution is dosed at an electrode and drawn off and accelerated from the electrode by the electric field. A largely homogeneous fiber is formed from each nozzle in a well-adjusted electrospinning process.
  • the first (inner) solution comprises or consists of the active ingredient that is to be present in the later core
  • the second (outer) solution comprises wall-formers, such as polymers and / or polymer precursors, which form the shell.
  • Hollow fibers according to the invention are preferred, the hollow fiber being an electrospun coaxial fiber.
  • Hollow fibers according to the invention can be spun from numerous materials.
  • polymers selected from the group consisting of polyvinyl alcohols, polyamides, polyurethanes, polyureas, polysulfones and Polyesters such as, for example, polylactides, in particular poly (L-lactide-co-D / L-lactide) or L-lactide / glycolide copolymers, polycaprolactones (PCL), polymers of unsaturated monomers, in particular polystyrene or polystyrene copolymers, poly (meth ) acrylates, especially poly (methyl methacrylate) and poly (methacrylate), perfluoropolymer, poly (vinylidene fluoride and their copolymers, proteins, especially collagen and gelatin and polysaccharides, especially alginate, dextran, levan, carboxymethyldextran and aminodextran.
  • PCL polycaprolactones
  • the polymer is thermoplastic or a thermoset.
  • Cross-linking of the polymer enables cross-linked polymers to be produced during electrospinning which have particularly good mechanical, chemical and thermal properties.
  • filled hollow fibers in which the polymer is cross-linked are particularly preferred.
  • Cross-linked thermoset polymers are sparingly soluble in most solvents and the hollow fibers made from them therefore have a particularly high stability towards solvents.
  • the hollow fibers have a high thermal resistance.
  • filled hollow fibers are preferred, the crosslinking of the polymer with a compound comprising two, three, four or more than four amino, hydroxyl, carboxyl, thiol, chloroformate or isocyanate groups.
  • a compound comprising two, three, four or more than four amino, hydroxyl, carboxyl, thiol, chloroformate or isocyanate groups.
  • Different crosslinking agents can be used depending on the polymer to be crosslinked. If the polymer to be crosslinked comprises amine groups or thiol groups, then it can be crosslinked, for example, with a crosslinking agent which has isocyanate and / or chloroformate groups.
  • the crosslinking of the polymer with a) Polyamines such as, for example, 1,6-diaminohexane, spermine, spermidine, putrescein, diethylenetriamine, polyethyleneimine or guandine carbonate (GUCA)
  • thiols such as 2,2 ' - (ethylenedioxy) diethanthiol, DL-dithiothreitol hexane 1,6-dithiol, thioglycol or thiopropionic acid esters such as pentaerythritol tetra (3-mercaptopropionate), di-pentaerythritol hexakis (3-mercaptopropionate), trimethylol propane tri (3-mercaptopropionate), di-trimethylol propane tetra (3-trimethylolpropane tetra), 3-trimethylolpropane tetra
  • 2-10 epoxy groups especially 1,4-butanediol diglycidyl ether, triglycidyl isocyanurate, 1,2-bis (2,3-epoxypropoxy) ethane, and / or polychloroformates with 2-6 chloroformate groups, especially tri (ethylene glycol) bis (chloroformate), 2,2-Dimethylpropane-1,3-diyl-bis (chloroformate), bisphenol A bis (chloroformate), triethylene glycol bis (chloroformate) and 3-methylpentane-1,5-diyl bis (chloroformate), took place.
  • a polyamine is understood to mean a compound which comprises more than one amino group. This should be distinguished from polymers that were produced from amines and no longer contain amine groups.
  • hollow fibers in the core of which the liquid is selected from the group consisting of fragrances, cosmetic active ingredients, fragrance mixtures, UV filters, preferably those mentioned in WO 2005/123101, repellants (preferably repellants against arthropods), coolants, TRPV1 and TRPV3 modulators, skin-cooling agents, preferably the skin-warming agents mentioned in WO 2005/123101, preferably those mentioned in WO 2005/123101, lubricants, adhesives, adhesive precursors, solvents and mixtures thereof.
  • the liquid is selected from the group consisting of fragrances, cosmetic active ingredients, fragrance mixtures, UV filters, preferably those mentioned in WO 2005/123101, repellants (preferably repellants against arthropods), coolants, TRPV1 and TRPV3 modulators, skin-cooling agents, preferably the skin-warming agents mentioned in WO 2005/123101, preferably those mentioned in WO 2005/123101, lubricants, adhesives, adhesive precursors, solvents and mixtures thereof.
  • fragrances are understood to mean a substance or a mixture of substances that is perceived olfactory.
  • fragrances which in principle can advantageously be used as a component of a hollow fiber according to the invention can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969, self-published or H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 5th Ed., Wiley-VCH, Weinheim 2006.
  • the further fragrance mixtures used according to the invention can also be essential oils, concrete, absolutes, resins, resinoids, balms and / or tinctures.
  • Preferred essential oils, concretes, absolutes, resins, resinoids, balsams and / or tinctures, which can serve as a liquid in the core of the filled hollow fiber, are preferably to be selected from the group consisting of: amber tint; Amyris oil; Angelica seed oil; Angelica root oil; Anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresine; Bergamot oil; Beeswax absolute; Birch tar oil; Bitter almond oil; Savory oil; Bucco leaf oil; Cabreuva oil; Cade oil; Calamus oil; Camphor oil; Cananga oil; Cardamom oil; Cascarilla oil; Cassia oil; Cassie Absolue; Castoreum absolute; Cedar leaf oil; Cedarwood oil; Cistus oil; Citronella oil; Citric oil; Copaiva balsam; Copaiva balsam oil; Coriander oil; Costus root oil; Cumin oil; Cypress oil; Davana oil
  • Preferred fragrances which can preferably serve as a liquid or a component of the liquid in the core of the filled hollow fiber, are selected from the group of hydrocarbons, preferably 3-carene; a-pinene; ß-pinene; a-terpinene; y-terpinene; p-cymene; Bisabolene; Camphene; Caryophyllene; Cedren; Ferns; Limonene; Longifolia; Myrcene; Ocimen; Valencene; (E, Z) -1, 3,5-undecatriene; Styrene; Diphenylmethane; of aliphatic alcohols, preferably hexanol; Octanol; 3-octanol; 2,6-dimethyl heptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; (E) - and (Z) -3-
  • filled hollow fibers are preferred, the melting point of the liquid being less than or equal to + 30 ° C. This can ensure that the liquid does not freeze during normal use and that the hollow fiber is possibly damaged.
  • filled hollow fibers are preferred, the liquid being a homogeneous mixture of at least two chemical substances. It is particularly preferred here if the liquid is not an emulsion. According to an alternative embodiment, the liquid is a single chemical compound. According to the invention, filled hollow fibers are preferred, the liquid not being water or not comprising water. According to the invention, filled hollow fibers are preferred, the liquid being a homogeneous mixture of a maximum of 75 chemical substances.
  • filled hollow fibers are preferred, the liquid being a solution and / or all components of the liquid being miscible.
  • the liquid is an emulsion, preferably an oil in water emulsion, or a suspension.
  • An alternative embodiment of the present invention involves hollow fibers comprising or consisting of a first core and a first sheath surrounding the first core, the core being filled with a first liquid and the first sheath consisting of a first polymer, and with the first cladding, a second cladding is arranged and a second core is arranged between the first cladding and the second cladding, wherein the first cladding consists of a polymer and the second core is filled with a second liquid and wherein the average, outer fiber diameter has a value from 100 nm to 4,000 nm.
  • the first liquid and the second liquid can be configured identically or differently, with the configurations defined above.
  • the first polymer (or the first jacket) and the second polymer (or the second jacket) can be designed identically or differently, with the configurations defined above.
  • a further aspect of the present invention relates to a method for releasing the liquid (preferably as described herein; what is described in the context of the further aspects relating to "liquid", in particular with regard to preferred configurations, preferably also applies accordingly to the method described here) with the following steps: Producing or providing a hollow fiber according to the invention or a fiber fleece according to the invention,
  • the hollow fiber or the fiber fleece is preferably manipulated by mechanical stress, chemical influences and / or a change in temperature.
  • Another aspect of the present invention relates to a method for producing a hollow fiber or a fiber fleece, preferably a hollow fiber according to the invention or a fiber fleece according to the invention, comprising the following steps: - producing or providing a first solution comprising a polymer and / or a polymer precursor,
  • a method according to the invention is preferred, the electrospinning taking place with a coaxial nozzle.
  • Another aspect of the present invention relates to the use of a hollow fiber according to the invention or a fiber fleece according to the invention in medical products, detergents and cleaning agents, textiles, cosmetic products, adhesives, agricultural applications, surfaces (e.g. of packaging), air fresheners and technical products.
  • Another aspect of the present invention relates to a product comprising a hollow fiber according to the invention or a fiber fleece according to the invention.
  • the present invention is illustrated in more detail below on the basis of selected examples. Unless otherwise stated, all data relate to weight.
  • Example 1 Filled hollow fibers made of polyurethane-1 and a fragrance oil (266485 Tomcap, Fa.
  • the synthetically produced polyurethane PU-DIAZA-07 with 201,000 g / mol was used to produce a 10% spinning solution of 0.5 g PU-DIAZA-07 in 4.5 g HFIP.
  • the coaxial electrospinning took place under the following process parameters: 24 kV, 15 cm distance, 35% LF, 22 ° C, flow rate outer phase (PU-DIAZA-07): 1.50 ml / h,
  • Filled hollow fibers with diameters of 1.0-2.1 ⁇ m could be obtained.
  • FIG. 1 shows a light microscope image at a magnification of 100 of filled hollow fibers produced in Example 1.
  • FIG. 2 shows a scanning electron microscope image (SEM) of filled hollow fibers produced in Example 1.
  • EXAMPLE 2 Fiber Yillocks Made of Filled Hollow Fibers made of Polyurethane-1 and a Fragrance Oil (266485 Tomcap. Svmrise. Holzminden) as the core produced and spun under the following parameters: 20 kV, 20 cm distance, 30% air humidity, 22 ° C, flow rate outer phase (PU-DIAZA-07): 1.50 ml / h, flow rate inner phase (266485 Tomcap, Symrise , Holzminden): 0.01 ml / h.
  • FIG. 3 shows a light microscope picture at a magnification of 100 of filled hollow fibers produced in Example 2.
  • FIG. 4 shows a scanning electron microscope image (SEM) of filled hollow fibers produced in Example 2.
  • Example 3 Filled hollow fibers made of polyurethane-2 and a fragrance oil (266485 Tomcap, Fa.
  • Flow rate inner phase (266485 Tomcap, Symrise, Holzminden): 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.68-2.94 ⁇ m could be obtained.
  • Example 4 Coaxial fiber yarn made of polyurethane-2 and a fragrance oil (266485 Tomcap. Fa.
  • the fleeces had a diameter of approx. 12 cm.
  • the fiber diameters were between 1.55 and 2.97 ⁇ m.
  • Example 5 Filled hollow fibers made from Perfluorpolvmer Polv (vinylidene fluoride-co-hexafluoropropylene and a fragrance oil (266485 Tomcap. Svmrise. Holzminden) as the core
  • the coaxial electrospinning was carried out using the following process parameters :
  • FIG. 5 shows a light microscope picture at a magnification of 100 of filled hollow fibers produced in Example 5.
  • FIG. 6 shows a scanning electron microscope image (SEM) of filled hollow fibers produced in Example 5.
  • Example 6 Coaxial fiber yarn made of Polv (vinylidene fluoride-co-hexafluoropropylene and a
  • the fleeces had a diameter of approx. 9 cm.
  • the fiber diameters were between 0.66 and 1.69 ⁇ m.
  • Example 7 Filled hollow fibers made from polycaprolactone and a fragrance oil (266485 Tomcap, from Svmrise. Holzminden) as the core
  • a 5% spinning solution of 0.3 g CAPA6800 and 5.7 g HFIP was produced from the polycaprolactone CAPA6800.
  • the coaxial electrospinning took place under the following process parameters: 24 kV, 22 cm distance, 22 ° C, 30% LF, flow rate outer phase (CAPA6800): 1.0 ml / h, flow rate inner phase (266485 Tomcap, Symrise, Holzmin - den): 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 2.56-2.95 ⁇ m could be obtained.
  • FIG. 7 shows an optical micrograph at a magnification of 100 of filled hollow fibers produced in Example 7.
  • Example 8 Filled hollow fibers made from polylactide-co-glycolide (PLGA 8523) and a fragrance oil (Tomcap. Svmrise) as the core
  • the polylactide-co-glycolide (PLGA 8523) was used to prepare an 8% spinning solution of 0.56 g of PLGA 8523 and 6.44 g of HFIP.
  • the coaxial electrospinning took place under the following process parameters: 26 kV, 20 cm distance, 22 ° C, ⁇ 35% LF, rotation collector, 1000 rpm, flow rate outer phase (PLGA 8523): 1.0 ml / h, flow rate inner phase (Tomcap , Company Symrise): 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.8-3.0 ⁇ m could be obtained.
  • FIG. 8 shows a scanning electron microscope image (SEM) of filled hollow fibers produced in Example 8.
  • Example 9 Filled hollow fibers made from polylactide-co-glycolide (PLGA 8523) and a fragrance oil
  • a 10% spinning solution of 0.4 g PLGA 8523 and 3.6 g THF / acetone (3: 1) was prepared from the polylactide-co-glycolide (PLGA 8523).
  • the coaxial electrospinning took place under the following process parameters: 30 kV, 15 cm distance, 22 ° C., ⁇ 70% air flow, rotation collector, 1000 rpm, flow rate outer phase (PLGA 8523): 1.0 ml / h, flow rate inner phase (266485 Tomcap, Symrise, Holzminden): 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 1.03 to 3.76 gm could be obtained.
  • EXAMPLE 10 Coaxial fiber yarn made of polylactide-co-glycolide (PLGA 8523) and a fragrance oil (266485 Tomcap. Fa. Svmrise. Holzminden) as the core.
  • a 7% solution of 0.56 g of polylactide-co-glycolide (PLGA 8523 ) and 7.44 g HFIP produced and spun under the following parameters: 30 kV, 20 cm distance, 30% LF, 23 ° C, flow rate outer phase (PLGA 8523): 1.0 ml / h, flow rate inner phase (Tomcap, Symrise): 0.01 ml / h.
  • FIG. 9 shows a photomicrograph at a magnification of 20 of filled hollow fibers produced in Example 7.
  • Example 1 1 Filled hollow fibers made from polylactide-co-glycolide (PLGA 1017) and a fragrance oil (266485 Tomcap. Svmrise. Holzminden) as the core
  • a 5% spinning solution of 0.15 g PLGA 1017 and 2.85 g HFIP was prepared from the polylactide-co-glycolide (PLGA 1017).
  • the coaxial electrospinning took place under the following process parameters: 28 kV, 20 cm distance, 23 ° C, 35% air flow rate, outer phase flow rate (PLGA 1017): 1.0 ml / h, flow rate inner phase (Tomcap, Symrise): 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 1.04 to 3.25 ⁇ m could be obtained.
  • Example 12 Crosslinked, filled hollow fibers made from polycaprolactone / spermidine with a 266485 Tomcap. Svmrise, Holzminden / TEBC
  • a 5% spinning solution of 0.3 g CAPA6800 and 0.2 ml spermidine in 5.7 g HFIP was prepared from the polycaprolactone (CAPA6800).
  • a mixture of 12.5% TEBC in Tomcap (1.75 ml 266485 Tomcap, Symrise, Holzminden / 0.25 ml tri (ethylene glycol) bis (chloroformate) (TEBC)) was used for the inner phase.
  • the coaxial electrospinning took place under the following process parameters: 20 kV, 20 cm distance, 22 ° C., 30% conductivity, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with mean diameters of 2.5 ⁇ m could be obtained.
  • Example 13 Crosslinked, filled hollow fibers made from poly-caprolactone / DETA with a 266485 Tomcap. Svmrise. Holzminden / TEBC
  • a 5% spinning solution of 0.3 g CAPA6800 and 0.2 ml diethylenetriamine (DETA) in 5.7 g HFIP was prepared from the polycaprolactone (CAPA6800).
  • the coaxial electrospinning took place under the following process parameters: 20 kV, 20 cm distance, 22 ° C., 30% conductivity, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with an average diameter of 2.0 ⁇ m could be obtained.
  • Example 14 Cross-linked, filled hollow fibers made from poly-caprolactone / 2,2 ' - (ethylene-dioxy) diethanthiol + DBU and 266485 tomcap. Svmrise. Holzminden / HDI + MDI A 5% spinning solution of 0.3 g CAPA6800, 60 mg dithiol and 30 ⁇ l DBU in 5.7 g HFIP was produced from the polycaprolactone (CAPA6800). A mixture of 1.90 g Tomcap, 0.8 g HDI and 0.2 g MDI was prepared for the inner phase.
  • Example 15 Crosslinked filled hollow fibers made from polycaprolactone / DL-dithiotreitol + DBU and
  • a 5% spinning solution of 0.3 g CAPA6800, 60 mg dithiol and 30 ⁇ l DBU in 5.7 g HFIP was prepared from the polycaprolactone (CAPA6800).
  • a mixture of 1.75 ml Tomcap and 0.25 ml TEBC was used for the inner phase. manufactured.
  • the coaxial electrospinning took place under the following process parameters: 26 kV, 22 cm distance, 22 ° C., 40% LF, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.60-1.15 ⁇ m could be obtained.
  • Example 16 Crosslinked filled hollow fibers made from polycaprolactone / DL-dithiotreitol + DBU and 266485 Tomcap. Svmrise. Holzminden / LDI
  • a 5% spinning solution of 0.3 g CAPA6800, 60 mg dithiol and 30 ⁇ l DBU in 5.7 g HFIP was prepared from the polycaprolactone (CAPA6800).
  • CAPA6800 polycaprolactone
  • a mixture of 1.75 ml Tomcap and 0.25 ml lysine diisocyanate (LDI) was prepared.
  • the coaxial electrospinning took place under the following process parameters: 26 kV, 22 cm distance, 22 ° C., 40% LF, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.60-0.89 ⁇ m could be obtained.
  • Example 17 Cross-linked, filled hollow fibers made from poly-caprolactone / DL-dithiotreitol + DABCO and 266485 Tomcap. Svmrise. Holzminden / LDI A 5% spinning solution of 0.3 g CAPA6800, 60 mg dithiol and 30 ⁇ l DABCO in 5.7 g HFIP was produced from the polycaprolactone (CAPA6800). For the internal phase, a mixture of 1.75 ml Tomcap and 0.25 ml lysine diisocyanate (LDI) was prepared.
  • the coaxial electrospinning took place under the following process parameters: 26 kV, 22 cm distance, 22 ° C., 40% LF, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.52-0.66 ⁇ m could be obtained.
  • Example 18 Crosslinked filled hollow fibers made from poly-caprolactone / DL-dithiotreitol + DBU and Tomcap / HDI / MDI
  • a 5% spinning solution of 0.3 g CAPA6800, 60 mg dithiol and 30 ⁇ l DBU in 5.7 g HFIP was prepared from the polycaprolactone (CAPA6800).
  • CAPA6800 polycaprolactone
  • For the inner phase a mixture of 1.90 g 266485 Tomcap, from Symrise, Holzminden, 0.8 g HDI and 0.2 g of MDI produced.
  • the coaxial electrospinning took place under the following process parameters: 26 kV, 22 cm distance, 22 ° C., 40% moisture content, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.50-0.70 ⁇ m could be obtained.
  • Example 19 Crosslinked, filled hollow fibers made from poly-caprolactone / DL-dithiotreitol + DABCO and 266485 Tomcap, from Svmrise, Holzminden
  • a 5% spinning solution of 0.3 g CAPA6800, 60 mg dithiol and 30 ⁇ l DABCO in 5.7 g HFIP was produced from the polycaprolactone (CAPA6800).
  • a mixture of 1.90 g Tomcap, 0.8 g HDI and 0.2 g MDI was prepared for the inner phase.
  • the coaxial electrospinning took place under the following process parameters: 26 kV, 22 cm distance, 22 ° C., 40% LF, flow rate outer phase: 1.0 ml / h, flow rate inner phase: 0.01 ml / h. Filled hollow fibers (coaxial fibers) with diameters of 0.52-0.84 ⁇ m could be obtained.
  • Example 20 Fluorescence-marked, filled hollow fibers made from polylactide and test mix / BPEA
  • Example 21 Fluorescence-marked, filled hollow fibers made from polylactide and 354320 Testmix Capsules from Svmrise. Holzminden / BPEA
  • a 2% spinning solution of 0.12 g PLA in 5.88 g HFIP was produced from poly (L-lactide-co-D, L-lactide) (70/30, PLA, M approx. 800,000 g / mol).
  • poly (L-lactide-co-D, L-lactide) 70/30, PLA, M approx. 800,000 g / mol).
  • DPEA diphenylethynyl anthracene
  • the coaxial electrospinning took place under the following process parameters: 24 kV, 17 cm distance, 23 ° C., 38% air flow rate, flow rate outer phase: 1.5 ml / h, flow rate inner phase: 0.05 ml / h. Filled hollow fibers (coaxial fibers) with a mean diameter of approx.
  • FIG. 10 shows a light micrograph at a magnification of 100 of fluorescence-marked, filled hollow fibers produced in Example 21.
  • FIG. 11 shows a light microscope picture at a magnification of 100 of fluorescence-marked, filled hollow fibers produced in Example 21, while the filled hollow fibers are excited to fluoresce.
  • Example 22 Fluorescence detection for filled hollow fibers made of polylactide and 354320 test mix capsules from Svmrise, Holzminden / BPEA
  • FIG. 12 shows a photomicrograph at a magnification of 100 of the cut edges of the fluorescence-marked, filled hollow fibers produced in Example 22, while the filled hollow fibers are excited to fluoresce.
  • FIG. 13 shows a further light microscope image at a magnification of 100 of the cut edges of the fluorescence-marked, filled hollow fibers produced in Example 22, while the filled hollow fibers are excited to fluoresce.
  • fibers were produced as in Example 9 and spun onto aluminum-coated polymer films. These were cut with a scalpel to reveal hollow fibers at the cut edge
  • FIG. 14 shows a scanning electron microscope picture (SEM) of the filled hollow fibers cut in Example 21.

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Abstract

L'invention concerne des fibres creuses remplies d'un liquide, en particulier un agent aromatique liquide, le diamètre extérieur des fibres présentant une valeur comprise entre 100 nm et 4000 nm. Cette invention concerne également un non-tissé comprenant ou étant constitué des fibres creuses selon l'invention, ainsi que des produits comprenant les fibres creuses selon l'invention. La présente invention concerne aussi un procédé pour libérer le liquide ainsi qu'un procédé pour produire une fibre creuse selon l'invention. Cette invention concerne en outre l'utilisation d'une fibre creuse selon l'invention dans divers produits, tels que des textiles, produits cosmétiques, substances adhésives et détergents.
EP19740547.5A 2019-07-15 2019-07-15 Fibres coaxiales contenant un liquide Pending EP3999126A1 (fr)

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FR2766829B1 (fr) * 1997-07-31 1999-10-22 Hospal Ind Compositions generatrices de polyurethane non cytotoxique
KR100446070B1 (ko) * 2001-03-26 2004-08-30 주식회사 제닉스엔지니어링 악취 및 휘발성 유기 화합물(브이오씨) 제거를 위한 장치및 방법
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DE102004009887A1 (de) * 2004-02-26 2005-07-21 Ticona Gmbh Verfahren zum elektrostatischen Verspinnen oder Versprühen von Polymeren
EP1761271B1 (fr) 2004-06-18 2008-12-03 Symrise GmbH & Co. KG Extrait de mures sauvages
DE102006050279A1 (de) * 2006-10-23 2008-04-30 Philipps-Universität Marburg Verfahren zur Herstellung von Nano- und Mesopolymerfasern durch Elektrospinnen von Polyelektrolyten gegensätzlicher Ladung
US20160355951A1 (en) * 2013-03-15 2016-12-08 Arsenal Medical, Inc. Core-sheath fibers and methods of making and using same
CN109152711B (zh) 2016-02-29 2021-10-22 西姆莱斯股份公司 生产具备改善的表面活性剂稳定性的香料胶囊的方法
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CN109161986A (zh) * 2018-08-15 2019-01-08 成都新柯力化工科技有限公司 一种空气净化除尘用自修复石墨烯复合纤维及制备方法
CN109402775A (zh) * 2018-09-25 2019-03-01 杭州气味王国科技有限公司 一种精油缓释纳米纤维及其制备方法

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