EP0814188A1 - Vliesstoff aus sehr feinen Endlosfilamenten - Google Patents
Vliesstoff aus sehr feinen Endlosfilamenten Download PDFInfo
- Publication number
- EP0814188A1 EP0814188A1 EP97108364A EP97108364A EP0814188A1 EP 0814188 A1 EP0814188 A1 EP 0814188A1 EP 97108364 A EP97108364 A EP 97108364A EP 97108364 A EP97108364 A EP 97108364A EP 0814188 A1 EP0814188 A1 EP 0814188A1
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- EP
- European Patent Office
- Prior art keywords
- filaments
- elementary
- composite
- tablecloth according
- dtex
- 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.)
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Classifications
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/11—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- 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
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/018—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the shape
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/105—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by needling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/609—Cross-sectional configuration of strand or fiber material is specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/609—Cross-sectional configuration of strand or fiber material is specified
- Y10T442/611—Cross-sectional configuration of strand or fiber material is other than circular
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/609—Cross-sectional configuration of strand or fiber material is specified
- Y10T442/612—Hollow strand or fiber material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/627—Strand or fiber material is specified as non-linear [e.g., crimped, coiled, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
- Y10T442/666—Mechanically interengaged by needling or impingement of fluid [e.g., gas or liquid stream, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
- Y10T442/668—Separate nonwoven fabric layers comprise chemically different strand or fiber material
Definitions
- the present invention relates to the field of textile products and their applications, and relates to a nonwoven web of very fine continuous filaments or micro-filaments.
- the present invention aims in particular to broaden the traditional scope of nonwovens by giving them physical properties and characteristics, more particularly textile and mechanical, similar to those of woven and knitted textile products, while retaining the advantageous properties and characteristics of nonwovens of continuous filaments.
- Synthetic textile fibers are already known, generally designated by the term “Shin-Gosen”, whose characteristics of touch and appearance are very close to natural fibers.
- These known fibers are obtained by spinning techniques which make it possible to obtain ultra-fine fibers or microfibers, of various sections, and of variable polymeric constitution. After spinning, these fibers are transformed by known techniques of weaving or knitting and treated according to more or less complex finishing techniques.
- An object of the present invention is to obtain nonwoven products having characteristics and properties at least equal to those of woven or knitted products obtained by means of the above-mentioned ultra-fine fibers, while applying manufacturing techniques which are clearly more efficient and less costly. , resulting in greater flexibility in the variability of the nature and properties of the filaments, consolidation methods and properties of the products obtained.
- the subject of the present invention is a nonwoven web of continuous filaments, crimped or not, obtained by means of a controlled direct spinning process, having a grammage between 5 g / m 2 and 600 g / m 2 and formed, after lapping, of composite filaments separable in the direction of their length, characterized in that said composite filaments have a count between 0.3 dTex and 10 dTex and are formed, each, by at least three elementary filaments in at least two different materials and comprising between them at least one plane of separation or cleavage, each elementary filament having a titer between 0.005 dTex and 2 dTex and the ratio between the area of the cross section of each elementary filament and the total area of the cross section of the unitary filament being between 0.5% and 90%.
- FIGS. 1 to 7 represent cross sections of continuous composite filaments according to the invention, before separation into elementary filaments.
- the invention relates to a nonwoven web of continuous filaments, crimped or not, obtained by means of a controlled direct spinning process, having a grammage between 5 g / m 2 and 600 g / m 2 and formed, after lapping, separable composite filaments.
- said composite filaments have a titer between 0.3 dTex and 10 dTex and are each formed by at least three elementary filaments made of at least two different materials and comprising between them at least one separation plane or cleavage, each elementary filament having a titer between 0.005 dTex and 2 dTex and the ratio between the cross-sectional area of each elementary filament and the total cross-sectional area of the unitary filament being between 0.5% and 90 %.
- the composite filaments have a titer greater than 0.5 dTex and each elementary filament has a titer less than 0.5 dTex.
- the composite filaments have a titer between 0.6 dTex and 3 dTex and the elementary filaments have titer between 0.02 dTex and 0.5 dTex.
- the sheet obtained can be designated as being a nonwoven sheet of continuous micro-filaments.
- the nonwoven web is, after the controlled operations of extrusion / spinning, drawing / cooling and coating, subjected, simultaneously or successively, to operations of binding and consolidation by means of means (s ) mechanical (s), such as intense needling, the action of jets of pressurized fluid, the action of ultrasound and / or mechanical friction, of thermal means (s), such (s) as boiling water, steam or microwaves or chemical means (s), such as treatment with active blowing chemical agents for at least one of the materials composing the composite filaments, the composite filaments being at least partially separated into their elementary filaments during the said binding and consolidation operations.
- means s mechanical (s), such as intense needling, the action of jets of pressurized fluid, the action of ultrasound and / or mechanical friction
- thermal means such (s) as boiling water, steam or microwaves
- chemical means such as treatment with active blowing chemical agents for at least one of the materials composing the composite filaments, the composite filaments being at least partially separated into their elementary filaments during the said binding and consolidation operations.
- the various polymeric materials forming the composite filaments are distributed in distinct zones in the cross section of the latter, so as to allow their separation into elementary filaments each corresponding, in cross section, to one of said zones.
- the various polymer materials constituting the composite filaments are advantageously immiscible and / or incompatible with one another. made by nature or following treatment of at least one of said polymeric materials.
- the group of polymeric materials forming the elementary filaments is chosen from the following groups: (polyester / polyamide); (polyamide / polyolefin); (polyester / polyolefin); (polyurethane / polyolefin); (polyester / polyester modified with at least one additive); (polyamide / polyamide modified by an additive); (polyester / polyurethane); (polyamide / polyurethane); (polyester / polyamide / polyolefin); (polyester / polyester modified with at least one additive / polyamide): (polyester / polyurethane / polyolefin / polyamide).
- the composite filaments have, in cross section, a configuration of the zones representing the cross sections of the various elementary filaments, in the form of orange wedges or sectors of pie chart.
- Said districts or sectors, forming the pattern of the cross section of the composite elements may have different dimensions, thus generating, after separation and separation of the initial composite filaments, elementary filaments of clearly different titles.
- said composite filaments may comprise a longitudinal tubular hollow cavity, centered or not relative to the median axis of said composite filaments.
- this arrangement eliminates the intimate contact between the edges of the elementary filaments formed by the interior angles of the quarters or sectors, before separation of the composite filaments, and the contact at this level of different elementary filaments made of the same polymer material.
- the elementary filaments are integrated into an enveloping matrix of an easily fractionable or dissolvable material, the material of said matrix also being present in the interstices separating said elementary filaments or be replaced by another dissolvable or incompatible polymeric material with respect to the polymeric material forming the elementary filaments (see FIG. 3).
- the contours of the cross sections of the elementary filaments can be any, and in particular be in the form of orange wedges or sectors of pie chart, the enveloping matrix forming the receiving compartments of said quarters or sectors as well as a outer envelope surrounding all of said districts or sectors (see Figure 4).
- the outer contours of the cross sections of the composite filaments have a multilobed configuration, defining several sectors or zones each corresponding to an elementary filament .
- the elementary filaments have, in cross section, a configuration in the form of a daisy whose pistil is formed by an elementary filament and whose petals are formed by the other elementary filaments forming each of said composite filaments .
- the composite filaments may exhibit a latent or spontaneous crimp resulting from an asymmetry of behavior of said filaments with respect to their longitudinal median axis, said crimp being activated or accentuated, where appropriate, by an asymmetry of the geometry of the configuration of the cross section of said composite filaments.
- the composite filaments may exhibit a latent or spontaneous crimp resulting from a differentiation of the physical properties of the polymeric materials forming the elementary filaments during the spinning, cooling and / or drawing operations of the composite filaments resulting in generated distortions by asymmetrical internal stresses with respect to the longitudinal median axis of said composite filaments, said crimp being activated or accentuated, if necessary, by an asymmetry of the geometry of the configuration of the cross section of said composite filaments.
- the composite filaments can have a latent crimp which is activated by heat, mechanical or chemical treatment before the formation of the nonwoven web.
- the crimp can be accentuated by a complementary treatment of the consolidated or unconsolidated sheet, of the thermal type (tunnel oven, boiling water, steam, heating drum, microwave, infrared waves) or of the chemical type, with possible controlled retraction. of the tablecloth.
- the elementary filaments are strongly entangled, during or after the division of the composite filaments, by mechanical means (needling, jets of fluid under pressure) acting mainly in one direction perpendicular to the plane of the tablecloth.
- the initial composite filaments can be obtained, for example, by electrostatic, mechanical and / or pneumatic deflection (a combination of at least two of these types of deflection is possible) and projection onto an endless moving belt and can be entangled mechanically by needling (on one or two sides with needles and under adequate perforation conditions depending on the properties required for the nonwoven web) or by the action of jets of pressurized fluid, loaded or not with solid microparticles, possibly after calendering.
- the sheet is composed of several superimposed nonwoven layers.
- each layer consists of filaments originating from a single die.
- At least one layer consists of filaments originating from at least two separate dies, said filaments being mixed during the stretching phase, before lapping.
- the operations of entangling and separating the composite filaments into elementary filaments can be carried out in the same process step and with the same device, the more or less complete separation of said elementary filaments being able to be completed by an additional operation more targeted at said separation .
- the cohesion and the mechanical resistance of the nonwoven web can also be appreciably increased, by providing for bonding of the elementary filaments with one another by one or more of them formed from a polymeric material. lower melting point, by calendering by means of smooth or engraved heated rollers, by passage through a hot air tunnel oven, by passage over a through hot air drum and / or by application of a binding agent contained in a dispersion , in solution or in powder form.
- the consolidation of the sheet can, as a variant, also be carried out, for example by hot calendering, before any separation of the unitary composite filaments into elementary filaments or micro-filaments, said separation being carried out after consolidation of the sheet.
- the structure of said sheet can also be consolidated by a chemical treatment (as described for example in French patent n ° 2,546,536 in the name of the applicant) or thermal resulting in a controlled retraction of at least part of the elementary filaments, after having, if necessary, separated them, resulting in a retraction of the web in the direction of its width and / or in the direction of its length.
- the nonwoven web may be subjected, after consolidation, to a binding or finishing treatment of the chemical type, such as an anti-pilling, hydrophylizing, anti-static treatment. , improvement of fire resistance and / or modification of touch or luster, of the mechanical type, such as scraping, sanforizing, emery or passage through a trumbler, and / or of the type modifying the external appearance such as dyeing or printing.
- the chemical type such as an anti-pilling, hydrophylizing, anti-static treatment.
- improvement of fire resistance and / or modification of touch or luster, of the mechanical type such as scraping, sanforizing, emery or passage through a trumbler, and / or of the type modifying the external appearance such as dyeing or printing.
- a sheet of two-component polyethylene terephthalate / polyamide 6 continuous filaments is produced.
- the materials used have the following characteristics: POLYESTER POLYAMIDE Nature Polyethylene terephthalate Polyamide 6 Intrinsic viscosity 0.64 2.6 * TiO 2 0.4% 1.7% Fusion point 256 ° C 222 ° C Melted viscosity 190 Pa.s at 290 ° C 170 Pa.s at 265 ° C Origin Rhone Poulenc Company Nylstar Company * Viscosity: concentration 1% in sulfuric acid at 96% and 20 ° C.
- the spinning unit 1 consists of two chambers, one of which is located in the axis of said unit (PA6 spinning) and the second, of annular shape, surrounds the first (PET spinning).
- the two distribution plates allow distribution both circular and radial.
- the stacking of the three final distribution plates allows an alveolar supply of each of the holes of the die.
- Each of said holes thus has its own supply circuit and makes it possible to spin a unitary composite filament.
- the die itself is made up of 180 capillary holes with a diameter of 0.28 mm and a length of 0.56 mm.
- a schematic representation of an orifice of such a die is reproduced in Figure 10 of the accompanying drawings.
- the extrusion temperatures of the two polymers are respectively 295 ° C for PET and 255 ° C for PA6, the spinning boat itself being at a temperature of 278 ° C, the spinning speed is about 4,500 m / min and the flow rate per die hole of 0.7 g / min (0.35 g / min per polymer).
- the drying of PA6 and the supply of the extruder are carried out under a nitrogen atmosphere and the polymer transfer circuits to the die are designed so that the residence and transport times of said polymers are sufficiently short to avoid any significant deterioration of these.
- the nonwoven ply obtained has a grammage of 120 g / m 2 and consists of continuous non-crimped filaments having a titer of 1.6 dTex and having in cross section a configuration in orange wedges with a central orifice, said districts or sectors being alternately composed of one of the two aforementioned polymer materials and in direct contact with the adjacent districts or sectors (structure of the section comparable to that shown in FIG. 2 of the accompanying drawings).
- Each composite filament consists of six elementary polyethylene terephthalate filaments with a titer of 0.15 dTex and six elementary polyamide 6 filaments with a titer of 0.11 dTex, resulting in a weight ratio of polyethylene terephthalate / polyamide 6 of 60/40.
- the aforementioned nonwoven layer is subjected to the action of jets of fluid (water) under pressure with a view to achieving the separation of the composite filaments into elementary filaments, as well as the entanglement and binding of the latter.
- said hydraulic binding consists, successively, of a passage of the nonwoven ply under a first wetting ramp, of a wringing of the wetted ply (by passage between two pressure rollers or by suction, for example) and finally by a passage of the ply at the level of the three successive sets of hydraulic binding on a suction drum, said assemblies acting respectively on the front, back and front sides of the sheet and each comprising three bars or lines of jets spaced 0.6 mm apart.
- the nonwoven web moves on a metallic mesh of 80 mesch (80 threads / 2.54 cm) with 70% opening.
- Bed processing speed in this case is about 15m / min.
- the nonwoven web is wrung by compression between two pressure rollers, dried on a through air drum heated to 160 ° C and, finally, wound.
- this sheet has appearance and texture of a "flannel” type fabric, high breaking load and tear resistance characteristics, good drapability and good abrasion resistance.
- the tablecloth obtained by the above-mentioned process in fact forming a nonwoven fabric, can be advantageously used, after dyeing or printing and possibly hot embossing, as an interior covering for a car roof or a wall covering.
- a nonwoven web of continuous filaments is produced according to a process similar to that described in Example 1, said web being subjected to a hydraulic bonding identical to that described above.
- the sheet obtained however, has a grammage of 130 g / m 2 and is subjected, following the hydraulic bonding, to a calendering by points by means of two heated metal rollers, namely a roll engraved at 232 ° C and a smooth roll at 215 ° C (pressing force: 50daN / cm of width; speed: 15m / min; 52 points / cm 2 ; percentage of bonded surface: 13%).
- the sheet obtained can advantageously be used for pigment printing or, after dyeing, as an apparent coating of door panels for motor vehicles, coating of injected or molded parts intended to be mounted in the cockpits of vehicles, for the manufacture of inner linings for shoes or for making workwear.
- said tablecloth can also be used, after printing (in particular of the "fixed-washed” type), for the production of drapes or curtains for interior furnishings.
- a sheet of continuous curly composite filaments is produced, composed of polyethylene terephthalate / polyamide 66 polymer materials, present in identical weight proportions.
- the PET used is identical to that of Example 1.
- Polyamide 66 (PA66) is of the type known under the designation 44AM30 by the company Rhone Poulenc (melt viscosity: 170 Pa.s and IV 137).
- the melting and spinning temperatures are 285 ° C. for the two polymers and the title pumps used have a flow rate of 10 cm 3 per revolution.
- the supply and distribution system of the spinning unit is similar to that of Example 1.
- Each die has 180 holes with an outside diameter of 1.35 mm and an inside diameter of 1.0 mm off center.
- This arrangement makes it possible to end up with an annular slot, the width of which varies as a function of the circumferential position (for example of the half-circumference) and which can be produced by forecasting and the cutting of two half-discs of different radii, ending in an annular slot of which a half-circumference has a width of 0.15 mm and of which the other half-circumference has a width of 0.2 mm (see FIG. 9 of attached drawings).
- the cooling system located under the die is annular in shape and blows fresh air at 17 ° C and with 80% RH, at a speed of 0.8 m / s.
- the stretching and tablecloth system is similar to that described in French patent n ° 74 20254 in the name of the applicant.
- the continuous spun composite filaments have twelve crimps per centimeter and a crimp rate of 180%.
- the nonwoven ply obtained has a grammage of 140 g / m 2 and is made up of composite filaments having a titer of 1.6 dTex and having in cross section an orange quarter configuration with an off-centered orifice, resulting in an asymmetrical behavior of the composite filament. and the formation of elementary filaments having different titles.
- Said ply is subjected to a hydraulic bonding (use of the same assemblies as those used in Example 1, but with a pressure of 180 bars for the second and third assemblies), then to a chemical shrinkage treatment as described in particular in the French Patent No. 2,546,536 in the name of the plaintiff.
- the bath is brought to a temperature of 18 ° C and has a formic acid level of 64%.
- the contact time of the tablecloth with the bath is approximately 25 seconds and the soaking of the tablecloth is followed by successive operations of rinsing with water at room temperature, spinning and drying at 120 ° C.
- the sheet is also subjected, consecutively, to darning and dyeing operations, in particular of the high temperature "Jigger" type.
- the nonwoven product, weighing 172 g / m 2 , obtained by the process described above has properties and an appearance similar to leather and can be advantageously used for the manufacture of shoes, leather goods and luggage and luggage.
- a sheet of continuous filaments is produced having a fibrous constitution identical to that described in Example 3, but showing a latent crimp.
- the unitary composite filaments are advantageously spun at a speed of around 3,200 m / min and subjected, after lapping, to a hydraulic binding operation under conditions substantially similar to those described in the example. 3.
- the sheet is subjected to a drying and heat treatment operation between 160 ° C and 180 ° C (temperature below the yellowing temperature of the polyamide polymer) resulting in the revelation or activation of the latent crimp and shrinkage of said sheet, the time of submission of the sheet to the heat treatment being less than one minute.
- a pliers ream which grips said ply by pinching at each longitudinal lateral edge, said pliers having a configuration in top view in a V shape (narrowing of the spacing of the lateral pliers in the direction of the advancement of the water table).
- the retraction rate of the free filaments at 180 ° C is approximately 50% to 60%, which results in a retraction rate for the web of between 12% and 15% (in the longitudinal direction and in the transverse direction) and an increase in grammage between 30% and 35%.
- the sheet thus retracted is then subjected to additional treatments identical to those described in the context of Example 3 (from the impregnation using a polyurethane solution) and can be used in applications similar to those described in this example.
- a web of polyethylene terephthalate / polybutylene terephthalate bicomponent continuous filaments is produced.
- the structure of the spinning unit used in this example is substantially similar to that of the spinning unit used in Example 3, with the presence of two distribution plates intended to cross flows and three distribution plates, the orifices are shaped and grouped in the form of daisies.
- the distribution system is produced on the basis of a coaxial distribution of the polymers, but using a multi-lobed die.
- the heart, or the central element, of each daisy structure being supplied by the distribution circuit of two PBTs and the eight lobes of each daisy structure being supplied with PET.
- the PET used is identical to that used in the context of Example 1, while being added in a small percentage of silicone oil of the organosiloxane type (approximately 0.3%).
- the PBT used is of the type known under the designation TQ9 / 04 from the company ENICHEM, has a melt viscosity of 290 Pa.s at 265 ° C. and is charged with 0.4% of TiO 2 .
- the extrusion temperatures are respectively 290 ° C (PET) and 260 ° C (PBT) and the temperature of the spinning boat is approximately 280 ° C.
- the annular cooling device blows air at 20 ° C and 75% RH, with a speed of 1.2 m / s.
- the spinneret / drawing nozzle distance is 1.1 meters for a spinning speed of 5,600 m / min.
- the flow rate per die hole is 0.9 gr / min for PET and 0.11 gr / min for PBT.
- the nonwoven ply obtained has a grammage of 145 g / m 2 and consists of continuous non-crimped filaments having a titer of 1.8 dTex and having in cross section a daisy-like configuration in which the pistil is formed by an elementary cylindrical filament central in polybutylenetrephthalate (title 0.2 dTex) and the petals are formed by elementary filaments in polyethylene terephthalate (title 0.2 dTex), with elongated elliptical section, arranged circumferentially around said central elementary filament by being adjacent to the latter at the level of one of the ends of the ellipse delimiting the contour of said peripheral elementary filaments in cross section (see FIG. 7).
- Said peripheral elementary filaments with an elongated ellipse section advantageously consist of polyethylene terephthalate added with silicone as described in particular in French patent No. 2,657,893 in the name of the applicant.
- the injected silicone (approximately 0.3% by weight relative to the polyethylene terephthalate) serves as a spinning lubricant for the peripheral elementary filaments and, by partially migrating at least partially on the surface of said peripheral elementary filaments forms the interfaces between the latter and the elementary filament central, which significantly facilitates the separation of composite filaments into elementary filaments (energy required for lower separation).
- the level of silicone must be relatively limited so as not to disturb subsequent treatments (in particular the finishing), dyeing or printing.
- the nonwoven web of composite continuous filaments After the formation of the nonwoven web of composite continuous filaments, the latter is subjected to mechanical needling, followed by hydraulic bonding, resulting in at least partial separation of the various elementary filaments.
- Said sheet is then subjected to a punctual calendering at a temperature between the melting temperatures of the two polymers, that is to say between 256 ° C (melting temperature of PET) and 226 ° C (melting temperature of PBT ), so as to merge the PBT and create solid point bonds between the elementary PET filaments.
- a punctual calendering at a temperature between the melting temperatures of the two polymers, that is to say between 256 ° C (melting temperature of PET) and 226 ° C (melting temperature of PBT ), so as to merge the PBT and create solid point bonds between the elementary PET filaments.
- the resulting nonwoven product can be used, after pigmentary printing, as a substrate for the manufacture of cushions, garden chairs, parasols and table cloths.
- the aforementioned nonwoven product can also be used, after dyeing or printing (in particular by a "fixed-washed” type process) for the production of interior coatings for motor vehicles, uppers (uppers) for sports and leisure shoes, luggage or leather goods.
- a web of three-component continuous filaments formed from polyethylene terephthalate, polyamide 6 and polypropylene is produced with respective total titers of 1.08 dTex, 1.08 dTex and 0.24 dTex.
- the spinning unit consists of an annular chamber for polypropylene and two symmetrical axial chambers for polyamide 6 and polyethylene terephthalate.
- the polymer distribution system is composed of three flow crossing plates and the separation system is composed of three cellular distribution plates, similar to those used in the context of Example 3.
- the polypropylene of MFI 25 is extruded at 250 ° C. and the conditions for extruding polyamide 6 and polyethylene terephthalate are identical to those of Example 1.
- the polypropylene is loaded with titanium oxide, introduced at the rate of 1% at the feed to the extruder, and the spinning speed is of the order of about 5000 m / min.
- the nonwoven ply obtained has a grammage of 90 g / m 2 and consists of continuous curly composite filaments having a titer of 2.4 dTex and having in cross section a configuration in orange wedges with an off-centered orifice (see FIG. 3) .
- the separation of the composite filaments into elementary filaments is carried out during a hydraulic bonding operation.
- the sheet is then subjected to drying at 180 ° C. on a through air drum, during which the elementary polypropylene filaments undergo total or partial melting, depending on the contact time (greater than about 12 seconds). This fusion of the polypropylene filamentary component leads to an intimate connection between the elementary filaments of polyethylene terephthalate and polyamide 6.
- the nonwoven product thus obtained simultaneously has a very absorbent structure, due to its high capillarity, and good resistance to repeated use in household and industrial cleaning and wiping applications.
- the aforementioned product withstands (in terms of structural cohesion and pilling) repeated washing with water at 50 ° and dry degreasing (possibility of repeated reuse of the product and economical use).
- such a product by virtue of its constitution in continuous filaments and of the excellent cohesion resulting from hydraulic bonding and thermobinding, has the advantage of not emitting fibrous particles during use. This property is very important for the use in cleaning substrate for clean rooms and in electronics.
- a sheet of 120 g / m 2 is produced, consisting of bicomponent filaments of 1.6 dTex as defined in Example 3 and of monoconstituting polyester filaments of 1.6 dTex, spun together in the same die, with a proportion of 80%.
- This sheet is then subjected to a binding by punctual calendering using etched metal rollers, at a temperature of 238 ° C, and a counterpart made up of a smooth metal roller, at a temperature of 223 ° C. (Pressing force: 50daN / cm of width; speed of 22m / min; 55 points / cm 2 ; percentage of bound surface: 17%).
- the two-component filaments and the single-component filaments can be extruded at the same die, or can be extruded at two separate successive dies, the extruded filaments then being mixed at the drawing station.
- the nonwoven fabric obtained combines very good mechanical properties, in particular of tear resistance, with good properties of appearance, flexibility, drape and resilience, making it particularly suitable for making work clothes.
- Example 6 Using the continuous crimped filaments described in Example 6, a nonwoven ply is produced directly by 120 g / m 2 using a topping system in eight unitary plies of 15 grams each, successively deposited one on top of the other according to the method described in French patent n ° 74 20254. Between layers 4 and 5, a stabilized knitted textile weft knit of 20gr / m 2 of polyamide 6 is introduced.
- the laminate assembly is linked by a hydraulic tying device comprising successively high-pressure water jet ramps (250 bars) on both sides, leading to the separation of the strands and the entanglement of the microfilaments formed by the individual elementary filaments and of the cited textile reinforcement, in a very cohesive manner.
- the three-layer assembly obtained is then dried at 180 ° C., in order to melt the polypropylene microfilaments which act as a binder.
- the resulting nonwoven fabric can be dyed or printed by conventional methods and then treated in a tumbler, to improve feel and flexibility.
- This fabric with flannel feel very favorably combine the mechanical characteristics, appearance, flexibility, drooping and resistance to abrasion, and the limitation of the bagging due to the textile reinforcement used, for the production of leisure clothes.
- sports jackets and jackets or indoor clothing such as dressing gowns.
- a sheet of bicomponent filaments as defined in example 3 is produced, but with a grammage of 32 g / m 2 and linked by the hydraulic bonding process - in treatment on both sides (pressures identical to those used in example 1, with a running speed of 65 m / min).
- This nonwoven is coated by the point dusting technique (16 gr / m 2 ) with a terpolyamide powder (PA66, 612), having a melting temperature of 120 ° (see on this subject DE-PS-3610029, example 1 ).
- the product obtained has very good flexibility and good elasticity, and is resistant to dry degreasing. This product can be advantageously used as a fusible lining for clothing.
- a multi-layer web of total grammage 140 gr / m 2 is produced formed of five layers (70 gr / m 2 ) of filaments of the type of those produced in the context of Example 1 and five other layers (70 gr / m 2 ) made up of bimetallic curly filaments, having a titer of 1.5 dTex and formed from polyethylene terephthalate and polybutylene terephthalate (such as those described in French Patent No. 2,705,698).
- a hydraulic bonding is then carried out as described in the aforementioned French patent, followed by a smooth calendering between a hot roller at 225 ° C. (in contact with the face of the nonwoven with a constitution similar to that described in Example 1) and a cold roller at 125 ° C, at a speed of 18m / min and with a pressing force of 25 daN / cm of calender width.
- the product obtained can advantageously be used in filtration applications, in particular for draining milk or filtering edible oil.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR9607659A FR2749860B1 (fr) | 1996-06-17 | 1996-06-17 | Nappe non tissee formee de filaments continus tres fins |
FR9607659 | 1996-06-17 |
Publications (2)
Publication Number | Publication Date |
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EP0814188A1 true EP0814188A1 (de) | 1997-12-29 |
EP0814188B1 EP0814188B1 (de) | 2003-09-24 |
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Application Number | Title | Priority Date | Filing Date |
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EP97108364A Expired - Lifetime EP0814188B1 (de) | 1996-06-17 | 1997-05-23 | Vliesstoff aus sehr feinen Endlosfilamenten |
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US (1) | US5899785A (de) |
EP (1) | EP0814188B1 (de) |
JP (1) | JPH1053948A (de) |
CN (1) | CN1093191C (de) |
BR (1) | BR9703602A (de) |
CA (1) | CA2208117C (de) |
DE (1) | DE69725051T2 (de) |
FR (1) | FR2749860B1 (de) |
TW (1) | TW348192B (de) |
ZA (1) | ZA975216B (de) |
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CN106536804A (zh) * | 2014-07-30 | 2017-03-22 | 沙特基础工业全球技术公司 | 纺粘法聚碳酸酯树脂过滤介质 |
CN106536804B (zh) * | 2014-07-30 | 2020-05-05 | 沙特基础工业全球技术公司 | 纺粘法聚碳酸酯树脂过滤介质 |
US10744435B2 (en) | 2014-07-30 | 2020-08-18 | Sabic Global Technologies B.V. | Spunbond polycarbonate resin filter media |
DE102016010163A1 (de) | 2016-08-25 | 2018-03-01 | Carl Freudenberg Kg | Technisches Verpackungsmaterial |
EP4506155A1 (de) | 2023-08-07 | 2025-02-12 | Carl Freudenberg KG | Verbundvliesstoff |
EP4506153A1 (de) | 2023-08-07 | 2025-02-12 | Carl Freudenberg KG | Verwendung eines textilen flächengebildes als kapillarer geotextilie |
Also Published As
Publication number | Publication date |
---|---|
EP0814188B1 (de) | 2003-09-24 |
TW348192B (en) | 1998-12-21 |
JPH1053948A (ja) | 1998-02-24 |
CN1171463A (zh) | 1998-01-28 |
DE69725051T2 (de) | 2004-07-15 |
FR2749860A1 (fr) | 1997-12-19 |
DE69725051D1 (de) | 2003-10-30 |
BR9703602A (pt) | 1998-11-10 |
FR2749860B1 (fr) | 1998-08-28 |
CN1093191C (zh) | 2002-10-23 |
CA2208117C (fr) | 2001-01-16 |
US5899785A (en) | 1999-05-04 |
ZA975216B (en) | 1998-01-05 |
CA2208117A1 (fr) | 1997-12-17 |
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