Sizing agent composition for fibers, fiber bundle, textile product, and composite material

Abstract

A purpose of the present invention is to provide a sizing agent composition for fibers which has a fluffing-inhibiting effect and which, when emulsified in water, brings about excellent emulsion stability. This sizing agent composition for fibers comprises a novolak-type epoxy resin (A), an aromatic nonionic surfactant (B), and a polyester resin (C), wherein the polyester resin (C) comprises a constituent unit derived from an aromatic dicarboxylic acid (d) and a constituent unit derived from a diol (e), the content of aromatic moieties in the polyester resin (C) being 4.00-5.05 mmol / g with respect to the weight of the polyester resin (C), and the oxyethylene group content of the diol (e) being 9.50-15.00 mmol / g with respect to the weight of the diol (e).

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] In recent years, composite materials of matrix resins such as unsaturated polyester resins, phenolic resins, epoxy resins, and polypropylene resins with various fibers have been widely used in fields such as sports equipment, leisure goods, and aircraft. These composite materials utilize fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slug fibers. These fibers are treated with sizing agents during the processing steps to create the composite materials (see, for example, Patent Document 1).

[0003] International Publication No. 2013 / 146024

[0004] In the sizing process, which involves applying a sizing agent to fibers to form fiber bundles, it is necessary for the sizing solution (sizing agent) to penetrate between the fibers of the fiber bundle. However, with the sizing agent described in Patent Document 1, when the number of fibers in the fiber bundle is large, the sizing solution (sizing agent) does not penetrate sufficiently between the fibers, resulting in a problem in that the fluffing of the fiber bundle cannot be adequately suppressed. Furthermore, there is a problem in that the emulsification stability is insufficient when it is made into an aqueous emulsion.

[0005] The present invention aims to provide a fiber bundling agent composition that has an effect of suppressing fluffing of fiber bundles and exhibits excellent emulsification stability when made into an aqueous emulsion.

[0006] The present inventors have diligently studied to solve these problems and have arrived at the present invention. Specifically, the present invention comprises a novolac-type epoxy resin (A), an aromatic nonionic surfactant (B), and a polyester resin (C), wherein the polyester resin (C) has constituent units derived from an aromatic dicarboxylic acid (d) and constituent units derived from a diol (e), the content of the aromatic portion of the polyester resin (C) based on the weight of the polyester resin (C) is 4.00 to 5.05 mmol / g, and the oxyethylene group content of the diol (e) based on the weight of the diol (e) is 9.50 to 15.00 mmol / g; 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 bundle composition; a textile product containing the fiber bundle; and a composite material containing the fiber bundle or the textile product and a matrix resin.

[0007] The fiber sizing agent composition of the present invention has an effect of suppressing fluffing of fiber bundles and exhibits excellent emulsification stability when made into an aqueous emulsion.

[0008] Figure 1 is a schematic side view showing the evaluation apparatus and the arrangement of carbon fiber bundles used in the evaluation of fluffiness.

[0009] The present invention will be described in detail below. The fiber sizing agent composition of the present invention contains a novolac-type epoxy resin (A). The epoxy group concentration of the novolac-type epoxy resin (A) is more preferably 4 to 7 meq / g, and even more preferably 5 to 6 meq / g, from the viewpoint of sizing properties. In the present invention, the epoxy group concentration is a value obtained from the epoxy equivalent measured by the method specified in JIS K 7236:2009. Specifically, it is a value obtained by the following calculation formula: Epoxy group concentration (meq / g) = 1000 ÷ epoxy equivalent (g / eq)

[0010] Examples of novolac-type epoxy resins (A) include bisphenol A novolac-type epoxy resin, phenol novolac-type epoxy resin, and cresol novolac-type epoxy resin. Novolac-type epoxy resin (A) may be used alone or in combination of two or more types.

[0011] A commercially available product may be used as the novolac-type epoxy resin (A). Examples of commercially available bisphenol A novolac-type epoxy resins include "157S70" manufactured by Mitsubishi Chemical Corporation.

[0012] Commercially available phenol novolac type epoxy resins include "jER154" from Mitsubishi Chemical Corporation, "EPICLON N-740" and "EPICLON N-770" from DIC Corporation, "YDPN-638" from Nippon Steel Chemical & Material Co., Ltd., and "EPPN-201" from Nippon Kayaku Co., Ltd.

[0013] Commercially available cresol novolac type epoxy resins include "YDCN-700-7" manufactured by Nippon Steel Chemical & Material Co., Ltd., and "EOCN-103S" and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.

[0014] Of the above novolac-type epoxy resins (A), phenol novolac-type epoxy resins and cresol novolac-type epoxy resins are preferred from the viewpoint of bundling properties.

[0015] The content of the novolac-type epoxy resin (A) is preferably 10 to 60% by weight, and more preferably 20 to 50% by weight, based on the total weight of the novolac-type epoxy resin (A), aromatic nonionic surfactant (B), and polyester resin (C), from the viewpoint of cohesiveness.

[0016] The fiber sizing agent composition of the present invention may contain an epoxy resin (A') other than the novolac-type epoxy resin (A). Examples of the epoxy resin (A') include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, and glycidylamine-type epoxy resin.

[0017] Examples of commercially available bisphenol A type epoxy resins include "RE310S" and "RE410S" manufactured by Nippon Kayaku Co., Ltd., "jER828" and "jER825" manufactured by Mitsubishi Chemical Corporation, and "Epiclon 1050" manufactured by DIC Corporation.

[0018] Examples of commercially available bisphenol F type epoxy resins include "RE303S", "RE303S", "RE304S", "RE403S", and "RE404S" manufactured by Nippon Kayaku Co., Ltd., and "jER807" and "jER1750" manufactured by Mitsubishi Chemical Corporation.

[0019] Examples of commercially available bisphenol AF type epoxy resins include "ZX-1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. Examples of commercially available naphthalene type epoxy resins include "HP-4032", "HP-4032D", and "HP-4032SS" manufactured by DIC Corporation. Examples of commercially available glycidyl ester type epoxy resins include "EX-721" manufactured by Nagase ChemteX Co., Ltd. Examples of commercially available glycidylamine type epoxy resins include "jER630" and "jER630LSD" manufactured by Mitsubishi Chemical Corporation.

[0020] The fiber sizing agent composition of the present invention contains an aromatic nonionic surfactant (B). Examples of aromatic nonionic surfactants (B) include compounds obtained by adding an alkylene oxide (hereinafter sometimes abbreviated as AO) to a compound having an aromatic ring. Specifically, examples include compounds obtained by adding AO to alkyl (alkyl group with 1 to 18 carbon atoms) phenol, compounds obtained by adding AO to styrene (1 to 10 moles) phenol, and compounds obtained by adding AO to styrene (1 to 10 moles) cumylphenol. Examples of AO include those with 2 to 4 carbon atoms, such as ethylene oxide (hereinafter sometimes abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter sometimes abbreviated as PO), 1,2-, 1,3-, 2,3- or 1,4-butylene oxide (hereinafter sometimes abbreviated as BO), and combinations of two or more of these. The average number of moles of AO added is preferably 5 to 65. If multiple types of AO are included, the sum of the average number of moles added for each type of AO will be the average number of moles added for all AOs.

[0021] As the aromatic nonionic surfactant (B), commercially available products may be used. Examples of commercially available aromatic nonionic surfactants include "Soprophor 796 / P", "Soprophor TSP / 724", and "Soprophor TSP / 461" manufactured by Science Co., Ltd. (all are PO and / or EO adducts of styrene-phenol). The aromatic nonionic surfactant (B) is preferably a compound in which AO is directly added to styrene-phenol (1 to 10 moles), and more preferably a PO and / or EO adduct of styrene-phenol (1 to 10 moles). The aromatic nonionic surfactant (B) may be used alone or in combination of two or more types.

[0022] As the aromatic nonionic surfactant (B), one with an HLB (Hydrophile-Lipophile Balance) value of 11 to 14 is preferred from the viewpoint of suppressing fluffing. The HLB value of the aromatic nonionic surfactant (B) is more preferably 11.5 to 13.7.

[0023] In the present invention, the HLB value is a numerical value representing the balance between hydrophilicity and lipophilicity. In the case of a single compound, it is determined from the following formula (1) (see the Oda method described in "Synthesis and Applications of Surfactants", page 501, published by Makino Shoten in 1957; "Introduction to Surfactants", pages 212-213, published by Sanyo Chemical Industries, Ltd. in 2007, etc.). HLB value = 10 × (inorganicity / organicity) (1) In formula (1), "inorganicity / organicity" represents the ratio of the inorganic value and the organic value of the compound, and this ratio can be calculated from the values described in the above-mentioned literature. Regarding the organic value and the inorganic value, as the organic value, it is determined as 20 per carbon atom, and as the inorganic value, the value in the table described on page 213 of the above-mentioned "Introduction to Surfactants" (the "numerical value" in the inorganic group or the "inorganic" numerical value in the organic-inorganic group) is used for calculation. As a calculation example, -CH ３ group: organic value 20, inorganic value 0 -CH ２ - group: organic value 20, inorganic value 0 =CH ２ group: 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 can be mentioned. For example, in the case of dodecanol {CH ３ (CH ２ ) １１ OH}, it is as follows. HLB value = 10 × (100) / (20 × 11 + 20) = 4.17

[0024] The HLB value of the aromatic nonionic surfactant (B) can be adjusted by adjusting the type and blending amount of the surfactant used. When the aromatic nonionic surfactant (B) contains two or more surfactants, its HLB value can be calculated by weighted-averaging the HLB values of each surfactant.

[0025] The content of the aromatic nonionic surfactant (B) is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, based on the total weight of the novolak type epoxy resin (A), the aromatic nonionic surfactant (B), and the polyester resin (C) from the viewpoint of the effect of suppressing hairiness.

[0026] The fiber bundling agent composition of the present invention contains a polyester resin (C). The content ratio of the aromatic portion of the polyester resin (C) based on the weight of the polyester resin (C) (hereinafter also referred to as "aromatic concentration") is 4.00 to 5.05 mmol / g, preferably 4.30 to 4.80 mmol / g, and more preferably 4.30 to 4.60 mmol / g. When the aromatic concentration is 4.00 to 5.05 mmol / g, the emulsifying stability of the fiber bundling agent composition of the present invention in the form of an aqueous emulsion is excellent. If the aromatic concentration is less than 4.00 mmol / g or exceeds 5.05 mmol / g, the emulsifying stability of the fiber bundling agent composition of the present invention in the form of an aqueous emulsion becomes poor. The above-mentioned aromatic portion in the present invention means an aromatic ring. The aromatic ring may be a monocyclic one (such as a benzene ring) or a condensed polycyclic one (such as a naphthalene ring, an anthracene ring, etc.), but a benzene ring is preferred. The aromatic concentration of the polyester resin (C) is the amount of substance (mmol) of the aromatic ring contained per 1 g of the polyester resin (C) and can be determined by the following formula. Aromatic concentration of polyester resin (C) (mmol / g) = [N Ａｒ (mol) / M ｒｅｓｉｎ (g)] × 1000 (In the formula, N Ａｒ is the total number of moles of the aromatic rings constituting the polyester resin (C). For each constituent monomer i, the number of aromatic rings contained in one molecule of the monomer is a ｉ (pieces / molecule), the molecular weight (formula weight) of the monomer is MW ｉ (g / mol), and the amount of use (mass) of the monomer is m ｉ (g), and it is determined by the following formula. N Ａｒ = Σ ｉ a ｉ × (m ｉ / MW ｉ ). Also, M ｒｅｓｉｎis the mass (g) of the polyester resin (C) obtained after the condensation reaction, and is determined by the following formula by subtracting the mass of water (condensation elimination amount) condensed and eliminated from the total usage amount (mass) of the constituent monomers. M ｒｅｓｉｎ = (Σ ｉ m ｉ ) - (condensation elimination amount). The condensation elimination amount is {the smaller of the total number of moles of carboxyl groups (COOH groups) and the total number of moles of hydroxyl groups (OH groups) contained in the raw materials (constituent monomers)} × (molecular weight of water).) For example, in the case of the polyester resin (C-1) produced using 206.9 g of terephthalic acid, 454.1 g of Newpol BP - 20 (an EO adduct of bisphenol A with 2 moles of EO added per 1 mole of bisphenol A), and 383.3 g of an EO 60 - mole adduct of bisphenol A as constituent monomers, the aromatic concentration is 4.38 mmol / g by the following calculation. Aromatic concentration (mmol / g) of polyester resin (C - 1) = { (1×206.9 / 166.1) + (2×454.1 / 316.4) + (2×383.3 / 2868)} ÷ { (206.9 + 454.1 + 383.3) - 44.8} × 1000 = 4.39. However, the condensation elimination amount is 44.8 g. The aromatic concentration of the polyester resin (C) can be set to a desired value by appropriately selecting the types and usage amounts of the constituent monomers.

[0027] The polyester resin (C) has a structural unit derived from an aromatic dicarboxylic acid (d) and a structural unit derived from a diol (e).

[0028] The constituent units derived from aromatic dicarboxylic acid (d) are formed by using aromatic dicarboxylic acid (d) or its derivatives as constituent monomers and reacting them with other constituent monomers. Examples of aromatic dicarboxylic acid (d) include aromatic dicarboxylic acids having 8 to 14 carbon atoms (terephthalic acid, isophthalic acid, orthophthalic acid, phenylmalonic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, 2,2'- and 4,4'-biphenyldicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate, and potassium 5-sulfoisophthalate, etc.). Among these, phthalic acid (orthophthalic acid), terephthalic acid, and isophthalic acid are preferred from the viewpoint of convergence. Examples of derivatives of aromatic dicarboxylic acid (d) include anhydrides of aromatic dicarboxylic acid (d), alkyl esters of aromatic dicarboxylic acid (d), and chlorides of aromatic dicarboxylic acid (d).

[0029] The constituent units derived from diol(e) are formed by using diol(e) as a constituent monomer and reacting it with other constituent monomers.

[0030] Diol(e) is a compound having two hydroxyl groups in one molecule, and may be used alone or in combination of two or more types. Diol(e) is an oxyethylene group (-CH ２ CH ２ It contains one or more diol compounds having an O-.

[0031] The oxyethylene group content of diol(e) based on its weight is 9.50 to 15.00 mmol / g, preferably 9.90 to 15.00 mmol / g. The oxyethylene group content of diol(e) can be determined from the molar ratio of the raw materials used in the synthesis of the compound. In the case of compounds with a molecular weight distribution, such as polyethylene glycol, it can be determined from the hydroxyl value measured by the method specified in JIS K 1557-1:2007. In this case, first, the molecular weight of diol(e) is calculated from the hydroxyl value of diol(e). Molecular weight of diol(e) (g / mol) = 56.1 (g / mol) × 1000 × 2 / hydroxyl value of diol(e) (mgKOH / g) (In the above formula, the molecular weight of potassium hydroxide is assumed to be 56.1 g / mol.) Next, in the case of polyethylene glycol, the number of oxyethylene groups added in one molecule is calculated according to the following formula. The number of oxyethylene groups added = [Molecular weight of diol(e) (g / mol) - 18 (g / mol)] / Molecular weight of oxyethylene group (g / mol) If diol(e) is an EO adduct other than polyethylene glycol, the number of oxyethylene groups added in one molecule of diol(e) is calculated from the difference in molecular weight between diol(e) and the starting material (compound before EO addition). Number of oxyethylene groups added = [Molecular weight of diol(e) (g / mol) - Molecular weight of the starting material of diol(e) (g / mol)] / Molecular weight of oxyethylene group (g / mol) The oxyethylene group content is calculated using the following formula: Oxyethylene group content (mol / g) = [Number of oxyethylene groups added / Molecular weight of diol(e) (g / mol)] × 1000

[0032] The oxyethylene group content of a diol compound having both an oxyethylene group and other oxyalkylene groups such as an oxypropylene group can be calculated, for example, based on the molecular weight of the diol compound calculated from its hydroxyl value and the composition ratio of the oxyethylene group to other oxyalkylene groups determined by nuclear magnetic resonance spectroscopy (NMR) or the like. Specifically, the molecular weight of the diol compound is calculated from the hydroxyl value measured by the method specified in JIS K 1557-1:2007, and the amount of oxyethylene groups contained per gram of the diol compound (mol / g) is calculated based on the total amount of oxyalkylene groups added, obtained from the difference between the molecular weight of the diol compound and the molecular weight of the starting material (the compound before the addition of EO or AO), and the mole fraction of the oxyethylene group determined by NMR or the like.

[0033] When two or more diol compounds are used in combination, the oxyethylene group content of diol(e) is obtained by the following formula: Oxyethylene group content of diol(e) (mol / g) = Total number of moles of oxyethylene groups in all diol compounds (mol / g) / Total weight of all diol compounds (g) (For diol compounds that do not contain oxyethylene groups, their oxyethylene content is set to 0 mmol / g.)

[0034] The diol (e) preferably includes a diol (e1) having a bisphenol skeleton and a polyoxyalkylene chain. The bisphenol skeleton refers to a divalent residue obtained by removing two hydroxyl groups from a bisphenol compound (such as bisphenol A, bisphenol F, and bisphenol S). Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, a poly(oxyethylene / oxypropylene) chain, and a polyoxybutylene chain, with polyoxyethylene and / or polyoxypropylene chains being more preferred from the viewpoint of flocculation. The diol (e1) may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. It is also preferable to use one or more types that contain a bisphenol skeleton and an oxyethylene group. The total number of moles of oxyalkylene groups added per mole of diol (e1) is preferably 2 to 200, and more preferably 2 to 120, from the viewpoint of reducing fluffiness. Furthermore, when two or more types of diol (e1) are used in combination, it is preferable to use a combination of diol (e1) with a total number of added moles of oxyalkylene groups of 2 to 6 and a combination of diol (e1) with a total number of added moles of 2 to 120, and more preferably a combination of diol (e1) with a total number of added moles of 2 to 4 and a combination of diol (e1) with a total number of added moles of 30 to 120. The number of polyoxyalkylene chains in diol (e1) may be one, but two is preferred. The two polyoxyalkylene chains may be of different types and have different numbers of added moles of oxyalkylene groups, or they may be the same, but it is preferable that they be the same. When diol (e1) has two polyoxyalkylene chains, both have the same number of added moles of oxyalkylene groups, preferably 1 to 100, and more preferably 1 to 60. Diol (e1) may be commercially available or manufactured. There are no particular restrictions on the method of manufacturing diol (e1), and it can be manufactured, for example, by the method described in Manufacturing Example 1 of this application.

[0035] In addition to the aforementioned diol (e1), diol (e) may also include aliphatic alkanediols, AO adducts of aliphatic alkanediols, and AO adducts of primary amines.

[0036] The aliphatic alkanediol is preferably a diol having 2 to 16 carbon atoms, and specifically includes ethylene 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.

[0037] Examples of AO adducts of the aliphatic alkanediol include compounds obtained by adding a carbon atom having 2 to 4 atoms to the aliphatic alkanediol. Compounds with two or more carbon atoms added are also acceptable. The number of moles of added carbon atom per molecule of aliphatic alkanediol is preferably 1 to 120 moles. EO adducts of aliphatic alkanediols are preferred. Examples of EO adducts of aliphatic alkanediols include PEG-1000, PEG-2000, and PEG-4000S (all manufactured by Sanyo Chemical Industries, Ltd.).

[0038] Examples of primary amines in the AO adducts of primary amines include primary amines having 1 to 22 carbon atoms, such as methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine, and dodecylamine. Examples of AO adducts of primary amines include compounds obtained by adding an AO having 2 to 4 carbon atoms to the primary amine.

[0039] Among the above, EO adducts of aliphatic alkanediols are preferred, and polyethylene glycol is more preferred.

[0040] The oxyethylene group content of polyester resin (C) based on weight is preferably 9.90 to 15.00 mmol / g, and more preferably 9.90 to 13.5 mmol / g. The present invention also provides a fiber sizing agent composition comprising a novolac-type epoxy resin (A), an aromatic nonionic surfactant (B), and a polyester resin (C), wherein the polyester resin (C) has constituent units derived from an aromatic dicarboxylic acid (d) and constituent units derived from a diol (e), the aromatic portion content of polyester resin (C) based on weight is 4.00 to 5.05 mmol / g, and the oxyethylene group content of polyester resin (C) based on weight is 9.50 to 13.5 mmol / g. Details of the components and preferred embodiments of this fiber sizing agent composition are as described above.

[0041] The polyester resin (C) preferably has a number average molecular weight (hereinafter sometimes abbreviated as Mn) of 1,000 to 50,000, more preferably 1,000 to 30,000, even more preferably 1,500 to 5,000, and particularly preferably 2,500 to 5,000. If Mn is 1,000 or more, it has sufficient cohesiveness, and if it is 50,000 or less, it has high affinity for water and excellent emulsion stability. The Mn values ​​used herein are measured using GPC under the conditions described in the examples.

[0042] The HLB value of polyester resin (C) is preferably 5.0 or higher, more preferably 6.0 or higher, even more preferably 8.0 or higher, preferably 16.0 or lower, more preferably 15.0 or lower, and even more preferably 13.0 or lower. The HLB value is preferably 5.0 to 16.0, more preferably 6.0 to 15.0, even more preferably 8.0 to 13.0, and particularly preferably 9.0 to 11.0. The HLB value of polyester resin (C) is the value obtained by the calculation method described above.

[0043] Polyester resin (C) can be produced by known manufacturing methods. For example, an aromatic dicarboxylic acid (d) (or its derivative) and a diol (e) are charged in a predetermined molar ratio, and the water is removed by distillation while stirring at a reaction temperature of 100 to 250°C and a pressure of -0.1 to 1.2 MPa. The charging molar ratio of aromatic dicarboxylic acid (d) and diol (e) [number of moles of aromatic dicarboxylic acid (d) / number of moles of diol (e)] is preferably 0.7 to 1.5, and more preferably 0.8 to 1.25, from the viewpoint of keeping Mn within the above range and improving the convergence properties.

[0044] When producing polyester resin (C), it is preferable to add 0.05 to 0.5% by weight of the catalyst based on the weight of the polyester resin (C). Examples of catalysts include p-toluenesulfonic acid, dibutyltin oxide, tetraisopropoxytitanate, and potassium titanate oxalate, with tetraisopropoxytitanate, p-toluenesulfonic acid, and potassium titanate oxalate being preferred from the viewpoint of reactivity and environmental impact.

[0045] The content of polyester resin (C) is preferably 30 to 70% by weight, and more preferably 40 to 60% by weight, based on the total weight of novolac-type epoxy resin (A), aromatic nonionic surfactant (B), and polyester resin (C) from the viewpoint of emulsification stability.

[0046] The fiber sizing agent composition of the present invention may further contain an aliphatic nonionic surfactant (D) as a component other than the novolac-type epoxy resin (A), aromatic nonionic surfactant (B), and polyester resin (C). Including the aliphatic nonionic surfactant (D) can further improve the fluff suppression effect.

[0047] Examples of aliphatic nonionic surfactants (D) include AO adducts of aliphatic monoalcohols having 8 to 18 carbon atoms, AO adducts of higher fatty acids (having 12 to 24 carbon atoms), polyalkylene glycols obtained by adding AO (excluding EO) to glycols and reacting them with higher fatty acids, esterified products obtained by reacting polyhydric alcohols (polyhydric alcohols of 2 or more carbon atoms such as ethylene glycol, propylene glycol, glycerin, and sorbitan) with higher fatty acids and adding AO (excluding EO), and polyhydric alcohol (3 to 60 carbon atoms) type nonionic surfactants [such as fatty acid (3 to 60 carbon atoms) esters of polyhydric alcohols of 2 or more carbon atoms]. Aliphatic nonionic surfactants (D) may be used alone or in combination of two or more.

[0048] As the aliphatic nonionic surfactant (D), from the viewpoint of suppressing fluffing, an AO adduct of an aliphatic monoalcohol having 8 to 18 carbon atoms is preferred, and an aliphatic alkylene oxide adduct represented by the following general formula (2) (hereinafter also referred to as "compound of general formula (2)") is more preferred. １ O (AO) ｍ H (2) (R in general formula (2)) １ is an aliphatic hydrocarbon group having 8 to 11 carbon atoms and possessing three or more methyl groups. AO is an alkylene oxy group having 2 to 4 carbon atoms. m represents the average number of moles of AO added, ranging from 1 to 10. R １ The number of carbon atoms is preferably 9 or more, from the viewpoint of further suppressing fluffing of the fiber bundle.

[0049] The aliphatic hydrocarbon group having 8 to 11 carbon atoms may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups having 8 to 11 carbon atoms include aliphatic hydrocarbon groups having three methyl groups, aliphatic hydrocarbon groups having four methyl groups, and aliphatic hydrocarbon groups having five or more methyl groups. In expressions such as "aliphatic hydrocarbon group having three methyl groups," the term "methyl group" refers to the -CH group contained in the aliphatic hydrocarbon group. ３ This means, for example, a 1-ethylbutyl group [CH ３ (CH ２ ) ２ (CH ３ CH２ )CH-] has -CH at the ends of the ethyl group and the butyl group, respectively. ３ Because of the presence of these groups, it has a total of two methyl groups.

[0050] When the fiber sizing agent composition of the present invention contains an aliphatic nonionic surfactant (D), R in all compounds of general formula (2) １ The methyl group inside (-CH ３ The number of R(R) per molecule of compound of general formula (2) is preferably 3.5 or more. When it is 3.5 or more, the fluffing of the fiber bundle can be further suppressed when the fiber sizing agent composition is used. In addition, the impregnation of the fiber sizing agent composition into the matrix resin can be improved. １ The number of methyl groups in the compound is preferably 5 or less. １ The number of methyl groups inside may be a decimal. １ The number of methyl groups in the compound is, for example, the number of alcohols (R) used as raw materials when synthesizing the compound of general formula (2). １ Regarding -OH), １ The compound can be calculated by performing 1H-NMR measurement and gas chromatography analysis. There are no particular restrictions on the method of producing the compound of general formula (2), and it can be produced, for example, by the method described in the production example of this application. Commercially available products may also be used.

[0051] In general formula (2), (AO) is an alkylene oxy group (oxyalkylene group) having 2 to 4 carbon atoms, specifically an oxyethylene group, a 1,2- or 1,3-oxypropylene group, and a 1,2-, 1,3-, 2,3- or 1,4-oxybutylene group. Of these, the oxyethylene group is preferred. When a compound of general formula (2) has two or more (AO) groups (m is 2 or more), the m (AO) groups may be the same or different.

[0052] Specific examples of compounds of general formula (2) include EO adducts, PO adducts, BO adducts of aliphatic alcohols having 8 to 11 carbon atoms, EO and PO adducts (random adducts, adducts of EO blocks and PO blocks, and adducts of PO blocks and EO blocks), and EO and BO adducts (random adducts, adducts of EO blocks and BO blocks, and adducts of BO blocks and EO blocks). Of these, EO adducts of aliphatic alcohols having 8 to 11 carbon atoms are preferred, and EO adducts of decanol are more preferred from the viewpoint of suppressing fluffing.

[0053] When the fiber sizing agent composition of the present invention contains an aliphatic nonionic surfactant (D), its content is preferably 1 to 10% by weight or more, and more preferably 2 to 8% by weight or more, based on the weight of the solid content in the fiber sizing agent composition, from the viewpoint of the fluff suppression effect. In the present invention, the solid content refers to a non-volatile component, and more specifically, it is the residue after heating and drying a sample (e.g., 1 g) in a glass petri dish without a lid in a circulating air dryer at 130°C for 45 minutes.

[0054] The fiber sizing agent composition of the present invention may further contain, in addition to the above-mentioned components, a resin other than epoxy resin (E), an aromatic nonionic surfactant (B), a surfactant other than aliphatic nonionic surfactant (D) (F), and an additive (G).

[0055] Examples of resin (E) include vinyl ester resin and unsaturated polyester resin. Those resins described in Japanese Patent Publication No. 2022-169361 can be used.

[0056] Examples of surfactants (F) include cationic surfactants, anionic surfactants, and amphoteric surfactants. Examples of cationic surfactants include quaternary ammonium salts [tetraalkyl (1-30 carbon atoms) ammonium salts (lauryltrimethylammonium chloride, didecyldimethylammonium chloride, and stearyltrimethylammonium bromide, etc.); polyoxyalkylene (2-4 carbon atoms) trialkyl (1-30 carbon atoms) ammonium salts (polyoxyethylenetrimethylammonium chloride, etc.)] and amine salts [inorganic or organic acid salts of aliphatic higher (12-60 carbon atoms) amines (laurylamine, stearylamine, etc.); and inorganic or organic acid salts of EO adducts of aliphatic amines (1-30 carbon atoms), etc.].

[0057] Examples of anionic surfactants include carboxylic acids (saturated or unsaturated fatty acids with 8 to 22 carbon atoms) or their salts (salts of sodium, potassium, ammonium, alkanolamines, etc.), sulfates of higher alcohols (8 to 18 carbon atoms), sulfates of higher alkyl ethers [sulfates of EO (1 to 10 moles) adducts of aliphatic alcohols with 8 to 18 carbon atoms, sulfates of AO adducts of alkylphenols, sulfates of AO adducts of arylalkylphenols, etc.], sulfonates [alkyl (1 to 20 carbon atoms) benzenesulfonates, alkyl (1 to 20 carbon atoms) naphthalenesulfonates, dialkyl (1 to 20 carbon atoms) sulfosuccinates, and α-olefin (12 to 18 carbon atoms) sulfonates, etc.], and phosphate esters [phosphates of higher alcohols (8 to 60 carbon atoms) and phosphates of EO adducts of higher alcohols (8 to 60 carbon atoms), etc.].

[0058] Examples of amphoteric surfactants include amino acid-type amphoteric surfactants [such as sodium propionate of higher alkylamines (12-18 carbon atoms)], betaine-type amphoteric surfactants [such as alkyl (12-18 carbon atoms) dimethyl betaine], sulfate-type amphoteric surfactants [such as sodium sulfate salts of higher alkyl (8-18 carbon atoms) amines and sodium hydroxyethylimidazoline sulfate], sulfonate-type amphoteric surfactants [such as pentadecyl sulfotaurine and imidazoline sulfonic acid], and phosphate-type amphoteric surfactants [phosphate esteramine salts of glycerin-based higher fatty acid (8-22 carbon atoms) esters].

[0059] As the surfactant (F), anionic surfactants are preferred, and sulfate ester salts of alkylphenol AO adducts, sulfate ester salts of arylalkylphenol AO adducts, and mixtures thereof are more preferred.

[0060] Additives (G) include smoothing agents, preservatives, and antioxidants. Examples of smoothing agents include waxes (polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, modified polyethylene, and modified polypropylene, etc.), higher fatty acid alkyl (1-24 carbon atoms) esters (methyl stearate, ethyl stearate, propru stearate, butyl stearate, octyl stearate, and stearyl stearate, etc.), higher fatty acids (myristic acid, palmitic acid, and stearic acid, etc.), natural oils and fats (coconut oil, beef tallow, olive oil, and rapeseed oil, etc.), and liquid paraffin. Examples of preservatives include benzoic acids, salicylic acids, sorbic acids, and 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.).

[0061] The total content of resins other than epoxy resin (E), surfactants (F), and additives (G) is preferably 0 to 60% by weight, and more preferably 0 to 20% by weight, based on the weight of solids contained in the fiber sizing agent composition.

[0062] There are no particular limitations on the method for producing the fiber sizing agent composition of the present invention, but for example, one method involves adding a novolac-type epoxy resin (A), an aromatic nonionic surfactant (B), and a polyester resin (C), and optionally an epoxy resin (A'), an aliphatic nonionic surfactant (D), a resin (E), a surfactant (F), and an additive (G) to a mixing container, and stirring at preferably 20 to 150°C, more preferably 50 to 120°C, until homogeneous. There are no particular limitations on the order in which the components constituting the composition are added.

[0063] 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.

[0064] The epoxy group concentration of the solid content in the fiber sizing agent composition of the present invention is preferably 1.5 meq / g or higher. By having an epoxy group concentration of 1.5 meq / g or higher, a fiber sizing agent composition with excellent sizing properties can be provided. From the viewpoint of sizing properties, the epoxy group concentration is preferably 1.6 to 3.0 meq / g, and more preferably 1.7 to 2.5 meq / g. The epoxy group concentration can be adjusted by adjusting the type and amount of novolac-type epoxy resin (A). In the present invention, the epoxy group concentration can be determined by the method described above.

[0065] The fiber sizing agent composition of the present invention preferably contains an aqueous medium so as to be in the form of an aqueous solution or aqueous emulsion. The inclusion of an aqueous medium makes it easy to adjust the amount of solids contained in the fiber sizing agent composition to adhere to the fibers, thereby enabling the production of fiber bundles with even greater strength in the molded composite material. As the aqueous medium, known aqueous media can be used, 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 atoms) ethers, dimethylformamide, and alkyl acetate esters having 3 to 5 carbon atoms (methyl acetate and ethyl acetate, etc.)]. Two or more of these may be used in combination. Of these, from the viewpoint of safety, water and a mixed solvent of hydrophilic organic solvent and water are preferred, and water is more preferred.

[0066] From the viewpoint of cost and other factors, the fiber sizing agent composition of the present invention is preferably highly concentrated during distribution and at a low concentration during the manufacture of fiber bundles. That is, distributing at a high concentration reduces transportation and storage costs, and treating the fibers at a low concentration makes it easier to adjust the amount of sizing agent attached during the manufacture of fiber bundles. The concentration of the aqueous solution or emulsion (weight ratio of solids in the fiber sizing agent composition) can be adjusted as appropriate depending on the purpose. For example, from the viewpoint of storage stability, the concentration is preferably 20 to 80% by weight, and more preferably 30 to 70% by weight. On the other hand, from the viewpoint of ensuring an appropriate amount of sizing agent is attached during the manufacture of fiber bundles, the concentration is preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight.

[0067] Fibers to which the fiber sizing agent composition of the present invention can be applied include inorganic fibers (carbon fibers, glass fibers, ceramic fibers, metal fibers, mineral fibers, and slug fibers, etc.) and organic fibers (aramid fibers, etc.). From the viewpoint of the strength of the fiber sizing agent composition and the molded article of the composite material using the fiber, carbon fibers are preferred among these.

[0068] 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 fiber sizing agent composition of the present invention.

[0069] The present invention provides a method for producing fiber bundles, which involves 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 or fiber sizing agent solution (a dispersion of the fiber sizing agent composition) of the present invention to obtain a fiber bundle. The fiber bundle of the present invention preferably consists of 3,000 to 50,000 fibers bundled together. The fiber sizing agent composition or fiber sizing agent solution of the present invention can sufficiently suppress fluffing even when the number of fibers in the fiber bundle is large (20,000 or more).

[0070] Methods for processing fibers include spraying and immersion. The amount of solid content (by weight) adhering to the fibers from the fiber sizing agent is preferably 0.05 to 5% by weight, and more preferably 0.2 to 2.5% by weight, based on the weight of the fibers. Within this range, the strength of the molded article (which may be referred to as a composite material below) can be further improved. The amount of solid content adhering to the fibers can be adjusted by changing the number of spraying or immersion cycles, or by adjusting the concentration of solid content in the fiber sizing agent.

[0071] 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.

[0072] The composite material of the present invention comprises a fiber bundle and / or a fiber product of the present invention and a matrix resin.

[0073] Examples of matrix resins include thermoplastic resins (such as polypropylene, polyamide, polyethylene terephthalate, polycarbonate, and polyphenylene sulfide) and thermosetting resins [similar to epoxy resins, unsaturated polyester resins, and vinyl ester resins used as resin (D), as well as phenolic resins (such as those described in Japanese Patent No. 3723462)].

[0074] The composite material of the present invention may contain a catalyst as needed. When the matrix resin is an epoxy resin, known catalysts (such as those described in Japanese Patent Application Publication No. 2005-213337) for epoxy resin curing catalysts and curing accelerators can be used. When the matrix resin is the unsaturated polyester resin or vinyl ester resin, examples of catalysts include peroxides (such as benzoyl peroxide, t-butyl perbenzoate, t-butylcumyl peroxide, methyl ethyl ketone peroxide, 1,1-di(t-butylperoxy)butane, di(4-t-butylcyclohexyl)peroxydicarbonate, etc.) and azo compounds (such as azobisisovaleronitrile).

[0075] In the composite material of the present invention, the weight ratio of matrix resin to fiber bundle (matrix resin / fiber bundle) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 70 / 30, and particularly preferably 30 / 70 to 60 / 40, from the viewpoint of the strength of the molded composite article. If the composite material contains a catalyst, the catalyst content is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 1 to 3 parts by weight per 100 parts by weight of matrix resin, from the viewpoint of the strength of the molded composite article.

[0076] The composite materials of the present invention include prepregs, molded articles, and the like. Prepregs can be produced, for example, by impregnating fiber bundles and / or textile products with a matrix resin that has been thermally 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 using a solvent, it is preferable to further dry the material to remove the solvent.

[0077] If the matrix resin is a thermoplastic resin, the prepreg can be heat-molded and solidified at room temperature to form a molded article. If the matrix resin is a thermosetting resin, the prepreg can be heat-molded and cured to form a molded article. These resins do not need to be completely cured, but it is preferable that they be cured to a degree that the molded article can maintain its shape. After molding, they may be further heated to completely cure. The method of heat molding is not particularly limited and includes methods such as filament winding (a method of winding the material around a rotating mandrel under tension and then heat-molding), press molding (a method of laminating prepreg sheets and then heat-molding), autoclave (a method of pressing prepreg sheets into a mold under pressure and then heat-molding), and injection molding by mixing chopped fiber or milled fiber with the matrix resin.

[0078] This specification discloses the following: Disclosure (1) is a fiber sizing agent composition comprising a novolac-type epoxy resin (A), an aromatic nonionic surfactant (B), and a polyester resin (C), wherein the polyester resin (C) has constituent units derived from an aromatic dicarboxylic acid (d) and constituent units derived from a diol (e), the content of the aromatic portion of the polyester resin (C) based on the weight of the polyester resin (C) is 4.00 to 5.05 mmol / g, and the oxyethylene group content of the diol (e) based on the weight of the diol (e) is 9.50 to 15.00 mmol / g.

[0079] Disclosure (2) is a fiber sizing agent composition according to Disclosure (1), wherein the content ratio of the aromatic portion of the polyester resin (C) based on the weight of the polyester resin (C) is 4.30 to 4.80 mmol / g.

[0080] The present disclosure (3) is a fiber scrubbing agent composition according to the present disclosure (1) or (2), wherein the diol (e) comprises a diol (e1) having a bisphenol skeleton and a polyoxyalkylene chain.

[0081] Disclosure (4) is a fiber scrubbing agent composition according to any one of Disclosures (1) to (3), wherein the aromatic dicarboxylic acid (d) is at least one selected from the group consisting of phthalic acid, terephthalic acid, and isophthalic acid.

[0082] Disclosure (5) is a fiber scrubbing agent composition according to Disclosure (3) or (4), wherein the total number of moles of oxyalkylene groups added per mole of diol (e1) is 2 to 120 mol.

[0083] Disclosure (6) 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 for fibers described in any of Disclosures (1) to (5).

[0084] Disclosure (7) is a textile product comprising the fiber bundle described in Disclosure (6).

[0085] Disclosure (8) is a composite material comprising the fiber bundle and matrix resin described in Disclosure (6).

[0086] Disclosure (9) is a composite material comprising the textile product described in Disclosure (7) and a matrix resin.

[0087] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" refers to parts by weight, and "%" refers to percentage by weight.

[0088] Manufacturing Example 1 [Synthesis of Polyester Resin (C-1)] 454.1 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 206.9 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at reduced pressure to -0.1 MPa for 10 hours while distilling off the water. To this, 383.3 parts of bisphenol A-EO60 molar adduct, in which 60 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C-1). The bisphenol A-EO60 molar adduct was manufactured as follows. In a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device, and dropping cylinder, 228 parts (1 mole) of bisphenol A, 1000 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 2640 parts (60 moles) of ethylene oxide were added dropwise over 6 hours while adjusting the pressure to 0.5 MPaG or less. The mixture was then aged at 130°C for 3 hours. After cooling to 100°C, 30 parts of the adsorbent "Kyoward 600" [manufactured by Kyowa Chemical Industry Co., Ltd.] were added, and the mixture was stirred at 100°C for 1 hour. The adsorbent was then filtered to obtain a 60 mole adduct of bisphenol A-EO.

[0089] Manufacturing Example 2 [Synthesis of Polyester Resin (C-2)] 500.4 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 225.2 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow, under reduced pressure to -0.1 MPa, while distilling off the water for 10 hours. To this, 322.8 parts of polyoxyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd.: PEG-4000S) were added, and the mixture was reacted at 145°C under reduced pressure to -0.1 MPa, while distilling off the water for 10 hours to obtain 1,000 parts of polyester resin (C-2).

[0090] Manufacturing Example 3 [Synthesis of Polyester Resin (C-3)] 364.1 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 50.6 parts of bisphenol A PO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BP-3P), in which 3 molar parts of PO were added to 1 molar part of bisphenol A, 169.6 parts of terephthalic acid, 28.2 parts of fumaric acid, and 0.4 parts of p-toluenesulfonic acid were reacted in a glass reaction vessel at 170°C under nitrogen flow for 10 hours while distilling off the water. 432.5 parts of bisphenol A-EO30 molar adduct, in which 30 molar parts of EO were added to 1 molar part of bisphenol A, were added and reacted at 140°C for 4 hours to obtain 1,000 parts of polyester resin (C-3). The bisphenol A-EO 30 molar adduct was produced under the same conditions as the method for producing the bisphenol A-EO 60 molar adduct described in Production Example 1, except that 2,640 parts of ethylene oxide were replaced with 1,320 parts (30 moles).

[0091] Manufacturing Example 4 [Synthesis of Polyester Resin (C-4)] 454.1 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 206.9 parts of isophthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at a reduced pressure to -0.1 MPa for 10 hours while distilling off the water. To this, 383.4 parts of bisphenol A-EO60 molar adduct, in which 60 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under a reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C-4).

[0092] Manufacturing Example 5 [Synthesis of Polyester Resin (C-5)] 454.1 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 206.9 parts of phthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow, reduced pressure to -0.1 MPa, and water was removed by distillation for 10 hours. To this, 383.4 parts of bisphenol A-EO60 molar adduct, in which 60 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under reduced pressure to -0.1 MPa, and water was removed by distillation for 10 hours to obtain 1,000 parts of polyester resin (C-5).

[0093] Manufacturing Example 6 [Synthesis of Polyester Resin (C-6)] 252.2 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20) in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 201.8 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-40) in which 4 molar parts of EO were added to 1 molar part of bisphenol A, 206.9 parts of terephthalic acid and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under a nitrogen flow, under reduced pressure to -0.1 MPa, while distilling off the water for 10 hours. To this, 383.4 parts of a bisphenol A-EO 40 molar adduct, in which 40 molar parts of EO were added to 1 molar part of bisphenol A, were added, and the mixture was reacted for 10 hours at 145°C under reduced pressure to -0.1 MPa while distilling off the water, to obtain 1,000 parts of polyester resin (C-6). The bisphenol A-EO 40 molar adduct was produced under the same conditions as the method for producing the bisphenol A-EO 60 molar adduct described in Production Example 1, except that 2,640 parts of ethylene oxide were changed to 1,760 parts (40 molar parts).

[0094] Manufacturing Example 7 [Synthesis of Polyester Resin (C-7)] 484.9 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 223.1 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at reduced pressure to -0.1 MPa for 10 hours while distilling off the water. To this, 339.4 parts of bisphenol A-EO80 molar adduct, in which 80 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C-7). The bisphenol A-EO 80 molar adduct was produced under the same conditions as the method for producing the bisphenol A-EO 60 molar adduct described in Production Example 1, except that the amount of ethylene oxide was changed from 2,640 parts to 3,520 parts (80 molar parts).

[0095] Production Example 8 [Synthesis of Polyester Resin (C-8)] 481.9 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 221.3 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at a reduced pressure of -0.1 MPa for 10 hours while removing water by distillation. To this, 344.2 parts of bisphenol A-EO 120 molar adduct, in which 120 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under a reduced pressure of -0.1 MPa for 10 hours while removing water by distillation to obtain 1,000 parts of polyester resin (C-8). The bisphenol A-EO 120 molar adduct was produced under the same conditions as the method for producing the bisphenol A-EO 60 molar adduct described in Production Example 1, except that 2,640 parts of ethylene oxide were replaced with 5,280 parts (120 moles).

[0096] Manufacturing Example 9 [Synthesis of Polyester Resin (C-9)] 556.7 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 155.0 parts of terephthalic acid, 59.0 parts of fumaric acid, and 0.4 parts of p-toluenesulfonic acid were reacted in a glass reaction vessel at 170°C under nitrogen flow for 10 hours while distilling off the water. To this, 280.1 parts of bisphenol A-EO30 molar adduct, in which 30 molar parts of EO were added to 1 molar part of bisphenol A, were added and reacted at 140°C for 4 hours to obtain 1,000 parts of polyester resin (C-9).

[0097] Manufacturing Example 10 [Synthesis of Polyester Resin (C-10)] 545.9 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 210.3 parts of terephthalic acid, 31.0 parts of fumaric acid, and 0.4 parts of p-toluenesulfonic acid were reacted in a glass reaction vessel at 170°C under nitrogen flow for 10 hours while distilling off the water. To this, 274.6 parts of bisphenol A-EO30 molar adduct, in which 30 molar parts of EO were added to 1 molar part of bisphenol A, were added and reacted at 140°C for 4 hours to obtain 1,000 parts of polyester resin (C-10).

[0098] Manufacturing Example 11 [Synthesis of Polyester Resin (C-11)] 875.6 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-40), in which 4 molar parts of EO were added to 1 molar part of bisphenol A, 70.7 parts of terephthalic acid, 98.7 parts of fumaric acid, and 0.4 parts of p-toluenesulfonic acid were reacted in a glass reaction vessel at 170°C under nitrogen flow for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C-11).

[0099] Comparative Manufacturing Example 1 [Synthesis of Polyester Resin (C'-1)] 445.2 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-40), in which 4 molar parts of EO were added to 1 molar part of bisphenol A, 168.2 parts of terephthalic acid, 0.3 parts of adipic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at reduced pressure to -0.1 MPa for 10 hours while distilling off the water. To this, 218 parts of polyoxyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd.: PEG-1000) and 204.5 parts of polyoxyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd.: PEG-2000) were added and the mixture was reacted at 145°C under reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C'-1).

[0100] Comparative Manufacturing Example 2 [Synthesis of Polyester Resin (C'-2)] 612.8 parts of a bisphenol A PO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BP-3P), in which 3 molar parts of PO were added to 1 molar part of bisphenol A, 169.1 parts of fumaric acid, and 0.4 parts of p-toluenesulfonic acid were reacted in a glass reaction vessel at 170°C under nitrogen flow for 10 hours while distilling off the water. To this, 269.6 parts of a bisphenol A-EO30 molar adduct, in which 30 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C'-2).

[0101] Comparative Manufacturing Example 3 [Synthesis of Polyester Resin (C'-3)] 426.9 parts of a bisphenol A PO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BP-3P), in which 3 molar parts of PO were added to 1 molar part of bisphenol A, 173.3 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at a reduced pressure to -0.1 MPa for 10 hours while distilling off the water. To this, 436.9 parts of a bisphenol A-EO30 molar adduct, in which 30 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under a reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C'-3).

[0102] Comparative Production Example 4 [Synthesis of Polyester Resin (C'-4)] 805.2 parts of bisphenol A EO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newport BPE-20), in which 2 molar parts of EO were added to 1 molar part of bisphenol A, 248 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under a nitrogen flow, under reduced pressure to -0.1 MPa, while distilling off the water for 10 hours to obtain 1,000 parts of polyester resin (C'-4).

[0103] Comparative Manufacturing Example 5 [Synthesis of Polyester Resin (C'-5)] 520.9 parts of a bisphenol A PO adduct (manufactured by Sanyo Chemical Industries, Ltd.: Newpol BP-3P), in which 3 molar parts of PO were added to 1 molar part of bisphenol A, 184.2 parts of terephthalic acid, and 1.8 parts of tetraisopropoxytitanate were reacted in a glass reaction vessel at 225°C under nitrogen flow at a reduced pressure to -0.1 MPa for 10 hours while distilling off the water. To this, 342.1 parts of a bisphenol A-EO60 molar adduct, in which 60 molar parts of EO were added to 1 molar part of bisphenol A, were added and the mixture was reacted at 145°C under a reduced pressure to -0.1 MPa for 10 hours while distilling off the water to obtain 1,000 parts of polyester resin (C'-5).

[0104] The number-average molecular weight, aromatic concentration, and HLB values ​​were determined for the polyester resins (C-1) to (C-11) of Production Examples 1 to 11 and the polyester resins (C'-1) to (C'-5) of Comparative Production Examples 1 to 5, and the results are shown in Tables 1-1, 1-2, and 2.

[0105] Table 3 shows the molecular weight, number of EO additions, oxyethylene group content, and aromatic concentration of each component.

[0106]

[0107]

[0108]

[0109]

[0110] <Measurement of Number-Average Molecular Weight> In this invention, Mn was measured by GPC under the following conditions: Instrument: Alliance (Liquid chromatograph manufactured by Waters Japan Ltd.) 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% by weight Injection volume: 10 μl Standard substance: Polystyrene (manufactured by Tosoh Corporation; TSK STANDARD POLYSTYRENE)

[0111] Production Example 12 [Production of Decanol EO 6-mol adduct (D-1)] 158 parts (1 mole) of decanol (manufactured by KH Neochem Co., Ltd.) and 0.5 parts (0.009 moles) of potassium hydroxide were added to a pressure-resistant reaction vessel equipped with a stirrer, heating and cooling device and dropping cylinder. After purging with nitrogen, the vessel was sealed and the temperature was raised to 70°C, where dehydration was carried out under reduced pressure for 1 hour. The temperature was raised to 160°C, and 264 parts (6 moles) of EO were added dropwise over 5 hours while adjusting the pressure to 0.5 MPaG or less. The mixture was then aged at 160°C for 2 hours. After cooling to 70°C, 10 parts of the adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 70°C for 1 hour. The adsorbent was then filtered to obtain Decanol EO 6-mol adduct (D-1).

[0112] Production Example 13 [Production of Decanol EO 7-mol adduct (D-2)] 158 parts (1 mole) of decanol (manufactured by KH Neochem Co., Ltd.) and 0.5 parts (0.009 moles) of potassium hydroxide were added to a pressure-resistant reaction vessel equipped with a stirrer, heating and cooling device, and dropping cylinder. After purging with nitrogen, the vessel was sealed and the temperature was raised to 70°C, where dehydration was carried out under reduced pressure for 1 hour. The temperature was raised to 160°C, and 308 parts (7 moles) of EO were added dropwise over 5 hours while adjusting the pressure to 0.5 MPaG or less. The mixture was then aged at 160°C for 2 hours. After cooling to 70°C, 10 parts of the adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 70°C for 1 hour. The adsorbent was then filtered to obtain Decanol EO 7-mol adduct (D-2).

[0113] <Examples 1-14 and Comparative Examples 1-5> Materials of the types and amounts listed in Tables 4-1, 4-2, and 5 were added to a reaction vessel equipped with a stirring device, a heating / cooling device, a thermometer, and a dropping funnel, and stirred at 60°C for 5 minutes to obtain a fiber sizing agent composition. Next, water was added dropwise to the fiber sizing agent composition from a dropping funnel over 1 hour and stirred to prepare fiber sizing agent solutions (X1)-(X14) and (X'1)-(X'5), which are dispersions (emulsions) of the fiber sizing agent composition with a solid content of 40%. The emulsion stability (median diameter, dispersion stability), sizing ability, fluffiness of fiber bundles, and strength of molded articles (composite materials) of the prepared fiber sizing agent solutions (X1)-(X14) and (X'1)-(X'5) were evaluated by the following methods. The results are shown in Tables 4-1, 4-2, and 5. In Comparative Examples 2 to 5, the compositions did not disperse properly, and therefore a fiber sizing agent solution could not be obtained. As a result, it was not possible to evaluate the sizing properties, fluffiness, and molded article strength (indicated as "unmeasurable" in Table 5).

[0114]

[0115]

[0116]

[0117] The materials used in the production of the fiber sizing agent solutions in the examples and comparative examples are as follows: <Novolac-type epoxy resin (A)> (A-1): Cresol novolac-type epoxy resin [manufactured by Nippon Steel Chemical & Material Co., Ltd., "YDCN-700-7", epoxy group concentration: 5.00 meq / g] (A-2): Phenol novolac-type epoxy resin [manufactured by DIC Corporation, "EPICLON N-740", epoxy group concentration: 5.49 meq / g] <Bisphenol A-type epoxy resin (A')> (A'-1): Bisphenol A-type epoxy resin [manufactured by DIC Corporation, "Epiclon 1050", epoxy group concentration: 2.11 meq / g] (A'-2): Bisphenol A-type epoxy resin [manufactured by Mitsubishi Chemical Corporation, "jER828", epoxy group concentration: 5.29 meq / g] <Aromatic nonionic surfactant (B)> (B-1): Propylene oxide ethylene oxide adduct of styrene-phenol [manufactured by Science Co., Ltd., "Soprophor 796 / P", HLB value 13.7] (B-2): Propylene oxide ethylene oxide adduct of styrene-phenol [manufactured by Science Co., Ltd., "Soprophor TSP / 724", HLB value 11.9]

[0118] [Evaluation of Median Diameter] For the fiber sizing agent solutions of the examples and comparative examples, the median diameter of the particles in the solution was measured using a laser diffraction / scattering particle size distribution analyzer LA-950 manufactured by Horiba, Ltd., and evaluated based on the following evaluation criteria. The refractive index conditions were 1.470 (particles) and 1.333 (dispersion medium). A smaller median diameter is preferable. <Evaluation Criteria> ○ (Good): Median diameter is 0.150 μm or less △ (Acceptable): Median diameter is greater than 0.150 μm to 0.200 μm × (Poor): Median diameter is greater than 0.200 μm or cannot be emulsified

[0119] [Evaluation of Dispersion Stability] The fiber sizing agent compositions obtained in the examples and comparative examples were stored in a 40°C constant temperature bath and visually inspected every week to check for separation. <Evaluation Criteria> ○ (Good): No separation occurs even after more than 3 months (12 weeks) △ (Acceptable): Separation occurs between more than 1 week and 12 weeks × (Poor): Separation occurs within 1 week

[0120] [Evaluation of fiber bundle bundling properties, fiber bundle fuzzing, and molded product strength] <Preparation of carbon fiber bundles for evaluation tests> Water was added to the fiber bundling agent solutions obtained in the examples and comparative examples to make a dispersion with a solid content concentration of 1.5%, and untreated carbon fibers (24,000 filaments) were immersed in the dispersion to impregnate them. After that, 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) in the dispersion was prepared so that the carbon fiber bundles were 1.5%. 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 bundling properties and fuzzing.

[0121] <Evaluation Test of Focusing Performance> Focusing performance was evaluated using a carbon fiber bundle for testing, in accordance with JIS L 1096:2010 8.21.1 Method A (45° cantilever method). A larger measured value (cm) indicates better focusing performance. The focusing performance value measured by this evaluation method is preferably 20 cm or more, and particularly preferably 25 cm or more. A value of 19 cm or less indicates insufficient improvement in focusing performance.

[0122] <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 HL. Furthermore, before and after the passage of the second and fourth 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 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 forms an angle of 120 degrees). The unwinding roll 2 and the winding roll 3 are set to rotate in the direction of the arrows drawn near each roll.

[0123] (2) The weight of the fluff was measured using a carbon fiber bundle for the fluff weight measurement test, following the procedure below. 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 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 is transported from the unwinding roll 2 to the winding roll 3, "upstream side" means upstream in the transport direction, i.e., the unwinding roll 2 side. 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 of the lint attached to the two urethane foam sheets was measured and evaluated based on the following evaluation criteria. A smaller amount of lint indicates better suppression of lint formation. <Evaluation Criteria> ◎ (Excellent): Amount of lint 0.5 mg or less 〇 (Good): Amount of lint greater than 0.5 mg but 2 mg or less × (Poor): Amount of lint greater than 2 mg

[0124] <Evaluation Test of Molded Body Strength> The carbon fiber bundles used for the above test were evaluated according to the following procedure: (1) Preparation of Test Pieces Carbon fiber bundles were placed in a mold so that the volume content (Vf) of carbon fibers was 60%, and matrix resin (composition is shown below) was poured in, followed by vacuum degassing while heating. After degassing, the bundles were set in a press machine and the resin was cured by heating under pressure to produce a flat plate with a width of 6 mm and a thickness of 2.5 mm. This flat plate was then cut to a length of 18 mm to be used as a test piece. (Composition of matrix resin placed in the mold) ・Bisphenol A type epoxy resin (Ep828, manufactured by Japan Epoxy Resin Co., Ltd.) 100 parts by weight ・Boron trifluoride monoethylamine (manufactured by Stella Chemifa Co., Ltd.) 3 parts by weight (Molding conditions) ・Degassing: Under vacuum (-0.08 MPa or less), 70°C for 4 hours ・Molding: Press pressure (4.9 MPa), 170°C for 1 hour ・After-cure: 170°C for 2 hours (2) Measurement of molded body strength (CFRP strength) The obtained test piece (molded body) was measured for ILSS (interlaminar shear strength) in accordance with JIS K 7078. The larger the measured value, the higher the strength and the higher the adhesion between the fibers and the matrix resin. <Evaluation criteria> ◎ (Excellent): ILSS of 90 MPa or higher 〇 (Good): ILSS of 80 MPa or higher and less than 90 MPa × (Poor): ILSS of less than 80 MPa

[0125] As shown in Tables 4-1 and 4-2, when the fiber sizing agent compositions of the examples are made into aqueous emulsions, the emulsion stability is good. Furthermore, it can be seen that the fiber bundles treated with the fiber sizing agent compositions have good bundling properties and fuzzing is suppressed. Moreover, it can be seen that the molded articles containing these fiber bundles have high strength. On the other hand, as shown in Table 5, the fiber sizing agent compositions of Comparative Examples 1 to 5, which used polyester resins (C'-1) to (C'-5) other than polyester resin (C) in the present invention, either did not produce a dispersion or the dispersion stability of the dispersion was low. Since the fiber sizing agent compositions of the present invention have good emulsion stability when made into aqueous emulsions, it can be stored for a long period of time, and it can be seen that the variation in the amount of solids adhering to the fibers treated with the fiber sizing agent composition is small.

[0126] The fiber sizing agent composition, fiber products, and composite materials of the present invention can be used in fields such as sports equipment, leisure goods, and aircraft.

[0127] 1A, 1B, 1C, 1D, 1E Stainless steel rod 2 Unwinding roll 3 Rewinding roll 3A Winding start point 4 Carbon fiber bundle 5A Region 10 cm upstream from 3A HL Horizontal plane

Claims

1. A fiber sizing agent composition comprising a novolac-type epoxy resin (A), an aromatic nonionic surfactant (B), and a polyester resin (C), wherein the polyester resin (C) has constituent units derived from an aromatic dicarboxylic acid (d) and constituent units derived from a diol (e), the content of the aromatic portion of the polyester resin (C) based on the weight of the polyester resin (C) is 4.00 to 5.05 mmol / g, and the oxyethylene group content of the diol (e) based on the weight of the diol (e) is 9.50 to 15.00 mmol / g.

2. The fiber sizing agent composition according to claim 1, wherein the content ratio of the aromatic portion of the polyester resin (C) based on the weight of the polyester resin (C) is 4.30 to 4.80 mmol / g.

3. The fiber sizing agent composition according to claim 1, wherein the diol (e) comprises a diol (e1) having a bisphenol skeleton and a polyoxyalkylene chain.

4. The fiber sizing agent composition according to claim 1, wherein the aromatic dicarboxylic acid (d) is at least one selected from the group consisting of phthalic acid, terephthalic acid, and isophthalic acid.

5. The fiber sizing agent composition according to claim 3, wherein the total number of moles of oxyalkylene groups added per mole of the diol (e1) is 2 to 120 mol.

6. 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 5.

7. A textile product comprising the fiber bundle described in claim 6.

8. A composite material comprising the fiber bundle and matrix resin according to claim 6.

9. A composite material comprising the textile product and matrix resin described in claim 7.

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