EP3867434A1 - Flame-retardant non-woven fibrous webs - Google Patents
Flame-retardant non-woven fibrous websInfo
- Publication number
- EP3867434A1 EP3867434A1 EP19872860.2A EP19872860A EP3867434A1 EP 3867434 A1 EP3867434 A1 EP 3867434A1 EP 19872860 A EP19872860 A EP 19872860A EP 3867434 A1 EP3867434 A1 EP 3867434A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- fibrous web
- polymer
- randomly
- melt
- 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.)
- Withdrawn
Links
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
- 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
- D04H1/542—Adhesive fibres
- D04H1/544—Olefin series
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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
- D04H3/16—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 thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
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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
- D04H1/42—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
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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
- D04H1/42—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
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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
- D04H1/42—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
- D04H1/43—Acrylonitrile series
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- 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
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- 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
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- D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/465—Hydraulic needling
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- 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
- D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/48—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
- D04H1/485—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation in combination with weld-bonding
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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
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
- D04H1/5418—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
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- 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
- D04H1/542—Adhesive fibres
- D04H1/55—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
- 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
- D04H1/559—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 the fibres being within layered webs
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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
- D04H1/56—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 in association with fibre formation, e.g. immediately following extrusion of staple fibres
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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
- D04H1/56—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 in association with fibre formation, e.g. immediately following extrusion of staple fibres
- D04H1/565—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 in association with fibre formation, e.g. immediately following extrusion of staple fibres by melt-blowing
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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
- D04H3/011—Polyesters
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- 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
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- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/06—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by welding-together thermoplastic fibres, filaments, or yarns
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
Definitions
- non-woven fibrous webs and related articles including melt-blown fibers, and methods for preparing and using such fibrous webs, articles, and assemblies.
- the non- woven fibrous webs can be used in thermal and acoustic applications.
- Non-woven articles capable of resisting high temperatures are of great interest in the aerospace, automotive, construction, transportation and electronics industries.
- High temperature resistant materials can be made from, for example, glass, basalt, and / or polyimide fibers. Such fibers can be formed into a non-woven web structure with a binder to provide structural integrity.
- Melamine foam, polyimide foam, and aramid felt materials are also known flame-retardant insulation materials.
- melt blowing is a manufacturing technology capable of making fibers with diameters of less than 10 micrometers, many times finer than a human hair. Fine fibers can help achieve high performance properties in many thermal, acoustic, absorbent, and filtration applications.
- non-woven fibrous combo webs made from a melt blowing microfiber fabrication process including a crystalline (co)polymer and a plurality of randomly- oriented staple fibers.
- the provided non-woven fibrous webs can be dimensionally stable at elevated temperatures, have very fine fibers for superior acoustic and thermal insulation properties, and display flame-retardant properties.
- the product prepared by the method can have a high flame-retardant performance and can make flame-retardant ultra-fine non-woven fibrous webs with the flame-retardant property of 94ULV-0 level, VTM-0 level and FAR25-856(a) level.
- a nonwoven fibrous web in a first aspect, includes greater than 0% but no greater than 30 wt% of a plurality of melt-blown fibers comprised of a crystalline (co)polymer; and at least 70 wt% of a plurality of randomly-oriented staple fibers, the plurality of randomly-oriented staple fibers comprising: at least 60 wt% of oxidized polyacrylonitrile fibers; and from 0 to 40 wt% of reinforcing fibers having an outer surface comprised of a (co) polymer with a melting temperature of from l00°C to 350°C;
- the plurality of melt-blown fibers and the plurality of randomly-oriented staple fibers are bonded together to form a cohesive non-woven fibrous web, optionally wherein the crystalline (co)poiymer exhibits a melting temperature from l00°C to 250°C.
- a nonwoven fibrous web in a second aspect, includes a cohesive nonwoven fibrous matrix comprising of a plurality of randomly-oriented staple fibers, the plurality of randomly-oriented staple fibers comprising: at least 60 wt% of oxidized polyacrylonitrile fibers; and from 0 to 40 wt% of reinforcing fibers having an outer surface comprised of a (co) polymer with a melting temperature of from l00°C to 350°C;
- the plurality of randomly-oriented staple fibers are bonded together to form the cohesive non-woven fibrous matrix; and a plurality of discrete domains of at least partially melted melt- blown fibers distributed within the cohesive nonwoven fibrous matrix, wherein the at least partially melted melt-blown fibers comprise a crystalline (co)polymer, optionally wherein the crystalline (co (polymer exhibits a melting temperature from l00°C to 250°C.
- a method of making a cohesive nonwoven fibrous web includes mixing a plurality of oxidized polyacrylonitrile fibers with a plurality of reinforcing fibers to form a mixture of randomly-oriented fibers, wherein the plurality of reinforcing fibers have outer fiber surfaces comprised of a (co)polymer with a melting temperature between l00°C and 350°C; combining the mixture of randomly-oriented fibers with a plurality of melt-blown fibers comprised of a crystalline (co)polymer to form nonwoven fibrous web; and heating the mixture of randomly-oriented fibers combined with the plurality of melt-blown fibers to a temperature sufficient to melt the outer surfaces of the plurality of reinforcing fibers; optionally wherein the crystalline (co)polymer exhibits a melting temperature from l00°C to 250°C.
- FIGS. 1-2 are a side, cross-sectional views of a non-woven fibrous web assemblies according to respective exemplary embodiments.
- FIG 3 is a microscopic image of a non-woven fibrous web assemblies according to one exemplary embodiment.
- “Ambient conditions” means at 25°C and 101.3 kPa (1 atm) pressure.
- “Ambient temperature” means at 25°C.
- Basis weight is calculated as the weight of a 10 cm x 10 cm web sample multiplied by 100, and is expressed in grams per square meter (gsm).
- “Bulk density” is the mass per unit volume of a non-woven fibrous web.
- Copolymer refers to polymers made from repeat units of two or more different polymers and includes random, block and star (e.g. dendritic) copolymers.
- “Dimensionally stable” refers to a structure that resists shrinkage when subjected to elevated temperatures for a given period of time, where elevated temperatures can be
- Die means a processing assembly including at least one orifice for use in polymer melt processing and fiber extrusion processes, including but not limited to melt-blowing.
- “Discontinuous” when used with respect to a fiber or plurality of fibers means fibers having a limited aspect ratio (e.g., a ratio of length to diameter of e.g., less than 10,000).
- Median fiber diameter of fibers in a non-woven fibrous web is determined by producing one or more images of the fiber structure, such as by using a scanning electron microscope; measuring the transverse dimension of clearly visible fibers in the one or more images resulting in a total number of fiber diameters; and calculating the median fiber diameter based on that total number of fiber diameters.
- Melting temperature for a polymer represents the temperature at which a polymer changes state from a solid to a liquid, and can be determined as the peak maximum of a first-heat total-heat flow plot obtained using modulated differential scanning calorimetry, occurring in the melting region of the polymer or fiber if there is only one maximum in the melting region; and, if there is more than one maximum indicating more than one melting point (e.g., because of the presence of two distinct crystalline phases), as the temperature corresponding to the highest- amplitude melting peak.
- Non-woven fibrous web means a plurality of fibers characterized by entanglement or inter-fiber bonding of the fibers to form a sheet or mat exhibiting a structure of individual fibers or filaments which are interlaid, but not in an identifiable manner as in a knitted fabric.
- Oriented when used with respect to a fiber means that at least portions of the polymer molecules within the fibers are aligned with the longitudinal axis of the fibers, for example, by use of a drawing process or attenuator upon a stream of fibers exiting from a die.
- “Substantially” means a majority of, or mostly, as in an amount of at least 50%, 60, 70,
- the non-woven fibrous web 100 of the present disclosure contain greater than 0% but no greater than 30 wt% of a plurality of melt-blown fibers 110 formed from a crystalline (co)polymer and at least 70 wt% of a plurality of randomly-oriented staple fibers 120.
- the plurality of melt-blown fibers and the plurality of randomly-oriented staple fibers are bonded together to form a cohesive non-woven fibrous web.
- Melt-blown fibers can increase the surface area so that to increase the acoustic absorption properties of the non-woven fibrous webs.
- the non-woven fibrous web 200 of the present disclosure can contain a cohesive nonwoven fibrous matrix comprising of a plurality of randomly-oriented staple fibers 220 and a plurality of discrete domains 230 of at least partially melted melt-blown fibers distributed within the cohesive nonwoven fibrous matrix.
- the plurality of randomly-oriented staple fibers are bonded together to form the cohesive non-woven fibrous matrix.
- the at least partially melted melt-blown fibers can be formed from a crystalline (co)polymer.
- plurality of discrete domains 230 of at least partially melted melt-blown fibers can bind to the cohesive nonwoven fibrous matrix so that the discrete domains 230 of at least partially melted melt-blown fibers can be remain in the non-woven fibrous web when the non-woven fibrous web is moved, transported, or shaked.
- Exemplary crystalline (co)polymer can include polyolefins such as polypropylene and polyethylene, polybutylene, polyisobutylene, poly(4-methyl-l-pentene), polyurethane, polybutene, polylactic acid, polyphenylene sulfide, polysulfone, liquid crystalline polymer, polyethylene-co-vinylacetate, polyacrylonitrile, cyclic polyolefins, along with copolymers and blends thereof.
- polyolefins such as polypropylene and polyethylene, polybutylene, polyisobutylene, poly(4-methyl-l-pentene), polyurethane, polybutene, polylactic acid, polyphenylene sulfide, polysulfone, liquid crystalline polymer, polyethylene-co-vinylacetate, polyacrylonitrile, cyclic polyolefins, along with copolymers and blends thereof.
- the crystalline (co)polymer preferably has an intrinsic viscosity (IV) suitable for preparation of fine fibers in a melt blowing process.
- the intrinsic viscosity of a given polymer is defined as the limiting value of the reduced viscosity, or inherent viscosity, at infinite dilution of the polymer. This parameter can be correlated with the melting point, crystallinity and tensile strength of the polymer.
- Various methods can be used to determine intrinsic viscosity. For example, intrinsic viscosity can be measured using a Ubbelohde viscometer or obtained by measuring melt flow index of the polymer using an extrusion plastometer and correlating the melt flow index to intrinsic viscosity based on internal calibration curves of the equipment.
- Intrinsic viscosity can be in the range of from 0.4 to 0.7, from 0.4 to 0.6, from 0.4 to 0.5, or in some embodiments, less than, equal to, or greater than 0.4, 0.42, 0.45, 0.47, 0.5, 0.52, 0.55, 0.57, 0.6, 0.62, 0.65, 0.67, or 0.7.
- the crystalline (co)polymer can exhibit a melting temperature from l00°C to 250°C, from l00°C to 200°C, or in some embodiments, less than, equal to, or greater than l00°C, l20°C, l40°C, l50°C, l60°C, l70°C, l80°C, l90°C, 200°C, 2lO°C, 220°C, 230°C, 240°C, or 250°C.
- the median fiber diameter of the plurality of melt-blown fibers in the non-woven fibrous web can be engineered to provide properties desired in the end application.
- the minimum fiber diameters achievable are at least partially dependent on the melt viscosities of the polymers used to form the fibers.
- these fibers can have a median diameter of from 0.2 micrometers to 20 micrometers, from 0.5 micrometers to 15 micrometers, from 1 micrometers to 20
- micrometers from 1 micrometers to 10 micrometers, or in some embodiments, less than, equal to, or greater than 0.2 micrometers, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 micrometers.
- Fine melt-blown fibers are of great technical benefit in thermal and acoustic insulation applications.
- the high surface area per unit volume results in enhanced viscous dissipation of sound energy within the non-woven fibrous web.
- the fine fibers trap air and block radiant heat loss, making the non-woven fibrous web an effective insulator.
- the provided non-woven fibrous webs can have a wide range of bulk densities.
- the provided webs can display a bulk density of from 1 kg/m 3 to 1000 kg/m 3 , 1 kg/m 3 to 100 kg/m 3 , 1 kg/m 3 to 50 kg/m 3 , or in some embodiments, less than, equal to, or greater than 1 kg/m 3 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 17, 20, 25, 30, 35, 40, 45, 50,
- Average bulk density has significant bearing on the insulation performance of the non- woven fibrous web.
- the non-woven fibrous web has a basis weight of from 100 gsm to 500 gsm, 150 gsm to 450 gsm, 200 gsm to 400 gsm, or in some embodiments less than, equal to, or greater than 100, 150, 200, 250, 300, 350, 400, or 450 gsm.
- the non-woven fibrous web has a thermal conductivity coefficient of less than 0.04, 0.03, 0.02, 0.01 W/K-m at 25°C in its relaxed configuration.
- the non-woven fibrous web has a sound absorption coefficient of 0.2 to 0.99, or in some embodiments less than, equal to, or greater than 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 0.99 at lOOOHz at normal sound incidance.
- the plurality of randomly-oriented staple fibers can be present in any amount suitable to obtain the degree of flame retardancy desired and obtain acceptable fibers diameter in the melt blowing manufacturing process for a given raw materials cost. While not particularly restricted, the amount of randomly-oriented staple fibers present can be in an amount ranging greater than 70 wt%, 75, 80, 90 or 95 wt%, based on the overall weight of the nonwoven fibrous web. Often, randomly-oriented staple fibers are significantly thicker than the melt-blown fibers to provide mechanical reinforcement. Incorporation of randomly-oriented staple fibers can provide many potential benefits to the web, including increased loft (or lower density), resilience, and/or strength. These fibers can also improve the thermal or acoustic insulation properties of the web.
- randomly-oriented staple fibers can be made from non-meltable materials.
- Non-meltable materials do not become a liquid at any temperature and may be polymeric or non-polymeric. Many of these materials do not melt because they oxidize or otherwise degrade first when heated in the presence of air.
- Non-meltable polymeric fibers can include carbon fibers, carbon fiber precursors, or a combination thereof. If incorporated in sufficient amounts, these randomly-oriented staple fibers can significantly enhance the flame retardancy of the overall web.
- Carbon fiber precursors can include oxidized acrylic precursors, such as oxidized polyacrylonitrile.
- Polyacrylonitrile is a useful acrylic precursor that can be used widely to produce the carbon fibers.
- the polyacrylonitrile contains more than 60 wt%, 70 wt%, more than 75 wt%, more than 80 wt%, or more than 85 wt% acrylonitrile repeat units.
- the non-meltable fibers are comprised of oxidized
- the oxidized polyacrylonitrile fibers can include, for example, those available under the trade designations PYRON (Zoltek Corporation, Bridgeton, MO) and PANOX (SGL Group, Meitingen, Germany).
- Oxidized polyacrylonitrile fibers can be made from precursor fibers containing a copolymer of acrylonitrile and one or more co-monomers.
- Useful co-monomers include, for example, methyl methacrylate, methyl acrylate, vinyl acetate, and vinyl chloride.
- the co- monomer(s) may be present in an amount of up to 15 wt%, 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, or 8 wt%, relative to the overall weight of the monomer mixture prior to copolymerization.
- the precursor fibers can be oxidized in a multi-step process.
- the fibers are initially stabilized at high temperatures to prevent melting or fusion of the fibers, then carbonized to eliminate the non-carbon elements, and finally graphitized at even higher temperatures to enhance the mechanical properties of the fibers.
- Oxidized polyacrylonitrile fibers include polyacrylonitrile fibers that are either partially or fully oxidized, and may or may not be graphitized.
- the randomly-oriented staple fibers can have a fiber diameter and length that enables the fibers to become entangled within the non-woven fibrous web.
- the fibers are preferably not so thin that web strength is unduly compromised.
- the randomly-oriented staple fibers can have a median fiber diameter in the range from 5
- micrometers to 1000 micrometers from 5 micrometers to 300 micrometers, from 5 micrometers to 100 micrometers, or in some embodiments, less than, equal to, or greater than 5 micrometer,
- the randomly-oriented staple fibers can have an average fiber length in the range from 3 millimeters to 100 millimeters, from 15 millimeters to 100 millimeters, from 25 millimeters to 75 millimeters, or in some embodiments, less than, equal to, or greater than 3, 5, 10 millimeters, 12, 15, 17, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 millimeters.
- the plurality of randomly-oriented staple fibers can include from 0 to 40 wt% of reinforcing fibers.
- the reinforcing fibers may include binder fibers, which have a sufficiently low melting temperature.
- Binder fibers are generally polymeric, and may have uniform composition or contain two or more components.
- the binder fibers are bi- component fibers comprised of a core polymer that extends along the axis of the fibers and is surrounded by a cylindrical shell polymer.
- the shell polymer can have a melting temperature less than that of the core polymer.
- the reinforcing fibers can include at least one of monocomponent or multi-component fibers.
- the reinforcing fiber can include polyethylene terephthalate, polyphenylene sulfide, poly-aramide, polylactic acid.
- the reinforcing fibers can be multicomponent fibers having an outer shealth comprising polyolefin.
- the polyolefin can be selected from the group consisting of polyethylene fibers, polypropylene fibers, polybutylene fibers, polyisobutylene fibers, poly(4-methyl-l- pentene), and combinations thereof.
- melting refers to a gradual transformation of the fibers or, in the case of a bi-component shell/core fiber, an outer surface of the fiber, at elevated temperatures at which the polyester becomes sufficiently soft and tacky to bond to other fibers with which it comes into contact, including oxidized polyacrylonitrile fibers and any other binder fibers having its same characteristics and, as described above, which may have a higher or lower melting temperature.
- Useful binder fibers have an outer surface comprised of a (co) polymer having a melting temperature of from l00°C to 450°C, l00°C to 350°C or in some embodiments, less than, equal to, or greater than, l00°C, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 325, 350, 375, 400, 425°C.
- a (co) polymer having a melting temperature of from l00°C to 450°C, l00°C to 350°C or in some embodiments, less than, equal to, or greater than, l00°C, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240,
- any meltable fibers present can be blended with flame-retardant randomly- oriented staple fibers.
- thermal and acoustic applications include, for example, battery compartments for electric vehicles, engine compartments, automotive vehicle doors and ceilings, railway car insulation applications such as under window and floor treatments in trains, automotive trunks, automotive under hood applications, building and utility wraps, furniture upholstery, exit walkways on aircraft or in buildings, heating ventilation and air conditioning (HVAC) systems, rotorcraft cabins, and aerospace fuselages.
- HVAC heating ventilation and air conditioning
- the provided non-woven fibrous webs and assemblies display numerous advantages, at least some of which are unexpected. These materials can be used in thermal and acoustic insulation applications at high temperatures where conventional insulation materials would thermally degrade or fail. Particularly demanding are automotive and aerospace vehicle applications, where insulation materials operate in environments that are not only noisy but can reach extreme temperatures.
- the provided webs are capable of passing standardized flammability and flame propagation tests used in regulated industries such as automotive and aerospace vehicles.
- a 20-millimeter thick sample of the non-woven fibrous web is capable of passing one or more of the flammability tests UL 94 V0, FAR 25.853(a), and FAR 25.856(a).
- the provided non-woven fibrous webs can provide acoustic absorption over a wide range of frequencies.
- the ratio of the absorbed sound energy to the incident energy represents a sound absorption coefficient.
- a 400 gsm sample of the provided web can, in various embodiments, display a sound absorption coefficient that is greater than 0.2, greater than 0.3, greater than 0.4, or in some embodiments, less than, equal to, or greater than 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7 or 0.8, 0.9 at normal sound incidence, for example, an acoustic frequency of 1000 Hz when tested under ambient conditions.
- Melt-blown fibers are formed from a crystalline (co)polymer using a melt blowing process.
- a melt-blowing process one or more a crystalline (co)polymer streams are extruded through a die containing closely arranged orifices and attenuated by convergent streams of hot air at high velocities to form fine fibers. These fine fibers can be collected on a surface to provide a melt- blown non-woven fibrous web.
- the collected fibers can be semi-continuous or essentially discontinuous.
- the melt-blown fibers of the present disclosure may be oriented on a molecular level.
- at least some of the plurality of fibers in the non-woven fibrous web are physically bonded to each other through heat and pressure applied or by calendering.
- the process includes providing to a melt-blowing die a molten stream of a thermoplastic material including at least one thermoplastic semicrystalline polymer and subjecting the at least one fiber immediately upon exiting the melt-blowing die and prior to collection as a non-woven fibrous web on a collector, to a controlled in-flight heat treatment operation at a temperature below a melting temperature of the at least one thermoplastic semi crystalline polymer for a time sufficient for the non-woven fibrous web to exhibit a Shrinkage less than a Shrinkage measured on an identically-prepared structure that is not subjected to the controlled in-flight heat treatment operation.
- Randomly-oriented staple fibers can be generally obtained from bulk fibers.
- One technical challenge with incorporating randomly-oriented staple fibers into a non-woven fibrous web arises out of difficulties in handling and feeding these fibers into a large-scale manufacturing process. This is especially problematic when dealing with non-meltable fibers such as oxidized polyacrylonitrile fibers which tend to be weakly entangled and can unravel easily in bulk form.
- a pre-formed feed web could be obtained by blending oxidized polyacrylonitrile fibers having a median fiber diameter in the range of 5 micrometers to 15 micrometers and polyethylene terephthalate staple fibers having a median fiber diameter in the range of 30 micrometers to 60 micrometers.
- polyethylene terephthalate staple fibers provides significant strength to the feed web.
- the blended fibers can be substantially entangled with each other using a process such as needle tacking or hydroentangling.
- these fibers are crimped to provide greater web thickness and reduce bulk density. Details in the process of making these webs are described in co-pending International Patent Application No. PCT/CN2017/ 110372 (Cai, et ak).
- melt-blown microfiber web can be made according to any of the methods described in U.S. Patent Nos. 4,118,531 (Hauser); 5,298,694 (Thompson et ak); 5,773,375 (Swan, et ak); 5,961,905 (Swan, et ak); and 7,476,632 (Olson, et ak).
- flow stream of a crystalline (co)polymer is fed into a manifold.
- the flow stream is then fed into the die and through a series of die orifices.
- Air slots are disposed on either side of the die orifices and direct uniform heated air at high velocities at the extruded melt stream.
- the hot high velocity air draws and attenuates the extruded polymeric material which solidifies after traveling a relatively short distance from the die.
- the high velocity air becomes turbulent between the die and the collector surface causing the melt-blown fibers entrained in the airstream to become intimately mixed.
- this mixed stream of melt- blown fibers is blended with randomly-oriented staple fibers from the feed web, which can be continuously plucked from a leading edge of the feed web by a rotating lickerin roll.
- the plucked randomly-oriented staple fibers are directed into the turbulent airstream, where it is uniformly dispersed and distributed along with the melt-blown fibers and eventually gathered on a perforated collector drum or mesh belt to provide a coherent non-woven web.
- a subsequent activation process can be used to bind meltable fibers to each other at points of inter-fiber contact. This can be achieved by passing the web through an oven heated to a temperature at or above the softening point of the meltable fibers or the meltable sheath of the shear/core plurality of reinforcing fibers, if used.
- Such inter-fiber bonded webs can have increased physical integrity and tensile strength as a result of the additional bonds formed between fibers.
- a nonwoven fibrous web comprising greater than 0% but no greater than 30 wt% of a plurality of melt-blown fibers comprised of a crystalline (co)polymer; and at least 70 wt% of a plurality of randomly-oriented staple fibers, the plurality of randomly-oriented staple fibers comprising: at least 60 wt% of oxidized polyacrylonitrile fibers; and from 0 to 40 wt% of reinforcing fibers having an outer surface comprised of a (co) polymer with a melting temperature of from l00°C to 350°C; wherein the plurality of melt-blown fibers and the plurality of randomly-oriented staple fibers are bonded together to form a cohesive non-woven fibrous web, optionally wherein the crystalline (co)polymer exhibits a melting temperature from l00°C to 250°C.
- polyolefin fibers are selected from the group consisting of polyethylene fibers, polypropylene fibers, polybutylene fibers, polyisobutylene fibers, poly(4-methyl-l-pentene), and combinations thereof.
- nonwoven fibrous web of any one of embodiments 1-8 wherein the non-woven fibrous web has a sound absorption coefficient of greater than 0.08 at lOOOHz at normal sound incidence.
- the nonwoven fibrous web of any one of embodiments 1-9 wherein the non- woven fibrous web has a base weight of from 100 gsm to 500 gsm.
- An article comprising the nonwoven fibrous web of any one of embodiments 1-10, wherein the article is an acoustic insulation article, a thermal insulation article, or combinations thereof.
- a non-woven fibrous web comprising a cohesive nonwoven fibrous matrix comprising of a plurality of randomly-oriented staple fibers, the plurality of randomly-oriented staple fibers comprising: at least 60 wt% of oxidized polyacrylonitrile fibers; and
- reinforcing fibers having an outer surface comprised of a (co) polymer with a melting temperature of from l00°C to 350°C; wherein the plurality of randomly-oriented staple fibers are bonded together to form the cohesive non-woven fibrous matrix; and a plurality of discrete domains of at least partially melted melt-blown fibers distributed within the cohesive nonwoven fibrous matrix, wherein the at least partially melted melt-blown fibers comprise a crystalline (co)polymer, optionally wherein the crystalline (co)poiymer exhibits a melting temperature from l00°C to 250°C.
- a method of making a cohesive nonwoven fibrous web comprising: mixing a plurality of oxidized polyacrylonitrile fibers with a plurality of reinforcing fibers to form a mixture of randomly-oriented fibers, wherein the plurality of reinforcing fibers have outer fiber surfaces comprised of a (co)polymer with a melting temperature between l00°C and 350°C; combining the mixture of randomly-oriented fibers with a plurality of melt-blown fibers comprised of a crystalline (co)polymer to form nonwoven fibrous web; and heating the mixture of randomly- oriented fibers combined with the plurality of melt-blown fibers to a temperature sufficient to melt the outer surfaces of the plurality of reinforcing fibers; optionally wherein the crystalline (co)polymer exhibits a melting temperature from l00°C to 250°C.
- UL94-V0 Flame Test Reference to UL94-V0 standard with flame height 20-mm, bottom edge of the sample lO-mm into the flame and burn twice at 10 seconds each. A flame propagation height under l25-mm (5 inches) was considered a pass.
- Normal Incident Acoustical Absorption Test Normal incident acoustical absorption was tested according to ASTM E1050-12,“Standard Test Method for Impedance and Absorption of Acoustical Materials Using a Tube, Two Microphones and a Digital Frequency Analysis System”. An“IMPEDANCE TUBE KIT (50 HZ - 6.4 KHZ) TYPE 4206” available from Bruel & Kjser (Denmark) was used. The normal incident absorption coefficient was reported, using the abbreviation“a”.
- Step 1 Staple Fiber Preparation
- Blends of OP AN, LENZING, T270, and T270 as represented in Table 1 were combined on a RANDO-WEBBER from Rando Machine Corporation of Ard, NY. United States to produce staple fiber webs.
- the basis weight for each sample was 130 gsm.
- the webs were then folded (changing basis weight to 260 gsm) and conveyed into a Dilo Needle Loom, Model DI- Loom OD-l 6 from Eberbach, Germany having a needleboard array of 23 rows of 75
- the needles were Foster 20 3-22-1.5B needles.
- the array was roughly 17.8 cm (7 inches) deep in the machine direction and nominally 61 cm (24 inches) wide with needle spacings of roughly 7.6-mm (0.30 inch).
- the needleboard was operated at 91 strokes/minute to entangle and compact the web to a roughly 5. l-mm (0.20 inch) thickness.
- Sample webs were produced by processes and techniques described in the commonly owned PCT Patent Publication No. WO 2015/080913 (Zillig et al) with exception that the in-flight heat treatment step was not performed.
- Sample fiber weight percentages to produce the webs and the resulting basis weights are represented in Table 1.
- Air heater (operating at 1 lOkW obtained from Sylvania of Danvers, MA. United States) temperatures were set at 375°C (707°F) and die/neck tube temperature were set at 320°C (608°F).
- Examples 1-5 underwent UL94-V0 Flame testing and the results are represented in Table 2.
- Example 4 also underwent Thermal Conductivity and Normal Incident Acoustical Absorption testing. At 1 l.5°C (52.7°F) and 20°C (68°F), thermal conductivity results were 0.0270 W/K-m and 0.0283 W/K-m respectfully. Normal Incident Acoustical Absorption test results are represented in Table 3.
- 3M THINSEILATE TAI 2099 (200 gsm, 8 mm thickness) obtained from 3M Company of St. Paul, MN. ETnited States underwent Normal Incident Acoustical Absorption testing and the results are represented in Table 3.
- Table 3 Normal Incident Acoustical Absorption Test Results
- Example 4 A sample identically constructed as described in Example 4 was heated in an oven for three minutes at 232.2°C (450°F). A microscopic image highlighting the randomly-oriented staple fibers bonded to the melt-blown fibers to form a cohesive non-woven fibrous web was captured immediately upon removal from the oven and the image is represented in FIG. 3.
Abstract
Description
Claims
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PCT/IB2019/058525 WO2020079525A1 (en) | 2018-10-16 | 2019-10-07 | Flame-retardant non-woven fibrous webs |
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CA1073648A (en) | 1976-08-02 | 1980-03-18 | Edward R. Hauser | Web of blended microfibers and crimped bulking fibers |
US5441550A (en) * | 1992-03-26 | 1995-08-15 | The University Of Tennessee Research Corporation | Post-treatment of laminated nonwoven cellulosic fiber webs |
US5298694A (en) | 1993-01-21 | 1994-03-29 | Minnesota Mining And Manufacturing Company | Acoustical insulating web |
US5773375A (en) | 1996-05-29 | 1998-06-30 | Swan; Michael D. | Thermally stable acoustical insulation |
US6129301A (en) | 1997-05-23 | 2000-10-10 | Verbatim Corporation | Molded roller for tape cartridge |
CA2402598A1 (en) * | 2000-03-13 | 2001-09-20 | Steven Ogle | Method for forming fire combustion modified batt |
US7279440B2 (en) | 2002-05-20 | 2007-10-09 | 3M Innovative Properties Company | Nonwoven amorphous fibrous webs and methods for making them |
US7476632B2 (en) | 2002-11-15 | 2009-01-13 | 3M Innovative Properties Company | Fibrous nonwoven web |
US9139940B2 (en) | 2006-07-31 | 2015-09-22 | 3M Innovative Properties Company | Bonded nonwoven fibrous webs comprising softenable oriented semicrystalline polymeric fibers and apparatus and methods for preparing such webs |
US7989372B2 (en) * | 2007-06-22 | 2011-08-02 | 3M Innovative Properties Company | Molded respirator comprising meltblown fiber web with staple fibers |
JP6508942B2 (en) | 2011-12-22 | 2019-05-08 | スリーエム イノベイティブ プロパティズ カンパニー | Melt blow process, low shrinkage melt blow polymer fibers and fiber structures, and melt blowable polymer compositions |
CN105765124B (en) | 2013-11-26 | 2019-02-19 | 3M创新有限公司 | Meltblown nonwoven fibrous structure of dimensionally stable and preparation method thereof and equipment |
JP6362400B2 (en) * | 2014-05-02 | 2018-07-25 | スリーエム イノベイティブ プロパティズ カンパニー | Nonwoven web |
CN106574413B (en) * | 2014-06-26 | 2019-06-28 | 3M创新有限公司 | Thermostabilization nonwoven webs comprising being meltblown polymer blend fiber |
JP6817709B2 (en) * | 2016-03-11 | 2021-01-20 | スリーエム イノベイティブ プロパティズ カンパニー | Vehicle parts |
JP2020503464A (en) * | 2016-12-29 | 2020-01-30 | スリーエム イノベイティブ プロパティズ カンパニー | Dimensionally stable refractory meltblown fibers and nonwoven structures comprising flame retardant polymers |
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2019
- 2019-10-07 EP EP19872860.2A patent/EP3867434A4/en not_active Withdrawn
- 2019-10-07 CN CN201980066694.XA patent/CN112840074A/en active Pending
- 2019-10-07 WO PCT/IB2019/058525 patent/WO2020079525A1/en unknown
- 2019-10-07 US US17/250,645 patent/US20220396903A1/en not_active Abandoned
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US20220396903A1 (en) | 2022-12-15 |
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