WO1998042898A1 - Utilisation d'amphiphiles pour l'hydrophilisation de corps moules, de fibres et de films a base de polyolefine - Google Patents

Utilisation d'amphiphiles pour l'hydrophilisation de corps moules, de fibres et de films a base de polyolefine Download PDF

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Publication number
WO1998042898A1
WO1998042898A1 PCT/EP1998/001505 EP9801505W WO9842898A1 WO 1998042898 A1 WO1998042898 A1 WO 1998042898A1 EP 9801505 W EP9801505 W EP 9801505W WO 9842898 A1 WO9842898 A1 WO 9842898A1
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Prior art keywords
transition metal
polyolefins
use according
additives
metal compounds
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PCT/EP1998/001505
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German (de)
English (en)
Inventor
Norbert Bialas
Paul Birnbrich
Herbert Fischer
Jörg-Dieter KLAMANN
Raymond Mathis
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1998042898A1 publication Critical patent/WO1998042898A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

  • amphiphiles for the hydrophilization of polyolefin-based moldings, fibers and films
  • the invention relates to the use of amphiphiles for the permanent hydrophilization of the surfaces of polyolefin-based moldings, fibers and films.
  • the surface of plastic products must be provided with special effects that can either not be created at all or only incompletely for technical reasons, or can only be produced disadvantageously for economic reasons.
  • Such effects are, for example, the improvement of the wettability with polar liquids such as water - technical applications here are, for example, in the field of the manufacture of hygiene articles or geoswoven fabrics - or the improvement of the antistatic properties.
  • absorbent materials are used to absorb aqueous liquids.
  • this material is covered with a thin, water-permeable nonwoven.
  • nonwovens are usually made from synthetic fibers, such as polyolefin or polyester fibers, since these fibers are inexpensive to produce, have good mechanical properties and are thermally resilient.
  • untreated polyolefin or polyester fibers are not suitable for this purpose because their hydrophobic surface means that they are not sufficiently permeable to aqueous liquids.
  • the fiber surface must be made hydrophilic by an appropriate preparation. It is also desirable that the hydrophilic finish of the fiber is preserved as long as possible without the water permeability of the nonwoven being reduced. If such nonwovens are processed, for example, in diapers, they can be used several times without becoming leaky. In this way, the wearing time of the diapers is increased and the waste caused by used diapers is reduced.
  • the specialist understands geovlies to be special covers - mostly based on polyolefin-based fabrics - which are intended to protect soil such as arable land or cultivated land or tailings piles against mechanical stress such as wind erosion or treading by humans and animals and / or thermal loads such as heat or frost.
  • soil such as arable land or cultivated land or tailings piles against mechanical stress such as wind erosion or treading by humans and animals and / or thermal loads such as heat or frost.
  • the floor coverings which are usually applied in the form of thin foils, are sufficiently permeable to air humidity and rain in order to provide a desired microclimate in the sense of growth-promoting climatic conditions.
  • US Pat. No. 5,045,387 describes an agent for the hydrophilic finishing of polyolefin fibers which is a mixture of an alkoxylated ricinoleic acid derivative, a hydrogenated ricinoleic acid derivative, a cig fatty acid and one contains polyalkoxylated polymethylsiloxane.
  • This agent must be applied from the outside to the surface of the fibers or films.
  • the state of the art is to improve the properties of the plastic surface in order to achieve special effects by, for example, oxidative aftertreatment methods such as corona or plasma treatment.
  • oxidative aftertreatment methods such as corona or plasma treatment.
  • the plastic is oxidized or chemically modified in the presence of gases and discharges on the surface, which means that certain surface properties of the plastic can be modified.
  • these methods always require an additional operation in addition to high energy consumption and lead to ozone emissions in the manufacture of plastic parts.
  • EP-B-372 890 describes fibers based on polyolefm or polyester with a lubricant adhered to the surface.
  • This lubricant comprises a mixture of (1) fatty acid diethanolamide, (2) a polyether-modified silicone, (3) a sorbitan fatty acid ester and (4) a metal salt of an alkyl sulfonate; Components (1) to (4) are available in special proportions. According to page 3, lines 20-26, the mixture of components (1) to (4) is applied to the surface. This technique of applying the mixture containing the four components to the surface of finished fibers is also explained in more detail on page 4, lines 6-9. There are listed as application techniques: a) the use of rollers, b) spraying and c) immersion.
  • EP-B-616 622 relates to extrudable, compostable polymer compositions comprising an extrudable, thermoplastic polymer, copolymer or mixtures thereof which contains a degradation-promoting system composed of an autooxidative component and a transition metal.
  • the autooxidative system comprises a fatty acid, a substituted fatty acid or derivatives or mixtures thereof, the fatty acid having 10 to 22 carbon atoms and containing at least 0.1% by weight of unsaturated compounds and at least 0.1% by weight of free acid .
  • the transition metal is contained in the composition in an amount of 5-500 ppm in the form of a salt and selected from the group cobalt, manganese, copper, cerium, vanadium and iron.
  • the composition should be in the form of a film about 100 microns thick at 60 ° C and a relative humidity of at least 80% biodegradable within 14 days for embrittlement. Description of the invention
  • the object of the present invention was to provide tools with which a permanent and effective hydrophilization of the surfaces of polyolefin-based moldings, fibers and films can be achieved.
  • this was intended to achieve a lasting improvement in the surfaces of polyolefin-based moldings, fibers and films with regard to their wettability with respect to polar liquids such as water and with regard to their antistatic properties.
  • hydrophilization more recently, one often speaks of “hydrophilization” - is well known to the person skilled in the art.
  • hydrophobic fibers are made wettable by water by hydrophilization, which for example improves the washability of Synthetic fiber articles as well as for a better wearing comfort of such articles makes sense; further advantages of the hydrophilization are mentioned the reduction of the dirtiness and the electrostatic charge.
  • measurement-technical indicators of a successful hydrophilization are the wetting (the surface spread of a liquid), the rise (a Measure of the speed at which water is transported against the force of gravity in textile fabrics, the determination of the static charge and discharge.
  • fabrics are understood to be flat structures, the uniform shaped bodies or foils represent or in which the flatness is achieved in that they are made up of fibers.
  • hydrophilization is understood to mean that polyolefin surfaces which form a wetting angle of more than 90 ° with water - that is to say “hydrophobic” interfaces - are modified by a special measure in such a way that their critical angle becomes smaller after this measure Examples of this are given in the example section of the present application
  • the outstanding positive properties of hydrophilized surfaces namely an improvement in the wettability against polar liquids such as water and / or a reduction in electrostatic charge are expressly included in the scope of the present invention
  • These are rather dynamic interactions of appropriately modified polyolefin surfaces with molecules or substrates that are not immobilized but are in flexible contact with the polyolefin surface Effects that fall under the concept of hydrophilization expressly depend on phenomena in which molecules or substrates are in permanent fixation in contact with the polyolefin surface, as is the case with coatings and bonds or with dyeing and printing.
  • the present invention relates to the use of amphiphiles for the permanent hydrophilization of the surfaces of polyolefin-based moldings, fibers and films, with a mixture containing
  • transition metal compounds (II) 0.01 to 1000 ppm of one or more transition metal compounds (II) - metal content of the transition metal compounds (II) based on the polyolefins - at temperatures in the range of 180 to 320 ° C in a conventional manner, a shaping processing such as extrusion, calendering, injection molding and the like.
  • the additives according to the invention are also called additives (I) below. These are compounds of an amphiphilic nature.
  • An amphiphilic is understood here - in line with common usage - to mean a compound that combines hydrophobic and hydrophilic parts of the molecule.
  • substituents with increased polarity are formed in a known manner by molecular components containing heteroatoms, where the heteroatoms oxygen, nitrogen and / or halogen are of particular importance for the formation of the functional group (s) of increased polarity.
  • amphiphiles ensures that the surfaces of polyolefin-based moldings, fibers and films are permanently hydrophilized and without additional pretreatment, so that, for example, improved wettability with polar liquids such as water and / or improved antistatic properties result. Once set, the hydrophilicity values are retained over long periods or even increase with further storage.
  • the mixture containing components a), b) and c) is used by customary shaping processing techniques, such as extrusion, calendering, injection molding and the like, which are well known to those skilled in the art. It is preferred in the context of the teaching of the present inventions if, in the course of the shaping processing, the melt of the mixture comprising components a), b) and c) comes into contact with oxygen - in particular atmospheric oxygen is coming. This is the case, for example, in the case of extrusion when the melt leaves the extruder through the outlet nozzle.
  • the preferred embodiment mentioned enables - optionally catalytically supported - oxidative processes, for example an oxidatively induced crosslinking - and thus ultimately immobilization - of olefinically unsaturated molecular constituents of the additives (I) with the formation of higher molecular weight compounds, an oxidatively induced oxidation of activated methylene groups which occur in the immediate vicinity Neighboring to the polar groups of the amphiphiles (I), as well as further oxidative reactions and secondary reactions can take place. (Air) oxygen can act on the surface itself, on the one hand, and also inside the plastic - especially in areas close to the surface - where it can get through diffusion.
  • the additives (I) which are suitable in the context of the teaching of the present invention have relatively low molecular weights - a prerequisite for an appropriately rapid migration.
  • An upper limit for the molecular weight of suitable internal additives (I) is approximately 5,000 D (Dalton), preferably a maximum value of approximately 3,000 D and in particular a maximum value of approximately 1,000 D.
  • the molecular weight specification in "Dalton” is the definition of the absolute molecular weight .
  • the lower limits for the molecular weight of these internal additives (I) are approximately 50 to 100 D, preferably 150 to 180 D and in particular approximately 200 to 300 D.
  • the additives (I) preferred according to the invention are those amphiphiles whose hydrophobic molecular parts at least partially contain olefinically unsaturated functions which are particularly easily accessible to free-radically induced crosslinking reactions in the region of the plastic surface.
  • Such ad additives (I) which, in the unreacted state, have iodine numbers of at least about 10, preferably of at least about 30 to 40 and in particular of at least about 45 to 50.
  • the choice of the method for determining the iodine number is of minor importance. For the purposes of the present invention, however, express reference is made to the methods according to Hanus or Wijs, which have long been part of the CV section of the "DGF standard methods", and to the equivalent method according to Fiebig (cf. Fat Sei. Technol. 1991 , No. 1, pages 13-19).
  • both monoolefinically unsaturated hydrocarbon radicals and polyolefinically unsaturated hydrocarbon radicals can be provided in the context of the additives (I) used according to the invention.
  • Combinations of a plurality of corresponding compounds are also important auxiliary substances for the action according to the invention.
  • the respective iodine numbers of the additives (I) used can assume values above 80 to 90 and in particular also values above 100.
  • Highly unsaturated additive components with iodine numbers of up to about 200 or even more, for example in the range from 120 to 170, are auxiliary substances in the sense of the action according to the invention.
  • these internal additives (I) can be both straight-chain and branched and / or have a cyclic structure.
  • Substituents of increased polarity are in principle those functional groups which are distinguished in particular by a content of heteroatoms and in turn preferably by a content of O, N and / or halogen.
  • Residues from the classes carboxyl, hydroxyl, amino, oxazoline, imidazoline, epoxy and / or isocyanate and / or derivatives derived therefrom may be mentioned here merely by way of example.
  • the group of such derivatives includes, for example, ester groups, ether groups, amide groups / alkanolamine and / or alkanolamide groups.
  • a very important class of substituents of increased polarity in the context of the present invention are N-containing heterocycles and / or their derivatives. Examples of these are pyridazine, pyrimidine, pyrazine, pyridine, azane and azinane groups; thiazole, thiazolane, thiazolidine, pyrrole, azolane, azolidine, pyrazole and isooxazole groups are particularly suitable imidazole, imidazoline, diazolidine, oxazoline, oxazole, oxazolidine and oxazolidane groups are particularly suitable.
  • a particularly preferred class of additives (I) are compounds which on the one hand have one or more olefinically unsaturated functions in the hydrophobic part of the molecule and on the other hand extremely polar functions such as oxazoline, imidazoline, sulfonate, phosphonate or carboxyl groups (or their salts) contain hydrophilic part of the molecule.
  • additives of the type shown here can be used as additive (I).
  • suitable selection of the substituents with Increased polarity of the additives of this class of additives added in each case can be influenced in a predeterminable manner the hydrophilicity properties which can be set on the finished product.
  • mixtures of valuable substances of the type concerned here are also corresponding mixtures of substances which can be assigned to a specific subclass in terms of their functional group - for example have carboxyl groups as substituents of increased polarity - but have different basic structures in their hydrocarbon molecule.
  • Corresponding mixtures of substances are known to occur particularly when mixtures of the type concerned here are used based on natural substances.
  • olefinically unsaturated fatty acid mixtures of vegetable and / or animal origin or derivatives derived therefrom can be valuable additives of the type of additives (I) in the sense of the teaching according to the invention.
  • Another possible variation in the design of the internal additives (I) according to the invention lies in the number of functional substituents of increased polarity on the respective hydrocarbon backbone. Even a substituent of increased polarity - especially after coordinating the type and amount of functional groups provided - can lead to the desired permanent and at the same time intensive increase in the hydrophilicity properties. However, it has also been found that the presence of two or more such substituents of increased polarity in the respective molecule of the additive (I) can be an important additional feature for increasing the hydrophilicity properties. For example, reference is made here to the class of the so-called dimer fatty acids.
  • Dimer fatty acids are - as is common in the art - to be understood as those carboxylic acids which are accessible by oligomerizing unsaturated carboxylic acids, generally fatty acids such as oleic acid, linoleic acid, erucic acid and the like.
  • the oligomerization is usually carried out at elevated temperature in the presence of a catalyst made of, for example, alumina.
  • the products obtained are mixtures of different substances, with the dimersization products predominating. However, small proportions of higher oligomers, in particular the trimer fatty acids, are also present.
  • the dimer fatty acids also contain monomers or monofunctional fatty acids due to their production. Dimer fatty acids are commercially available products and are offered in various compositions and qualities.
  • trimer fatty acids are oligomerization products of unsaturated fatty acids, but the proportion of trimers in the product predominates. Dimer and trimer fatty acids have olefinic double bonds which enable them to be solidified in the area of the polyolefin surface.
  • Dialkanolamines with at least partially olefinically unsaturated hydrocarbon radicals or dialkanolamides of unsaturated fatty acids are highly effective in terms of improving the hydrophilicity properties in the sense of the teaching according to the invention.
  • This class includes, for example, oleic acid diethanolamide and linoleic acid diethanolamide.
  • Technical products known to the person skilled in the art, including the secondary components usually occurring therein, are expressly included in this connection. Examples of this are "Comperlan OD" (technical oleic acid dhanolamide) and “Comperlan F” (technical linoleic acid diethanolamide), both known commercial products from the applicant.
  • Comperlan OD technical oleic acid dhanolamide
  • Comperlan F technical linoleic acid diethanolamide
  • the migration rate to be expected on the basis of the molecular structure of the additives (I) used in each case can be one of the factors which also determine the amount of these additives (I) to be used in the individual case.
  • Lower limits for the amount of these additives of the additive (I) to the polyolefin are about 0.01% by weight and in particular about 0.1% by weight.
  • Optimized hydrophilicity property values for the representatives of this substance class for the additive (I) used in each individual case are generally in the range from about 0.3 to 5% by weight and in particular in the range from 0.4 to about 1% by weight. -% set.
  • the optimal surface hydrophilicity to be set is understandably determined by the chemical nature and the possible interaction of the substituents of increased polarity and, if appropriate, reactivity on the additive (I).
  • the additives (I) are used in the shaping processing of the polyolefins in combination with transition metal compounds (II).
  • the amount of the transition metal compound (II) - metal content of the transition metal compound (II) based on the polyolefins - 0.01 to 1000 ppm.
  • transition metal compounds (II) there is no particular restriction per se. Accordingly, in principle all transition metal compounds known to the person skilled in the art can be used in the context of the teaching of the present invention.
  • transition metal salts preferably salts based on organic acids having 8 to 22 carbon atoms, are used as transition metal compounds (II).
  • the transition metals are selected from the group lead, nickel, zirconium con, chrome, titanium and tin.
  • the transition metal compounds are used in an amount which is below 5 ppm, the metal content of the transition metal compound (II), based on the polyolefins.
  • cobalt, copper, iron, vanadium, cerium and manganese can also be used instead of or in addition to the metals just mentioned.
  • the weight ratio of the additives (I) to the metal content of the transition metal compounds (II) is set in the range from 10: 0.1 and 10: 10 " 7.
  • the transition metal compounds (II) are used in combination with such additives (I) which are selected from the class of the diefhanolamides of unsaturated fatty acids.
  • additives (I) which are selected from the class of the diefhanolamides of unsaturated fatty acids.
  • the diethanolamides are preferably used as technical goods.
  • amphiphilic additives (I) are used according to the invention in the course of customary shaping processing processes such as extrusion, ca Landing, injection molding and the like. It may be desirable to use a pre-assembled mixture of components a), b) and c).
  • Other customary auxiliaries which have been used and which have generally proven themselves in the processing of plastics and which are known to the person skilled in the art, for example slip agents, antistatic agents, lubricants, mold release agents, UV stabilizers, antioxidants, fillers, fire retardants, mold release agents, nucleating agents and anti-blocking agents can be used accordingly pre-assembled in separate form and added during the final mixing of the finished products.
  • oleophilic polyolefin base material As an oleophilic polyolefin base material, all known polymer and copolymer types based on ethylene or propylene are suitable per se.
  • Poly (ethylene) such as HDPE (high density polyethylene), LDPE (low density polyethylene), VLDPE (very low density polyethylene), LLDPE (linear low density polyethylene), MDPE (medium density polyethylene), UHMPE (ultra high molecular polyethylene), VPE (cross-linked polyethylene), HPPE (high pressure polyethylene); isotactic polypropylene; syndiotactic polypropylene; Metallocene catalyzed polypropylene, impact modified polypropylene, random copolymers based on ethylene and propylene, block copolymers based on ethylene and propylene; EPM (poly [ethylene-co-propylene]); EPDM (Pol
  • polystyrene polystyrene
  • Poly methyl styrene
  • Poly poly (oxymethylene); Metallocene-catalyzed alpha-olefin or cycloolefin copolymers such as norbornene-ethylene copolymers; Copolymers containing at least 80% ethylene and / or styrene and less than 20% monomers such as vinyl acetate, acrylic acid ester, methacrylic acid ester, acrylic acid, acrylonitrile, vinyl chloride.
  • polymers examples include: poly (ethylene-co-ethyl acrylate), poly (ethylene-co-vinyl acetate), poly (ethylene-co-vinyl chloride), poly (styrene-co-acrylonitrile).
  • Graft copolymers and polymer blends that is to say mixtures of polymers which contain, inter alia, the abovementioned polymers, for example polymer blends based on polyethylene and polypropylene, are also suitable.
  • homopolymers and copolymers based on ethylene and propylene are particularly preferred.
  • polyethylene is used as the polyolefin
  • polypropylene in another embodiment, copolymers based on ethylene and propylene.
  • Another object of the invention is a process for the permanent improvement of the surface hydrophilicity of polyolefin-based moldings, fibers and films, wherein one containing a mixture
  • Another object of the invention is the use of polyolefin-based moldings, fibers and films with permanently improved surface hydrophilicity, which can be obtained by the above-mentioned method according to the invention, for the production of textile fabrics.
  • Non-woven fabrics - such as those used in the area of hygiene articles - and geoylites - such as those used in the area of ground coverings are preferred.
  • General requirement profiles for nonwovens and geovlies have already been described above. They are fulfilled in an excellent manner by the use according to the invention mentioned here.
  • the following examples serve to illustrate the invention and are not to be understood as restrictive.
  • PE high molecular weight polyethylene granulate (commercial product "Lupolen 1800 H” from BASF AG)
  • PP high-molecular polyolefin, a polypropylene granulate commercial product "Hostalen PPH 2150" from Hoechst AG)
  • Ricinic acid (commercial product "Edenor Ri 90" from Henkel KGaA)
  • Comperlan F linoleic acid diethanolamide, technical quality (commercial product "Comperlan F” from Henkel KGaA, Düsseldorf)
  • Pb-C8 lead 2-ethylhexanoate (lead salt of 2-ethylhexanoic acid)
  • Ni-acac nickel acetylacetonate
  • Co / Zr / Pb-lig mixture of a cobalt, zirconium and lead 2-ethylhexanoate (contains 1.04% by weight of Co; 2.48% by weight of Zr; 9.93% by weight of Pb ) 2.
  • Co / Zr / Pb-lig mixture of a cobalt, zirconium and lead 2-ethylhexanoate (contains 1.04% by weight of Co; 2.48% by weight of Zr; 9.93% by weight of Pb ) 2.
  • polyethylene or polypropylene tapes were first produced. To do this, each
  • An extruder is - as is well known to the person skilled in the art - a plastic processing machine which is suitable for the continuous mixing and plasticizing of both powder and granular thermoplastics.
  • a counter-rotating twin screw which is divided lengthways into three heating zones.
  • the temperature of the heating zones and the speed of the twin screw can be controlled via a PL 2000 data processing plast corder, which is connected to the extruder via a PC interface.
  • the following temperatures were set for the production of the polyolefin tapes: heating zone I: 250 ° C., heating zone II: 270 ° C., heating zone III: 290 ° C., the three heating zones being air-cooled in order to keep the temperatures constant.
  • the polyolefin granules (including the respective additive (I) and the transition metal compound II) were automatically drawn into the extruder by the twin screw running counter to one another and conveyed along the screw. The speed was 25 revolutions per minute. This ensured a relatively long residence time in the extruder and, accordingly, good mixing and homogenization. This homogeneous and practically bubble-free mixture finally came into a nozzle, which is a fourth heating zone. The temperature of the nozzle was 300 ° C - at this temperature the mixture left the extruder.
  • the hot mixture flowed onto a conveyor belt, the speed of which was adjusted in such a way that a smooth and uniformly thick and wide belt was formed when cooling in air.
  • the speed was set so that the polyolefin tape was about 35 mm wide and about 0.35 mm thick. Square test specimens were punched out of this material and used for the experiments described in more detail below.
  • test specimens made of pure polyethylene or polypropylene were used. The production was carried out using the extrusion technique just described, but only polyethylene or polypropylene granules were used without the addition of additive (I) and transition metal compound (II). The test results based on this material are identified in Table 1 in the first column in each case by the indication "compare”. 3. Determination of the hydrophilicity properties
  • Untreated and surface-modified polypropylene test specimens according to the present invention were first stored for 7 days at 60 ° C. and then the wetting tension and the contact angle against water were determined at 25 ° C. using a Kl 4 tensiometer from Krüss. The corresponding polyethylene test specimens were examined immediately after manufacture, ie without storage.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne l'utilisation d'amphiphiles pour hydrophiliser de manière durable les surfaces de corps moulés, de fibres et de films à base de polyoléfine. Selon l'invention, on soumet à un traitement un mélange contenant: a) principalement une ou plusieurs polyoléfines, b) entre 0,01 et 10 % en poids, par rapport aux polyoléfines, d'un ou de plusieurs amphiphiles (additifs I) aptes à la migration et c) entre 0,01 et 1000 ppm d'un ou de plusieurs composés de métal de transition (II) (la teneur en composés de métal de transition (II) figurant par rapport aux polyoléfines). Ce mélange est soumis, à des températures comprises entre 180 et 320 °C, de manière habituelle, à un traitement de formage tel que l'extrusion, le laminage, le moulage par injection ou similaire.
PCT/EP1998/001505 1997-03-25 1998-03-16 Utilisation d'amphiphiles pour l'hydrophilisation de corps moules, de fibres et de films a base de polyolefine WO1998042898A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19712379A DE19712379A1 (de) 1997-03-25 1997-03-25 Verwendung von Amphiphilen zur Hydrophilisierung von Polyolefin-basierten Formkörpern, Fasern und Folien
DE19712379.1 1997-03-25

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Publication Number Publication Date
WO1998042898A1 true WO1998042898A1 (fr) 1998-10-01

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000028131A2 (fr) * 1998-11-10 2000-05-18 Cognis Deutschland Gmbh Procede de traitement de fibres a base de polyolefines ou de polyester a l'aide d'appret hydrophile avec utilisation d'heterocycles
WO2002055011A3 (fr) * 2001-01-16 2003-02-27 Ben Gurion University Of The Negev Research And Development Authority Derives amphiphiles pour la production de vesicules, de micelles et de complexants, et precurseurs de ceux-ci
US8030231B2 (en) 2004-07-09 2011-10-04 Johnson & Johnson Gmbh Absorbent personal care and/or cleansing product for cosmetic and/or dermatological applications comprising at least one absorbent sheet
CN102597350A (zh) * 2009-11-11 2012-07-18 帝人株式会社 纤维成形体
US10428454B2 (en) 2013-12-27 2019-10-01 Dow Global Technologies Llc Textile treatment compositions including quternary bis-imidazoline compounds derived from linear tetramines useful to improve moisture management and provide antimicrobial protection

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19851691A1 (de) * 1998-11-10 2000-05-11 Cognis Deutschland Gmbh Verwendung von Amiden aromatischer Carbonsäuren zur dauerhaften Verbesserung der Klebstoff- und/oder Beschichtungs-Kompatibilität von Polyolefin-basierten Formkörpern, Fasern und Folien
DE10144713B4 (de) * 2001-09-11 2004-05-13 Sandler Ag Permanent hydrophile Flüssigkeitstransportlage

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GB444375A (en) * 1934-07-06 1936-03-19 Georg Goll Improvements in or relating to rubber and rubber compounds and methods of treating them
DE1569008A1 (de) * 1963-04-05 1970-10-22 Hardman & Holden Ltd Verfahren zum Stabilisieren von Vinylhalogenidpolymeren und Copolymeren
EP0057388A2 (fr) * 1981-01-29 1982-08-11 Dr. Bernhard Joos Procédé pour améliorer la mouillabilité de substrats
EP0099581A2 (fr) * 1982-07-21 1984-02-01 E.I. Du Pont De Nemours And Company Résines de moulages à base de mélanges de copolymères acides, de polyoléfines, de fibres de renforcement et d'agent humidifiant
US4578414A (en) * 1984-02-17 1986-03-25 The Dow Chemical Company Wettable olefin polymer fibers
EP0400622A2 (fr) * 1989-06-01 1990-12-05 Hercules Incorporated Fibres mouillables de polyoléfine et non tissés contenant ces fibres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB444375A (en) * 1934-07-06 1936-03-19 Georg Goll Improvements in or relating to rubber and rubber compounds and methods of treating them
DE1569008A1 (de) * 1963-04-05 1970-10-22 Hardman & Holden Ltd Verfahren zum Stabilisieren von Vinylhalogenidpolymeren und Copolymeren
EP0057388A2 (fr) * 1981-01-29 1982-08-11 Dr. Bernhard Joos Procédé pour améliorer la mouillabilité de substrats
EP0099581A2 (fr) * 1982-07-21 1984-02-01 E.I. Du Pont De Nemours And Company Résines de moulages à base de mélanges de copolymères acides, de polyoléfines, de fibres de renforcement et d'agent humidifiant
US4578414A (en) * 1984-02-17 1986-03-25 The Dow Chemical Company Wettable olefin polymer fibers
EP0400622A2 (fr) * 1989-06-01 1990-12-05 Hercules Incorporated Fibres mouillables de polyoléfine et non tissés contenant ces fibres

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000028131A2 (fr) * 1998-11-10 2000-05-18 Cognis Deutschland Gmbh Procede de traitement de fibres a base de polyolefines ou de polyester a l'aide d'appret hydrophile avec utilisation d'heterocycles
WO2000028131A3 (fr) * 1998-11-10 2000-08-03 Cognis Deutschland Gmbh Procede de traitement de fibres a base de polyolefines ou de polyester a l'aide d'appret hydrophile avec utilisation d'heterocycles
WO2002055011A3 (fr) * 2001-01-16 2003-02-27 Ben Gurion University Of The Negev Research And Development Authority Derives amphiphiles pour la production de vesicules, de micelles et de complexants, et precurseurs de ceux-ci
US7939562B2 (en) 2001-01-16 2011-05-10 Ben-Gurion University Of The Negev Research And Development Authority Amphiphilic derivatives for the production of vesicles, micelles and complexants, and precursors thereof
US8030231B2 (en) 2004-07-09 2011-10-04 Johnson & Johnson Gmbh Absorbent personal care and/or cleansing product for cosmetic and/or dermatological applications comprising at least one absorbent sheet
CN102597350A (zh) * 2009-11-11 2012-07-18 帝人株式会社 纤维成形体
EP2500456A1 (fr) * 2009-11-11 2012-09-19 Teijin Limited Article à base de fibres moulées
EP2500456A4 (fr) * 2009-11-11 2013-10-16 Teijin Ltd Article à base de fibres moulées
JP5563590B2 (ja) * 2009-11-11 2014-07-30 帝人株式会社 繊維成形体
US10428454B2 (en) 2013-12-27 2019-10-01 Dow Global Technologies Llc Textile treatment compositions including quternary bis-imidazoline compounds derived from linear tetramines useful to improve moisture management and provide antimicrobial protection

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