CN103328704A - Polyphenylene sulfide composite fiber and nonwoven fabric - Google Patents
Polyphenylene sulfide composite fiber and nonwoven fabric Download PDFInfo
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- CN103328704A CN103328704A CN201280006269XA CN201280006269A CN103328704A CN 103328704 A CN103328704 A CN 103328704A CN 201280006269X A CN201280006269X A CN 201280006269XA CN 201280006269 A CN201280006269 A CN 201280006269A CN 103328704 A CN103328704 A CN 103328704A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/43828—Composite fibres sheath-core
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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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/4383—Composite fibres sea-island
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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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/43832—Composite fibres side-by-side
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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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—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
-
- 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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
- Y10T442/641—Sheath-core multicomponent strand or fiber material
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
Abstract
Provided is a polyphenylene sulfide composite fiber which consists mainly of a component (A) and a component (B), the component (A) being a resin mainly comprising poylphenylene sulfide that comprises p-phenylene sulfide as the main units and the component (B) being a resin mainly comprising a copolyphenylene sulfide that contains at least one kind of comonomer units besides p-phenylene sulfide, characterized in that at least some of the surface of the fiber is constituted of the component (B). The composite fiber, which is constituted of resins that comprise polyphenylene sulfide as a main component, is heat-bondable and is excellent in terms of heat resistance, flame retardancy, and chemical resistance. Also provided is nonwoven fabric.
Description
Technical field
The present invention relates to reach the nonwoven fabric that is consisted of by this fiber by fiber that forms as the resin of main component with polyphenylene sulfide (following sometimes also brief note make " PPS "), heat resistance and chemical proofing excellence.
Background technology
The PPS resin has the characteristic of heat resistance, anti-flammability and chemical proofing excellence, is suitable as engineering plastics, film, fiber and nonwoven fabric etc.Particularly for nonwoven fabric, the above-mentioned characteristic of expectation performance is used for the industry purposes such as heat-resistant filter, electrically insulating material and battery diaphragm.
Up to the present, about having used the nonwoven fabric of PPS resin, kinds of schemes is disclosed.A kind of following nonwoven fabric of long fibers that obtains is for example disclosed: by spun-bond process the PPS resin is carried out spinning, make cloth and silk, carry out under the temperature more than the vitrification point stretch processing, preferably carry out biaxial stretch-formed processing after, implement heat bonding (referring to patent documentation 1).In addition, a kind of following nonwoven fabric of long fibers that obtains is disclosed: by spun-bond process the PPS resin is carried out spin-drawing, under its condition below the 1st crystallized temperature, implement temporarily bonding to the gained cloth and silk, afterwards, heat-treat under the condition under tension, more than the 1st crystallized temperature, then, implement heat bonding (referring to patent documentation 2).And then, disclose the above degree of crystallinity of a kind of 30wt% of containing and be 25～50% PPS fiber, carried out integrated heat-resistant non-woven fabric (referring to patent documentation 3) by heat bonding.But above-mentioned motion all is that the fiber by single component consists of nonwoven fabric, therefore, is difficult to carrying out between the fiber integratedly when having heat bonding, is difficult to obtain the problem of the high nonwoven fabric of mechanical strength.
On the other hand, in order to improve Thermoadhesive, the present known Thermoadhesive conjugate fiber that contains the low melting point composition that has.Up to the present, as the nonwoven fabric that is consisted of by the composite fibre that has used the PPS resin, a kind of nonwoven fabric of long fibers that is consisted of, formed by carrying out heat bonding by the core-sheath-type composite fibre is disclosed, wherein, the sheath composition of described core-sheath-type composite fibre is made of the PPS resin, and the core composition consists of (referring to patent documentation 4) by pet resin.But, because the fusing point of sheath composition is higher than the core composition, thus the Fiber Phase of Thermoadhesive and single component than without any change, and then, because pet resin is wanting in anti-flammability and chemical proofing, so aspect durability, there is larger problem.
As mentioned above, also do not obtain bringing into play the heat resistance of PPS resin and chemical proofing, simultaneously fiber and the high nonwoven fabric of mechanical strength of Thermoadhesive excellence.
Patent documentation 1: TOHKEMY 2005-154919 communique
Patent documentation 2: TOHKEMY 2008-223209 communique
Patent documentation 3: international disclosing No. 2008/035775
Patent documentation 4: TOHKEMY 2009-155764 communique
Summary of the invention
The object of the present invention is to provide heat resistance, anti-flammability and the chemical proofing etc. of performance PPS resin and fiber and the high nonwoven fabric of mechanical strength of Thermoadhesive excellence.
Namely, the present invention is a kind of polyphenyl thioether complex fiber, it is characterized in that, described polyphenyl thioether complex fiber is mainly formed by composition A and composition B, described composition A is the resin that mainly contains polyphenylene sulfide, described polyphenylene sulfide with to diphenyl sulfide as formant, described composition B is the resin that mainly contains copolymerized polyphenylene sulfide, described copolymerized polyphenylene sulfide is except contain also containing the copolymerization units more than a kind the diphenyl sulfide at least, and composition B forms at least a portion of fiber surface.
In addition, the present invention is a kind of nonwoven fabric, it is characterized in that, described nonwoven fabric is made of polyphenyl thioether complex fiber of the present invention.
PPS composite fibre of the present invention has the characteristic of heat resistance, chemical proofing and the anti-flammability of PPS resin, and Thermoadhesive is excellent.Therefore, nonwoven fabric of the present invention has the characteristic of heat resistance, chemical proofing and the anti-flammability of PPS resin, and mechanical strength is excellent, can be used for various industry purposes.
The specific embodiment
The important part of composite fibre of the present invention is, is mainly formed by composition A and composition B, and they all mainly contain PPS.Thus, can obtain excellent heat resistance, anti-flammability and chemical proofing.
In addition, the important part of PPS composite fibre of the present invention is, to mainly contain during as composition A, to use the resin that mainly contains copolymerization PPS as the composition B compound with composition A as the resin of the PPS of formant to diphenyl sulfide, composition B forms at least a portion of fiber surface.Thus, composition B plays a role as adhesive composition, can make the nonwoven fabric of mechanical strength excellence.
The content to the diphenyl sulfide unit as among the PPS of composition A is preferably more than 93 % by mole.By contain more than 93 % by mole, more preferably more than 95 % by mole to the diphenyl sulfide unit, can make the fiber of stringiness and mechanical strength excellence.
As the content of the PPS resin among the composition A, consider from aspects such as heat resistance, chemical proofings, be preferably more than the 85 quality %, more preferably be more than the 90 quality %, more preferably more than the 95 quality %.
In addition, in the scope of not destroying effect of the present invention, also can in composition A, mix the thermoplastic resin outside the PPS resin.As the thermoplastic resin outside the PPS resin, can enumerate such as PEI, polyether sulfone, polysulfones, polyphenylene oxide, polyester, polyarylate, polyamide, polyamidoimide, Merlon, polyolefin, polyether-ether-ketone etc.
In addition, in the scope of not destroying effect of the present invention, also can in composition A, add Nucleating Agent, delustering agent, pigment, mould inhibitor, antiseptic, fire retardant or hydrophilizing agent etc.
In addition, the melt flow rate (MFR) (the following MFR that sometimes simply is denoted as) of measuring based on ASTM D1238-70 (measuring temperature is 315.5 ℃, mensuration is loaded is the 5kg load) of preferred component A is 100～300g/10 minute.By make MFR be more than 100g/10 minute, more preferably for more than 140g/10 minute, can obtain suitable flowability, suppress the rising of nozzle backside pressure in the melt spinning, also can suppress to draw the fracture of wire when stretching.On the other hand, be below 300g/10 minute, more preferably for below 225g/10 minute by making MFR, can suitably improve the degree of polymerization or molecular weight, obtain being suitable for practical mechanical strength and heat resistance.
Among the present invention, the copolymerization PPS of composition B, with to diphenyl sulfide as main repetitive, make to the diphenyl sulfide unit with except the copolymerization units copolymerization more than a kind the diphenyl sulfide unit is consisted of.With respect to whole repetitives, the content to the diphenyl sulfide unit in this copolymerization PPS resin is preferably 70～97 % by mole.By making content to the diphenyl sulfide unit be more than 70 % by mole, more preferably be more than 80 % by mole, more preferably more than 85 % by mole, can suppress heat resistance and reduce.On the other hand, by making content to the diphenyl sulfide unit be below 97 % by mole, more preferably be below 96 % by mole, more preferably below 95 % by mole, can obtaining the composite fibre of Thermoadhesive excellence.
As copolymerization units, can preferably enumerate the unit shown in the isophthalic thio-ether units shown in the following formula (1) and formula (2)～(5) etc.
(herein, X represents alkylidene, CO, SO
2The unit.)
(herein, R represents alkyl, nitro, phenylene, alkoxyl.)。
In addition, as described abovely also can exist multiple to the copolymerization units outside the diphenyl sulfide.Wherein, consider from the aspect of the stringiness excellence that is easy to have obtained obtaining Thermoadhesive and stable on heating balanced fusing point and fiber, preferred between diphenyl sulfide.
As the copolymerization amount among the copolymerization PPS, be preferably 5～30 % by mole.By making copolymerization amount among the copolymerization PPS be more than 5 % by mole, more preferably be more than 7 % by mole, more preferably more than 9 % by mole, can obtaining the composite fibre of Thermoadhesive excellence.On the other hand, by making copolymerization amount among the copolymerization PPS be below 30 % by mole, more preferably be below 25 % by mole, more preferably below 20 % by mole, can suppress heat resistance and reduce.
On the other hand, consider from the aspect of the stringiness excellence of fiber, preferably for example 3 functionality diphenyl sulfides take following formula as representative are suppressed at below 1 % by mole of copolymerization PPS.
In addition, as the mode of the copolymerization among the copolymerization PPS, can enumerate random copolymerization, block copolymerization etc.Wherein, consider preferred random copolymerization from being easy to be controlled to be the aspect that has obtained Thermoadhesive and stable on heating balanced fusing point.
As the content of the copolymerization PPS among the composition B, consider from aspects such as heat resistance, chemical proofings, be preferably more than the 85 quality %, more preferably be more than the 90 quality %, more preferably more than the 95 quality %.
In addition, in the scope of not destroying effect of the present invention, also can in composition B, mix the thermoplastic resin outside the PPS.As the thermoplastic resin outside the PPS, can enumerate various thermoplastic resins such as PEI, polyether sulfone, polysulfones, polyphenylene oxide, polyester, polyarylate, polyamide, polyamidoimide, Merlon, polyolefin, polyether-ether-ketone.
In addition, in the scope of not destroying effect of the present invention, also can in composition B, add Nucleating Agent, delustering agent, pigment, mould inhibitor, antiseptic, fire retardant or hydrophilizing agent etc.
In addition, the MFR that measures based on ASTM D1238-70 (measuring temperature is 315.5 ℃, mensuration is loaded is the 5kg load) of preferred component B is 100～300g/10 minute.By make MFR be more than 100g/10 minute, more preferably for more than 120g/10 minute, can suppress the rising of nozzle backside pressure in the melt spinning, also can suppress to draw the fracture of wire when stretching.On the other hand, be below 300g/10 minute, more preferably for below 225g/10 minute by making MFR, can obtain suitable flowability, stably be compounded to form.
Among the present invention, owing to using composition B as the heat bonding composition, so the fusing point of preferred component B is lower than the fusing point of composition A.
As the fusing point of composition B, be preferably 200～275 ℃.Be more than 200 ℃, more preferably be more than 230 ℃, more preferably more than 240 ℃, can suppress heat resistance and reduce by the fusing point that makes the heat bonding composition.On the other hand, be below 275 ℃, more preferably be below 270 ℃, more preferably below 265 ℃, can obtain the composite fibre of Thermoadhesive excellence by the fusing point that makes the heat bonding composition.The fusing point of composition B can suitably be regulated by the mol ratio of copolymer composition.
In addition, poor as the fusing point of the fusing point of the fusing point of composition A and composition B, be preferably 5～80 ℃.By making fusing point poorly be more than 5 ℃, more preferably be more than 10 ℃, more preferably more than 15 ℃, can obtaining the composite fibre of Thermoadhesive excellence.On the other hand, by making fusing point poorly be below 80 ℃, more preferably be below 50 ℃, more preferably below 40 ℃, can suppress heat resistance and reduce.
The shared ratio of composition B as in the PPS composite fibre of the present invention is preferably 5～70 quality %.By making the shared ratio of composition B be more than the 5 quality %, more preferably be 10 quality %, more preferably more than the 15 quality %, can efficient obtain well firmly heat bonding.On the other hand, by making the shared ratio of composition B be below the 70 quality %, more preferably be below the 50 quality %, more preferably below the 30 quality %, can suppress mechanical strength and reduce.
As the complex morphological in the PPS composite fibre of the present invention, at least a portion that composition B forms fiber surface is important.As above-mentioned complex morphological, can enumerate the core-sheath-type that for example circular composition A is surrounded by the composition B of the identical annular in center in the fibre section; The core sheath eccentric type of the misalignment of the center of composition A and composition B; With composition A as island component, the composition B fabric of island-in-sea type as sea component; The parallel type that two compositions are arranged side by side; Two compositions are with the radial radial pattern of alternately arranging; A plurality of composition B are disposed at the Multiblade on every side of composition A etc.Wherein, preferred component B occupies the core-sheath-type of the stringiness excellence of fiber surface integral body and fiber.
Average single fiber fiber number as PPS composite fibre of the present invention is preferably 0.5～10dtex.By make the average single fiber fiber number be more than the 0.5dtex, more preferably for more than the 1dtex, more preferably more than the 2dtex, can keep the stringiness of fiber, suppress in the spinning fracture of wire multiple.In addition, by make the average single fiber fiber number be below the 10dtex, more preferably for below the 5dtex, more preferably below the 4dtex, the spray volume that can suppress the molten resin of each spinning-nozzle single hole, fiber is implemented fully cooling, and the spinnability that can suppress to be caused by the fusible between the fiber reduces.In addition, the weight per unit area in the time of can suppressing to make nonwoven fabric is irregular, makes to have excellent surface quality.In addition, the viewpoint of the dust arrestment performance when nonwoven fabric being used for filter etc. considers, the average single fiber fiber number also is preferably below the 10dtex, more preferably is below the 5dtex, more preferably below the 4dtex.
PPS composite fibre of the present invention can use with any the form in multifilament (Multifilament), monofilament (monofilament) or the staple fibre, and the fiber that also can be used as all cloth and silks such as consisting of fabric or nonwoven fabric uses.Wherein, PPS composite fibre of the present invention preferably uses as the formation fiber of nonwoven fabric.This is owing in nonwoven fabric, consisting of the intensity that is conducive to nonwoven fabric between the fiber by heat bonding.
As nonwoven fabric, can enumerate such as needle punched non-woven fabrics, Wet-laid non-woven fabric, spunlace non-woven cloth (spunlace nonwoven), spun-bonded nonwoven fabric, melt spraying non-woven fabrics, resin-bonding nonwoven fabric, chemical adhesion nonwoven fabric, heat bonding nonwoven fabric, tow and open fine formula nonwoven fabric, air-laid nonwoven fabrics etc.Wherein, the spun-bonded nonwoven fabric of preferred productivity ratio and mechanical strength excellence.
In addition, for the nonwoven fabric that is consisted of by PPS composite fibre of the present invention, owing to can obtain high mechanical strength by heat bonding, therefore preferably carry out integrated formation by heat bonding.
Weight per unit area as nonwoven fabric of the present invention is preferably 10～1000g/m
2Be 10g/m by making weight per unit area
2Above, more preferably be 100g/m
2Above, 200g/m more preferably
2Above, can obtain being suitable for the nonwoven fabric of practical mechanical strength.On the other hand, be 1000g/m by making weight per unit area
2Below, more preferably be 700g/m
2Below, 500g/m more preferably
2Below, can have suitable aeration, be suppressed at and cause high pressure loss when using in the filter etc.
In the nonwoven fabric that is consisted of by Thermoadhesive conjugate fiber of the present invention, preferably by endwise tensile strength, longitudinal stretching percentage elongation and the weight per unit area of nonwoven fabric, to utilize the Qiang Shenji of the per unit area weight that following formula calculates be more than 10.
Per unit area weight stretch by force long-pending=endwise tensile strength (N/5cm) * longitudinal stretching percentage elongation (%)/weight per unit area (g/m
2)
Be more than 10, more preferably be more than 13, more preferably more than 15, form and have under harsh environment the also nonwoven fabric of operable mechanical strength by the Qiang Shenji that makes per unit area weight.In addition, the upper limit is not particularly limited, and considers from preventing the aspect that nonwoven fabric hardening, operability worsen, and is preferably below 100.
The nonwoven fabric that is consisted of by Thermoadhesive conjugate fiber of the present invention preferably in air, the endwise tensile strength conservation rate that exposes under 180 ℃ the temperature in 1300 hours the heat-resisting exposure test is more than 80%.The endwise tensile strength conservation rate is more than 80%, more preferably be more than 85%, more preferably 90% when above, also can withstand high temperatures under the application of the long-term heat-resistant filter that uses etc.The higher limit of endwise tensile strength conservation rate is not particularly limited, and is preferably below 150%.
Then, the preferred version of the manufacture method of PPS composite fibre of the present invention and nonwoven fabric described.
Polymerization as the copolymerization PPS that uses among the present invention, comprise the whole bag of tricks, following methods easily makes the degree of polymerization of resulting polymers rise, for preferably, described method is: cooperate with the molar ratio corresponding with above-mentioned copolymerization rate with alkali metal sulphide with to phenyl-dihalide (main component monomer) and accessory ingredient monomer, in polar solvent, reagent and additive in polymerization in the presence of, the method for under high temperature, condition of high voltage, carrying out polymerization.Particularly preferably use vulcanized sodium as alkali metal sulphide, use paracide as the main component monomer, use 1-METHYLPYRROLIDONE as solvent.
As the accessory ingredient monomer, can enumerate following monomer:
When wish imports the isophthalic thio-ether units of above-mentioned formula (1), can use the monomer shown in the following formula;
In addition, when wish imports the copolymerization units of above-mentioned formula (2), can use the monomer shown in the following formula;
In addition, when wish imports the copolymerization units of above-mentioned formula (3), can use the monomer shown in the following formula;
(herein, X represents alkylidene, CO, SO
2The unit.)
In addition, when wish imports the copolymerization units of above-mentioned formula (4), can use the monomer shown in the following formula;
In addition, when wish imports the copolymerization units of above-mentioned formula (5), can use the monomer shown in the following formula,
(herein, R represents alkyl, nitro, phenylene, alkoxyl.)
Can there be multiple above-mentioned accessory ingredient monomer.
On the other hand, for the PPS that uses among the present invention, can adopt with the same method of copolymerization PPS and carry out polymerization, but mismatch the accessory ingredient monomer or reduce its cooperation.
Method for making PPS composite fibre of the present invention can adopt known melt spinning method.For example in the situation of core-sheath-type composite fibre, the core composition respectively with different extruder is carried out melting with the sheath composition with copolymerization PPS resin with the PPS resin, metering, be supplied to the core-sheath-type composite nozzle, melt spinning uses the cooling devices such as present known transverse injection or ring-type injection that strand is cooled off, afterwards, give finish, be wound on the up-coiler via the form of pulling roll with undrawn yarn.Form as fiber, when wanting to obtain staple fibre, can followingly carry out: utilize known stretching-machine between the different roller group of peripheral speed, to stretch through the undrawn yarn of reeling, utilization be pressed into type crimping machine etc. give curling after, use the cutting machine such as EC cutting machine to be cut into desired length.As the form of fiber, when wanting to obtain long fiber, can followingly carry out: after utilizing stretching-machine to stretch, reel, carry out as required the processing such as twisted filament processing, false twist yarn processing.
Then, carry out following explanation to making as the method for utilizing the composite fibre nonwoven cloth that spun-bond process obtains of the preferred configuration of nonwoven fabric of the present invention.
Spun-bond process is for carrying out the manufacture method of following operation: with resin melting, after carrying out spinning by spinning-nozzle, utilize injector that the strand through cooling curing is drawn, stretches, trap mobile carry out the non woven fibre networking on the net after, carry out heat bonding.
As the shape of spinning-nozzle or injector, can adopt the various shapes such as circle or rectangle.Wherein, the combination of preferred rectangular nozzle and rectangular jet device is considered in aspect less from compressed-air actuated use amount, that be difficult for causing fusible between the strand or friction.
Spinning temperature when carrying out melt spinning is preferably 290～380 ℃, more preferably is 295～360 ℃, more preferably 300～340 ℃.By making spinning temperature in above-mentioned scope, can form stable molten condition, obtain excellent stability of spinning process.
Composition A and composition B are carried out melting with different extruders respectively, and metering is supplied to the composite spinning nozzle, spins with the form of composite fibre.
As will by the method for the strand of spun composite fibre cooling, for example adopting following method: the method for forcibly blowing strand with cold wind; The method of utilizing strand atmosphere temperature on every side to carry out the nature cooling; Regulate the method for the distance between spinning-nozzle and the injector; Or their combination.In addition, for cooling condition, can consider that the spray volume of each single hole of spinning-nozzle, the temperature of carrying out spinning, atmosphere temperature etc. suitably regulate and adopt.
Then, utilize the compressed air that is sprayed by injector that the strand through cooling curing is drawn, stretches.Utilize the traction of injector, method and the condition of stretching to be not particularly limited, consider from the aspect of the crystallization that can effectively promote the PPS fiber, preferred following method: will be heated at least by the compressed air that injector sprays more than 100 ℃, the method of utilizing compressed air after the above-mentioned heating, drawing, stretch more than take spinning speed as 3,000m/ minute; Maybe the distance of the compressed air ejiction opening from the spinning-nozzle lower surface to injector is set to 450～650mm, utilize the compressed air (normal temperature) of injector, with 5, the method of drawing, stretching more than 000m/ minute and less than 6,000m/ minute spinning speed.
Then, will trap by the PPS composite fibre that stretching obtains the mobile non woven fibre networking of carrying out on the net, the nonwoven web of gained be undertaken integrated by heat bonding, can obtain nonwoven fabric thus.
Method as heat bonding, for example can use following method: the thermo-compressed of utilizing various rollers to carry out, described roller for implement respectively to carve on pair of rolls surface up and down the heat embossing roller of gained, by a side roller surface for the roller of flat (smoothly) and the opposing party's roller surface is implemented the roller of engraving gained the heat embossing roller that constitutes, by about the hot calender roll that constitutes etc. of a pair of smooth (smoothly) roller; With make hot blast pass through the gas pass-through mode of the thickness direction of nonwoven web.Wherein, preferred employing can improve mechanical strength and can keep suitable aeration use the heat bonding of heat embossing roller.
As the shape of the engraving that the heat embossing roller is implemented, can use circle, ellipse, square, rectangle, parallelogram, rhombus, regular hexagon and octagon etc.
As the surface temperature of heat embossing roller, be preferably in the scope of fusing point-5 ℃ of the fusing point-30 ℃ of low melting point composition B～low melting point composition B.By the surface temperature that makes the heat embossing roller be more than the fusing point-30 ℃ of composition B, more preferably-25 ℃ more than, more preferably-20 ℃ more than, can carry out fully heat bonding, suppress nonwoven fabric and peel off and produce fluffing.In addition, be below the fusing point-5 ℃ of composition B by the surface temperature that makes the heat embossing roller, can prevent from being melted by fiber and cause producing perforate at pressure contact portion.
The line pressure of the heat embossing roller during as heat bonding is preferably 200～1500N/cm.By the line pressure that makes roller be more than the 200N/cm, more preferably for more than the 300N/cm, can carry out fully heat bonding, can suppress sheet material and peel off and produce fluffing.On the other hand, be that can prevent following phenomenon: the protuberance of engraving inserts in the nonwoven fabric, thereby nonwoven fabric is difficult to from roller peel off below the 1500N/cm, more preferably for below the 1000N/cm by the line pressure that makes roller, perhaps nonwoven fabric fracture.
Bond area as forming by the heat embossing roller is preferably 8～40%.By making bond area be more than 8%, more preferably be more than 10%, more preferably more than 12%, can obtain to be suitable for practical intensity as nonwoven fabric.On the other hand, by making bond area be below 40%, more preferably be below 30%, more preferably below 20%, can preventing following phenomenon: become film sample thing (film like), be difficult to obtain aeration etc. as the speciality of nonwoven fabric.So-called bond area herein, when referring to carry out heat bonding by the irregular roller of a pair of tool, the protuberance of the protuberance of upside roller and downside roller is overlapping, account for the ratio of nonwoven fabric integral body with the part of nonwoven web butt.In addition, when carrying out heat bonding by the irregular roller of tool and plain-barreled roll, refer to that the part of the protuberance of the irregular roller of tool and nonwoven web butt accounts for the ratio of nonwoven fabric integral body.
In addition, in order to improve the thickness of carrying property, control nonwoven fabric, also can under 70～120 ℃ of temperature, line pressure 50～700N/cm, implement to utilize stack to carry out interim bonding operation to the nonwoven web before the heat bonding.As stack, can use the up and down combination of metallic roll or the combination of metallic roll and resin roll or paper bowl.
And then, in order to improve the stability to heat, also can to the nonwoven web before the heat bonding carry out heat treatment under the tension condition of having used pin stenter or clip stenter (clip tenter) etc. or used air drier etc. without the heat treatment under tension (relaxing) condition.As heat treated temperature, be preferably the crystallized temperature of nonwoven web above and for below the fusing point of sheath composition.
Embodiment
Next, specifically describe the present invention based on embodiment.But the present invention is not only limited to these embodiment.
[assay method]
(1) melt flow rate (MFR) (MFR) (g/10 minute)
The MFR of the resin that uses based on ASTM D1238-70, measuring under 315.5 ℃ of the temperature, measuring under the condition of load 5kg and measure.
(2) fusing point (℃)
Use differential scanning calorimetry (DSC) (Q100 processed of TA Instruments company), measure under the following conditions, calculate the mean value of endothermic peak summit temperature, with the fusing point of this mean value as determination object.Need to prove, exist in the resin before fiber forms in the situation of a plurality of endothermic peaks, with the peak maximum temperature of maximum temperature side as fusing point.In addition, fiber during as determination object, is similarly measured, can be inferred by a plurality of endothermic peaks the fusing point of each composition.
Measure atmosphere: nitrogen stream (150ml/ minute)
Temperature range: 30～350 ℃
Programming rate: 20 ℃/minute
Sample size: 5mg
(3) average single fiber fiber number (dtex)
10 sample cuttings of random acquisition from trap online nonwoven web utilize the surface picture of 500～1000 times of microscope photographings, measure in each sample each 10, amount to the width of 100 fiber, calculate mean value.With the average diameter of filamentary width mean value as the fiber with circular section shape, to be obtained whenever 10 by the solid-state density of the resin that uses, the weight of 000m length is as the average single fiber fiber number, second behind the decimal point is rounded up and calculates.
(4) spinning speed (m/ minute)
By the average single fiber fiber number F (dtex) of fiber and the spray volume D (the single hole spray volume made in following brief note) (g/ minute) by the resin of spinning-nozzle single hole ejection that under each condition, sets, calculate spinning speed V (m/ minute) based on following formula.
V＝(10000×D)/F
(5) weight per unit area (g/m of nonwoven fabric
2)
Based on JIS L1913 (2010) 6.2 " quality of per unit area ", from every 1m width of sample, gather the test film of 3 20cm * 25cm, each quality (g) under the weighing standard state is with the every 1m of its mean value
2Quality (g/m
2) expression.
(6) the per unit area weight of nonwoven fabric stretch by force long-pending
6.3.1 based on JIS L1913 (2010), at sample size 5cm * 30cm, clamp interval 20cm, carry out vertical 3 tension tests under draw speed 10cm/ minute the condition, intensity during with sample breakage is as endwise tensile strength (N/5cm), in addition, the elongation of the sample of busy hour measured be accurate to 1mm unit, with above-mentioned percentage elongation (length after the elongation is with respect to initial length) as longitudinal stretching percentage elongation (%), for minute other mean value of endwise tensile strength (N/5cm) and longitudinal stretching percentage elongation (%), with behind the decimal point first round up and calculate.Then, by the weight per unit area (g/m that obtains in the endwise tensile strength of calculating (N/5cm) and longitudinal stretching percentage elongation (%) and (5)
2), utilize following formula, with behind the decimal point first round up, calculate stretching by force of per unit area weight long-pending.
Per unit area weight stretch by force long-pending=endwise tensile strength (N/5cm) * longitudinal stretching percentage elongation (%)/weight per unit area (g/m
2).
(7) percent thermal shrinkage of nonwoven fabric (%)
Measure based on JIS L1906 (2000) 5.9 " percent thermal shrinkages ".Temperature in the freeze-day with constant temperature machine is made as 200 ℃, heat-treated 10 minutes.
(8) heat-resisting exposure test and endwise tensile strength conservation rate
Use hot-blast stove (Espec system, TABAI SAFETY OVEN SHPS-222), input needs vertical sample of the long 30cm of number, wide 5cm, under the hot blast air atmosphere, under the condition of 180 ℃ * 1300 hours, amount of air circulation 300L/ minute, sample is exposed.According to above-mentioned (6) described method the tensile strength of the sample before and after the heat-resisting exposure test is measured, used following formula to calculate the endwise tensile strength conservation rate.
Endwise tensile strength (N/5cm) * 100 before endwise tensile strength (N/5cm)/heat-resisting exposure test after endwise tensile strength conservation rate (%)=heat-resisting exposure test
[embodiment 1]
(composition B)
In autoclave, drop into 100 moles nine water cure sodium, 45 moles sodium acetate and 25 liters 1-METHYLPYRROLIDONE (NMP), be warming up to lentamente 220 ℃ temperature while stir, remove the moisture that contains by distillation.In the system of having finished dehydration with 5 liters NMP add paracide as 91 moles (89.8 % by mole) of main component monomer, as the m-dichlorobenzene of 10 moles (10 % by mole) of accessory ingredient monomer, and 0.2 mole (0.2 % by mole) 1,2, the 4-trichloro-benzenes, under 170 ℃ temperature with nitrogen with 3kg/cm
2After pressurization is enclosed, heat up, polymerization is 4 hours under 260 ℃ temperature.Polymerization is cooled off after finishing, and makes polymer precipitation in distilled water, by having the wire netting of 150 order meshes, collects little bulk polymer.After the fritter shaped polymer that will obtain as mentioned above with 90 ℃ distilled water cleans 5 times, under reduced pressure, under 120 ℃ temperature, carry out drying, obtain MFR and be 152g/10 minute, fusing point and be 257 ℃ copolymerization PPS resin.In blanket of nitrogen, under 160 ℃ temperature, with above-mentioned copolymerization PPS resin drying 10 hours, it is used as composition B.
(composition A)
Use 101 moles paracide as the main component monomer, do not use accessory ingredient monomer and 1,2,4-trichloro-benzenes, in addition, all similarly make the PPS resin with the manufacturing of above-mentioned copolymerization PPS resin.The MFR of the PPS resin of making is 160g/10 minute, and fusing point is 281 ℃.In blanket of nitrogen, under 160 ℃ temperature, with above-mentioned PPS resin drying 10 hours, use as composition A.
(spunlaid nonwoven web)
With mentioned component B (copolymerization PPS resin) sheath composition extruder melting, with mentioned component A (PPS resin) core composition extruder melting, measure take the mass ratio of composition A and composition B as the mode of 80:20, under 325 ℃ of spinning temperatures, with single hole spray volume 1.2g/ minute from the aperture
Rectangle core-sheath-type spinning-nozzle in spin the core-sheath-type composite fibre.Under the atmosphere of 20 ℃ of room temperatures, with spun fiber cooling curing, making it is the rectangular jet device of the position of 550mm by the distance that is arranged at apart from said nozzle, under the condition of injector pressure 0.17MPa, is heated to 200 from injector injection air heater.℃ the air of temperature, with the strand traction, stretch, it is trapped mobile online, carry out the non woven fibre networking.The average single fiber fiber number of the core-sheath-type composite long fiber of gained is 2.4dtex, and spinning speed is 5,012m/ minute, and in 1 hour the spinning, fracture of wire is 0 time, and spinnability is good.
(interim adhesion heat is bonding)
Then, use up and down a pair of stack of the metal-made be arranged on the production line (in line), under the condition of 90 ℃ of line pressure 200N/cm and interim tack temperature, above-mentioned nonwoven web is carried out temporarily bonding.Then, use by metal-made and be carved with globule pattern top roll, and the up and down a pair of bond area that consists of of metal-made and flat lower roll be 12% knurling rolls, under the condition of 250 ℃ of line pressure 1000N/cm, heat bonding temperature, carry out heat bonding, obtain core-sheath-type composite long fiber nonwoven fabric.The weight per unit area of gained core-sheath-type composite long fiber nonwoven fabric is 256g/m
2, the Qiang Shenji of per unit area weight is 20, and percent thermal shrinkage is 0.1% in the vertical, be 0.1% in the horizontal, and the endwise tensile strength conservation rate is 99%.
[embodiment 2]
(composition B)
Use with embodiment 1 in the same copolymerization PPS resin of the resin that uses as composition B.
(composition A)
Use with embodiment 1 in the same PPS resin of the resin that uses as composition A.
(spunlaid nonwoven web)
With compressed-air actuated temperature be made as normal temperature (20 ℃), injector pressure is made as 0.25Mpa, in addition, carries out similarly to Example 1 core-sheath-type composite spinning, non woven fibre networking.The average single fiber fiber number of gained core-sheath-type composite long fiber is 2.3dtex, and spinning speed is 5,250m/ minute, and in the spinning in 1 hour, fracture of wire is 0 time, and spinnability is good.
(interim adhesion heat is bonding)
Then, similarly to Example 1 above-mentioned nonwoven web is implemented interim bonding and heat bonding, obtain core-sheath-type composite long fiber nonwoven fabric.The weight per unit area of gained core-sheath-type composite long fiber nonwoven fabric is 263g/m
2, the Qiang Shenji of per unit area weight is 15, and percent thermal shrinkage is 0.1% in the vertical, be 0.0% in the horizontal, and the endwise tensile strength conservation rate is 98%.
[embodiment 3]
(composition B)
Addition as monomer, paracide is 94.8 moles (94.8 % by mole), m-dichlorobenzene is 5 moles (5 % by mole), 1,2,4-trichloro-benzenes is 0.2 mole (0.2 % by mole), in addition, under the condition of embodiment 1, carry out polymerization, make copolymerization PPS resin, obtain MFR and be 142g/10 minute, fusing point and be 263 ℃ copolymerization PPS resin.With above-mentioned copolymerization PPS resin drying, use as composition B similarly to Example 1.
(composition A)
Use with embodiment 1 in the same PPS resin of the resin that uses as composition A.
(spunlaid nonwoven web)
Use mentioned component A, B, under condition similarly to Example 1, carry out core-sheath-type composite spinning, non woven fibre networking.The average single fiber fiber number of gained core-sheath-type composite long fiber is 2.5dtex, and spinning speed is 4,856m/ minute, and in 1 hour the spinning, fracture of wire is 0 time, and spinnability is good.
(interim adhesion heat is bonding)
Then, except the heat bonding temperature with knurling rolls is made as 255 ℃, similarly to Example 1 above-mentioned nonwoven web is implemented interim bonding and heat bonding, obtain core-sheath-type composite long fiber nonwoven fabric.The weight per unit area of gained core-sheath-type composite long fiber nonwoven fabric is 258g/m
2, the Qiang Shenji of per unit area weight is 11, and percent thermal shrinkage is 0.1% in the vertical, be 0.0% in the horizontal, and the endwise tensile strength conservation rate is 99%.
[embodiment 4]
(composition B)
Addition as monomer, paracide is 84.8 moles (84.8 % by mole), m-dichlorobenzene is 15 moles (15 % by mole), 1,2,4-trichloro-benzenes is 0.2 mole (0.2 % by mole), in addition, under the condition of embodiment 1, carry out polymerization, make copolymerization PPS resin, obtain MFR and be 165g/10 minute, fusing point and be 239 ℃ copolymerization PPS resin.Similarly to Example 1 above-mentioned copolymerization PPS resin is carried out drying, use as composition B.
(composition A)
Use with embodiment 1 in the same PPS resin of the resin that uses as composition A.
(spunlaid nonwoven web)
Use mentioned component A, B, under condition similarly to Example 1, carry out core-sheath-type composite spinning, non woven fibre networking.The average single fiber fiber number of gained core-sheath-type composite long fiber is 2.4dtex, and spinning speed is 5,062m/ minute, and in 1 hour the spinning, fracture of wire is 0 time, and spinnability is good.
(interim adhesion heat is bonding)
Then, except the heat bonding temperature with knurling rolls is made as 230 ℃, similarly to Example 1 above-mentioned nonwoven web is implemented interim bonding and heat bonding, obtain core-sheath-type composite long fiber nonwoven fabric.The weight per unit area of gained core-sheath-type composite long fiber nonwoven fabric is 255g/m
2, the Qiang Shenji of per unit area weight is 19, and percent thermal shrinkage is 0.2% in the vertical, be 0.1% in the horizontal, and the endwise tensile strength conservation rate is 98%.
[comparative example 1]
(composition B)
Do not use composition B.
(composition A)
Use with embodiment 1 in the same PPS resin of the resin that uses as composition A.
(spunlaid nonwoven web)
With mentioned component A melting in extruder, metering, under 325 ℃ of spinning temperatures, with single hole spray volume 1.2g/ minute from the aperture
Rectangle single component spinning-nozzle in spin.Carry out similarly to Example 1 afterwards spinning, non woven fibre networking.The long stapled average single fiber fiber number of gained single component type is 2.4dtex, and spinning speed is 4,920m/ minute, and in 1 hour the spinning, fracture of wire is 0 time, and spinnability is good.
(interim adhesion heat is bonding)
Then, except the heat bonding temperature with knurling rolls is made as 260 ℃, similarly to Example 1 above-mentioned nonwoven web is implemented interim bonding and heat bonding, obtain single component type nonwoven fabric of long fibers.The weight per unit area of gained single component type nonwoven fabric of long fibers is 263g/m
2, the Qiang Shenji of per unit area weight is 4, and percent thermal shrinkage is 0.0% in the vertical, be 0.1% in the horizontal, and the endwise tensile strength conservation rate is 99%.
[comparative example 2]
(composition B)
Do not use composition B.
(composition A)
Use with embodiment 1 in the same PPS resin of the resin that uses as composition A.
(spunlaid nonwoven web)
With mentioned component A melting in extruder, metering, under 325 ℃ of spinning temperatures, with single hole spray volume 1.2g/ minute from the aperture
Rectangle single component spinning-nozzle in spin.Later on except compressed-air actuated temperature is made as normal temperature (20 ℃), injector pressure is made as the 0.25MPa, carries out similarly to Example 1 spinning, non woven fibre networking.The long stapled average single fiber fiber number of gained single component type is 2.0dtex, and spinning speed is 5,935m/ minute, and in 1 hour the spinning, fracture of wire is 0 time, and spinnability is good.
(interim adhesion heat is bonding)
Then, except the heat bonding temperature with knurling rolls is made as 260 ℃, similarly to Example 1 above-mentioned nonwoven web is implemented interim bonding and heat bonding, obtain single component type nonwoven fabric of long fibers.The weight per unit area of gained single component type nonwoven fabric of long fibers is 266g/m
2, the Qiang Shenji of per unit area weight is 3, and percent thermal shrinkage is 0.1% in the vertical, be 0.1% in the horizontal, and the endwise tensile strength conservation rate is 99%.
Will be so that diphenyl sulfide be compared as the core-sheath-type composite long fiber nonwoven fabric of the embodiment 1～4 of sheath composition and comparative example 1,2 single component type nonwoven fabric of long fibers as core composition, copolymerization PPS resin as the PPS resin of formant, the Qiang Shenji of per unit area weight improves significantly, and mechanical strength is excellent.
Utilizability on the industry
The nonwoven fabric that is made of Thermoadhesive conjugate fiber of the present invention has the characteristic of heat resistance, chemical proofing and the anti-flammability of PPS resin, and mechanical strength is excellent, therefore can be suitable for various filter for industry uses, electrically insulating material, battery diaphragm, water treatment film base material, heat insulation base material and protective clothing etc.
Claims (8)
1. polyphenyl thioether complex fiber, it is characterized in that, described polyphenyl thioether complex fiber is mainly formed by composition A and composition B, described composition A is the resin that mainly contains polyphenylene sulfide, described polyphenylene sulfide with to diphenyl sulfide as formant, described composition B is the resin that mainly contains copolymerized polyphenylene sulfide, and described copolymerized polyphenylene sulfide is except contain also containing the copolymerization units more than a kind the diphenyl sulfide at least, and composition B forms at least a portion of fiber surface.
2. polyphenyl thioether complex fiber as claimed in claim 1, it is the core-sheath-type composite fibre take described composition A as the core composition, take described composition B as the sheath composition.
3. polyphenyl thioether complex fiber as claimed in claim 1 or 2, wherein, described composition B contain 70～97 % by mole of repetitive by diphenyl sulfide is consisted of, 3～30 % by mole of copolymerized polyphenylene sulfides that consisted of by a diphenyl sulfide of repetitive.
4. such as each described polyphenyl thioether complex fiber in the claim 1～3, wherein, the fusing point Tm (A) of described composition A and the fusing point Tm (B) of described composition B satisfy following formula:
5(℃)≤Tm(A)-Tm(B)≤80(℃)。
5. a nonwoven fabric is characterized in that, described nonwoven fabric is made of each described polyphenyl thioether complex fiber in the claim 1～4.
6. nonwoven fabric as claimed in claim 5, wherein, described nonwoven fabric is spun-bonded nonwoven fabric.
7. such as claim 5 or 6 described nonwoven fabric, wherein, described nonwoven fabric carries out integrated formation with described polyphenyl thioether complex fiber by heat bonding.
8. such as each described nonwoven fabric in the claim 5～7, wherein, the endwise tensile strength conservation rate in air, under 180 ℃ temperature in 1300 hours the heat-resisting exposure test is more than 80%.
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| JP2011-062745 | 2011-03-22 | ||
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| PCT/JP2012/054906 WO2012127997A1 (en) | 2011-03-22 | 2012-02-28 | Polyphenylene sulfide composite fiber and nonwoven fabric |
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| CN103328704B CN103328704B (en) | 2015-03-18 |
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| EP (1) | EP2690208B1 (en) |
| JP (1) | JP5725426B2 (en) |
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| CN112424410A (en) * | 2018-07-27 | 2021-02-26 | 东丽株式会社 | Spun-bonded nonwoven fabric and air filter composed of spun-bonded nonwoven fabric |
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| US20150240390A1 (en) * | 2012-09-21 | 2015-08-27 | Toray Industries, Inc. | Polyphenylene sulfide composite fiber and nonwoven fabric |
| JP6357747B2 (en) * | 2013-09-26 | 2018-07-18 | 東レ株式会社 | Melt blown nonwoven fabric made of polyphenylene sulfide fiber |
| US10177471B2 (en) * | 2014-11-14 | 2019-01-08 | The Boeing Company | Composite and nanowire conduit |
| JP2021074674A (en) * | 2019-11-08 | 2021-05-20 | 日本バイリーン株式会社 | Membrane support |
| US20230323120A1 (en) * | 2020-08-06 | 2023-10-12 | Kureha Corporation | Poly (phenylene sulfide) resin composition and vibration damping material including same |
| CN114293282A (en) * | 2021-12-09 | 2022-04-08 | 安徽元琛环保科技股份有限公司 | Preparation method of antioxidant polyphenylene sulfide fiber and prepared antioxidant polyphenylene sulfide fiber |
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| CN112424410A (en) * | 2018-07-27 | 2021-02-26 | 东丽株式会社 | Spun-bonded nonwoven fabric and air filter composed of spun-bonded nonwoven fabric |
| US11975281B2 (en) | 2018-07-27 | 2024-05-07 | Toray Industries, Inc. | Spun-bonded nonwoven fabric and air filter constituted from spun-bonded nonwoven fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012127997A1 (en) | 2014-07-24 |
| EP2690208A1 (en) | 2014-01-29 |
| AU2012232449A1 (en) | 2013-10-03 |
| EP2690208A4 (en) | 2014-08-20 |
| CN103328704B (en) | 2015-03-18 |
| JP5725426B2 (en) | 2015-05-27 |
| KR20140039158A (en) | 2014-04-01 |
| WO2012127997A1 (en) | 2012-09-27 |
| EP2690208B1 (en) | 2016-05-11 |
| ES2572933T3 (en) | 2016-06-03 |
| US20140017966A1 (en) | 2014-01-16 |
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