Fiber bundling agent, fiber bundle, forming material, and formed product

Abstract

Provided is a fiber bundling agent that comprises an aqueous urethane resin composition containing a urethane resin and an aqueous medium, and that is characterized in that: the urethane resin is obtained by using, as essential raw materials, a polyol compound, a diisocyanate compound, a nonionic group-containing compound, and a hydrazine derivative having an active hydrogen atom; the polyol compound includes a polyester polyol; the diisocyanate compound includes an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound; the nonionic group-containing compound includes polyoxyethylene monomethyl ether and / or polyethylene glycol; and the percentage content of the nonionic group-containing compound is in the range of 3-10 mass% of the raw materials of the urethane resin. The fiber bundling agent exhibits excellent storage stability and bundling properties, generates less pyrolysis gases during molding, and can contribute to yellowing resistance of a formed product.

Description

Fiber bundling agent, fiber bundle, molding material, and molded product

[0008] ,

[0007] ,

[0001] The present invention relates to a fiber bundling agent, a fiber bundle, a molding material, and a molded product.

[0002] Glass fibers and carbon fibers are used as reinforcing materials for matrix resins such as thermoplastic resins and thermosetting resins, and fiber-reinforced plastics obtained from glass fibers or carbon fibers and matrix resins are used as automobile parts and aircraft parts that require high strength and excellent durability.

[0003] As fiber materials such as glass fibers and carbon fibers used in the fiber-reinforced plastics, usually, from the viewpoint of facilitating handling and imparting high strength and high durability to the fiber-reinforced plastics, fiber materials bundled to approximately several thousand to several tens of thousands by a fiber bundling agent are often used, and various fiber bundling agents have been proposed (see, for example, Patent Document 1).

[0004] Among them, an aqueous urethane resin-based fiber bundling agent (see, for example, Patent Document 2) that has excellent bundling properties to prevent fuzzing generated by friction when kneading the fiber material and the matrix resin, has excellent heat discoloration resistance and is less likely to yellow even under high-temperature molding conditions, and generates less thermal decomposition gas during molding has been studied, but its storage stability is insufficient, and there are problems with workability when using the fiber bundling agent. [[ID=~]]

[0005] Therefore, there has been a demand for a material that has excellent storage stability and bundling properties, generates less thermal decomposition gas during molding, and contributes to the yellowing resistance of the molded product.

[0006] Japanese Patent Publication No. 2002-541280, Japanese Unexamined Patent Application Publication No. 4-338140

[0007] The problem to be solved by the present invention is to provide a fiber bundling agent that has excellent storage stability and bundling properties, generates less thermal decomposition gas during molding, and contributes to the yellowing resistance of the molded product.

[0008] The inventors of the present invention conducted diligent research to solve the above problems and found that the above problems can be solved by using an aqueous urethane resin composition containing a urethane resin made from specific raw materials and an aqueous medium, thereby completing the present invention.

[0009] In other words, the present invention relates to a fiber scrubber comprising an aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B), wherein the urethane resin (A) is made up of essential raw materials a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), and a hydrazine derivative (a4) having an active hydrogen atom, wherein the polyol compound (a1) includes a polyester polyol, the diisocyanate compound (a2) includes an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound, the nonionic group-containing compound (a3) ​​includes polyoxyethylene monomethyl ether and / or polyethylene glycol, and the content of the nonionic group-containing compound (a3) ​​is in the range of 3 to 10% by mass in the raw materials of the urethane resin (A), the fiber scrubber, a molding material containing the fiber bundle and a matrix resin, and a molded article which is a cured product of the molding material.

[0010] The present invention provides the following embodiments: [1] A fiber scrubbing agent comprising an aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B), wherein the urethane resin (A) is made up of essential raw materials a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), and a hydrazine derivative (a4) having an active hydrogen atom, wherein the polyol compound (a1) includes a polyester polyol, the diisocyanate compound (a2) includes an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound, the nonionic group-containing compound (a3) ​​includes polyoxyethylene monomethyl ether and / or polyethylene glycol, and the content of the nonionic group-containing compound (a3) ​​is in the range of 3 to 10% by mass in the raw materials of the urethane resin (A). [2] [1] The fiber scrubbing agent according to [1], wherein the weight loss rate of the urethane resin (A) when heated in nitrogen at 350°C is 8% or less, under the conditions that the starting temperature for heating is 30°C and the heating rate is 20°C / min. [3] The fiber scrubbing agent according to [1] or [2], wherein the urethane bond concentration of the urethane resin (A) is in the range of 0.1 to 0.9 mmol / g. [4] A fiber bundle characterized by being bundled with the fiber scrubbing agent according to any one of [1] to [3]. [5] A molding material characterized by containing the fiber bundle and matrix resin according to [4]. [6] A molded article characterized by being a cured product of the molding material according to [5].

[0011] The fiber scrubbing agent of the present invention uses one that includes an aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B).

[0012] The fiber sizing agent of the present invention is characterized by comprising an aqueous urethane resin composition.

[0013] The aqueous urethane resin composition used contains a urethane resin (A) and an aqueous medium (B).

[0014] The urethane resin (A) used is one that requires a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), and a hydrazine derivative (a4) having an active hydrogen atom as essential raw materials.

[0015] The polyol compound (a1) is essentially a polyester polyol.

[0016] Examples of the aforementioned polyester polyols include aromatic polyester polyols and aliphatic polyester polyols.

[0017] Examples of the aromatic polyester polyols include those obtained by esterifying an aromatic polycarboxylic acid with an aromatic polyhydric alcohol, those obtained by esterifying an aromatic polycarboxylic acid with an aliphatic polyhydric alcohol, and those obtained by esterifying an aliphatic polycarboxylic acid with an aromatic polyhydric alcohol.

[0018] Examples of the aforementioned aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and other aromatic polycarboxylic acids or their esterified products. These aromatic polycarboxylic acids or their esterified products can be used individually or in combination of two or more.

[0019] Examples of the aforementioned aliphatic polycarboxylic acids include succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4-butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, and other aliphatic polycarboxylic acids or their esters. These aliphatic polycarboxylic acids or their esters can be used individually or in combination of two or more.

[0020] Examples of the aforementioned aromatic polyhydric alcohols include benzenedimethanol, toluenedimethanol, and xylenedimethanol. These aromatic polyhydric alcohols can be used individually or in combination of two or more.

[0021] Examples of the aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propylenediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol. These aliphatic polyhydric alcohols can be used individually or in combination of two or more.

[0022] The number-average molecular weight of the aromatic polyester polyol is preferably in the range of 1,500 to 100,000, and more preferably in the range of 2,000 to 10,000, in order to obtain a fiber sizing agent that has excellent bundling properties and generates little thermal decomposition gas during molding. In this invention, the number-average molecular weight of the aromatic polyester polyol is the value measured by gel permeation chromatography (GPC) under the conditions described in the examples.

[0023] Examples of the aliphatic polyester polyol include those obtained by esterifying an aliphatic polycarboxylic acid and an aliphatic polyalcohol.

[0024] Examples of the aliphatic polycarboxylic acid include those similar to those exemplified above as "aliphatic polycarboxylic acids."

[0025] Examples of the aforementioned aliphatic polyhydric alcohols include those similar to those exemplified above as "aliphatic polyhydric alcohols."

[0026] The number-average molecular weight of the aliphatic polyester polyol is preferably in the range of 2,500 to 100,000, and more preferably in the range of 3,000 to 10,000, in order to obtain a fiber sizing agent that has excellent bundling properties and generates little thermal decomposition gas during molding. In this invention, the number-average molecular weight of the aliphatic polyester polyol is the value measured by gel permeation chromatography (GPC) under the conditions described in the examples.

[0027] In the esterification reaction for producing the polyester polyol, it is preferable to use an esterification catalyst to promote the esterification reaction. Examples of such esterification catalysts include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; and metal compounds such as titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octanoate, 2-ethylhexanotin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium. These esterification catalysts can be used individually or in combination of two or more.

[0028] The amount of the polyol compound (a1) used is preferably in the range of 60 to 90% by mass, and more preferably in the range of 70 to 85% by mass, in the raw material of the urethane resin (A), since this yields a fiber sizing agent that has excellent bundling properties and generates little thermal decomposition gas during molding.

[0029] Furthermore, as the polyol compound (a1), a polyol compound other than the polyester polyol (hereinafter abbreviated as "other polyol compounds") may be used as necessary.

[0030] Other polyol compounds include polyether polyols, polycarbonate polyols, and polybutadiene polyols, other than the nonionic group-containing compound (a3) ​​described later. These polyol compounds can be used individually or in combination of two or more.

[0031] Examples of the aforementioned polyether polyols include polypropylene glycol and polytetramethylene glycol. These polyether polyols can be used individually or in combination of two or more.

[0032] Examples of the polycarbonate polyols include polycarbonate polyols obtained by reacting a carbonate ester and / or phosgene with a diol compound.

[0033] Examples of the aforementioned carbonate esters include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. These carbonate esters can be used individually or in combination of two or more.

[0034] Examples of the diol compounds include aliphatic diol compounds such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 1,10-decanediol, 2-ethyl-2-butyl-1,3-propanediol, and 1,12-dodecanediol; and alicyclic diol compounds such as 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. These diol compounds can be used individually or in combination of two or more.

[0035] The number-average molecular weight of the other polyol compounds is preferably in the range of 2,500 to 100,000, and more preferably in the range of 3,000 to 10,000, in order to obtain a fiber sizing agent that has excellent sizing properties and generates little thermal decomposition gas during molding. In this invention, the number-average molecular weight of the other polyol compounds is the value measured by gel permeation chromatography (GPC) under the conditions described in the examples.

[0036] The amount of the other polyol compounds used is preferably in the range of 0 to 20% by mass, more preferably in the range of 0 to 10% by mass, and even more preferably in the range of 0 to 5% by mass, in the polyol compound (a1).

[0037] The diisocyanate compound (a2) must be an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound.

[0038] Examples of the aliphatic diisocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These aliphatic diisocyanate compounds can be used individually or in combination of two or more. Among these, hexamethylene diisocyanate is preferred because it provides excellent flocculation properties, generates little thermal decomposition gas during molding, and yields a fiber flocculator that contributes to the resistance of molded products to yellowing.

[0039] Examples of the alicyclic diisocyanate compounds include cyclopentylene diisocyanate, cyclohexylene diisocyanate, di(isocyanate-methyl)cyclohexane, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and norbornane diisocyanate. These alicyclic diisocyanate compounds can be used individually or in combination of two or more. Among these, isophorone diisocyanate and dicyclohexylmethane diisocyanate are preferred because they provide excellent filamentation properties, generate little thermal decomposition gas during molding, and contribute to the yellowing resistance of the molded product.

[0040] The amount of the diisocyanate compound (a2) used is preferably in the range of 5 to 30% by mass, more preferably in the range of 5 to 25% by mass, and even more preferably in the range of 5 to 20% by mass, in the raw material of the urethane resin (A), since this provides a fiber sizing agent that has excellent bundling properties, generates little thermal decomposition gas during molding, and contributes to the resistance of the molded product to yellowing.

[0041] Further, as the diisocyanate compound (a2), an aromatic diisocyanate compound can be used in combination as needed.

[0042] Examples of the aromatic diisocyanate compound include phenylenediisocyanate, toluenediisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and the like.

[0043] The total usage amount of the aromatic diisocyanate compound is preferably in the range of 0 to 10% by mass, more preferably 0 to 5% by mass in the diisocyanate compound (a2) because a fiber bundling agent having excellent bundling property, less generation of thermal decomposition gas during molding, and contributing to the yellowing resistance of the molded product can be obtained.

[0044] Examples of the nonionic group-containing compound (a3) include polyethylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and butylene oxide, a copolymer of ethylene oxide and other alkylene oxides, and their monoalkyl ethers. These nonionic group-containing compounds can be used alone or in combination of two or more. Among them, polyoxyethylene monomethyl ether and polyethylene glycol are preferred because a fiber bundling agent having excellent storage stability and bundling property and less generation of thermal decomposition gas during molding can be obtained.

[0045] The usage amount of the nonionic group-containing compound (a3) is in the range of 3 to 10% by mass in the raw materials of the urethane resin (A). Preferably, it is in the range of 4 to 9% by mass, more preferably 5 to 8% by mass because a fiber bundling agent having excellent storage stability and bundling property and less generation of thermal decomposition gas during molding can be obtained.

[0046] Examples of the hydrazine derivative (a4) having an active hydrogen atom include hydrazine compounds such as hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, or hydrates thereof, dihydrazide compounds such as adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide compounds such as β-semicarbazidepropionic acid hydrazide, 3-semicarbazide methyl-3,5,5-trimethylcyclohexane, and the like. These hydrazine derivatives can be used alone or in combination of two or more. Among these, hydrazine or a hydrate of hydrazine is preferable because a fiber bundling agent having excellent bundling property, generating less pyrolysis gas during molding, and contributing to the yellowing resistance of the molded product can be obtained.

[0047] The amount of the hydrazine derivative (a4) having an active hydrogen atom used is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.3 to 5% by mass, in the raw materials of the urethane resin (A) because a fiber bundling agent having excellent bundling property, generating less pyrolysis gas during molding, and contributing to the yellowing resistance of the molded product can be obtained.

[0048] The urethane resin (A) can, if necessary, be used in combination with a compound (a5) having a hydrophilic group as a raw material in addition to the polyol compound (a1), the diisocyanate compound (a2), the nonionic group-containing compound (a3), and the hydrazine compound (a4) having an active hydrogen atom.

[0049] Examples of the compound (a5) having a hydrophilic group include a compound having a carboxyl group as a hydrophilic group, a compound having a sulfonic acid group as a hydrophilic group, and the like.

[0050] Examples of compounds having a carboxyl group as the hydrophilic group include compounds having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2'-dimethylolvaleric acid, as well as polyol compounds obtained by esterifying the compounds having a carboxyl group.

[0051] As compounds having a sulfonic acid group as the hydrophilic group, for example, diamines or polyamines containing alkali metal sulfonate groups such as alkali metal salts of N-(2-aminoethyl)-2-aminoethanesulfonic acid, polyol compounds obtained by esterifying compounds having sulfonic acid groups such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5[4-sulfophenoxy]isophthalic acid with the polyhydric alcohol can also be used.

[0052] These hydrophilic compounds (a5) can be used individually or in combination of two or more.

[0053] The amount of the hydrophilic compound (a5) used is preferably in the range of 0.1 to 5% by mass, and more preferably in the range of 0.2 to 3% by mass, of the total mass of the raw materials of the urethane resin (A), since this provides a fiber sizing agent that has excellent bundling properties, generates little thermal decomposition gas during molding, and contributes to the resistance of the molded product to yellowing.

[0054] The urethane bond concentration of the urethane resin (A) is preferably in the range of 0.1 to 0.9 mmol / g, and more preferably in the range of 0.1 to 0.7 mmol / g, because it provides a fiber sizing agent that has excellent bundling properties, generates little thermal decomposition gas during molding, and contributes to the resistance of the molded product to yellowing.

[0055] The method for producing the urethane resin (A) is not particularly limited and can be any method. For example, it may be produced by reacting all of the reaction materials, including a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), a hydrazine compound having an active hydrogen atom (a4), and an optional compound having a hydrophilic group (a5), all at once, or by reacting the reaction materials sequentially. These reactions are preferably carried out at a temperature of 50 to 100°C for 3 to 10 hours.

[0056] The urethane resin (A) may also be manufactured under organic solvent conditions if necessary.

[0057] Examples of the organic solvents include ketone compounds such as acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, and dioxane; acetic acid ester compounds such as ethyl acetate, butyl acetate, and propyl acetate; nitrile compounds such as acetonitrile; hydrocarbon compounds such as n-pentane, n-hexane, cyclohexane, n-heptane, benzene, toluene, and xylene; chlorinated hydrocarbon compounds such as carbon tetrachloride, dichloromethane, chloroform, and trichloroethane; and amide compounds such as dimethylformamide and N-methylpyrrolidone. It is preferable to remove the organic solvent during or after the reaction, for example, by methods such as reduced-pressure heating.

[0058] Examples of the aqueous medium (B) include ion-exchanged water and distilled water. These aqueous mediums can be used individually or in combination of two or more.

[0059] The mass ratio [(A) / (B)] of the urethane resin (A) to the aqueous medium (B) is preferably in the range of 20 / 80 to 80 / 20, and more preferably in the range of 30 / 70 to 70 / 30, because it provides a fiber sizing agent that has excellent storage stability and bundling properties, generates little thermal decomposition gas during molding, and contributes to the resistance of the molded product to yellowing.

[0060] The method for producing the aqueous urethane resin composition is not particularly limited and can be produced by any method. For example, a method of obtaining it by mixing a urethane resin (A) and an aqueous medium (B) (Method 1), a method of synthesizing a prepolymer by reacting a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), a hydrazine compound having an active hydrogen atom (a4), and an optional compound having a hydrophilic group (a5) all at once, and dispersing it in an aqueous medium (B) (Method 2), a method of producing the aqueous urethane resin composition by reacting a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), and an optional compound having a hydrophilic group (a5) Methods include: synthesizing a prepolymer having an isocyanate group by reacting (a) with (a), reacting with the hydrazine compound (a4) having the active hydrogen atom and dispersing it in an aqueous medium (B) (Method 3); synthesizing a prepolymer having an isocyanate group by reacting a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), and an optional compound having a hydrophilic group (a5), dispersing it in an aqueous medium (B), and then reacting with the hydrazine compound (a4) having the active hydrogen atom (Method 4).

[0061] Furthermore, in the above methods (1) to (4), a neutralizing agent may be used as needed.

[0062] Methods for mixing the urethane resin (A) and the aqueous medium (B) include, for example, a reaction vessel equipped with stirring blades; a kneader such as a kneader, continuous kneader, tapered roll, single-screw extruder, twin-screw extruder, tri-screw extruder, universal mixer, Plastmill, Bodeta type kneader; a rotary dispersion mixer such as a homomixer, static mixer, Filmix, Ebara Milder, Creamix, Ultra Turlux, Cavitron, Biomix; an ultrasonic dispersion device; and an in-line mixer or other device that has no moving parts and can mix by the flow of the fluid itself.

[0063] The aqueous urethane resin composition of the present invention may also contain other additives as needed.

[0064] Examples of the aforementioned other additives include emulsifiers, thickeners, urethane catalysts, fillers, flame retardants, leveling agents, and anti-blocking agents. These additives can be used individually or in combination of two or more types.

[0065] Examples of the emulsifiers include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer; anionic emulsifiers such as fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkanesulfonates, and sodium alkyldiphenyl ethersulfonates; and cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. These emulsifiers can be used alone or in combination of two or more.

[0066] Examples of the aforementioned thickening agents include association-type and acid-based thickening agents.

[0067] Examples of the urethane catalyst include tin-based and bismuth-based catalysts.

[0068] Examples of the filler include calcium carbonate and silica.

[0069] Examples of the aforementioned flame retardants include phosphorus-based flame retardants.

[0070] Examples of the leveling agent include silicone-based leveling agents.

[0071] Examples of the aforementioned blocking inhibitors include acrylics, cellulose esters, and the like.

[0072] The fiber sizing agent of the present invention has excellent sizing properties, generates little thermal decomposition gas during molding, and contributes to the resistance of molded products to yellowing. Therefore, it is preferable that the weight loss rate of the urethane resin (A) when heated in nitrogen at 350°C is 8% or less, under the conditions that the starting temperature for heating is 30°C and the heating rate is 20°C / min. In this invention, the "weight loss rate" refers to the value calculated by the calculation method described in the examples.

[0073] The fiber sizing agent of the present invention comprises the aqueous urethane resin composition, but may optionally contain additives such as silane coupling agents, curing catalysts, lubricants, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, foaming agents, pH adjusters, leveling agents, gelation inhibitors, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparters, inorganic fillers, organic fillers, plasticizers, reinforcing agents, catalysts, antibacterial agents, antifungal agents, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity imparters, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, water-containing compounds, flame retardants, water absorbents, moisture absorbers, deodorants, foam stabilizers, defoamers, antifungal agents, preservatives, antialgal agents, pigment dispersants, blocking inhibitors, and hydrolysis inhibitors.

[0074] When using the fiber sizing agent of the present invention as a sizing agent for glass fibers, it is preferable to use a silane coupling agent in combination to further improve the adhesive strength of the sizing agent to the glass fibers.

[0075] Examples of the silane coupling agent include γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-hydroxylethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-hydroxylethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-hydroxylethyl)aminopropyl You can use dimethyl methoxysilane, γ-(2-hydroxylethyl)aminopropylmethyldiethoxysilane or γ-(N,N-di-2-hydroxylethyl)aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane or γ-(N-phenyl)aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptophenyltrimethoxysilane, etc.

[0076] Furthermore, the fiber sizing agent of the present invention can be used in combination with emulsions such as vinyl acetate-based, ethylene vinyl acetate-based, acrylic-based, epoxy-based, urethane-based, polyester-based, and polyamide-based; latexes such as styrene-butadiene-based, acrylonitrile-butadiene-based, and acrylic-butadiene-based; and even with water-soluble resins such as polyvinyl alcohol (PVA) and cellulose.

[0077] The fiber sizing agent of the present invention can be used for bundling multiple fibers and surface treatment, for example, to prevent breakage and fraying of glass fibers, carbon fibers, and other fibers.

[0078] Examples of fiber materials that can be processed using the fiber sizing agent of the present invention include glass fibers, carbon fibers, silicon carbide fibers, pulp, hemp, cotton, nylon, polyester, acrylic, polyurethane, polyimide, or polyamide fibers made of aramid such as Kevlar® and Nomex. Among these, glass fibers and carbon fibers are preferred due to their high strength.

[0079] Glass fibers that can be processed using the aforementioned fiber sizing agent can be, for example, those obtained from alkali-containing glass, low-alkali glass, or alkali-free glass as raw materials, but it is particularly preferable to use alkali-free glass (E-glass), which exhibits little deterioration over time and stable mechanical properties.

[0080] Furthermore, as carbon fibers that can be processed using the aforementioned fiber sizing agent, polyacrylonitrile-based, pitch-based, and other types of carbon fibers can generally be used. Among these, polyacrylonitrile-based carbon fibers are preferred from the viewpoint of providing excellent strength.

[0081] Furthermore, from the viewpoint of providing even better strength and other properties, it is preferable to use carbon fibers having a single filament diameter of 0.5 to 20 μm, and more preferably carbon fibers having a diameter of 2 to 15 μm.

[0082] As the carbon fiber, for example, twisted yarn, spun yarn, spinning process, or nonwoven process carbon fiber can be used. In addition, as the carbon fiber, filaments, yarn, roving, strand, chopped strand, felt, needle-punched, cloth, roving cloth, milled fiber, etc. can be used.

[0083] A method for bundling the aforementioned glass fibers or carbon fibers using the fiber sizing agent of the present invention and forming a film on the surface of the glass fiber bundle or carbon fiber bundle includes, for example, a method of uniformly applying the fiber sizing agent to the fiber surface by a kiss coater method, roller method, immersion method, spray method, brush, or other known method. If the fiber sizing agent contains an aqueous medium or an organic solvent as a solvent, it is preferable to heat-dry it after application using a heating roller, hot air, hot plate, etc.

[0084] The amount of film attached to the surface of the fiber material is preferably 0.1 to 5% by mass, and more preferably 0.3 to 1.5% by mass, relative to the total mass of the bundled and surface-treated fiber bundle.

[0085] The bundled and surface-treated fiber materials obtained by the above method, particularly glass fibers and carbon fibers, can be used as molding materials for producing high-strength molded products by combining them with a matrix resin or the like, as described later.

[0086] In particular, when a fiber material surface-treated with the fiber sizing agent of the present invention is used in combination with a matrix resin to form a molded product, the adhesion at the interface between the fiber and the matrix resin can be significantly improved, thereby improving the strength of the molded product.

[0087] As the matrix resin, for example, a thermosetting resin or a thermoplastic resin can be used. As the thermosetting resin, phenolic resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, epoxy resin, vinyl ester resin, etc. As the thermoplastic resin, for example, saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polypropylene, polystyrene, polycarbonate, polyphenylene sulfide, polyphenylene oxide, 6-nylon, 6,6-nylon, etc., polyamide resins, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyacetal, polyetherimide, polyetheretherketone, etc. can be used.

[0088] Fibers bundled using the fiber sizing agent of the present invention are more preferably used in combination with matrix resins such as epoxy resin, unsaturated polyester resin, polyamide resins such as 6-nylon and 6,6-nylon, polyphenylene sulfide, polybutylene terephthalate, polycarbonate, and polyetheretherketone to obtain high-strength molded articles.

[0089] Examples of molding materials that include the surface-treated fiber material, the matrix resin, and optionally polymerizable monomers include prepregs and sheet molding compounds (SMCs).

[0090] The prepreg can be manufactured, for example, by applying the matrix resin onto a release paper, placing a surface-treated fiber material on the applied surface, and pressing and impregnating it using a roller or the like as needed.

[0091] When manufacturing the prepreg, it is preferable to use an epoxy resin such as a bisphenol A type epoxy resin, a glycidylamine type epoxy resin such as tetraglycidylaminodiphenylmethane, or a novolac type epoxy resin as the matrix resin.

[0092] Furthermore, the sheet molding compound can be manufactured, for example, by thoroughly impregnating a surface-treated fiber material with a mixture of the matrix resin and a polymerizable unsaturated monomer such as styrene, and then processing it into a sheet. When manufacturing the sheet molding compound, it is preferable to use an unsaturated polyester resin or a vinyl ester resin as the matrix resin.

[0093] The curing of the molding material proceeds, for example, by radical polymerization under pressure or atmospheric pressure, heating, or light irradiation. In such cases, known thermosetting agents, photocuring agents, etc., can be used in combination.

[0094] Furthermore, examples of the molding material include a mixture of the thermoplastic resin and the surface-treated fiber material obtained by kneading under heat. Such a molding material can be used for secondary processing, such as by injection molding.

[0095] Furthermore, the prepreg made of the thermoplastic resin can be manufactured, for example, by placing a surface-treated fiber material in a sheet shape and impregnating it with the molten thermoplastic resin.

[0096] The aforementioned thermoplastic resin prepreg can be used for secondary processing, such as by laminating one or more sheets and then heating and molding them under pressure or normal pressure.

[0097] Because the molded products obtained using the aforementioned molding material have high strength, they can be used, for example, in automotive components, aircraft components, industrial components, and the like.

[0098] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples listed below.

[0099] The number-average molecular weights of the polyol compounds used in the examples and comparative examples are those measured by gel permeation chromatography (GPC) under the following conditions.

[0100] Measurement device: High-speed GPC instrument (HLC-8220GPC manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series: "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard samples: Calibration curves were prepared using the following standard polystyrene.

[0101] (Standard Polystyrene) TSKgel Standard Polystyrene A-500 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-1000 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-2500 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-5000 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-1 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-2 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-4 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-10 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-20 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-40 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-80 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-128 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-288 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-550 (manufactured by Tosoh Corporation)

[0102] The weight loss rates used in the examples and comparative examples are values ​​calculated using the following method.

[0103] [Method for Calculating Weight Loss Rate] A test specimen was prepared by applying the fiber sizing agent of the present invention to a polypropylene film to a dry film thickness of 150 μm, drying it at 23°C for one day, then at 108°C for two hours, and finally at 150°C for five minutes. The weight of this test specimen was measured before heating and at 350°C using a differential thermogravimetric analyzer (for example, "TG / DTA6200" manufactured by Hitachi High-Tech Science Corporation) under conditions of a heating start temperature of 30°C, a heating rate of 20°C / min, and a nitrogen atmosphere, and the weight loss rate before and after the test was calculated.

[0104] (Example 1: Preparation of Fiber Swarming Agent (1)) 240 parts by mass of polyester polyol (number average molecular weight; 3,000, hereinafter abbreviated as "polyester polyol (1)") obtained by reacting 1,4-butanediol with adipic acid, 17.6 parts by mass of polyoxyethylene monomethyl ether (number average molecular weight; 1,000, hereinafter abbreviated as "nonionic group-containing compound (1)") and 73.2 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was stirred and mixed uniformly. After stirring and mixing, 35.6 parts by mass of isophorone diisocyanate (hereinafter abbreviated as "diisocyanate compound (1)") and 0.06 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 52.3 parts by mass of ethyl acetate and 73.3 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 594 parts by mass of ion-exchanged water was added, followed by 3.6 parts by mass of 80% hydrated hydrazine (hereinafter abbreviated as "hydrazine derivative (1)") and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (1) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (1) was 6.0% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.60 mmol / g, and the weight loss rate when reaching 350°C was 4.5%.

[0105] (Example 2: Preparation of Fiber Swarming Agent (2)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (1), 18.0 parts by mass of nonionic group-containing compound (1), and 74.9 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 42.0 parts by mass of dicyclohexylmethane diisocyanate (hereinafter abbreviated as "diisocyanate compound (2)") and 0.06 parts by mass of stannous octylate were added and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 53.6 parts by mass of ethyl acetate and 75.0 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 607 parts by mass of ion-exchanged water was added, followed by 4.0 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (2) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (2) was 6.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.59 mmol / g, and the weight loss rate when reaching 350°C was 4.4%.

[0106] (Example 3: Preparation of Fiber Swarming Agent (3)) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of polyester polyol (1), 17.0 parts by mass of nonionic group-containing compound (1), and 70.9 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 26.9 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as "diisocyanate compound (3)") and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 50.7 parts by mass of ethyl acetate and 71.0 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 575 parts by mass of ion-exchanged water was added, followed by 4.0 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (3) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (3) was 6.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.62 mmol / g, and the weight loss rate when reaching 350°C was 6.3%.

[0107] (Example 4: Preparation of Fiber Scrubbing Agent (4)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (1), 29.6 parts by mass of nonionic group-containing compound (1), and 76.2 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 35.6 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 54.5 parts by mass of ethyl acetate and 76.3 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 618 parts by mass of ion-exchanged water was added, followed by 3.3 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubbing agent (4) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (4) was 9.6% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.62 mmol / g, and the weight loss rate when reaching 350°C was 4.7%.

[0108] (Example 5: Preparation of Fiber Swarming Agent (5)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (1), 17.0 parts by mass of polyoxyethylene monomethyl ether (number average molecular weight; 2,000, hereinafter abbreviated as "nonionic group-containing compound (2)"), and 70.9 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 26.7 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 50.7 parts by mass of ethyl acetate and 70.9 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 575 parts by mass of ion-exchanged water was added, followed by 1.8 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (5) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (5) was 6.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.59 mmol / g, and the weight loss rate when reaching 350°C was 4.2%.

[0109] (Example 6: Preparation of Fiber Swarming Agent (6)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (1), 5.9 parts by mass of nonionic group-containing compound (2), 11.7 parts by mass of polyethylene glycol (number average molecular weight; 2,000, hereinafter abbreviated as "nonionic group-containing compound (3)"), and 73.2 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 35.6 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 52.3 parts by mass of ethyl acetate and 73.3 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 594 parts by mass of ion-exchanged water was added, followed by 3.6 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (6) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (6) was 6.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.59 mmol / g, and the weight loss rate when reaching 350°C was 5.1%.

[0110] (Example 7: Preparation of Fiber Swarming Agent (7)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (1), 17.6 parts by mass of nonionic group-containing compound (1), and 73.2 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 35.6 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 52.3 parts by mass of ethyl acetate and 73.3 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution and diluted. After cooling to 35°C, 519 parts by mass of ion-exchanged water was added, and then 109.2 parts by mass of an aqueous solution containing 9.9 parts by mass of adipic acid dihydrazide (hereinafter abbreviated as "hydrazine derivative (2)") was added and reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (7) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (7) was 5.8% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.59 mmol / g, and the weight loss rate when reaching 350°C was 6.3%.

[0111] (Example 8: Preparation of fiber sizing agent (8)) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of polyester polyol (1), 5.9 parts by mass of nonionic group-containing compound (2), 8.7 parts by mass of nonionic group-containing compound (3), 0.9 parts by mass of 2,2-dimethylolpropionic acid (hereinafter abbreviated as "hydrophilic group-containing compound (1)"), and 72.7 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 35.6 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 52.0 parts by mass of ethyl acetate and 72.7 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 0.8 parts by mass of triethylamine was added to neutralize the carboxyl groups in the urethane prepolymer. Next, 589 parts by mass of deionized water was added, followed by 3.4 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber sizing agent (8) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (8) was 5.0% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.63 mmol / g, and the weight loss rate when reaching 350°C was 4.9%.

[0112] (Example 9: Preparation of Fiber Swarming Agent (9)) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of polyester polyol (1), 5.7 parts by mass of nonionic group-containing compound (2), 4.6 parts by mass of polyethylene glycol (number average molecular weight; 600, hereinafter abbreviated as "nonionic group-containing compound (4)"), 0.9 parts by mass of hydrophilic group-containing compound (1), and 71.6 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 35.6 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 51.2 parts by mass of ethyl acetate and 71.7 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 0.8 parts by mass of triethylamine was added to neutralize the carboxyl groups in the urethane prepolymer. Next, 580 parts by mass of deionized water was added, followed by 3.3 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, the ethyl acetate was removed under reduced pressure to obtain a fiber sizing agent (9) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (9) was 3.6% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.66 mmol / g, and the weight loss rate when reaching 350°C was 4.6%.

[0113] (Example 10: Preparation of fiber sizing agent (10)) 240 parts by mass of polyester polyol (number average molecular weight; 2,000, hereinafter abbreviated as "polyester polyol (2)") obtained by reacting 1,4-butanediol, neopentyl glycol, and terephthalic acid, 29.0 parts by mass of nonionic group-containing compound (1), and 80.5 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was uniformly stirred and mixed. After stirring and mixing, 53.4 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 57.6 parts by mass of ethyl acetate and 80.6 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 653 parts by mass of deionized water was added. Subsequently, 5.3 parts by mass of hydrazine derivative (1) was added and the mixture was reacted. After that, the ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (10) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (10) was 8.9% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.83 mmol / g, and the weight loss rate when reaching 350°C was 5.8%.

[0114] (Example 11: Preparation of fiber sizing agent (11)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (2), 6.3 parts by mass of nonionic group-containing compound (2), 12.5 parts by mass of nonionic group-containing compound (3), 0.9 parts by mass of hydrophilic group-containing compound (1), and 78.2 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 53.4 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 55.9 parts by mass of ethyl acetate and 78.3 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 0.9 parts by mass of triethylamine was added to neutralize the carboxyl groups in the urethane prepolymer. Next, 633 parts by mass of deionized water was added, followed by 5.3 parts by mass of hydrazine derivative (1), and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (11) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (11) was 5.9% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.85 mmol / g, and the weight loss rate when reaching 350°C was 6.1%.

[0115] (Example 12: Preparation of fiber sizing agent (12)) 240 parts by mass of polyester polyol (number average molecular weight; 4500; hereinafter abbreviated as "polyester polyol (3)") obtained by reacting 1,6-hexanediol with adipic acid, 23.3 parts by mass of nonionic group-containing compound (1), and 72.8 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, and the mixture was stirred and mixed uniformly. After stirring and mixing, 28.0 parts by mass of diisocyanate compound (2) and 0.06 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 52.0 parts by mass of ethyl acetate and 72.8 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 590 parts by mass of ion-exchanged water was added, followed by 2.3 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (12) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (12) was 8.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.44 mmol / g, and the weight loss rate when reaching 350°C was 3.4%.

[0116] (Example 13: Preparation of fiber sizing agent (13)) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 120 parts by mass of polyester polyol (1), 160.2 parts by mass of polyester polyol obtained by reacting 1,6-hexanediol with phthalic acid (number average molecular weight: 2,000, hereinafter abbreviated as "polyester polyol (4)"), 21.9 parts by mass of nonionic group-containing compound (1), and 91.2 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 63.0 parts by mass of diisocyanate compound (2) and 0.07 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 65.2 parts by mass of ethyl acetate and 91.3 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 740 parts by mass of deionized water was added. Subsequently, 6.1 parts by mass of hydrazine derivative (1) was added and the mixture was reacted. After that, the ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (13) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (13) was 5.9% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.71 mmol / g, and the weight loss rate when reaching 350°C was 7.1%.

[0117] (Example 14: Preparation of fiber sizing agent (14)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 120 parts by mass of polyester polyol (1), 160.2 parts by mass of polyester polyol (4), 7.1 parts by mass of nonionic group-containing compound (2), 14.2 parts by mass of nonionic group-containing compound (3), 1.1 parts by mass of hydrophilic group-containing compound (1), and 88.9 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 53.4 parts by mass of diisocyanate compound (1) and 0.07 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 63.6 parts by mass of ethyl acetate and 89.0 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 1.0 part by mass of triethylamine was added to neutralize the carboxyl groups in the urethane prepolymer. Next, 720 parts by mass of deionized water was added, followed by 5.2 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber sizing agent (14) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (14) was 5.9% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.76 mmol / g, and the weight loss rate when reaching 350°C was 7.4%.

[0118] (Example 15: Preparation of fiber sizing agent (15)) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 120 parts by mass of polyester polyol (1), 160.2 parts by mass of polyester polyol (4), 7.3 parts by mass of nonionic group-containing compound (2), 14.7 parts by mass of nonionic group-containing compound (3), 1.1 parts by mass of hydrophilic group-containing compound (1), and 91.5 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 63.0 parts by mass of diisocyanate compound (2) and 0.07 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 65.4 parts by mass of ethyl acetate and 91.6 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 1.0 part by mass of triethylamine was added to neutralize the carboxyl groups in the urethane prepolymer. Next, 720 parts by mass of deionized water was added, followed by 5.8 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber sizing agent (15) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (15) was 5.9% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.74 mmol / g, and the weight loss rate when reaching 350°C was 7.3%.

[0119] (Example 16: Preparation of fiber sizing agent (16)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 120 parts by mass of polyester polyol (1), 160.2 parts by mass of polyester polyol (2), 7.2 parts by mass of nonionic group-containing compound (2), 6.4 parts by mass of nonionic group-containing compound (3), 1.1 parts by mass of hydrophilic group-containing compound (1), and 89.4 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 63.0 parts by mass of diisocyanate compound (2) and 0.07 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 63.9 parts by mass of ethyl acetate and 89.5 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 1.0 part by mass of triethylamine was added to neutralize the carboxyl groups in the urethane prepolymer. Next, 720 parts by mass of deionized water was added, followed by 6.0 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber sizing agent (16) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (16) was 3.8% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.74 mmol / g, and the weight loss rate when reaching 350°C was 5.9%.

[0120] (Example 17: Preparation of fiber sizing agent (17)) 240 parts by mass of polyester polyol (number average molecular weight; 2400, hereinafter abbreviated as "polyester polyol (5)") obtained by reacting 1,4-butanediol with adipic acid, 18.2 parts by mass of nonionic group-containing compound (1), and 75.6 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was stirred and mixed uniformly. After stirring and mixing, 44.5 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 54.0 parts by mass of ethyl acetate and 75.7 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 613 parts by mass of ion-exchanged water was added, followed by 4.6 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (17) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (17) was 6.0% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.72 mmol / g, and the weight loss rate when reaching 350°C was 8.3%.

[0121] (Example 18: Preparation of fiber sizing agent (18)) 240 parts by mass of polyester polyol (number average molecular weight; 1500, hereinafter abbreviated as "polyester polyol (6)") obtained by reacting 1,4-butanediol, neopentyl glycol, and terephthalic acid, 19.9 parts by mass of nonionic group-containing compound (1), and 82.7 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was stirred and mixed uniformly. After stirring and mixing, 71.1 parts by mass of diisocyanate compound (1) and 0.07 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 59.1 parts by mass of ethyl acetate and 82.7 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 670 parts by mass of ion-exchanged water was added, followed by 7.5 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (18) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (18) was 6.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 1.01 mmol / g, and the weight loss rate when reaching 350°C was 7.8%.

[0122] (Comparative Example 1: Preparation of Fiber Scrubbing Agent (R1)) 240 parts by mass of polyester polyol (1) and 68.8 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was uniformly stirred and mixed. After stirring and mixing, 35.6 parts by mass of diisocyanate compound (1) and 0.06 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 49.2 parts by mass of ethyl acetate was added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 589 parts of an aqueous solution containing 19.3 parts of polyoxyethylene / polyoxypropylene glycol copolymer (molecular weight approximately 16000) as an emulsifier were added, followed by the addition of 4.8 parts by mass of hydrazine derivative (1) and the reaction was carried out. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubbing agent (R1) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The urethane bonding concentration of this fiber sizing agent (R1) was 0.54 mmol / g, and the weight loss rate upon reaching 350°C was 4.1%.

[0123] (Comparative Example 2: Preparation of Fiber Scrubbing Agent (R2)) 240 parts by mass of polyester polyol (1), 50.9 parts by mass of nonionic group-containing compound (1), and 83.2 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was uniformly stirred and mixed. After stirring and mixing, 42.0 parts by mass of diisocyanate compound (2) and 0.07 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 59.4 parts by mass of ethyl acetate and 83.2 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 674 parts by mass of ion-exchanged water was added, followed by 3.1 parts by mass of hydrazine derivative (1) and the mixture was reacted. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubbing agent (R2) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (R2) was 15.2% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.63 mmol / g, and the weight loss rate when reaching 350°C was 4.8%.

[0124] (Comparative Example 3: Preparation of Fiber Swarming Agent (R3)) 240 parts by mass of polyester polyol (number average molecular weight; 1,000, hereinafter abbreviated as "polyester polyol (7)") obtained by reacting 1,4-butanediol with adipic acid, 42.0 parts by mass of nonionic group-containing compound (1), and 97.1 parts by mass of ethyl acetate were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, and the mixture was uniformly stirred and mixed. After stirring and mixing, 106.7 parts by mass of diisocyanate compound (1) and 0.08 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, the urethane prepolymer solution was diluted with 69.4 parts by mass of ethyl acetate and 97.1 parts by mass of N-methylpyrrolidone, cooled to 35°C, and then 787 parts by mass of deionized water was added. Subsequently, 11.0 parts by mass of hydrazine derivative (1) was added and the mixture was reacted. After that, the ethyl acetate was removed under reduced pressure to obtain a fiber scrubber (R3) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber scrubber (R3) was 10.6% by mass of the solid content of the aqueous urethane resin composition, the urethane bond concentration was 1.32 mmol / g, and the weight loss rate when reaching 350°C was 14.1%.

[0125] (Comparative Example 4: Preparation of Fiber Scrubbing Agent (R4)) In a four-necked flask equipped with a thermometer, a stirrer, reflux condenser, and dropping device, 240 parts by mass of polyester polyol (1), 18.0 parts by mass of nonionic group-containing compound (1), and 74.9 parts by mass of ethyl acetate were added and mixed uniformly by stirring. After stirring, 42.0 parts by mass of diisocyanate compound (2) and 0.06 parts by mass of stannous octylate were added and reacted at 75°C for 4 hours to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 53.6 parts by mass of ethyl acetate and 75.0 parts by mass of N-methylpyrrolidone were added to the urethane prepolymer solution to dilute it, and after cooling to 35°C, 607 parts by mass of ion-exchanged water was added and reacted at 50°C for 6 hours. Subsequently, ethyl acetate was removed under reduced pressure to obtain a fiber scrubbing agent (R4) consisting of an aqueous urethane resin composition with a solid content of 40% by mass. The content of the nonionic group-containing compound in this fiber sizing agent (R4) was 6.0% by mass in the solid content of the aqueous urethane resin composition, the urethane bond concentration was 0.59 mmol / g, and the weight loss rate when reaching 350°C was 8.4%.

[0126] The following evaluations were performed using the fiber sizing agents (1) to (18) and (R1) to (R4) obtained in the above examples and comparative examples.

[0127] [Evaluation of Storage Stability] The fiber scrubbing agents obtained in the above examples and comparative examples were left standing at 40°C for 30 days, and the presence or absence of precipitate formation or solidification of the liquid was observed to evaluate the storage stability. A: No change. B: A small amount of precipitate formed. C: A large amount of precipitate formed or solidified.

[0128] [Preparation of Chopped Strands] A glass fiber scrubbing agent was prepared by mixing 7.5 parts by mass (3 parts by mass as solids) of the fiber scrubbing agent obtained in the above examples and comparative examples, 0.3 parts by mass of γ-aminopropyltriethoxysilane, and 92.2 parts by mass of ion-exchanged water. This glass fiber scrubbing agent was uniformly applied to the surface of 13 μm diameter glass fibers at a rate of 1% by mass relative to the fiber mass, the fibers were scrubbed, then cut to a length of 3 mm, and dried to produce chopped strands.

[0129] [Method for evaluating the bundling properties] 50 g of the chopped strand and 100 g of polyamide 66 (nylon 66) resin were placed in a 1 L tumbler and mixed for 10 minutes. The resulting fluff was then collected, its mass measured, and evaluated according to the following criteria.

[0130] A: Less than 0.15g. B: 0.15g or more but less than 0.30g. C: 0.30g or more but less than 0.90g. D: 0.90g or more.

[0131] [Method for evaluating gas generation during pellet preparation and molding] A mixture consisting of 30% by mass of the chopped strand and 70.0% by mass of polyamide 66 (nylon 66) resin was kneaded, extruded, and cut in an extruder to obtain glass fiber-containing pellets. At that time, the presence or absence of gas generation was checked and evaluated according to the following criteria.

[0132] A: No gas was emitted at all. B: A small amount of gas was emitted. C: A moderate amount of gas was emitted. D: A significant amount of gas was emitted.

[0133] [Color Tone Evaluation] Using the aforementioned pellets, test pieces (100 mm x 100 mm x 2 mm) were prepared by injection molding, and their color tones were measured using a spectrophotometer (Konica Minolta Japan, Inc. "Spectrophotometer CM-5"). The color difference with glass fiber unreinforced polyamide 66 (nylon 66) was evaluated according to the following criteria.

[0134] A: No discoloration at all. B: Slight discoloration. C: Some discoloration. D: Significant discoloration.

[0135] Table 1 shows the evaluation results of the fiber scrubbing agents (1) to (18) and (R1) to (R4) obtained in the above examples and comparative examples.

[0136]

[0137]

[0138]

[0139] From the evaluation results in Tables 1 and 2, it was confirmed that the fiber sizing agent of the present invention has excellent storage stability and sizing properties, generates little pyrolysis gas during molding, and contributes to the resistance of molded products to yellowing.

[0140] On the other hand, Comparative Examples 1 to 4 shown in Table 3 are examples of fiber scrubbers using aqueous urethane resin compositions that do not satisfy the requirements of the present invention. It was confirmed that at least one of the following was insufficient: storage stability, scrubbing ability, amount of gas generated during molding, and color tone.

Claims

1. A fiber scrubbing agent comprising an aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B), wherein the urethane resin (A) is characterized in that it uses a polyol compound (a1), a diisocyanate compound (a2), a nonionic group-containing compound (a3), and a hydrazine derivative (a4) having an active hydrogen atom as essential raw materials, the polyol compound (a1) includes a polyester polyol, the diisocyanate compound (a2) includes an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound, the nonionic group-containing compound (a3) ​​includes polyoxyethylene monomethyl ether and / or polyethylene glycol, and the content of the nonionic group-containing compound (a3) ​​is in the range of 3 to 10% by mass in the raw materials of the urethane resin (A).

2. The fiber scrubbing agent according to claim 1, wherein, under the conditions that the starting temperature for heating is 30°C and the heating rate is 20°C / min, the weight loss rate of the urethane resin (A) when it reaches 350°C is 8% or less when heated in nitrogen.

3. The fiber scrubbing agent according to claim 1, wherein the urethane bond concentration of the urethane resin (A) is in the range of 0.1 to 0.9 mmol / g.

4. A fiber bundle characterized by being bundled with a fiber sizing agent according to any one of claims 1 to 3.

5. A molding material characterized by containing the fiber bundle and matrix resin described in claim 4.

6. A molded article characterized by being a cured product of the molding material described in claim 5.

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