Fiber sizing agents, fiber bundles, fiber products, resin compositions, and molded articles

Abstract

To provide a fiber sizing agent which imparts excellent strength to a molded body.SOLUTION: A fiber sizing agent contains a modified product (B) of at least one kind of resin (A) selected from the group consisting of a polyarylate resin (A2), a polysulfone resin (A3), a polyether sulfone resin (A4), an aromatic polyimide resin (A5), an aromatic polyether imide resin (A6), an aromatic polyether ketone resin (A7), an aromatic polyether ether ketone resin (A8) and an aromatic polyether ketone ketone resin (A9).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fiber sizing agent, a fiber bundle, a fiber product, a resin composition, and a molded article. [Background technology]

[0002] Because carbon fibers and glass fibers are lightweight and have excellent strength and elastic modulus, fiber-reinforced composite materials made by combining these with various matrix resins are widely used in fields such as sports equipment, leisure goods, and aircraft. In recent years, they have also begun to be used in engines, automobile components, electronics, and the machinery industry, where higher heat resistance is required. Therefore, it is important that fiber-reinforced composite materials have excellent moldability in addition to heat resistance and physical properties. Meanwhile, thermosetting resins such as epoxy resins, vinyl ester resins, unsaturated polyester resins, and phenolic resins have traditionally been the mainstream matrix resins used in fiber-reinforced composite materials. However, from the standpoint of moldability, polypropylene resins, polyamide resins, polycarbonate resins, and polyphenylene sulfide resins have recently been used, and in particular, for carbon fiber-reinforced composite materials, polyetherimide resins and polyether ether ketone resins, which have high heat resistance and can be molded at temperatures exceeding 350°C, are beginning to be used.

[0003] As sizing agents used to reinforce these thermoplastic resins with excellent heat resistance using carbon fibers, those containing polycarbonate resins or imide resins having a siloxane structure (e.g., Patent Documents 1 and 2) and those containing aromatic polyester-based urethane resins (e.g., Patent Document 3) have been proposed. However, even with the technology disclosed in the patent document, there was a problem in that the strength of the composite material was not sufficiently exhibited. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-57640 [Patent Document 2] Japanese Patent Application Publication No. 6-2279 [Patent Document 3] Patent No. 5802834 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a fiber sizing agent that imparts excellent strength to a molded article. [Means for solving the problem]

[0006] The present inventors have conducted research to achieve the above object and have arrived at the present invention. That is, the present invention provides a fiber sizing agent containing a modified product (B) of at least one resin (A) selected from the group consisting of polyarylate resin (A2), polysulfone resin (A3), polyethersulfone resin (A4), aromatic polyimide resin (A5), aromatic polyetherimide resin (A6), aromatic polyetherketone resin (A7), aromatic polyetheretherketone resin (A8) and aromatic polyetherketoneketone resin (A9), wherein the modified product (B) is a modified product of the resin (A) containing a group selected from the group consisting of a (poly)oxyalkylene group, a sulfo group, a carboxyl group and a 1,3-dioxo-2-oxapropylene group. a fiber sizing agent in which the modified resin (B) has been introduced with at least one functional group selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, rock fiber, and slag fiber, and the weight loss at 400°C is 20% by weight or less when heated in nitrogen to 500°C under conditions of a heating start temperature of 30°C and a heating rate of 5°C / min; a fiber bundle in which at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, rock fiber, and slag fiber is treated with the fiber sizing agent; a fiber product containing the fiber bundle; a resin composition containing the fiber bundle and / or the fiber product and a thermoplastic resin (E); and a molded product obtained by molding the resin composition. [Effects of the Invention]

[0007] The fiber sizing agent of the present invention has the following effects. -Gives excellent strength to the molded body. Gives the molded product an excellent appearance. - Provides excellent bundling properties to fiber bundles. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Textile sizing agent> The fiber sizing agent of the present invention is a fiber sizing agent containing a modified product (B) of at least one resin (A) selected from the group consisting of polyphenylene ether resin (A1), polyarylate resin (A2), polysulfone resin (A3), polyethersulfone resin (A4), aromatic polyimide resin (A5), aromatic polyetherimide resin (A6), aromatic polyetherketone resin (A7), aromatic polyetheretherketone resin (A8), and aromatic polyetherketoneketone resin (A9), wherein the modified product (B) is a modified resin obtained by introducing at least one functional group selected from the group consisting of a (poly)oxyalkylene group, a sulfo group, a carboxyl group, and a 1,3-dioxo-2-oxapropylene group into the resin (A), and wherein the modified product (B) has a heat loss of 20% by weight or less at 400°C when heated in nitrogen under conditions of a heating start temperature of 30°C and a heating rate of 5°C / min up to 500°C.

[0009] The polyphenylene ether resin (A1) is a resin having a structure obtained by polycondensation of an aromatic compound (a12) having two hydroxyl groups, and includes resins obtained by oxidative coupling polymerization of an aromatic compound (a11) having one hydroxyl group and / or an aromatic compound (a12) having two hydroxyl groups.

[0010] The aromatic compound (a11) having one hydroxyl group includes a compound in which one hydroxyl group is directly bonded to an aromatic ring, and specifically includes a compound in which at least two of the hydrogen atoms (preferably at the 2nd and 6th positions) of a phenol are substituted with at least one group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, and an n-triacontyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group, a phenylmethyl group, and a phenylethyl group.

[0011] Specific examples of the aromatic compound (a11) include 2,6-dimethylphenol (sometimes referred to as 2,6-xylenol), 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-dibutylphenol, 2,6-dipentylphenol, 2,6-dihexylphenol, 2,6-diheptylphenol, 2,6-dioctylphenol, 2,6-dinonylphenol, 2,6-didecylphenol, 2,6-didodecylphenol, 2,6-ditetradecylphenol, 2, Examples include dialkylphenols such as 6-dihexadecylphenol, 2,6-dioctadecylphenol, 2,6-diicosylphenol, 2,6-ditriacontylphenol, 2-methyl-6-ethylphenol, and 2,5-dimethylphenol; diarylphenols such as 2,6-diphenylphenol, 2,6-dinaphthylphenol, and 2,5-diphenylphenol; and diaralkylphenols such as 2,6-dibenzylphenol and 2,6-diphenylethylphenol.

[0012] The aromatic compound (a12) having two hydroxyl groups includes a compound in which two hydroxyl groups are directly bonded to one aromatic ring and a compound in which two aromatic rings, each having a hydroxyl group directly bonded to an aromatic ring, are bonded together. Specific examples include hydroquinone, naphthalenediol (e.g., 2,7-naphthalenediol), 4,4'-biphenol, bisphenol S [bis(4-hydroxyphenyl)sulfone], compounds in which a hydroxyaryl group is bonded via a divalent hydrocarbon group having 1 to 20 carbon atoms (including those in which some of the hydrogen atoms of the hydrocarbon group are substituted with halogen groups), and derivatives thereof (e.g., those in which the hydrogen atoms bonded to the aromatic ring are substituted with a hydrocarbon group having 1 to 20 carbon atoms) (a121), an aromatic compound (a122) in which two aromatic rings, each having a hydroxyl group directly bonded to an aromatic ring, are bonded together via a carbonyl group, and an aromatic compound (a123) in which two aromatic rings, each having a hydroxyl group directly bonded to an aromatic ring, are bonded together via an ether bond. In (a121), examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include alkylene groups having 1 to 20 carbon atoms (for example, methylene, ethylene, 1,2- or 1,3-propylene, and 1,2-, 1,3-, 1,4- or 2,3-butylene), cycloalkylene groups having 3 to 20 carbon atoms (for example, 1,2-, 1,3- or 1,4-cyclohexylene), divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms (for example, 1,2-, 1,3- or 1,4-phenylene), and divalent aromatic-aliphatic hydrocarbon groups having 7 to 20 carbon atoms (for example, 1-methyl-2,3-phenylene). Specific examples of (a121) include those bonded via an alkylene group {for example, bisphenol F (1,1-bis(4-hydroxyphenyl)methane), tetramethylbisphenol F (1,1-bis(4-hydroxy-3,5-dimethylphenyl)methane), bisphenol E (1,1-bis(4-hydroxyphenyl)ethane), tetramethylbisphenol E (1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethane), bisphenol A (2,2-bis(4-hydroxyphenyl)propane), tetramethylbisphenol A (2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane), bisphenol B (2,2-bis(4-hydroxyphenyl)butane), tetramethylbisphenol B (2,2-bis(4-hydroxy-3,5-dimethylphenyl)butane), bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane), bisphenol G (2,2 -bis(4-hydroxy-3-isopropylphenyl)propane), bisphenol PH (5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane), etc.}, those bonded via a cycloalkylene group {bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), etc.}, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol BP (bis(4-hydroxyphenyl)diphenylmethane), bisphenol M (1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene), bisphenol P (1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene), bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafluoropropane), etc. Specific examples of (a122) include 4,4'-dihydroxybenzophenone and 2,4'-dihydroxybenzophenone. Specific examples of (a123) include 4,4'-dihydroxyphenyl ether.

[0013] In the polyphenylene ether resin (A1), among the aromatic compounds (a11), dialkylphenols are preferred, and 2,6-dimethylphenol and 2,6-diethylphenol are more preferred, from the viewpoint of emulsion stability of the modified product (B). The polyphenylene ether resin (A1) can be obtained by a known method (for example, JP 2019-189686 A, etc.). As the polyphenylene ether resin (A1), Noryl (manufactured by SABIC) and Zylon (manufactured by Asahi Kasei Corporation) are commercially available and are available.

[0014] The polyarylate resin (A2) is a resin having a structure obtained by polycondensation of an aromatic compound (a12) having two hydroxyl groups and an aromatic compound (a22) having two carboxyl groups, and includes resins obtained by an esterification reaction between (a12) and (a22), and an esterification reaction between (a12) and an aromatic compound (a72) having two acyl halide groups obtained by converting the carboxyl groups of (a22) into acid chlorides (acyl halide groups).

[0015] Examples of the aromatic compound (a12) having two hydroxyl groups include the compounds exemplified above in the description of the polyphenylene ether resin (A1). In the polyarylate resin (A2), from the viewpoint of the appearance of the molded product, the aromatic compound (a12) having two hydroxyl groups is preferably naphthalenediol, bisphenol S, a compound in which a hydroxyaryl group is bonded via a divalent hydrocarbon group having 1 to 20 carbon atoms, or a derivative (a121) thereof, and more preferably a compound in which a hydroxyaryl group is bonded via a divalent hydrocarbon group having 1 to 20 carbon atoms, or a derivative (a121) thereof.

[0016] The aromatic compound (a22) having two carboxyl groups is a compound in which two carboxyl groups are directly bonded to an aromatic ring, and an aromatic compound in which two aromatic rings, each having a carboxyl group directly bonded to an aromatic ring, are bonded, and includes aromatic dicarboxylic acids having 8 to 40 carbon atoms. Specific examples include phthalic acid, isophthalic acid, terephthalic acid, diphenyl ether dicarboxylic acids (e.g., diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, etc.), naphthalenedicarboxylic acids (e.g., 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, etc.), and derivatives, acid anhydrides, and lower alkyl (having 1 to 4 carbon atoms) esters of these dicarboxylic acids. In the present invention, examples of the derivative include those in which a hydrogen atom bonded to an aromatic ring is substituted with a hydrocarbon group having 1 to 20 carbon atoms. Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms.

[0017] In the polyarylate resin (A2), from the viewpoint of the emulsion stability of the modified product (B), among the aromatic compounds (a22), phthalic acid, isophthalic acid, terephthalic acid, and diphenyl ether dicarboxylic acid are preferred, and phthalic acid, isophthalic acid, and terephthalic acid are more preferred.

[0018] The aromatic compound (a72) having two acyl halide groups includes compounds obtained by converting the carboxyl group of the aromatic compound (a22) into an acid chloride (acyl halide group), and specifically includes phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, aromatic compounds (a721) having two aromatic rings bonded together and one acyl halide group directly bonded to the aromatic ring {for example, diphenyl ether dicarboxylic acid dichloride (e.g., diphenyl ether-2,2'-dicarboxylic acid dichloride, diphenyl ether-2,3'-dicarboxylic acid dichloride, diphenyl ether-2,4'-dicarboxylic acid dichloride, diphenyl ether-3,3'-dicarboxylic acid dichloride, diphenyl ether-3,4'-dicarboxylic acid dichloride, diphenyl ether-4,4'-dicarboxylic acid dichloride, etc.}, naphthalenedicarboxylic acid dichlorides (for example, 1,5-naphthalenedicarboxylic acid dichloride and 2,6-naphthalenedicarboxylic acid dichloride, etc.), 4,4'-(1,4-phenylenebisoxy)bis(benzoic acid chloride), 4,4'-(1,2-phenylenebisoxy)bis(benzoic acid chloride), 4,4'-(1,3-phenylenebisoxy)bis(benzoic acid chloride), 4,4'-[(2,6-naphthalenediyl)bisoxy]bis(benzoic acid chloride), 4,4'-[(1,5-naphthalenediyl)bisoxy]bis(benzoic acid chloride), 4,4'-[(1,4-naphthalenediyl)bisoxy]bis(benzoic acid chloride), and derivatives of these dicarboxylic acid dichlorides.

[0019] In the polyarylate resin (A2), from the viewpoint of the emulsion stability of the modified product (B), among the aromatic compounds (a72), phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, and diphenyl ether dicarboxylic acid dichloride are preferred, and phthalic acid dichloride, isophthalic acid dichloride, and terephthalic acid dichloride are more preferred.

[0020] The polyarylate resin (A2) may contain residues of other components such as aliphatic diols, alicyclic diols, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Examples of aliphatic diols include ethylene glycol and propylene glycol. Examples of alicyclic diols include 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol. Examples of aliphatic dicarboxylic acids include adipic acid and sebacic acid. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. The content of residues of other components is preferably less than 10 mol% relative to the total number of moles of raw material monomers, and more preferably is substantially free of such residues.

[0021] The polyarylate resin (A2) can be obtained by a known method (for example, JP-A No. 2010-65155). As the polyarylate resin (A2), Unifiner (manufactured by Unitika Ltd.) is commercially available and is available.

[0022] The polysulfone resin (A3) is a resin having a structure obtained by polycondensation of an aromatic compound (a12) having two hydroxyl groups and an aromatic compound in which two aromatic rings are bonded via a sulfonyl group, and includes a resin obtained by desalting polycondensation of (a12) with an aromatic compound (a52) in which two aromatic rings, each having a halogen group bonded directly to the aromatic ring, are bonded via a sulfonyl group.

[0023] Examples of the aromatic compound (a12) having two hydroxyl groups include the compounds exemplified in the description of the polyphenylene ether resin (A1). In the polysulfone resin (A3), the aromatic compound (a12) having two hydroxyl groups is preferably naphthalenediol, bisphenol S, a compound in which a hydroxyaryl group is bonded via a divalent hydrocarbon group having 1 to 20 carbon atoms, or a derivative (a121) thereof, or an aromatic compound (a122) in which two aromatic rings each having a hydroxyl group bonded directly to the aromatic ring are bonded via a carbonyl group, from the viewpoint of the appearance of the molded product, and more preferably a compound in which a hydroxyaryl group is bonded via a divalent hydrocarbon group having 1 to 20 carbon atoms, or a derivative (a121) thereof, or an aromatic compound (a122) in which two aromatic rings each having a hydroxyl group bonded directly to the aromatic ring are bonded via a carbonyl group.

[0024] The aromatic compound (a52) in which two aromatic rings each having a halogen group directly bonded to the aromatic ring are bonded via a sulfonyl group includes those having 12 to 40 carbon atoms, and specific examples thereof include 4,4'-dichlorodiphenyl sulfone, 3,4'-dichlorodiphenyl sulfone, 4,4'-bis(4-chlorophenylsulfonyl)biphenyl, and derivatives thereof (in which a hydrogen atom bonded to the aromatic ring is substituted with a hydrocarbon group having 1 to 20 carbon atoms). In the polysulfone resin (A3), the aromatic compound (a52) is preferably 4,4'-dichlorodiphenyl sulfone or 3,4'-dichlorodiphenyl sulfone, more preferably 4,4'-dichlorodiphenyl sulfone, from the viewpoint of emulsion stability of the modified product (B).

[0025] The polysulfone resin (A3) can be obtained by a known method (for example, JP 2017-226804 A, etc.). As the polysulfone resin (A3), Udel (manufactured by Solvay) is commercially available.

[0026] The polyethersulfone resin (A4) is a resin having a structure obtained by polycondensation of bisphenol S and its derivatives (in which the hydrogen atoms bonded to the aromatic rings are substituted with hydrocarbon groups having 1 to 20 carbon atoms) among aromatic compounds (a12) having two hydroxyl groups, with an aromatic compound (a5) in which two aromatic rings are bonded via sulfonyl groups, and includes resins obtained by desalting polycondensation of bisphenol S and its derivatives with an aromatic compound (a52) in which two aromatic rings, each having a halogen group bonded directly to the aromatic ring, are bonded via a sulfonyl group. Examples of the aromatic compound (a52) include the same compounds as those mentioned above. In (A4), the aromatic compound (a52) is preferably 4,4'-dichlorodiphenyl sulfone or 3,4'-dichlorodiphenyl sulfone from the viewpoint of emulsion stability of the modified product (B). The polyethersulfone resin (A4) can be obtained by a known method (for example, JP-A No. 3-95220). As the polyethersulfone resin (A4), Sumikaexcel (manufactured by Sumitomo Chemical Co., Ltd.) is commercially available and is available.

[0027] The aromatic polyimide resin (A5) is a resin having a structure obtained by polycondensation of an aromatic compound (a32) having two amino groups and an aromatic compound (a42) having two 1,3-dioxo-2-oxapropylene groups, and is a resin obtained by a ring-opening polyaddition and cyclodehydration reaction between (a32) and (a42), and includes those other than the aromatic polyetherimide resin (A6) described later.

[0028] The aromatic compound (a32) having two amino groups has 6 to 40 carbon atoms and includes an aromatic compound in which two amino groups are directly bonded to one aromatic ring and an aromatic compound in which two aromatic rings are bonded, each having an amino group directly bonded to an aromatic ring. Specific examples thereof include phenylenediamine (e.g., o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine), 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and the like. phenol, 4,4'-bis(4-aminophenyl)sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2'-bis(4-(4-aminophenoxy)phenyl)propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and derivatives thereof (wherein the hydrogen atoms bonded to the aromatic rings are substituted with hydrocarbon groups having 1 to 20 carbon atoms).

[0029] In the aromatic polyimide resin (A5), from the viewpoint of emulsion stability of the modified product (B), among the aromatic compounds (a32) having two amino groups, phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-bis(3-aminophenoxy)biphenyl and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl are preferred, and phenylenediamine and 4,4'-bis(3-aminophenoxy)biphenyl are more preferred.

[0030] The aromatic monomer (a42) having two 1,3-dioxo-2-oxapropylene groups includes a compound having 8 to 40 carbon atoms and in which two 1,3-dioxo-2-oxapropylene groups are directly bonded to one aromatic ring, and an aromatic compound in which two aromatic rings are bonded, each having a 1,3-dioxo-2-oxapropylene group directly bonded to an aromatic ring. Specific examples of the aromatic monomer (a42) include pyromellitic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, and derivatives thereof (wherein the hydrogen atoms bonded to the aromatic rings are substituted with hydrocarbon groups having 1 to 20 carbon atoms).

[0031] In the aromatic polyimide resin (A5), from the viewpoint of emulsion stability of the modified product (B), the aromatic compound (a42) having two 1,3-dioxo-2-oxapropylene groups is preferably pyromellitic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and more preferably pyromellitic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

[0032] The aromatic polyimide resin (A5) can be obtained by a known method (for example, JP-A No. 2007-16182). As the aromatic polyimide resin (A5), UIP (manufactured by Ube Industries, Ltd.) is commercially available and is available.

[0033] The aromatic polyetherimide resin (A6) is a resin having a structure obtained by polycondensation of an aromatic compound (a32) having two amino groups and an aromatic compound (a421) in which two aromatic rings each having a 1,3-dioxo-2-oxapropylene group directly bonded to the aromatic ring are bonded via an ether bond, and includes resins obtained by ring-opening polyaddition and cyclodehydration reaction of (a32) and (a421).

[0034] Examples of the aromatic compound (a32) having two amino groups include the same compounds as those exemplified in the description of the aromatic polyimide resin (A5). In the aromatic polyetherimide resin (A6), from the viewpoint of emulsion stability of the modified product (B), the aromatic compound (a32) having two amino groups is preferably phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-bis(4-(4-aminophenoxy)phenyl)propane, and 3,3'-dimethyl-4,4'-diaminobiphenyl, and more preferably phenylenediamine and 2,2'-bis(4-(4-aminophenoxy)phenyl)propane.

[0035] The aromatic compound (a421) in which two aromatic rings, each having a 1,3-dioxo-2-oxapropylene group directly bonded to the other aromatic ring, are bonded via an ether bond [hereinafter also referred to as "aromatic compound (a421)"] includes those having 16 to 40 carbon atoms, and specific examples thereof include 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride. In the aromatic polyetherimide resin (A6), 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride are preferred as the aromatic compound (a421) from the viewpoint of the emulsion stability of the modified product (B).

[0036] The aromatic polyetherimide resin (A6) can be obtained by a known method (for example, Japanese Patent No. 6382988, etc.). As the aromatic polyetherimide resin (A6), ULTEM (manufactured by SABIC) is commercially available.

[0037] The aromatic polyetherketone resin (A7) is a resin having a structure obtained by polycondensation of a compound (a121) in which two aromatic rings, each having a hydroxyl group bonded directly to the aromatic ring, are bonded together, or an aromatic compound (a122) in which two aromatic rings, each having a hydroxyl group bonded directly to the aromatic ring, are bonded together via a carbonyl group [hereinafter also referred to as "aromatic compound (a122)], with an aromatic compound (a6) in which two aromatic rings are bonded together via a carbonyl group. Examples of the aromatic polyetherketone resin (A7) include resins obtained by polycondensation of the compound (a121) or the aromatic compound (a122) with an aromatic compound (a62) in which two aromatic rings, each having a halogen group bonded directly to the aromatic ring, are bonded together via a carbonyl group.

[0038] An example of the compound (a121) having two aromatic rings bonded together, each having a hydroxyl group directly bonded to the other aromatic ring, is 4,4'-biphenol. Examples of the aromatic compound (a122) include the same compounds as those exemplified in the description of the polyphenylene ether resin (A1). In the aromatic polyether ketone resin (A7), the aromatic compound (a122) is preferably 4,4'-dihydroxybenzophenone or 2,4'-dihydroxybenzophenone from the viewpoint of emulsion stability of the modified product (B). In the aromatic polyether ketone resin (A7), the compound (a121) in which two aromatic rings, each having a hydroxyl group directly bonded to the aromatic ring, are bonded is preferably 4,4'-biphenol.

[0039] An example of the aromatic compound (a6) in which two aromatic rings are bonded via a carbonyl group is the aromatic compound (a62) in which two aromatic rings each having a halogen group bonded directly to the aromatic ring are bonded via a carbonyl group (hereinafter also referred to as "aromatic compound (a62)").

[0040] The aromatic compound (a62) includes those having 13 to 40 carbon atoms, and specific examples thereof include 4,4'-dichlorobenzophenone, 2,4'-dichlorobenzophenone, 1,4-bis(4-chlorobenzoyl)benzene, 1,3-bis(4-chlorobenzoyl)benzene, 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 1,4-bis(4-fluorobenzoyl)benzene, 1,3-bis(4-fluorobenzoyl)benzene, and derivatives thereof (in which a hydrogen atom bonded to an aromatic ring is substituted with a hydrocarbon group having 1 to 20 carbon atoms). In the aromatic polyether ketone resin (A7), from the viewpoint of the emulsion stability of the modified product (B), 4,4'-dichlorobenzophenone, 2,4'-dichlorobenzophenone, 1,4-bis(4-chlorobenzoyl)benzene, 1,3-bis(4-chlorobenzoyl)benzene, 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 1,4-bis(4-fluorobenzoyl)benzene and 1,3-bis(4-fluorobenzoyl)benzene are preferred as the aromatic compound (a62).

[0041] The aromatic polyether ketone resin (A7) can be obtained by a known method (for example, JP-A No. 2002-322271). As the aromatic polyether ketone resin (A7), Victrex HT (manufactured by Victrex) is commercially available.

[0042] The aromatic polyether ether ketone resin (A8) is a resin having a structure obtained by polycondensation of an aromatic compound (a12) having two hydroxyl groups and an aromatic compound (a6) in which two aromatic rings are bonded via a carbonyl group. Examples of the aromatic compound (a12) having two hydroxyl groups include the compounds exemplified above in the description of the polyphenylene ether resin (A1). Examples of the aromatic compound (a6) having two aromatic rings bonded via a carbonyl group include the compounds exemplified above in the description of the aromatic polyether ketone resin (A7). The aromatic polyether ether ketone resin (A8) includes a resin obtained by a nucleophilic substitution reaction of an aromatic compound (a81) having a structure in which an aromatic ring having one hydroxyl group and an aromatic ring having one halogen group are bonded via a carbonyl group; a resin obtained by a Friedel-Crafts reaction of an aromatic compound (a71) in which an aromatic ring having one halogenated acyl group and an aromatic ring having no functional group are bonded via an ether bond; and a resin obtained by a Friedel-Crafts reaction of an aromatic compound (a721) in which two aromatic rings, each having one halogenated acyl group bonded directly to the aromatic ring, are bonded via an ether bond with diphenyl ether and its derivatives.

[0043] The aromatic compound (a81) having a structure in which an aromatic ring having one hydroxyl group and an aromatic ring having one halogen group are bonded via a carbonyl group [hereinafter also referred to as "aromatic compound (a81)"] includes aromatic compounds having 12 to 40 carbon atoms in which an aromatic ring having one hydroxyl group directly bonded to the aromatic ring and an aromatic ring having one halogen group directly bonded to the aromatic ring are bonded via a carbonyl group, and specific examples thereof include 4-chloro-4'-hydroxybenzophenone, 4-fluoro-4'-hydroxybenzophenone, and derivatives thereof (in which a hydrogen atom bonded to the aromatic ring is substituted with a hydrocarbon group having 1 to 20 carbon atoms), etc. In the aromatic polyether ether ketone resin (A8), the aromatic compound (a81) is preferably 4-chloro-4'-hydroxybenzophenone or 4-fluoro-4'-hydroxybenzophenone from the viewpoint of emulsion stability of the modified product (B).

[0044] The aromatic compound (a71) in which an aromatic ring having one halogenated acyl group and an aromatic ring having no functional group are bonded via an ether bond [hereinafter also referred to as "aromatic compound (a71)"] includes aromatic compounds having 13 to 40 carbon atoms in which an aromatic ring having one halogenated acyl group directly bonded to the aromatic ring and an aromatic ring in which some of the hydrogen atoms of the aromatic ring may be substituted with a hydrocarbon group having 1 to 27 carbon atoms are bonded via an ether bond, and specific examples thereof include 4-phenoxybenzoyl chloride and derivatives thereof (in which a hydrogen atom bonded to the aromatic ring is substituted with a hydrocarbon group having 1 to 20 carbon atoms). In the aromatic polyether ether ketone resin (A8), the aromatic compound (a71) is preferably 4-phenoxybenzoyl chloride from the viewpoint of the emulsion stability of the modified product (B).

[0045] Aromatic compounds (a721) in which two aromatic rings, each having one halogenated acyl group directly bonded to the aromatic ring, are bonded via an ether bond [hereinafter also referred to as "aromatic compounds (a721)"] include those having 14 to 40 carbon atoms, and specific examples thereof include diphenyl ether-2,2'-dicarboxylic acid dichloride, diphenyl ether-2,3'-dicarboxylic acid dichloride, diphenyl ether-2,4'-dicarboxylic acid dichloride, diphenyl ether-3,3'-dicarboxylic acid dichloride, diphenyl ether-3,4'-dicarboxylic acid dichloride, and diphenyl ether-4,4'-dicarboxylic acid dichloride, as well as derivatives thereof (in which the hydrogen atoms bonded to the aromatic rings are substituted with hydrocarbon groups having 1 to 20 carbon atoms). In the aromatic polyether ether ketone resin (A8), from the viewpoint of the emulsion stability of the modified product (B), the aromatic compound (a721) is preferably diphenyl ether-2,2'-dicarboxylic acid dichloride, diphenyl ether-2,3'-dicarboxylic acid dichloride, diphenyl ether-2,4'-dicarboxylic acid dichloride, diphenyl ether-3,3'-dicarboxylic acid dichloride, diphenyl ether-3,4'-dicarboxylic acid dichloride, or diphenyl ether-4,4'-dicarboxylic acid dichloride.

[0046] The aromatic polyether ether ketone resin (A8) can be obtained by a known method (for example, JP-A No. 2010-95614). As the aromatic polyether ether ketone resin (A8), VESTAKEEP (manufactured by Daicel-Evonik) is commercially available.

[0047] The aromatic polyether ketone ketone resin (A9) is a resin having a structure obtained by polycondensation of an aromatic compound (a22) having two carboxyl groups and an aromatic compound (a123) in which two aromatic rings each having a hydroxyl group bonded directly to the aromatic ring are bonded via an ether bond, and includes resins obtained by the Friedel-Crafts reaction of an aromatic compound (a72) having two halogenated acyl groups [hereinafter also referred to as "aromatic compound (a72)"] with diphenyl ether and its derivatives.

[0048] Examples of (a72) include the same as above. In the aromatic polyether ketone ketone resin (A9), from the viewpoint of the appearance of the molded product, the aromatic compound (a72) is preferably one having no ether bond (such as phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, and naphthalenedicarboxylic acid dichloride), and more preferably phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, and naphthalenedicarboxylic acid dichloride.

[0049] The aromatic polyether ketone ketone resin (A9) can be obtained by a known method (for example, US Pat. No. 3,065,205). Kepstan (manufactured by Arkema) is commercially available as the aromatic polyether ketone ketone resin (A9).

[0050] As the resin (A), polyphenylene ether resin (A1) and polyarylate resin (A2) are preferred from the viewpoints of the appearance of the molded product and emulsion stability.

[0051] The glass transition temperature of resin (A) (hereinafter sometimes abbreviated as Tg) is preferably 10 to 350°C, more preferably 100 to 300°C, from the viewpoints of moldability and the strength of the molded article. The Tg of resin (A) can be measured by using a differential scanning calorimetry (DSC) apparatus (for example, "Shimadzu DSC-60" manufactured by Shimadzu Corporation) in a nitrogen atmosphere and raising the temperature at a rate of 20°C / min from 40 to 300°C in accordance with JIS K7121 (1987). Incidentally, the Tg of resin (A) can be increased by increasing the aromatic ring concentration (weight ratio of aromatic rings in the resin), and can be decreased by increasing the number of alkyl groups or increasing the carbon number of the alkyl groups.

[0052] In the present invention, the weight average molecular weight of resin (A) (hereinafter sometimes abbreviated as Mw) is preferably 1000 to 20000, more preferably 1200 to 15000, from the viewpoints of emulsion stability and aggregability. In the present invention, Mw and the number average molecular weight (hereinafter sometimes abbreviated as Mn) can be determined in terms of polystyrene under the following conditions by using gel permeation chromatography (GPC). <Measurement conditions of GPC> Liquid delivery device: Isocratic HPLC Pump 1515 manufactured by Waters Detector: Refractive Index Detector 2-414 manufactured by Waters Column: Mixed-D (packed silica gel particle size 5 μm, tube length 300 mm, inner diameter 7.5 mm) Solvent: chloroform Flow rate: 1 mL / min Measurement temperature: 35°C

[0053] The fiber aggregating agent of the present invention contains a modified product (B) of the above resin (A). In the fiber aggregating agent of the present invention, one kind of the modified product (B) may be used, or two or more kinds may be used in combination. In the present invention, the modified product (B) is a modified resin obtained by introducing at least one group selected from the group consisting of a (poly)oxyalkylene group, a sulfo group, a carboxyl group, and a 1,3-dioxo-2-oxapropylene group into the resin (A). Examples of modified resins in which sulfo groups have been introduced into resin (A) include those in which a sulfonating agent (such as chlorosulfuric acid or fuming sulfuric acid) is reacted with resin (A) to introduce sulfo groups into aromatic rings of resin (A). Furthermore, modified resins obtained by introducing a (poly)oxyalkylene group and / or a sulfo group into resin (A) include the following modified products depending on the type of functional group possessed by resin (A). When the resin (A) is a resin having hydroxyl groups (including resins obtained by reaction with an aromatic compound having hydroxyl groups, specifically, polyphenylene ether resin (A1), polyarylate resin (A2), polysulfone resin (A3), polyethersulfone resin (A4), aromatic polyetherketone (A7), aromatic polyetheretherketone resin (A8), etc.), examples of the resin include a reaction product of the hydroxyl group with at least one selected from the group consisting of alkylene oxide, sulfamic acid, chlorosulfuric acid, and sultones (e.g., 1,3-propane sultone). The reaction with alkylene oxide can produce a modified product having (poly)oxyalkylene groups, and the reaction with at least one selected from sulfamic acid, chlorosulfuric acid, and sultones can add a sulfo group (—SO3H) to the hydroxyl group. In the present invention, the (poly)oxyalkylene group means an "oxyalkylene group and / or a polyoxyalkylene group." In the present invention, alkylene oxides include those having 2 to 4 carbon atoms, and specific examples thereof include ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, etc.

[0054] When the resin (A) is a resin having a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group (for example, a resin obtained by a reaction using an aromatic compound having a carboxyl group or an aromatic compound having a 1,3-dioxo-2-oxapropylene group, specifically, a polyarylate resin (A2), an aromatic polyimide resin (A5), an aromatic polyetherimide resin (A6), etc.), examples of the resin include a reaction product of a carboxyl group with an alkylene oxide. A modified product having a (poly)oxyalkylene group can be obtained by reaction with an alkylene oxide, and a sulfo group (—SO3H) can be added to a hydroxyl group by reaction with at least one of sulfamic acid, chlorosulfuric acid, and sultones.

[0055] When the resin (A) is a resin having an amino group (for example, a resin obtained by a reaction using an aromatic compound having an amino group, specifically, an aromatic polyimide resin (A5), an aromatic polyetherimide resin (A6), etc.), examples of the resin include a reaction product of an amino group with at least one selected from the group consisting of alkylene oxide, sulfamic acid, chlorosulfuric acid, and sultones (for example, 1,3-propane sultone). A modified product having a (poly)oxyalkylene group can be obtained by the reaction with an alkylene oxide, and a sulfo group (—SO3H) can be added to a hydroxyl group by the reaction with at least one selected from sulfamic acid, chlorosulfuric acid, and sultones.

[0056] A modified resin in which a carboxyl group and / or a 1,3-dioxo-2-oxapropylene group is introduced into resin (A) can be obtained by heating and mixing resin (A) with an unsaturated carboxylic acid and / or its acid anhydride, followed by an addition reaction. The unsaturated carboxylic acid includes an unsaturated monocarboxylic acid and an unsaturated dicarboxylic acid. Examples of the unsaturated monocarboxylic acid include chain aliphatic unsaturated monocarboxylic acids having 3 to 24 carbon atoms (such as acrylic acid and methacrylic acid), alicyclic unsaturated monocarboxylic acids having 7 to 24 carbon atoms (such as cyclohexenecarboxylic acid, cycloheptenecarboxylic acid, bicycloheptenecarboxylic acid, and methyltetrahexenecarboxylic acid), and aromatic unsaturated monocarboxylic acids having 7 to 24 carbon atoms (such as 4-vinylbenzoic acid). Examples of the unsaturated dicarboxylic acid include chain aliphatic dicarboxylic acids having 4 to 24 carbon atoms (maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc.), and alicyclic dicarboxylic acids having 8 to 24 carbon atoms (cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, etc.). Of these, maleic acid, maleic anhydride and fumaric acid are preferred.

[0057] When the resin (A) is a polyphenylene ether resin (A1), for example, methods described in JP-A-8-311196, JP-A-2005-8829, etc. can be used. Specifically, for example, the polyphenylene ether resin (A1) and an unsaturated carboxylic acid and / or its acid anhydride can be reacted by melt-kneading them at a temperature of 150 to 350°C using a twin-screw extruder, a roll mill, etc. in the presence of a radical generator (benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, azobisisovaleronitrile, 2,3-diphenyl-2,3-dimethylbutane, etc.) using a known method, for example, or by reacting them by heating them in a solvent (for example, benzene, toluene, xylene, etc.).

[0058] From the viewpoint of the strength of the molded article, the modified product (B) is preferably a modified resin obtained by introducing at least one group selected from the group consisting of a sulfo group, a carboxyl group, and a 1,3-dioxo-2-oxapropylene group into the resin (A).

[0059] In the modified product (B), the oxyalkylene group is preferably an oxyethylene group or a combination of an oxyethylene group and an oxypropylene group, more preferably an oxyethylene group, from the viewpoint of emulsion stability.

[0060] From the viewpoint of emulsion stability, the modified product (B) preferably has 5 to 50% by weight, and more preferably 7 to 40% by weight, of oxyalkylene groups based on the weight of the modified product (B).

[0061] The glass transition temperature (hereinafter sometimes abbreviated as Tg) of the modified product (B) is preferably from 10 to 350°C, more preferably from 100 to 300°C, from the viewpoints of moldability and strength of molded articles.

[0062] The Mw of the modified product (B) is preferably from 1,500 to 30,000, more preferably from 1,700 to 25,000, from the viewpoint of sizing ability.

[0063] In the present invention, the average number of hydroxyl groups per molecule in the resin (A) is preferably 1.5 or more from the viewpoint of emulsion stability. From the viewpoint of emulsion stability, the average total number of hydroxyl groups, sulfo groups, and carboxyl groups per molecule in all modified products (B) contained in the fiber sizing agent of the present invention is preferably 1.5 or more, more preferably 2 to 10. In the present invention, one 1,3-dioxo-2-oxapropylene group (acid anhydride group) is calculated as two carboxyl groups. The average number of hydroxyl groups, sulfo groups and carboxyl groups per molecule can be measured by Mn, hydroxyl value, strong acid value and acid value. Specifically, the average number of hydroxyl groups per molecule can be calculated from the hydroxyl value (JIS K0070, pyridine-acetyl chloride method) and Mn (the above-mentioned GPC measurement conditions) of the modified product (B) using the following formula: Average number of hydroxyl groups per molecule = Mn / 56100 × hydroxyl value The average number of sulfo groups per molecule can be calculated from the strong acid value and Mn (the above-mentioned GPC measurement conditions) of the modified product (B) using the following formula. Average number of sulfo groups per molecule = Mn / 56100 x strong acid value When the resin (A) is a resin whose hydroxyl value is difficult to measure, such as the polyphenylene ether resin (A1) and the polyarylate resin (A2), the hydroxyl value can be measured by the method described below.

[0064] <Method for measuring strong acid value> In accordance with JIS K0070-1992 (neutralization titration method), titrate with KOH titration solution using thymol blue indicator as the indicator, and the point at which the color changes from red to yellow and persists for approximately 30 seconds is taken as the endpoint. Calculate the strong acid number using the number of mL (S) of KOH titration solution required for the titration using the following formula. Note that if the sample remains yellow even after adding the indicator, the strong acid number is considered to be 0. Strong acid number = S x f x Y S: ml of KOH titration solution required for titration f: Potency of KOH titration solution Y: If the KOH solution used for titration is 0.1 mol / L, use 5.61. If it is 0.01 mol / L, use 0.561.

[0065] The average number of carboxyl groups per molecule can be calculated from the acid value, strong acid value and Mn (the above-mentioned GPC measurement conditions) of the modified product (B) by the following mathematical formula. Average number of carboxyl groups per molecule = Mn / 56100 x (acid value - strong acid value) The acid value in the present invention is a value obtained by measuring in accordance with JIS K0070 according to the following procedures (1) to (3). <Acid value measurement method> (1) Dissolve 1 g of (X) in 100 g of THF adjusted to 100°C. (2) At the same temperature, titration is carried out with 0.1 mol / L potassium hydroxide aqueous solution (trade name "0.1 mol / L potassium hydroxide aqueous solution", manufactured by Wako Pure Chemical Industries, Ltd.) using phenolphthalein as an indicator. (3) Convert the amount of potassium hydroxide required for titration into mg to calculate the acid value (unit: mgKOH / g). The acid value of the modified product (B) is preferably from 5 to 112 mgKOH / g, more preferably from 10 to 80 mgKOH / g, from the viewpoint of emulsion stability.

[0066] In the present invention, when the modified product (B) is heated in nitrogen to 500°C under conditions of a temperature rise starting temperature of 30°C and a temperature rise rate of 5°C / min, the heating weight loss ratio at 400°C (hereinafter abbreviated as heating weight loss ratio (400°C)) is 20% by weight or less, preferably 10% by weight or less, and more preferably 8% by weight or less, from the viewpoint of the appearance and strength of the molded product. If the heating weight loss ratio exceeds 20% by weight, gas, which is a component derived from heating weight loss, is generated during molding, which may deteriorate the appearance on the surface of the molded product and cause void formation inside the molded product, resulting in a decrease in strength. The heating weight loss ratio (400°C) can be determined by using a heating weight loss analyzer (TG / DTA6200 [Seiko Instruments Inc.]) to heat approximately 10 mg of a sample in nitrogen from 30°C to 500°C at a rate of 5°C / min, and analyzing the resulting TG curve to calculate the heating weight loss ratio at 400°C based on the weight of the sample used in the measurement (measurement atmosphere: nitrogen at 200 ml / min, sample container: aluminum pan). The heat loss rate (400°C) can be reduced by improving the aromatic ring concentration or molecular weight of the modified product (B), specifically by reducing the amount of oxyalkylene groups in (B), by using a modified product (B) of a resin (A) with a high molecular weight, or by using a modified product (B) of a resin (A) with fewer substituents such as alkyl groups. In the fiber sizing agent of the present invention, the heat loss ratio (400°C) of the resin (A) and the modified substance (B) is 10% by weight or less, so that defects do not occur in the molded product, and the appearance and strength of the molded product can be improved.

[0067] The fiber sizing agent of the present invention may contain a surfactant (C) and other additives in addition to the modified substance (B).

[0068] Examples of the surfactant (C) include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. The surfactant (C) may be used alone or in combination of two or more. Among the surfactants (C), anionic surfactants, nonionic surfactants, and combinations thereof are preferred from the viewpoint of ease of preparation of an aqueous emulsion. More preferred are alkylene oxide adducts of alkyl phenols (preferably alkyl groups having 9 to 15 carbon atoms), alkylene oxide adducts of aryl alkyl phenols (preferably alkyl groups having 2 to 10 carbon atoms) (styrenated phenol, styrenated cumylphenol, styrenated cresol, etc.), sulfate ester salts of the alkylene oxide adducts of the alkyl phenols, sulfate ester salts of the alkylene oxide adducts of aryl alkyl phenols, urethane joint compounds of the alkylene oxide adducts of aryl alkyl phenols and polyethylene glycol, and mixtures thereof, and particularly preferred are alkylene oxide adducts of aryl alkyl phenols, sulfate ester salts of the alkylene oxide adducts of aryl alkyl phenols, and mixtures thereof.

[0069] Other additives include neutralizing agents, smoothing agents, preservatives, and antioxidants. Examples of the neutralizing agent include potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, monolaurylamine, trimethylamine, dimethylmonoethanolamine, triethanolamine, ethylenediamine, and ammonia. Examples of the smoothing agent include waxes (polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, modified polyethylene, modified polypropylene, etc.), higher fatty acid (fatty acid having 6 to 30 carbon atoms) alkyl (alkyl having 1 to 24 carbon atoms) esters (methyl stearate, ethyl stearate, propyl stearate, butyl stearate, octyl stearate, stearyl stearate, etc.), higher fatty acids (fatty acid having 6 to 30 carbon atoms) (myristic acid, palmitic acid, stearic acid, etc.), natural fats and oils (coconut oil, beef tallow, olive oil, rapeseed oil, etc.), and liquid paraffin. Preservatives include benzoic acid, salicylic acid, sorbic acid, quaternary ammonium salts, and imidazole. Examples of antioxidants include phenols (such as 2,6-di-t-butyl-p-cresol), thiodipropionates (such as dilauryl 3,3'-thiodipropionate), and phosphites (such as triphenyl phosphite).

[0070] From the viewpoint of emulsion stability, the weight proportion of the modified substance (B) is preferably 40 to 99.5% by weight, more preferably 50 to 99% by weight, and particularly preferably 60 to 98.5% by weight, based on the weight of the solid content contained in the fiber sizing agent. From the viewpoint of emulsion stability, the weight proportion of the surfactant (C) is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, and particularly preferably 1 to 30% by weight, based on the weight of the solid content contained in the fiber sizing agent. The total weight proportion of the neutralizing agent, smoothing agent, preservative, and antioxidant as other additives is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, and particularly preferably 0.1 to 10% by weight, based on the weight of the solid content contained in the fiber sizing agent, from the viewpoints of fluidity and stability over time. Here, the solid content is the residue remaining after heating and drying 1 g of the sample at 130°C for 45 minutes in a circulating air dryer.

[0071] The fiber sizing agent of the present invention preferably contains an aqueous medium so as to be in the form of an aqueous solution or an aqueous emulsion. When an aqueous medium is contained, it is easy to adjust the amount of solid matter contained in the fiber sizing agent to adhere to the fibers to an appropriate amount, so that a fiber bundle having even greater strength in a molded body of the composite material can be obtained. As the aqueous medium, known aqueous media can be used, and specific examples thereof include water and hydrophilic organic solvents [monohydric alcohols having 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol, etc.), ketones having 3 to 6 carbon atoms (e.g., acetone, ethyl methyl ketone, methyl isobutyl ketone, etc.), glycols having 2 to 6 carbon atoms (e.g., ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, etc.) and their monoalkyl (e.g., 1 to 2 carbon atoms) ethers, dimethylformamide, and alkyl acetates having 3 to 5 carbon atoms (e.g., methyl acetate, ethyl acetate, etc.)]. These may be used in combination of two or more kinds. Among these, from the viewpoint of safety etc., water and mixed solvents of hydrophilic organic solvents and water are preferred, and water is more preferred.

[0072] From the viewpoint of cost, etc., it is preferable that the fiber sizing agent of the present invention be distributed at a high concentration and be distributed at a low concentration when fiber bundles are produced. That is, by distributing the agent at a high concentration, transportation costs and storage costs can be reduced, and by treating fibers at a low concentration, fiber bundles that can increase the strength of molded composite materials can be produced. The concentration of the high-concentration aqueous solution or emulsion (weight ratio of solid content to fiber sizing agent) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, from the viewpoint of storage stability and the like. On the other hand, the concentration of the low-concentration aqueous solution or emulsion (weight ratio of solid content to fiber sizing agent) is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, from the viewpoint of ensuring an appropriate amount of sizing agent adhered during fiber bundle production.

[0073] The fiber sizing agent of the present invention can be produced by mixing the modified substance (B) with, if necessary, an aqueous medium, a surfactant (C), and other additives in any order. When an aqueous solvent is contained, it is preferable to premix the components other than the aqueous medium, and then add the aqueous medium to the resulting mixture to dissolve or emulsify the mixture.

[0074] When components other than the aqueous medium are mixed in advance, the temperature is preferably 20 to 90°C, more preferably 40 to 90°C, from the viewpoint of ease of mixing, and the same applies to the temperature for the subsequent dissolution or emulsification dispersion. The time for the dissolving or emulsifying dispersion is preferably 1 to 20 hours, and more preferably 2 to 10 hours.

[0075] There are no restrictions on the mixing equipment, dissolving equipment, and emulsifying / dispersing equipment, and examples that can be used include stirring blades (blade shape: paddle-shaped, three-stage paddle, etc.), Nauta mixers, ribbon mixers, conical blenders, mortar mixers, universal mixers (Universal Mixing Agitator 5DM-L, manufactured by San-ei Seisakusho Co., Ltd., etc.), and Henschel mixers.

[0076] Examples of fibers to which the fiber sizing agent of the present invention can be applied include known fibers such as glass fibers, carbon fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slag fibers (e.g., those described in WO 2003 / 47830), and from the viewpoint of improving the strength of a molded body of a composite material, the fiber is preferably at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, and slag fibers, and more preferably carbon fibers. Two or more of these fibers may be used in combination.

[0077] The fiber bundle of the present invention is a fiber bundle (a fiber bundle of approximately 3,000 to 50,000 fibers) obtained by treating at least one type of fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, and slug fibers with the fiber sizing agent of the present invention. That is, the fiber bundle of the present invention contains at least one type of fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slug fiber, and the modified product (B).

[0078] Fiber treatment methods include spraying and dipping. The amount (wt%) of solids contained in the fiber sizing agent adhered to the fibers is preferably 0.05 to 5 wt%, more preferably 0.2 to 2.5 wt%, based on the weight of the fibers. Within this range, the strength of the molded body (hereinafter sometimes referred to as a composite material) can be further improved.

[0079] The textile product of the present invention is a product made using the fiber bundle, and includes textile products obtained by processing the fiber bundle, such as woven fabrics, knitted fabrics, nonwoven fabrics (felt, mats, paper, etc.), chopped fibers, and milled fibers.

[0080] The resin composition of the present invention is a resin composition containing the fiber bundle and / or fiber product and a thermoplastic resin (E). The weight ratio of the thermoplastic resin (E) to the fiber bundles and fiber products (matrix resin / fiber bundles and fiber products) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 70 / 30, and particularly preferably 30 / 70 to 60 / 40, from the viewpoint of the strength of the composite material to be molded.

[0081] The thermoplastic resin (E) may be at least one selected from the group consisting of phenolic resins, melamine resins, urea resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyetherketoneketone resins, and polyphenylene sulfide resins. Of these, from the viewpoint of the strength of the molded product, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyetherketoneketone resins, and polyphenylene sulfide resins are preferred, and polyimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, and polyetheretherketone resins are more preferred.

[0082] The molded article of the present invention is obtained by molding the above-described resin composition of the present invention. The molding method for the molded article of the present invention is not particularly limited to a heat molding method, and examples include a filament winding molding method (a method in which prepreg sheets are wound around a rotating mandrel under tension and then heat molded), a press molding method (a method in which prepreg sheets are stacked and then heat molded), an autoclave method (a method in which prepreg sheets are pressed against a mold under pressure and then heat molded), and a method in which chopped fibers or milled fibers are mixed with a thermoplastic resin to form a resin composition, which is then injection molded. [Example]

[0083] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, % means % by weight and parts means parts by weight. Examples 1 to 4 below are reference examples.

[0084] <Production Example 1: Production of Polyphenylene Ether Resin (A-1)> A 1.5-liter jacketed reactor equipped with a sparger at the bottom for introducing oxygen-containing gas, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top was charged with 0.271 g of cupric chloride dihydrate, 1.20 g of 35% hydrochloric acid, 10.6 g of N,N,N',N'-tetramethylpropanediamine, 230 g of n-butanol, 535 g of methanol, 164 g of 2,6-dimethylphenol (referred to as "2,6-xylenol" in Table 1), and 32.0 g of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane (referred to as "bisphenol" in Table 1). The weight ratio of the solvents used was n-butanol:methanol = 30:70. Next, oxygen was introduced into the reactor via the sparger at a rate of 180 mL / min with vigorous stirring. At the same time, a heat transfer medium was passed through the jacket to maintain the polymerization temperature at 45 °C. The polymerization solution gradually took on the form of a slurry. 120 minutes after the start of oxygen introduction, the oxygen-containing gas flow was stopped, and a 50% aqueous solution of 1.40 g of ethylenediaminetetraacetic acid tripotassium salt (reagent, Dojindo Laboratories) was added to the polymerization mixture. Then, 1.75 g of hydroquinone (reagent, Wako Pure Chemical Industries, Ltd.) was added in small portions. The reaction was continued at 45°C for 1 hour until the polyphenylene ether slurry turned white. After the reaction was completed, the mixture was filtered and washed three times with methanol washing solution (b) in an amount such that the mass ratio (b / a) of the washed polyphenylene ether (a) to the washed solution (b) was 4. The mixture was then vacuum-dried at 120°C for 1 hour to obtain polyphenylene ether resin (A-1). The analytical results of (A-1) are shown in Table 1.

[0085] <Production Example 2: Production of Polyphenylene Ether Resin (A-2)> A polyphenylene ether resin (A-2) was obtained in the same manner as in Example 1, except that the phenolic compounds used were 136 g of 2,6-dimethylphenol and 64.0 g of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane. The analytical results are shown in Table 1.

[0086] <Production Example 3: Production of polyphenylene ether resin (A-3)> A polyphenylene ether resin (A-3) was obtained in the same manner as in Example 2, except that the amines used were 5.20 g of dibutylamine and 8.80 g of N,N,N',N'-tetramethylpropanediamine. The analytical results are shown in Table 1.

[0087] [Table 1]

[0088] <Production Example 4: Production of polyarylate resin (A-4)> A reactor equipped with a stirrer was charged with 20 g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as Bis A), 9.74 g of sodium hydroxide (hereinafter referred to as NaOH), and 3.36 g of tri-n-butylbenzylammonium chloride (hereinafter referred to as TBBAC), which were then dissolved in 59.2 mL of purified water to prepare an aqueous phase. Separately, an organic phase was prepared by dissolving 16.48 g of a 50 / 50 mixture of terephthalic acid dichloride and isophthalic acid dichloride as aromatic dicarboxylic acids in 350 mL of dichloromethane. While stirring the aqueous phase at a rotation speed of 400 rpm, the organic phase was gradually added dropwise at 20 mL / sec. Stirring was continued for four hours to allow interfacial polycondensation. The temperature was maintained at 15°C during the polymerization. After four hours, stirring was stopped, the mixture was allowed to stand, and the aqueous phase was separated and removed. Next, 550 ml of pure water and 2.74 ml of acetic acid were added to the organic phase, and the mixture was stirred again at 400 rpm for 30 minutes. After 30 minutes, the stirring was stopped, the mixture was allowed to stand, and the aqueous phase was removed. The remaining organic phase was repeatedly washed by adding pure water and stirring until it became neutral. Then, 137.4 ml of dichloromethane was added to the organic phase, and the insoluble matter was removed through a 2 μm diameter filter to obtain a resin solution. This resin solution was gradually added to 2060 ml of methanol while stirring to precipitate the resin. After the entire amount was added dropwise, the mixture was stirred for an additional 30 seconds. The stirring was stopped, the precipitated resin was separated, and the mixture was dried at 80°C and 13 Pa under reduced pressure for 12 hours to obtain polyarylate resin (A-4). The analytical results are shown in Table 2.

[0089] <Production Example 5: Production of polyarylate resin (A-5)> A polyarylate resin (A-5) was obtained in the same manner as in Production Example 4, except that 12.7 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter referred to as BisAP) and 11.0 g of bis(4-hydroxyphenyl)sulfone (hereinafter referred to as BisS) were added as dihydric phenol components. The analytical results are shown in Table 2.

[0090] <Production Example 6: Production of Polysulfone Resin (A-6)> In a reaction vessel equipped with a stirrer, nitrogen inlet tube, thermometer, and condenser, 77.02 parts by mass of 4,4'-dichlorodiphenyl sulfone, 75.08 parts by mass of 4,4'-dihydroxydiphenyl sulfone (bisphenol S), 43.54 parts by mass of potassium carbonate, and 165 parts by mass of N-methyl-2-pyrrolidone (hereinafter abbreviated as "NMP") were mixed and reacted at 190°C for 6 hours. The resulting reaction mixture was then diluted with NMP and cooled to room temperature to precipitate unreacted potassium carbonate and by-product potassium chloride. These inorganic salts were filtered to remove the polysulfone, resulting in a polysulfone solution in which polysulfone was dissolved in NMP. This solution was then added dropwise to water to precipitate the polysulfone, and unnecessary NMP was removed by filtration to obtain a precipitate. The resulting precipitate was repeatedly washed with methanol and dried by heating at 150°C to obtain polysulfone resin (A-6). Analysis of the polysulfone resin (A-6) revealed that it had an Mw of 7,000, an average number of hydroxyl groups per molecule of 2, and a glass transition temperature of 170°C.

[0091] <Production Example 7: Production of polyethersulfone resin (A-7)> A reaction vessel equipped with a stirrer, nitrogen inlet tube, thermometer, and condenser was charged with 214.22 parts by weight of powdered 4,4'-dihydroxybenzophenone, 500 ml of 4N aqueous potassium hydroxide, and 200 parts by weight of methanol, and the mixture was stirred at room temperature for 1 hour. At this point, the contents of the reaction vessel had become a pale yellow, homogeneous solution. This solution was transferred to an eggplant-shaped flask, and the methanol and most of the water were removed using a rotary evaporator. The resulting solid was pulverized to a fine powder of 0.150 mm diameter or less, and the water was removed using a vacuum dryer. After drying, the content of the dipotassium salt of 4,4'-dihydroxybenzophenone was analyzed by neutralization titration and found to be 94.8% by weight. Next, 61.3 parts by weight of powdered dipotassium salt of 4,4'-dihydroxybenzophenone (94.8% by weight) and 106.7 parts by weight of diphenyl sulfone were added to a reaction vessel equipped with a stirrer, nitrogen inlet tube, thermometer, and condenser, and the mixture was heated to 230°C. Next, water was completely removed under reduced pressure, and nitrogen was introduced to return the pressure to normal. Next, 52.22 parts by weight of powdered 4,4'-dichlorodiphenyl sulfone and 40.00 parts by weight of diphenyl sulfone were added, and the temperature was raised to 290°C while flowing nitrogen. Stirring was continued at the same temperature for 8 hours while flowing nitrogen. After cooling to room temperature, the solidified reaction mixture was pulverized, washed repeatedly with methanol, and dried at 150°C to obtain polyethersulfone resin (A-7). Analysis of polyethersulfone resin (A-7) revealed that it had an Mw of 8,000, an average number of hydroxyl groups per molecule of 2, and a glass transition temperature of 205°C.

[0092] <Production Example 8: Production of aromatic polyimide resin (A-8)> A pressure-resistant reactor equipped with a stirrer, nitrogen inlet tube, thermometer, and condenser was charged with 44.21 g (0.12 mol) of 4,4'-bis(3-aminophenoxy)biphenyl, 24.58 g (0.1127 mol) of pyromellitic dianhydride, 2.17 g (0.01416 mol) of phthalic anhydride, and 212.9 g of distilled water. The atmosphere inside the pressure-resistant reactor was thoroughly purged with nitrogen while stirring. The temperature was raised to 180°C. The internal pressure at this time was approximately 0.8 MPa. The mixture was then stirred at 180°C (0.8 MPa) for 3 hours. After cooling, water was distilled off from the reaction system, and the mixture was dried in nitrogen at 300°C for 8 hours to obtain aromatic polyimide resin (A-8). Analysis of the aromatic polyimide resin (A-8) revealed that it had a Mw of 16,000, an average number of hydroxyl groups per molecule of 0, and a glass transition temperature of 210°C.

[0093] <Production Example 9: Production of aromatic polyetherimide resin (A-9)> A pressure-resistant reactor equipped with a stirrer, nitrogen inlet tube, thermometer, and condenser was charged with 43 parts by weight of 2,2'-bis(4-(4-aminophenoxy)phenyl)propane, 52 parts by weight of 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 1,000 parts by weight of N-methylpyrrolidone, and 300 parts by weight of toluene. The mixture was stirred at room temperature for 1 hour, then heated to 150°C and refluxed and stirred for another 1 hour. The mixture was then heated to 180°C while distilling off the toluene, and then cooled. The reaction solution was poured into methanol, and the polymer was isolated. The polymer was washed repeatedly with methanol and dried at 150°C to obtain aromatic polyetherimide resin (A-9). Analysis of the aromatic polyetherimide resin (A-9) revealed that it had an Mw of 11,000, an average number of hydroxyl groups per molecule of 0, and a glass transition temperature of 195°C.

[0094] <Production Example 10: Production of aromatic polyether ketone resin (A-10)> A reaction vessel equipped with a stirrer and nitrogen inlet was charged with 10.66 parts by weight of 4,4'-dichlorobenzophenone, 6.46 parts by weight of 1,3-bis(4-chlorobenzoyl)benzene, 16.76 parts by weight of 4,4'-biphenol, 13.06 parts by weight of potassium carbonate, and 100 parts by weight of diphenyl sulfone. Nitrogen was blown in and the temperature was raised to 140°C to dissolve the diphenyl sulfone. The temperature was raised to 250°C in 50 minutes, held at this temperature for 90 minutes, and then raised to 340°C in 40 minutes and maintained at this temperature for 35 minutes. The reaction solution was poured into a stainless steel tray and solidified. The solidified reaction mixture was crushed, washed repeatedly with methanol, and dried at 150°C to obtain aromatic polyetherketone resin (A-10). Analysis of the aromatic polyetherketone resin (A-10) revealed a Mw of 1,100, an average number of hydroxyl groups per molecule of 2, and a glass transition temperature of 130°C.

[0095] <Production Example 11: Production of aromatic polyether ether ketone resin (A-11)> A pressure-resistant reactor equipped with a stirrer and a nitrogen inlet tube was charged with 32.73 parts by weight of 4,4'-difluorobenzophenone, 17.18 parts by weight of hydroquinone, 90.15 parts by weight of diphenyl sulfone, and 15.05 parts by weight of potassium carbonate. Nitrogen was then blown in and the temperature was raised to 140°C to dissolve the diphenyl sulfone. The temperature was raised to 250°C in 50 minutes, held at this temperature for 90 minutes, and then raised to 340°C in 40 minutes. Polymerization was carried out at this temperature for 35 minutes, and the reaction solution was poured into a stainless steel tray and solidified. The solidified reaction mixture was crushed, washed repeatedly with methanol, and dried at 150°C to obtain aromatic polyether ether ketone resin (A-11). Analysis of the aromatic polyether ether ketone resin (A-11) revealed a Mw of 9,000, an average number of hydroxyl groups per molecule of 2, and a glass transition temperature of 135°C.

[0096] <Comparative Production Example 1: Production of Polyarylate Resin (A'-1)> In a reaction vessel equipped with a stirring device, 42.7 g of bisphenol A as a divalent phenol component, 0.800 g of p-tert-butylphenol (PTBP) as a terminal blocking agent, 16.3 g of NaOH as an alkali, 0.730 g of a 50% by mass aqueous solution of TBBAC as a polymerization catalyst, and 0.260 g of sodium hydrosulfite as an antioxidant were charged and dissolved in 1250 parts by mass of water (aqueous phase). Separately, 37.9 g of a mixture of isophthaloyl chloride / terephthaloyl chloride = 1 / 1 (molar ratio) (MPC) was dissolved in 1000 g of methylene chloride (organic phase). The aqueous phase was stirred in advance, and the organic phase was added to the aqueous phase under strong stirring, and polymerization was carried out by an interfacial polymerization method at 15 °C for 2 hours. After that, stirring was stopped, and the aqueous phase and the organic phase were separated by decantation. After removing the aqueous phase, 250 g of methylene chloride, 1500 g of pure water, and 5.00 g of acetic acid were added to stop the reaction, and the mixture was stirred at 15 °C for 30 minutes. Then, the organic phase was washed 10 times with pure water, and the organic phase was added to methanol to precipitate the polymer. After filtering the precipitated polymer, vacuum drying was carried out at 165 °C for 24 hours to obtain a polyarylate resin (A'-1). The analysis results are shown in Table 2.

[0097]

Table 2

[0098] <Measurement method of Mw of resins (A-1) to (A-11), resin (A'-1), modified products (B-1) to (B-19), and modified products (B'-1) to (B'-3)> The Mw of each resin and the Mw of each modified product were determined by gel permeation chromatography (GPC) in terms of polystyrene under the following conditions. <Measurement conditions of GPC> Liquid delivery device: Waters, Isocratic HPLC Pump 1515 Detector: Waters, Refractive Index Detector 2414 Column: Mixed-D (packed silica gel particle size 5 μm, tube length 300 mm, inner diameter 7.5 mm) Solvent: chloroform Flow rate: 1mL / min Measurement temperature: 35℃

[0099] <Method for measuring the average number of hydroxyl groups per molecule of polyphenylene ether resin> 5.0 mg of polyphenylene ether resin was weighed out. This weighed polyphenylene ether resin was then dissolved in 25 mL of methylene chloride. 150 μL of a 2% by mass tetraethylammonium hydroxide (TEAH) ethanol solution was added to 2.0 mL of the prepared solution, and the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (Hitachi, Ltd.: U-3210 model) (a 1 cm long absorbance measurement cell was used). Based on the measurement results, the pseudo molecular weight obtained from the absorbance was calculated using the following formula: Furthermore, the average number of hydroxyl groups per molecule of the polyphenylene ether resin was calculated using the number average molecular weight determined by gel permeation chromatography using the method described above. The pseudo molecular weight (g / mol) obtained from absorbance is [(ε × 5) / (25 × Abs)], where ε is the extinction coefficient, which is 4700 L / mol cm. Number of hydroxyl groups per molecule of polyphenylene ether (number / molecule) = (number average molecular weight determined using gel permeation chromatography) / (pseudo molecular weight obtained from absorbance)

[0100] <Method for measuring the average number of hydroxyl groups per molecule of polyarylate resin> Using a high-resolution nuclear magnetic resonance spectrometer (JEOL LA-400 NMR), 1 The composition and molar ratio of the monomer components constituting the polyarylate resin were determined from the peak areas of each by H-NMR analysis. The amount of hydroxyl groups (mol%) was quantified from the peak area of ​​the protons located at the ortho- or meta-position relative to the phenolic hydroxyl groups. The average number of hydroxyl groups was calculated from the obtained amount of hydroxyl groups (mol%) and the Mn of the polyarylate resin using the following formula: NMR measurement conditions Resolution: 400MHz Solvent: Mixture of deuterated trifluoroacetic acid and deuterated tetrachloroethane in a volume ratio of 1 / 11 Temperature: 50℃ Average number of hydroxyl groups per molecule of polyarylate resin = Amount of hydroxyl groups (mol%) × Mn / 100

[0101] <Method for measuring the average number of hydroxyl groups per molecule of resins (A-6) to (A-11)> The average number of hydroxyl groups per molecule of each resin was determined by the same method as in the above "Method for measuring the average number of hydroxyl groups per molecule of polyarylate resin."

[0102] <Method for measuring the glass transition temperature (Tg) of resins (A-1) to (A-11), resin (A'-1), modified products (B-1) to (B-19), and modified products (B'-1) to (B'-3)> The Tg of each resin and each modified product was measured in accordance with JIS K7121 (1987) using a differential scanning calorimeter (DSC) (e.g., Shimadzu DSC-60 manufactured by Shimadzu Corporation) by heating from 40 to 300°C at a rate of 20°C / min in a nitrogen atmosphere.

[0103] <Production Example 12> A glass autoclave was charged with 100 g of the polyphenylene ether resin (A-1) obtained in Production Example 1 and 100 g of methyl ethyl ketone (MEK) and the mixture was uniformly dissolved at 150°C. 20 g of EO was added dropwise from a pressure-resistant dropping funnel over 6 hours while maintaining the reaction temperature at 135-150°C, and the mixture was then aged for an additional 3 hours at 135°C. The MEK was then distilled off to obtain a modified product (B-1). The weight of the resulting (B-1) was 120 g, indicating that all of the EO had reacted. The oxyalkylene group content was calculated from the amount of EO charged and the weight of the resulting (B-1). The analytical results are shown in Table 3.

[0104] <Production Examples 13 to 18, Production Examples 25 to 26, Production Examples 29 to 30, Comparative Production Examples 2 to 4> Modified products (B-2) to (B-7), (B-14), (B-15), (B-18), (B-19) and modified products (B'-1) to (B'-3) were obtained by the same procedure as in Production Example 12, except that the type and amount of resin (A) used and the type and amount of alkylene oxide used were changed to those shown in Table 3 or Table 4. The analytical results are shown in Table 3 or Table 4.

[0105] <Production Example 19> 2042 g of orthodichlorobenzene was placed in a flask equipped with a stirrer, and 100 g of the polyphenylene ether resin (A-1) obtained in Production Example 1 was added thereto and stirred at 90°C. After (A-1) was completely dissolved in orthodichlorobenzene, the mixture was cooled, and a mixed solution of 29.9 g of chlorosulfonic acid and 46.0 g of sulfolane was added dropwise at 40°C over 30 minutes and then maintained at 40°C for 4.5 hours. No precipitate was observed in the solution. The reaction solution was then added dropwise to 3.2 L of ion-exchanged water, and the resulting slurry containing white particles was filtered. This slurry was washed and filtered with heptane and ion-exchanged water until the pH of the filtrate reached 5.0 or higher. The resulting mixture was then dried in a vacuum dryer at 80°C and a pressure of 7 kPa or less for 24 hours to obtain the modified product (B-8). The analytical results are shown in Table 3.

[0106] <Production Examples 20-21> Modified products (B-9) and (B-10) were obtained by the same procedure as in Production Example 19, except that the type and amount of resin (A) used and the amount of chlorosulfonic acid used were changed to the amounts shown in Table 3. The analytical results are shown in Table 3.

[0107] <Production Example 22> A reaction vessel was charged with 100 g of the polyphenylene ether resin (A-1) obtained in Production Example 1 and 3.7 g of maleic anhydride. After purging with nitrogen, the mixture was heated to 180°C under nitrogen flow to achieve a uniform solution. A solution of 0.5 g of a radical generator (dicumyl peroxide, trade name "Percumyl D," manufactured by NOF Corporation) (C-1) dissolved in 5 g of xylene was added dropwise over 5 minutes, followed by stirring at 150°C for 3 hours. Unreacted maleic anhydride was then removed by distillation under reduced pressure (1.5 kPa, hereinafter the same) to obtain a modified product (B-11). The analytical results are shown in Table 3.

[0108] <Production Examples 23-24, Production Examples 27-28> Modified products (B-12), (B-13), (B-16) and (B-17) were obtained in the same manner as in Production Example 22, except that the type and amount of resin (A), the amount of radical generator and the amount of maleic anhydride used were changed to those shown in Table 3 or Table 4. The analytical results are shown in Table 3 or Table 4.

[0109] [Table 3]

[0110] [Table 4]

[0111] <Method for measuring the average number of hydroxyl groups per molecule of modified products (B-1) to (B-19) and modified products (B'-1) to (B'-3)> The hydroxyl value was measured in accordance with JIS K0070 (pyridine-acetyl chloride method), Mn was measured under the above-mentioned GPC measurement conditions, and Mn was calculated from the obtained hydroxyl value and Mn using the following mathematical formula. Average number of hydroxyl groups per molecule = Mn / 56100 x hydroxyl value

[0112] <Average number of sulfo groups per molecule of modified products (B-1) to (B-19) and modified products (B'-1) to (B'-3)> The average number of sulfo groups per molecule was calculated from the strong acid value and Mn (the above-mentioned GPC measurement conditions) of each modified product using the following formula. Average number of sulfo groups per molecule = Mn / 56100 x strong acid value

[0113] <Average number of carboxyl groups per molecule of modified products (B-1) to (B-19) and modified products (B'-1) to (B'-3)> The average number of carboxyl groups per molecule was calculated from the acid value, strong acid value, and Mn (the above-mentioned GPC measurement conditions) of each modified product using the following formula. Average number of carboxyl groups per molecule = Mn / 56100 x (acid value - strong acid value)

[0114] <Method for measuring heat loss ratio> Using a heat loss analyzer ("TG / DTA6200" [Seiko Instruments Inc.]), approximately 10 mg of sample was heated in nitrogen from 30°C to 500°C at a rate of 5°C / min, and the resulting TG curve was analyzed to calculate the heat loss ratio at 400°C based on the weight of the sample used in the measurement (measurement atmosphere: nitrogen at 200 ml / min, sample container: aluminum pan).

[0115] Example 1 A reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer was charged with 300 parts of (B-1) and 300 parts of MEK, and the mixture was stirred and the temperature was adjusted to 150°C to dissolve uniformly. 700 parts of water was then added little by little over 5 hours at 110 to 150°C to carry out phase inversion emulsification. After cooling to room temperature, MEK was removed under reduced pressure, and water was added so that the solid content became 30.0% by weight, to obtain a fiber sizing agent (X-1).

[0116] <Example 2> A reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer was charged with 290 parts of the modified product (B-1) and 300 parts of MEK, and the mixture was uniformly dissolved by adjusting the temperature to 150°C under stirring. 10 parts of a propylene oxide / ethylene oxide adduct of styrenated phenol "Soprophor 796 / P" [manufactured by Solvay Nicca Co., Ltd.] (C-1) was then charged and mixed uniformly, after which 700 parts of water was added little by little over 5 hours at 110-150°C to carry out phase inversion emulsification. After cooling to room temperature, the MEK was removed under reduced pressure, and water was added so that the solid content was 30.0% by weight, to obtain a fiber sizing agent (X-2).

[0117] <Examples 3 to 7, Comparative Examples 2 to 3> Fiber sizing agents (X-3) to (X-7), (X'-2) and (X'-3) were obtained by the same procedure as in Example 1, except that the formulation in Example 1 was changed as shown in Table 5 or Table 6.

[0118] <Examples 8, 15-16, 19-20 and Comparative Example 1> In Example 2, the same procedure as in Example 2 was carried out, except that the type and amount of the modified substance and the amount of (C-1) used were those shown in Table 5 or Table 6, to obtain fiber sizing agents (X-8), (X-15) to (X-16), (X-19) to (X-20), and (X'-1).

[0119] Example 9 A reaction vessel equipped with a stirrer, a heater / cooler, and a thermometer was charged with 300 parts of (B-8), 7.3 parts of sodium hydroxide, and 300 parts of MEK, and the mixture was stirred and the temperature was adjusted to 150°C to dissolve uniformly. 700 parts of water was then added little by little over 5 hours at 110 to 150°C to carry out phase inversion emulsification. After cooling to room temperature, MEK was removed under reduced pressure, and water was added so that the solid content became 30.0% by weight, to obtain a fiber sizing agent (X-9).

[0120] <Examples 10 to 14, 17 to 18> In Example 9, fiber sizing agents (X-10) to (X-14), (X-17) and (X-18) were obtained in the same manner as in Example 9, except that the type and amount of the modified substance and the amount of sodium hydroxide used were those shown in Table 5 or Table 6.

[0121] [Table 5]

[0122] [Table 6]

[0123] <Creating test specimens for evaluating carbon fiber bundles and evaluating bundleability> (1) Untreated carbon fibers (fineness 800 tex, number of filaments 12,000) were immersed in an aqueous solution in which the fiber sizing agent (X) was further diluted with water to a solids concentration of 1.5% by weight, and the fibers were impregnated with the sizing agent, followed by hot air drying at 180°C for 3 minutes to produce a carbon fiber bundle. (2) The sizing property of the obtained carbon fiber bundle was evaluated in accordance with JIS L1096-2010 8.21.1 Method A (45° cantilever method). The larger the value (cm), the better the focusing performance. The bundle of carbon fibers obtained under these treatment conditions preferably has a bundle length of 18 cm or more when evaluated with a cantilever.

[0124] <Creating a molded body> (1) Fiber sizing agent (X) was diluted with water to a solids concentration of 1.5% by weight, and untreated carbon fibers (fineness 800 tex, number of filaments 12,000) were immersed in the aqueous solution to impregnate the fibers with the sizing agent, and the resulting carbon fiber bundles were dried with hot air at 180°C for 3 minutes, and cut to a length of 6 mm to produce short fiber bundles. The amount of solids attached to the fiber sizing agent was 1.5% by weight based on the untreated carbon fibers. (2) 70 parts by weight of polyether ether ketone resin (PEEK) [KetaSpire KT-820NT, manufactured by Solvay] was added to 30 parts by weight of the resulting short fiber bundle, and the mixture was dry-blended in a V-type blender. (3) This dry blend was kneaded in a vented twin-screw extruder at 385°C, a rotation speed of 70 rpm, and a residence time of 5 minutes to obtain each resin composition (Y), which was extruded into a strand shape and cut with a pelletizer to obtain resin pellets of the resin composition. (4) The obtained resin pellets were molded into evaluation test pieces using an injection molding machine "PS40EASE" manufactured by Nissei Plastic Industrial Co., Ltd., at a cylinder temperature of 385°C and a mold temperature of 150°C.

[0125] <Appearance of molded product> The molded article obtained above was observed under a microscope at 20x magnification, and the appearance was evaluated according to the following evaluation criteria. <Evaluation criteria> ◎: No fog at all 〇: Almost no voids (10cm 2 (1 to 5 locations per ×: Voids are noticeable (10cm 2 (6 or more per

[0126] <Flexural strength of molded product> Using the evaluation test piece obtained above, the flexural strength of the molded article was measured in accordance with JIS K 7171. The greater the flexural strength of the molded article, the more preferable it is. [Industrial Applicability]

[0127] The fiber sizing agent of the present invention can impart excellent strength to molded articles and has excellent convergence properties, and therefore can be used as a sizing agent for glass fibers, carbon fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, or slug fibers. Furthermore, a prepreg can be obtained by using a fiber bundle or fiber product obtained by treating with the fiber sizing composition of the present invention as a reinforcing fiber and a thermoplastic resin as a matrix.

Claims

1. A fiber sizing agent containing a modified product (B) of at least one resin (A) selected from the group consisting of polyarylate resin (A2), polysulfone resin (A3), polyethersulfone resin (A4), aromatic polyimide resin (A5), aromatic polyetherimide resin (A6), aromatic polyetherketone resin (A7), aromatic polyetheretherketone resin (A8), and aromatic polyetherketoneketone resin (A9), wherein the modified product (B) is a modified resin obtained by introducing at least one functional group selected from the group consisting of a (poly)oxyalkylene group, a sulfo group, a carboxyl group, and a 1,3-dioxo-2-oxapropylene group into the resin (A), and wherein the modified product (B) has a heat loss rate of 20% by weight or less at 400°C when heated in nitrogen under conditions of a temperature rise starting temperature of 30°C and a temperature rise rate of 5°C / min up to 500°C, and the modified product (B) is any of the modified resins (i) to (vii) below: (i) A modified resin obtained by introducing at least one functional group selected from the group consisting of a (poly)oxyalkylene group, a sulfo group, a carboxyl group, and a 1,3-dioxo-2-oxapropylene group into a polyarylate resin (A2). (ii) Modified resin obtained by introducing (poly)oxyalkylene groups into polysulfone resin (A3) (iii) Modified resin obtained by introducing (poly)oxyalkylene groups into polyethersulfone resin (A4) (iv) Modified resin obtained by introducing carboxyl groups and / or 1,3-dioxo-2-oxapropylene groups into aromatic polyimide resin (A5) (v) Modified resin obtained by introducing carboxyl groups and / or 1,3-dioxo-2-oxapropylene groups into aromatic polyetherimide resin (A6) (vi) Modified resin obtained by introducing a (poly)oxyalkylene group into aromatic polyether ketone resin (A7) (vii) Modified resin obtained by introducing a (poly)oxyalkylene group into aromatic polyether ether ketone resin (A8)

2. The fiber sizing agent according to claim 1, wherein the resin (A) is a polyarylate resin (A2), and the modified product (B) is (i) a modified resin obtained by introducing at least one functional group selected from the group consisting of a (poly)oxyalkylene group, a sulfo group, a carboxyl group, and a 1,3-dioxo-2-oxapropylene group into the polyarylate resin (A2).

3. The fiber sizing agent according to claim 1 or 2, wherein the total average number of hydroxyl groups, sulfo groups, and carboxyl groups (one 1,3-dioxo-2-oxapropylene group is equivalent to two carboxyl groups) per molecule in all of the modified products (B) contained in the fiber sizing agent is 1.5 or more.

4. The fiber sizing agent according to any one of claims 1 to 3, wherein the weight average molecular weight of the modified product (B) is 1,500 to 30,000.

5. A fiber bundle in which at least one type of fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, rock fiber, and slag fiber is treated with the fiber sizing agent according to any one of claims 1 to 4.

6. A fiber product comprising the fiber bundle according to claim 5.

7. A resin composition comprising the fiber bundle according to claim 5 and a thermoplastic resin (E).

8. A resin composition comprising the fiber product according to claim 6 and a thermoplastic resin (E).

9. 9. The resin composition according to claim 7 or 8, wherein the thermoplastic resin (E) is at least one selected from the group consisting of a phenolic resin, a melamine resin, a urea resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyetheretherketone resin, a polyetherketoneketone resin, and a polyphenylene sulfide resin.

10. A molded article obtained by molding the resin composition according to any one of claims 7 to 9.

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