Fiber sizing agent compositions, fiber bundles, textile products, and composite materials

Abstract

The present invention aims to provide a fiber bundling agent composition that exhibits excellent bundling and unbundling properties, produces fiber bundles with minimal fluffing, provides high adhesion between the fibers and the matrix resin, and has excellent storage stability. [Solution] A fiber sizing agent composition comprising a compound having a urethane group (A), a polyester resin (B), a bisphenol A type epoxy resin (C), and a nonionic surfactant (D), wherein the number average molecular weight of the compound having a urethane group (A) is 1000 to 10000, the compound having a urethane group (A) is water-insoluble, and the polyester resin (B) is composed of a diol component (b1) and a dicarboxylic acid component (b2), and 5 to 100% by weight of the diol component (b1) is a bisphenol A alkylene oxide adduct (b11).

Description

Technical Field

[0001] The present invention relates to a fiber sizing agent composition, a fiber bundle, a fiber product, and a composite material including a fiber bundle and / or a fiber product and a matrix resin.

Background Art

[0002] Composite materials of matrix resins such as saturated polyester resins, phenolic resins, epoxy resins, and polypropylene resins and various fibers are widely used in fields such as sports equipment, leisure goods, and aircraft. As the fibers used in these composite materials, fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slag fibers are used. In the processing step of using these fibers as the above composite materials, a sizing agent is usually applied to prevent fiber fluffing and yarn breakage. In the manufacturing process of the composite material, before combining the fiber bundle with the matrix resin, a process of widening the width of the fiber bundle (fiber opening process) is performed. When the fiber opening process is performed, the wider the width of the fiber bundle (the better the fiber opening property), the better the impregnation property of the matrix resin, and thus it is suitable for producing a thin and high-quality prepreg. However, the fiber opening property and the bundling property are inherently contradictory, and it is difficult to achieve both at a high level. As the sizing agent, a solvent solution of a sizing agent composed of polyglycidyl ethers (for example, Patent Document 1), an aqueous emulsion obtained by emulsifying bisphenol type polyalkylene ether epoxy compounds with a small amount of an emulsifier (for example, Patent Document 2), and an aqueous emulsion composed of an epoxy resin and a urethane resin having an oxyalkylene unit (for example, Patent Document 3) are known.

[0003] However, when using solvent solutions as in Patent Document 1, there are problems with low industrial handling and safety during sizing. Furthermore, the sizing agents proposed in Patent Documents 2 and 3 have problems with low emulsification stability of the aqueous emulsion, making it impossible to create stable and uniform fiber bundles, resulting in insufficient fiber bundle gathering, excessive fluffing, and consequently, insufficient composite material strength. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 50-59589 [Patent Document 2] Japanese Patent Application Publication No. 61-28074 [Patent Document 3] Japanese Patent Application Publication No. 5-132863 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a fiber bundling agent composition that exhibits excellent bundling and unbundling properties, produces fiber bundles with minimal fluffing, provides high adhesion between the fibers and the matrix resin, and has excellent storage stability. [Means for solving the problem]

[0006] The inventors of this invention arrived at this present invention after diligently studying to solve these problems. In other words, the present invention is a fiber sizing agent composition comprising a compound having a urethane group (A), a polyester resin (B), a bisphenol A type epoxy resin (C), and a nonionic surfactant (D), wherein the number average molecular weight of the compound having a urethane group (A) is 1000 to 10000, the compound having a urethane group (A) is water-insoluble, the polyester resin (B) is composed of a diol component (b1) and a dicarboxylic acid component (b2), 5 to 100 mol% of the diol component (b1) is a bisphenol A alkylene oxide adduct (b11), the weight ratio of (B) to the total weight of (B) and (C) is 30 to 70% by weight, the weight ratio of (B) to the total weight of (B) and (D) is 50 to 90% by weight, and the weight ratio of (C) to the total weight of (C) and (D) is 50 to 90% by weight. [Effects of the Invention]

[0007] The fiber sizing agent composition of the present invention exhibits excellent sizing and fiber-opening properties, can create fiber bundles with minimal fluffing, provides adhesion between fibers and matrix resin, and offers excellent storage stability. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic side view showing the evaluation apparatus and carbon fiber bundle arrangement used in the evaluation tests for fiber opening properties and fluffiness.

[0009] The present invention will be described in detail below. The present invention relates to a fiber sizing agent composition comprising a compound having a urethane group (A), a polyester resin (B), a bisphenol A type epoxy resin (C), and a nonionic surfactant (D), wherein the number average molecular weight of the compound having a urethane group (A) is 1000 to 10000, the compound having a urethane group (A) is water-insoluble, the polyester resin (B) is composed of a diol component (b1) and a dicarboxylic acid component (b2), 5 to 100 mol% of the diol component (b1) is an alkylene oxide adduct of bisphenol A (b11), the weight ratio of (B) to the total weight of (B) and (C) is 30 to 70% by weight, the weight ratio of (B) to the total weight of (B) and (D) is 50 to 90% by weight, and the weight ratio of (C) to the total weight of (C) and (D) is 50 to 90% by weight.

[0010] Compound (A), which has a urethane group, is a reaction product of diisocyanate (a1) and polyol (a2). Examples of diisocyanates (a1) include aliphatic diisocyanates, alicyclic diisocyanates, aromatic aliphatic diisocyanates, and aromatic diisocyanates.

[0011] Examples of the aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and dodecamethylene diisocyanate.

[0012] Examples of the alicyclic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

[0013] Examples of the aforementioned aromatic aliphatic diisocyanates include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate, and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0014] Examples of the aromatic diisocyanates include 1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylenediisocyanate (TDI), and 4,4'- or 2,4'-diphenylmethanediisocyanate (MDI).

[0015] Of these diisocyanates (a1), aromatic aliphatic diisocyanates and aromatic diisocyanates are preferred from the viewpoint of fiber bundle aggregation (fluffing) and adhesion between fibers and matrix resin, more preferably aromatic diisocyanates, and particularly preferably TDI and MDI.

[0016] Examples of polyols (a2) include polyether diols (a21), polyester diols (a22), polycaprolactone diols (a23), polycarbonate diols (a24), diallyl alkanates (a25), and aliphatic dihydric alcohols having 2 to 12 carbon atoms (a26).

[0017] Examples of polyetherdiols (a21) include aliphatic polyetherdiols and aromatic polyetherdiols. Examples of the aliphatic polyether diol include polyoxyethylene polyol [polyethylene glycol (hereinafter sometimes abbreviated as PEG)], polyoxypropylene polyol [polypropylene glycol], polyoxyethylene / propylene polyol, and polytetramethylene ether glycol (hereinafter sometimes abbreviated as PTMG).

[0018] Examples of the aromatic polyether diol include polyols having a bisphenol skeleton such as ethylene oxide (hereinafter sometimes abbreviated as EO) adducts of bisphenol A [EO2 molar adduct of bisphenol A, EO4 molar adduct of bisphenol A, EO6 molar adduct of bisphenol A, EO8 molar adduct of bisphenol A, EO10 molar adduct of bisphenol A, EO20 molar adduct of bisphenol A, etc.] and propylene oxide (hereinafter sometimes abbreviated as PO) adducts of bisphenol A [PO2 molar adduct of bisphenol A, PO3 molar adduct of bisphenol A, PO5 molar adduct of bisphenol A, PO10 molar adduct of bisphenol A, etc.], and EO or PO adducts of resorcinol, etc.

[0019] The polyester diol (a22) may be a commercially available product. Specifically, “PolyLite OD-X-2523”, “PolyLite OD-X-2547”, “PolyLite OD-X-2420”, “PolyLite OD-X-2692”, “PolyLite OD-X-2108” manufactured by DIC Corporation, “ETERNACOLL 3000” manufactured by Ube Industries, Ltd., “Kuraray Polyol P-1010”, “Kuraray Polyol P-2010”, “Kuraray Polyol P-3010”, “Kuraray Polyol P-4010”, “Kuraray Polyol P-5010”, “Kuraray Polyol P-6010” manufactured by Kuraray Co., Ltd., etc. can be mentioned.

[0020] The polycaprolactone diol (a23) is a polyaddition product of lactone to a low molecular weight dihydric alcohol. Examples of the lactone include lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone). As the low molecular weight dihydric alcohol, a dihydric aliphatic dihydric alcohol having a number average molecular weight (hereinafter sometimes abbreviated as Mn) of less than 300 and a low molar adduct of alkylene oxide (hereinafter sometimes abbreviated as AO) of a dihydric phenol having an Mn of less than 300 can be used.

[0021] The polycaprolactone diol (a23) can be a commercially available product. Specifically, examples include "Praxel PCL-205U" manufactured by Daicel Corporation.

[0022] Examples of polycarbonate diols (a24) include polycarbonate diols produced by condensing a low molecular weight dihydric alcohol with a low molecular weight carbonate compound (for example, a dialkyl carbonate with an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group with 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group with 6 to 9 carbon atoms) while undergoing a dealcoholization reaction. Two or more types of low molecular weight dihydric alcohols and alkylene carbonates may be used in combination. The low molecular weight dihydric alcohol may contain a trivalent or higher alcohol.

[0023] Specific examples of polycarbonate diols (a24) include aliphatic polycarbonates such as polyhexamethylene carbonate diol, polypentamethylene carbonate diol, 3-methyl-5-pentane-carbonate diol, polytetramethylene carbonate diol, and poly(tetramethylene / hexamethylene) carbonate diol (for example, a diol obtained by condensing 1,4-butanediol and 1,6-hexanediol with a dialkyl carbonate while de-alcoholizing). Aromatic polycarbonates include poly1,4-xylylene carbonate diol, bisphenol A type polycarbonate diol, and bisphenol F type polycarbonate diol.

[0024] As for polycarbonate diol (a24), commercially available products may be used. Specifically, "Kuraray Polyol C-590", "Kuraray Polyol C-1090", "Kuraray Polyol C-2050", "Kuraray Polyol C-2090", and "Kuraray Polyol C-3090" from Kuraray Co., Ltd., "ETERNACOLL UP-50", "ETERNACOLL UP-100", "ETERNACOLL UP-200", "ETERNACOLL PH-50", "ETERNACOLL PH-100", "ETERNACOLL PH-200", and "ETERNACOLL PH-300" from Ube Industries, Ltd., and "BENEBiOL NL1005B", "BENEBiOL NL2005B", "BENEBiOL NL1030B", and "BENEBiOL" from Mitsubishi Chemical Corporation. Examples include "NL2030B," and Asahi Kasei Corporation's "Duranole T5650E," "Duranole T5650J," "Duranole T5651," and "Duranole T5652."

[0025] Examples of dialkylol alkanoic acid (a25) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, and 2,2-dimethyloloctanoic acid.

[0026] Examples of aliphatic dihydric alcohols (a26) having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol.

[0027] The manganese content of polyol (a2) can be measured by gel permeation chromatography (GPC). The measurement conditions for the GPC method are, for example, those described in the examples.

[0028] Among the polyols (a2), polyetherdiol (a21) is preferred from the viewpoint of emulsification stability. Furthermore, aromatic polyetherdiols are preferred from the viewpoint of fiber bundle gathering, fluffing, and adhesion between fibers and matrix resin, and aliphatic polyetherdiols are preferred from the viewpoint of emulsification stability.

[0029] The polymerization ratio of (a21) in polyol (a2) is preferably 40 to 100% by weight, and more preferably 50 to 100% by weight, based on the weight of (a2), from the viewpoint of emulsification stability.

[0030] Compound (A) having a urethane group can be obtained by reacting a diisocyanate (a1) with a polyol (a2). The method of preparation is not particularly limited, but one example is a method in which the diisocyanate (a1) and polyol (a2) are mixed and reacted in a single shot in a batch reaction vessel with a stirrer, either in the presence or absence of an organic solvent. The equivalent ratio of diisocyanate (a1) to polyol (a2) is not particularly limited, but it is preferable that the equivalent amount of isocyanate groups does not exceed the equivalent amount. If the equivalent amount of isocyanate groups exceeds the equivalent amount, it is preferable to use a reaction stopper such as monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, etc.). The equivalent ratio of diisocyanate (a1) to polyol (a2) is preferably selected to be in the range of 5:95 to 70:30, more preferably in the range of 10:90 to 60:40, and most preferably in the range of 10:90 to 55:45.

[0031] Compound (A) having a urethane group preferably has an aromatic skeleton. Having an aromatic component provides excellent emulsification stability. By using an aromatic diisocyanate (a1) and / or an aromatic polyol (a2), (A) can have an aromatic skeleton. Examples of the aromatic skeletons include naphthalene skeletons, fluorene skeletons, phenyl skeletons, biphenyl skeletons, anthracene skeletons, pyrene skeletons, xanthene skeletons, adamantane skeletons, and bisphenol A type skeletons.

[0032] The Mn value of compound (A) having a urethane group is 1,000 to 10,000, from the viewpoint of fuzziness (fluffing) and adhesion between the fibers and the matrix resin. The manganese content of compound (A) having a urethane group can be measured by gel permeation chromatography (GPC). The measurement conditions for the GPC method are, for example, those described in the examples.

[0033] The urethane group concentration of compound (A) having urethane groups is preferably 0.1 to 20.0 mmol / g, more preferably 0.5 to 5.0 mmol / g, and most preferably 1.0 to 4.0 mmol / g, based on the weight of (A), from the viewpoint of fuzziness, fluffiness, and adhesion between the fibers and the matrix resin.

[0034] Compound (A), which has a urethane group, is water-insoluble. Compound (A), which contains a urethane group, has the effect of suppressing pilling because it is water-insoluble. In this invention, "water-insoluble" means that the solubility in water at 25°C is 1 mg or less per 100 g of water.

[0035] The polyester resin (B) is composed of a diol component (b1) and a dicarboxylic acid component (b2). The diol component (b1) contains a bisphenol A AO adduct (b11) from the viewpoint of reducing clumping and fluffing. The AO adduct (b11) of bisphenol A includes at least one selected from the group consisting of EO, PO, 1,2-butylene oxide, and 1,4-butylene oxide (hereinafter sometimes abbreviated as BO), and two or more may be added. From the viewpoint of focusing properties, at least one selected from the group consisting of EO and PO is preferred as the AO, and EO is more preferred. The number of moles of AO added is more preferably 1 to 200, even more preferably 1 to 150, and most preferably 1 to 90, from the viewpoint of reducing fluffiness.

[0036] In addition to (b11), the diol component (b1) may also be an aliphatic alkanediol and / or an AO adduct of an aliphatic alkanediol.

[0037] Examples of the aliphatic alkanediols include ethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, hexadecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.

[0038] Examples of AO adducts of the aliphatic alkanediol include compounds obtained by adding a carbon atom having 2 to 4 carbon atoms to the diol. Examples of carbon atom having 2 to 4 carbon atoms include EO, PO, and BO. Two or more of these AOs may be used in combination. The number of moles of AO added per molecule of aliphatic alkanediol is preferably 1 to 120 moles.

[0039] From the viewpoint of reducing clumping and fluffing, the alkylene oxide adduct of bisphenol A (b11) is preferably present in an amount of 5 to 100% by weight, and more preferably 35 to 100% by weight, relative to the diol component (b1).

[0040] Examples of dicarboxylic acid components (b2) include aliphatic dicarboxylic acids (b21) and aromatic dicarboxylic acids (b22).

[0041] Examples of aliphatic dicarboxylic acids (b21) include chain-type saturated dicarboxylic acids, chain-type unsaturated dicarboxylic acids, alicyclic dicarboxylic acids, and dimer acids.

[0042] Examples of the aforementioned chain-type saturated dicarboxylic acids include linear or branched chain-type saturated dicarboxylic acids having 2 to 22 carbon atoms (oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, ethylsuccinic acid, dimethylmalonic acid, α-methylglutaric acid, β-methylglutaric acid, 2,4-diethylglutaric acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosanedicarboxylic acid, decylsuccinic acid, dodecylsuccinic acid, and octadecylsuccinic acid, etc.).

[0043] Examples of the aforementioned chain-type unsaturated dicarboxylic acids include linear or branched chain-type unsaturated dicarboxylic acids having 4 to 22 carbon atoms (such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid, and octadecenylsuccinic acid).

[0044] Examples of the alicyclic dicarboxylic acid include alicyclic dicarboxylic acids having 7 to 14 carbon atoms (such as 1,3- or 1,2-cyclopentanedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanediacetic acid, and dicyclohexyl-4,4'-dicarboxylic acid).

[0045] Examples of the dimer acid include dimers of chain-type unsaturated carboxylic acids having 8 to 24 carbon atoms (such as oleic acid, linoleic acid, and linolenic acid).

[0046] Examples of aromatic dicarboxylic acids (b22) include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'- and 4,4'-dicarboxylic acids, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate, and potassium 5-sulfoisophthalate.

[0047] The dicarboxylic acid component (b2) may be used alone or in combination of two or more types. From the viewpoint of focusing properties, it is preferable to use an aromatic dicarboxylic acid (b22) as the dicarboxylic acid component (b2).

[0048] One method for producing polyester resin (B) is to charge a diol component (b1) and a dicarboxylic acid component (b2), and then remove the water while stirring at a reaction temperature of 100 to 250°C and a pressure of -0.1 to 1.2 MPa. In the method for producing polyester resin (B), it is preferable to add a catalyst in an amount of 0.05 to 0.5% by weight based on the weight of polyester resin (B). Examples of catalysts include p-toluenesulfonic acid, dibutyltin oxide, tetraisopropoxytitanate, and potassium titanate oxalate. From the viewpoint of reactivity and environmental impact, tetraisopropoxytitanate and potassium titanate oxalate are preferred, and potassium titanate oxalate is even more preferred.

[0049] The Mn content of polyester resin (B) is preferably 1000 to 10000, from the viewpoint of suppressing fluffing of the fiber bundles.

[0050] Bisphenol A type epoxy resin (C) is an epoxy resin formed by the condensation of diglycidyl ether of bisphenol A and an epihalohydrin (e.g., epichlorohydrin). Examples of commercially available bisphenol A type epoxy resins include jER834 [manufactured by Mitsubishi Chemical Corporation] and jER1001 [manufactured by Mitsubishi Chemical Corporation].

[0051] The inclusion of a nonionic surfactant (D) makes it easier to create aqueous emulsions. The nonionic surfactant (D) is preferably an alkylene oxide adduct of an alkylphenol and / or an alkylene oxide adduct of an arylalkylphenol. The alkyl group of the alkylphenol preferably has 9 to 15 carbon atoms. The alkyl group of the arylalkylphenol preferably has 2 to 10 carbon atoms. Examples of the arylalkylphenols mentioned above include styrenelated phenol, styrenelated cumylphenol, and styrenelated cresol. The alkylene oxide is preferably PO and / or EO.

[0052] Examples of commercially available alkylphenol alkylene oxide adducts include "Sunnonic SS-50," "Sunnonic SS-90," and "Sunnonic SS-70" manufactured by Sanyo Chemical Industries, Ltd. Examples of alkylene oxide adducts of arylalkylphenols include "Soprophor 796 / P" and "Soprophor TSP / 724" manufactured by Solvay Nikka Co., Ltd.

[0053] The fiber sizing agent composition of the present invention contains a compound having a urethane group (A), a polyester resin (B), a bisphenol A type epoxy resin (C), and a nonionic surfactant (D). The weight ratio of (B) to the total weight of (C) is 30-70% by weight, from the viewpoint of the bundle-forming properties of the fiber bundles. The weight ratio of (B) to the total weight of (D) is 50 to 90% by weight, preferably 60 to 90% by weight, from the viewpoint of the bundle-forming properties of the fiber bundles. The weight ratio of (C) to the total weight of (D) is 50 to 90% by weight, preferably 60 to 90% by weight, from the viewpoint of the bundle-forming properties of the fiber bundles.

[0054] The fiber sizing agent composition of the present invention may contain additives as needed, such as smoothing agents, preservatives, and antioxidants. Examples of smoothing agents include waxes (polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, modified polyethylene, modified polypropylene, etc.), higher fatty acid alkyl (1-24 carbon atoms) esters (methyl stearate, ethyl stearate, propru stearate, butyl stearate, octyl stearate, stearyl stearate, etc.), and higher fatty acids (myristic acid, palmitic acid, stearic acid). Examples of preservatives include benzoic acids, salicylic acids, sorbic acids, quaternary ammonium salts, and imidazoles. Antioxidants include phenols (such as 2,6-di-t-butyl-p-cresol), thiodipropionates (such as dilauryl 3,3'-thiodipropionate), and phosphites (such as triphenyl phosphite).

[0055] The fiber sizing agent composition of the present invention can be produced by mixing a compound having a urethane group (A), a polyester resin (B), a bisphenol A type epoxy resin (C), a nonionic surfactant (D), and other additives in any order. When an aqueous solvent is included, it is preferable to pre-mix the components other than the aqueous medium, and then add the aqueous medium to the resulting mixture to dissolve or emulsify and disperse it.

[0056] When pre-mixing components other than aqueous media, the temperature is preferably 20-90°C, more preferably 40-90°C, from the viewpoint of ease of mixing, and the temperature for subsequent dissolution or emulsification dispersion is similar. The time for dissolving or emulsifying / dispersing is preferably 1 to 20 hours, and more preferably 2 to 10 hours.

[0057] There are no restrictions on mixing, dissolving, and emulsifying / dispersing equipment. Stirring blades (blade shape: oyster type and three-stage paddle, etc.), Nauter mixers, ribbon mixers, conical blenders, mortar mixers, multi-purpose mixers (multi-purpose mixing and stirring machine 5DM-L, manufactured by San-ei Seisakusho Co., Ltd., etc.), and Henschel mixers can be used.

[0058] Fibers to which the fiber sizing agent composition of the present invention can be applied include known fibers such as carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slug fibers (such as those described in International Publication No. 2003 / 47830). From the viewpoint of molded article strength, it is preferable to use at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, and slug fibers, and more preferably carbon fibers. Two or more of these fibers may be used in combination.

[0059] The fiber bundle of the present invention is a fiber bundle obtained by treating at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, and slug fiber with the above-mentioned fiber sizing agent composition (for example, a fiber bundle of about 3,000 to 50,000 fibers).

[0060] Methods for treating the fibers include spraying and immersion. The amount (by weight) of solid components contained in the fiber sizing agent composition adhering to the fibers is preferably 0.05 to 5% by weight, and more preferably 0.2 to 4% by weight, based on the weight of the untreated fibers. Within this range, the strength of the molded article is further improved.

[0061] The textile products of the present invention consist of the fiber bundles, and include textile products made by processing the fiber bundles, including woven fabrics, knitted fabrics, nonwoven fabrics (felt, mats and paper, etc.), chopped fibers and milled fibers, etc.

[0062] The composite material of the present invention comprises the fiber bundle and / or fiber product of the present invention described above and a matrix resin. The matrix resin includes thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, polyethersulfone, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, acrylic resin, polycarbonate, polyetherimide, polyetheretherketone, polyacetal, polyphenylene oxide, and polyphenylene sulfide. Examples of thermosetting resins include epoxy resins, unsaturated polyester resins, and vinyl ester resins. When a thermosetting resin is used, the composite material may contain a catalyst. Any known catalyst can be used without limitation; for example, when the thermosetting resin is an epoxy resin, the catalyst described in Japanese Patent Application Publication No. 2005-213337 is an example.

[0063] From the viewpoint of molded article strength, the weight ratio of matrix resin to fiber bundles and fiber products (matrix resin / fiber bundles and fiber products) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 70 / 30, and particularly preferably 30 / 70 to 60 / 40. If a catalyst is included, the catalyst content is preferably 0.01 to 10% by weight relative to the matrix resin, more preferably 0.1 to 5% by weight, and particularly preferably 1 to 3%.

[0064] The composite material of the present invention can be obtained by impregnating a textile product (woven fabric, knitted fabric, nonwoven fabric, etc.) of the present invention with a thermoplastic matrix resin that has been melted by heat (melting temperature: 60-150°C) or diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and ethyl acetate, etc.) and molding it, or by adding a fiber bundle of the present invention or chopped fiber obtained by cutting it into a molten thermoplastic matrix resin, kneading it, and then injection molding it, etc. Furthermore, if the matrix resin is a thermosetting resin, it can be molded by heating and molding, and then solidifying at room temperature. Complete curing is not required, but it is preferable that the molded body is hardened to a degree that allows it to maintain its shape. After molding, it may be further heated to completely harden. [Examples]

[0065] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0066] <Production Example 1> Production of 10-mol bisphenol A adduct In a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device, and dropping cylinder, 402 parts by weight (1 mole) of bisphenol A PO3 molar adduct (product name: Newport BP-3P, manufactured by Sanyo Chemical Industries, Ltd.) and 2 parts by weight of potassium hydroxide were added. After nitrogen purging, the pressure was reduced to -0.08 MPa. The temperature was raised to 120°C, and 6 parts by weight (7 moles) of PO40 were added dropwise over 6 hours while adjusting the pressure to 0.5 MPaG or less. The mixture was then aged at 120°C for 5 hours. After cooling to 100°C, 30 parts by weight of an adsorbent (product name: Kyoward 600, manufactured by Kyowa Chemical Industry Co., Ltd.) were added. The mixture was stirred at 100°C for 1 hour, and the adsorbent was filtered to obtain bisphenol A PO10 molar adduct (a2-3).

[0067] <Manufacturing Example 2> Manufacturing of a compound (A-1) containing a urethane group Into a reaction vessel equipped with a stirring device and a temperature control device, 202 parts by weight of a PO3 adduct of bisphenol A "trade name: Newpole BP-3P, manufactured by Sanyo Chemical Industries, Ltd." (a2-1) and 498 parts by weight of polypropylene glycol (Mn = 1000) "trade name: Sunix PP-1000, manufactured by Sanyo Chemical Industries, Ltd." (a2-5) were charged and purged with nitrogen. The temperature was raised to 80 °C under a dry nitrogen atmosphere, and after 116 parts by weight of toluene diisocyanate [trade name: Coronate T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.] (a1-1) was charged, it was aged at 80 °C for 5 hours to obtain a compound (A-1) having a urethane group. (A-1) was water-insoluble, Mn was 2370, and the urethane group concentration was 1.63 mmol / g.

[0068] <Measurement method of Mn> In the present invention, Mn was measured by GPC under the following conditions. Model: Alliance (liquid chromatograph manufactured by Waters K.K.) Column: Guardcolumn Super H-L + TSK gel Super H4000 + TSK gel Super H3000 + TSK gel Super H2000 (All manufactured by Tosoh Corporation) Column temperature: 40 °C Detector: RI (Refractive Index) Eluent: Tetrahydrofuran Eluent flow rate: 0.6 ml / min Sample concentration: 0.25 wt% Injection volume: 10 μl Standard substance: Polystyrene (manufactured by Tosoh Corporation; TSK STANDARD POLYSTYRENE)

[0069] <Urethane group concentration> In the present invention, the urethane group concentration of the compound (A) having a urethane group is determined by the N atom content quantified by a nitrogen analyzer [ANTEK7000 (manufactured by ANTEK)] and 1The ratio of urethane groups to urea groups was quantified by 1H-NMR, and the content of alohanate and biuret groups, as described later, was used to determine the ratio. 1 The 1H-NMR measurements were performed using the method described in "Structural Study of Polyurethane Resins by NMR: Takeda Research Institute Report 34(2), 224-323 (1975)". 1 When an aliphatic group was used, the weight ratio of urea groups to urethane groups was determined by measuring 1H-NMR and the ratio of the integrated hydrogen from urea groups around a chemical shift of 6 ppm to the integrated hydrogen from urethane groups around a chemical shift of 7 ppm. The urethane group content was calculated from this weight ratio and the above-mentioned N atom content and alohanate and biuret group content. This calculated value was defined as the urethane group concentration. When an aromatic isocyanate was used, the weight ratio of urea groups to urethane groups was calculated by the ratio of the integrated hydrogen from urea groups around a chemical shift of 8 ppm to the integrated hydrogen from urethane groups around a chemical shift of 9 ppm. The urethane group content was calculated from this weight ratio and the above-mentioned N atom content, and this calculated value was defined as the urethane group concentration.

[0070] <Water-soluble> Compound (A) containing 100 mg of urethane group was added to 100 mL (25°C) of water and stirred with a stirrer for 24 hours. The solution (or suspension) was then centrifuged at 3000 × g at 25°C for 30 minutes, and the insoluble residue was collected. This residue was dried at 105°C for 3 days, and the weight after drying (dry weight) was measured. If the dry weight was less than 99 mg, it was considered water-soluble; if it was 99 mg or more, it was considered insoluble.

[0071] <Manufacturing Examples 3-12 and Comparative Manufacturing Examples 1-3> In a reaction vessel equipped with a stirring device and a temperature control device, the raw materials in parts of polyol (a2) listed in Table 1 were added and the mixture was purged with nitrogen. The temperature was raised to 80°C under a dry nitrogen atmosphere, and the raw materials in parts of diisocyanate (a1) listed in Table 1 were added. The mixture was then aged at 80°C for 5 hours to obtain compounds (A-2) to (A-11) and (A'-1) to (A'-3) that contain urethane groups. The values ​​of Mn, urethane group concentration, and water solubility measurements of the obtained compounds containing urethane groups are shown in Table 1.

[0072] [Table 1]

[0073] The chemical composition of the raw materials indicated by the symbols in Table 1 is as follows: (a1-1): Toluene diisocyanate [Product name: Coronate T-80, manufactured by Nippon Polyurethane Industries Co., Ltd.] (a1-2): 4,4'- or 2,4'-diphenylmethane diisocyanate [Trade name: Myrionate MT, manufactured by Tosoh Corporation] (a1-3): Hexamethylene diisocyanate (a1-4): Isophorone diisocyanate (a1-5): Dicyclohexylmethane-4,4'-diisocyanate (a2-1): Bisphenol A PO3 molar adduct [Product name: Newpol BP-3P, manufactured by Sanyo Chemical Industries, Ltd.] (a2-2): PO10 molar adduct of bisphenol A prepared in Production Example 1 (a2-3): Polypropylene glycol (Mn=200) [Product name: Sannix PP-200, manufactured by Sanyo Chemical Industries, Ltd.] (a2-4): Polypropylene glycol (Mn=400) [Product name: Sannix PP-400, manufactured by Sanyo Chemical Industries, Ltd.] (a2-5): Polypropylene glycol (Mn=1000) [Product name: Sannix PP-1000, manufactured by Sanyo Chemical Industries, Ltd.] (a2-6): Polytetramethylene ether glycol (Mn=1000) (a2-7): Polyethylene glycol (Mn=1000) [Product name: PEG-1000, manufactured by Sanyo Chemical Industries, Ltd.] (a2-8): Polyethylene glycol (Mn=2000) [Product name: PEG-2000, manufactured by Sanyo Chemical Industries, Ltd.] (a2-9) Polyesterdiol (Mn=2000) [Product name: Polylight OD-X-2420, manufactured by DIC Corporation] (a2-10) Polycaprolactone diol (Mn=530) [Product name: Praxel 205U, manufactured by Daicel Corporation] (a2-11) Polycarbonate diol [Product name: ETERNACOLL PH-50, manufactured by Ube Industries, Ltd.] (a2-12) Dimethylolpropionic acid [manufactured by Tokyo Chemical Industry Co., Ltd.] (a2-13): Neopentyl glycol

[0074] <Production Example 13: Production of 40-mol EO adduct of bisphenol A (b1-4)> In a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device, and dropping cylinder, 228 parts by weight (1 mole) of bisphenol A, 400 parts by weight of toluene, and 2 parts by weight of potassium hydroxide were charged, and the pressure was set to -0.08 MPa. The temperature was raised to 130°C, and 1760 parts by weight of EO was added dropwise over 6 hours while adjusting the pressure to 0.5 MPaG or less, and then the mixture was aged at 130°C for 3 hours. After cooling to 100°C, 30 parts of an adsorbent (product name: Kyoward 600, manufactured by Kyowa Chemical Industry Co., Ltd.) were added. After stirring at 100°C for 1 hour, the adsorbent was filtered to obtain a 40 mole EO adduct of bisphenol A (b1-4).

[0075] <Production Example 14: Production of 80 EO adduct of bisphenol A (b1-5)> In the same manner as in Production Example 13, except that 400 parts by weight of toluene was changed to 1000 parts by weight of toluene, and 1760 parts by weight of EO was changed to 3520 parts by weight (80 moles), a bisphenol A EO 80 mole adduct (b1-5) was obtained.

[0076] <Manufacturing Example 15: Manufacturing of Polyester (B-1)> 632 parts by weight (2 moles) of bisphenol A EO 2 molar adduct (b1-2), 795 parts by weight (0.40 moles) of bisphenol A EO 40 molar adduct (b1-4), 498 parts by weight (3 moles) of terephthalic acid (b2-1), and 3 parts by weight of potassium titanate oxalate were reacted in a glass reaction vessel at 230°C under reduced pressure to 0.001 MPa for 15 hours while distilling off the water, to obtain a polyester resin (B-1) with a number average molecular weight of 1850.

[0077] <Manufacturing of Manufacturing Examples 16-24 and Comparative Manufacturing Example 4> In Production Example 15, polyester resins (B-2) to (B-10) and polyester resin (B'-1) were obtained in the same manner as in Production Example 15, except that the type and amount of dicarboxylic acid component (b2) and the type and amount of diol component (b1) used were as shown in Table 2. The measurement results of Mn for the obtained polyester resin (B) are shown in Table 2.

[0078] [Table 2]

[0079] The materials used in the manufacture of polyester resins (B-1) to (B-10) and polyester resin (B'-1) are as follows. <Dicarboxylic acid component (b2)> (b2-1): Terephthalic acid (b2-2): Fumaric acid <Diol component (b1)> (b1-1): Bisphenol A PO3 molar adduct [Product name: Newpol BP-3P, manufactured by Sanyo Chemical Industries, Ltd.] (b1-2): Bisphenol A EO2 molar adduct [Product name: Newpol BPE-20, manufactured by Sanyo Chemical Industries, Ltd.] (b1-3): Bisphenol A EO4 molar adduct [Product name: Newpol BPE-40, manufactured by Sanyo Chemical Industries, Ltd.] (b1-4): EO40 molar adduct of bisphenol A prepared in Production Example 13 (b1-5): EO80 molar adduct of bisphenol A prepared in Production Example 14 (b1-6): Polyethylene glycol [Product name: PEG-200, manufactured by Sanyo Chemical Industries, Ltd.] (b1-7): Polyethylene glycol [Product name: PEG-2000, manufactured by Sanyo Chemical Industries, Ltd.] (b1-8): Neopentyl glycol

[0080] <Examples 1-14 and Comparative Examples 1-8> In a reaction vessel equipped with a stirring device, a heating / cooling device, a thermometer, and a dropping funnel, the types and amounts of urethane group-containing compounds (A), polyester resin (B), bisphenol A type epoxy resin (C), and nonionic surfactant (D) listed in Table 3 were added. After stirring for 5 minutes while heating to 60°C, water was added dropwise from the dropping funnel in the amounts listed in Tables 3 and 4 over 1 hour to prepare fiber sizing agent solutions (X1) to (X14) and comparative fiber sizing agent solutions (X'1) to (X'9), which are dispersions of fiber sizing agent compositions with a solid content of 40%. Here, the solid content refers to the residue after heating and drying 1 g of the sample in a circulating air dryer at 130°C for 45 minutes.

[0081] [Table 3]

[0082] The bisphenol A type epoxy resin (C) used in the production of the fiber sizing agent solutions (X1) to (X14) and the comparative fiber sizing agent solutions (X'1) to (X'9) is as follows. <Bisphenol A type epoxy resin (C)> (C-1): Epoxy resin [Product name: jER834, condensate of bisphenol A diglycidyl ether and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation] (C-2): Epoxy resin [Product name: jER1001, condensate of bisphenol A diglycidyl ether and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation]

[0083] The nonionic surfactant (D) used in the preparation of the fiber sizing agent solutions (X1) to (X14) and the comparative fiber sizing agent solutions (X'1) to (X'9) is as follows. <Nonionic surfactant (D)> (D-1): Propylene oxide ethylene oxide adduct of styrene-phenol [Product name: Soprophor 796 / P, manufactured by Solvay Nikka Co., Ltd.] (D-2): Propylene oxide ethylene oxide adduct of styrene-phenol [Product name: Soprophor TSP / 724, manufactured by Solvay Nikka Co., Ltd.] (D-3): Polyoxyethylene alkyl ether [Product name: Sannonic SS-50, manufactured by Sanyo Chemical Industries, Ltd.] (D-4): Ethylene oxide 9-mol adduct of a secondary alcohol with 12-14 carbon atoms [Product name: Sannonic SS-90, manufactured by Sanyo Chemical Industries, Ltd.]

[0084] The storage stability of the fiber sizing agent solutions (X1) to (X14) and (X'1) to (X'9) obtained in Examples 1 to 15 and Comparative Examples 1 to 8, as well as the sizing, unfolding, fluffing, and adhesion properties of carbon fiber bundles prepared using the fiber sizing agent solutions obtained in each example, were evaluated by the following methods. The results are shown in Tables 2 and 3.

[0085] <Manufacturing of carbon fiber bundles for evaluation testing> Water was added to each example's fiber sizing agent solution to create a dispersion with a solid content concentration of 1.5%. Untreated carbon fibers (24,000 filaments) were immersed in the dispersion to impregnate them with the fiber sizing agent composition. Subsequently, the carbon fibers were removed from the dispersion and dried with hot air at 180°C for 3 minutes to obtain carbon fiber bundles. The amount of solid content adhering to the fibers (percentage based on the weight of carbon fibers before immersion) from the dispersion of the fiber sizing agent composition was 1.5% when preparing the carbon fiber bundles. These carbon fiber bundles were subjected to evaluation tests for sizing, unfraying, and fluffing properties.

[0086] <Evaluation test of focusing ability> The focusing ability of carbon fiber bundles was evaluated according to JIS L1096-2010 8.21.1 Method A (45° cantilever method). Carbon fiber bundles obtained under the processing conditions specified in the JIS were evaluated using a cantilever. A larger measured value (cm) indicates better focusing ability. A focusing ability value of 14 cm or higher measured by this evaluation method is preferable.

[0087] <Evaluation test for fiber separation> A bundle of carbon fibers for the above test was wound onto a roll, and the fiber-opening properties were evaluated using the following method. (1) Description of the evaluation device As shown in Figure 1, five 10 mm diameter stainless steel rods (1A, 1B, 1C, 1D, 1E) with smooth surfaces and temperature-controlled to 25°C were arranged parallel to each other, with a horizontal spacing of 50 mm between adjacent stainless steel rods, and the carbon fiber bundle 4 passed through them in a zigzag pattern while in contact with the stainless steel rods 1A, 1B, 1C, 1D, 1E. The horizontal direction is indicated by the arrow X-X' in the figure, and is parallel to the horizontal plane HL. Furthermore, the straight lines connecting the centers of the stainless steel rods 1A, 1C, and 1E, through which the carbon fiber bundle 4 passes the 1st, 3rd, and 5th times, and the straight lines connecting the centers of the stainless steel rods 1B and 1D, through which the carbon fiber bundle 4 passes the 2nd and 4th times, were arranged to be parallel to the horizontal plane. In addition, before and after the passage of the 2nd to 4th stainless steel rods 1B and 1D, the straight line representing the direction of travel of the carbon fiber bundle before passage and the straight line representing the direction of travel of the carbon fiber bundle after passage were arranged to form an angle of 120 degrees (for example, the angle between the straight line parallel to the direction of travel of the carbon fiber bundle passing between the 1st stainless steel rod 1A and the 2nd stainless steel rod 1B, and the straight line parallel to the direction of travel of the carbon fiber bundle passing between the 2nd stainless steel rod 1B and the 3rd stainless steel rod 1C, was arranged to form an angle of 120 degrees). (2) Measurement of the extent of carbon fiber bundle Two unwinding rolls, each wound with a test carbon fiber bundle, were prepared. The carbon fiber bundles 4 unwound from the two unwinding rolls 2A and 2B were zigzag-wound between stainless steel rods 1A, 1B, 1C, 1D, and 1E. The tension between the winding roll 3 and the unwinding rolls 2A and 2B was set to 14.7 N (1500 gf), and each carbon fiber bundle was wound from the unwinding rolls 2A and 2B to the winding roll 3 at a speed of 3 m / min. The winding of the carbon fiber bundles involved overlapping the two carbon fiber bundles 4 drawn from the two unwinding rolls 2A and 2B vertically on the first stainless steel rod 1A, and then passing them through the five stainless steel rods 1A, 1B, 1C, 1D, and 1E. The fiber-spreading ability was evaluated by measuring the spread width (cm) of the carbon fiber bundles 4 in the region 5 from the time they passed through the five stainless steel rods until they reached the winding roll 3. The expansion width of the carbon fiber bundle was measured using a yarn running test device manufactured by Asano Machinery Works Co., Ltd. A carbon fiber bundle expansion width of 2 cm or more is preferred under these conditions.

[0088] <Evaluation test for pilling> (1) Description of the evaluation device As shown in Figure 1, five 10 mm diameter stainless steel rods (1A, 1B, 1C, 1D, 1E) with smooth surfaces and temperature-controlled to 25°C were arranged parallel to each other, with a horizontal spacing of 50 mm between adjacent stainless steel rods, and the carbon fiber bundle 4 passed through them in a zigzag pattern while in contact with the stainless steel rods 1A, 1B, 1C, 1D, 1E. The horizontal direction is indicated by the arrow X-X' in the figure, and is parallel to the horizontal plane HL. Furthermore, the straight lines connecting the centers of the stainless steel rods 1A, 1C, and 1E, through which the carbon fiber bundle 4 passes the 1st, 3rd, and 5th times, and the straight lines connecting the centers of the stainless steel rods 1B and 1D, through which the carbon fiber bundle 4 passes the 2nd and 4th times, were arranged to be parallel to the horizontal plane. In addition, before and after the passage of the 2nd to 4th stainless steel rods 1B and 1D, the straight line representing the direction of travel of the carbon fiber bundle before passage and the straight line representing the direction of travel of the carbon fiber bundle after passage were arranged to form an angle of 120 degrees (for example, the angle between the straight line parallel to the direction of travel of the carbon fiber bundle passing between the 1st stainless steel rod 1A and the 2nd stainless steel rod 1B, and the straight line parallel to the direction of travel of the carbon fiber bundle passing between the 2nd stainless steel rod 1B and the 3rd stainless steel rod 1C, was arranged to form an angle of 120 degrees). The unwinding roll 2 and the rewinding roll 3 were set to rotate in the direction of the arrows drawn near each roll. (2) Measurement of the weight of the fibers The carbon fiber bundle 4 was strung in a zigzag pattern between stainless steel rods 1A, 1B, 1C, 1D, and 1E. After passing through stainless steel rod 1E, in the region just before it was wound onto the winding roll 3 (region 5A, 10 cm upstream from the winding start point 3A of the winding roll 3), the carbon fiber bundle 4 was sandwiched between two 10 cm x 10 cm rectangular urethane foam sheets with a load of 1 kg applied to them, from the thickness direction of the fiber bundle (up and down direction in the illustration). In this example, the carbon fiber bundle is transported from the unwinding roll 2 to the winding roll 3, so "upstream side" means upstream in the transport direction, i.e., the unwinding roll 2 side. The carbon fiber bundle 4, sandwiched between urethane foam, was wound from the unwinding roll 2 to the winding roll 3 at a speed of 1 m / min for 5 minutes with an unwinding tension of 9.8 N (1 kgf). During this time, the weight of the fluff adhering to the two urethane foam sheets was measured. A smaller value indicates better suppression of fluffing.

[0089] <Evaluation of Adhesion> Adhesion was evaluated using the microdroplet method. (1) Carbon fiber filaments were taken from the carbon fiber bundles obtained in the production of the carbon fiber bundles for the evaluation test described above and set in a sample holder. (2) Microdroplets made from a mixture of 100 parts by weight of pentaerythritol propylene oxide adduct [Sannix HD-402, manufactured by Sanyo Chemical Industries, Ltd.], which is a raw material for the matrix resin, and 198 parts by weight of polymeric MDI [Millionate MR-200, manufactured by Tosoh Corporation] were formed on carbon fiber filaments, cured at 25°C for 24 hours, and then cured at 120°C for 5 hours to obtain samples for adhesion measurement. (3) The sample to be measured was placed in the composite material interface property evaluation device HM410 [manufactured by Toei Sangyo Co., Ltd.], and the maximum pull-out load F when pulling out microdroplets from the carbon fiber filament was measured. (4) Using the measurement results, the interfacial shear strength τ was calculated using the following formula (1). Interfacial shear strength τ (unit: MPa) = F / πdL (1) [F represents the maximum pull-out load (N), d represents the carbon fiber filament diameter (μm), and L represents the particle size (μm) in the pull-out direction of the microdroplet.] A higher interfacial shear strength τ indicates better adhesion, and generally, 45 MPa or higher is preferred.

[0090] <Evaluation of storage stability (5°C)> 30 g each of the fiber sizing agent solutions (X1) to (X15) and (X'1) to (X'9) prepared in the examples and comparative examples were placed in a screw-cap bottle [50 mL (body diameter 35 mm × height 78 mm)] and stored at 5°C for 14 days. The median diameter (μm) was measured before and after storage, and the storage stability at 5°C was calculated using the following formula (2) based on the measurement results. The median diameter was measured using a laser diffraction particle size distribution analyzer "LA-750, manufactured by Horiba, Ltd." (the same method was used in the evaluation tests below). Storage stability at 5°C was evaluated according to the following criteria. Storage stability at 5°C (%) = 100 × (median diameter after storage) / (median diameter before storage) (2) (Evaluation Criteria) A: Less than 110% B: 110% or more, less than 115% C: 115% or more, less than 120% D: 120% or more

[0091] <Evaluation of storage stability (40°C)> 30 g each of the fiber sizing agent solutions (X1) to (X15) and (X'1) to (X'9) prepared in the examples and comparative examples were placed in a screw-cap bottle [50 mL (body diameter 35 mm × height 78 mm)] and stored at 40°C for 14 days. The median diameter (μm) was measured before and after storage, and the storage stability at 40°C was calculated using the following formula (3) based on the measurement results. Storage stability at 40°C was evaluated according to the following criteria. Storage stability at 40°C (%) = 100 × (median diameter after storage) / (median diameter before storage) (3) (Evaluation Criteria) A: Less than 110% B: 110% or more, less than 115% C: 115% or more, less than 120% D: 120% or more

[0092] Compared to the comparative examples listed in Table 4, as shown in Table 3, the fiber sizing agent composition of the example demonstrated excellent sizing and unfiber properties, produced fiber bundles with minimal fluffing, provided adhesion between the fibers and the matrix resin, and exhibited superior storage stability as a fiber sizing agent composition.

[0093] [Table 4] [Industrial applicability]

[0094] The fiber sizing agent composition of the present invention can be used as a sizing agent for glass fibers, carbon fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, or slug fibers. Furthermore, a prepreg can be obtained by treating a fiber bundle or fiber product obtained with the fiber sizing agent composition of the present invention, using the fiber bundle or fiber product as a reinforcing fiber and a thermoplastic resin or thermosetting resin as a matrix. [Explanation of Symbols]

[0095] 1A, 1B, 1C, 1D, 1E… Stainless steel rods 2, 2A, 2B... unwinding rolls 3... Reel roll 3A... Start point of winding 4…Carbon fiber bundle 5…The area from passing through five stainless steel rods to reaching the winding roll. 5A…The area 10cm upstream from 3A HL…Horizontal plane

Claims

1. Compound having a urethane group (A), Polyester resin (B), Bisphenol A type epoxy resin (C), and It contains a nonionic surfactant (D), The number average molecular weight of the compound (A) having the urethane group is 1,000 to 10,000. The compound (A) having the urethane group is water-insoluble, The polyester resin (B) is composed of a diol component (b1) and a dicarboxylic acid component (b2), and 5 to 100% by weight of the diol component (b1) is an alkylene oxide adduct (b11) of bisphenol A. The weight ratio of (B) to the total weight of (C) is 30 to 70% by weight. The weight ratio of (B) to the total weight of (D) is 50 to 90% by weight. The weight ratio of (C) to the total weight of (C) and (D) is 50 to 90% by weight. A fiber sizing agent composition.

2. The fiber sizing agent composition according to claim 1, wherein the compound (A) having the urethane group contains an aromatic skeleton.

3. The fiber sizing agent composition according to claim 1, wherein the nonionic surfactant (D) is an alkylene oxide adduct of an alkylphenol and / or an alkylene oxide adduct of an arylalkylphenol.

4. Carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slur A fiber bundle obtained by treating at least one fiber selected from the group consisting of buck fibers with the fiber sizing agent composition described in any one of claims 1 to 3.

5. A textile product comprising a fiber bundle as described in claim 4.

6. A composite material comprising a fiber bundle according to claim 4 and / or a fiber product according to claim 5 and a matrix resin.

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