Fiber sizing agent composition, fiber bundle, textile product, and composite material

Abstract

The present invention is a fiber sizing agent composition comprising a polyester resin (A) having an acid value of 10.0-60.0 mgKOH / g, a bisphenol A-type epoxy resin (B) that is solid at 20°C, a nonionic surfactant (C) having an aromatic ring in the molecule, and a polyoxyalkylene alkyl ether (D), wherein the polyester resin (A) is constituted of a diol component (a1) and a dicarboxylic acid component (a2), 5-100 wt% of the diol component (a1) is an alkylene oxide adduct (a11) of bisphenol A, the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the bisphenol A-type epoxy resin (B) is 10.0-95.0 wt%, the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the nonionic surfactant (C) is 50.0-85.0 wt%, the weight ratio of the bisphenol A-type epoxy resin (B) to the total weight of the bisphenol A-type epoxy resin (B) and the nonionic surfactant (C) is 20.0-95.0 wt%, and the weight ratio of the polyoxyalkylene alkyl ether (D) to the total weight of the polyoxyalkylene alkyl ether (D) and the nonionic surfactant (C) is 10.0-80.0 wt%.

Description

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

[0001] The present invention relates to fiber sizing agent compositions, fiber bundles, textile products, and composite materials.

[0002] Composite materials made of matrix resins such as unsaturated 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. Fibers used in these composite materials include glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slug fibers. In the processing steps to create these composite materials, sizing agents are applied to prevent fuzzing and fiber breakage. In the manufacturing process of these composite materials, a process to widen the fiber bundles (fiber opening process) is performed before combining them with the matrix resin. Fiber bundles with wider widths after the fiber opening process (those with superior fiber opening properties) have better matrix resin impregnation properties, making them suitable for producing thin, high-quality prepregs. Known sizing agents include solvent solutions of sizing agents made of polyglycidyl ethers (e.g., Patent Document 1), aqueous emulsions of bisphenol-type polyalkylene ether epoxy compounds emulsified with a small amount of emulsifier (e.g., Patent Document 2), and aqueous emulsions made of epoxy resin and urethane resin having oxyalkylene units (e.g., Patent Document 3).

[0003] JP-A-50-59589 JP-A-61-28074 JP-A-5-132863

[0004] However, fiber spreading and bundling are inherently contradictory, and it is difficult to achieve both at a high level. Furthermore, when using solvent solutions, as in Patent Document 1, there are problems with industrial handling and safety during sizing. In addition, the bundling agents proposed in Patent Documents 2 and 3 have problems with the emulsification stability of the aqueous emulsion, making it difficult to produce stable and uniform fiber bundles, resulting in insufficient fiber bundle bundling, excessive fluffing, and consequently, insufficient strength in the resulting composite material.

[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 fiber bundle and the matrix resin, and has excellent storage stability.

[0006] The present inventors have diligently studied to solve these problems and have arrived at the present invention. Specifically, the present invention contains a polyester resin (A) with an acid value of 10.0 to 60.0 mg KOH / g, a bisphenol A type epoxy resin (B) that is solid at 20°C, a nonionic surfactant (C) having an aromatic ring in its molecule, and a polyoxyalkylene alkyl ether (D), wherein the polyester resin (A) is composed of a diol component (a1) and a dicarboxylic acid component (a2), and 5 to 100% by weight of the diol component (a1) is an alkylene oxide adduct of bisphenol A (a11), and the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the bisphenol A type epoxy resin (B) is 10.0 to 95.0% by weight, and the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the nonionic surfactant (C) is A) is a fiber sizing agent composition wherein the weight percentage of A) is 50.0 to 85.0% by weight, the weight percentage of the bisphenol A type epoxy resin (B) to the total weight of the bisphenol A type epoxy resin (B) and the nonionic surfactant (C) is 20.0 to 95.0% by weight, and the weight percentage of the polyoxyalkylene alkyl ether (D) to the total weight of the polyoxyalkylene alkyl ether (D) and the nonionic surfactant (C) is 10.0 to 80.0% by weight; 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 fiber sizing agent composition; a textile product containing the fiber bundle; and a composite material containing the fiber bundle and / or the textile product and a matrix resin.

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

[0008] Figure 1 is a schematic side view showing the evaluation apparatus and the arrangement of carbon fiber bundles in the evaluation test for fiber opening and fluffing.

[0009] The present invention will be described in detail below. The fiber sizing agent composition of the present invention (hereinafter also referred to as the sizing agent composition) contains a polyester resin (A) with an acid value of 10.0 to 60.0 mg KOH / g, a bisphenol A type epoxy resin (B) that is solid at 20°C, a nonionic surfactant (C) having an aromatic ring in its molecule, and a polyoxyalkylene alkyl ether (D).

[0010] Polyester resin (A) has an acid value of 10.0 to 60.0 mgKOH / g. By using such polyester resin (A), it is possible to create fiber bundles with less fluffing. The acid value of polyester resin (A) can be adjusted, for example, by the polymerization temperature during the production of the polyester resin. The acid value in this invention is the value measured by the method specified in JIS K 0070:1992.

[0011] The polyester resin (A) may be one that has been manufactured to have an acid value of 10.0 to 60.0 mgKOH / g, or a commercially available polyester resin may be used.

[0012] The polyester resin (A) is composed of a diol component (a1) and a dicarboxylic acid component (a2). The diol component (a1) contains 5 to 100% by weight of an alkylene oxide (hereinafter sometimes abbreviated as AO) adduct (a11) of bisphenol A, preferably 20 to 100% by weight, from the viewpoint of cohesiveness, suppression of fluffing, and storage stability.

[0013] The AO in the bisphenol A AO adduct (a11) includes at least one selected from the group consisting of ethylene oxide (hereinafter sometimes abbreviated as EO), propylene oxide (hereinafter sometimes abbreviated as PO), 1,2-butylene oxide, and 1,4-butylene oxide (hereinafter sometimes abbreviated as BO), and two or more types may be added. From the viewpoint of flocculation, at least one selected from the group consisting of EO and PO is preferred as the AO, and EO is more preferred. From the viewpoint of reducing fluffiness, the number of moles of AO added in the bisphenol A AO adduct (a11) is preferably 1 to 200, more preferably 1 to 150, even more preferably 1 to 90, and particularly preferably 1 to 50.

[0014] In addition to the AO adduct of bisphenol A (a11), the diol component (a1) may also be an aliphatic alkanediol and / or an AO adduct of an aliphatic alkanediol.

[0015] Examples of aliphatic alkanediols include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, hexadecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.

[0016] Examples of AO adducts of aliphatic alkanediols include compounds obtained by adding a carbon atom (AO) having 2 to 4 carbon atoms to the diol. Examples of carbon atom (AO) having 2 to 4 carbon atoms include EO, PO, and BO. Examples of AO adducts of aliphatic alkanediols include polyethylene glycol and polypropylene glycol. Two or more of these AOs may be used in combination.

[0017] Examples of the dicarboxylic acid component (a2) include aliphatic dicarboxylic acids (a21) and aromatic dicarboxylic acids (a22).

[0018] Examples of the aliphatic dicarboxylic acid (a21) include chain saturated dicarboxylic acids and chain unsaturated dicarboxylic acids. Examples of the chain saturated dicarboxylic acid include linear or branched chain 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, icosanedicarboxylic acid, decylsuccinic acid, dodecylsuccinic acid, and octadecylsuccinic acid, etc.). Examples of the chain unsaturated dicarboxylic acid include linear or branched chain unsaturated dicarboxylic acids having 4 to 22 carbon atoms (maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid, and octadecenylsuccinic acid, etc.).

[0019] Examples of the aromatic dicarboxylic acid (a22) include terephthalic acid, isophthalic acid, orthophthalic acid, phenylmalonic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate, and potassium 5-sulfoisophthalate, etc.

[0020] From the viewpoint of convergence property, it is preferable to use the aromatic dicarboxylic acid (a22) as the dicarboxylic acid component (a2).

[0021] The diol component (a1) and the dicarboxylic acid component (a2) may each be used alone or in combination of two or more kinds thereof.

[0022] One method for producing polyester resin (A) is to perform condensation polymerization of a diol component (a1) and a dicarboxylic acid component (a2). The condensation polymerization reaction can be carried out by known methods, for example, by charging the diol component (a1) and the dicarboxylic acid component (a2), and distilling off the water while stirring at a reaction temperature of 100 to 250°C and a pressure of -0.1 to 1.2 MPa. The condensation polymerization reaction may be carried out in two stages, for example, by reacting a portion of the diol component (a1) with the dicarboxylic acid component (a2) in the first stage, and adding the remaining diol component (a1) in the second stage and reacting them. The reaction time is preferably less than 25 hours, and more preferably 5 to 24 hours. In the method for producing polyester resin (A), it is preferable to add a catalyst in an amount of 0.05 to 0.5% by weight based on the weight of the polyester resin (A). 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.

[0023] The number-average molecular weight (hereinafter also referred to as Mn) of the polyester resin (A) is preferably 750 to 3000, and more preferably 1000 to 3000. Within this range, fluffing of the fiber bundle can be further suppressed.

[0024] In this invention, Mn is a value measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) under the following conditions. Apparatus: HLC-8120 [Tosoh Corporation] Column: TSK GEL GMH6 x 2 [Tosoh Corporation] Measurement temperature: 40°C Sample solution: 0.25 wt% THF solution (undissolved components filtered out with a glass filter) Solution injection volume: 100 μL Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) samples (molecular weight 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 1090000, 2890000) [Tosoh Corporation]

[0025] The solubility parameter (hereinafter also referred to as SP value) of the polyester resin (A) is preferably 10.0 to 12.0 (cal / cm ３ ) １／２ , more preferably 10.0 to 11.5 (cal / cm ３ ) １／２ . The solubility parameter is a value calculated by the method described in formula (28) on page 153 of the Fedors method (Polymer Engineering and Science, February, 1974, Vol.14, No.2, P.147-154), using the numerical values (heat of evaporation and molar volume of atoms or atomic groups at 25°C) described on page 152 (Table 5) of the same document. Specifically, it can be calculated by applying numerical values corresponding to the types of atoms and atomic groups in the molecular structure from Δe ｉ and Δv ｉ described in the following Tables 1-1 to 1-3, which are parameters of the Fedors method, to the following formula: SP value = (ΣΔe ｉ / ΣΔv ｉ ) １／２ [wherein, ΣΔe ｉ (unit: cal / mol) is cohesive energy density (unit: cal / mol), and ΣΔv ｉ is molar volume (unit: cm ３ / mol).]

[0026]

[0027]

[0028]

[0029] Bisphenol A type epoxy resin (B) is solid at 20°C. Bisphenol A type epoxy resin is an epoxy resin obtained by the condensation reaction of bisphenol A and epihalohydrin (e.g., epichlorohydrin). By using bisphenol A type epoxy resin (B), it is possible to create fiber bundles with less fluffing. Bisphenol A type epoxy resin (B) may be used alone or in combination of two or more types. In this invention, "solid at 20°C" means that the object placed in the container does not flow within 10 seconds after the container is tilted under conditions of 1 atmosphere and a temperature of 20°C. Furthermore, "the container is tilted" means that the container placed on a horizontal surface is tilted by 10° or more from its original position. Examples of bisphenol A type epoxy resin (B) include jER834 [manufactured by Mitsubishi Chemical Corporation], jER1001 [manufactured by Mitsubishi Chemical Corporation], jER1002 [manufactured by Mitsubishi Chemical Corporation], jER1004 [manufactured by Mitsubishi Chemical Corporation], EPICLON860 [manufactured by DIC Corporation], EPICLON1050 [manufactured by DIC Corporation], EPICLON1055 [manufactured by DIC Corporation], and EPICLON3050 [manufactured by DIC Corporation].

[0030] The nonionic surfactant (C) having an aromatic ring in the molecule is preferably an alkylene oxide adduct of alkylphenol and an alkylene oxide adduct of arylalkylphenol, with the alkylene oxide adduct of arylalkylphenol being more preferred. 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 arylalkylphenols include styrene-containing phenol, styrene-containing cumylphenol, and styrene-containing cresol. The alkylene oxide is preferably PO and / or EO. The inclusion of the nonionic surfactant (C) facilitates the preparation of aqueous emulsions. The nonionic surfactant (C) is preferably a propylene oxide ethylene oxide adduct of styrene-containing phenol.

[0031] Polyoxyalkylene alkyl ether (D) is an ether of polyoxyalkylene and alcohol, and acts as a nonionic surfactant. Examples of (D) include the compound represented by the following formula (1). １ - (AO) ｎ H (1) R １ is an alkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms. n is the average number of moles of AO added, preferably 3 to 50 from the viewpoint of reducing fluffiness. The average number of moles added is １ It can be measured by 1H-NMR. AO is an alkylene oxide, including EO, PO, and BO, and two or more types may be added. From the viewpoint of focusing, at least one of the group consisting of EO and PO is preferred as AO, and EO is more preferred.

[0032] The polyoxyalkylene alkyl ether (D) preferably has an HLB value of 4 to 14, and more preferably has an HLB value of 8 to 14, in order to facilitate the penetration of the sizing agent composition into the fibers.

[0033] In this specification, the HLB value is an indicator showing the balance between hydrophilicity and lipophilicity, and in the case of a single compound, it is a value calculated using the following formula (2) (see Oda method described in "Synthesis and Applications of Surfactants," p. 501, published by Maki Shoten in 1957; "Introduction to Surfactants," pp. 212-213, published by Sanyo Chemical Industries, Ltd. in 2007, etc.). HLB value = 10 × (inorganic / organic) (2) In formula (2), "inorganic / organic" represents the ratio of the inorganic value to the organic value of the compound, and this ratio can be calculated from the values ​​described in the above literature. For the organic value and inorganic value, the organic value is set at 20 per carbon atom, and the inorganic value is calculated using the values ​​in the table described on page 213 of "Introduction to Surfactants" (the "numerical value" for inorganic groups, or the "inorganic" value for organic and inorganic groups). As an example of calculation, -CH ３ Base: Organic value 20, Inorganic value 0 -CH ２ - Group: Organic value 20, Inorganic value 0 = CH ２Group: Organic value 20, Inorganic value 2 =CH- group: Organic value 20, Inorganic value 2 iso branched carbon: Organic value -10, Inorganic value 0 tert branched carbon: Organic value -20, Inorganic value 0 Benzene ring: Organic value 120, Inorganic value 15 -O- group: Organic value 0, Inorganic value 20 -COO-: Organic value 20, Inorganic value 60 -OH group: Organic value 0, Inorganic value 100 -COOH group: Organic value 20, Inorganic value 150 -CH ２ CH ２ O-group (oxyethylene group): Organic value 40, inorganic value 75. For example, dodecanol {CH ３ (CH ２ ) １１ In the case of OH, the calculation is as follows: HLB value = 10 × (100) / (20 × 11 + 20) = 4.17

[0034] Examples of polyoxyalkylene alkyl ethers (D) include Sannonic SS-90 (manufactured by Sanyo Chemical Industries, Ltd., an ether of a secondary alcohol and polyoxyethylene, average number of moles of oxyethylene added: 9.5, HLB value: 13.2), Sannonic SS-50 (manufactured by Sanyo Chemical Industries, Ltd., an ether of a secondary alcohol and polyoxyethylene, average number of moles of oxyethylene added: 5, HLB value: 10.5), Naroacty ID-70 (manufactured by Sanyo Chemical Industries, Ltd., an ether of a primary alcohol and polyoxyethylene, average number of moles of oxyethylene added: 9.5, HLB value: 13.2), and Neugen SD-30 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene tridecyl ether, HLB: 10.1).

[0035] The weight ratio of polyester resin (A) to the total weight of polyester resin (A) and bisphenol A type epoxy resin (B) is 10.0 to 95.0% by weight, preferably 20.0 to 90.0% by weight, from the viewpoint of fiber bundle cohesion. The weight ratio of polyester resin (A) to the total weight of polyester resin (A) and nonionic surfactant (C) is 50.0 to 85.0% by weight, preferably 55.0 to 82.0% by weight, from the viewpoint of fiber bundle cohesion. The weight ratio of bisphenol A type epoxy resin (B) to the total weight of bisphenol A type epoxy resin (B) and nonionic surfactant (C) is 20.0 to 95.0% by weight, preferably 20.0 to 85.0% by weight, more preferably 25.0 to 80.0% by weight, from the viewpoint of fiber bundle cohesion. The weight ratio of polyoxyalkylene alkyl ether (D) to the total weight of polyoxyalkylene alkyl ether (D) and nonionic surfactant (C) is 10.0 to 80.0% by weight, preferably 10.0 to 50.0% by weight, and more preferably 10.0 to 30.0% by weight, in order to facilitate the penetration of the sizing agent composition into the fiber bundle and to facilitate the exertion of the effects of the invention.

[0036] The fiber sizing agent composition of the present invention may further contain a bisphenol A type epoxy resin (E) that is liquid at 20°C. In the present invention, "liquid at 20°C" means that when an object placed in a container is tilted at 1 atmosphere and a temperature of 20°C, the object becomes fluid within 10 seconds. The use of bisphenol A type epoxy resin (E) tends to improve the storage stability of the fiber sizing agent composition. Bisphenol A type epoxy resin (E) may be used alone or in combination of two or more types. Examples of bisphenol A type epoxy resin (E) include jER825, jER827, jER828 [all manufactured by Mitsubishi Chemical Corporation], EPICLON840, EPICLON850 [all manufactured by DIC Corporation], etc. The content of bisphenol A type epoxy resin (E) is preferably 0 to 30 parts by weight per 100 parts by weight of the fiber sizing agent composition.

[0037] The fiber sizing agent composition of the present invention may further contain epoxy (meth)acrylate (F). The inclusion of epoxy (meth)acrylate (F) tends to improve adhesion to the matrix resin. Epoxy (meth)acrylate (F) may be used alone or in combination of two or more types. Examples of epoxy (meth)acrylate (F) include (meth)acrylic acid adducts of aliphatic polyol polyglycidyl ethers (e.g., (meth)acrylic acid adduct of diethylene glycol diglycidyl ether, (meth)acrylic acid adduct of neopentyl glycol diglycidyl ether, (meth)acrylic acid adduct of glycerin diglycidyl ether, etc.) and (meth)acrylic acid adducts of aromatic polyol polyglycidyl ethers (e.g., (meth)acrylic acid adduct of bisphenol A diglycidyl ether, (meth)acrylic acid adduct of bisphenol F diglycidyl ether, (meth)acrylic acid adduct of cresol novolac type epoxy resin, etc.), with bisphenol A diglycidyl ether acrylic acid adduct being preferred. In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic" means acrylic or methacrylic. When the fiber sizing agent composition of the present invention contains epoxy (meth)acrylate (F), the weight ratio of epoxy (meth)acrylate (F) to the total weight of epoxy (meth)acrylate (F) and nonionic surfactant (C) is preferably 10.0 to 80.0% by weight, and more preferably 20.0 to 70.0% by weight. When the weight ratio is within the range of 10.0 to 80.0% by weight, the adhesion to the matrix resin (vinyl ester resin, urethane resin, etc.) and the storage stability of the fiber sizing agent composition tend to be good.

[0038] The fiber sizing agent composition of the present invention may further contain a polyester resin (G) with an acid value of 5.0 mg KOH / g or less. The inclusion of polyester resin (G) tends to improve the storage stability of the fiber sizing agent composition of the present invention. Polyester resin (G) may be used alone or in combination of two or more types.

[0039] The number-average molecular weight of the polyester resin (G) is preferably 750 to 3000, and more preferably 1000 to 2700. A molecular weight within the range of 750 to 3000 tends to suppress fluffing of the fiber bundles.

[0040] The SP value of the polyester resin (G) is preferably 10.0 to 11.2 (cal / cm³). ３ ) １／２ And more preferably 10.1 to 11.0 (cal / cm³). ３ ) １／２ It is 10.0 to 11.2 (cal / cm³). ３ ) １／２ Within this range, the convergence of fiber bundles and the emulsification stability of the sizing agent composition tend to improve.

[0041] The polyester resin (G) may be one that has been manufactured to have an acid value of 5.0 mgKOH / g or less, or a commercially available polyester resin may be used. Examples of constituent monomers of the polyester resin (G) include the aforementioned diol component (a1) and dicarboxylic acid component (a2). The polyester resin (G) can be manufactured in the same manner as the polyester resin (A) described above, and a polyester resin (G) with a desired acid value can be obtained by adjusting conditions such as reaction time. The reaction time is preferably 25 hours or more, more preferably 25 to 60 hours, and most preferably 25 to 40 hours. From the viewpoint of storage stability, the content of the polyester resin (G) is preferably 0 to 50 parts by weight per 100 parts by weight of the fiber sizing agent composition.

[0042] 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. Examples of antioxidants include phenols (2,6-di-t-butyl-p-cresol, etc.), thiodipropionates (dilauryl 3,3'-thiodipropionate, etc.), and phosphites (triphenyl phosphite, etc.).

[0043] The fiber sizing agent composition of the present invention can be produced by mixing a polyester resin (A) with an acid value of 10.0 to 60.0 mg KOH / g, a bisphenol A type epoxy resin (B) that is solid at 20°C, a nonionic surfactant (C) having an aromatic ring in its molecule, a polyoxyalkylene alkyl ether (D), and, if necessary, a bisphenol A type epoxy resin (E) that is liquid at 20°C, epoxy (meth)acrylate (F), a polyester resin (G) with an acid value of 5.0 mg KOH / g or less, and other additives in any order.

[0044] The fiber sizing agent composition of the present invention may contain an aqueous medium. Known aqueous media can be used as the aqueous medium, specifically including water and hydrophilic organic solvents [monohydric alcohols having 1 to 4 carbon atoms (methanol, ethanol, and isopropanol, etc.), ketones having 3 to 6 carbon atoms (acetone, ethyl methyl ketone, and methyl isobutyl ketone, etc.), glycols having 2 to 6 carbon atoms (ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol, etc.) and their monoalkyl (1 to 2 carbon atom) ethers, dimethylformamide, and alkyl acetate esters having 3 to 5 carbon atoms (methyl acetate and ethyl acetate, etc.)]. Of these, from the viewpoint of safety, water and a mixed solvent of hydrophilic organic solvent and water are preferred, with water being more preferred. Two or more aqueous media may be used in combination.

[0045] When the sizing agent composition contains an aqueous medium, 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. The temperature at which the components other than the aqueous medium are pre-mixed is preferably 20 to 90°C, more preferably 40 to 90°C, from the viewpoint of ease of mixing, and the temperature for subsequent dissolution or emulsification and dispersion is similar. The time for dissolution or emulsification and dispersion is preferably 1 to 20 hours, more preferably 2 to 10 hours.

[0046] There are no restrictions on mixing, dissolving, and emulsifying / dispersing equipment. Stirring blades (blade shapes: 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.

[0047] Fibers to which the fiber sizing agent composition of the present invention can be applied include known fibers such as inorganic fibers (carbon fibers, glass fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slug fibers, etc.) and organic fibers (aramid fibers, etc.) (as described in International Publication No. 2003 / 47830, etc.). From the viewpoint of the strength of the molded composite material, carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, and slug fibers are preferred, and carbon fibers are more preferred. Two or more of these fibers may be used in combination.

[0048] The fiber bundle of the present invention is 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 fiber sizing agent composition of the present invention. The fiber bundle is, for example, a bundle of about 3,000 to 50,000 fibers.

[0049] Methods for treating the fibers include spraying and immersion. The amount (by weight) of solid components contained in the fiber sizing agent composition attached 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. When the amount is in the range of 0.05 to 5% by weight, the strength of the molded composite material tends to be even better.

[0050] The textile products of the present invention include the fiber bundles of the present invention. The textile products include those made by processing the fiber bundles of the present invention, and include woven fabrics, knitted fabrics, nonwoven fabrics (felt, mats and paper, etc.), chopped fibers and milled fibers, etc.

[0051] The composite material of the present invention comprises a fiber bundle and / or fiber product of the present invention and a matrix resin. Examples of the matrix resin include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, polystyrene resin, polyethersulfone resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, acrylic resin, polycarbonate resin, polyetherimide resin, polyetheretherketone resin, polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, etc. Examples of thermosetting resins include epoxy resin, unsaturated polyester resin, phenolic resin, urethane resin, and vinyl ester resin. The composite material may optionally contain a catalyst. Any known catalyst can be used without limitation; for example, when the matrix resin is an epoxy resin, the catalyst described in Japanese Patent Application Publication No. 2005-213337 is an example.

[0052] The weight ratio of the matrix resin to the fiber bundles contained in the composite material (matrix resin / fiber bundles) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 70 / 30, and even more preferably 30 / 70 to 60 / 40, from the viewpoint of the strength of the molded article of the composite material. If the composite material contains a catalyst, the catalyst content is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and even more preferably 1 to 3% by weight, relative to the weight of the matrix resin.

[0053] The composite materials of the present invention include prepregs and molded articles. A prepreg can be produced, for example, by impregnating a fiber bundle and / or textile product (woven fabric, knitted fabric, nonwoven fabric, etc.) with a matrix resin that has been heat-melted (preferred melting temperature: 60 to 350°C), or a matrix resin diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and ethyl acetate, etc.). When a solvent is used, it is preferable to further dry the material to remove the solvent. If the matrix resin is a thermoplastic resin, the prepreg can be heat-molded and solidified at room temperature to form a molded article. A molded article can also be obtained by adding the fiber bundle (including chopped fibers) of the present invention to a molten thermoplastic matrix resin, kneading it, and then injection molding it. If the matrix resin is a thermosetting resin, the prepreg can be heat-molded and solidified to form a molded article. The solidification of these resins does not need to be complete, but it is preferable that they are solidified to the extent that the molded article can maintain its shape. After molding, the material may be further heated to completely cure it.

[0054] This specification discloses the following: This disclosure (1) contains a polyester resin (A) having an acid value of 10.0 to 60.0 mg KOH / g, a bisphenol A type epoxy resin (B) that is solid at 20°C, a nonionic surfactant (C) having an aromatic ring in its molecule, and a polyoxyalkylene alkyl ether (D), wherein the polyester resin (A) is composed of a diol component (a1) and a dicarboxylic acid component (a2), and 5 to 100% by weight of the diol component (a1) is an alkylene oxide adduct of bisphenol A (a11), and the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the bisphenol A type epoxy resin (B) is 1 The present disclosure (2) is a fiber sizing agent composition wherein the number average molecular weight of the polyester resin (A) is 0.0 to 95.0% by weight, the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the nonionic surfactant (C) is 50.0 to 85.0% by weight, the weight ratio of the bisphenol A type epoxy resin (B) to the total weight of the bisphenol A type epoxy resin (B) and the nonionic surfactant (C) is 20.0 to 95.0% by weight, and the weight ratio of the polyoxyalkylene alkyl ether (D) to the total weight of the polyoxyalkylene alkyl ether (D) and the nonionic surfactant (C) is 10.0 to 80.0% by weight. Disclosure (3) is a fiber sizing agent composition according to Disclosure (1) or (2), wherein the nonionic surfactant (C) is an alkylene oxide adduct of an arylalkylphenol. Disclosure (4) is a fiber sizing agent composition according to any one of Disclosures (1) to (3), further containing a bisphenol A type epoxy resin (E) that is liquid at 20°C. Disclosure (5) is a fiber sizing agent composition according to any one of Disclosures (1) to (4), further containing an epoxy (meth)acrylate (F).Disclosure (6) is a fiber sizing agent composition according to Disclosure (5), wherein the weight ratio of the epoxy (meth)acrylate (F) to the total weight of the epoxy (meth)acrylate (F) and the nonionic surfactant (C) is 10.0 to 80.0% by weight. Disclosure (7) is a fiber sizing agent composition according to any one of Disclosures (1) to (6), further containing a polyester resin (G) with an acid value of 5.0 mg KOH / g or less. Disclosure (8) 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 a fiber sizing agent composition according to any one of Disclosures (1) to (7). Disclosure (9) is a fiber product comprising the fiber bundle according to Disclosure (8). Disclosure (10) is a composite material comprising the fiber bundle according to Disclosure (8) and a matrix resin. Disclosure (11) is a composite material comprising the textile product described in Disclosure (9) and a matrix resin.

[0055] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, parts refer to parts by weight.

[0056] <Production Example 1: Production of Bisphenol A EO 40 molar adduct (a1-3)> In a pressure-resistant reaction vessel equipped with a stirrer, heating and cooling device and dropping cylinder, 228 parts (1 mole) of bisphenol A, 400 parts of toluene, and 2 parts of potassium hydroxide were charged, and the pressure was set to -0.08 MPa. The temperature was raised to 130°C, and 1760 parts (40 moles) of EO were 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 Bisphenol A EO 40 molar adduct (a1-3).

[0057] <Production of Polyester Resins (A) and (A')> <Production Example 2> In the first step, 498 parts of terephthalic acid (a2-1), 633 parts of 2 molar EO adduct of bisphenol A [product name: Newport BPE-20, manufactured by Sanyo Chemical Industries, Ltd.] (a1-1), and 2 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 170°C under reduced pressure to 0.001 MPa for 12 hours while removing water by distillation. In the second step, 1000 parts of polyethylene glycol [product name: PEG-2000, manufactured by Sanyo Chemical Industries, Ltd.] (a1-6) were added, and the mixture was reacted at 180°C under reduced pressure to -0.1 MPa for 8 hours while removing water to obtain polyester resin (A-1). The number-average molecular weight and acid value of the obtained polyester resin (A-1) were measured by the method described above, and the SP value was calculated by the method described above. The number-average molecular weight is 2200, and the SP value is 10.6 (cal / cm³). ３ ) １／２ The acid value was 39.7 mg KOH / g.

[0058] <Production Examples 3-11 and Comparative Production Examples 1-3> Polyester resins (A-2) to (A-10) and polyester resins (A'-1) to (A'-3) were obtained in the same manner as in Production Example 2, except that the type and amount of dicarboxylic acid component (a2) and the type and amount of diol component (a1) used were as shown in Tables 2-1 and 2-2, and the reaction time was as shown in Tables 2-1 and 2-2. The measurement results of Mn and acid value, and the calculation results of SP values ​​for each obtained polyester resin are shown in Tables 2-1 and 2-2.

[0059]

[0060]

[0061] <Production of Polyester Resin (G)> <Production Example 12> In the first step, 332 parts of terephthalic acid (a2-1), 791 parts of 2 molar EO adduct of bisphenol A [product name: Newport BPE-20, manufactured by Sanyo Chemical Industries, Ltd.] (a1-1), and 2 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 170°C under reduced pressure to 0.001 MPa for 15 hours while removing water by distillation. In the second step, 1100 parts of polyethylene glycol [product name: PEG-1000, manufactured by Sanyo Chemical Industries, Ltd.] (a1-5) were added, and the mixture was reacted at 180°C under reduced pressure to -0.1 MPa for 12 hours while removing water to obtain polyester resin (G-1). The number average molecular weight of the obtained polyester resin (G-1) was 1323, and the SP value was 10.8 (cal / cm²). ３ ) １／２ The acid value was 1.0 mg KOH / g.

[0062] <Production Examples 13-17> Polyester resins (G-2) to (G-6) were obtained in the same manner as in Production Example 12, except that the type and amount of dicarboxylic acid component (a2) and the type and amount of diol component (a1) used were as shown in Table 3, and the reaction time was as shown in Table 3. The measurement results of Mn and acid value, and the calculation results of SP values ​​for each obtained polyester resin are shown in Table 3.

[0063]

[0064] The raw materials listed in Tables 2-1, 2-2, and 3 are as follows: <Dicarboxylic acid component (a2)> (a2-1): Terephthalic acid (a2-2): Fumaric acid <Diol component (a1)> (a1-1): Bisphenol A EO 2 molar adduct [Product name: Newport BPE-20, manufactured by Sanyo Chemical Industries, Ltd.] (a1-2): Bisphenol A PO 3 molar adduct [Product name: Newport BP-3P, manufactured by Sanyo Chemical Industries, Ltd.] (a1-3): Bisphenol A EO 40 molar adduct produced in Production Example 1 (a1-4): Polyethylene glycol [Product name: PEG-600, manufactured by Sanyo Chemical Industries, Ltd.] (a1-5): Polyethylene glycol [Product name: PEG-1000, manufactured by Sanyo Chemical Industries, Ltd.] (a1-6): Polyethylene glycol [Product name: PEG-2000, manufactured by Sanyo Chemical Industries, Ltd.] (a1-7): Polyethylene glycol [Product name: PEG-4000, manufactured by Sanyo Chemical Industries, Ltd.]

[0065] <Examples 1-21 and Comparative Examples 1-7> In a reaction vessel equipped with a stirring device, a heating / cooling device, a thermometer, and a dropping funnel, the types and amounts of polyester resin (A), bisphenol A type epoxy resin (B), nonionic surfactant (C), polyoxyalkylene alkyl ether (D), bisphenol A type epoxy resin (E), epoxy (meth)acrylate (F), and polyester resin (G) listed in Tables 4-1 to 4-5 were added and stirred for 5 minutes while heating to 60°C. Next, the amounts of water listed in Tables 4-1 to 4-5 were added dropwise from the dropping funnel over 1 hour to prepare fiber sizing agent solutions (X1) to (X21) and (X'1) to (X'7), which are dispersions (emulsions) of fiber sizing agent compositions with a solid content concentration of 40% by weight. Here, the solid content is the residue after heating and drying 1 g of the sample in a circulating air dryer at 130°C for 45 minutes.

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] The raw materials listed in Tables 4-1 to 4-5 are as follows: <Bisphenol A type epoxy resin (B)> (B-1): Epoxy resin [Product name: jER834, condensate of bisphenol A and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation] (B-2): Epoxy resin [Product name: jER1001, condensate of bisphenol A and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation]

[0072] <Nonionic surfactants (C)> (C-1): Propylene oxide ethylene oxide adduct of styrene-phenol [Product name: Soprophor 796 / P, manufactured by Solvay Nikka Co., Ltd.] (C-2): Propylene oxide ethylene oxide adduct of styrene-phenol [Product name: Soprophor TSP / 724, manufactured by Solvay Nikka Co., Ltd.]

[0073] <Polyoxyalkylene alkyl ethers (D)> (D-1): Polyoxyethylene alkyl ether [Product name: Sunnonic SS-50, manufactured by Sanyo Chemical Industries, Ltd.] (D-2): Nine-mol adduct of ethylene oxide of a secondary alcohol having 12 to 14 carbon atoms [Product name: Sunnonic SS-90, manufactured by Sanyo Chemical Industries, Ltd.]

[0074] <Bisphenol A type epoxy resin (E)> (E-1): Epoxy resin [Product name: jER828, manufactured by Mitsubishi Chemical Corporation]

[0075] <Epoxy (meth)acrylate (F)> (F-1): Bisphenol A diglycidyl ether 2-mol adduct of acrylic acid [Product name: Epoxy Ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.] (F-2): Bisphenol A epoxy acrylate [Product name: ETERCURE 621-100, manufactured by Choko Materials Industry Co., Ltd.]

[0076] Tables 4-1 to 4-5 also show the following values: [(A) / ((A) + (B))] × 100: Weight percentage of polyester resin (A) relative to the total weight of polyester resin (A) and bisphenol A type epoxy resin (B) [(A) / ((A) + (C))] × 100: Weight percentage of polyester resin (A) relative to the total weight of polyester resin (A) and nonionic surfactant (C) [(B) / ((B) + (C))] × 100: Weight percentage of bisphenol A type epoxy resin (B) relative to the total weight of bisphenol A type epoxy resin (B) and nonionic surfactant (C) [(D) / ((D) + (C))] × 100: Weight percentage of polyoxyalkylene alkyl ether (D) relative to the total weight of polyoxyalkylene alkyl ether (D) and nonionic surfactant (C) [(F) / ((F) + (C))] × 100: Weight percentage of epoxy (meth)acrylate (F) relative to the total weight of epoxy (meth)acrylate (F) and nonionic surfactant (C)

[0077] The storage stability of the fiber sizing agent solutions (X1) to (X21) and (X'1) to (X'7) obtained in Examples 1 to 21 and Comparative Examples 1 to 7, as well as the sizing properties, fiber opening properties, fluffing, and adhesion to the matrix resin of carbon fiber bundles prepared using each fiber sizing agent solution, were evaluated by the following methods. The results are shown in Tables 4-1 to 4-5.

[0078] <Preparation of carbon fiber bundles for evaluation testing> Water was added to each fiber sizing agent solution to create a dispersion with a solid content concentration of 1.5% by weight. Untreated carbon fibers (24,000 filaments) were immersed in the dispersion to impregnate them. The carbon fibers were then 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 the carbon fibers before immersion) was 1.5% when preparing the carbon fiber bundles. Amount of solid content adhering to fibers (%) = [(Weight of carbon fiber bundle - Weight of untreated carbon fibers) / Weight of untreated carbon fibers] × 100 The carbon fiber bundles were subjected to evaluation tests for sizing, unfraying, and fluffing properties.

[0079] <Evaluation Test of Focusing Performance> Using the carbon fiber bundles for the evaluation test described above, the focusing performance was evaluated according to JIS L 1096:2010 8.21.1 Method A (45° cantilever method). The obtained values ​​are shown in Tables 4-1 to 4-5. A larger measured value (cm) indicates better focusing performance. A focusing performance value of 14 cm or higher measured by this evaluation method is preferable.

[0080] <Evaluation Test of Fiber Opening Ability> A carbon fiber bundle for the above evaluation test was prepared by winding it onto a roll, and the fiber opening ability evaluation test was performed using the following method. (1) Explanation of the evaluation apparatus As shown in Figure 1, five stainless steel rods (1A, 1B, 1C, 1D, 1E) with a smooth surface and a diameter of 10 mm, which were temperature-adjusted to 25°C, were arranged parallel to each other so that the horizontal distance between adjacent stainless steel rods was 50 mm, and the carbon fiber bundle 4 passed through the stainless steel rods 1A, 1B, 1C, 1D, and 1E in a zigzag pattern while in contact with them. The horizontal direction is the direction indicated by the arrow X-X' in the figure, and is parallel to the horizontal plane HL. The straight line connecting the centers of the stainless steel rods 1A, 1C, and 1E, which the carbon fiber bundle 4 passes through for the 1st, 3rd, and 5th times, and the straight line connecting the centers of the stainless steel rods 1B and 1D, which the carbon fiber bundle 4 passes through for the 2nd and 4th times, were arranged to be parallel to the horizontal plane. Furthermore, before and after the passage of the second to fourth stainless steel rods 1B to 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 first stainless steel rod 1A and the second stainless steel rod 1B and the straight line parallel to the direction of travel of the carbon fiber bundle passing between the second stainless steel rod 1B and the third stainless steel rod 1C was set to form an angle of 120 degrees). (2) Measurement of the spreading width of the carbon fiber bundle This was measured using the carbon fiber bundle used for the evaluation test described above. One unwinding roll with a carbon fiber bundle wound around it was prepared. The carbon fiber bundle 4 unwound from the unwinding roll 2 was zigzag-wound between stainless steel rods 1A, 1B, 1C, 1D, and 1E. The tension between the winding roll 3 and the unwinding roll 2 was set to 14.7 N (1500 gf), and the carbon fiber bundle 4 was wound from the unwinding roll 2 to the winding roll 3 at a speed of 3 m / min. During this process, the carbon fiber bundle 4 pulled out from the unwinding roll 2 was passed through five stainless steel rods 1A, 1B, 1C, 1D, and 1E. The fiber-spreading ability was evaluated by measuring the spread width (in cm) of the carbon fiber bundle 4 in a specific region 5 from after passing through stainless steel rod 1E until reaching the winding start point 3A. The spread width of the carbon fiber bundle was measured using a yarn running test device manufactured by Asano Machinery Works Co., Ltd. The obtained values ​​(fiber-spreading ability: cm) are shown in Tables 4-1 to 4-5.The spread width of the carbon fiber bundle measured under these conditions is preferably 2.0 cm or more.

[0081] <Evaluation Test for Fraying> (1) Explanation of the Evaluation Apparatus As shown in Figure 1, five stainless steel rods (1A, 1B, 1C, 1D, 1E) with a smooth surface and a diameter of 10 mm, whose temperature was adjusted to 25°C, were arranged parallel to each other so that the horizontal distance between adjacent stainless steel rods was 50 mm, and the carbon fiber bundle 4 passed through the stainless steel rods 1A, 1B, 1C, 1D, and 1E in a zigzag pattern while in contact with them. The horizontal direction is indicated by the arrow X-X' in the figure, and is parallel to the horizontal plane HL. The straight line connecting the centers of the stainless steel rods 1A, 1C, and 1E through which the carbon fiber bundle 4 passes for the 1st, 3rd, and 5th times, and the straight line connecting the centers of the stainless steel rods 1B and 1D through which the carbon fiber bundle 4 passes for the 2nd and 4th times, were arranged to be parallel to the horizontal plane. Furthermore, before and after the passage of the second to fourth stainless steel rods 1B to 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 first stainless steel rod 1A and the second stainless steel rod 1B and the straight line parallel to the direction of travel of the carbon fiber bundle passing between the second stainless steel rod 1B and the third stainless steel rod 1C was set to form an angle of 120 degrees). The unwinding roll 2 and the winding roll 3 were set to rotate in the direction of the arrows drawn near each roll. (2) Measurement of fluff weight The weight was measured using the carbon fiber bundle used for the evaluation test described above. One unwinding roll with a carbon fiber bundle wound around it was prepared. The carbon fiber bundle 4 unwound from the unwinding roll 2 was zigzagged 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 10-20 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 pieces with a load of 1 kgf applied, from the thickness direction of the fiber bundle (up and down direction in the illustration). In this example, since the carbon fiber bundle 4 is transported from the unwinding roll 2 to the winding roll 3, "upstream side" means upstream in the transport direction, i.e., the side of the unwinding roll 2. For winding from the unwinding roll 2, the unwinding tension was set to 9.8 N (1 kgf), and the carbon fiber bundle 4 was wound from the unwinding roll 2 to the winding roll 3 at a speed of 1 m / min for 5 minutes.During this time, the weight (in mg) of the lint adhering to the two urethane foam sheets was measured. The obtained values ​​(lint: mg) are shown in Tables 4-1 to 4-5. A smaller weight of lint indicates that lint production has been suppressed.

[0082] <Evaluation Test of Adhesion to Matrix Resin> (1) Evaluation of Adhesion to Epoxy Resin The interfacial adhesion strength between the fiber bundle of the present invention and the epoxy resin as the matrix resin was evaluated by the fragmentation method and measured by the following method. Carbon fiber filaments were removed from the carbon fiber bundle for the above evaluation test, fixed in a mold with tape, and then a mixture of 100 parts by weight of bisphenol A epoxy resin [jER828, manufactured by Mitsubishi Chemical Corporation], 89 parts by weight of 4-methylhexahydrophthalic anhydride [Ricacid MH-700, manufactured by Shin Nippon Rika Co., Ltd.], and 1 part by weight of tetraphenylphosphonium tetraphenylborate [manufactured by Tokyo Chemical Industry Co., Ltd.], which are the raw materials for the matrix resin, was poured into the mold and cured at 120°C for 5 hours to obtain an adhesion measurement sample (evaluation area: 30 mm, width: 6 mm, thickness: 2 mm) in which the carbon fiber filaments were embedded in the epoxy resin. Five measurement samples were prepared for each of the multiple production lots of carbon fiber filaments.

[0083] The sample was mounted on an autograph device (manufactured by Shimadzu Corporation) and pulled at a tensile speed of 0.2 mm / min, generating a tensile strain of 6.7% of the initial length (pulled until the length of the evaluation section reached 32 mm). The maximum tensile strength during this period was used to determine the breaking strength of the fiber (σ). ｆｕ Next, the samples were observed using a digital microscope (manufactured by Keyence Corporation), the number of fractures within the evaluation area was counted, and the average fracture length (length of the measurement area / number of fragments after fracture) was calculated. Fragmentation tests were performed on five samples, and the shear stress (τ) at any position on the interface between the fiber bundle and the epoxy resin as the matrix resin was measured. ｉ The (unit: MPa) was calculated using the following formula (3). The average values ​​of the calculated values ​​for the five samples are shown in Tables 4-1 to 4-5. ｉ = (3σ) ｆｕ d ｆ ) / (8l) (3) τｉ σ: Shear stress at any position on the interface between the fiber bundle and the matrix resin ｆｕ :Fiber breaking strength l:Average breaking length d ｆ : Diameter of carbon fiber filament The shear stress (τ ｉ A higher value indicates better adhesion to the matrix resin, and generally, 45 MPa or higher is preferred.

[0084] (2) Evaluation of Adhesion to Vinyl Ester Resin The interfacial adhesion strength between the fiber bundle of the present invention and the vinyl ester resin as the matrix resin was evaluated by the fragmentation method and measured by the following method. Carbon fiber filaments were removed from the carbon fiber bundle for the above evaluation test and fixed in a mold with tape. Then, a mixture of 80 parts by weight of dimethacrylate [Light Ester BP-2EM, manufactured by Kyoeisha Chemical Co., Ltd.], 20 parts by weight of phenoxyethyl methacrylate [Light Ester PO, manufactured by Kyoeisha Chemical Co., Ltd.], 1 part by weight of methyl ethyl ketone peroxide [Permec D, manufactured by NOF Corporation], and 0.1 parts by weight of cobalt naphthenate [manufactured by Tokyo Chemical Industry Co., Ltd.], which are raw materials for the matrix resin, was poured into the mold and cured at 120°C for 5 hours to obtain an adhesion test sample (evaluation area: 30 mm, width: 6 mm, thickness: 2 mm) in which the carbon fiber filaments were embedded in the vinyl ester resin. Five samples were prepared for each of the multiple production lots of carbon fiber filaments used for measurement.

[0085] Using the same method as described in "Evaluation of Adhesion to Epoxy Resin" above, the shear stress (τ) at any position on the interface between the fiber bundle and the vinyl ester resin as the matrix resin is measured. ｉ The shear stress (τ) was calculated (unit: MPa). The obtained values ​​are shown in Tables 4-1 to 4-5. ｉ A higher value indicates better adhesion to the matrix resin, and generally, 45 MPa or higher is preferred.

[0086] (3) Evaluation of Adhesion to Urethane Resin The interfacial adhesion strength between the fiber bundle of the present invention and the urethane resin as the matrix resin was evaluated by the fragmentation method and measured by the following method. Carbon fiber filaments were removed from the carbon fiber bundle used for the evaluation test, fixed in a mold with tape, and then a mixture of 100 parts by weight of pentaerythritol propylene oxide adduct [Sannix HD-402, manufactured by Sanyo Chemical Industries, Ltd.] and 198 parts by weight of polymeric MDI [Millionate MR-200, manufactured by Tosoh Corporation], which are raw materials for the matrix resin, was poured into the mold and cured at 120°C for 5 hours to obtain an adhesion test sample (evaluation area: 30 mm, width: 6 mm, thickness: 2 mm) in which the carbon fiber filaments were embedded in the urethane resin. Five samples were prepared for each of the multiple production lots of carbon fiber filaments.

[0087] Using the same method as described in "Evaluation of Adhesion to Epoxy Resin" above, the shear stress (τ) at any position on the interface between the fiber bundle and the urethane resin as the matrix resin is measured. ｉ The shear stress (τ) was calculated (unit: MPa). The obtained values ​​are shown in Tables 4-1 to 4-5. ｉ A higher value indicates better adhesion to the matrix resin, and generally, 45 MPa or higher is preferred.

[0088] <Evaluation of Storage Stability (5°C)> 30 g each of the fiber sizing agent solutions (X1) to (X21) and (X'1) to (X'7) prepared in the examples and comparative examples were placed in screw-cap bottles [50 mL (body diameter 35 mm x height 78 mm)] and stored at 5°C for 14 days. The median diameter (μm) of particles in the solution was measured before and after storage, and the storage stability at 5°C was calculated using the following formula (4) based on the measurement results. The median diameter was measured using a laser diffraction particle size distribution analyzer [LA-750, manufactured by Horiba, Ltd.]. Storage stability (%) = 100 × (median diameter after storage) / (median diameter before storage) (4) (Evaluation Criteria) A smaller storage stability (%) indicates higher emulsion stability. Storage stability was evaluated according to the following evaluation criteria. A: Less than 110% B: 110% or more, less than 115% C: 115% or more, less than 120% D: 120% or more

[0089] <Evaluation of Storage Stability (40°C)> The evaluation was carried out in the same manner as described above for "Evaluation of Storage Stability (5°C)," except that each fiber sizing agent solution was stored at 40°C for 14 days.

[0090] As shown in Tables 4-1 to 4-5, compared to the comparative examples, the fiber sizing agent compositions of the examples exhibit superior sizing and unfiber properties, can produce fiber bundles with less fluffing, and can provide high adhesion between the fiber bundles and the matrix resin. Furthermore, it was confirmed that the fiber sizing agent compositions of the examples have excellent storage stability.

[0091] The fiber sizing agent composition of the present invention can be used as a sizing agent for fibers such as glass fibers, carbon fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slug fibers. Furthermore, a prepreg can be obtained by treating fibers with the fiber sizing agent composition of the present invention to obtain a fiber bundle or fiber product as a reinforcing fiber, and using a thermoplastic resin or thermosetting resin as the matrix resin.

[0092] 1A, 1B, 1C, 1D, 1E...Stainless steel rods 2...Unwinding roll 3...Take-in roll 3A...Starting point of winding 4...Carbon fiber bundle 5...Specific region after passing stainless steel rod 1E and up to the starting point of winding 3A 5A...Region 10-20 cm upstream from the starting point of winding 3A HL...Horizontal plane

Claims

1. The material contains a polyester resin (A) with an acid value of 10.0 to 60.0 mg KOH / g, a bisphenol A type epoxy resin (B) that is solid at 20°C, a nonionic surfactant (C) having an aromatic ring in its molecule, and a polyoxyalkylene alkyl ether (D), wherein the polyester resin (A) is composed of a diol component (a1) and a dicarboxylic acid component (a2), and 5 to 100% by weight of the diol component (a1) is an alkylene oxide adduct (a11) of bisphenol A, the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the bisphenol A type epoxy resin (B) is 10.0 to 95.0% by weight, and the weight ratio of the polyester resin (A) to the total weight of the polyester resin (A) and the nonionic surfactant (C) is 50.0 to 85.0% by weight. A fiber sizing agent composition wherein the weight ratio of the bisphenol A type epoxy resin (B) to the total weight of the bisphenol A type epoxy resin (B) and the nonionic surfactant (C) is 20.0 to 95.0% by weight, and the weight ratio of the polyoxyalkylene alkyl ether (D) to the total weight of the polyoxyalkylene alkyl ether (D) and the nonionic surfactant (C) is 10.0 to 80.0% by weight.

2. The fiber sizing agent composition according to claim 1, wherein the number average molecular weight of the polyester resin (A) is 750 to 3000.

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

4. The fiber sizing agent composition according to claim 1, further comprising a bisphenol A type epoxy resin (E) that is liquid at 20°C.

5. The fiber sizing agent composition according to claim 1, further comprising epoxy (meth)acrylate (F).

6. The fiber sizing agent composition according to claim 5, wherein the weight ratio of the epoxy (meth)acrylate (F) to the total weight of the epoxy (meth)acrylate (F) and the nonionic surfactant (C) is 10.0 to 80.0% by weight.

7. The fiber sizing agent composition according to claim 1, further comprising a polyester resin (G) with an acid value of 5.0 mg KOH / g or less.

8. 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 fiber sizing agent composition for fibers described in any one of claims 1 to 7.

9. A textile product comprising the fiber bundle described in claim 8.

10. A composite material comprising the fiber bundle and matrix resin according to claim 8.

11. A composite material comprising the textile product and matrix resin according to claim 9.

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