EP2559806A1 - Verfahren zum Steigern der Hydrophilie polymerer Materialien - Google Patents

Verfahren zum Steigern der Hydrophilie polymerer Materialien Download PDF

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Publication number
EP2559806A1
EP2559806A1 EP20110006735 EP11006735A EP2559806A1 EP 2559806 A1 EP2559806 A1 EP 2559806A1 EP 20110006735 EP20110006735 EP 20110006735 EP 11006735 A EP11006735 A EP 11006735A EP 2559806 A1 EP2559806 A1 EP 2559806A1
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European Patent Office
Prior art keywords
sample
hydrophilicity
polymeric material
oxidizing component
oxidizing
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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.)
Withdrawn
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EP20110006735
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English (en)
French (fr)
Inventor
Miran Mozetic
Alenka Vesel
Karin Stana-Kleinschek
Zdenka Persin
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Center of Excellence Polymer Materials and Technologies (Polimat)
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Center of Excellence Polymer Materials and Technologies (Polimat)
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Priority to EP20110006735 priority Critical patent/EP2559806A1/de
Publication of EP2559806A1 publication Critical patent/EP2559806A1/de
Withdrawn legal-status Critical Current

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    • 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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • 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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides

Definitions

  • the present invention relates to methods of increasing the hydrophilicity of porous or fibrous polymeric materials, as well as materials and products produced thereby.
  • Porous or fibrous polymeric materials are used as absorbent material in numerous industrial products, such as, e.g., absorbent products, diapers, incontinence products, wound dressings and the like. They also find application in the garment products, in particular functional sportswear, and footwear. In such products, a high degree of hydrophilicity is desired, because a strongly hydrophilic material will result in a faster and more complete uptake of aqueous liquids into the material.
  • Various methods of increasing the hydrophilicity of polymeric materials have been described to date.
  • JP10088478 describes the improved hydrophilicity of cellulose fiber on the basis of its wetting in non-ionic tenside.
  • thermodynamically unstable physical technologies using gas plasma is an environmentally-friendly alternative. Depending on the type and nature of the gas used various surface modifications can be achieved.
  • oxygen plasma to improve the hydrophilicity of non-cellulosic membranes and films is described in the JP2009126758 , JP2003342400 , JP2208333 and JP59089758 .
  • corona plasma to improve the hydrophilicity of resins is described in the JP2000143850 and JP2000109580 .
  • Atmospheric plasma has been shown to be an effective activation technique for resin surfaces and the surfaces of materials in powder or particle form ( KR20020090583 , JP9141087 and JP6134296 ).
  • EP0127149 describes the use of vacuum plasma to improve the adhesion of polyolefin films.
  • US2010028572 describes the industrial use of water vapour plasma to improve the hydrophilicity of electronic components (metal, ceramic, fluorocarbon and polyamide resins).
  • the plasma-based ion deposition technique (NaCl or MgCl 2 solution) with the purpose of improving the wetting of the implant's surface is described in the GB2468198 .
  • Cold plasma using polar gases causes the incorporation of hydroxyl, amino, imido, carboxyl etc. radicals onto the surface of the polymer and consequently lowers the water contact angle, i.e. improves hydrophilicity ( CN1858334 ).
  • Plasma using an O 2 and N 2 gas mixture ensured the long-term hydrophilicity of the surface of fuel cells with bipolar plates ( US2006263670 ) and improved the adhesion of the protective metal coating in electrical installations ( EP1312696 ).
  • Plasma from a mixture of inert gases and oxygen was used to improve or to ensure the long-term hydrophilicity of samples made of plastic ( JP8176327 ).
  • Plasma based on an O 2 , N 2 , O 2 /N 2 , N 2 O, CO 2 , NH 3 and H 2 gas mixture was used as a pre-treatment to improve the hydrophilicity of materials in powder or granule form in the final production process of thermoplastic products ( DE4141805 ).
  • the surface of a polymer containing fluorine-containing functional groups was treated with atmospheric plasma using a mixture of fluoride-carbon gases, oxygen gas or gas containing oxygen and gas containing nitrogen functional groups ( JP3290442 ).
  • graft polymerisation good wetting of various materials such as the combustible cell separator ( US2009098431 ), fluoride resin ( US2003008935 ), and polyolephine foam ( JP63223046 ) can also be achieved.
  • Treatment with ionising radiation to increase hydrophilic properties is also effective for porous materials (non-wovens, knitted products, membranes) ( JP11012376 , JP7138391 , and JP1030606 ).
  • KR20080001444 describes the procedure of forming an oxygen coating on the surface of a superconductor
  • TW276476 describes the formation of an inorganic coating on glass, porcelain and graphite.
  • TW588432 describes the manufacture of isolators using the plasma modification process, which results in Si-N, Si-O and Si-H coatings on surfaces that improve the hydrophilicity of the material.
  • a thin film i.e. a polyamine layer that can be applied to any surface results in extreme hydrophilicity and anti-dew properties of the material ( JP2070768 ).
  • JP3254752 describes the use of such a combination for the surface treatment of a hydrophobic material (artificial vein).
  • GB2430201 describes a combination of both techniques on a thin layer of a transistor or diode by using plasma to achieve an etching effect followed by chemical treatment with fluoroalkyl silanizing agents. Thereby the difference between hydrophilic or oil-repellent properties is clearly shown on the material's surface.
  • the MX01011851 describes the modification of a contact lens surface to improve hydrophilicity by creating a carbon surface layer followed by plasma oxidation and plasma polymerisation.
  • the production of a thin film to improve hydrophilicity includes a chemical treatment with organic solvents, acidic and alkaline treatments and a physical treatment using the so-called “after glow discharge” plasma ( JP2001049444 ).
  • the activation of aliphatic polyester surfaces for improved bio-compatibility or bio-absorbency is performed in the following phases: acidic or alkaline hydrolysis, cold plasma treatment, chemical reactions or electromagnetic radiation.
  • Corona or oxygen plasma were used to activate the synthetic polymer and produce a cross-linked polysaccharide layer on the surface and thereby improve the hydrophilicity, mechanical properties and resistance to chemicals ( JP63301234 ).
  • the JP59215328 describes the process of achieving a permanent hydrophilicity effect by creating a surface methacrylate layer that is polymerised into a thin film when using plasma and shows a hydrophilic effect upon subsequent water vapour treatment.
  • the process of treating silicone resin to achieve a permanent hydrophilic effect is described in the JP56000831 , where the product was first exposed to plasma containing inorganic gases, and subsequently treated with a solution of surfactants.
  • JP9143884 is well-known in the field of textile materials; it describes a combination of chemical and physical treatments of a synthetic garment, namely crosslinking with polysiloxane derivatives, followed by treatment with oxygen plasma to achieve hydrophilicity and resistance to melting.
  • the present invention addresses the need for further and improved methods of increasing the hydrophilicity of polymeric materials.
  • the present methods do not only increase the hydrophilicity of a sample at its outer surface, but also fibers and pores in the interior of the sample will be affected.
  • the present invention is defined by the appended claims. Hence, it provides a method for increasing the hydrophilicity and/or wettability of a sample comprising porous or fibrous polymeric materials by contacting the sample with an oxidizing gas comprising an oxidizing component, such as, e.g., a gas comprising atomic oxygen.
  • an oxidizing gas comprising an oxidizing component, such as, e.g., a gas comprising atomic oxygen.
  • the present invention also relates to materials produced (i.e., modified) by methods of the present invention, and to products produced from such materials.
  • the present invention hence relates to a method for increasing the hydrophilicity of a polymeric material in a sample comprising said material, said method comprising contacting said sample with an oxidizing gas comprising an oxidizing component.
  • the present invention also relates to methods for increasing the wettability of a polymeric material by measures described in this application.
  • said oxidizing component is atomic oxygen.
  • said polymeric material is selected from the group consisting of biopolymers, synthetic polymers, cellulose, starch, protein, polyethylene, polypropylene, polyurethane, polyterpene, inorganic polymers, phenolic resins, polyanhydrides, polyester, polyolefins, polyalkenes, polyamide, polyacetal, polyethylene terephthalate, polycarbonate, and cellulose acetate.
  • a particularly preferred polymeric material is cellulose.
  • the polymeric material is a porous or fibrous material.
  • the method preferably comprises perfusing said sample with said oxidizing gas.
  • a pressure difference is preferably established between two opposing sides of said sample.
  • the porous or fibrous polymeric material is a woven material, a non-woven material, a knitted material, a crocheted material, a spun-bonded material, melt-blown material, a foamed material, or a sintered material.
  • the flux of the oxidizing component, e.g., atomic oxygen, into the sample is between 10 20 atoms/m 2 /s and 10 23 atoms/m 2 /s.
  • the ratio between the flux of the oxidizing component out of the sample [atoms/m2/s] and the flux of the oxidizing component into the sample [atoms/m 2 /s] is between 0.01 and 0.999, preferably between 0.1 and 0.9, most preferred between 0.3 and 0.7. The ratio can thereby be adjusted to obtain the homogenous modification of the material throughout the entire sample, while at the same time ensuring efficient use of the oxidizing component.
  • the contacting is at a maximum temperature of between 20°C and 300°C, preferably between 20°C and 150°C, most preferred between 20° and 80°C. This is to ensure that no uncontrolled oxidation occurs, which may negatively affect the material's properties.
  • the contacting step is preferably in a dry state.
  • the present invention also relates to polymeric material modified by a method of any one of claims 1 to 11.
  • Such material has advantageous properties, in particular, significantly increased hydrophilicity.
  • the modified material of the invention is a porous or fibrous material.
  • the present invention also relates to a product comprising the polymeric material of the invention.
  • the product is selected from the group of products consisting of diapers, incontinence products, wound dressings, medical patches, hygienic pads, feminine hygiene articles, sanitary towels, garment products, footwear products, sintered products, membranes, filters, implantable medical products.
  • hydrophilicity shall be understood to define the tendency of a material to be wetted by aqueous liquids. Accordingly, the hydrophilicity of a polymeric material is the tendency of water to adhere to or spread over the material's surface. In accordance with one aspect of the invention, the expression hydrophilicity can be equated with "wettability".
  • increasing the hydrophilicity of a sample shall be understood as meaning an increase in the capillary velocity of a sample, measured by the method of Example 2, by at least 10%, preferably at least 50%, or at least 100%, or at least 500%, most preferably at least 1000%.
  • the increased hydrophilicity of a sample of polymeric material manifests itself in an decreased average contact angle determined by the Powder Contact Angle method described in Persin Z, Stana-Kleinschek K, Sfiligoj-Smole M, Kreze T and Ribitsch V. Determining the surface free energy of cellulose materials with the powder contact angle method. Textil Res J 2004; 74: 55-62 .
  • the average contact angle is reduced by at least 10%, or by 20%, or by at least 40%, according to the above method.
  • an “oxidizing gas”, according to the invention, shall be understood as being a gas, comprising at least one oxidizing component, said gas being capable of oxidizing polymeric materials.
  • the oxidizing gas is capable of oxidizing the polymeric materials of the invention at a temperature below 300°C, even more preferred, below 80°C.
  • the oxidizing gas may comprise at least one oxidizing component, e.g., atomic oxygen, or ozone, as well as non-oxidizing components, such as air, nitrogen gas, molecular oxygen (O 2 ) and/or carbon dioxide.
  • the oxidizing component is electronically excited oxygen molecule.
  • Electronically excited oxygen molecule shall be understood to be oxygen molecule having electrons in an excited energy state, excited by at least 1 eV (per oxygen atom).
  • “Atomic oxygen”, according to the invention, shall be understood to relate to a single oxygen atom (O 1 ) not covalently bound, or connected to, a further atom.
  • the atomic oxygen is in free radical form.
  • Atomic oxygen, according to the invention, is preferably not electrically charged. Hence, oxygen plasma is excluded.
  • Porous or fibrous material shall be understood as relating to the act of establishing forced migration of a gas through a sample of the porous or fibrous material.
  • perfusion of the sample with gas is effected by establishing a pressure gradient within (or across) said sample. Perfusion is thus the passing through of gas through the porous or fibrous material.
  • Cellulose shall be understood to be the organic compound with the formula (C 6 H 10 O 5 ) n , a polysaccharide comprising a linear chain of ⁇ (1 ⁇ 4) linked D-glucose units.
  • the method according to the invention encompasses a treatment for the interior of porous material using gas atoms and molecules that cause oxidation of the organic material through a procedure conducted in an apparatus shown schematically in Figure 1 .
  • the apparatus includes a chamber 1 having two compartments: A high-pressure compartment 2 and a low-pressure compartment 3.
  • the sample 4 of a porous or fibrous material is placed in between the two compartments 2, 3 of the chamber 1.
  • the sample is preferably supported by a support 5, such as a firm mesh, a frit, or sintered material, which enables the sample 4 to maintain its shape despite a substantial pressure difference between its opposing surfaces facing the high-pressure compartment 2 and the low-pressure compartment 3.
  • a pressure difference is generated by pressure generating means 9, e.g., a pump.
  • the arrangement shown in Figure 1 includes a source 8 of oxidizing gas, providing a continuous stream of oxidizing gas comprising a preferably constant amount of an oxidizing component, in this case, atomic oxygen.
  • atomic oxygen can be generated by heating oxygen molecules to temperatures above 1000°C, and allowing surface dissociation of oxygen molecules on selected catalytic materials (usually platinum).
  • atomic oxygen can be produced, e.g., by passing pure oxygen gas (O 2 ) through a glass tube having external electric coils connected to a radio frequency generator.
  • the gas is heated to a temperature of e.g. 1000°C prior to entering the radio frequency field.
  • a suitable concentration of atomic oxygen in the oxidizing gas is 1%-100%, preferably 1-50%, more preferred 1-20%, most preferred 10% (mol/mol).
  • the oxidizing component of the oxidizing gas enables oxidation of the polymeric material (e.g. polymeric organic material) at a temperature significantly lower than that needed for thermal degradation/pyrolysis of the polymeric material.
  • the concentration of the oxidizing component in the oxidizing gas in each of the high-pressure compartment 2 and the low-pressure compartment 3 is approximately constant / homogeneous.
  • the oxidizing component first contacts the polymeric material of sample 4 at the side of the sample facing the high-pressure compartment 2.
  • the atoms or molecules of the oxidizing component do not adhere on or bounce off the surface of the sample 4, but they penetrate or pass through the sample 4, due to the pressure gradient produced by the difference in pressure between the high-pressure compartment 2 and the low-pressure compartment 3.
  • Gas meters 6, 7 for metering the concentration of the oxidizing component in the oxidizing gas are arranged in the high-pressure compartment 2 and in the low-pressure compartment 3, respectively.
  • the gas meter arranged in the high-pressure compartment 6 measures the concentration of the oxidizing component in the high-pressure compartment 2
  • the gas meter arranged in the low-pressure compartment 7 measures the concentration of the oxidizing component in the low-pressure compartment 3. Since the concentration of the oxidizing component in both compartments of the chamber 1 is approximately constant and homogeneous, the difference in concentration of the oxidizing component detected by the meters 6, 7 is a measure of the oxidizing component lost due to the reaction with the material in sample 4. If the loss is high, the meter 7 shows a value significantly lower than the value shown by the meter 6. If the loss is very low, the meter 7 shows substantially the same value as meter 6.
  • a low loss of oxidizing component results in a balanced treatment of all parts of sample 4. This is desirable. However, an unfavorable effect is the poor yield (inefficient use) of the reactive atoms/molecules in the oxidizing component. Optimal conditions, in the sense of satisfactory uniformity and a good yield of atoms and molecules, are achieved when approximately 3% to 70% of the oxidizing component is lost due to the oxidation reaction.
  • the reaction between the oxidizing component and the polymeric material of sample 4 is exothermic and results in heating of the sample 4. To a certain degree, such heating is desirable, since it intensifies the interaction and promotes oxidation. However, a high temperature is not desired, since it can also lead to uncontrolled oxidation (pyrolysis) and thereby change the properties of the material to the worse.
  • Treating a sample of a polymeric material with an oxidizing gas by methods according to the invention leads to greatly improved hydrophilicity and/or wettability of the sample of porous or fibrous material not only at the sample's outer surface, but throughout the entire sample. Thereby, a very homogenous and complete modification of the material's properties, in particular hydrophilicity and wettability, is achieved.
  • Figure 2 shows the depletion of the oxidizing component (in this case, atomic oxygen) in the oxidizing gas, upon forced migration through a sample of cellulose. Shown is the ratio between the flux of the oxidizing component flowing out of the sample (at the side facing the low-pressure compartment 3; [atoms/m 2 /s]) relative to the flux of the oxidizing component into the sample (at the side facing the high-pressure compartment 2; [atoms/m2/s]), as a function of the flux of the oxidizing component into the sample (at the side facing the low-pressure part 3; [10 23 atoms/m2/s]).
  • the depletion of oxidizing component is around 50%, which provides efficient use of the oxidizing component (in this case, atomic oxygen) in the oxidizing gas, but also provides sufficiently uniform treatment of the polymeric material.
  • hydrophilicity of polysaccharide sample treated in accordance with a method of the present invention is measured. Hydrophilicity is assessed in terms of the time required for a liquid to be taken up by treated and non-treated samples of polymeric materials, respectively.
  • the polymeric material is cellulose.
  • the oxidizing component is atomic oxygen.
  • the results of the measurement are presented in Figure 3 .
  • the capillary velocities of non-treated porous material are compared to the same material treated by methods of the invention.
  • the treatment of the material was performed in an apparatus as shown in Figure 1 .
  • the flux of the oxidizing component, in this case atomic oxygen, at the side facing the high-pressure compartment 2 of chamber 1, was 2.5 x 10 23 atoms/m 2 /s.
  • Capillary velocities were monitored using a modified Powder Contact Angle method developed for determining the hydrophilic/hydrophobic properties of porous materials.
  • Figure 3 shows the squared adsorbed mass versus time. At the beginning of the absorption, the slope is steep, while after a certain period of time the curve reaches a plateau, indicating that complete wetting occurred.
  • the results in Figure 3 indicate that the imbibition of water was significantly slower for the non-treated sample, as compared to the treated sample. Even after 100 s, the non-treated sample was not completely wetted (i.e. a plateau was not yet reached). Within 100 s, the non-treated sample absorbed approx. 1.06 g of water. Significantly faster capillary velocity was observed in the cellulose sample treated according to the invention.
  • the treatment procedure resulted in a significant increase in the absorption velocity and absorption capacity.
  • a porous or fibrous sample is cut into a disc-shape having a diameter of 2.5 cm and a thickness of 0.3 cm.
  • the disc is disposed in an upright (vertical) orientation above a water surface (de-ionized water, preferably equal to or greater than 100 cm 2 ), and brought into contact with said liquid surface at its lower peripheral edge, whereupon the weight gain m [g] is measured over time.
  • the temperature is 20°C.
  • An increase of the capillary velocity is determined as the percent increase of the capillary velocity of a treated sample over a non-treated (but otherwise identical) second sample.
  • a porous or fibrous sample is cut into a disc-shape having a diameter of 2.5 cm and a thickness of 0.3 cm.
  • the disc is disposed in an upright (vertical) orientation above a water surface (de-ionized water, preferably equal to or greater than 100 cm 2 ), and brought into contact with said liquid surface at its lower peripheral edge, whereupon the weight gain m [g] is measured over time.
  • the temperature is 20°C.
  • An increase of the absorption capacity is determined as the percent increase of the absorption capacity of a treated sample over a non-treated (but otherwise identical) second sample.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
EP20110006735 2011-08-17 2011-08-17 Verfahren zum Steigern der Hydrophilie polymerer Materialien Withdrawn EP2559806A1 (de)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015023116A1 (ko) * 2013-08-12 2015-02-19 성균관대학교산학협력단 고내열성 분리막, 이의 제조 방법, 및 이를 포함하는 전지
KR101499787B1 (ko) * 2013-08-12 2015-03-18 성균관대학교산학협력단 고내열성 분리막, 이의 제조 방법, 및 이를 포함하는 전지
WO2016044696A1 (en) 2014-09-18 2016-03-24 Momentive Performance Materials Inc. αω-FUNCTIONALIZED POLYOXYALKYLENE-SILOXANE POLYMERS AND COPOLYMERS MADE THEREFROM
US9453996B2 (en) 2013-10-23 2016-09-27 Tokitae Llc Devices and methods for staining and microscopy
WO2021229069A1 (en) * 2020-05-15 2021-11-18 Jt International S.A. Plasma treatment of a tobacco product filter material

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