CN103328704B - Polyphenylene sulfide composite fiber and nonwoven fabric - Google Patents
Polyphenylene sulfide composite fiber and nonwoven fabric Download PDFInfo
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- CN103328704B CN103328704B CN201280006269.XA CN201280006269A CN103328704B CN 103328704 B CN103328704 B CN 103328704B CN 201280006269 A CN201280006269 A CN 201280006269A CN 103328704 B CN103328704 B CN 103328704B
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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
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 by formed using polyphenylene sulfide (sometimes also noting work " PPS " by abridging below) as the resin of main component, the fiber of heat resistance and chemical proofing excellence and the nonwoven fabric that is made up of this fiber.
Background technology
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, expect to play above-mentioned characteristic, for industrial applications such as heat-resistant filter, electrically insulating material and battery diaphragms.
Up to the present, about the nonwoven fabric employing PPS resin, kinds of schemes is disclosed.Such as disclose a kind of nonwoven fabric of long fibers obtained as follows: by spun-bond process, spinning is carried out to PPS resin, make cloth and silk, after carrying out stretch processing at temperature more than vitrification point, preferably carrying out biaxial stretch-formed process, implement heat bonding (see patent document 1).In addition, disclose a kind of nonwoven fabric of long fibers obtained as follows: by spun-bond process, spin-drawing is carried out to PPS resin, under condition below its 1st crystallized temperature, temporary adhesion is implemented to gained cloth and silk, afterwards, heat-treat under condition under tension, more than 1st crystallized temperature, then, heat bonding (see patent document 2) is implemented.And then, disclose a kind of degree of crystallinity containing more than 30wt% be 25 ~ 50% PPS fiber, carried out the heat-resistant non-woven fabric (see patent document 3) of integration by heat bonding.But above-mentioned motion is all form nonwoven fabric by the fiber of single component, therefore, be difficult to when there is heat bonding carry out integration by between fiber, be difficult to the problem obtaining the high nonwoven fabric of mechanical strength.
On the other hand, in order to improve Thermoadhesive, there will be a known the Thermoadhesive conjugate fiber containing low melting point composition at present.Up to the present, as the nonwoven fabric be made up of the composite fibre employing PPS resin, disclose a kind of nonwoven fabric of long fibers being made up of sheath-core type conjugate fiber, being formed by carrying out heat bonding, wherein, the sheath composition of described sheath-core type conjugate fiber is made up of PPS resin, and core composition is made up of (see patent document 4) pet resin.But, because the fusing point of sheath composition is higher than core composition, thus Thermoadhesive compared with the fiber of single component without any change, and then, because pet resin is wanting in anti-flammability and chemical proofing, so there is larger problem in durability.
As mentioned above, also do not obtain playing the high nonwoven fabric of the heat resistance of PPS resin and the fiber of chemical proofing, simultaneously Thermoadhesive excellence and mechanical strength.
Patent document 1: Japanese Unexamined Patent Publication 2005-154919 publication
Patent document 2: Japanese Unexamined Patent Publication 2008-223209 publication
Patent document 3: No. 2008/035775th, International Publication
Patent document 4: Japanese Unexamined Patent Publication 2009-155764 publication
Summary of the invention
The object of the present invention is to provide heat resistance, anti-flammability and the chemical proofing etc. and the fiber of Thermoadhesive excellence that play PPS resin and the high nonwoven fabric of mechanical strength.
Namely, the present invention is a kind of polyphenyl thioether complex fiber, it is characterized in that, described polyphenyl thioether complex fiber is formed primarily of composition A and composition B, described composition A is mainly containing the resin of polyphenylene sulfide, described polyphenylene sulfide using to diphenyl sulfide as formant, described composition B is the resin mainly containing copolymerized polyphenylene sulfide, described copolymerized polyphenylene sulfide is except containing the copolymerization units also containing more than at least a kind except diphenyl sulfide, and composition B forms fiber surface at least partially.
In addition, the present invention is a kind of nonwoven fabric, it is characterized in that, described nonwoven fabric is made up of polyphenyl thioether complex fiber of the present invention.
PPS composite fibre of the present invention has the characteristic of the heat resistance of PPS resin, chemical proofing and anti-flammability, and Thermoadhesive is excellent.Therefore, nonwoven fabric of the present invention has the characteristic of the heat resistance of PPS resin, chemical proofing and anti-flammability, and mechanical strength, may be used for various industrial applications.
Detailed description of the invention
The important part of composite fibre of the present invention is, is formed primarily of composition A and composition B, and they are all mainly containing PPS.Thus, excellent heat resistance, anti-flammability and chemical proofing can be obtained.
In addition, the important part of PPS composite fibre of the present invention is, by mainly containing using to diphenyl sulfide as the resin of the PPS of formant as composition A time, use the main resin containing copolymerization PPS to form fiber surface at least partially as the composition B with composition A compound, composition B.Thus, composition B plays a role as adhesive composition, can make the nonwoven fabric of mechanical strength.
As the content to diphenyl sulfide unit in the PPS of composition A, be preferably more than 93 % by mole.By containing more than 93 % by mole, more preferably more than 95 % by mole to diphenyl sulfide unit, the fiber of stringiness and mechanical strength can be made.
As the content of the PPS resin in composition A, from the viewpoint of heat resistance, chemical proofing etc., be preferably more than 85 quality %, be more preferably more than 90 quality %, be more preferably more than 95 quality %.
In addition, in the scope not destroying effect of the present invention, also can mix the thermoplastic resin outside PPS resin in composition A.As the thermoplastic resin outside PPS resin, such as PEI, polyether sulfone, polysulfones, polyphenylene oxide, polyester, polyarylate, polyamide, polyamidoimide, Merlon, polyolefin, polyether-ether-ketone etc. can be enumerated.
In addition, in the scope not destroying effect of the present invention, also can add Nucleating Agent, delustering agent, pigment, mould inhibitor, antiseptic, fire retardant or hydrophilizing agent etc. in composition A.
In addition, the melt flow rate (MFR) (being sometimes simply denoted as MFR below) measured based on ASTM D1238-70 (measure temperature is 315.5 DEG C, to measure load be 5kg load) of preferred component A is 100 ~ 300g/10 minute.Being more than 100g/10 minute by making MFR, being more preferably more than 140g/10 minute, suitable mobility can be obtained, suppress the rising of nozzle back surface pressure in melt spinning, also can suppress to carry out drawing fracture of wire when stretching.On the other hand, being less than 300g/10 minute by making MFR, being more preferably less than 225g/10 minute, suitably can improve the degree of polymerization or molecular weight, obtain being suitable for practical mechanical strength and heat resistance.
In the present invention, the copolymerization PPS of composition B, using to diphenyl sulfide as predominant repeat unit, make to form with except to copolymerization units copolymerization more than 1 except diphenyl sulfide unit kind diphenyl sulfide unit.Relative to whole repetitive, in this copolymerization PPS resin, 70 ~ 97 % by mole are preferably to the content of diphenyl sulfide unit.By make to the content of diphenyl sulfide unit be more than 70 % by mole, be more preferably more than 80 % by mole, be more preferably more than 85 % by mole, heat resistance can be suppressed to reduce.On the other hand, by make to the content of diphenyl sulfide unit be less than 97 % by mole, be more preferably less than 96 % by mole, be more preferably less than 95 % by mole, the composite fibre of Thermoadhesive excellence can be obtained.
As copolymerization units, the isophthalic thio-ether units shown in following formula (1) and the unit etc. shown in formula (2) ~ (5) preferably can be enumerated.
(herein, X represents alkylidene, CO, SO
2unit.)
(herein, R represents alkyl, nitro, phenylene, alkoxyl.)。
In addition, as described above also can exist multiple to the copolymerization units outside diphenyl sulfide.Wherein, from the viewpoint of being easy to obtain obtaining balanced fusing point of Thermoadhesive and heat resistance and the stringiness excellence of fiber, diphenyl sulfide preferably.
As the copolymerization amount in copolymerization PPS, be preferably 5 ~ 30 % by mole.Be more than 5 % by mole by making the copolymerization amount in copolymerization PPS, be more preferably more than 7 % by mole, be more preferably more than 9 % by mole, the composite fibre of Thermoadhesive excellence can be obtained.On the other hand, be less than 30 % by mole by making the copolymerization amount in copolymerization PPS, be more preferably less than 25 % by mole, be more preferably less than 20 % by mole, heat resistance can be suppressed to reduce.
On the other hand, from the viewpoint of the stringiness excellence of fiber, preferably the 3 functionality diphenyl sulfides with following formula being such as representative are suppressed less than 1 % by mole at copolymerization PPS.
In addition, as the mode of the copolymerization in copolymerization PPS, random copolymerization, block copolymerization etc. can be enumerated.Wherein, from the viewpoint of the balanced fusing point being easy to control as obtaining Thermoadhesive and heat resistance, preferred random copolymerization.
As the content of the copolymerization PPS in composition B, from the viewpoint of heat resistance, chemical proofing etc., be preferably more than 85 quality %, be more preferably more than 90 quality %, be more preferably more than 95 quality %.
In addition, in the scope not destroying effect of the present invention, also can mix the thermoplastic resin outside PPS in composition B.As the thermoplastic resin outside PPS, the various thermoplastic resins such as such as PEI, polyether sulfone, polysulfones, polyphenylene oxide, polyester, polyarylate, polyamide, polyamidoimide, Merlon, polyolefin, polyether-ether-ketone can be enumerated.
In addition, in the scope not destroying effect of the present invention, also can add Nucleating Agent, delustering agent, pigment, mould inhibitor, antiseptic, fire retardant or hydrophilizing agent etc. in composition B.
In addition, the MFR measured based on ASTM D1238-70 (measure temperature is 315.5 DEG C, to measure load be 5kg load) of preferred component B is 100 ~ 300g/10 minute.Being more than 100g/10 minute by making MFR, being more preferably more than 120g/10 minute, the rising of nozzle back surface pressure in melt spinning can be suppressed, also can suppress to carry out drawing fracture of wire when stretching.On the other hand, being less than 300g/10 minute by making MFR, being more preferably less than 225g/10 minute, suitable mobility can be obtained, be stably compounded to form.
In the present invention, owing to using composition B as 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 DEG C.Be more than 200 DEG C by making the fusing point of heat bonding composition, be more preferably more than 230 DEG C, be more preferably more than 240 DEG C, heat resistance can be suppressed to reduce.On the other hand, be less than 275 DEG C by making the fusing point of heat bonding composition, be more preferably less than 270 DEG C, be more preferably less than 265 DEG C, the composite fibre of Thermoadhesive excellence can be obtained.The fusing point of composition B suitably can be regulated by the mol ratio of copolymer composition.
In addition, the fusing point as the fusing point of composition A and the fusing point of composition B is poor, is preferably 5 ~ 80 DEG C.Be more than 5 DEG C by making fusing point difference, be more preferably more than 10 DEG C, be more preferably more than 15 DEG C, the composite fibre of Thermoadhesive excellence can be obtained.On the other hand, be less than 80 DEG C by making fusing point difference, be more preferably less than 50 DEG C, be more preferably less than 40 DEG C, heat resistance can be suppressed to reduce.
As the ratio shared by the composition B in PPS composite fibre of the present invention, be preferably 5 ~ 70 quality %.By make the ratio shared by composition B be more than 5 quality %, be more preferably 10 quality %, be more preferably more than 15 quality %, efficiency can obtain firmly heat bonding well.On the other hand, by make the ratio shared by composition B be below 70 quality %, be more preferably below 50 quality %, be more preferably below 30 quality %, mechanical strength can be suppressed to reduce.
As the complex morphological in PPS composite fibre of the present invention, what composition B formed fiber surface is important at least partially.As above-mentioned complex morphological, the core-sheath-type that such as circular in fibre section composition A is surrounded by the composition B of the identical annular in center can be enumerated; The core sheath eccentric type of the center of composition A and the misalignment of composition B; Using composition A as island component, composition B is as the fabric of island-in-sea type of sea component; The parallel type that two-component is arranged side by side; Two-component is with the radial radial pattern alternately arranged; Multiple composition B are configured at the Multiblade etc. of the surrounding of composition A.Wherein, preferred component B occupies fiber surface entirety and the core-sheath-type of the stringiness excellence of fiber.
As the average single fiber fiber number of PPS composite fibre of the present invention, be preferably 0.5 ~ 10dtex.By make average single fiber fiber number be more than 0.5dtex, more preferably for more than 1dtex, be more preferably more than 2dtex, the stringiness of fiber can be kept, suppress fracture of wire in spinning multiple.In addition, by make average single fiber fiber number be below 10dtex, more preferably for below 5dtex, be more preferably below 4dtex, the spray volume of the molten resin of each spinning-nozzle single hole can be suppressed, implement fully cooling to fiber, the fusible spinnability caused between can suppressing by fiber reduces.In addition, weight per unit area when making nonwoven fabric can be suppressed irregular, make to have excellent surface quality.In addition, from the viewpoint of dust arrestment performance when nonwoven fabric being used for filter etc., average single fiber fiber number is also preferably below 10dtex, is more preferably below 5dtex, is more preferably below 4dtex.
PPS composite fibre of the present invention can use with the form of any one in multifilament (Multifilament), monofilament (monofilament) or staple fibre, also can use as the fiber forming all cloth and silks such as fabric or nonwoven fabric.Wherein, PPS composite fibre of the present invention preferably uses as the formation fiber of nonwoven fabric.This is due in nonwoven fabric, forms the intensity being conducive to nonwoven fabric between fiber by heat bonding.
As nonwoven fabric, 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 bonded non-woven cloth, chemical adhesion nonwoven fabric, heat bonding nonwoven fabric, tow fibrillation formula nonwoven fabric, air-laid nonwoven fabrics etc. can be enumerated.Wherein, the spun-bonded nonwoven fabric of preferred productivity ratio and mechanical strength.
In addition, for the nonwoven fabric be made up of PPS composite fibre of the present invention, due to high mechanical strength can be obtained by heat bonding, therefore carry out integration preferably by heat bonding and formed.
As the weight per unit area of nonwoven fabric of the present invention, be preferably 10 ~ 1000g/m
2.Be 10g/m by making weight per unit area
2above, be more preferably 100g/m
2above, 200g/m is more preferably
2above, the nonwoven fabric that can be suitable for practical mechanical strength can be obtained.On the other hand, by making weight per unit area be 1000g/m
2below, be more preferably 700g/m
2below, 500g/m is more preferably
2below, suitable aeration can be had, suppress to cause high pressure loss when middle uses such as filters.
In the nonwoven fabric be made up of Thermoadhesive conjugate fiber of the present invention, be preferably more than 10 by the endwise tensile strength of nonwoven fabric, longitudinal stretching percentage elongation and weight per unit area, the Qiang Shenji of per unit area weight that utilizes following formula to calculate.
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 by making the Qiang Shenji of per unit area weight, be more preferably more than 13, be more preferably more than 15, form the nonwoven fabric with also operable mechanical strength under harsh environment.In addition, the upper limit is not particularly limited, and from the viewpoint of preventing, nonwoven fabric is hardening, operability worsens, and is preferably less than 100.
The endwise tensile strength conservation rate exposed in the heat-resisting exposure test of 1300 hours is more than 80% to the nonwoven fabric be made up of Thermoadhesive conjugate fiber of the present invention preferably in atmosphere, at the temperature of 180 DEG C.Endwise tensile strength conservation rate is more than 80%, be more preferably more than 85%, when being more preferably more than 90%, also can the application of the heat-resistant filter etc. of Long-Time Service under withstand high temperatures.The higher limit of endwise tensile strength conservation rate is not particularly limited, and is preferably less than 150%.
Then, the preferred version of the manufacture method of PPS composite fibre of the present invention and nonwoven fabric is described.
As the polymerization of the copolymerization PPS used in the present invention, comprise various method, following methods easily makes the degree of polymerization of resulting polymers rise, for preferably, described method is: coordinate by alkali metal sulphide with to phenyl-dihalide (main component monomer) and accessory ingredient monomer with the molar ratio corresponding with above-mentioned copolymerization rate, in polar solvent, under the existence of reagent and additive in polymerization, under high temperature, condition of high voltage, carry out the method for being polymerized.Particularly preferably use vulcanized sodium as alkali metal sulphide, use paracide as main component monomer, use 1-METHYLPYRROLIDONE as solvent.
As accessory ingredient monomer, following monomer can be enumerated:
When wish imports the isophthalic thio-ether units of above-mentioned formula (1), the monomer shown in following formula can be used;
In addition, when wish imports the copolymerization units of above-mentioned formula (2), the monomer shown in following formula can be used;
In addition, when wish imports the copolymerization units of above-mentioned formula (3), the monomer shown in following formula can be used;
(herein, X represents alkylidene, CO, SO
2unit.)
In addition, when wish imports the copolymerization units of above-mentioned formula (4), the monomer shown in following formula can be used;
In addition, when wish imports the copolymerization units of above-mentioned formula (5), the monomer shown in following formula can be used,
(herein, R represents alkyl, nitro, phenylene, alkoxyl.)
Multiple above-mentioned accessory ingredient monomer can be there is.
On the other hand, for the PPS used in the present invention, the method same with copolymerization PPS can be adopted to be polymerized, but mismatch accessory ingredient monomer or reduce its cooperation.
For the method manufacturing PPS composite fibre of the present invention, known melt spinning method can be adopted.Such as when sheath-core type conjugate fiber, core composition PPS resin and sheath composition copolymerization PPS resin are carried out melting with different extruders respectively, metering, be supplied to core-sheath-type composite nozzle, melt spinning, uses the cooling devices such as current known transverse injection or ring-type injection to be cooled by strand, afterwards, give finish, via pulling roll with the form of undrawn yarn winding on the winder.As the form of fiber, when wanting to obtain staple fibre, can carry out as follows: utilize known stretching-machine to be stretched between the roller group that peripheral speed is different by the undrawn yarn through winding, after utilizing the impartings such as press-in type crimping machine curling, the cutting machines such as EC cutting machine are used to be cut into desired length.As the form of fiber, when wanting to obtain long fiber, can carry out as follows: after utilizing stretching-machine to stretch, winding, carries out the processing such as twisted filament processing, false twist yarn processing as required.
Then, as the method for the composite fibre nonwoven cloth utilizing spun-bond process to obtain of the preferred configuration of nonwoven fabric of the present invention, following explanation is carried out to manufacture.
Spun-bond process is the manufacture method needing to carry out following operation: by resin melting, after carrying out spinning by spinning-nozzle, utilize injector to draw the strand through cooling curing, stretch, trap movement carry out non woven fibre networking on the net after, carry out heat bonding.
As the shape of spinning-nozzle or injector, the various shape such as circle or rectangle can be adopted.Wherein, less from the viewpoint of compressed-air actuated use amount, not easily cause fusible between strand or friction, the combination of preferred rectangular nozzle and rectangular jet device.
Spinning temperature when carrying out melt spinning is preferably 290 ~ 380 DEG C, is more preferably 295 ~ 360 DEG C, is more preferably 300 ~ 340 DEG C.By making spinning temperature in above-mentioned scope, stable molten condition can be formed, obtaining excellent stability of spinning process.
Composition A and composition B is carried out melting with different extruders respectively, and metering, is supplied to composite spinning nozzle, spins with the form of composite fibre.
As the method will cooled by the strand of spun composite fibre, such as, can adopt following method: the method for forcibly blowing strand with cold wind; The atmosphere temperature around strand is utilized to carry out the method for nature cooling; Regulate the method for the distance between spinning-nozzle and 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, the compressed air sprayed by injector is utilized to draw the strand through cooling curing, stretch.The traction of injector, the method for stretching and condition is utilized to be not particularly limited, from the viewpoint of effectively promoting the crystallization of PPS fiber, preferred following method: the compressed air sprayed by injector is at least heated to more than 100 DEG C, utilize the compressed air after above-mentioned heating, take spinning speed as the method for carrying out for more than 3,000m/ minute drawing, stretching; Or the distance of the compressed air ejiction opening from spinning-nozzle lower surface to injector is set to 450 ~ 650mm, utilize the compressed air (normal temperature) of injector, with 5, the method that more than 000m/ minute and the spinning speed being less than 6,000m/ minute carry out drawing, stretching.
Then, what the PPS composite fibre obtained by stretching is trapped movement carries out non woven fibre networking on the net, the nonwoven web of gained is carried out integration by heat bonding, can obtain nonwoven fabric thus.
As the method for heat bonding, such as can use following method: utilize the thermo-compressed that various roller carries out, the heat embossing roller that described roller is the heat embossing roller implementing engraving gained on upper and lower pair of rolls surface respectively, the combination of implementing the roller carving gained by the roller of roller surface for flat (smoothly) of a side and the surface of the roller to the opposing party is formed, the hot calender roll etc. be made up of the combination of upper and lower a pair smooth (smoothly) roller; With the gas pass-through mode making hot blast by the thickness direction of nonwoven web.Wherein, preferably employing can improve mechanical strength and can keep the heat bonding employing heat embossing roller of suitable aeration.
As the shape of the engraving implemented heat embossing roller, circle, ellipse, square, rectangle, parallelogram, rhombus, regular hexagon and octagon etc. can be used.
As the surface temperature of heat embossing roller, be preferably in the scope of the fusing point-5 DEG C of fusing point-30 DEG C ~ low melting point composition B of low melting point composition B.By making the surface temperature of heat embossing roller be fusing point more than-30 DEG C, more preferably more than-25 DEG C, more preferably more than-20 DEG C of composition B, heat bonding can be carried out fully, suppressing nonwoven fabric to be peeled off and producing fluffing.In addition, by making the surface temperature of heat embossing roller be the fusing point less than-5 DEG C of composition B, can prevent from being caused producing perforate at pressure contact portion by fiber melt.
As the line pressure of heat embossing roller during heat bonding, be preferably 200 ~ 1500N/cm.By making the line pressure of roller be more than 200N/cm, more preferably for more than 300N/cm, heat bonding can be carried out fully, sheet material can be suppressed to peel off and produce fluffing.On the other hand, be below 1500N/cm by making the line pressure of roller, more preferably for below 1000N/cm, following phenomenon can be prevented: the protuberance of engraving inserts in nonwoven fabric, thus nonwoven fabric is difficult to peel off from roller, or nonwoven fabric fracture.
As the bond area formed by heat embossing roller, be preferably 8 ~ 40%.Be more than 8% by making bond area, be more preferably more than 10%, be more preferably more than 12%, can obtain being suitable for practical intensity as nonwoven fabric.On the other hand, be less than 40% by making bond area, be more preferably less than 30%, be more preferably less than 20%, following phenomenon can be prevented: become film sample thing (film like), be difficult to obtain the speciality as nonwoven fabric such as aeration.So-called bond area herein, refers to when carrying out heat bonding by a pair irregular roller of tool, the ratio that the protuberance of upside roller is overlapping with the protuberance of downside roller, part that is that abut with nonwoven web accounts for nonwoven fabric entirety.In addition, when carrying out heat bonding by the irregular roller of tool and plain-barreled roll, refer to that part that the protuberance of the irregular roller of tool abuts with nonwoven web accounts for the ratio of nonwoven fabric entirety.
In addition, in order to improve carrying property, control the thickness of nonwoven fabric, also can, under temperature 70 ~ 120 DEG C, line pressure 50 ~ 700N/cm, implement to utilize stack to carry out the operation of temporary adhesion to the nonwoven web before heat bonding.As stack, the combination of upper and lower metallic roll or the combination of metallic roll and resin roll or paper bowl can be used.
And then, in order to improve the stability to heat, also can carry out the heat treatment under the tension condition employing pin stenter or clip stenter (clip tenter) etc. to the nonwoven web before heat bonding or employ air drier etc. without tension (relaxing) condition under heat treatment.As heat treated temperature, be preferably nonwoven web crystallized temperature more than and be sheath composition fusing point below.
Embodiment
Next, the present invention is specifically described based on embodiment.But the present invention is not only limited to these embodiments.
[assay method]
(1) melt flow rate (MFR) (MFR) (g/10 minute)
The MFR of the resin used measures based on ASTM D1238-70, measuring at temperature 315.5 DEG C, under the condition that measures load 5kg.
(2) fusing point (DEG C)
Use differential scanning calorimetry (DSC) (TA Instruments Inc. Q100), measure under the following conditions, calculate the mean value of endothermic peak summit temperature, using the fusing point of this mean value as determination object.It should be noted that, when there is multiple endothermic peak in the resin before processbearing astrocyte, using the peak maximum temperature of maximum temperature side as fusing point.In addition, during using fiber as determination object, similarly measure, the fusing point of each composition can be estimated by multiple endothermic peak.
Measure atmosphere: nitrogen stream (150ml/ minute)
Temperature range: 30 ~ 350 DEG C
Programming rate: 20 DEG C/min
Sample size: 5mg
(3) average single fiber fiber number (dtex)
From trapping random acquisition 10 sample cuttings online nonwoven web, utilizing the surface picture of microscope photographing 500 ~ 1000 times, measuring each 10 in each sample, amount to the width of the fiber of 100, calculate mean value.Using filamentary width mean value as the average diameter of fiber with circular section shape, obtain the weight of every 10,000m length as average single fiber fiber number by the solid state density of the resin used, second after 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 (single hole spray volume made in following brief note) (g/ minute) of the resin sprayed by spinning-nozzle single hole that sets in each condition, 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, weigh each quality (g) under standard state, by the every 1m of its mean value
2quality (g/m
2) represent.
(6) nonwoven fabric per unit area weight stretch by force long-pending
Based on the 6.3.1 of JIS L1913 (2010), at sample size 5cm × 30cm, clamp interval 20cm, longitudinal direction 3 tension tests are carried out under the condition of draw speed 10cm/ minute, using intensity during sample breakage as endwise tensile strength (N/5cm), in addition, mensuration is carried out to the elongation of the sample of busy hour and is accurate to 1mm unit, using above-mentioned percentage elongation (length after elongation is relative to initial length) as longitudinal stretching percentage elongation (%), for point other mean value of endwise tensile strength (N/5cm) and longitudinal stretching percentage elongation (%), by after decimal point first round up and calculate.Then, by the weight per unit area (g/m obtained in the endwise tensile strength calculated (N/5cm) and longitudinal stretching percentage elongation (%) and (5)
2), utilize following formula, by after 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 shrinkage ".Temperature in freeze-day with constant temperature machine is set to 200 DEG C, heat-treats 10 minutes.
(8) heat-resisting exposure test and endwise tensile strength conservation rate
Use hot-blast stove (Espec system, TABAI SAFETY OVEN SHPS-222), drop into and need the long 30cm of number, longitudinal sample of wide 5cm, under hot blast air atmosphere, 180 DEG C × 1300 hours, sample is exposed under the condition of amount of air circulation 300L/ minute.Measure according to the tensile strength of method to the sample before and after heat-resisting exposure test described in above-mentioned (6), use following formula to calculate 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 the 1-METHYLPYRROLIDONE (NMP) of the nine water cure sodium of 100 moles, the sodium acetate of 45 moles and 25 liters, stirs the temperature being warming up to 220 DEG C lentamente, by distilling the moisture that removing contains.The paracide of 91 moles (89.8 % by mole) as main component monomer is added together with the NMP of 5 liters, as the m-dichlorobenzene of 10 moles (10 % by mole) of accessory ingredient monomer and 1 of 0.2 mole (0.2 % by mole) in the system completing dehydration, 2,4-trichloro-benzenes, at the temperature of 170 DEG C by nitrogen with 3kg/cm
2after pressurization is enclosed, heat up, be polymerized 4 hours at the temperature of 260 DEG C.Cool after polymerization terminates, making polymer be deposited in distilled water, by having the wire netting of 150 order meshes, collecting little bulk polymer.After the little bulk polymer obtained as mentioned above being cleaned 5 times with the distilled water of 90 DEG C, under reduced pressure, at the temperature of 120 DEG C carry out drying, obtain the copolymerization PPS resin that MFR is 152g/10 minute, fusing point is 257 DEG C.In blanket of nitrogen, at the temperature of 160 DEG C, by above-mentioned copolymerization PPS resin drying 10 hours, composition B is it can be used as to use.
(composition A)
Use the paracide of 101 moles as main component monomer, do not use accessory ingredient monomer and 1,2,4-trichloro-benzenes, in addition, all manufacture PPS resin in the same manner as the manufacture of above-mentioned copolymerization PPS resin.The MFR of the PPS resin manufactured is 160g/10 minute, and fusing point is 281 DEG C.By above-mentioned PPS resin drying 10 hours in blanket of nitrogen, at the temperature of 160 DEG C, use as composition A.
(spunlaid nonwoven web)
By mentioned component B (copolymerization PPS resin) sheath composition extruder melting, by mentioned component A (PPS resin) core composition extruder melting, measure in the mode that the mass ratio of composition A and composition B is 80:20, at spinning temperature 325 DEG C, with single hole spray volume 1.2g/ minute from aperture
rectangular core sheath spinning-nozzle in spin sheath-core type conjugate fiber.Under the atmosphere of room temperature 20 DEG C, by spun fiber cooling curing, make its distance passing through to be arranged at distance said nozzle be the rectangular jet device of the position of 550mm, under the condition of injector pressure 0.17MPa, be heated to 200 from injector injection air heater.DEG C the air of temperature, strand is drawn, stretches, trapped the online of movement, carry out 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 the spinning of 1 hour, fracture of wire is 0 time, and spinnability is good.
(temporary adhesion heat bonding)
Then, use upper and lower a pair stack of metal that be arranged on production line (in line), under the condition of line pressure 200N/cm and temporary adhesion temperature 90 DEG C, above-mentioned nonwoven web is carried out temporary adhesion.Then, use by metal and be carved with the top roll of globule pattern and metal and a pair bond area up and down that flat lower roll is formed is the knurling rolls of 12%, under the condition of line pressure 1000N/cm, bonding temperature 250 DEG C, 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 endwise tensile strength conservation rate is 99%.
[embodiment 2]
(composition B)
Use the copolymerization PPS resin same with the resin used in embodiment 1 as composition B.
(composition A)
Use the PPS resin same with the resin used in embodiment 1 as composition A.
(spunlaid nonwoven web)
Compressed-air actuated temperature is set to normal temperature (20 DEG C), injector pressure is set to 0.25Mpa, in addition, carry out core-sheath-type composite spinning, non woven fibre networking similarly to Example 1.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 spinning in 1 hour, fracture of wire is 0 time, and spinnability is good.
(temporary adhesion heat bonding)
Then, similarly to Example 1 temporary adhesion and heat bonding are implemented to above-mentioned nonwoven web, 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 endwise tensile strength conservation rate is 98%.
[embodiment 3]
(composition B)
As the addition of 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, be polymerized under the condition of embodiment 1, manufacture copolymerization PPS resin, obtain the copolymerization PPS resin that MFR is 142g/10 minute, fusing point is 263 DEG C.Similarly to Example 1 by above-mentioned copolymerization PPS resin drying, use as composition B.
(composition A)
Use the PPS resin same with the resin used in embodiment 1 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 the spinning of 1 hour, fracture of wire is 0 time, and spinnability is good.
(temporary adhesion heat bonding)
Then, be set to except 255 DEG C except by the bonding temperature of knurling rolls, similarly to Example 1 temporary adhesion and heat bonding implemented to above-mentioned nonwoven web, 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 endwise tensile strength conservation rate is 99%.
[embodiment 4]
(composition B)
As the addition of 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, be polymerized under the condition of embodiment 1, manufacture copolymerization PPS resin, obtain the copolymerization PPS resin that MFR is 165g/10 minute, fusing point is 239 DEG C.Similarly to Example 1 above-mentioned copolymerization PPS resin is carried out drying, use as composition B.
(composition A)
Use the PPS resin same with the resin used in embodiment 1 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 the spinning of 1 hour, fracture of wire is 0 time, and spinnability is good.
(temporary adhesion heat bonding)
Then, be set to except 230 DEG C except by the bonding temperature of knurling rolls, similarly to Example 1 temporary adhesion and heat bonding implemented to above-mentioned nonwoven web, 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 endwise tensile strength conservation rate is 98%.
[comparative example 1]
(composition B)
Do not use composition B.
(composition A)
Use the PPS resin same with the resin used in embodiment 1 as composition A.
(spunlaid nonwoven web)
By mentioned component A melting in an extruder, metering, at spinning temperature 325 DEG C, with single hole spray volume 1.2g/ minute from aperture
rectangle single component spinning-nozzle in spin.Carry out spinning, non woven fibre networking similarly to Example 1 afterwards.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 the spinning of 1 hour, fracture of wire is 0 time, and spinnability is good.
(temporary adhesion heat bonding)
Then, be set to except 260 DEG C except by the bonding temperature of knurling rolls, similarly to Example 1 temporary adhesion and heat bonding implemented to above-mentioned nonwoven web, 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 endwise tensile strength conservation rate is 99%.
[comparative example 2]
(composition B)
Do not use composition B.
(composition A)
Use the PPS resin same with the resin used in embodiment 1 as composition A.
(spunlaid nonwoven web)
By mentioned component A melting in an extruder, metering, at spinning temperature 325 DEG C, with single hole spray volume 1.2g/ minute from aperture
rectangle single component spinning-nozzle in spin.Later except compressed-air actuated temperature being set to normal temperature (20 DEG C), injector pressure is set to except 0.25MPa, carries out spinning, non woven fibre networking similarly to Example 1.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 the spinning of 1 hour, fracture of wire is 0 time, and spinnability is good.
(temporary adhesion heat bonding)
Then, be set to except 260 DEG C except by the bonding temperature of knurling rolls, similarly to Example 1 temporary adhesion and heat bonding implemented to above-mentioned nonwoven web, 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 endwise tensile strength conservation rate is 99%.
By using the PPS resin that is formant to diphenyl sulfide as core composition, copolymerization PPS resin as the core-sheath-type composite long fiber nonwoven fabric of the embodiment 1 ~ 4 of sheath composition compared with the single component type nonwoven fabric of long fibers of comparative example 1,2, the Qiang Shenji of per unit area weight improves significantly, mechanical strength.
Utilizability in industry
The nonwoven fabric be made up of Thermoadhesive conjugate fiber of the present invention has the characteristic of the heat resistance of PPS resin, chemical proofing and anti-flammability, and mechanical strength, therefore can be suitable for various filter for industry use, electrically insulating material, battery diaphragm, water treatment film base material, heat insulation base material and protective clothing etc.
Claims (8)
1. a polyphenyl thioether complex fiber, it is characterized in that, described polyphenyl thioether complex fiber is formed primarily of composition A and composition B, described composition A is the resin mainly containing polyphenylene sulfide, described polyphenylene sulfide using to diphenyl sulfide as formant, described composition B is the resin mainly containing copolymerized polyphenylene sulfide, and described copolymerized polyphenylene sulfide is except containing the copolymerization units also containing more than at least a kind except diphenyl sulfide, and composition B forms fiber surface at least partially.
2. polyphenyl thioether complex fiber as claimed in claim 1, its be with described composition A be core composition, the sheath-core type conjugate fiber that is sheath composition with described composition B.
3. polyphenyl thioether complex fiber as claimed in claim 1 or 2, wherein, described composition B contain 70 ~ 97 % by mole of repetitive by forming diphenyl sulfide, 3 ~ 30 % by mole of copolymerized polyphenylene sulfides be made up of a diphenyl sulfide of repetitive.
4. polyphenyl thioether complex fiber as claimed in claim 1, wherein, the fusing point Tm (A) of described composition A and the fusing point Tm (B) of described composition B meets following formula:
5℃≦Tm(A)－Tm(B)≦80℃。
5. a nonwoven fabric, is characterized in that, described nonwoven fabric is that the polyphenyl thioether complex fiber according to any one of Claims 1 to 4 is formed.
6. nonwoven fabric as claimed in claim 5, wherein, described nonwoven fabric is spun-bonded nonwoven fabric.
7. the nonwoven fabric as described in claim 5 or 6, wherein, described polyphenyl thioether complex fiber is carried out integration by heat bonding and is formed by described nonwoven fabric.
8. nonwoven fabric as claimed in claim 5, wherein, the endwise tensile strength conservation rate in atmosphere, in the temperature of the 180 DEG C heat-resisting exposure test of lower 1300 hours is more than 80%.
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| JP2011062745 | 2011-03-22 | ||
| JP2011-062745 | 2011-03-22 | ||
| PCT/JP2012/054906 WO2012127997A1 (en) | 2011-03-22 | 2012-02-28 | Polyphenylene sulfide composite fiber and nonwoven fabric |
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| US (1) | US20140017966A1 (en) |
| EP (1) | EP2690208B1 (en) |
| JP (1) | JP5725426B2 (en) |
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| EP2899303B1 (en) * | 2012-09-21 | 2017-06-21 | Toray Industries, Inc. | Polyphenylene sulfide composite fiber and non-woven 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 |
| 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 |
| JP7373668B2 (en) * | 2020-08-06 | 2023-11-02 | 株式会社クレハ | Polyphenylene sulfide resin composition and vibration damping material containing the 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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- 2012-02-28 AU AU2012232449A patent/AU2012232449A1/en not_active Abandoned
- 2012-02-28 WO PCT/JP2012/054906 patent/WO2012127997A1/en active Application Filing
- 2012-02-28 JP JP2012515838A patent/JP5725426B2/en not_active Expired - Fee Related
- 2012-02-28 EP EP12760981.6A patent/EP2690208B1/en not_active Not-in-force
- 2012-02-28 KR KR1020137020879A patent/KR20140039158A/en not_active Application Discontinuation
- 2012-02-28 US US14/005,999 patent/US20140017966A1/en not_active Abandoned
- 2012-02-28 ES ES12760981.6T patent/ES2572933T3/en active Active
- 2012-02-28 CN CN201280006269.XA patent/CN103328704B/en not_active Expired - Fee Related
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| CN101187091A (en) * | 2007-12-18 | 2008-05-28 | 德阳科吉高新材料有限责任公司 | Copolymerized polyphenylene sulfide composite fiber manufacture method |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20140017966A1 (en) | 2014-01-16 |
| ES2572933T3 (en) | 2016-06-03 |
| CN103328704A (en) | 2013-09-25 |
| JP5725426B2 (en) | 2015-05-27 |
| EP2690208B1 (en) | 2016-05-11 |
| WO2012127997A1 (en) | 2012-09-27 |
| KR20140039158A (en) | 2014-04-01 |
| EP2690208A4 (en) | 2014-08-20 |
| EP2690208A1 (en) | 2014-01-29 |
| JPWO2012127997A1 (en) | 2014-07-24 |
| AU2012232449A1 (en) | 2013-10-03 |
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