WO2019039373A1 - Resin fiber and method for producing same - Google Patents

Resin fiber and method for producing same Download PDF

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Publication number
WO2019039373A1
WO2019039373A1 PCT/JP2018/030402 JP2018030402W WO2019039373A1 WO 2019039373 A1 WO2019039373 A1 WO 2019039373A1 JP 2018030402 W JP2018030402 W JP 2018030402W WO 2019039373 A1 WO2019039373 A1 WO 2019039373A1
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WO
WIPO (PCT)
Prior art keywords
resin
fiber
styrene
thermoplastic resin
thermoplastic
Prior art date
Application number
PCT/JP2018/030402
Other languages
French (fr)
Japanese (ja)
Inventor
伊藤雅典
Original Assignee
日本エイアンドエル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本エイアンドエル株式会社 filed Critical 日本エイアンドエル株式会社
Priority to JP2019537585A priority Critical patent/JP7139336B2/en
Publication of WO2019039373A1 publication Critical patent/WO2019039373A1/en
Priority to JP2021183304A priority patent/JP7360435B2/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/20—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • D01F6/22—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain from polystyrene
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/42—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • 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

Definitions

  • the present invention relates to a resin fiber comprising a thermoplastic resin composition and a method for producing the same. More specifically, the present invention relates to a resin fiber comprising a thermoplastic resin composition containing a styrenic resin, a resin fiber comprising a thermoplastic resin composition containing a styrenic resin and another thermoplastic resin, and a method for producing them.
  • a resin fiber comprising a thermoplastic resin composition containing a styrenic resin
  • a resin fiber comprising a thermoplastic resin composition containing a styrenic resin and another thermoplastic resin and a method for producing them.
  • a fiber-reinforced plastic in which reinforcing fibers such as carbon fibers are mixed with a resin can achieve weight reduction by thinning since the rigidity when forming a molded article is high. Therefore, it is used in various fields.
  • As a method of blending reinforcing fiber into resin there is a method of melt-kneading using an extrusion kneader, but there is a problem that the reinforcing fiber is cut during kneading, and the rigidity is lowered.
  • the resin of the thermoplastic resin fiber is a crystalline resin or a polycarbonate resin, and the hygroscopicity, the shrinkage, the warp and the durability of the molded product are still insufficient.
  • a styrenic resin as the thermoplastic resin fiber.
  • Patent Document 3 discloses a resin fiber containing a styrene-based resin, but a resin fiber containing a styrene-based resin having a sufficient strength and elongation and a resistance to the papermaking method and the non-woven fabric method is obtained. It is not the current situation.
  • An object of the present invention is to provide a resin fiber having both strength and elongation which can withstand the production of a fiber reinforced plastic by a papermaking method or a non-woven method, and further capable of continuous production, and a method of producing the same.
  • the present inventor has found that the above problems can be solved by defining the melt volume rate of a thermoplastic resin composition containing a styrene-based resin in a specific range, and the present invention has been completed. Furthermore, the present inventors have found that the above-mentioned problems can be solved by dispersing a styrenic resin in nano units, containing styrenic resins and other thermoplastic resins, and have completed the present invention.
  • the present invention is constituted by the following items 1 to 6.
  • Item 1 A resin fiber comprising a thermoplastic resin composition containing a styrene resin, wherein the melt volume rate of the thermoplastic resin composition measured under the conditions of a temperature of 220 ° C. and a load of 10 kg according to ISO 1133 is 20 ( resin fiber characterized by cm 3/10 min) or less.
  • Item 2 The resin fiber according to Item 1, wherein the thermoplastic resin further contains another thermoplastic resin other than a styrene resin.
  • Item 3 A resin fiber comprising a thermoplastic resin composition containing a styrene-based resin, wherein the thermoplastic resin composition further includes another thermoplastic resin other than a styrene-based resin, and the styrene-based resin is nano A resin fiber characterized by being dispersed in units.
  • the above-mentioned other thermoplastic resin is at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin.
  • Item 5 A fiber reinforced plastic comprising a reinforcing fiber and the resin fiber according to any one of items 1 to 4.
  • Item 6 A method for producing a resin fiber according to any one of items 1 to 4, which is obtained by a melt spinning method or a melt blowing method.
  • resin fibers excellent in strength and elongation and capable of continuous production can be obtained.
  • the product of the present invention is used for producing a fiber-reinforced plastic in a paper-making method or a non-woven fabric method, it is excellent in processability, handleability and deformability, and shaping to a three-dimensional shape becomes easy.
  • the resin fiber of the first invention is a resin fiber comprising a first thermoplastic resin composition containing a styrene resin, and according to ISO 1133 of the first thermoplastic resin composition, a temperature of 220 ° C., a load melt volume rate measured under conditions of 10kg is equal to or less than 20 (cm 3/10 min).
  • the resin fiber of the second invention is a resin fiber comprising a second thermoplastic resin composition containing a styrene resin, and the second thermoplastic resin composition is other than a styrene resin. And the styrenic resin dispersed in nano units.
  • the resin fibers of the first and second inventions may be collectively referred to as "the resin fibers of the invention”.
  • the said 1st and 2nd thermoplastic resin composition may be generically named "the thermoplastic resin composition of this invention.”
  • preferred embodiments of the present invention will be described.
  • Styrene-based resins that can be used in the present invention include styrene homopolymers, copolymers of styrene and other copolymerizable vinyl monomers, and rubber-reinforced styrene-based polymers, and one or more of these may be used. Two or more can be used.
  • an aromatic vinyl monomer other than styrene such as ⁇ -methylstyrene
  • Vinyl cyanide monomers such as acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate )
  • Acrylic acid ester type monomers maleimide type monomers such as N-phenyl maleimide, N-cyclohexyl maleimide, amide type monomers such as acrylamide and methacrylamide, acrylic acid, methacrylic acid, maleic acid, fumaric acid, Unsaturated carboxylic acid monomers such as itaconic acid, divinylbenzene, allyl (meth) acrylate, ethylene glycol (Meth)
  • the rubber-reinforced styrenic polymer is a styrenic polymer reinforced with one or more selected from diene rubbers, olefin rubbers, acrylic rubbers, silicone rubbers, and composite rubbers combining these.
  • Impact-resistant polystyrene resin HIPS resin
  • ABS resin acrylonitrile-butadiene rubber-styrene polymer
  • AS resin acrylonitrile-acrylic rubber-styrene polymer
  • AES resin acrylonitrile-ethylene rubber-styrene polymer
  • styrene-based resins of the present invention highly rigid resins such as polystyrene, acrylonitrile-styrene copolymer, ABS resin, AAS resin, and AES resin are preferable.
  • the content of the styrenic resin of the present invention is 5 to 95% by mass, 10 to 80% by mass, 10 to 90% by mass, 10 to 60% by mass with respect to 100% by mass of the resin component constituting the thermoplastic resin composition. %, Preferably 20 to 80% by mass, and more preferably 30 to 60% by mass.
  • the second thermoplastic resin composition contains another thermoplastic resin other than the styrenic resin.
  • the first thermoplastic resin composition can also contain the other thermoplastic resin.
  • said other thermoplastic resin Polyolefin resin, such as polyethylene resin and polypropylene resin; Polyimide resin; Acrylic resin, such as polymethyl methacrylate resin; Polycarbonate resin; Polyester resin, such as polybutylene terephthalate resin, polyethylene terephthalate resin, polylactic acid resin Polyamide resin; (modified) polyphenylene ether resin; polyoxymethylene resin; polysulfone resin; polyarylate resin, polyphenylene resin, polyurethane resin and the like, and one or more kinds can be used.
  • polyamide resins, polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, polyurethane resins and polyimide resins are preferable.
  • thermoplastic resin a thermoplastic resin selected from the group consisting of polyamide resin, polylactic acid resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polypropylene resin, acrylic resin, polycarbonate resin, and polyimide resin is preferable.
  • the polyamide resin is preferably at least one polyamide resin selected from the group consisting of PA-6, PA-66, PA-11, PA-12, PA-610, and PA-1010.
  • the polycarbonate resin (interfacial polymerization method polycarbonate resin) manufactured by the interfacial polymerization method and the polycarbonate resin (fusion transesterification method polycarbonate resin) manufactured by the melt transesterification method are preferable.
  • hindered amine-based light stabilizers such as hindered phenols, sulfur-containing organic compounds, phosphorus-containing organic compounds, etc. insofar as the effects of the present invention are not impaired; Thermal stabilizers such as phenol type and acrylate type; UV absorbers such as benzoate type, benzotriazole type, benzophenone type and salicylate type; lubricants such as organic nickel type and higher fatty acid amides; plasticizers such as phosphoric acid esters; Bromophenyl ether, tetrabromobisphenol-A, brominated epoxy oligomers, halogen-containing compounds such as brominated; phosphorus-based compounds, flame retardants and flame retardants such as antimony trioxide; odor masking agents; antistatic agents; carbon Pigments such as black and titanium oxide; dyes may also be added.
  • Thermal stabilizers such as phenol type and acrylate type
  • UV absorbers such as benzoate type, benzotriazole type, benzophenone
  • a styrenic resin is dispersed in nano units. Further, in the first thermoplastic resin composition, it is preferable that a styrenic resin is dispersed in nano units.
  • the term "nano unit" as used herein indicates that the dispersion unit observed with a transmission electron microscope is less than 1000 nm. More preferably, the nano unit has a dispersion unit observed by a transmission electron microscope of less than 1000 nm, less than 950 nm, less than 900 nm, or 850 nm or less. The lower limit of the dispersion unit is, for example, 10 nm.
  • the method of dispersing in nano units is not particularly limited, but for example, using a commonly used two or more-screw extrusion kneader, the L / D is preferably 35 or more, more preferably 50 or more. .
  • the upper limit of the L / D is, for example, 150.
  • the adjustment can be appropriately made by changing the mixing conditions such as the cylinder temperature, the discharge amount, the screw configuration and the screw rotation number. For example, a lower cylinder temperature is preferable for nano-dispersion, an excessively high discharge rate is not preferable for nano-dispersion, and a high screw rotation speed tends to be preferable for nano-dispersion.
  • Melt volume rate of the first thermoplastic resin composition (hereinafter, also referred to as MVR) is less than 20 (cm 3/10 min). Moreover, it is preferable that MVR of a 2nd thermoplastic resin composition is 20 (cm ⁇ 3 > / 10 minutes) or less. MVR is a value measured under the conditions of a temperature of 220 ° C. and a load of 10 kg in accordance with ISO 1133. MVR is inferior strength of 20 (cm 3/10 min) exceeds the resin fibers tend to be inferior to the continuous productivity. Furthermore, there is a tendency not to be able to withstand the production of fiber reinforced plastic by the papermaking method or the non-woven method.
  • the die swell at 220 ° C. of the thermoplastic resin composition of the present invention is 2.5 or less in order to reduce the variation of the resin fiber diameter. More preferably, it is 2.0 or less, more preferably 1.8 or less.
  • the die swell can be measured, for example, according to JIS K7199 using RH7 manufactured by MALVERUN.
  • the melt tension at 240 ° C. of the thermoplastic resin composition of the present invention is 0.18 N or less in order to reduce the variation of the resin fiber diameter. Particularly preferably, it is 0.16 N or less.
  • the lower limit of the melt tension is, for example, 0.05N.
  • the melt tension can be measured, for example, using Capirograph manufactured by Toyo Seiki.
  • the resin fiber of the present invention is preferably produced by melt spinning or melt blowing.
  • the processing temperature is preferably adjusted to 200 ° C. to 300 ° C., and more preferably adjusted to 220 ° C. to 290 ° C.
  • the temperature is 200 ° C. or more, the resin is sufficiently melted, and the resin pressure is unlikely to exceed the allowable upper limit or the melt fracture is unlikely to occur, so that stable spinning processing tends to be facilitated. If the temperature is 300 ° C. or less, discoloration due to decomposition or oxidative degradation of the resin tends to be difficult to occur.
  • the nozzle diameter of the melt spinning die of the spinning machine in the melt spinning method there is no particular limitation on the nozzle diameter of the melt spinning die of the spinning machine in the melt spinning method, and one having a range of 1.0 mm or less can be used. It is preferable to be in the range of 0.2 mm to 0.9 mm in consideration of productivity and extrusion pressure. If the diameter is 0.2 mm or more, the resin pressure in the melt-spinning nozzle portion can be suppressed from rising and the discharge tends to be less likely to be unstable. If it is 1.0 mm or less, the variation in resin fiber diameter tends to be reduced.
  • the fiber diameter of the resin fiber of the present invention is preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 40 ⁇ m or less, from the viewpoint of post-processability such as mixing with reinforcing fibers. It is particularly preferred that The lower limit of the fiber system is, for example, 5 ⁇ m. Moreover, about the fiber length of the resin fiber of this invention, it can adjust suitably according to the objective.
  • spinning processor in the melt spinning method, and known machines such as monofilament type and multifilament type can be used according to the purpose.
  • the process of manufacturing the resin fiber of the present invention it is preferable to have a process of filtering with a wire mesh having an opening of less than 60 ⁇ m.
  • a process of filtering with a wire mesh having an opening of less than 60 ⁇ m There is no limitation on the timing of filtration, and the steps of the process of manufacturing the resin constituting the thermoplastic resin composition, the step of melt-kneading the thermoplastic resin composition, the step of manufacturing resin fibers by melt spinning method etc. may be mentioned.
  • a wire mesh of 300 mesh or more is preferable
  • a wire mesh of 400 mesh or more is more preferable
  • a wire mesh of 500 mesh or more is more preferable.
  • the continuous productivity of resin fibers tends to be improved by filtering with a wire mesh having an opening of less than 60 ⁇ m.
  • the resin fiber obtained by the production method of the present invention may be subjected to a stretching process as necessary.
  • the processing temperature in this case is, for example, 50 ° C. or more, more preferably 80 ° C. or more.
  • the upper limit of the processing temperature is, for example, 200 ° C., 190 ° C., and preferably 180 ° C.
  • the temperature is 50 ° C. or more (particularly 80 ° C. or more)
  • the stretching can be sufficiently taken.
  • the temperature is 200 ° C. or lower (in particular, 180 ° C. or lower)
  • fusion between fibers and adhesion of the melted fiber to the stretching roller can be suppressed.
  • the temperature of the stretching process is preferably 50 to 200 ° C., and more preferably 80 to 180 ° C.
  • the resin fibers of the present invention can be used by mixing with reinforcing fibers such as glass fibers, carbon fibers and aramid fibers.
  • the fiber length and the fiber diameter of these reinforcing fibers are not particularly limited, and it is possible to use one having a length according to the purpose.
  • the fiber length is preferably 3 mm to 100 mm, and more preferably 5 mm to 80 mm from the viewpoint of the reinforcing effect of the final product.
  • the extruded melt strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a convergent agent applying roller applies 900 m / min while applying a silicone oil as a focusing agent. I wound up at the speed.
  • the fiber diameter of the obtained undrawn fiber was 26 ⁇ m.
  • Example 2 Claristic MM (manufactured by Nippon A & L Co., Ltd.) obtained by melt-kneading under conditions of a cylinder temperature of 230 ° C. and a screw rotation speed of 250 rpm using Toshiba Machine Co., Ltd.
  • TEM-35B (L / D 31) resin: except for using MVR 4.0 (cm 3/10 min)) was spun under the same conditions as in example 1.
  • the fiber diameter of the obtained undrawn fiber was 25 ⁇ m.
  • polybutylene terephthalate resin / ABS resin alloy using MVR detection limit of (0.1 (cm 3/10 min) or less), nozzle diameter 0.5 mm [phi, an extruder equipped with a spinning die for multifilament consisting of 24 holes
  • the extrusion temperature was 260 ° C.
  • the extrusion rate was 26 g / min
  • the extruded molten strand was passed through a 500 mesh wire mesh before being extruded from the die.
  • the fiber diameter of the obtained undrawn fiber was 15 micrometers.
  • the extruded melt strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a convergent agent applying roller applies 900 m / min while applying a silicone oil as a focusing agent.
  • a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm
  • a convergent agent applying roller applies 900 m / min while applying a silicone oil as a focusing agent.
  • PC Polycarbonate resin
  • PBT Polybutylene terephthalate resin
  • PA Polyamide resin
  • thermoplastic resin compositions of Examples 1-5 since the MVR defined in the present invention is less than 20 (cm 3/10 min), excellent resin fiber obtained in continuous production
  • Comparative Example 1 Since Comparative Example 1 was out of the specification of the present invention, it was inferior to continuous production, and the resin fiber diameter tended to be large.
  • Ultrathin sections were obtained by cutting the pellets of the thermoplastic resin compositions obtained in the following Examples 6 to 10 and Comparative Examples 2 to 4 at a low temperature of ⁇ 85 ° C. using a cryomicrotome.
  • the obtained ultrathin section is stained with osmium tetroxide (OsO4) and / or ruthenium tetroxide (RuO4), observed and photographed using a transmission electron microscope (JEM-1400: JEOL Ltd.), and an image analyzer ( Asahi Kasei IP-1000 PC) was used to obtain the average value of the circle-equivalent particle diameters of 100 dispersion units of the dispersed phase.
  • OsO4 osmium tetroxide
  • RuO4 ruthenium tetroxide
  • a polyamide resin UNITICA Co., Ltd. Unitika nylon 6 A 1030 BRL
  • the dispersion unit of the styrene resin was 850 nm.
  • the obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mm ⁇ and 24 holes.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. I wound up at the speed.
  • the fiber diameter of the obtained undrawn fiber was 12 ⁇ m.
  • Example 7 A mixed monomer consisting of 10 parts by mass of methacrylic acid, 15 parts by mass of styrene and 5 parts by mass of acrylonitrile is graft polymerized by an emulsion polymerization method in the presence of 70 parts by mass (solid content) of polybutadiene latex having a particle diameter of 0.1 ⁇ m. I got a resin. Ten parts by mass of the obtained styrene resin and 90 parts by mass of a polyamide resin (UNITICA Co., Ltd.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. I wound up at the speed.
  • the fiber diameter of the obtained undrawn fiber was 13 ⁇ m.
  • the dispersion unit of styrenic resin was 910 nm.
  • the obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mm ⁇ and 24 holes.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. I wound up at the speed.
  • the fiber diameter of the obtained undrawn fiber was 18 ⁇ m.
  • the dispersion unit of styrenic resin was 920 nm.
  • the obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mm ⁇ and 24 holes.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a silicone oil agent is applied as a focusing agent by a focusing agent applying roller to 1100 m / min. I wound up at the speed.
  • the fiber diameter of the obtained undrawn fiber was 22 ⁇ m.
  • the dispersion unit of styrenic resin was 920 nm.
  • the obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mm ⁇ and 24 holes.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a silicone oil agent is applied as a focusing agent by a focusing agent applying roller to 1100 m / min. I wound up at the speed.
  • the fiber diameter of the obtained undrawn fiber was 20 ⁇ m.
  • a polyamide resin UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL
  • distribution unit of styrene resin was 1000 nm or more.
  • the obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mm ⁇ and 24 holes.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent.
  • a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm
  • a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent.
  • Comparative example 3 A mixed monomer consisting of 5 parts by mass of methacrylic acid, 30 parts by mass of styrene and 15 parts by mass of acrylonitrile is graft polymerized by an emulsion polymerization method in the presence of 50 parts by mass (solid content) of a polybutadiene latex having a particle diameter of 0.4 ⁇ m. I got a resin. Ten parts by mass of the obtained styrene resin and 90 parts by mass of a polyamide resin (UNITICA Co., Ltd.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent.
  • a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm
  • a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent.
  • a polyamide resin UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL
  • distribution unit of styrene resin was 1000 nm or more.
  • the pellets were extruded at an extrusion temperature of 280 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mm ⁇ and 24 holes.
  • the extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent.
  • a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm
  • a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent.
  • a resin fiber comprising a thermoplastic resin composition containing a styrenic resin, wherein the thermoplastic resin composition has a melt volume rate of 20 measured at a temperature of 220 ° C. and a load of 10 kg according to ISO 1133. (cm 3/10 min) resin fibers, wherein less.
  • the melt volume rate is 20 (cm 3/10 min) or less, 15 (cm 3/10 min) or less, is 10 (cm 3/10 min) or less, or 5 (cm 3/10 min) or less , The resin fiber as described in [1].
  • thermoplastic resin further contains another thermoplastic resin other than a styrene resin.
  • thermoplastic resin other than the styrene-based resin contains at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin The resin fiber as described in [3].
  • thermoplastic resins other than the above-mentioned styrenic resin are PA-6, PA-66, PA-11, PA-12, PA-610, PA-1010, polylactic acid resin, polybutylene terephthalate resin, polyethylene
  • a resin fiber comprising a thermoplastic resin composition containing a styrene-based resin, wherein the thermoplastic resin composition further includes another thermoplastic resin other than the styrene-based resin, and the styrene-based resin is Resin fiber characterized by being dispersed in nano units.
  • the thermoplastic resin other than the styrene-based resin is at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin
  • the resin fiber according to [6] which is characterized by the above.
  • thermoplastic resins other than the styrene-based resin are PA-6, PA-66, PA-11, PA-12, PA-610, PA-1010, polylactic acid resin, polybutylene terephthalate resin, polyethylene terephthalate resin
  • the resin fiber according to any one of [1] to [9], which has been subjected to a stretching process and the processing temperature at that time is 50 to 160 ° C. or 60 to 150 ° C.
  • a fiber reinforced plastic comprising a reinforcing fiber and the resin fiber according to any one of [1] to [10].
  • the resin fiber of the present invention can be produced continuously, and is excellent in strength and elongation. Therefore, it can be suitably used as a material of fiber reinforced plastic in a papermaking method or a non-woven fabric method. Furthermore, it can be suitably used as a filter cloth for filters, a non-woven material for electrical insulation, and a packaging material such as packaging.

Abstract

The present invention provides: a resin fiber which has both strength and elongation that are capable of withstanding the production of a fiber-reinforced plastic by means of a papermaking method or a nonwoven fabric method, and which is able to be continuously produced; and a method for producing this resin fiber. A resin fiber according to the present invention is formed from a thermoplastic resin composition that contains a styrene resin, and is characterized in that the melt volume rate of the thermoplastic resin composition as determined at a temperature of 220°C under a load of 10 kg in accordance with ISO 1133 is 20 (cm3/10 min) or less; or alternatively, a resin fiber according to the present invention is formed from a thermoplastic resin composition which is characterized in that a styrene resin and another thermoplastic resin are contained therein and the styrene resin is dispersed on the order of nanometers.

Description

樹脂繊維およびその製造方法Resin fiber and method for producing the same
　本発明は、熱可塑性樹脂組成物からなる樹脂繊維およびその製造方法に関する。より詳細には、スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維、スチレン系樹脂及びその他の熱可塑性樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維、およびそれらの製造方法に関する。本願は、２０１７年８月２１日に日本に出願した特願２０１７－１５８３９２号、および２０１７年８月２１日に日本に出願した特願２０１７－１５８３９４号の優先権を主張し、その内容をここに援用する。 The present invention relates to a resin fiber comprising a thermoplastic resin composition and a method for producing the same. More specifically, the present invention relates to a resin fiber comprising a thermoplastic resin composition containing a styrenic resin, a resin fiber comprising a thermoplastic resin composition containing a styrenic resin and another thermoplastic resin, and a method for producing them. Priority is claimed on Japanese Patent Application No. 2017-158392 filed on Aug. 21, 2017, and Japanese Patent Application No. 2017-158394 filed on August 21, 2017, the contents of which are incorporated herein by reference. In the
　炭素繊維等の強化繊維を樹脂に配合した繊維強化プラスチックは、成形品にした際の剛性が高いことから薄肉化による軽量化を図ることが出来る。そのため、種々の分野で利用されている。強化繊維を樹脂に配合させる方法としては、押出混練機を用いて溶融混練する方法が挙げられるが、強化繊維が混練中に切断されてしまい、剛性が低下する課題がある。さらに、溶融混練後、射出成形された成形品では、強化繊維の配向が生じ、押出成形された成形品では、強化繊維の分布ムラが生じてしまうことで、機械的特性が不均一となる課題もある。そこで、強化繊維の長さを保ち、配向や分布ムラを解消させる繊維強化プラスチック成形品の製造方法として、強化繊維と熱可塑性樹脂繊維を抄造法や不織布法により混合させ加熱加圧する方法が試みられている（特許文献１及び２参照）。しかしながら、熱可塑性樹脂繊維の樹脂としては、結晶性樹脂やポリカーボネート樹脂であり、成形品の吸湿性、収縮性、反り及び耐久性については未だ不十分である。これら特性を改良するため、熱可塑性樹脂繊維としてスチレン系樹脂を配合することが考えられる。スチレン系樹脂を含む樹脂繊維としては、特許文献３に開示されているが、強度や伸びが未だ不十分であり、抄造法や不織布法に耐えうる性能のスチレン系樹脂を含む樹脂繊維が得られていないのが現状である。 A fiber-reinforced plastic in which reinforcing fibers such as carbon fibers are mixed with a resin can achieve weight reduction by thinning since the rigidity when forming a molded article is high. Therefore, it is used in various fields. As a method of blending reinforcing fiber into resin, there is a method of melt-kneading using an extrusion kneader, but there is a problem that the reinforcing fiber is cut during kneading, and the rigidity is lowered. Furthermore, in the case of a molded article obtained by injection molding after melt-kneading, the orientation of the reinforcing fiber is generated, and in the extruded molded article, the uneven distribution of the reinforced fiber is caused, and the mechanical properties become uneven. There is also. Therefore, as a method for producing a fiber-reinforced plastic molded product that maintains the length of the reinforcing fiber and eliminates the orientation and distribution unevenness, a method of mixing the reinforcing fiber and the thermoplastic resin fiber by the paper-making method or the nonwoven fabric method is tried (See Patent Documents 1 and 2). However, the resin of the thermoplastic resin fiber is a crystalline resin or a polycarbonate resin, and the hygroscopicity, the shrinkage, the warp and the durability of the molded product are still insufficient. In order to improve these properties, it is conceivable to blend a styrenic resin as the thermoplastic resin fiber. Patent Document 3 discloses a resin fiber containing a styrene-based resin, but a resin fiber containing a styrene-based resin having a sufficient strength and elongation and a resistance to the papermaking method and the non-woven fabric method is obtained. It is not the current situation.
特開２０１４－６２３３６号公報JP, 2014-62336, A 特開２０１４－２２４３３３号公報JP 2014-224333 A 特開平１－１８３５１６号公報Japanese Patent Application Laid-Open No. 1-183516
　本発明は、抄造法や不織布法での繊維強化プラスチックの製造に耐えうる強度と伸びを兼ね備え、さらに、連続生産可能な樹脂繊維およびその製造方法を提供することを目的とする。 An object of the present invention is to provide a resin fiber having both strength and elongation which can withstand the production of a fiber reinforced plastic by a papermaking method or a non-woven method, and further capable of continuous production, and a method of producing the same.
　本発明者は鋭意検討した結果、スチレン系樹脂を含む熱可塑性樹脂組成物のメルトボリュームレイトを特定範囲に規定することで、上記課題を解消できることを見出し、本発明を完成するに至った。
　さらに、本発明者は、スチレン系樹脂及びその他の熱可塑性樹脂を含み、かつ、スチレン系樹脂をナノ単位で分散させることで、上記課題を解消できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventor has found that the above problems can be solved by defining the melt volume rate of a thermoplastic resin composition containing a styrene-based resin in a specific range, and the present invention has been completed.
Furthermore, the present inventors have found that the above-mentioned problems can be solved by dispersing a styrenic resin in nano units, containing styrenic resins and other thermoplastic resins, and have completed the present invention.
　すなわち、本発明は以下の項１～項６で構成される。
項１　スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維であって、上記熱可塑樹脂組成物の、ＩＳＯ１１３３に準じ、温度２２０℃、荷重１０ｋｇの条件で測定されたメルトボリュームレイトが２０（ｃｍ3／１０分）以下であることを特徴とする樹脂繊維。
項２　上記熱可塑性樹脂はスチレン系樹脂以外の他の熱可塑性樹脂をさらに含む項１に記載の樹脂繊維。
項３　スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維であって、上記熱可塑性樹脂組成物は、スチレン系樹脂以外の他の熱可塑性樹脂をさらに含み、かつ、上記スチレン系樹脂がナノ単位で分散していることを特徴とする樹脂繊維。
項４　上記他の熱可塑性樹脂は、ポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、及びポリイミド樹脂からなる群より選ばれる少なくとも１種の樹脂であることを特徴とする項１～項３の何れかに記載の樹脂繊維。
項５　強化繊維と、項１～項４の何れかに記載の樹脂繊維を含む繊維強化プラスチック。
項６　溶融紡糸法またはメルトブロー法で得られることを特徴とする、項１～項４の何れかに記載の樹脂繊維の製造方法。 That is, the present invention is constituted by the following items 1 to 6.
Item 1 A resin fiber comprising a thermoplastic resin composition containing a styrene resin, wherein the melt volume rate of the thermoplastic resin composition measured under the conditions of a temperature of 220 ° C. and a load of 10 kg according to ISO 1133 is 20 ( resin fiber characterized by cm 3/10 min) or less.
Item 2 The resin fiber according to Item 1, wherein the thermoplastic resin further contains another thermoplastic resin other than a styrene resin.
Item 3 A resin fiber comprising a thermoplastic resin composition containing a styrene-based resin, wherein the thermoplastic resin composition further includes another thermoplastic resin other than a styrene-based resin, and the styrene-based resin is nano A resin fiber characterized by being dispersed in units.
Item 4 The above-mentioned other thermoplastic resin is at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin. The resin fiber according to any one of items 1 to 3.
Item 5 A fiber reinforced plastic comprising a reinforcing fiber and the resin fiber according to any one of items 1 to 4.
Item 6 A method for producing a resin fiber according to any one of items 1 to 4, which is obtained by a melt spinning method or a melt blowing method.
　本発明によれば、強度と伸びに優れ、連続生産可能な樹脂繊維が得られる。本発明品を使用すると、抄造法や不織布法での繊維強化プラスチックの作製に使用した際、加工性、取扱い性および変形性に優れ、立体形状への賦型も容易となる。 According to the present invention, resin fibers excellent in strength and elongation and capable of continuous production can be obtained. When the product of the present invention is used for producing a fiber-reinforced plastic in a paper-making method or a non-woven fabric method, it is excellent in processability, handleability and deformability, and shaping to a three-dimensional shape becomes easy.
　第一の本発明の樹脂繊維は、スチレン系樹脂を含む第一の熱可塑性樹脂組成物からなる樹脂繊維であって、上記第一の熱可塑樹脂組成物のＩＳＯ１１３３に準じ、温度２２０℃、荷重１０ｋｇの条件で測定されたメルトボリュームレイトが２０（ｃｍ3／１０分）以下であることを特徴とする。また、第二の本発明の樹脂繊維は、スチレン系樹脂を含む第二の熱可塑性樹脂組成物からなる樹脂繊維であって、上記第二の熱可塑性樹脂組成物は、スチレン系樹脂以外の他の熱可塑性樹脂をさらに含み、かつ、上記スチレン系樹脂がナノ単位で分散していることを特徴とする。本明細書において、第一及び第二の本発明の樹脂繊維を総称して「本発明の樹脂繊維」と称する場合がある。また、上記第一及び第二の熱可塑性樹脂組成物を総称して「本発明の熱可塑性樹脂組成物」と称する場合がある。
　以下、本発明の好適な実施形態について説明する。 The resin fiber of the first invention is a resin fiber comprising a first thermoplastic resin composition containing a styrene resin, and according to ISO 1133 of the first thermoplastic resin composition, a temperature of 220 ° C., a load melt volume rate measured under conditions of 10kg is equal to or less than 20 (cm 3/10 min). The resin fiber of the second invention is a resin fiber comprising a second thermoplastic resin composition containing a styrene resin, and the second thermoplastic resin composition is other than a styrene resin. And the styrenic resin dispersed in nano units. In the present specification, the resin fibers of the first and second inventions may be collectively referred to as "the resin fibers of the invention". Moreover, the said 1st and 2nd thermoplastic resin composition may be generically named "the thermoplastic resin composition of this invention."
Hereinafter, preferred embodiments of the present invention will be described.
　本発明に使用できるスチレン系樹脂としては、スチレン単独重合体、スチレンおよび共重合可能な他のビニル系単量体からなる共重合体、ゴム強化スチレン系重合体が挙げられ、これらを１種または２種以上用いることができる。 Styrene-based resins that can be used in the present invention include styrene homopolymers, copolymers of styrene and other copolymerizable vinyl monomers, and rubber-reinforced styrene-based polymers, and one or more of these may be used. Two or more can be used.
　上記、スチレンおよび共重合可能な他のビニル系単量体からなる共重合体の共重合可能な他のビニル系単量体としては、α－メチルスチレン等のスチレン以外の芳香族ビニル系単量体、アクリロニトリル等のシアン化ビニル系単量体、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、アクリル酸２－エチルヘキシル等の（メタ）アクリル酸エステル系単量体、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のマレイミド系単量体、アクリルアミド、メタクリルアミド等のアミド系単量体、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸等の不飽和カルボン酸系単量体、ジビニルベンゼン、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジアリルフタレート、ジシクロペンタジエンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート等の架橋性単量体が例示でき、１種または２種以上用いることができる。 As the other vinyl monomers copolymerizable with the copolymer consisting of styrene and other vinyl monomers copolymerizable as described above, an aromatic vinyl monomer other than styrene such as α-methylstyrene , Vinyl cyanide monomers such as acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate ) Acrylic acid ester type monomers, maleimide type monomers such as N-phenyl maleimide, N-cyclohexyl maleimide, amide type monomers such as acrylamide and methacrylamide, acrylic acid, methacrylic acid, maleic acid, fumaric acid, Unsaturated carboxylic acid monomers such as itaconic acid, divinylbenzene, allyl (meth) acrylate, ethylene glycol (Meth) acrylate, diallyl phthalate, dicyclopentadiene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Examples thereof include crosslinkable monomers such as hexanediol di (meth) acrylate, triallyl cyanurate, and triallyl isocyanurate, and one or more kinds of them may be used.
　上記、ゴム強化スチレン系重合体は、ジエン系ゴム、オレフィン系ゴム、アクリル系ゴム、シリコーン系ゴム、及びこれらを組み合わせた複合ゴムから選ばれる１種または２種以上により強化されたスチレン系重合体であり、耐衝撃性ポリスチレン樹脂（ＨＩＰＳ樹脂）、アクリロニトリル－ブタジエン系ゴム－スチレン重合体（ＡＢＳ樹脂）、アクリロニトリル－アクリル系ゴム－スチレン重合体（ＡＡＳ樹脂）、アクリロニトリル－エチレン系ゴム－スチレン重合体（ＡＥＳ樹脂）等が例示でき、１種または２種以上用いることができる。 The rubber-reinforced styrenic polymer is a styrenic polymer reinforced with one or more selected from diene rubbers, olefin rubbers, acrylic rubbers, silicone rubbers, and composite rubbers combining these. Impact-resistant polystyrene resin (HIPS resin), acrylonitrile-butadiene rubber-styrene polymer (ABS resin), acrylonitrile-acrylic rubber-styrene polymer (AAS resin), acrylonitrile-ethylene rubber-styrene polymer (AES resin) etc. can be illustrated and 1 type or 2 types or more can be used.
　本発明のスチレン系樹脂としては、中でもポリスチレン、アクリロニトリル－スチレン共重合体、ＡＢＳ樹脂、ＡＡＳ樹脂、ＡＥＳ樹脂等の剛性の高い樹脂が好ましい。 Among the styrene-based resins of the present invention, highly rigid resins such as polystyrene, acrylonitrile-styrene copolymer, ABS resin, AAS resin, and AES resin are preferable.
　本発明のスチレン系樹脂の含有量は、熱可塑性樹脂組成物を構成する樹脂成分１００質量％に対して、５～９５質量％、１０～８０質量％、１０～９０質量％、１０～６０質量％、２０～８０質量％が好ましく、３０～６０質量％がより好ましい。スチレン系樹脂を含むことで、最終製品の吸湿性、収縮性及び反りを抑制し、耐久性を向上させることができる。 The content of the styrenic resin of the present invention is 5 to 95% by mass, 10 to 80% by mass, 10 to 90% by mass, 10 to 60% by mass with respect to 100% by mass of the resin component constituting the thermoplastic resin composition. %, Preferably 20 to 80% by mass, and more preferably 30 to 60% by mass. By containing the styrene-based resin, the hygroscopicity, shrinkage and warpage of the final product can be suppressed, and the durability can be improved.
　第二の熱可塑性樹脂組成物は、スチレン系樹脂以外の他の熱可塑性樹脂を含有する。また、第一の熱可塑性樹脂組成物は、上記他の熱可塑性樹脂を含有することができる。上記他の熱可塑性樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂；ポリイミド樹脂；ポリメチルメタクリレート樹脂等のアクリル樹脂；ポリカーボネート樹脂；ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、ポリ乳酸樹脂等のポリエステル樹脂；ポリアミド樹脂；（変性）ポリフェニレンエーテル樹脂；ポリオキシメチレン樹脂；ポリスルフォン樹脂；ポリアリレート樹脂、ポリフェニレン樹脂、ポリウレタン樹脂等が挙げられ、１種または２種以上用いることができる。これらの中でも、ポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリイミド樹脂が好ましい。 The second thermoplastic resin composition contains another thermoplastic resin other than the styrenic resin. The first thermoplastic resin composition can also contain the other thermoplastic resin. As said other thermoplastic resin, Polyolefin resin, such as polyethylene resin and polypropylene resin; Polyimide resin; Acrylic resin, such as polymethyl methacrylate resin; Polycarbonate resin; Polyester resin, such as polybutylene terephthalate resin, polyethylene terephthalate resin, polylactic acid resin Polyamide resin; (modified) polyphenylene ether resin; polyoxymethylene resin; polysulfone resin; polyarylate resin, polyphenylene resin, polyurethane resin and the like, and one or more kinds can be used. Among these, polyamide resins, polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, polyurethane resins and polyimide resins are preferable.
　特に、上記他の熱可塑性樹脂としては、ポリアミド樹脂、ポリ乳酸樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、ポリプロピレン樹脂、アクリル樹脂、ポリカーボネート樹脂、及びポリイミド樹脂からなる群より選ばれる熱可塑性樹脂が好ましい。上記ポリアミド樹脂としては、ＰＡ－６、ＰＡ－６６、ＰＡ－１１、ＰＡ－１２、ＰＡ－６１０、及びＰＡ－１０１０からなる群より選ばれる少なくとも１種のポリアミド樹脂が好ましい。上記ポリカーボネート樹脂としては、界面重合法により製造されたポリカーボネート樹脂（界面重合法ポリカーボネート樹脂）、溶融エステル交換法により製造されたポリカーボネート樹脂（溶融エステル交換法ポリカーボネート樹脂）が好ましい。 In particular, as the other thermoplastic resin, a thermoplastic resin selected from the group consisting of polyamide resin, polylactic acid resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polypropylene resin, acrylic resin, polycarbonate resin, and polyimide resin is preferable. . The polyamide resin is preferably at least one polyamide resin selected from the group consisting of PA-6, PA-66, PA-11, PA-12, PA-610, and PA-1010. As said polycarbonate resin, the polycarbonate resin (interfacial polymerization method polycarbonate resin) manufactured by the interfacial polymerization method and the polycarbonate resin (fusion transesterification method polycarbonate resin) manufactured by the melt transesterification method are preferable.
　本発明の熱可塑性樹脂組成物には、本発明の効果を損なわない範囲で、ヒンダードアミン系の光安定剤；ヒンダードフェノール系、含硫黄有機化合物系、含リン有機化合物系等の酸化防止剤；フェノール系、アクリレート系等の熱安定剤；ベンゾエート系、ベンゾトリアゾール系、ベンゾフェノン系、サリシレート系の紫外線吸収剤；有機ニッケル系、高級脂肪酸アミド類等の滑剤；リン酸エステル類等の可塑剤；ポリブロモフェニルエーテル、テトラブロモビスフェノール－Ａ、臭素化エポキシオリゴマー、臭素化等の含ハロゲン系化合物；リン系化合物、三酸化アンチモン等の難燃剤・難燃助剤；臭気マスキング剤；帯電防止剤；カーボンブラック、酸化チタン等の顔料；染料等を添加することもできる。 In the thermoplastic resin composition of the present invention, hindered amine-based light stabilizers; antioxidants such as hindered phenols, sulfur-containing organic compounds, phosphorus-containing organic compounds, etc. insofar as the effects of the present invention are not impaired; Thermal stabilizers such as phenol type and acrylate type; UV absorbers such as benzoate type, benzotriazole type, benzophenone type and salicylate type; lubricants such as organic nickel type and higher fatty acid amides; plasticizers such as phosphoric acid esters; Bromophenyl ether, tetrabromobisphenol-A, brominated epoxy oligomers, halogen-containing compounds such as brominated; phosphorus-based compounds, flame retardants and flame retardants such as antimony trioxide; odor masking agents; antistatic agents; carbon Pigments such as black and titanium oxide; dyes may also be added.
第二の熱可塑性樹脂組成物は、スチレン系樹脂がナノ単位で分散している。また、第一の熱可塑性樹脂組成物は、スチレン系樹脂がナノ単位で分散していることが好ましい。ここで言う「ナノ単位」とは、透過電子顕微鏡で観察される分散単位が１０００ｎｍ未満であることを示す。上記ナノ単位は、透過電子顕微鏡で観察される分散単位が、１０００ｎｍ未満、９５０ｎｍ未満、９００ｎｍ未満、または８５０ｎｍ以下であることがさらに好ましい。上記分散単位の下限は、例えば１０ｎｍである。 In the second thermoplastic resin composition, a styrenic resin is dispersed in nano units. Further, in the first thermoplastic resin composition, it is preferable that a styrenic resin is dispersed in nano units. The term "nano unit" as used herein indicates that the dispersion unit observed with a transmission electron microscope is less than 1000 nm. More preferably, the nano unit has a dispersion unit observed by a transmission electron microscope of less than 1000 nm, less than 950 nm, less than 900 nm, or 850 nm or less. The lower limit of the dispersion unit is, for example, 10 nm.
ナノ単位で分散させる方法に特に制限はないが、例えば、通常使用される２軸以上の押出し混練機を用い、そのＬ／Ｄが３５以上であることが好ましく、５０以上であることがより好ましい。上記Ｌ／Ｄの上限は例えば１５０である。また、シリンダー温度、吐出量、スクリュー構成およびスクリュー回転数等、混合条件を変更することで適宜調整可能である。例えば、シリンダー温度は低い方がナノ分散には好ましく、吐出量は上げすぎるとナノ分散には好ましくなく、スクリュー回転数は高い方がナノ分散には好ましいという傾向がある。 The method of dispersing in nano units is not particularly limited, but for example, using a commonly used two or more-screw extrusion kneader, the L / D is preferably 35 or more, more preferably 50 or more. . The upper limit of the L / D is, for example, 150. In addition, the adjustment can be appropriately made by changing the mixing conditions such as the cylinder temperature, the discharge amount, the screw configuration and the screw rotation number. For example, a lower cylinder temperature is preferable for nano-dispersion, an excessively high discharge rate is not preferable for nano-dispersion, and a high screw rotation speed tends to be preferable for nano-dispersion.
第一の熱可塑性樹脂組成物のメルトボリュームレイト（以下、ＭＶＲとも呼ぶ）は２０（ｃｍ3／１０分）以下である。また、第二の熱可塑性樹脂組成物のＭＶＲは２０（ｃｍ3／１０分）以下であることが好ましい。ＭＶＲは、ＩＳＯ１１３３に準じ、温度２２０℃、荷重１０ｋｇの条件で測定された値である。ＭＶＲが２０（ｃｍ3／１０分）を超えると樹脂繊維の強度が劣り、連続生産性に劣る傾向にある。さらに、抄造法や不織布法での繊維強化プラスチックの作製に耐えられない傾向にある。さらに、直径１００μｍ以下の樹脂繊維を作成する加工性も考慮すると２０（ｃｍ3／１０分）未満であることがより好ましく、１５（ｃｍ3／１０分）以下、１０（ｃｍ3／１０分）以下、または５（ｃｍ3／１０分）以下であることがさらに好ましい。 Melt volume rate of the first thermoplastic resin composition (hereinafter, also referred to as MVR) is less than 20 (cm 3/10 min). Moreover, it is preferable that MVR of a 2nd thermoplastic resin composition is 20 (cm < 3 > / 10 minutes) or less. MVR is a value measured under the conditions of a temperature of 220 ° C. and a load of 10 kg in accordance with ISO 1133. MVR is inferior strength of 20 (cm 3/10 min) exceeds the resin fibers tend to be inferior to the continuous productivity. Furthermore, there is a tendency not to be able to withstand the production of fiber reinforced plastic by the papermaking method or the non-woven method. Further, more preferably less than considering workability to create the following resin fiber diameter 100μm 20 (cm 3/10 min), 15 (cm 3/10 min) or less, 10 (cm 3/10 min) or less, or 5 and still more preferably (cm 3/10 min) or less.
　また、本発明の熱可塑性樹脂組成物の２２０℃におけるダイスウェルは、２．５以下であることが樹脂繊維径のバラツキを低減させるためには好ましい。より好ましくは２．０以下、さらに好ましくは１．８以下である。ダイスウェルは、例えばＭＡＬＶＥＲＵＮ社製　ＲＨ７を用いてＪＩＳ　Ｋ７１９９に準じて測定することができる。 Moreover, it is preferable that the die swell at 220 ° C. of the thermoplastic resin composition of the present invention is 2.5 or less in order to reduce the variation of the resin fiber diameter. More preferably, it is 2.0 or less, more preferably 1.8 or less. The die swell can be measured, for example, according to JIS K7199 using RH7 manufactured by MALVERUN.
　さらに、本発明の熱可塑性樹脂組成物の２４０℃におけるメルトテンションは０．１８Ｎ以下であることが、樹脂繊維径のバラツキを低減させるためには好ましい。特に好ましくは０．１６Ｎ以下である。上記メルトテンションの下限は、例えば０．０５Ｎである。メルトテンションは、例えば東洋精機製キャピログラフを用いて測定することができる。 Furthermore, it is preferable that the melt tension at 240 ° C. of the thermoplastic resin composition of the present invention is 0.18 N or less in order to reduce the variation of the resin fiber diameter. Particularly preferably, it is 0.16 N or less. The lower limit of the melt tension is, for example, 0.05N. The melt tension can be measured, for example, using Capirograph manufactured by Toyo Seiki.
　本発明の樹脂繊維は、溶融紡糸法またはメルトブロー法で作製されることが好ましい。加工温度は、２００℃～３００℃に調整することが好ましく、２２０℃～２９０℃に調整することがより好ましい。２００℃以上であると、樹脂が十分に溶融し、樹脂圧力が許容上限を超えにくく、あるいはメルトフラクチャーを発生しにくいため、安定した紡糸加工が容易となる傾向にある。３００℃以下であると樹脂の分解や酸化劣化による変色が発生しにくくなる傾向にある。 The resin fiber of the present invention is preferably produced by melt spinning or melt blowing. The processing temperature is preferably adjusted to 200 ° C. to 300 ° C., and more preferably adjusted to 220 ° C. to 290 ° C. When the temperature is 200 ° C. or more, the resin is sufficiently melted, and the resin pressure is unlikely to exceed the allowable upper limit or the melt fracture is unlikely to occur, so that stable spinning processing tends to be facilitated. If the temperature is 300 ° C. or less, discoloration due to decomposition or oxidative degradation of the resin tends to be difficult to occur.
　溶融紡糸法における紡糸加工機の溶融紡糸ダイスのノズル径に特に制限はなく、１．０ｍｍ以下の範囲のものが使用できる。生産性、押出圧力を考慮すると０．２ｍｍ～０．９ｍｍの範囲にあることが好ましい。０．２ｍｍ以上であると、溶融紡糸ノズル部の樹脂圧力の上昇を抑制でき吐出が不安定となりにくい傾向にある。１．０ｍｍ以下であると樹脂繊維径のバラツキを小さくできる傾向にある。 There is no particular limitation on the nozzle diameter of the melt spinning die of the spinning machine in the melt spinning method, and one having a range of 1.0 mm or less can be used. It is preferable to be in the range of 0.2 mm to 0.9 mm in consideration of productivity and extrusion pressure. If the diameter is 0.2 mm or more, the resin pressure in the melt-spinning nozzle portion can be suppressed from rising and the discharge tends to be less likely to be unstable. If it is 1.0 mm or less, the variation in resin fiber diameter tends to be reduced.
本発明の樹脂繊維の繊維径は、強化繊維と混合する等の後加工性の観点から１００μｍ以下であることが好ましく、６０μｍ以下であることがより好ましく、４０μｍ以下であることがさらに好ましく、３０μｍ以下であることが特に好ましい。上記繊維系の下限は、例えば５μｍである。また、本発明の樹脂繊維の繊維長については、目的に応じて適宜調整することができる。 The fiber diameter of the resin fiber of the present invention is preferably 100 μm or less, more preferably 60 μm or less, still more preferably 40 μm or less, from the viewpoint of post-processability such as mixing with reinforcing fibers. It is particularly preferred that The lower limit of the fiber system is, for example, 5 μm. Moreover, about the fiber length of the resin fiber of this invention, it can adjust suitably according to the objective.
　溶融紡糸法における紡糸加工機には特に制限はなく、モノフィラメントタイプ、マルチフィラメントタイプ等、公知の機械を目的に応じて使用することができる。 There is no particular limitation on the spinning processor in the melt spinning method, and known machines such as monofilament type and multifilament type can be used according to the purpose.
　また、本発明の樹脂繊維を製造する工程において、目開き６０μｍ未満の金網で濾過する工程を有していることが好ましい。濾過するタイミングに制限はなく、熱可塑性樹脂組成物を構成する樹脂の製造工程の段階、熱可塑性樹脂組成物を溶融混練する段階、樹脂繊維を溶融紡糸法等で製造する段階が挙げられる。目開き６０μｍ未満の金網としては、具体的に、３００メッシュ以上の金網が好ましく、４００メッシュ以上の金網がより好ましく、５００メッシュ以上の金網がさらに好ましい。目開き６０μｍ未満の金網で濾過することで、樹脂繊維の連続生産性が向上する傾向にある。 Moreover, in the process of manufacturing the resin fiber of the present invention, it is preferable to have a process of filtering with a wire mesh having an opening of less than 60 μm. There is no limitation on the timing of filtration, and the steps of the process of manufacturing the resin constituting the thermoplastic resin composition, the step of melt-kneading the thermoplastic resin composition, the step of manufacturing resin fibers by melt spinning method etc. may be mentioned. Specifically, a wire mesh of 300 mesh or more is preferable, a wire mesh of 400 mesh or more is more preferable, and a wire mesh of 500 mesh or more is more preferable. The continuous productivity of resin fibers tends to be improved by filtering with a wire mesh having an opening of less than 60 μm.
　また、本発明の製造方法で得られた樹脂繊維は、必要に応じて延伸加工を施しても良い。この場合の加工温度は、例えば５０℃以上、さらに好ましくは８０℃以上である。上記加工温度の上限は、例えば２００℃、１９０℃、好ましくは１８０℃である。５０℃以上（特に８０℃以上）では延伸を充分にとることができる。２００℃以下（特に１８０℃以下）であると繊維同士の融着、溶けた繊維が延伸ローラーに粘着するのを抑制することができる。特に、延伸加工の温度は、５０～２００℃が好ましく、８０～１８０℃がより好ましい。 In addition, the resin fiber obtained by the production method of the present invention may be subjected to a stretching process as necessary. The processing temperature in this case is, for example, 50 ° C. or more, more preferably 80 ° C. or more. The upper limit of the processing temperature is, for example, 200 ° C., 190 ° C., and preferably 180 ° C. When the temperature is 50 ° C. or more (particularly 80 ° C. or more), the stretching can be sufficiently taken. When the temperature is 200 ° C. or lower (in particular, 180 ° C. or lower), fusion between fibers and adhesion of the melted fiber to the stretching roller can be suppressed. In particular, the temperature of the stretching process is preferably 50 to 200 ° C., and more preferably 80 to 180 ° C.
　本発明の樹脂繊維は、ガラス繊維、炭素繊維、アラミド繊維等の強化繊維と混合して使用することが可能である。混合の際、これらの強化繊維の繊維長、繊維径に特に制限はなく、目的に応じた長さのものを使用することが可能である。例えば、抄造法では、最終製品の補強効果の点から繊維長は、３ｍｍ～１００ｍｍであることが好ましく、５ｍｍ～８０ｍｍであることがより好ましい。 The resin fibers of the present invention can be used by mixing with reinforcing fibers such as glass fibers, carbon fibers and aramid fibers. At the time of mixing, the fiber length and the fiber diameter of these reinforcing fibers are not particularly limited, and it is possible to use one having a length according to the purpose. For example, in the papermaking method, the fiber length is preferably 3 mm to 100 mm, and more preferably 5 mm to 80 mm from the viewpoint of the reinforcing effect of the final product.
　樹脂繊維と強化繊維の混合方法に特に制限はなく、目的に応じて、不織布法、抄造法、強化繊維とのマルチフィラメント化等、公知の方法を採用することができる。 There is no restriction | limiting in particular in the mixing method of resin fiber and a reinforced fiber, According to the objective, well-known methods, such as a nonwoven fabric method, a paper-making method, multifilamentization with a reinforced fiber, are employable.
　以下に実施例を用いて本発明を具体的に説明するが、本発明はこれらによって何ら制限されるものではない。 EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited thereto.
（実施例１）
　東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２３０℃、スクリュー回転数２５０ｒｐｍの条件で溶融混練を行って得られた、クララスチックＫＵ－６００Ｒ－１（日本Ａ＆Ｌ株式会社製　ＡＢＳ樹脂：ＭＶＲ５．５（ｃｍ3／１０分））のペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２５０℃、２６ｇ／分の吐出量で押し出した。その際、ダイから押し出される前に５００メッシュ金網に通した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、９００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は２６μｍであった。 Example 1
Claristic KU-600R-1 (Nihon A & L) obtained by melt-kneading using Toshiba-TEM Co., Ltd. TEM-35B (L / D = 31) at a cylinder temperature of 230 ° C and a screw rotation speed of 250 rpm Ltd. ABS resin: MVR5.5 pellets (cm 3/10 min)), nozzle diameter 0.5 mm [phi, using an extruder equipped with a spinning die for multifilament consisting of 24 holes, an extrusion temperature of 250 ° C., It extruded with the discharge amount of 26 g / min. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. The extruded melt strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a convergent agent applying roller applies 900 m / min while applying a silicone oil as a focusing agent. I wound up at the speed. The fiber diameter of the obtained undrawn fiber was 26 μm.
（実施例２）
　東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２３０℃、スクリュー回転数２５０ｒｐｍの条件で溶融混練を行って得られた、クララスチックＭＭ（日本Ａ＆Ｌ株式会社製　ＡＢＳ樹脂：ＭＶＲ　４．０（ｃｍ3／１０分））を用いた以外は実施例１と同じ条件で紡糸した。得られた未延伸繊維の繊維径は２５μｍであった。 (Example 2)
Claristic MM (manufactured by Nippon A & L Co., Ltd.) obtained by melt-kneading under conditions of a cylinder temperature of 230 ° C. and a screw rotation speed of 250 rpm using Toshiba Machine Co., Ltd. TEM-35B (L / D = 31) resin: except for using MVR 4.0 (cm 3/10 min)) was spun under the same conditions as in example 1. The fiber diameter of the obtained undrawn fiber was 25 μm.
（実施例３）
　東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２５０℃、スクリュー回転数２５０ｒｐｍの条件で溶融混練を行って得られた、テクニエースＰＡＸ－１４３９（日本Ａ＆Ｌ株式会社製　ポリカーボネート樹脂／ＡＢＳ樹脂アロイ：ＭＶＲ　１３（ｃｍ3／１０分））を用いた以外は実施例１と同じ条件で紡糸した。得られた未延伸繊維の繊維径は２３μｍであった。 (Example 3)
Techniace PAX-1439 (Nippon A & L Co., Ltd.) obtained by melt kneading using a TEM-35B (L / D = 31) manufactured by Toshiba Machine Co., Ltd. at a cylinder temperature of 250 ° C. and a screw rotational speed of 250 rpm. Ltd. polycarbonate resin / ABS resin alloy: except for using MVR 13 (cm 3/10 min)) was spun under the same conditions as in example 1. The fiber diameter of the obtained undrawn fiber was 23 μm.
（実施例４）
　東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２５０℃、スクリュー回転数２５０ｒｐｍの条件で溶融混練を行って得られた、テクニエースＴＢ－１７０１（日本Ａ＆Ｌ株式会社製　ポリブチレンテレフタレート樹脂／ＡＢＳ樹脂アロイ：ＭＶＲ検出限界（０．１（ｃｍ3／１０分）以下）を、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２６０℃、２６ｇ／分の吐出量で押し出した。その際、ダイから押し出される前に５００メッシュ金網に通した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１５００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は１５μｍであった。 (Example 4)
Techniace TB-1701 (Nippon A & L Co., Ltd.) obtained by melt kneading using a TEM-35B (L / D = 31) manufactured by Toshiba Machine Co., Ltd. at a cylinder temperature of 250 ° C. and a screw rotational speed of 250 rpm. Ltd. polybutylene terephthalate resin / ABS resin alloy: using MVR detection limit of (0.1 (cm 3/10 min) or less), nozzle diameter 0.5 mm [phi, an extruder equipped with a spinning die for multifilament consisting of 24 holes The extrusion temperature was 260 ° C., and the extrusion rate was 26 g / min, and the extruded molten strand was passed through a 500 mesh wire mesh before being extruded from the die. After being cooled by a cooling duct consisting of a portion and a length of 900 mm, while applying a silicone-based oil as a focusing agent with a focusing agent applying roller, 1500 It wound up at the speed | rate of m / min. The fiber diameter of the obtained undrawn fiber was 15 micrometers.
（実施例５）
　東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２５０℃、スクリュー回転数２５０ｒｐｍの条件で溶融混練を行って得られた、テクニエースＴＡ－１１００（日本Ａ＆Ｌ株式会社製　ポリアミド樹脂／ＡＢＳ樹脂アロイ：ＭＶＲ検出限界以下）を用いた以外は、実施例４と同じ条件で紡糸した。得られた未延伸繊維の繊維径は１７μｍであった。 (Example 5)
Techniace TA-1100 (Nippon A & L Co., Ltd.) obtained by melt kneading using a TEM-35B (L / D = 31) manufactured by Toshiba Machine Co., Ltd. at a cylinder temperature of 250 ° C. and a screw rotational speed of 250 rpm. Spinning was performed under the same conditions as in Example 4 except that polyamide resin / ABS resin alloy (less than detection limit of MVR) was used. The fiber diameter of the obtained undrawn fiber was 17 μm.
（比較例１）
　東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２３０℃、スクリュー回転数２５０ｒｐｍの条件で溶融混練を行って得られた、クララスチックＧＡ－７０１（日本Ａ＆Ｌ株式会社製　ＡＢＳ樹脂：ＭＶＲ　６２（ｃｍ3／１０分））のペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２２０℃、２６ｇ／分の吐出量で押し出した。その際、ダイから押し出される前に５００メッシュ金網に通した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、９００ｍ／分の速度で巻き取ったところ、断糸が発生したため、巻き取り速度を８００ｍ／分へ変更した。得られた未延伸繊維の繊維径は、４０μｍであった。 (Comparative example 1)
Claristic GA-701 (Nippon A & L Co., Ltd.) obtained by melt kneading using a TEM-35B (L / D = 31) manufactured by Toshiba Machine Co., Ltd. at a cylinder temperature of 230 ° C. and a screw rotational speed of 250 rpm. Ltd. ABS resin: MVR 62 pellets (cm 3/10 min)), nozzle diameter 0.5 mm [phi, using an extruder equipped with a spinning die for multifilament consisting of 24 holes, an extrusion temperature of 220 ° C., 26 g / min It pushed out by the discharge amount of. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. The extruded melt strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a convergent agent applying roller applies 900 m / min while applying a silicone oil as a focusing agent. When winding was carried out at a speed, a thread breakage occurred, so the winding speed was changed to 800 m / min. The fiber diameter of the obtained undrawn fiber was 40 μm.
＜連続生産性の評価＞
　実施例１～５及び比較例１で樹脂繊維を製造する際、９００ｍ／分以上の速度で巻き取っても断糸せず連続生産可能であったものを「○」、９００ｍ／分以上の速度で巻き取ると断糸し連続生産できなかったものを「×」とした。結果を表１に示す。 <Evaluation of continuous productivity>
When resin fibers are produced in Examples 1 to 5 and Comparative Example 1, those which could be continuously produced without being broken even when wound up at a speed of 900 m / min or more are evaluated as "○", speed of 900 m / min or more When it was wound up with the above, it was broken and continuous production could not be performed, and it was regarded as "x". The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
 （略語）
ＰＣ：ポリカーボネート樹脂
ＰＢＴ：ポリブチレンテレフタレート樹脂
ＰＡ：ポリアミド樹脂
Figure JPOXMLDOC01-appb-T000001
 (Abbreviation)
PC: Polycarbonate resin PBT: Polybutylene terephthalate resin PA: Polyamide resin
　表１に示すとおり、実施例１～５の熱可塑性樹脂組成物は、本発明で規定するＭＶＲが２０（ｃｍ3／１０分）以下であることから、連続生産の良好な樹脂繊維が得られた。
比較例１は、本発明の規定外であるため、連続生産に劣り、樹脂繊維径も太くなる傾向にあった。 As shown in Table 1, the thermoplastic resin compositions of Examples 1-5, since the MVR defined in the present invention is less than 20 (cm 3/10 min), excellent resin fiber obtained in continuous production The
Since Comparative Example 1 was out of the specification of the present invention, it was inferior to continuous production, and the resin fiber diameter tended to be large.
（スチレン系樹脂の分散単位の測定方法）
　下記実施例６～１０及び比較例２～４で得られた熱可塑性樹脂組成物のペレットを、クライオミクロトームを用いて－８５℃の低温で切り出すことで、超薄切片を得た。得られた超薄切片を四酸化オスミウム（ＯｓＯ４）及び／又は四酸化ルテニウム（ＲｕＯ４）で染色し、透過電子顕微鏡（ＪＥＭ－１４００：日本電子製）を用いて観察及び写真撮影し画像解析装置（旭化成ＩＰ－１０００ＰＣ）を用いて、分散相の分散単位１００個の円相当粒子径の平均値から求めた。 (Measurement method of dispersion unit of styrenic resin)
Ultrathin sections were obtained by cutting the pellets of the thermoplastic resin compositions obtained in the following Examples 6 to 10 and Comparative Examples 2 to 4 at a low temperature of −85 ° C. using a cryomicrotome. The obtained ultrathin section is stained with osmium tetroxide (OsO4) and / or ruthenium tetroxide (RuO4), observed and photographed using a transmission electron microscope (JEM-1400: JEOL Ltd.), and an image analyzer ( Asahi Kasei IP-1000 PC) was used to obtain the average value of the circle-equivalent particle diameters of 100 dispersion units of the dispersed phase.
（実施例６）
　メタクリル酸１０質量部、スチレン９０質量部からなるモノマー混合物を公知の溶液重合法により重合し、スチレン系樹脂を得た。得られたスチレン系樹脂２０質量部とポリアミド樹脂（ユニチカ（株）製　ユニチカナイロン６　Ａ１０３０ＢＲＬ）８０質量部を混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を用い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は８５０ｎｍであった。得られたペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２６０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１２００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は１２μｍであった。 (Example 6)
A monomer mixture consisting of 10 parts by mass of methacrylic acid and 90 parts by mass of styrene was polymerized by a known solution polymerization method to obtain a styrene resin. 20 parts by mass of the obtained styrene resin and 80 parts by mass of a polyamide resin (UNITICA Co., Ltd. Unitika nylon 6 A 1030 BRL) are mixed, and using Technobel Co., Ltd. KZW15-90 (L / D = 90), cylinder temperature Melt-kneading was performed under the conditions of 260 ° C. and a screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the method described above, the dispersion unit of the styrene resin was 850 nm. The obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. I wound up at the speed. The fiber diameter of the obtained undrawn fiber was 12 μm.
（実施例７）
　粒子径０．１μｍのポリブタジエンラテックス７０質量部（固形分）の存在下で、メタクリル酸１０質量部、スチレン１５質量部、アクリロニトリル５質量部からなる混合モノマーを乳化重合法によりグラフト重合し、スチレン系樹脂を得た。得られたスチレン系樹脂１０質量部とポリアミド樹脂（ユニチカ（株）製　ユニチカナイロン６　Ａ１０３０ＢＲＬ）９０質量部を混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を使い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は８００ｎｍであった。このペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２８０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１２００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は１３μｍであった。 (Example 7)
A mixed monomer consisting of 10 parts by mass of methacrylic acid, 15 parts by mass of styrene and 5 parts by mass of acrylonitrile is graft polymerized by an emulsion polymerization method in the presence of 70 parts by mass (solid content) of polybutadiene latex having a particle diameter of 0.1 μm. I got a resin. Ten parts by mass of the obtained styrene resin and 90 parts by mass of a polyamide resin (UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL) are mixed, and using KZW15-90 (L / D = 90) manufactured by Technobel, cylinder temperature Melt-kneading was performed under the conditions of 260 ° C. and a screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the above-mentioned method, the dispersion unit of styrenic resin was 800 nm. The pellets were extruded at an extrusion temperature of 280 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. I wound up at the speed. The fiber diameter of the obtained undrawn fiber was 13 μm.
（実施例８）
　メタクリル酸１０質量部、スチレン６０質量部及びアクリロニトリル３０質量部からなるモノマー混合物を公知の溶液重合法により重合し、スチレン系樹脂を得た。得られたスチレン系樹脂５０質量部とポリアミド樹脂（ユニチカ（株）製　ユニチカナイロン６　Ａ１０３０ＢＲＬ）５０質量部混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を使い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は９１０ｎｍであった。得られたペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２６０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１２００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は１８μｍであった。 (Example 8)
A monomer mixture consisting of 10 parts by mass of methacrylic acid, 60 parts by mass of styrene and 30 parts by mass of acrylonitrile was polymerized by a known solution polymerization method to obtain a styrene resin. 50 parts by mass of the obtained styrene resin and 50 parts by mass of a polyamide resin (UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL) are mixed, and using KZW15-90 (L / D = 90) manufactured by Technobel, cylinder temperature 260 Melt-kneading was performed under the conditions of ° C. and screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the above-mentioned method, the dispersion unit of styrenic resin was 910 nm. The obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. I wound up at the speed. The fiber diameter of the obtained undrawn fiber was 18 μm.
（実施例９）
　グリシジルメタクリレート１０質量部、スチレン６０質量部及びアクリロニトリル３０質量部からなるモノマー混合物を公知の溶液重合法により重合し、スチレン系樹脂を得た。得られたスチレン系樹脂３０質量部とポリカーボネート樹脂（三菱エンジニアリングプラスチックス(株)製　ノバレックスＭ‐７０２２Ｊ）７０質量部を混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を使い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は９２０ｎｍであった。得られたペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２６０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１１００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は２２μｍであった。 (Example 9)
A monomer mixture consisting of 10 parts by mass of glycidyl methacrylate, 60 parts by mass of styrene and 30 parts by mass of acrylonitrile was polymerized by a known solution polymerization method to obtain a styrene resin. 30 parts by mass of the obtained styrene resin and 70 parts by mass of a polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd. Novarex M-7022J) are mixed, and KZW15-90 (L / D = 90) manufactured by Technobel Inc. Melt-kneading was performed under conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the above-mentioned method, the dispersion unit of styrenic resin was 920 nm. The obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a silicone oil agent is applied as a focusing agent by a focusing agent applying roller to 1100 m / min. I wound up at the speed. The fiber diameter of the obtained undrawn fiber was 22 μm.
（実施例１０）
　グリシジルメタクリレート１０質量部、スチレン６０質量部及びアクリロニトリル３０質量部からなるモノマー混合物を公知の溶液重合法により重合し、スチレン系樹脂を得た。得られたスチレン系樹脂３０質量部とポリブチレンテレフタレート樹脂（三菱エンジニアリングプラスチックス（株）製　ノバデュラン５０１０Ｒ５Ｌ２）７０質量部を混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を使い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は９２０ｎｍであった。得られたペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２６０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１１００ｍ／分の速度で巻き取った。得られた未延伸繊維の繊維径は２０μｍであった。 (Example 10)
A monomer mixture consisting of 10 parts by mass of glycidyl methacrylate, 60 parts by mass of styrene and 30 parts by mass of acrylonitrile was polymerized by a known solution polymerization method to obtain a styrene resin. 30 parts by mass of the obtained styrene resin and 70 parts by mass of polybutylene terephthalate resin (Mitsubishi Engineering Plastics Co., Ltd. Novaduran 5010R5L2) are mixed, and manufactured by Technobel Co., Ltd. KZW15-90 (L / D = 90) Melt-kneading was performed under the conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the above-mentioned method, the dispersion unit of styrenic resin was 920 nm. The obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a silicone oil agent is applied as a focusing agent by a focusing agent applying roller to 1100 m / min. I wound up at the speed. The fiber diameter of the obtained undrawn fiber was 20 μm.
（比較例２）
　アクリロニトリル１０質量部、スチレン９０質量部からなるモノマー混合物を公知の塊状重合法により重合し、スチレン系樹脂を得た。得られたスチレン系樹脂２０質量部とポリアミド樹脂（ユニチカ（株）製　ユニチカナイロン６　Ａ１０３０ＢＲＬ）８０質量部を混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を使い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は１０００ｎｍ以上であった。得られたペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２６０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１２００ｍ／分の速度で巻き取ったところ、断糸が発生したため、巻き取り速度を８００ｍ／分へ変更した。得られた未延伸繊維の繊維径は３０μｍであった。 (Comparative example 2)
A monomer mixture consisting of 10 parts by mass of acrylonitrile and 90 parts by mass of styrene was polymerized by a known bulk polymerization method to obtain a styrene resin. 20 parts by mass of the obtained styrene resin and 80 parts by mass of a polyamide resin (UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL) are mixed, and using KZW15-90 (L / D = 90) manufactured by Technobel, cylinder temperature Melt-kneading was performed under the conditions of 260 ° C. and a screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the method of the said description, the dispersion | distribution unit of styrene resin was 1000 nm or more. The obtained pellet was extruded at an extrusion temperature of 260 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. When winding was carried out at a speed, a thread breakage occurred, so the winding speed was changed to 800 m / min. The fiber diameter of the obtained undrawn fiber was 30 μm.
（比較例３）
　粒子径０．４μｍのポリブタジエンラテックス５０質量部（固形分）の存在下で、メタクリル酸５質量部、スチレン３０質量部、アクリロニトリル１５質量部からなる混合モノマーを乳化重合法によりグラフト重合し、スチレン系樹脂を得た。得られたスチレン系樹脂１０質量部とポリアミド樹脂（ユニチカ（株）製　ユニチカナイロン６　Ａ１０３０ＢＲＬ）９０質量部を混合し、（株）テクノベル製　ＫＺＷ１５－９０（Ｌ／Ｄ＝９０）を使い、シリンダー温度２８０℃、スクリュー回転数３５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は１０００ｎｍ以上であった。このペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２８０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１２００ｍ／分の速度で巻き取ったところ、断糸が発生したため、巻き取り速度を９００ｍ／分へ変更した。得られた未延伸繊維の繊維径は２８μｍであった。 (Comparative example 3)
A mixed monomer consisting of 5 parts by mass of methacrylic acid, 30 parts by mass of styrene and 15 parts by mass of acrylonitrile is graft polymerized by an emulsion polymerization method in the presence of 50 parts by mass (solid content) of a polybutadiene latex having a particle diameter of 0.4 μm. I got a resin. Ten parts by mass of the obtained styrene resin and 90 parts by mass of a polyamide resin (UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL) are mixed, and using KZW15-90 (L / D = 90) manufactured by Technobel, cylinder temperature Melt-kneading was performed under the conditions of 280 ° C. and screw rotation speed of 350 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the method of the said description, the dispersion | distribution unit of styrene resin was 1000 nm or more. The pellets were extruded at an extrusion temperature of 280 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. When winding was performed at a speed, a thread breakage occurred, so the winding speed was changed to 900 m / min. The fiber diameter of the obtained undrawn fiber was 28 μm.
（比較例４）
　メタクリル酸１０質量部、スチレン９０質量部からなるモノマー混合物を公知の溶液重合法により重合し、スチレン系樹脂を得た。得られたスチレン系樹脂２０質量部とポリアミド樹脂（ユニチカ（株）製　ユニチカナイロン６　Ａ１０３０ＢＲＬ）８０質量部を混合し、東芝機械（株）製　ＴＥＭ－３５Ｂ（Ｌ／Ｄ＝３１）を用い、シリンダー温度２６０℃、スクリュー回転数４５０ｒｐｍの条件で溶融混練を行った。その際、ダイから押し出される前に５００メッシュ金網に通した。得られた熱可塑性樹脂組成物のペレットを上記記載の方法で観察した結果、スチレン系樹脂の分散単位は１０００ｎｍ以上であった。このペレットを、ノズル径０．５ｍｍφ、２４孔からなるマルチフィラメント用紡糸ダイを備えた押出機を用いて、押出温度２８０℃、２６ｇ／分の吐出量で押し出した。押し出された溶融ストランドを冷却温度１５℃、冷却風速０．５ｍ／分、長さ９００ｍｍからなる冷却ダクトで冷却後、収束剤付与ローラーで収束剤としてシリコーン系油剤を付与しながら、１２００ｍ／分の速度で巻き取ったところ、断糸が発生したため、巻き取り速度を９００ｍ／分へ変更した。得られた未延伸繊維の繊維径は２７μｍであった。 (Comparative example 4)
A monomer mixture consisting of 10 parts by mass of methacrylic acid and 90 parts by mass of styrene was polymerized by a known solution polymerization method to obtain a styrene resin. Twenty parts by mass of the obtained styrene resin and 80 parts by mass of a polyamide resin (UNITICA Co., Ltd. Unitika nylon 6 A1030 BRL) are mixed, and a cylinder is used using Toshiba Machine Co. TEM-35B (L / D = 31). Melt-kneading was performed under the conditions of a temperature of 260 ° C. and a screw rotation speed of 450 rpm. At that time, it was passed through a 500 mesh wire mesh before being extruded from the die. As a result of observing the pellet of the obtained thermoplastic resin composition by the method of the said description, the dispersion | distribution unit of styrene resin was 1000 nm or more. The pellets were extruded at an extrusion temperature of 280 ° C. and a discharge rate of 26 g / min using an extruder equipped with a multifilament spinning die having a nozzle diameter of 0.5 mmφ and 24 holes. The extruded molten strand is cooled by a cooling duct consisting of a cooling temperature of 15 ° C., a cooling air velocity of 0.5 m / min, and a length of 900 mm, and then a converging agent-applying roller applies 1200 m / min while applying a silicone oil as a converging agent. When winding was performed at a speed, a thread breakage occurred, so the winding speed was changed to 900 m / min. The fiber diameter of the obtained undrawn fiber was 27 μm.
＜連続生産性の評価＞
　実施例６～１０及び比較例２～４で樹脂繊維を製造する際、１０００ｍ／分以上の速度で巻き取っても断糸せず連続生産可能であったものを「○」、１０００ｍ／分以上の速度で巻き取ると断糸し連続生産できなかったものを「×」とした。結果を表２に示す。 <Evaluation of continuous productivity>
When resin fibers are produced in Examples 6 to 10 and Comparative Examples 2 to 4, those which can be continuously produced without being broken even when wound up at a speed of 1000 m / min or more are evaluated as “○”, 1000 m / min or more When it was wound up at a speed of 1, it was broken and continuous production could not be made "x". The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
 （略語）
ＳＴ：スチレン系樹脂
ＰＡ：ポリアミド樹脂
ＰＣ：ポリカーボネート樹脂
ＰＢＴ：ポリブチレンテレフタレート樹脂
Figure JPOXMLDOC01-appb-T000002
 (Abbreviation)
ST: Styrene resin PA: Polyamide resin PC: Polycarbonate resin PBT: Polybutylene terephthalate resin
　表２に示すとおり、実施例６～１０は、スチレン系樹脂の分散単位が１０００ｎｍ未満であることから、連続生産の良好な樹脂繊維が得られた。比較例２～４は、本発明の規定外であるため、連続生産に劣り、樹脂繊維径も太くなる傾向にあった。 As shown in Table 2, in Examples 6 to 10, since the dispersion unit of the styrene resin was less than 1000 nm, good resin fibers for continuous production were obtained. Since Comparative Examples 2 to 4 were out of the specification of the present invention, they were inferior to continuous production, and the resin fiber diameter tended to be large.
　以上のまとめとして、本発明の構成及びそのバリエーションを以下に付記しておく。
［１］スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維であって、前記熱可塑樹脂組成物の、ＩＳＯ１１３３に準じ、温度２２０℃、荷重１０ｋｇの条件で測定されたメルトボリュームレイトが２０（ｃｍ3／１０分）以下であることを特徴とする樹脂繊維。
［２］前記メルトボリュームレイトが２０（ｃｍ3／１０分）以下、１５（ｃｍ3／１０分）以下、１０（ｃｍ3／１０分）以下、または５（ｃｍ3／１０分）以下である、［１］に記載の樹脂繊維。
［３］前記熱可塑性樹脂はスチレン系樹脂以外の他の熱可塑性樹脂をさらに含む［１］または［２］に記載の樹脂繊維。
［４］前記スチレン系樹脂以外の他の熱可塑性樹脂が、ポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、及びポリイミド樹脂からなる群より選ばれる少なくとも１種の樹脂を含有する［３］に記載の樹脂繊維。
［５］前記スチレン系樹脂以外の他の熱可塑性樹脂が、ＰＡ－６、ＰＡ－６６、ＰＡ－１１、ＰＡ－１２、ＰＡ－６１０、ＰＡ－１０１０、ポリ乳酸樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、ポリプロピレン樹脂、アクリル樹脂、界面重合法ポリカーボネート樹脂、溶融エステル交換法ポリカーボネート樹脂、並びにポリイミド樹脂からなる群より選ばれる、［３］または［４］に記載の樹脂繊維。
［６］スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維であって、前記熱可塑性樹脂組成物は、スチレン系樹脂以外の他の熱可塑性樹脂をさらに含み、かつ、前記スチレン系樹脂がナノ単位で分散していることを特徴とする樹脂繊維。
［７］前記スチレン系樹脂以外の熱可塑性樹脂が、ポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、及びポリイミド樹脂からなる群より選ばれる少なくとも１種の樹脂であることを特徴とする［６］に記載の樹脂繊維。
［８］前記スチレン系樹脂以外の熱可塑性樹脂が、ＰＡ－６、ＰＡ－６６、ＰＡ－１１、ＰＡ－１２、ＰＡ－６１０、ＰＡ－１０１０、ポリ乳酸樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、ポリプロピレン樹脂、アクリル樹脂、界面重合法ポリカーボネート樹脂、溶融エステル交換法ポリカーボネート樹脂、及びポリイミド樹脂からなる群より選ばれる１種以上の樹脂を含有する、［６］または［７］に記載の樹脂繊維。
［９］前記ナノ単位が、透過電子顕微鏡で観察される１０００ｎｍ未満、９５０ｎｍ未満、９００ｎｍ未満、または８５０ｎｍ以下の分散単位である、［６］～［８］のいずれか１つに記載の樹脂繊維。
［１０］延伸加工が施されており、その際の加工温度が、５０～１６０℃または６０～１５０℃である、［１］～［９］のいずれか１つに記載の樹脂繊維。
［１１］強化繊維と、［１］～［１０］の何れか１つに記載の樹脂繊維とを含む、繊維強化プラスチック。
［１２］前記強化繊維が炭素繊維である、［１１］に記載の繊維強化プラスチック。
［１３］溶融紡糸法またはメルトブロー法で得られることを特徴とする、［１］～［１０］の何れか１つに記載の樹脂繊維の製造方法。
［１４］加工温度が２００℃～３００℃または２２０～２９０℃である、［１２］に記載の樹脂繊維の製造方法。 As a summary of the above, the configuration of the present invention and the variations thereof are additionally described below.
[1] A resin fiber comprising a thermoplastic resin composition containing a styrenic resin, wherein the thermoplastic resin composition has a melt volume rate of 20 measured at a temperature of 220 ° C. and a load of 10 kg according to ISO 1133. (cm 3/10 min) resin fibers, wherein less.
[2] the melt volume rate is 20 (cm 3/10 min) or less, 15 (cm 3/10 min) or less, is 10 (cm 3/10 min) or less, or 5 (cm 3/10 min) or less , The resin fiber as described in [1].
[3] The resin fiber according to [1] or [2], wherein the thermoplastic resin further contains another thermoplastic resin other than a styrene resin.
[4] The thermoplastic resin other than the styrene-based resin contains at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin The resin fiber as described in [3].
[5] The thermoplastic resins other than the above-mentioned styrenic resin are PA-6, PA-66, PA-11, PA-12, PA-610, PA-1010, polylactic acid resin, polybutylene terephthalate resin, polyethylene The resin fiber according to [3] or [4], which is selected from the group consisting of a terephthalate resin, a polypropylene resin, an acrylic resin, an interfacial polymerization polycarbonate resin, a melt transesterification polycarbonate resin, and a polyimide resin.
[6] A resin fiber comprising a thermoplastic resin composition containing a styrene-based resin, wherein the thermoplastic resin composition further includes another thermoplastic resin other than the styrene-based resin, and the styrene-based resin is Resin fiber characterized by being dispersed in nano units.
[7] The thermoplastic resin other than the styrene-based resin is at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin The resin fiber according to [6], which is characterized by the above.
[8] The thermoplastic resins other than the styrene-based resin are PA-6, PA-66, PA-11, PA-12, PA-610, PA-1010, polylactic acid resin, polybutylene terephthalate resin, polyethylene terephthalate resin The resin fiber according to [6] or [7], comprising at least one resin selected from the group consisting of polypropylene resin, acrylic resin, interfacial polymerization polycarbonate resin, melt transesterification polycarbonate resin, and polyimide resin .
[9] The resin fiber according to any one of [6] to [8], wherein the nano unit is a dispersion unit of less than 1000 nm, less than 950 nm, less than 900 nm, or 850 nm or less observed with a transmission electron microscope .
[10] The resin fiber according to any one of [1] to [9], which has been subjected to a stretching process and the processing temperature at that time is 50 to 160 ° C. or 60 to 150 ° C.
[11] A fiber reinforced plastic comprising a reinforcing fiber and the resin fiber according to any one of [1] to [10].
[12] The fiber reinforced plastic according to [11], wherein the reinforcing fiber is a carbon fiber.
[13] The method for producing a resin fiber according to any one of [1] to [10], which is obtained by a melt spinning method or a melt blow method.
[14] The method for producing a resin fiber according to [12], wherein the processing temperature is 200 ° C to 300 ° C or 220 to 290 ° C.
　上記のとおり、本発明の樹脂繊維は、連続生産可能であり、強度と伸度に優れたものである。そのため、抄造法や不織布法での繊維強化プラスチックの材料として好適に使用することができる。さらに、フィルター用濾布、電気絶縁用の不織布材料、梱包等の包装材料としても好適に使用することができる。 As described above, the resin fiber of the present invention can be produced continuously, and is excellent in strength and elongation. Therefore, it can be suitably used as a material of fiber reinforced plastic in a papermaking method or a non-woven fabric method. Furthermore, it can be suitably used as a filter cloth for filters, a non-woven material for electrical insulation, and a packaging material such as packaging.

Claims (6)

  1. 　スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維であって、前記熱可塑樹脂組成物の、ＩＳＯ１１３３に準じ、温度２２０℃、荷重１０ｋｇの条件で測定されたメルトボリュームレイトが２０（ｃｍ3／１０分）以下であることを特徴とする樹脂繊維。 A resin fiber comprising a thermoplastic resin composition containing a styrenic resin, wherein the thermoplastic resin composition has a melt volume rate of 20 (cm 3) measured at a temperature of 220 ° C. and a load of 10 kg according to ISO 1133. Resin fiber characterized in that it is 10 minutes or less.
  2. 　前記熱可塑性樹脂はスチレン系樹脂以外の他の熱可塑性樹脂をさらに含む請求項１に記載の樹脂繊維。 The resin fiber according to claim 1, wherein the thermoplastic resin further comprises another thermoplastic resin other than a styrene resin.
  3. 　スチレン系樹脂を含む熱可塑性樹脂組成物からなる樹脂繊維であって、前記熱可塑性樹脂組成物は、スチレン系樹脂以外の他の熱可塑性樹脂をさらに含み、かつ、前記スチレン系樹脂がナノ単位で分散していることを特徴とする樹脂繊維。 It is a resin fiber which consists of a thermoplastic resin composition containing styrenic resin, and the thermoplastic resin composition further contains other thermoplastic resin other than styrenic resin, and the styrenic resin is nano unit. Resin fiber characterized by being dispersed.
  4. 　前記他の熱可塑性樹脂は、ポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、及びポリイミド樹脂からなる群より選ばれる少なくとも１種の樹脂を含有することを特徴とする請求項２～３の何れか１項に記載の樹脂繊維。 The other thermoplastic resin contains at least one resin selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin. The resin fiber according to any one of 2 to 3.
  5. 　強化繊維と、請求項１～４の何れか１項に記載の樹脂繊維とを含む、繊維強化プラスチック。 A fiber reinforced plastic comprising a reinforcing fiber and the resin fiber according to any one of claims 1 to 4.
  6. 　溶融紡糸法またはメルトブロー法で得られることを特徴とする、請求項１～４の何れか１項に記載の樹脂繊維の製造方法。 The method for producing a resin fiber according to any one of claims 1 to 4, which is obtained by a melt spinning method or a melt blow method.
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