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WO2019039373A1 - Fibre de résine et son procédé de production - Google Patents

Fibre de résine et son procédé de production 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
Authority
WO
WIPO (PCT)
Prior art keywords
resin
fiber
styrene
thermoplastic resin
thermoplastic
Prior art date
Application number
PCT/JP2018/030402
Other languages
English (en)
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/ja
Publication of WO2019039373A1 publication Critical patent/WO2019039373A1/fr
Priority to JP2021183304A priority patent/JP7360435B2/ja

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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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Reinforced Plastic Materials (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne : une fibre de résine qui présente à la fois une résistance et un allongement qui lui permettent de résister à la production d'une matière plastique renforcée par des fibres au moyen d'un procédé de fabrication de papier ou d'un procédé pour non-tissé, et qui peut être produite en continu ; et un procédé de production de cette fibre de résine. Une fibre de résine selon la présente invention est formée à partir d'une composition de résine thermoplastique qui contient une résine styrénique, et est caractérisée en ce que l'indice de fluidité en volume à l'état fondu de la composition de résine thermoplastique telle que déterminée à une température de 220 °C sous une charge de 10 kg conformément à la norme ISO 1133 est inférieur ou égal à 20(cm3/10 min) ; ou en variante, une fibre de résine selon la présente invention est formée à partir d'une composition de résine thermoplastique qui est caractérisée en ce qu'une résine styrénique et une autre résine thermoplastique sont contenues en son sein et la résine styrénique est dispersée de l'ordre de quelques nanomètres.
PCT/JP2018/030402 2017-08-21 2018-08-16 Fibre de résine et son procédé de production WO2019039373A1 (fr)

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JP2005538239A (ja) * 2002-09-09 2005-12-15 ビーエーエスエフ アクチェンゲゼルシャフト 良好な流動能を有する陰イオン重合された耐衝撃性ポリスチレン
JP2016530404A (ja) * 2013-06-12 2016-09-29 キンバリー クラーク ワールドワイド インコーポレイテッド 多孔質ポリオレフィン繊維
JP2017502179A (ja) * 2013-12-18 2017-01-19 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ ポリ（フェニレンエーテル）繊維、生成方法、及びその繊維による物品

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JP2995938B2 (ja) * 1991-08-28 1999-12-27 東レ株式会社 不織布およびフィラメント束の開繊方法および不織布の製造方法
JP4033655B2 (ja) * 2001-09-27 2008-01-16 三井化学株式会社 使い捨て着用物品用伸縮性繊維
JP2014043524A (ja) * 2012-08-28 2014-03-13 Teijin Ltd 繊維強化プラスチック成形用基材
JP2014062336A (ja) * 2012-09-19 2014-04-10 Teijin Ltd 繊維強化プラスチック用の半製品の製造方法
JP6239298B2 (ja) * 2013-03-25 2017-11-29 Art&Tech株式会社 多層シートおよび成形品
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JPH06316812A (ja) * 1993-05-06 1994-11-15 Showa Denko Kk スチレン系樹脂マルチフィラメント
JP2005530939A (ja) * 2002-06-27 2005-10-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリ（トリメチレンジカルボキシレート）繊維、それらの製造および使用
JP2005538239A (ja) * 2002-09-09 2005-12-15 ビーエーエスエフ アクチェンゲゼルシャフト 良好な流動能を有する陰イオン重合された耐衝撃性ポリスチレン
JP2016530404A (ja) * 2013-06-12 2016-09-29 キンバリー クラーク ワールドワイド インコーポレイテッド 多孔質ポリオレフィン繊維
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