CN102918191A - Process for making nonwoven webs - Google Patents

Process for making nonwoven webs Download PDF

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Publication number
CN102918191A
CN102918191A CN2011800159900A CN201180015990A CN102918191A CN 102918191 A CN102918191 A CN 102918191A CN 2011800159900 A CN2011800159900 A CN 2011800159900A CN 201180015990 A CN201180015990 A CN 201180015990A CN 102918191 A CN102918191 A CN 102918191A
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CN
China
Prior art keywords
additive
zinc
bromine
iodine
nitro
Prior art date
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Pending
Application number
CN2011800159900A
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Chinese (zh)
Inventor
L.克里什纳墨菲
J.C.里特
J.M.波利诺
M.T.波蒂格尔
J.C.豪
D.M.小劳拉
H.V.萨米尔森
R.J.杜夫
Z-Z.黄
Z.殷
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of CN102918191A publication Critical patent/CN102918191A/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D04H3/14—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 yarns or filaments produced by welding
    • D04H3/147—Composite yarns or filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • 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
    • 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
    • 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

Abstract

A nonwoven web comprising bicomponent fibers. The fibers have continuous phases each of a first polyarylene sulfide (PAS) component and a polymer component. The polymer component may also be a second polyarylene sulfide. The first polyarylene sulfide component contains a tin or a zinc additive or both, and the first polyarylene sulfide component of any given fiber is at least partially exposed to the external surface of that fiber.

Description

The method for preparing nonwoven web
Invention field
The present invention relates to prepare nonwoven web, relate to the fibroreticulate method that preparation is formed by poly arylidene thio-ester specifically.
Background of invention
The physical characteristic of known fiber net can be improved by rolling, and it is to make sheet material pass the process of roll gap to give the smooth smooth outward appearance of sheet material or in other words to improve selected physical characteristic between roller or the plate.
By calendering paper wood or other fibrous material, trial further improves the quality of the paper wood that forms or stable quality level is provided, so that make the higher or volume increase of the speed of service of paper wood.As everyone knows, the plasticity of paper wood or fiber or molding trend can increase by the plasticizer loading that improves temperature and/or paper wood or fiber.When the temperature of the polymer that comprises in the paper wood rises to or exceeds so-called glass transition temperature (T.sub.g), larger variation occurs in the mechanical property that comprises plasticity, and be easier to molding or formation when described material may be lower than this temperature than it subsequently or finish this moment.
Many bondedfibre fabrics are combined to give fabric integrity.Can for utilizing, in nonwoven industry, exercise the method that is thermally bonded in input research and the quantity of developing new product and time upper reaches although there is multiple combination technology.These methods are approved widely that this is to have a plurality of advantages because they use simple and compare the traditional chemical associated methods.Attractive characteristic comprises low energy consumption and the low cost of raw material, the productive rate of raising and the flexibility of product.Owing to do not use adhesive, therefore simplified used chemicals, reduced the problem of environmental correclation.United States Patent (USP) 4,035,219 and United States Patent (USP) 5,424,115 example of point bonding nonwoven web with the strengthening physical characteristic is provided.
Authorize the United States Patent (USP) 2,277,049 of Reed and introduced the use fusible fibers to make the imagination of bondedfibre fabric, it is by fusible the carrying out with non-fus fiber and with solvent or by the heat treated fiber web of the similar DENIER of blend and Cutting Length.Fusible fibers become be clamminess and use as adhesive.Obtain bondedfibre fabric in extruding and after cooling off the described fiber web that is clamminess.
Use is harmful to fibroreticulate quality near the temperature of the fusing point Tm of fiber in nanometer fiber net.Less fiber is tending towards producing inhomogeneous melting and bonding with non-uniform heat flux intrinsic in calender and causes described fiber web effectiveness in filtration and battery separators and other energy storage application to reduce.In EP 1 042 549 illustration at the low basic weight of prior art and comprise defective in the reinforcing fiber net field of little denier fiber, wherein the thermal in the pattern is for generation of the fiber web that is difficult to be out of shape.
The present invention has overcome former preparation by a kind of method and has rolled defective in the fibroreticulate method, and the method provides high-strength products so far under the lower condition of harsh degree.
Summary of the invention
The present invention relates to comprise the nonwoven web of bicomponent fiber, described fiber comprises in the first poly arylidene thio-ester (PAS) component and the polymers compositions continuous phase of each, wherein said the first polyarylene sulfide component comprises tin or zinc additive or the two all to be had, and the first polyarylene sulfide component of any given fiber is exposed to the outer surface of this fiber at least in part." partly expose " and refer to that at least a portion of described component appears on the outer surface of described fiber.The whole outer surface of described fiber can be a PAS component, also can surround at least in part described polymers compositions.
The present invention also relates to the improvement method for the manufacture of nonwoven web, said method comprising the steps of: be nonwoven web with the bicomponent fiber spinning (i), described fiber comprises in the first polyarylene sulfide component and the polymers compositions continuous phase of each, wherein said the first polyarylene sulfide component comprises tin or zinc additive or the two all to be had, and the first polyarylene sulfide component of any given fiber is exposed to the outer surface of this fiber at least in part, and (ii) rolls described nonwoven web with filamentary at least one subset that bonds.In a particular, calendering nonwoven web regular hour and temperature, its filamentary at least one subset that is enough to bond.
Detailed Description Of The Invention
When indefinite article " " or " a kind of " are used for statement or describe the step that the inventive method exists, should understand, unless opposite statement or description clearly is provided, and the use of this type of indefinite article is not restricted to one with the number of steps that exists in the described method.
When this paper described number range, except as otherwise noted, described scope was intended to comprise its end points, and all integers and mark in the described scope.Cited occurrence when not being intended to limit the scope of the present invention to limited range.
Definition
As used herein, term " spun-bonded fibre " refers to the fiber that diameter is less, it forms by the following method: molten thermoplastic is extruded from a plurality of tiny capillaries with spinning head of common circle with the form of long filament, the diameter of wherein extruding long filament reduces fast, as be described in such as the United States Patent (USP) 4 of authorizing the people such as Appel, 340,563 and authorize the people's such as Dorschner United States Patent (USP) 3,692,618, authorize the people's such as Matsuki United States Patent (USP) 3,802,817, authorize the United States Patent (USP) 3 of Kinney, 338,992 and 3,341,394, authorize the people's such as Dobo United States Patent (USP) 3, in 542,615 described like that, each all is incorporated herein by reference described patent in full.
As used herein, term " meltblown fibers " refers to the fiber that forms by the following method: make molten thermoplastic with the form of molten thread or long filament by many tiny, be generally circular die capillaries and enter in high-speed gas (for example air) logistics of gathering, this is so that the long filament of molten thermoplastic attenuates to reduce their diameter, and described diameter can be the microfiber diameter.Afterwards, meltblown fibers carries and is deposited on the surperficial fiber web of going up with the meltblown fibers that forms random dispersion of collection by the high-speed gas logistics.In a plurality of patents and publication, disclose this class methods, comprised NRL Report 4364, " the Manufacture of Super-Fine Organic Fibers " of B.A.Wendt, E.L.Boone and D.D.Fluharty; NRL Report 5265, " the An Improved Device For The Formation of Super-Fine Thermoplastic Fibers " of K.D.Lawrence, R.T.Lukas, J.A.Young; And be published on November 19th, 1974, and authorize the people's such as Butin United States Patent (USP) 3,849,241, this full patent texts is incorporated herein by reference.
As used herein, term " multicomponent fibre " refers to the fiber that formed by at least two kinds of component polymer, perhaps by the same polymer with different qualities or additive from the extruder that separates, extrude, but be woven in the fiber that forms together a kind of fiber.Multicomponent fibre also refers to conjugate fibre or bicomponent fiber sometimes.Polymer is disposed in the zones of different of stationary positioned basically, the cross section of described regional cross multicomponent fibre and always extending along the length of multicomponent fibre.The configuration of this type of multicomponent fibre can be for example skin/core pattern arrangement, wherein a kind of polymer surrounds another kind of polymer, perhaps can be arrangement arranged side by side, this is a kind of " fabric of island-in-sea type " arranged, and perhaps is arranged to cake-wedge shape or stripe-shaped at circular, oval or rectangular cross section fiber.Multicomponent fibre is set forth in such as the United States Patent (USP) 5,108,820 of authorizing the people such as Kaneko, authorizes the people's such as Strack United States Patent (USP) 5,336,552 and authorize in the people's such as Pike the United States Patent (USP) 5,382,400.For bicomponent fiber, described polymer can exist by the ratio of any expectation.
As used herein, term " biconstitutent fibre " or " multi-constituent fibre " refer to the fiber that formed by at least two kinds of polymer, perhaps refer to the fiber that formed by the same polymer with different qualities or additive, it is extruded with blend from identical extruder, and wherein said polymer is not disposed in the zones of different of stationary positioned basically, the cross section of described regional cross multicomponent fibre.The fiber of this general type is discussed in the United States Patent (USP) 5,108,827 of for example authorizing Gessner to some extent.
As used herein, term " nonwoven web " or " non-woven material " refer to have the fiber web of individual fibers or the filament structure of alternating layers, but are not the forms consistent with form in knitting or the Woven fabric.For example meltblown, spun-bond process, air lay method and carding method form nonwoven web by several different methods.Usually with ounce per square yard (osy) or g/m (gsm) expression, available fibre diameter represents with micron the basic weight of supatex fabric usually.(note, convert osy to gsm and can multiply by 33.91 with osy).
" partly surround " refers to that a kind of component in bi-component or the multicomponent fibre surrounds second component at least in part.A kind of component also can appear on the outer surface of described fiber.
" calendering " refers to fiber web is passed the process of two roll gaps between the roller.Roller can contact with each other, and perhaps fixing or variable gap can be arranged between the roller surface.Advantageously, in this calender line, roll gap forms between soft roller and hard roller." soft roller " refers at the roller that meeting is out of shape under the applied pressure in order to keep two rollers to contact in calender." hard roller " is the roller that has such as lower surface, and distortion that technique or product are made a significant impact can not occur under operation pressure on this surface.Hard roller can have pattern thereon at quarter, and perhaps it can be patternless." patternless " roller refers to have the roller of smooth surface in the process of making them.When fiber web when the roll gap, be different from a bond roll, not point or pattern can be on fiber web pattern generation specially.
Poly arylidene thio-ester (PAS) comprises straight chain, side chain or the cross-linked polymer that comprises the arylene sulfide ether unit.Poly arylidene thio-ester polymer and synthetic be well known in the art in addition also commercially available acquisition of this base polymer.
Available exemplary poly arylidene thio-ester comprises the poly arylidene thio-ester of the recurring unit that comprises following formula among the present invention :-[(Ar 1) n-X] m-[(Ar 2) i-Y] j-(Ar 3) k-Z] l-[(Ar 4) o-W] p-Ar wherein 1, Ar 2, Ar 3And Ar 4For identical or different, and it is the arlydene unit of 6 to 18 carbon atoms; W, X, Y and Z are identical or different, and for being selected from following divalent linker :-SO 2-,-S-,-SO-,-CO-,-O-,-alkylidene or the alkylidene of COO-or 1 to 6 carbon atom, and wherein at least one linking group is-S-; And n, m, i, j, k, l, o and p are 0 or 1,2,3 or 4 independently, and precondition is that their sum is not less than 2.Arylene units Ar 1, Ar 2, Ar 3And Ar 4Can be optionally replacement or unsubstituted.Favourable arlydene system is phenylene, biphenylene, naphthylene, anthracene and phenanthrene.Poly arylidene thio-ester comprises at least 30 % by mole usually, specifically at least 50 % by mole and at least 70 % by mole (arylene sulfide) (S-) unit more particularly.Preferably, the poly arylidene thio-ester polymer comprises at least 85 % by mole the thioether bond that is directly connected to two aromatic rings.Advantageously, the poly arylidene thio-ester polymer is polyphenylene sulfide (PPS), and it is defined as in this article and comprises poly (phenylene sulfide) ether structure-(C 6H 4-S) n-(wherein n be 1 or larger integer) as its component.
Can preferably use and have a kind of arlydene as the poly arylidene thio-ester polymer of key component.Yet, according to machinability and heat resistance, also can use the copolymer that comprises two or more arlydene.Comprising the phenylene sulfide repetitive is especially preferred as the PPS resin of key component because it have excellent machinability and industrial for being easy to obtain.In addition, also can use poly (arylene ether) ketone thioether, poly (arylene ether) ketone ketone thioether, polyaryl thioether sulfone etc.
The instantiation of feasible copolymer comprises the random or block copolymer, the random or block copolymer with phenylene sulfide repetitive and poly (arylene ketones) thioether repetitive that have phenylene sulfide repetitive and metaphenylene thioether repetitive, has the random or block copolymer of phenylene sulfide repetitive and poly (arylene ketones) ketone thioether repetitive and have the phenylene sulfide repetitive and the random or block copolymer of arlydene sulfone thioether repetitive.
Poly arylidene thio-ester can be chosen wantonly and comprise other component that its desired characteristic is had no adverse effect.The exemplary materials that can be used as annexing ingredient will include but not limited to antimicrobial, pigment, antioxidant, surfactant, wax, flow improver additive, particle and add to strengthen other material of polymer machinability.These additives and other additive can be measured use routinely.
Describe
When the present invention relates to comprise the nonwoven web of bicomponent fiber, described fiber comprises in the first poly arylidene thio-ester (PAS) component and the polymers compositions continuous phase of each, wherein said the first polyarylene sulfide component comprises tin or zinc additive or the two all to be had, and the first polyarylene sulfide component of any given fiber is exposed to the outside of this fiber at least in part." partly expose " and refer to that at least a portion of described component appears on the outer surface of described fiber.The whole outer surface of described fiber can be comprised of a described PAS component.A described PAS component also can be surrounded described the second polymers compositions at least in part.
The present invention also relates to the improvement method for the manufacture of nonwoven web, said method comprising the steps of: be nonwoven web with the bicomponent fiber spinning (i), described fiber comprises in the first polyarylene sulfide component and the polymers compositions continuous phase of each, wherein said the first polyarylene sulfide component comprises tin or zinc additive or the two all to be had, and the first polyarylene sulfide component of any given fiber is exposed to the outside of this fiber at least in part, and (ii) calendering described nonwoven web regular hour and temperature, its filamentary at least one subset that is enough to bond.
Spinning technique of the present invention can be any nonwoven spinning technique well known by persons skilled in the art, for example spun-bond process or meltblown.
The second polymers compositions can comprise any thermoplastic polymeric material.In other embodiments, described the second polymers compositions can comprise and is selected from following polymer: polyether-ether-ketone (PEEK), polyether-ketone (PEK), polyester, polypropylene, polyamide and their mixture.Polyester is preferably polyethylene terephthalate (PET), poly terephthalic acid trimethylene ester or polybutylene terephthalate (PBT) (PBT).The second polymers compositions also can comprise the 2nd PAS, and it also can comprise the calcium salt additive, preferred calcium stearate.
In one embodiment, a PAS component of fibre incrustation comprises at least a organic carboxyl acid tin (II) salt.Polyarylene sulfide composition can comprise at least a tin additive, and it comprises and is selected from following branched carboxylic acids tin (II) salt: Sn (O 2CR) 2, Sn (O 2CR) (O 2CR '), Sn (O 2CR) (O 2CR ") and their mixture, wherein carboxylate radical part O 2CR and O 2CR ' represents branched carboxylic acids root anion and carboxylate radical part O independently 2CR " represent straight-chain carboxylic acid's root anion.In one embodiment, branched carboxylic acids tin (II) comprises Sn (O 2CR) 2, Sn (O 2CR) (O 2CR ') or their mixture.In one embodiment, branched carboxylic acids tin (II) comprises Sn (O 2CR) 2In one embodiment, branched carboxylic acids tin (II) comprises Sn (O 2CR) (O 2CR ').In one embodiment, branched carboxylic acids tin (II) comprises Sn (O 2CR) (O 2CR ").
Randomly, the tin additive also can comprise straight-chain carboxylic acid's tin (II): Sn (O 2CR ") 2In general, select the relative quantity of side chain and straight-chain carboxylic acid's tin (II), so that branched carboxylic acids root portion [O 2CR+O 2CR '] and based on all carboxylate radicals part [O that comprise in the described additive 2CR+O 2CR '+O2CR "] molal quantity count at least about 25%.For example, the branched carboxylic acids root portion and can be all carboxylate radicals part of being contained in the tin additive at least about 33%, or at least about 40%, or at least about 50%, or at least about 66%, or at least about 75%, or at least about 90%.
In one embodiment, radicals R and R ' all comprise 6 to 30 carbon atoms and all comprise at least one secondary carbon or tertiary carbon atom.One or more secondary carbon or tertiary carbon can be positioned at carboxylate radical part O 2CR and O 2Any position among the CR ', for example in the α position of carboxyl carbon, in the ω position of carboxyl carbon, and in any centre position.Radicals R and R ' can be unsubstituted, maybe can choose wantonly by inertia group to replace, and are for example replaced by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxylate group.Suitable organic R and R ' group example comprise fat base, aryl, alcyl, oxygen heterocycle group, nitrogen heterocyclic ring group and sulfur heterocyclic ring group.Heterocyclic group can comprise carbon and oxygen, nitrogen or sulphur in ring structure.
In one embodiment, radicals R " for comprising the primary alkyl of 6 to 30 carbon atoms, randomly for example fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxylate group replace by inertia group.In one embodiment, radicals R " for comprising the primary alkyl of 6 to 20 carbon atoms.
In one embodiment, radicals R or R ' have or all have the structure by formula (I) expression independently:
Formula (I)
R wherein 1, R 2And R 3Be independently:
H；
Have the primary alkyl of 6 to 18 carbon atoms, secondary alkyl or tertiary alkyl, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted;
Aryl with 6 to 18 carbon atoms, optional by alkyl, fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted; And
Alcyl with 6 to 18 carbon atoms, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted;
Precondition is to work as R 2And R 3During for H, R 1For:
Secondary alkyl or tertiary alkyl with 6 to 18 carbon atoms, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted;
Have 6 to 18 carbon atoms and had the secondary alkyl of 6 to 18 carbon atoms or the aryl that tertiary alkyl replaces, described aryl and/or described secondary alkyl or tertiary alkyl are optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted; And
Alcyl with 6 to 18 carbon atoms, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted.
In one embodiment, radicals R or R ' or the two have the structure by formula (I) expression, and R 3Be H.
In another embodiment, radicals R or R ' or the two have the structure by formula (II) expression:
Figure BDA00002175999600081
Formula (II)
Wherein
R 4Be the primary alkyl with 4 to 6 carbon atoms, secondary alkyl or tertiary alkyl, optional by fluorine, chlorine, bromine, iodine, nitro and hydroxyl replacement; And
R 5Be methyl, ethyl, n-pro-pyl, Zhong Bingji, normal-butyl, sec-butyl or the tert-butyl group, optional by fluorine, chlorine, bromine, iodine, nitro and hydroxyl replacement.
In one embodiment, radicals R is identical with R ', and all has the structure by formula (II) expression, wherein R 4Be normal-butyl, and R 5Be ethyl.This embodiment has been described branched carboxylic acids tin (II) 2 ethyl hexanoic acid tin (II), and it also is called as thylhexoic acid tin (II) in this article.
The commercially available acquisition of one or more carboxylic acid tin (II), or can be generated by suitable tin (II) cationic source and the carboxylic acid original position corresponding with one or more required carboxylate radicals.Tin (II) additive may be to be enough to the providing heat-oxidation stability of improvement and/or the concentration of heat endurance to be present in the described poly arylidene thio-ester.In one embodiment, tin (II) additive can exist with about 10 % by weight or lower concentration based on the weighing scale of described poly arylidene thio-ester.For example, tin (II) additive may be with about 0.01 % by weight to about 5 % by weight, or for example about 0.25 % by weight to the concentration of about 2 % by weight exists.Usually, the tin in the concentrate composition (II) additive concentration is higher, for example is extremely about 10 % by weight of about 5 % by weight, or higher.Tin (II) additive can be added in melting or the solid poly arylidene thio-ester with solid, slurries or solution form.
In another embodiment, the polyarylene sulfide composition of fibre incrustation of the present invention also comprises at least a zinc (II) additive and/or zinc metal [Zn (0)].As long as described organic or inorganic equilibrium ion does not detrimentally affect the desired characteristic of described polyarylene sulfide composition, zinc (II) additive can be organic additive, for example zinc stearate, perhaps inorganic compound, for example zinc sulfate or zinc oxide.The commercially available acquisition of zinc (II) additive, but or original position generation.The zinc metal can be used as zinc (II) ion gun individually or with at least a zinc (II) additive combination in described composition.In one embodiment, described zinc (II) additive is selected from zinc oxide, zinc stearate and their mixture.
Zinc (II) additive and/or zinc metal can be present in the described poly arylidene thio-ester with about 10 % by weight or lower concentration based on the weighing scale of described poly arylidene thio-ester.For example, zinc (II) additive and/or zinc metal may be with about 0.01 % by weight to about 5 % by weight, or for example about 0.25 % by weight to the concentration of about 2 % by weight exists.Usually, (II) additive of the zinc in the concentrate composition and/or zinc metal concentration are higher, for example are extremely about 10 % by weight of about 5 % by weight, or higher.At least a zinc (II) additive and/or zinc metal can be added in melting or the solid poly arylidene thio-ester with solid, slurries or solution form.Zinc (II) additive and/or zinc metal can with the added together or independent use of tin (II) salt.
Embodiment
The nonwoven fabric of bi-component is made by polyethylene terephthalate (PET) component and polyphenylene sulfide (PPS) component.The PET component have the inherent viscosity of 0.633dl/g and with PET resin grades PQB8A-065 available from PolyQuest (Wilmington, NC).With trade name
Figure BDA00002175999600091
PPS is the mixture of 0317 grade of C1 of 0309 grade of C1 of 70wt% and 30wt% available from the PPS component of Ticona Engineering Polymers (Florence, KY).
Following material is used for embodiment.Except as otherwise noted, all commercial materials are all used by the former state of receiving.2 ethyl hexanoic acid tin (II) (90%) and zinc oxide (99%) derive from Sigma-Aldrich (St.Louis, MO).Stearic acid tin (II) (98%) (Sn stearate) derives from Acros Organics (Morris Plains, NJ).Zinc stearate (99%) (Zn stearate) derives from Honeywell Reidel-de Haen (Seelze, Germany).2 ethyl hexanoic acid tin (II) this paper is also referred to as thylhexoic acid tin (II) or SnEH.
If you are using, additive comprises required %PPS component gross mass with PPS melt blending so that it.Under 120 ℃ temperature, the PET resin is dried to moisture less than 50ppm in throughcirculation dryer.Under 115 ℃ temperature, the PPS resin is dried to moisture less than 150ppm in throughcirculation dryer.With pet polymer heating under 290 ℃ in extruder, and with the heating under 295 ℃ in independent extruder of PPS resin.Described two kinds of polymer are quantitatively sent in the spin pack, wherein described two melt-flow are filtered independently, then make up to provide many rows to have the spun-bonded fibre of sheath-core type cross section by a folded distribution plate.This type of process is well-known to those having ordinary skill in the art.The PET component consists of core, and the PPS component consists of skin.
To be heated to by the spin pack that 2158 circular capillaries openings form 295 ℃, and with 2.2 gram/holes/minute polymer-through-put rate spin PPS and pet polymer through each capillary.By the gross weight of spun-bonded fibre, the PET component forms by 70%.Be that the cross-flow cold quenching band of 122cm cools off fiber in length.The power of decay is provided to fibre bundle by the rectangular slot nozzle.Distance between spin pack and the nozzle entrance is 147cm.Collect the fiber of jetting nozzle at the forming strip that moves with 87.4m/min.Below forming strip, apply vacuum, to help that fiber is fixed to forming strip.Fiber web is passed through between two level and smooth metals so that long filament is bonded to one another, thereby smoothly roll spunbond layer.Bonding condition is 135 ℃ roll temperature and the nip pressure of 875N/cm.Behind the hot adhesion, make spunbond sheet shaped rolling with coil winding machine.
In additional step, the nonwoven web that subsequently smoothed calendering of nonwoven web has bondd with further compacting.Fiber web passes through between the stainless steel rider of 2 heating, and described roller has the diameter of 76.2cm, and nip pressure is 4200N/cm.Linear velocity is 61m/min and described roller is heated to surface temperature is 200 ℃.After calendering, the basic weight of spunbond sheet material is 51g/m 2
Following table has provided the extension test result of these samples, and wherein SnEH is thylhexoic acid tin (II), and ZnO is zinc oxide, and SnO is tin oxide, and Zn Stearate is zinc stearate, and Sn Stearate is stearic acid tin.According to ASTM D 828-97, use TENSILE STRENGTH and the work to break of the test nonwoven sheet that 2.54cm is wide, 18cm spaces at the Instron test apparatus.Only report vertically (MD) result.
The result
Figure BDA00002175999600111
Be clear that from these embodiment tin and/or zinc additive are to improving the effect of fibroreticulate TENSILE STRENGTH and total energy to fracture.

Claims (24)

1. for the manufacture of the method for nonwoven web, said method comprising the steps of: be nonwoven web with the bicomponent fiber spinning (i), described fiber comprises in the first poly arylidene thio-ester (PAS) component and the polymers compositions continuous phase of each, wherein said the first polyarylene sulfide component comprises tin or zinc additive or the two all to be had, and the first polyarylene sulfide component of any given fiber is exposed to the outer surface of this fiber at least in part, and (ii) rolls described nonwoven web.
2. the process of claim 1 wherein that described spinning step is spunbond process.
3. the process of claim 1 wherein that described polymers compositions comprises is selected from following polymer: polyether-ether-ketone (PEEK), polyether-ketone (PEK), polyester, polypropylene, polyamide and their mixture.
4. the method for claim 3, wherein said polyester comprises polyethylene terephthalate (PET), poly terephthalic acid trimethylene ester or polybutylene terephthalate (PBT) (PBT).
5. the process of claim 1 wherein that described the second polymers compositions comprises the second poly arylidene thio-ester.
6. the method for claim 5, wherein said the second poly arylidene thio-ester and calcium salt blend.
7. the method for claim 6, wherein said calcium salt is calcium stearate.
8. the process of claim 1 wherein that described tin additive is to be selected from following branched carboxylic acids salt: Sn (O 2CR) 2, Sn (O 2CR) (O 2CR '), Sn (O 2CR) (O 2CR ") and their mixture, wherein said carboxylate radical part O 2CR and O 2CR ' represents branched carboxylic acids root anion and described carboxylate radical part O independently 2CR " represent straight-chain carboxylic acid's root anion.
9. the method for claim 8, wherein the tin additive also comprises straight-chain carboxylic acid's tin (II): Sn (O 2CR ") 2
10. the method for claim 8, wherein said branched carboxylic acids root portion O 2CR and O 2The sum of CR ' is based on the total carboxylic acid's root portion O that comprises in the described tin additive 2CR, O 2CR ' and O 2CR " molal quantity count at least about 25%.
11. the method for claim 8, wherein said radicals R " for comprising the primary alkyl of 6 to 30 carbon atoms.
12. the method for claim 11, wherein said radicals R " group that is selected from fluorine, chlorine, bromine, iodine, nitro, hydroxyl, carboxylic acid group and their any combination replaces.
13. the method for claim 8, wherein said radicals R and R ' have independently or the two all has the structure that is represented by formula (I):
Figure FDA00002175999500021
Formula (I)
R wherein 1, R 2And R 3Be selected from:
H；
Have the primary alkyl of 6 to 18 carbon atoms, secondary alkyl or tertiary alkyl, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted;
Aryl with 6 to 18 carbon atoms, optional by alkyl, fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted; And
Alcyl with 6 to 18 carbon atoms, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted;
Precondition is to work as R 2And R 3During for H, R 1For:
Secondary alkyl or tertiary alkyl with 6 to 18 carbon atoms, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted;
Have 6 to 18 carbon atoms and had the secondary alkyl of 6 to 18 carbon atoms or the aryl that tertiary alkyl replaces, described aryl and/or described secondary alkyl or tertiary alkyl are optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted; And
Alcyl with 6 to 18 carbon atoms, optional by fluorine, chlorine, bromine, iodine, nitro, hydroxyl and carboxyl substituted.
14. the method for claim 8, wherein said radicals R and R ' have independently or the two all has the structure that is represented by formula (I), and R 3Be H.
15. the method for claim 8, wherein said radicals R and R ' have independently or the two all has the structure that is represented by formula (II):
Figure FDA00002175999500031
Formula (II)
Wherein
R 4Be the primary alkyl with 4 to 6 carbon atoms, secondary alkyl or tertiary alkyl, optional by fluorine, chlorine, bromine, iodine, nitro and hydroxyl replacement; And
R 5Be methyl, ethyl, n-pro-pyl, Zhong Bingji, normal-butyl, sec-butyl or the tert-butyl group, optional by fluorine, chlorine, bromine, iodine, nitro and hydroxyl replacement.
16. the method for claim 8, wherein said radicals R is identical with R ', and the two all has the structure by formula (II) expression, R 4Be normal-butyl, and R 5Be ethyl.
17. the process of claim 1 wherein that described tin additive exists with about 10 % by weight or the concentration still less of the weight of described the first polyarylene sulfide component.
18. the process of claim 1 wherein that described zinc additive comprises zinc (II) additive or zinc metal [Zn (0)] or the mixture of the two.
19. the method for claim 18, wherein said zinc (II) additive are organic additive or inorganic additive or the mixture of the two.
20. the method for claim 19, wherein said zinc (II) additive is selected from zinc oxide, zinc stearate, zinc sulfate and their mixture.
21. the process of claim 1 wherein that described zinc and tin additive exist with the total concentration that the weighing scale based on described poly arylidene thio-ester is equal to or less than about 25 % by weight.
22. the method for claim 21, wherein said zinc (II) additive and zinc metal exist to count zero extremely about 10 % by weight or lower total concentration based on the weight of described poly arylidene thio-ester.
23. the method for claim 5, the two is polyphenylene sulfide for wherein said the first poly arylidene thio-ester or described the second poly arylidene thio-ester or they.
24. the method for claim 1, described method comprise described nonwoven web regular hour of calendering and temperature, its filamentary at least one subset that is enough to bond.
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