WO2014196372A1 - Agent d'encollage pour fibre de renforcement et utilisations associées - Google Patents

Agent d'encollage pour fibre de renforcement et utilisations associées Download PDF

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Publication number
WO2014196372A1
WO2014196372A1 PCT/JP2014/063643 JP2014063643W WO2014196372A1 WO 2014196372 A1 WO2014196372 A1 WO 2014196372A1 JP 2014063643 W JP2014063643 W JP 2014063643W WO 2014196372 A1 WO2014196372 A1 WO 2014196372A1
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WIPO (PCT)
Prior art keywords
resin
sizing agent
epoxy resin
reinforcing fiber
weight
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PCT/JP2014/063643
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English (en)
Japanese (ja)
Inventor
吉田　昌彦
俊彦 菊田
淳 高谷
幹生 中川
Original Assignee
松本油脂製薬株式会社
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Priority to JP2015521382A priority Critical patent/JP6381527B2/ja
Publication of WO2014196372A1 publication Critical patent/WO2014196372A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a sizing agent for reinforcing fibers and its use. Specifically, the present invention relates to a sizing agent for reinforcing fibers used to reinforce a matrix resin, a reinforcing fiber strand using the reinforcing fiber, and a fiber-reinforced composite material.
  • Fiber reinforced composite materials in which plastic materials (called matrix resins) are reinforced with various synthetic fibers are widely used for automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like.
  • fibers used in these composite materials include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as aramid fibers, polyamide fibers, and polyethylene fibers.
  • These various synthetic fibers are usually manufactured in a filament shape, and then processed into a sheet-like intermediate material called a unidirectional prepreg by a hot melt method or a drum winding method, processed by a filament winding method, or in some cases a textile Or it is used as a reinforced fiber through various high-order processing steps, such as being processed into a chopped fiber shape.
  • Patent Document 1 a number of techniques for applying a sizing agent have been proposed (for example, Patent Document 1) for the purpose of imparting appropriate bundling properties to fibers, and are widely used industrially.
  • Patent Document 1 a number of techniques for applying a sizing agent for the purpose of imparting appropriate bundling properties to fibers, and are widely used industrially.
  • Patent Document 1 a number of techniques for applying a sizing agent for the purpose of imparting appropriate bundling properties to fibers, and are widely used industrially.
  • Patent Document 1 a number of techniques for applying a sizing agent for the purpose of imparting appropriate bundling properties to fibers, and are widely used industrially.
  • sizing agents those that have a high film-forming property and are solid at room temperature, for example, are used as sizing agents for reinforced fiber strands in the form of chopped fibers, and have excellent processability and good workability. Although it is advantageous in that it has a problem of poor flexibility in cases where it is used as a sizing agent for reinforcing fiber strands in the form of long fibers. Furthermore, when processing reinforcing fibers into a unidirectional sheet or woven fabric, it is important that the reinforcing fiber strands are quickly opened with a guide bar or the like in the molding process. Since the flexibility is inferior, the opening property may be remarkably inferior.
  • the texture of the reinforcing fiber strand to which the conventional sizing agent is applied may become too hard, and it may be difficult to make a product package by winding it tightly in a bobbin shape.
  • the reinforcing fiber strand of the package is collapsed when the product package is transported. Therefore, in the field of fiber reinforced composite materials, it is possible to increase the affinity between the reinforcing fiber strands and the matrix resin so that they can be firmly bonded, and further to provide excellent flexibility to the reinforcing fiber strands. Development is desired.
  • the object of the present invention is to provide a reinforcing fiber sizing agent capable of simultaneously imparting excellent adhesion and flexibility with a matrix resin to reinforcing fibers used to reinforce the matrix resin, It is to provide a reinforced fiber strand and a fiber reinforced composite material using the same.
  • the inventors of the present invention are superior to matrix resins with respect to reinforcing fibers by using a urethane-modified epoxy resin (A) and a specific resin component (B) in combination.
  • the present inventors have found that it is possible to simultaneously impart adhesiveness and flexibility, and have reached the present invention.
  • the sizing agent for reinforcing fibers of the present invention comprises a urethane-modified epoxy resin (A) and at least one resin component selected from an aromatic polyester resin, an aromatic polyester urethane resin, a polyamide resin, and a modified polyolefin resin ( And B).
  • the weight ratio (A / B) of the urethane-modified epoxy resin (A) and the resin component (B) is preferably 5/95 to 95/5.
  • the urethane-modified epoxy resin (A) preferably has a structure in which at least a part of the hydroxyl groups of the epoxy resin (A1) having a hydroxyl group is substituted with a modifying group represented by the following general formula (1).
  • R 1 is a residue obtained by removing an isocyanate group from the organic polyisocyanate compound (A2).
  • R 2 is an alkyl or alkenyl group having 1 to 18 carbon atoms.
  • M is 1 to 500.
  • N is a number from 1 to 3.
  • AO is an oxyalkylene group having 2 to 4 carbon atoms.
  • the urethane-modified epoxy resin (A) is a reactive component containing a hydroxyl group-containing epoxy resin (A1), an organic polyisocyanate compound (A2), and a polyoxyalkylene monoalkyl ether (A3) represented by the following general formula (2). It is preferable that it is a compound obtained by making it react.
  • R 2 is an alkyl or alkenyl group having 1 to 18 carbon atoms.
  • M is a number from 1 to 500.
  • AO is an oxyalkylene group having 2 to 4 carbon atoms.
  • the epoxy resin (A1) is preferably a bisphenol type epoxy resin.
  • the bisphenol-type epoxy resin is preferably an epoxy resin represented by the following general formula (3).
  • X is an organic group represented by the following general formula (4) or the following general formula (5).
  • P is a number of 1 to 30.
  • R 3 and R 4 each independently represent a hydrogen atom or a methyl group.
  • the reinforcing fiber strand of the present invention is obtained by adhering the above-described reinforcing fiber sizing agent to a raw material reinforcing fiber strand.
  • the bending strength of the reinforcing fiber strand is preferably 60 g or less.
  • the fiber-reinforced composite material of the present invention includes a matrix resin and the above-described reinforcing fiber strand.
  • the matrix resin is preferably a thermoplastic resin.
  • the sizing agent for reinforcing fibers of the present invention can simultaneously impart excellent adhesion and flexibility to the matrix resin to the reinforcing fibers.
  • the reinforcing fiber strand of the present invention is excellent in adhesion to the matrix resin and flexibility.
  • the present invention is a sizing agent for reinforcing fibers used to reinforce a matrix resin, and essentially contains a urethane-modified epoxy resin (A) and a specific resin component (B). Details will be described below.
  • the urethane-modified epoxy resin (A) is an essential component of the sizing agent of the present invention, and refers to a resin component in which a modified group having a urethane bond is introduced into the molecular structure of the epoxy resin.
  • the urethane-modified epoxy resin (A) can be obtained by polyaddition reaction of an epoxy resin (A1) having a hydroxyl group, an organic polyisocyanate compound (A2), and other active hydrogen group-containing compound as necessary.
  • the adhesiveness between the reinforcing fiber and the matrix resin can be drastically improved, and excellent flexibility with respect to the reinforcing fiber. Sex can also be imparted.
  • One or more urethane-modified epoxy resins (A) may be used.
  • the modifying group represented by the general formula (1) includes an epoxy resin (A1) having a hydroxyl group, an organic polyisocyanate compound (A2), and a polyoxyalkylene monoalkyl ether (A3) represented by the general formula (2). It is introduced by reacting.
  • R 1 is a residue obtained by removing all isocyanate groups from the organic polyisocyanate compound (A2).
  • the carbon number of R 1 is preferably 4 to 38, more preferably 4 to 26, and still more preferably 4 to 18. Details of the organic polyisocyanate compound (A2) will be described later.
  • R 2 is an alkyl group or alkenyl group having 1 to 18 carbon atoms.
  • the carbon skeleton of R 2 may have a straight chain structure or may have a branched structure, but preferably has a branched structure from the viewpoint of permeability into the strand when sized. .
  • R 2 is preferably an alkyl group.
  • R 2 preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • n is a number of 1 to 3, preferably 1 to 2, and more preferably 1.
  • m is a number from 1 to 500. From the standpoint that the effects of the present invention can be further exhibited, m is preferably 4 to 300, more preferably 6 to 200, still more preferably 8 to 150, particularly preferably 9 to 120, and most preferably 10 to 80.
  • AO is an oxyalkylene group having 2 to 4 carbon atoms. Accordingly, (AO) m is a polyoxyalkylene group (where m is 2 or more). Examples of AO include an oxyethylene group (EO), an oxypropylene group (PO), and an oxybutylene group (BO). (AO) AO constituting m may be one type or two or more types.
  • any of a block adduct, an alternating adduct, and a random adduct may be used.
  • the proportion of EO in the entire (AO) m is preferably 60 mol% or more, more preferably 65 to 100 mol%, and even more preferably 70 to 100 mol%.
  • the case where (AO) m contains EO and PO is preferable.
  • the proportion of EO in the total of (AO) m is preferably 60 to 99 mol% and the proportion of PO is 1 to 40 mol%, the proportion of EO is 65 to 97 mol% and the proportion of PO is 3 to 35 mol. More preferably, the mole percentage is more preferably 70 to 95 mole% and the PO ratio is more preferably 5 to 30 mole%.
  • the weight average molecular weight of the polyoxyalkylene group (AO) m is preferably 100 to 23000, more preferably 150 to 13500, 200 to 10,000, 250 to 5000, 300 to 6000, 350, from the viewpoint that the effects of the present invention can be further exhibited. It is preferable in the order of ⁇ 3500.
  • the epoxy resin having a hydroxyl group (A1) examples include a bisphenol type epoxy resin, a novolac type epoxy resin, an amine type epoxy resin, and an aliphatic epoxy resin.
  • the epoxy resin (A1) is a bisphenol type epoxy resin from the viewpoint that excellent adhesiveness and flexibility can be simultaneously imparted and further excellent heat resistance can be imparted.
  • Examples of the bisphenol type epoxy resin include an epoxy resin represented by the general formula (3).
  • X is an organic group represented by the general formula (4) or the general formula (5).
  • X is preferably an organic group represented by the general formula (4) from the viewpoint of imparting excellent adhesiveness and heat resistance.
  • R 3 and R 4 each independently represent a hydrogen atom or a methyl group. From the viewpoint of affinity with the matrix resin, R 3 and R 4 are preferably methyl groups.
  • p is a number of 1 to 30, preferably 1 to 25, more preferably 1 to 22, and still more preferably 1 to 18 from the viewpoint of adhesion and heat resistance.
  • the molar ratio of the unmodified hydroxyl group of the epoxy resin (A1) to the modified group represented by the general formula (1) (unmodified hydroxyl group: modified group) is 60: 40-0 : 100 is preferable, 40:60 to 0: 100 is more preferable, and 10:90 to 0: 100 is more preferable.
  • the urethane-modified epoxy resin (A) has a hydroxyl group-containing epoxy resin (A1), an organic polyisocyanate compound (A2), and a polyoxyalkylene monoester represented by the above general formula (2) from the viewpoint that the effects of the present invention can be further exhibited.
  • a compound obtained by reacting a reactive component containing an alkyl ether (A3) is preferable.
  • Such a compound has at least a structure in which at least a part of the hydroxyl groups of the epoxy resin (A1) having a hydroxyl group is substituted with a modifying group represented by the general formula (1).
  • the organic polyisocyanate compound (A2) contains two or more (preferably 2 to 6, more preferably 2 to 3, more preferably 2) isocyanate groups in the molecule. Only 1 type may be used for an organic polyisocyanate compound (A), and 2 or more types may be used for it. Examples of the organic polyisocyanate compound (A2) include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
  • aliphatic polyisocyanate examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl.
  • Diisocyanate Diisocyanate; 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hex Methylene triisocyanate and lysine ester triisocyanate (eg phosgenates of reaction products of lysine with alkanolamines, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and 2- or 3-isocyanatopropyl-2 , 6-diisocyanatohexanoate) and the like.
  • lysine ester triisocyanate eg phosgenates of reaction products of lysine with alkanolamines, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and 2- or 3-isocyanatopropyl-2 , 6-diisocyanatohexanoate
  • alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanatoethyl) -4.
  • IPDI isophorone diisocyanate
  • hydrochloride dicyclohexylene diisocyanate
  • methylcyclohexylene diisocyanate examples include bis (2-isocyanatoethyl) -4.
  • -Diisocyanates such as cyclohexylene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate; trifunctional or higher functional polyisocyanates such as bicycloheptane triisocyanate
  • aromatic polyisocyanate examples include 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 1,5-nephthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2, Examples include 6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like.
  • aromatic polyisocyanates are preferable, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, and xylylene diisocyanate. More preferred is 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • the polyoxyalkylene monoalkyl ether (A3) is a compound represented by the general formula (2).
  • R 2 is an alkyl group or alkenyl group having 1 to 18 carbon atoms.
  • m is a number from 1 to 500.
  • AO is an alkylene group having 2 to 4 carbon atoms.
  • Preferable ranges of R 2 , m and AO are the same as those described in the general formula (1).
  • the weight average molecular weight of the polyoxyalkylene group (AO) m is preferably 100 to 23000, more preferably 150 to 13500, 200 to 10,000, 250 to 5000, 300 to 6000, 350, from the viewpoint that the effects of the present invention can be further exhibited. It is preferable in the order of ⁇ 3500.
  • the proportion of the organic polyisocyanate compound (A2) when reacting the reactive component is preferably 40 to 100 mol%, more preferably 60 to 100 mol%, based on the hydroxyl group of the epoxy resin (A1). 90 to 100 mol% is more preferable.
  • the ratio of the polyoxyalkylene monoalkyl ether (A3) is preferably 40 to 100 mol%, more preferably 60 to 100 mol%, more preferably 90 to 100 mol% based on the hydroxyl group of the epoxy resin (A1). More preferred is mol%.
  • the urethane-modified epoxy resin (A) preferably includes a urethane-modified epoxy resin represented by the following general formula (6).
  • the urethane-modified epoxy resin represented by the following general formula (6) has a structure in which the hydroxyl group of the bisphenol-type epoxy resin represented by the above general formula (3) is substituted with the modifying group represented by the above general formula (1). It is.
  • X is an organic group represented by the above general formula (4) or the above general formula (5).
  • Y is a modifying group represented by the above general formula (1).
  • R 1 excludes an isocyanate group from the organic polyisocyanate compound (A2).
  • R 2 is an alkyl or alkenyl group having 1 to 18 carbon atoms, m is a number from 1 to 500, n is a number from 1 to 3, and AO is 2 to 4 carbon atoms. Oxyalkylene group.
  • X and p are the same as those described in the general formula (3).
  • R 1 , R 2 , m, n, and AO are the same as those described in the general formula (1).
  • the modification rate (q / p) is preferably 0.4 to 1, more preferably 0.6 to 1, and still more preferably 0.9 to 1.
  • an epoxy resin (A1) having a hydroxyl group is reacted with an organic polyisocyanate compound (A2), and then a polyoxyalkylene monoalkyl ether (A3) is reacted.
  • a reaction between the polyoxyalkylene monoalkyl ether (A3) and the organic polyisocyanate compound (A2), followed by a reaction with an epoxy resin (A1) having a hydroxyl group is usually performed in the presence of an inert gas, and may be performed in an organic solvent that does not react with an isocyanate group such as acetone or methyl ethyl ketone. These organic solvents can also be removed by evaporation after completion of the reaction.
  • the reactive component described above may contain a polyol in addition to the epoxy resin (A1) having a hydroxyl group, the organic polyisocyanate compound (A2), and the polyoxyalkylene monoalkyl ether (A3) as long as the effects of the present invention are not impaired. Good.
  • the polyol include the same compounds as those exemplified for the aromatic polyester resin described later.
  • the weight average molecular weight of the urethane-modified epoxy resin (A) is preferably 500 to 100,000, more preferably 800 to 75,000, and still more preferably 1,000 to 50,000. When the molecular weight is less than 500, neither good adhesiveness nor heat resistance may be obtained. On the other hand, when the molecular weight exceeds 100,000, gelation may be caused.
  • the weight average molecular weight as used in the field of this invention means the value converted into polystyrene by measuring with the gel permeation chromatograph (GPC) measuring method on the following measurement conditions.
  • GPC measurement conditions Device: Device name “HPLC LC-6A SYSTEM” (manufactured by SHIMAZU) Column: “KF-800P (10 mm ⁇ 4.6 mm ⁇ )”, “KF-804 (300 mm ⁇ 8 mm ⁇ )”, “KF-802.5 (300 mm ⁇ 8 mm ⁇ )”, “KF-801 (300 mm ⁇ 8 mm ⁇ )” ( (SHOEX manufactured by the above) Mobile phase: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Sample volume: 100 ⁇ l (100-fold dilution) Column temperature: 50 ° C Calibration curve creation reference material: polystyrene (PSt)
  • a urethanization catalyst When preparing the urethane-modified epoxy resin (A), a urethanization catalyst can be used if necessary.
  • the urethanization catalyst that can be used in the present invention include nitrogen-containing compounds such as triethylamine, triethylenediamine, or N-methylmorpholine, metal salts such as potassium acetate, zinc stearate, or tin octylate, and dibutyl laurate. Organometallic compounds and the like.
  • the resin component (B) is at least one selected from an aromatic polyester resin, an aromatic polyester urethane resin, a polyamide resin, and a modified polyolefin resin, and is an essential component of the sizing agent of the present invention.
  • the aromatic polyester resin is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and at least one of the polycarboxylic acid or the anhydride and the polyol is a polymer containing an aromatic compound. is there.
  • the sizing agent of the present invention when used in a water emulsion, it has a hydrophilic group in the molecular skeleton including the terminal and is self-emulsifying from the viewpoint of eliminating the need to add an emulsifier component such as a surfactant. It is preferable.
  • the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
  • a well-known method is employable.
  • One or more aromatic polyester resins may be used.
  • polycarboxylic acid examples include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.
  • Aromatic dicarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, phthalic anhydride, etc. Can be mentioned.
  • sulfonate-containing aromatic dicarboxylic acid examples include sulfoterephthalate and 5-sulfoisophthalate.
  • Aliphatic dicarboxylic acids or alicyclic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, anhydrous And maleic acid.
  • tri- or higher functional polycarboxylic acid examples include trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and the like.
  • Examples of the polyol include diols and trifunctional or higher polyols.
  • Diols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, tetramethylene glycol 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, resorcin, hydroquinone, bisphenol A or an alkylene oxide adduct thereof.
  • Examples of the tri- or higher functional polyol include trimethylolpropane, glycerin, pentaerythritol and the like.
  • At least one of the polycarboxylic acid or its anhydride (sometimes referred to as the total polycarboxylic acid component) and the polyol may contain an aromatic compound.
  • 40 to 99 mol% of the total polycarboxylic acid component is preferably an aromatic dicarboxylic acid, and more preferably 80 to 99 mol%.
  • 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.
  • the polycarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid. Acid, diphenoxyethanedicarboxylic acid, phthalic anhydride, sulfoterephthalate, and 5-sulfoisophthalate are preferable.
  • the polyol ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol are preferable. .
  • the weight average molecular weight of the aromatic polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000.
  • the weight average molecular weight is less than 3,000, the heat resistance is inferior, and when it exceeds 100,000, the emulsion stability in the case of a water emulsion is inferior, which is not preferable.
  • the aromatic polyester urethane resin is a polymer obtained by a polyaddition reaction between the aromatic polyester polyol and the above-mentioned organic polyisocyanate compound (A2).
  • the sizing agent of the present invention when used in a water emulsion, it has a hydrophilic group in the molecular skeleton including the terminal and is self-emulsifying from the viewpoint of eliminating the need to add an emulsifier component such as a surfactant. It is preferable.
  • the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
  • a well-known method is employable.
  • One or two or more aromatic polyester-based urethane resins may be used.
  • the aromatic polyester polyol is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and at least one of the polycarboxylic acid or an anhydride thereof and the polyol contains an aromatic compound.
  • polycarboxylic acid or its anhydride, and a polyol, the compound illustrated in the above-mentioned aromatic polyester resin is mentioned.
  • Examples of the organic polyisocyanate compound (A2) include the same compounds as those described for the urethane-modified epoxy resin (A).
  • At least one of the polycarboxylic acid or its anhydride and the polyol may contain an aromatic compound.
  • 40 of polycarboxylic acid or its anhydride is preferable.
  • ⁇ 100 mol% is preferably an aromatic dicarboxylic acid, more preferably 80 to 100 mol%.
  • Preferred polycarboxylic acid and polyol combinations are the same as those described for the aromatic polyester resin.
  • Organic polyisocyanate compounds (A2) include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene Diisocyanate is preferred.
  • the weight average molecular weight of the aromatic polyester-based urethane resin is preferably 3,000 to 100,000, more preferably 10,000 to 50,000.
  • the weight average molecular weight is less than 3,000, the heat resistance is inferior, and when it exceeds 10,000, the emulsion stability in the case of a water emulsion is inferior.
  • a polyamide-based resin is a polymer compound having a plurality of amide groups in the main chain, which is synthesized from dicarboxylic acid and diamine, ⁇ -amino acid, lactam or derivatives thereof, and also includes homopolymers and copolymers (copolymers). included. Moreover, the modified body which introduce
  • the amount of the terminal carboxyl group is not particularly limited, but is preferably in the range of 50 to 3000 mmol, more preferably in the range of 70 to 2500 mmol, and more preferably in the range of 100 to 2000 mmol from the viewpoint of obtaining a stable water emulsion. A range is further preferred.
  • the amount of the terminal carboxyl group can be calculated by measuring the acid value of the polyamide resin.
  • the ratio of terminal carboxyl groups and terminal amino groups of the polyamide-based resin is preferably 60/40 to 100/0, more preferably 63/37 to 96/4, and more preferably 66/34 to 96 from the viewpoint of obtaining a stable water emulsion. 92/8 is more preferable.
  • the amount of the terminal amino group can be calculated by measuring the amine value of the polyamide resin.
  • the weight average molecular weight of the polyamide-based resin is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and further preferably 10,000 to 100,000.
  • a known method is used as a method for producing the polyamide-based resin.
  • a method such as polycondensation of diamine, dicarboxylic acid, ⁇ -amino- ⁇ ′ carboxylic acid or ring-opening polymerization of cyclic lactam can be mentioned.
  • a polyamide-based resin can be easily produced by using a predetermined amount of dicarboxylic acid or monocarboxylic acid as a polymerization regulator during polycondensation or ring-opening polymerization.
  • diamines examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and phenylene.
  • diamines include diamine and metaxylylenediamine.
  • Dicarboxylic acids include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, xylylene dicarboxylic acid, etc. Is mentioned.
  • Examples of the ⁇ -amino- ⁇ ′ carboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
  • polyamide resin examples include 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymer nylon, 6/610 copolymer nylon, 6/11 copolymer nylon, 6/12 copolymer nylon, 6/66/11 copolymer nylon, 6/66/12 copolymer nylon, 6/66/11/12 copolymer nylon, 6/66/610/11/12 copolymer nylon, etc. Can be mentioned. These polymers or copolymers may be used alone or as a mixture of two or more.
  • the polyamide resin preferably forms a salt with a carboxyl group at its end and a basic substance.
  • the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, and amine compounds.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferable from the viewpoint of dispersion effect and improvement of heat resistance of the sizing agent.
  • the content of the basic substance is preferably 0.2 to 3 mol, more preferably 0.4 to 2 mol, and still more preferably 0.6 to 1.5 mol, per mol of the terminal carboxyl group of the polyamide resin. . If the content of the basic substance is less than 0.2 mol, an excessive amount of unneutralized polyamide resin is present, so that the heat resistance is deteriorated, and there is a possibility of causing an adhesion inhibition by a decomposition gas. When the content of the basic substance exceeds 3 mol, an excess of alkali metal exists, which may cause an adhesion inhibition between the matrix resin and the reinforcing fiber.
  • the modified polyolefin resin is a copolymer of an olefin monomer such as ethylene or propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid, and can be produced by a known method.
  • a random copolymer obtained by copolymerizing an olefin and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting an unsaturated carboxylic acid on an olefin may be used.
  • One or two or more modified polyolefin resins may be used.
  • Examples of the olefin monomer include ethylene, propylene, 1-butene and the like. These may be used alone or in combination of two or more.
  • Examples of the monomer copolymerizable with the olefin monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and fumaric acid. These can be used alone or in combination of two or more.
  • the copolymerization ratio of the above olefinic monomer and the monomer copolymerizable with the olefinic monomer is 80% to 99.5% by weight of olefinic monomer, 100% by weight of the total weight of copolymerization,
  • the copolymerizable monomer is preferably 0.5 to 20% by weight, more preferably 90 to 99% by weight of the olefinic monomer, and further preferably 1 to 10% by weight of the monomer copolymerizable with the olefinic monomer.
  • the monomer content is particularly preferably 95 to 98% by weight and the monomer copolymerizable with the olefinic monomer 2 to 5% by weight.
  • the weight percent of the olefin monomer When the weight percent of the olefin monomer is less than 80 weight percent, the compatibility with the matrix resin may be lowered. When the weight percent of the olefin monomer exceeds 99.5 weight percent, the adhesion between the fiber and the matrix resin may be inhibited. Further, when the sizing agent is a water emulsion, the emulsion stability is lowered, and it may be difficult to uniformly apply to the fiber.
  • a modified group such as a carboxyl group introduced by copolymerization is preferably neutralized with a basic compound.
  • basic compounds include metal salts such as sodium hydroxide and potassium hydroxide; ammonia; laurylamine, ethylenediamine, trimethylamine, dimethylethanolamine, dibutylethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, Examples include amines such as dipropanolamine and monobutanolamine. Among these, amines are more preferable, and diethanolamine is particularly preferable.
  • the weight average molecular weight of the modified polyolefin resin of the present invention is preferably 5000 to 200000, and more preferably 50000 to 150,000.
  • the weight average molecular weight is less than 5,000, the heat resistance is inferior, and when it exceeds 200,000, the emulsion stability may be lowered in the case of a water emulsion.
  • the sizing agent for reinforcing fibers of the present invention essentially contains the aforementioned urethane-modified epoxy resin (A) and resin component (B).
  • the weight ratio (A / B) between the urethane-modified epoxy resin (A) and the resin component (B) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and 15/85 Is more preferably 85/15, and particularly preferably 25/75 to 75/25.
  • the weight ratio is less than 5/95, the sizing-treated strand may be insufficient in flexibility.
  • the weight ratio is more than 95/5, the sizing-treated strands may be insufficiently focused.
  • the weight ratio of the urethane-modified epoxy resin (A) in the nonvolatile content of the sizing agent is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and even more preferably 15 to 85% by weight.
  • the weight ratio of the resin component (B) to the nonvolatile content of the sizing agent is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and further preferably 15 to 85% by weight.
  • the non-volatile content in the present invention refers to an absolutely dry component when the sizing agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
  • the total weight ratio of the urethane-modified epoxy resin (A) and the resin component (B) in the nonvolatile content of the sizing agent is preferably 50% by weight or more, more preferably 60 to 99.5% by weight, and 70 to 99% by weight. Is more preferable.
  • the sizing agent of the present invention preferably further contains polyoxyalkylene alkyl ether (C) which is an alkylene oxide adduct of a monohydric alcohol having 4 to 14 carbon atoms.
  • polyoxyalkylene alkyl ether (C) which is an alkylene oxide adduct of a monohydric alcohol having 4 to 14 carbon atoms.
  • the monohydric alcohol having 4 to 14 carbon atoms may be linear, branched or cyclic (alicyclic or araliphatic), and may be saturated or unsaturated.
  • Examples of the linear saturated alcohol include butyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, lauryl (dodecyl) alcohol, and tetradecyl alcohol.
  • Examples of the branched saturated alcohol include 2-ethylhexyl alcohol.
  • Examples of the cyclic alcohol include cyclohexyl alcohol and benzyl alcohol. Among these, from the viewpoint of uniform adhesion, linear or branched saturated alcohols having 6 to 12 carbon atoms are preferable, and hexyl alcohol and 2-ethylhexyl alcohol are more preferable.
  • the alkylene oxide is preferably an alkylene oxide having 2 to 4 carbon atoms. Specifically, ethylene oxide (hereinafter sometimes referred to as EO), propylene oxide (hereinafter also referred to as PO), 1,2-, 1,3-, 2,3- or 1,4-butylene oxide (hereinafter referred to as “PO”). BO)). Two or more alkylene oxides may be used. Among these, EO and / or PO are preferable from the viewpoint of uniform adhesion.
  • the addition method of alkylene oxide in the case of using 2 or more types includes random addition, block addition, and a combination thereof, but block addition and block addition after random addition are preferable.
  • the added mole number of alkylene oxide is preferably 1 to 12 moles, more preferably 1 to 10 moles, and further preferably 1 to 8 moles from the viewpoint of uniform adhesion.
  • the weight average molecular weight of the polyoxyalkylene alkyl ether (C) is preferably from 200 to 2000, more preferably from 250 to 1800, and even more preferably from 280 to 1500.
  • the weight ratio of the polyoxyalkylene alkyl ether (C) in the nonvolatile content of the sizing agent is preferably 0.5 to 10% by weight. It is more preferably ⁇ 8% by weight, further preferably 3-5% by weight.
  • the weight ratio of the polyoxyalkylene alkyl ether (C) exceeds 10% by weight, the sizing agent may bleed out on the reinforcing fiber and the adhesiveness may decrease.
  • the weight reduction rate at 300 ° C. when the nonvolatile content of the sizing agent is measured with a differential type differential thermal balance (TG-DTA) is preferably 25% by weight or less, and 20% by weight. The following is more preferable. If the weight reduction rate at 300 ° C. exceeds 25% by weight, adhesion of the matrix resin and the reinforcing fibers may be inhibited due to generation of pyrolysis gas of the sizing agent.
  • the sizing agent of the present invention may contain water from the viewpoints of safety to the human body during handling, prevention of disasters such as fire, and prevention of pollution of the natural environment.
  • An organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, or methyl ethyl ketone may be used as long as the effects of the present invention are not impaired.
  • the urethane-modified epoxy resin (A) is self-emulsified and / or emulsified and dispersed in water.
  • the average particle diameter of the urethane-modified epoxy resin (A) is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 0.01 to 1 ⁇ m, and still more preferably 0.01 to 0.5 ⁇ m.
  • the average particle size is more than 10 ⁇ m, not only the sizing agent can be uniformly adhered to the reinforcing fibers, but also the sizing agent itself may be separated in a few days, and the storage stability may be poor and impractical.
  • the resin component (B) is self-emulsified and / or emulsified and dispersed in water.
  • the average particle size of the resin component (B) is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 0.03 to 10 ⁇ m, further preferably 0.05 to 5 ⁇ m, and particularly preferably 0.1 to 1 ⁇ m.
  • the average particle size is more than 10 ⁇ m, not only the sizing agent can be uniformly adhered to the reinforcing fibers, but also the sizing agent itself may be separated in a few days, and the storage stability may be poor and impractical.
  • the average particle diameter as used in the field of this invention means the average value computed from the particle size distribution measured with the laser diffraction / scattering type particle size distribution measuring apparatus (LA-910 by Horiba).
  • the sizing agent of the present invention includes other components other than the urethane-modified epoxy resin (A), the resin component (B), and the polyoxyalkylene alkyl ether (C) described above as long as the effects of the present invention are not impaired. But you can.
  • other components include various surfactants (excluding polyoxyalkylene alkyl ether (C)), various smoothing agents, antioxidants, flame retardants, antibacterial agents, crystal nucleating agents, antifoaming agents, and the like. 1 type, or 2 or more types may be used in combination.
  • the surfactant contains a water-insoluble or hardly soluble resin in the urethane-modified epoxy resin (A) and the resin component (B) and other sizing agents, the aqueous emulsification is efficiently carried out by using it as an emulsifier. can do.
  • the surfactant is not particularly limited, and a known one can be appropriately selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Surfactant may use together 1 type (s) or 2 or more types.
  • Nonionic surfactants include, for example, alkylene oxide-added nonionic surfactants (higher alcohols, higher fatty acids, alkylphenols, styrenated phenols, benzylphenols, sorbitans, sorbitan esters, castor oil, hydrogenated castor oil, etc. And alkylene oxides such as oxides and propylene oxides (two or more types can be used together), polyalkylene glycols added with higher fatty acids, and ethylene oxide / propylene oxide copolymers.
  • the anionic surfactant include carboxylic acid (salt), sulfate ester salt of higher alcohol / higher alcohol ether, sulfonate salt, phosphate ester salt of higher alcohol / higher alcohol ether, and the like.
  • cationic surfactants include quaternary ammonium salt type cationic surfactants (such as lauryltrimethylammonium chloride and oleylmethylethylammonium etosulphate), amine salt type cationic surfactants (polyoxyethylene laurylamine), and the like. Lactate etc.).
  • amphoteric surfactants include amino acid type amphoteric surfactants (such as sodium laurylaminopropionate), betaine type amphoteric surfactants (such as stearyl dimethyl betaine, lauryl dihydroxyethyl betaine), and the like.
  • the sizing agent of the present invention can exhibit excellent film flexibility and uniform adhesion after limiting the use of a surfactant. If the surfactant is contained in a large amount, the heat resistance of the sizing agent is lowered, which is not preferable. From such a viewpoint, the proportion of the surfactant in the nonvolatile content of the sizing agent is preferably 20% by weight or less, more preferably 10% by weight or less, further preferably 5% by weight or less, and particularly preferably 1% by weight or less.
  • the concentration of the nonvolatile content of the sizing agent of the present invention is not particularly limited, and is appropriately selected in consideration of the stability as a water emulsion, the viscosity that is easy to handle as a product, and the like.
  • the weight ratio of the non-volatile content in the entire sizing agent is preferably 10 to 100% by weight, more preferably 15 to 100% by weight, and particularly preferably 20 to 100% by weight.
  • the total weight ratio of water and non-volatile components in the entire sizing agent is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 99% by weight or more, and particularly preferably 100% by weight.
  • the water emulsion does not contain or contains a solvent other than water, such as an organic solvent, from the viewpoint of preventing thickening and solidification of the water emulsion over time. Even so, it is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less based on the entire sizing agent.
  • the method for producing the sizing agent of the present invention as a water emulsion is not particularly limited, and a known method can be employed.
  • each component which comprises a sizing agent each is made into a water emulsion, the method of mixing them, The method of throwing each component which comprises a sizing agent into warm water under stirring, and emulsifying and dispersing , A method of mixing an emulsified dispersion in which each component constituting the sizing agent is pre-emulsified and dispersed, each component constituting the sizing agent is mixed, and after heating the resulting mixture above the softening point, a homogenizer, a homomixer, Examples of the method include phase inversion emulsification by gradually adding water while applying a mechanical shearing force using a ball mill or the like.
  • the reinforcing fiber strand of the present invention is obtained by adhering the above-mentioned reinforcing fiber sizing agent to the raw material reinforcing fiber strand, and is a reinforcing fiber for reinforcing the matrix resin.
  • the reinforcing fiber strand of the present invention is excellent in adhesiveness with the matrix resin. Furthermore, because the sizing agent for reinforcing fibers with excellent heat resistance is treated, thermal decomposition of the sizing agent can be suppressed during high-temperature treatment with the matrix resin, and adhesion inhibition with the matrix resin due to thermal decomposition can be suppressed. Can be suppressed.
  • the matrix resin is preferably a thermoplastic matrix resin because the effect of improving the adhesion by the sizing agent of the present invention is higher.
  • the adhering amount of the non-volatile component of the sizing agent to the raw material reinforcing fiber strand can be appropriately selected and may be set to a necessary amount for the reinforcing fiber strand to have a desired function. It is preferably 1 to 20% by weight.
  • the adhesion amount is more preferably 0.1 to 10% by weight, and further preferably 0.5 to 5% by weight with respect to the raw material reinforcing fiber strand.
  • the strand in the form of chopped fiber is more preferably 0.5 to 20% by weight, and further preferably 1 to 10% by weight.
  • the adhesion amount of the sizing agent is small, the effects of the present invention relating to heat resistance, resin impregnation property, and adhesiveness are difficult to obtain, and the binding property of the reinforcing fiber strands is insufficient, and the handling property may be deteriorated.
  • the amount of the sizing agent attached is too large, the reinforcing fiber strands become too stiff and the handling property becomes worse, and the resin impregnation property becomes worse at the time of composite molding.
  • a method for producing a reinforcing fiber strand includes a treatment liquid containing the above-described sizing agent, having a nonvolatile weight ratio of 0.5 to 10% by weight, and a total weight ratio of water and nonvolatile components of 90% by weight or more. And a preparation step of preparing, and an attachment step of attaching the treatment liquid to the raw material reinforcing fiber strand so that the amount of non-volatile matter attached to the raw material reinforcing fiber strand is 0.1 to 20% by weight.
  • the weight ratio of the nonvolatile content in the treatment liquid is more preferably 0.5 to 10% by weight, and further preferably 1 to 5% by weight.
  • the total weight ratio of water and nonvolatile components is more preferably 95% by weight or more, further preferably 99% by weight or more, and particularly preferably 100% by weight.
  • the preferable adhering amount of the nonvolatile content is as described in the previous paragraph.
  • the method for adhering the sizing agent to the raw material reinforcing fiber strand is not particularly limited as long as the sizing agent is attached to the raw material reinforcing fiber strand by a kiss roller method, roller dipping method, spray method or other known methods. Good. Among these methods, the roller dipping method is preferable because the sizing agent can be uniformly attached to the raw material reinforcing fiber strand.
  • the drying method of the obtained deposit For example, it can heat-dry with a heating roller, a hot air, a hot plate, etc.
  • thermosetting resins such as epoxy resins, unsaturated polyester resins, vinyl ester resins, phenol resins, etc.
  • thermoplastic resin such as a polyolefin resin, a polyester resin, a nylon resin, or an acrylic resin may be attached to the raw material reinforcing fiber strand.
  • the reinforcing fiber strand of the present invention is used as a reinforcing fiber of a composite material using various resins as a matrix resin, and the form to be used may be a long fiber form or a chopped fiber form.
  • raw material reinforcing fiber strand to which the sizing agent of the present invention can be applied various inorganic fibers such as carbon fiber, glass fiber, ceramic fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber,
  • the strand include various organic fibers such as polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber, and polyketone fiber.
  • raw material reinforcing fiber strand carbon fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, At least one strand selected from PBO fiber, polyphenylene sulfide fiber and polyketone fiber is preferable, and carbon fiber strand is more preferable.
  • the reinforcing fiber strand to which the sizing agent for reinforcing fibers of the present invention is attached has excellent bundling properties.
  • the adhesiveness to the matrix resin is excellent and the flexibility is excellent.
  • the bending strength of the reinforcing fiber strand can be used.
  • the reinforcing fiber strand of the present invention can have a bending strength of 60 g or less while having excellent bundling properties and adhesiveness with a matrix resin. When the strength is more than 60 g, the strand at the time of sizing treatment becomes too hard, and the handleability may be lowered in a later step.
  • the strength is preferably 20 to 57 g, more preferably 20 to 55 g, still more preferably 20 to 50 g.
  • the bending strength is a value obtained by measuring a reinforcing fiber strand (length: about 50 cm) with a texture tester (HANDLE-O-METERHOM-2, manufactured by Daiei Kagaku Seisakusho Co., Ltd., slit width 5 mm).
  • the fiber-reinforced composite material of the present invention includes a matrix resin and the above-described reinforcing fiber strand. Reinforcing fiber strands are treated with the sizing agent of the present invention, and the sizing agent is uniformly attached to the fibers, so that the affinity with the reinforcing fiber strands and the matrix resin is good, and a fiber-reinforced composite material having excellent adhesion is obtained. Furthermore, thermal decomposition of the sizing agent during high temperature treatment can be suppressed, and adhesion inhibition with the matrix resin due to thermal decomposition can be suppressed.
  • the matrix resin refers to a matrix resin made of a thermosetting resin or a thermoplastic resin, and may include one or more kinds.
  • a thermosetting resin An epoxy resin, a phenol resin, unsaturated polyester resin, a vinyl ester resin, cyanate ester resin, a polyimide resin etc. are mentioned.
  • the thermoplastic matrix resin is not particularly limited, and is a polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethyl methacrylate resin, polyphenylene sulfide resin, polyetherimide resin, Examples include polyether ketone resins.
  • thermoplastic matrix resin is preferable and a polyamide-based resin is more preferable because the effect of improving the adhesiveness by the sizing agent of the present invention is higher.
  • the polyamide-based resin is a polymer compound having a plurality of amide groups in the main chain, which is synthesized from dicarboxylic acid and diamine, ⁇ -amino acid, lactam or derivatives thereof, and is a homopolymer or copolymer (copolymer). Merging) and the like.
  • transduced the substituent into the principal chain or the terminal may be sufficient.
  • These matrix resins may be partially or wholly modified for the purpose of further improving the adhesiveness with the reinforcing fiber strands.
  • the method for producing the fiber reinforced composite material is not particularly limited, and known methods such as compound injection molding using chopped fibers and long fiber pellets, press molding using UD sheets and woven sheets, and other filament winding molding can be employed.
  • the thermoplastic matrix resin has a high melting point such as general-purpose engineer plastic or super engineer plastic, knead with the reinforcing fiber at a temperature of 200 ° C to 400 ° C above the melting point.
  • Manufacture fiber reinforced composite materials is not particularly limited, and may be appropriately selected depending on the type of fiber, the form, the type of matrix resin, and the like. 70% by weight is preferable, and 20 to 60% by weight is more preferable.
  • the composite material interface property evaluation apparatus HM410 manufactured by Toei Sangyo Co., Ltd. was used, and the adhesiveness was evaluated by the microdroplet method. Carbon fiber filaments are taken out from the carbon fiber strands produced in the examples and comparative examples, and set in a composite material interface property evaluation apparatus. A drop of the matrix resin melted on the apparatus was formed on the carbon fiber filament and sufficiently cooled at room temperature to obtain a sample for measurement. The measurement sample was set in the apparatus again, the drop was sandwiched between apparatus blades, the carbon fiber filament was run on the apparatus at a speed of 0.06 mm / min, and the maximum pulling load F when the drop was pulled out from the carbon fiber filament was measured. .
  • the matrix resin is polyamide resin T-663 (manufactured by Toyobo Co., Ltd.) in the examples and comparative examples of Tables 2 to 4, and polypropylene resin J-900GP (manufactured by Idemitsu Petrochemical Co., Ltd.) in the examples and comparative examples of Tables 5 and 6.
  • the interfacial shear strength ⁇ was calculated by the following formula, and the adhesion between the carbon fiber filament and the matrix resin was evaluated.
  • Interfacial shear strength ⁇ (unit: MPa) F / ⁇ dl (F: Maximum pulling load d: Carbon fiber filament diameter l: Particle diameter in the pulling direction of the drop)
  • the sizing agent was attached to the sizing agent-untreated carbon fiber strand (fineness: 800 tex, number of filaments: 12,000) so that the non-volatile content of the sizing agent was 1.0% by weight.
  • the flexibility of the obtained sizing agent-attached carbon fiber strand was measured with a texture tester (HANDLE-O-METERHOM-2 manufactured by Daiei Scientific Instruments Co., Ltd., slit width 5 mm). In addition, the measurement was performed 10 times, and it was judged that the carbon fiber strand was more flexible as the average value was smaller.
  • Weight reduction rate (%) ((W 1 ⁇ W 2 ) / W 1 ) ⁇ 100
  • the sizing agent was attached to the sizing agent-untreated carbon fiber strand (fineness: 800 tex, number of filaments: 12,000) so that the non-volatile content of the sizing agent was 1.0% by weight.
  • TM-type friction conjugation force tester TM-200 manufactured by Daiei Kagaku Seisakusho Co., Ltd.
  • the fluffing was carried out (reciprocating speed 300 times / min), and the fluffing state of the carbon fiber strand was visually determined according to the following criteria.
  • epoxy resin (A1), organic polyisocyanate compound (A2), and polyoxyalkylene monoalkyl ether (A3) in Table 1 are as follows.
  • JER1001 is an organic group represented by the general formula (4) in the general formula (3), R 3 and R 4 are methyl groups, p is an average value of 5 and ranges from 1 to 10 Including an epoxy resin having a distribution.
  • JER4004P is an organic group represented by the general formula (4) in the general formula (3), R 3 and R 4 are hydrogen atoms, p is an average value of 5 and ranges from 1 to 10 Including an epoxy resin having a distribution.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • A3-1 In general formula (2), m is 76, R 2 is 2-ethylhexyl group, AO consists EO and PO, and (AO) m Polyoxyalkylene monoalkyl ether in which the ratio of EO to the whole is 80 mol%.
  • A3-2 In the general formula (2), m is 13, R 2 is a methyl group, AO is EO, and polyoxyethylene monoalkyl ether.
  • A3-3 A polyoxyalkylene monoester represented by the general formula (2), wherein m is 76, R 2 is a stearyl group, AO is composed of EO and PO, and (AO) the proportion of EO in the entire m is 80 mol%.
  • PEG 3000 Polyoxyethylene glycol having a weight average molecular weight of 3000.
  • the reaction mixture was cooled to 40 ° C., 11.5 parts of dimethylethanolamine was added and neutralized, and 1200 parts of water was added to form a water emulsion.
  • the water emulsion thus obtained was treated at 65 ° C. under reduced pressure to distill off methyl ethyl ketone, and the water content was adjusted to obtain an aqueous emulsion B-2 of an aromatic polyester urethane resin having a nonvolatile content of 20% by weight.
  • Examples 1 to 34 Comparative Examples 1 to 22
  • the non-volatile compositions shown in Tables 2 to 6 were used.
  • the mixture was stirred and diluted with water to prepare a sizing agent having a nonvolatile content concentration of 10% by weight.
  • surface shows the weight ratio of each component (in the case of an aqueous dispersion, the non volatile matter) to the non volatile matter of a sizing agent.
  • the numerical values of A-1 to A-8 in the table indicate the weight ratio of the non-volatile content of the urethane-modified epoxy resin water emulsion A-1 to A-8 in the non-volatile content of the sizing agent.
  • focusing property, bending strength, and weight reduction rate were evaluated by the above-described methods. These results are shown in Tables 2-6.
  • the sizing agent was dried with hot air at 105 ° C. for 15 minutes.
  • a sizing agent-treated carbon fiber strand of 5% by weight with respect to the carbon fiber strand was obtained.
  • the matrix resin adhesiveness was evaluated by the above-mentioned method. These results are shown in Tables 2-6.
  • the examples and comparative examples in Tables 2 to 4 are examples in which a polyamide resin is used as the matrix resin in the adhesive evaluation, and the examples and comparative examples in Tables 5 and 6 are polypropylenes in the matrix resin in the adhesive evaluation. This is the case where resin is used.
  • C-1 Polyoxyethylene polyoxypropylene 2-ethylhexyl ether having a weight average molecular weight of 290 and a ratio of EO to the whole polyoxyalkylene group of 33 mol%.
  • C-2 polyoxyethylene 2-ethylhexyl ether having a weight average molecular weight of 465.
  • D-1 A polyoxyethylene polyoxypropylene block polymer having a weight average molecular weight of 3,500 and a ratio of EO to the whole polyoxyalkylene group of 80 mol%.
  • Examples 1-34 are excellent in convergence. Moreover, the adhesiveness and the softness
  • the fiber reinforced composite material in which the matrix resin is reinforced with the reinforcing fiber is used for automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like.
  • the reinforcing fiber include various inorganic fibers such as carbon fiber, glass fiber, and ceramic fiber, and various organic fibers such as aramid fiber, polyamide fiber, and polyethylene fiber.
  • the sizing agent of this invention can be used conveniently with respect to the reinforced fiber for reinforcing a matrix resin.

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  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Le but de l'invention est de proposer un agent d'encollage pour fibre de renforcement, qui peut améliorer une fibre de renforcement et est utilisé pour renforcer une résine de matrice en lui conférant une excellente adhésivité et une flexibilité; un brin de fibre de renforcement doté de l'agent d'encollage; et un matériau composite renforcé par des fibres. L'agent d'encollage pour fibre de renforcement selon l'invention contient une résine époxy modifiée à l'uréthane (A) et au moins un type de composant de résine (B) choisi parmi des résines de polyester aromatique, des résines d'uréthane de polyester aromatique, des résines de polyamide et des résines de polyoléfine modifiée.
PCT/JP2014/063643 2013-06-06 2014-05-23 Agent d'encollage pour fibre de renforcement et utilisations associées WO2014196372A1 (fr)

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JP2015521382A JP6381527B2 (ja) 2013-06-06 2014-05-23 強化繊維用サイジング剤及びその用途

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JP2013119750 2013-06-06
JP2013-119750 2013-06-06

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WO2014196372A1 true WO2014196372A1 (fr) 2014-12-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016160567A (ja) * 2015-03-05 2016-09-05 Dic株式会社 繊維集束剤ならびに集束されたガラス繊維及び炭素繊維
JP2016196711A (ja) * 2015-04-03 2016-11-24 Dic株式会社 繊維集束剤ならびに集束されたガラス繊維及び炭素繊維
JP2017014628A (ja) * 2015-06-26 2017-01-19 Dic株式会社 炭素繊維集束剤及び炭素繊維
WO2018139158A1 (fr) * 2017-01-25 2018-08-02 松本油脂製薬株式会社 Agent de collage pour fibres de renforcement et son utilisation
CN111094449A (zh) * 2017-09-15 2020-05-01 住友精化株式会社 环氧树脂组合物

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JPS63256771A (ja) * 1987-03-06 1988-10-24 新日本製鐵株式会社 炭素繊維のサイジング方法
JP2004190201A (ja) * 2002-12-13 2004-07-08 Mitsubishi Rayon Co Ltd 高導電性を発現する繊維強化樹脂用の炭素繊維束及びチョップド炭素繊維束並びに炭素繊維強化樹脂組成物
JP2006188782A (ja) * 2005-01-05 2006-07-20 Toray Ind Inc 炭素繊維束およびその製造方法
JP2008002046A (ja) * 2006-06-23 2008-01-10 Matsumoto Yushi Seiyaku Co Ltd サイジング剤およびこれを用いた炭素繊維ストランドの製造方法
JP2008274520A (ja) * 2007-04-04 2008-11-13 Toray Ind Inc 炭素繊維用サイジング剤および炭素繊維束
JP2011231414A (ja) * 2010-04-23 2011-11-17 Matsumoto Yushi Seiyaku Co Ltd 強化繊維用サイジング剤、合成繊維ストランドおよび繊維強化複合材料
WO2012165055A1 (fr) * 2011-05-27 2012-12-06 Dic株式会社 Composition de résine époxy, agent de liaison de fibres, matériau de fibres, et matériau de moulage

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63256771A (ja) * 1987-03-06 1988-10-24 新日本製鐵株式会社 炭素繊維のサイジング方法
JP2004190201A (ja) * 2002-12-13 2004-07-08 Mitsubishi Rayon Co Ltd 高導電性を発現する繊維強化樹脂用の炭素繊維束及びチョップド炭素繊維束並びに炭素繊維強化樹脂組成物
JP2006188782A (ja) * 2005-01-05 2006-07-20 Toray Ind Inc 炭素繊維束およびその製造方法
JP2008002046A (ja) * 2006-06-23 2008-01-10 Matsumoto Yushi Seiyaku Co Ltd サイジング剤およびこれを用いた炭素繊維ストランドの製造方法
JP2008274520A (ja) * 2007-04-04 2008-11-13 Toray Ind Inc 炭素繊維用サイジング剤および炭素繊維束
JP2011231414A (ja) * 2010-04-23 2011-11-17 Matsumoto Yushi Seiyaku Co Ltd 強化繊維用サイジング剤、合成繊維ストランドおよび繊維強化複合材料
WO2012165055A1 (fr) * 2011-05-27 2012-12-06 Dic株式会社 Composition de résine époxy, agent de liaison de fibres, matériau de fibres, et matériau de moulage

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016160567A (ja) * 2015-03-05 2016-09-05 Dic株式会社 繊維集束剤ならびに集束されたガラス繊維及び炭素繊維
JP2016196711A (ja) * 2015-04-03 2016-11-24 Dic株式会社 繊維集束剤ならびに集束されたガラス繊維及び炭素繊維
JP2017014628A (ja) * 2015-06-26 2017-01-19 Dic株式会社 炭素繊維集束剤及び炭素繊維
WO2018139158A1 (fr) * 2017-01-25 2018-08-02 松本油脂製薬株式会社 Agent de collage pour fibres de renforcement et son utilisation
JPWO2018139158A1 (ja) * 2017-01-25 2019-11-07 松本油脂製薬株式会社 強化繊維用サイジング剤及びその用途
CN111094449A (zh) * 2017-09-15 2020-05-01 住友精化株式会社 环氧树脂组合物
EP3683269A4 (fr) * 2017-09-15 2021-06-09 Sumitomo Seika Chemicals Co., Ltd. Composition de résine époxyde

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