JP7248733B2 - Fiber sizing agent composition, fiber sizing agent solution, fiber bundle, fiber product and composite material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fiber sizing agent composition, a fiber sizing agent solution, a fiber bundle, a fiber product and a composite material.

In recent years, composite materials of matrix resins such as unsaturated polyester resins, phenolic resins, epoxy resins and polypropylene resins and various fibers have been widely used in fields such as sports equipment, leisure goods and aircraft. Fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers and slag fibers are used in these composite materials. These fibers are usually provided with a sizing agent in the process of forming the composite material (see, for example, Patent Document 1).

WO2013/146024

In the sizing step of applying a sizing agent to fibers to form a fiber bundle, it is required that the sizing liquid (sizing agent) permeates between the fibers of the fiber bundle. However, with the sizing agent described in Patent Document 1, when the number of fibers in the fiber bundle is large, the sizing liquid (sizing agent) does not sufficiently permeate between the fibers, so it is said that the fiber bundle cannot sufficiently suppress the fluffing. I had a problem.
A fiber bundle obtained by applying a sizing agent to fibers is subjected to a step of widening the width of the fiber bundle (opening step) before being combined with the matrix resin. A fiber with good filamentity (the wider the width of the fiber bundle, the better the openability and lineability) is required. Although the technique described in Patent Document 1 can improve the openability, there is a demand for further improvement.

An object of the present invention is to provide a fiber sizing agent that suppresses fluffing and has excellent fiber opening properties.

The present inventor has arrived at the present invention as a result of conducting studies to achieve the above object.
That is, the present invention provides a fiber sizing agent composition containing a polyether-containing compound (A) and a nonionic surfactant (B), wherein the polyether-containing compound (A) comprises an ester compound (A1), At least one compound selected from the group consisting of urethane compounds (A2) and polyether diols (A3), wherein one or more polyoxyethylene groups consisting of two or more consecutive oxyethylene groups are contained in one molecule. and the number of oxyethylene groups per polyoxyethylene group is 2 to 60, and the nonionic surfactant (B) is a compound other than the polyether-containing compound (A), and is aromatic The fiber sizing agent composition comprising at least one each of a nonionic surfactant (B1) and an aliphatic nonionic surfactant (B2), wherein the nonionic surfactant (B) has an HLB value of 11 to 15. a fiber sizing agent composition having a viscosity of 200 to 2,000 mPa·s at 100°C and a viscosity of 3,000 to 20,000 mPa·s at 60°C; A fiber sizing agent solution in which the composition is dissolved or dispersed in water and/or an organic solvent; at least one selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slag fiber A fiber bundle obtained by treating a seed fiber with the above-described fiber sizing agent composition; a fiber product containing the fiber bundle; a composite material containing the fiber bundle and a matrix resin; and the fiber product and the matrix resin. It is a composite material containing

ADVANTAGE OF THE INVENTION According to this invention, the fiber sizing agent composition which suppresses fluffing and is excellent in opening property can be provided.

FIG. 1 is a side view schematically showing the arrangement of carbon fiber bundles in the evaluation of openability. FIG. 2 is a side view schematically showing the arrangement of carbon fiber bundles in evaluation of fluffiness.

<Fiber sizing agent composition>
The fiber sizing agent composition of the present invention contains a polyether-containing compound (A) and a nonionic surfactant (B).

In the present invention, the polyether-containing compound (A) is at least one compound selected from the group consisting of ester compounds (A1), urethane compounds (A2) and polyether diols (A3). Further, the polyether-containing compound (A) has one or more polyoxyethylene groups consisting of two or more continuous oxyethylene groups in one molecule, and the oxyethylene group per one polyoxyethylene group is 2 to 60.
The polyether-containing compound (A) has one or more polyoxyethylene groups consisting of 2 to 60 consecutive oxyethylene groups in one molecule, whereby the sizing agent composition has excellent fiber-opening properties. can be If the polyether-containing compound (A) does not have a polyoxyethylene group consisting of 2 to 60 consecutive oxyethylene groups, the sizing agent composition may not be sufficiently open. Hereinafter, "polyether-containing compound (A)" may be referred to as "compound (A)".
In the present invention, "two or more continuous oxyethylene groups" means a group in which two or more oxyethylene groups are connected to each other by directly bonding one oxyethylene group to another oxyethylene group. . In the present invention, "polyoxyethylene group" means a group composed of two or more oxyethylene groups directly bonded.

The polyether-containing compound (A) is at least one compound selected from the group consisting of ester compounds (A1), urethane compounds (A2) and polyether diols (A3). Each of the ester compound (A1), urethane compound (A2), and polyether diol (A3) is a compound having one or more polyoxyethylene groups consisting of 2 to 60 consecutive oxyethylene groups per molecule. .

The ester compound (A1) is a compound having an ester group obtained by reacting the diol (a2) with a dicarboxylic acid or its anhydride (a1).

Examples of the dicarboxylic acid or its anhydride (a1) that constitutes the ester compound (A1) include an aliphatic dicarboxylic acid (a11), an aromatic dicarboxylic acid (a12), and acid anhydrides thereof.

Examples of the aliphatic dicarboxylic acid (a11) include saturated chain dicarboxylic acids, unsaturated chain dicarboxylic acids, alicyclic dicarboxylic acids and dimer acids.

Examples of saturated chain dicarboxylic acids include linear or branched saturated dicarboxylic acids having 2 to 22 carbon atoms (oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, ethylsuccinic acid, dimethylmalonic acid, α-methyl Glutaric acid, β-methylglutaric acid, 2,4-diethylglutaric acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecane dicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, icosanedicarboxylic acid, decylsuccinic acid, dodecylsuccinic acid, octadecylsuccinic acid, etc.).

Examples of unsaturated chain dicarboxylic acids include linear or branched chain unsaturated dicarboxylic acids having 4 to 22 carbon atoms (maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid and octadecenylsuccinic acid). decenylsuccinic acid, etc.).

The alicyclic dicarboxylic acid includes alicyclic dicarboxylic acids having 7 to 14 carbon atoms (1,3- or 1,2-cyclopentanedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid acids, 1,2-, 1,3- or 1,4-cyclohexanediacetic acid and dicyclohexyl-4,4'-dicarboxylic acid) and the like.

Dimer acids include dimers of unsaturated chain carboxylic acids having 8 to 24 carbon atoms (oleic acid, linoleic acid, linolenic acid, etc.).

Examples of aromatic dicarboxylic acids include aromatic dicarboxylic acids having 8 to 14 carbon atoms (terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyl adipic acid, biphenyl-2,2′- and 4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate, etc.).

Anhydrides of dicarboxylic acids include anhydrides of the above aliphatic dicarboxylic acids (a11) or aromatic dicarboxylic acids (a12), such as succinic anhydride, maleic anhydride and phthalic anhydride.

Dicarboxylic acids and their anhydrides may be used alone or in combination of two or more. Among these, from the viewpoint of convergence, saturated chain dicarboxylic acids, chain unsaturated dicarboxylic acids and aromatic dicarboxylic acids are preferred, and oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid and maleic acid are more preferred. acid, fumaric acid, terephthalic acid, isophthalic acid and phthalic acid, particularly preferably adipic acid, maleic acid, fumaric acid, terephthalic acid, isophthalic acid and combinations of two or more of these.

The diol (a2) constituting the ester compound (A1) contains a polyoxyethylene group consisting of two or more continuous oxyethylene groups in one molecule from the viewpoint that it can be made excellent in opening property. It is preferable to include a diol (a21) having one or more and having 2 to 60 oxyethylene groups per polyoxyethylene group.

Examples of the diol (a21) include polyethylene glycol obtained by adding 1 to 59 mol of ethylene oxide (EO) to ethylene glycol [having one polyoxyethylene group in one molecule and one (poly)oxyethylene group Examples of compounds having 2 to 60 oxyethylene groups per group], compounds obtained by adding 4 to 120 moles of EO to compounds having two hydroxyl groups (excluding ethylene glycol), and EO to primary amines A compound obtained by adding 4 to 120 mol of [Example of a compound having two polyoxyethylene groups in one molecule and having 2 to 60 oxyethylene groups per (poly)oxyethylene group ] and the like. In addition to the above, the diol (a21) is a compound obtained by adding an alkylene oxide other than EO to a compound obtained by adding 4 to 120 mol of EO to a compound having two hydroxyl groups, and then further adding EO. Alternatively, a diol or the like having one or more polyoxyethylene groups in one molecule and having 2 to 60 oxyethylene groups per one (poly)oxyethylene group may be used. Examples of the above-mentioned "alkylene oxide adducts other than EO" include 1,2- or 1,3-propylene oxide (hereinafter, "propylene oxide" may be abbreviated as PO) adducts, 1,2-, 1, 3-, 2,3- or 1,4-butylene oxide (hereinafter, "butylene oxide" may be abbreviated as BO) adducts, and the like.

Examples of compounds having two hydroxyl groups include aliphatic alkanediols, alicyclic diols, and aromatic ring-containing dihydric phenols.
Aliphatic alkanediols (excluding ethylene glycol) include alkanediols having 2 to 16 carbon atoms (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1, 6-hexanediol, octanediol, decanediol, dodecanediol, hexadecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc.).

Alicyclic diols include alicyclic diols having 4 to 16 carbon atoms (eg, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.).

Examples of aromatic ring-containing dihydric phenols include bisphenol A, bisphenol S, cresol and hydroquinone.

The primary amine in the compound obtained by adding 4 to 120 mol of EO to a primary amine includes primary amines having 1 to 18 carbon atoms, such as methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine and dodecylamine. etc.

The diol (a21) is preferably at least one diol selected from the group consisting of polyethylene glycol obtained by adding 1 to 59 moles of EO to ethylene glycol and adducts of 4 to 120 moles of EO of aromatic ring-containing dihydric phenols. and more preferably at least one diol selected from the group consisting of polyethylene glycol obtained by adding 3 to 50 moles of EO to ethylene glycol and adducts of bisphenol A with 4 to 120 moles of EO.

The diol (a2) constituting the ester compound (A1) may contain a diol (a22) other than the diol (a21).
As the other diol (a22), a diol (a221) having at least one polyoxyethylene group in one molecule and having at least 61 oxyethylene groups per polyoxyethylene group (a221), 1 molecule A diol (a222) having one or two oxyethylene groups that are not continuous with another oxyethylene group, a diol (a223) having no oxyalkylene group, a diol having an oxyalkylene group other than an oxyethylene group (a224 ) and the like.
As used herein, "an oxyethylene group that is not continuous with other oxyethylene groups" means that an oxyethylene group is not directly bonded to another oxyethylene group.

As the diol (a221) having one or more polyoxyethylene groups in one molecule and having 61 or more oxyethylene groups per polyoxyethylene group, 60 mol or more of EO is added to ethylene glycol. Polyethylene glycol [an example of a compound having one polyoxyethylene group in one molecule and having 61 or more oxyethylene groups per polyoxyethylene group], a compound having two hydroxyl groups A compound obtained by adding 122 mol or more of EO to (excluding ethylene glycol) and a compound obtained by adding 122 mol or more of EO to a primary amine [having two polyoxyethylene groups in one molecule, polyoxyethylene Examples of compounds having 61 or more oxyethylene groups per group]. As the diol (a221), in addition to the above, a compound having two hydroxyl groups (excluding ethylene glycol) to which 122 moles or more of EO is added is added with an alkylene oxide other than EO (such as PO and BO). A diol, etc., which is a compound obtained by further adding EO, having one or more polyoxyethylene groups in one molecule, and having 61 or more oxyethylene groups per polyoxyethylene group. may be used.
Examples of the compound having two hydroxyl groups and the primary amine in these compounds are the same as those described above for the diol (a21).

The diol (a222) having one or two oxyethylene groups that are not continuous with another oxyethylene group in one molecule includes, for example, ethylene glycol (a diol having one oxyethylene group in one molecule) and a hydroxyl group. A compound obtained by adding EO to both ends of a compound having two (excluding ethylene glycol), and an EO 2-mol adduct of a primary amine (a diol having two oxyethylene groups in one molecule).
Examples of the compound having two hydroxyl groups and the primary amine in these compounds are the same as those described above for the diol (a21).

Examples of diols having no oxyalkylene group (a223) include compounds having two hydroxyl groups (aliphatic alkane diols other than ethylene glycol, alicyclic diols, aromatic ring-containing dihydric phenols, etc.). Examples of the compound having two hydroxyl groups include the same compounds as those described for the diol (a21).

Examples of the diol (a224) having an oxyalkylene group other than an oxyethylene group include PO and/or BO adducts of compounds having two hydroxyl groups (excluding ethylene glycol) and PO and/or BO adducts of primary amines. things, etc. PO in these compounds includes 1,2- or 1,3-propylene oxide. BO in these compounds includes 1,2-, 1,3-, 2,3- or 1,4-butylene oxide.
Examples of the compound having two hydroxyl groups and the primary amine in these compounds are the same as those described above for the diol (a21).

As the other diol (a22), preferably, a diol (a224) having an oxyalkylene group other than an oxyethylene group and a diol (a224) having one or more polyoxyethylene groups in one molecule and It is a diol (a221) having 61 or more oxyethylene groups, more preferably a PO adduct of bisphenol A and polyethylene glycol obtained by adding 60 to 90 mol of EO to ethylene glycol.

The content of the diol (a21) in the diol (a2) should be 45 to 100% by weight, based on the weight of the diol (a2), from the viewpoint of improving the openability. is preferred, and 50 to 100% by weight is more preferred.

The number of continuous oxyethylene groups in the diol (a2) and ester compound (A1) can be measured, for example, by the following method. For example, the ester compound (A1) is hydrolyzed to extract a diol component, further fractionated by preparative gel permeation chromatography (hereinafter referred to as preparative GPC), and the structure is identified by NMR measurement of each fraction component. , the number and weight percent of the oxyethylene groups can be calculated from the structure and the weight of the fractionated components.
Measurement conditions for preparative GPC are, for example, as follows.
Model: LC-09 (manufactured by Japan Analytical Industry Co., Ltd.)
Column: JAIGEL-3H
+ JAIGEL-2H
+ JAIGEL-1H
Column temperature: 25°C
Solvent: chloroform Flow rate: 3 ml/min Sample concentration: 2% by weight
Injection volume: 3ml

As a method for producing the ester compound (A1), for example, a dicarboxylic acid or its anhydride (a1) and a diol (a2) are charged at a predetermined molar ratio, and the reaction temperature is 100 to 250° C. and the pressure is −0.1 to 1. A method of distilling off water under stirring at .2 MPa can be mentioned. In the method for producing the ester compound (A1), it is preferable to add 0.05 to 0.5% by weight of the catalyst based on the weight of the ester compound (A1). Examples of the catalyst include p-toluenesulfonic acid, dibutyltin oxide, tetraisopropoxytitanate and potassium oxalate titanate, with tetraisopropoxytitanate and potassium oxalate titanate being preferred from the viewpoint of reactivity and environmental impact. and more preferred is potassium oxalate titanate.

The urethane compound (A2) is a compound obtained by reacting a polyol and a diisocyanate.

The polyol constituting the urethane compound (A2) contains one or more polyoxyethylene groups consisting of two or more continuous oxyethylene groups in one molecule, from the viewpoint of being able to have excellent fiber opening properties. and having 2 to 60 oxyethylene groups per polyoxyethylene group. The diol is a compound having one or more polyoxyethylene groups consisting of 2 to 60 consecutive oxyethylene groups in one molecule, and can be included in the diol (a2) constituting the ester compound (A1). It is a compound similar to (a21).

The polyol constituting the urethane compound (A2) contains other polyols other than the diol (a diol having one or more polyoxyethylene groups consisting of 2 to 60 consecutive oxyethylene groups in one molecule). good too. Other polyols include other diols (a22) that can be contained in the diol (a2) that constitutes the ester compound (A1), polyester polyols (polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, polycaprolactone diol, polyvalerolactone diol, polyhexamethylene carbonate diol, etc.).

The polyol constituting the urethane compound (A2) preferably contains at least the diol (a21) (a diol having one or more polyoxyethylene groups consisting of 2 to 60 consecutive oxyethylene groups in one molecule). and the diol (a222) (a diol having one or two oxyethylene groups that are not continuous with another oxyethylene group in one molecule), more preferably an aromatic ring-containing dihydric phenol and an EO 2 mol adduct of an aromatic ring-containing dihydric phenol, more preferably an EO 4 to 120 mol adduct of bisphenol A and an EO 2 mol adduct of bisphenol A. .

Specific examples of the diisocyanate constituting the urethane compound (A2) include, for example, aromatic diisocyanates having 8 to 30 carbon atoms [2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2 ,6-tolylene diisocyanate (TDI), 4,4′-dibenzyl diisocyanate, 1,3- or 1,4-phenylene diisocyanate and 1,5-naphthylene diisocyanate, xylylene diisocyanate, etc.]; of aliphatic diisocyanates [ethylene diisocyanate, hexamethylene diisocyanate (HDI) and lysine diisocyanate, etc.]; and mixtures of two or more of

The diisocyanate constituting the urethane compound (A2) is preferably an aromatic diisocyanate having 8 to 30 carbon atoms, more preferably 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI).

As a method for producing the urethane compound (A2), for example, a polyol containing at least one polyol having one or more polyoxyethylene groups consisting of 2 to 60 consecutive oxyethylene groups and a diisocyanate are mixed at a predetermined molar ratio. A method of charging, adding a chain extender and/or a cross-linking agent to the reaction system if necessary, and stirring at a reaction temperature of 30 to 130° C. for 1 to 24 hours.

The polyether diol (A3) has one or more polyoxyethylene groups consisting of two or more continuous oxyethylene groups in one molecule, and the number of oxyethylene groups per polyoxyethylene group is There is no particular limitation as long as the number of compounds is 2 to 60.

Specific examples of the polyether diol (A3) include the compounds described as specific examples of the diol (a21) [polyethylene glycol obtained by adding 1 to 59 mol of ethylene oxide (EO) to ethylene glycol, having two hydroxyl groups, compound obtained by adding 4 to 120 mol of EO to a compound and a compound obtained by adding 4 to 120 mol of EO to a primary amine] and polyether glycol (polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol) and a compound obtained by adding 4 to 120 mol of EO to. In addition to the above, the polyether diol (A3) is a compound obtained by adding an alkylene oxide other than EO to a compound obtained by adding 3 to 120 mol of EO to a polyether glycol, and then further adding EO. , a compound having one or more polyoxyethylene groups in one molecule and having 2 to 60 oxyethylene groups per polyoxyethylene group may be used. Examples of the compound having two hydroxyl groups and the primary amine are the same as those exemplified for the diol (a21).

The polyether diol (A3) is preferably a compound obtained by adding PO to an EO adduct of polyether glycol and further adding EO (the number of oxyethylene groups per polyoxyethylene group is 2 to 60), more preferably a compound obtained by adding PO to an EO adduct of polypropylene glycol and further adding EO (the number of oxyethylene groups per polyoxyethylene group is 2 to 60).

The polyether-containing compound (A) preferably contains an ester compound (A1), more preferably a dicarboxylic acid or its anhydride (a1) and two or more consecutive oxy groups in one molecule. It is reacted with a diol (a2) containing a compound (diol) having one or more polyoxyethylene groups consisting of ethylene groups and having 2 to 60 oxyethylene groups per polyoxyethylene group. It is an ester compound that consists of

In the present invention, the polyether-containing compound (A) preferably has a number average molecular weight (Mn) of 1,500 to 10,000. When the Mn of the polyether-containing compound (A) is 1,500 or more, the polyether-containing compound (A) has sufficient sizing properties, and when it is 10,000 or less, the affinity for water is high and the emulsion stability is excellent. Mn is measured by gel permeation chromatography (GPC). Mn is more preferably 1,800 to 5,000 from the viewpoint of excellent concentration and affinity for water.
Mn of compound (A) can be measured, for example, under the following conditions.
(Measurement condition)
Model: HLC-8220GPC [manufactured by Tosoh Corporation, liquid chromatograph]
Column: TSK gel Super H4000
TSK gel Super H3000
TSK gel Super H2000
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Detector: RI
Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min Sample concentration: 0.25% by weight
Injection volume: 10 μl
Standard material: Polystyrene [manufactured by Tosoh Corporation; TSK STANDARD]

The content of the polyether-containing compound (A) in the fiber sizing agent composition of the present invention is 20% by weight or more, based on the solid content of the fiber sizing agent composition, from the viewpoint of fiber opening. is preferred, and 25% by weight or more is more preferred. In addition, from the viewpoint of sizing properties of the fiber bundle, the content of the polyether-containing compound (A) is preferably 90% by weight or less, based on the weight of the solid content of the fiber sizing agent composition, and 70% by weight. More preferably: As used herein, the solid content is the residue after drying 1 g of a sample by heating with a circulating air dryer at 130° C. for 45 minutes.

The fiber sizing agent composition of the present invention contains a nonionic surfactant (B). The nonionic surfactant (B) is a compound other than the polyether-containing compound (A).

In the present invention, the nonionic surfactant (B) includes at least one aromatic nonionic surfactant (B1) and at least one aliphatic nonionic surfactant (B2). The nonionic surfactant (B) contains at least one each of an aromatic nonionic surfactant (B1) and an aliphatic nonionic surfactant (B2), thereby suppressing fluffing and improving openability. An excellent fiber sizing agent composition can be provided. If the nonionic surfactant (B) does not contain the aromatic nonionic surfactant (B1), the anti-fluffing effect may be insufficient. In addition, if the nonionic surfactant (B) does not contain the aliphatic nonionic surfactant (B2), the anti-fluffing effect and the openability may be insufficient.

Examples of the aromatic nonionic surfactant (B1) include compounds obtained by adding alkylene oxide (AO) to a compound having an aromatic ring. Specifically, compounds obtained by directly adding AO to alkyl (alkyl group having 1 to 18 carbon atoms) phenol, compounds obtained by directly adding AO to styrenated (1 to 10 mol) phenol, and styrenated (1 to 10 mol) compounds obtained by directly adding AO to cumylphenol. AO includes those having 2 to 4 carbon atoms, such as EO, PO, BO and combinations of two or more thereof.

Commercially available products may be used as the aromatic nonionic surfactant (B1). Commercially available aromatic nonionic surfactants include Soprophor 796/P [manufactured by Solvay Nicca Co., Ltd.], Soprophor TSP/724 [manufactured by Solvay Nicca Co., Ltd.], Soprophor TSP/461 [manufactured by Solvay Nicca Co., Ltd.]. (both are PO and EO adducts of styrenated phenol).
The aromatic nonionic surfactant (B1) is preferably a compound obtained by directly adding AO to styrenated (1 to 10 mol) phenol, more preferably PO and EO adducts of styrenated phenol. be. The aromatic nonionic surfactant (B1) may be used alone or in combination of two or more.

Aliphatic nonionic surfactants (B2) include AO adducts of aliphatic monoalcohols having 8 to 18 carbon atoms, AO adducts of higher fatty acids (12 to 24 carbon atoms), glycols and AO (excluding EO) Polyalkylene glycol obtained by adding (molecular weight 150 to Mw 6,000) reacted with higher fatty acid [excluding those used as compound (A)], polyhydric alcohol (ethylene glycol, propylene glycol, glycerin, AO (excluding EO) added to an esterified product obtained by reacting a higher fatty acid with a dihydric to octahydric or higher polyhydric alcohol such as sorbitan (molecular weight 250 to Mw 30,000)] and polyhydric alcohol (3 to 60 carbon atoms) type nonionic surfactants [fatty acid (3 to 60 carbon atoms) esters of dihydric to octahydric or higher polyhydric alcohols] and the like. The aliphatic nonionic surfactant (B2) may be used alone or in combination of two or more.

The aliphatic nonionic surfactant (B2) contains an AO adduct of an aliphatic monoalcohol having 8 to 18 carbon atoms from the viewpoint of suppressing the fluffing of fiber bundles when the fiber sizing agent composition is used. are preferred, and those containing an aliphatic alkylene oxide adduct represented by the following general formula (1) are more preferred.
Hereinafter, the "aliphatic alkylene oxide adduct represented by the general formula (1)" is also referred to as the "compound of the general formula (1)".
R ¹ O(AO) _m H (1)

R ¹ in the general formula (1) is an aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups. If the number of carbon atoms in R ¹ is less than 8 or more than 11, it becomes difficult to sufficiently suppress fluffing of the fiber bundle when the fiber sizing agent composition is used. The number of carbon atoms in R ¹ is preferably 9 or more from the viewpoint of further suppressing fluffing of the fiber bundle. In addition, the number of carbon atoms in R ¹ is preferably 10 or less from the viewpoint of further suppressing fluffing of the fiber bundle and impregnation into the matrix resin, which will be described in detail later.

The aliphatic hydrocarbon group having 8 to 11 carbon atoms may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group having 8 to 11 carbon atoms include an aliphatic hydrocarbon group having 3 methyl groups, an aliphatic hydrocarbon group having 4 methyl groups, and an aliphatic hydrocarbon group having 5 or more methyl groups. A hydrogen group and the like can be mentioned.

Examples of the aliphatic hydrocarbon group having three methyl groups include alkyl groups having three methyl groups (3-methylheptan-3-yl group, 3,5-dimethylhexan-1-yl group, 2-methylnonane -3-yl group, 6-methylheptan-2-yl group and 2-methyldecan-2-yl group), an alkenyl group having three methyl groups (3,7-dimethyl-6-octen-1-yl group etc.) and a cycloalkyl group having three methyl groups (4-tert-butylcyclohexan-1-yl group).

As the aliphatic hydrocarbon group having four methyl groups, an alkyl group having four methyl groups (2,4-dimethylpentan-3-yl group, 3,5,5-trimethylhexan-1-yl group , 2,6-dimethylheptan-4-yl group, 2,3,5-trimethylhexan-1-yl group, 3,5,5-trimethylheptan-1-yl group and 3,5,5-trimethyloctane- 1-yl group, etc.), an alkenyl group having four methyl groups (3,7-dimethyl-6-octen-2-yl group) and a cycloalkyl group having four methyl groups (4-tert-butyl-2- methylcyclohexan-1-yl group) and the like.

As the aliphatic hydrocarbon group having 5 or more methyl groups, an alkyl group having 5 methyl groups (2,2-dimethyl-5-methylhexan-4-yl group, etc.), having 5 methyl groups an alkenyl group (4,7,7-trimethyl-5-octen-2-yl group) and a cycloalkyl group having five methyl groups (4-tert-butyl-2,6-dimethylcyclohexan-1-yl group), etc. is mentioned.

Among the aliphatic hydrocarbon groups having 8 to 11 carbon atoms, alkyl groups and alkenyl groups are preferred, and alkyl groups are more preferred.

The number of methyl groups in R ¹ in all the compounds of general formula (1) contained in the fiber sizing agent composition of the present invention is 3.5 or more per molecule of the compound of general formula (1). preferable. If it is 3.5 or more, it is possible to further suppress fluffing of the fiber bundle when the fiber sizing agent composition is used. In addition, it is possible to improve the impregnation of the fiber sizing agent composition into the matrix resin, which will be described in detail later. The number of methyl groups in R ¹ per molecule of the compound of general formula (1) is preferably 5 or less. The number of methyl groups in R ¹ per molecule of the compound of general formula (1) may be a fractional number.
The number of methyl groups in R ¹ is, for example ^{, 1} H - can be calculated by performing NMR measurement and gas chromatography analysis.

AO in the general formula (1) is an alkyleneoxy group having 2 to 4 carbon atoms, specifically an ethyleneoxy group, a 1,2- or 1,3-propyleneoxy group and a 1,2-, 1,3 -, 2,3- or 1,4-butyleneoxy groups. Of these, an ethyleneoxy group is preferred. The compound of general formula (1) has m AOs (m is 3 to 10), and m AOs may be the same or different.

m in the general formula (1) represents the number of alkylene oxide addition moles per molecule of the aliphatic alcohol alkylene oxide adduct, and is a number of 3-10. If the number of moles of alkylene oxide to be added is less than 3, the suppression of fluffing of fiber bundles becomes insufficient and the solubility of the fiber sizing agent composition in water becomes insufficient. Also, when the number of moles of alkylene oxide added exceeds 10, the fiber bundle becomes insufficiently fluffed.
The added mole number m of the alkylene oxide per molecule of the compound of the general formula (1) is determined from the viewpoint of further suppressing the fluffing of the fiber bundle and impregnating the fiber sizing agent composition into the matrix resin, which will be described in detail later. It is preferably 4 or more. Further, the number of moles of alkylene oxide added per molecule of the compound of general formula (1) is preferably 7 or less from the viewpoint of further suppressing fluffing.

The compound of general formula (1) preferably contains a molecule having 3 to 10 alkyleneoxy groups. In addition, from the viewpoint of further suppression of fiber bundle fluffing and impregnation of the fiber sizing agent composition into a matrix resin, which will be described in detail later, it is preferable to contain a molecule having 4 or more alkyleneoxy groups. . In addition, from the viewpoint of further suppressing fluffing, it is preferable to contain a molecule having 7 or less alkyleneoxy groups.

Specific examples of the compound of general formula (1) include ethylene oxide (hereinafter sometimes abbreviated as EO) adducts of aliphatic alcohols having 8 to 11 carbon atoms, and 1,2- or 1,3-propylene oxide. (hereinafter sometimes abbreviated as PO) adduct, 1,2-, 1,3-, 2,3- or 1,4-butylene oxide (hereinafter sometimes abbreviated as BO) adduct, EO and PO random adducts, EO-PO block adducts, PO-EO block adducts, EO and BO random adducts, EO-BO block adducts and BO-EO block adducts.

The compound of general formula (1) is an EO adduct of an aliphatic alcohol having 8 to 11 carbon atoms and a fat It is more preferred to include PO-EO block adducts of group alcohols. In addition, from the viewpoint of further suppressing the fluffing of the fiber bundle and impregnating the fiber sizing agent composition into the matrix resin, which will be described in detail later, an EO single addition product of an aliphatic alcohol having 8 to 11 carbon atoms is used. Preferably.
In addition, the molar ratio of the ethyleneoxy group and the propyleneoxy group in the compound of the general formula (1) [moles of ethyleneoxy group:moles of propyleneoxy group] suppresses the fluffing of the fiber bundle and the fibers to the matrix resin. From the viewpoint of impregnating properties of the sizing agent composition, the ratio is preferably 100:0 to 70:30, more preferably 100:0 to 80:20.
The compounds of formula (1) may be used singly or in combination of two or more.

The number average molecular weight of the compound of formula (1) is preferably 260 to 892, more preferably 300 to 500, from the viewpoint of suppressing fluffiness of the fiber bundle. The number average molecular weight can be measured at 40° C. by gel permeation chromatography (hereinafter referred to as GPC) using polyethylene oxide as a reference substance.
The measurement conditions of GPC are as follows.
(GPC measurement conditions)
Model: HLC-8120 (manufactured by Tosoh Corporation)
Column: TSK gel Super H4000
TSK gel Super H3000
TSK gel Super H2000
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Detector: RI
Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min Sample concentration: 0.25% by weight
Injection volume: 10 μl
Reference material: polyoxyethylene glycol
(manufactured by Tosoh Corporation; TSK STANDARD
POLYETHYLENE OXIDE)
Data processing device: SC-8020 (manufactured by Tosoh Corporation)

As a method for producing the compound of general formula (1), there is a method of adding an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 8 to 11 carbon atoms using an acidic catalyst, an alkaline catalyst or the like described later as a catalyst. mentioned. Examples of aliphatic alcohols having 8 to 11 carbon atoms include alcohols in which a hydroxyl group is bonded to the aforementioned R ¹ having an aliphatic hydrocarbon group.

Aliphatic alcohols having 8 to 11 carbon atoms that constitute the compound of general formula (1) include aliphatic alcohols having three methyl groups (3-methylheptanol, 3,5-dimethylhexanol, 2-methylnonanol , 6-methylheptanol, 2-methyldecanol, 3,7-dimethyl-6-octenol and 4-tert-butylcyclohexanol), aliphatic alcohols having four methyl groups (2,4-dimethylpentanol , 3,5,5-trimethylhexanol, 2,6-dimethylheptanol, 2,3,5-trimethylhexanol, 3,5,5-trimethylheptanol, 3,5,5-trimethyloctanol, 3,7- Dimethyl-6-octanol and 4-tert-butyl-2-methylcyclohexanol, etc.), aliphatic alcohols having 5 or more methyl groups (2,2-dimethyl-5-methylhexanol, 4,7,7-trimethyl- 5-octanol and 4-tert-butyl-2,6-dimethylcyclohexanol, etc.).

Examples of the alkylene oxides having 2 to 4 carbon atoms include EO, PO and BO.

As a method for adding an alkylene oxide having 2 to 4 carbon atoms to the aliphatic alcohol having 8 to 11 carbon atoms, a general method can be used, but from the viewpoint of suppressing odor, the following is preferable. and a method of reacting in two stages.
An aliphatic alcohol having 9 to 10 carbon atoms is charged into a pressurized reaction vessel, and an alkylene oxide having 2 to 4 carbon atoms is blown in in the presence of an acidic catalyst [0.5 to 5 mol per 1 mol of the aliphatic alcohol], The reaction is carried out under normal or elevated pressure. The reaction temperature is preferably 50-200° C., and the reaction time is preferably 2-20 hours.
After the completion of the addition reaction of alkylene oxide, the catalyst is neutralized, treated with an adsorbent to remove and purify the catalyst, and alkylene which is a precursor of the compound of general formula (1) (aliphatic alcohol alkylene oxide adduct) Oxide adducts can be obtained. An alkali catalyst is added to the alkylene oxide adduct thus obtained, and an alkylene oxide that is the same or different from the above is further added in the same manner as described above to obtain the desired aliphatic alcohol alkylene oxide adduct [ compound of general formula (1)].

Examples of acidic catalysts include perhalic acid (salts), sulfuric acid (salts), phosphoric acid (salts), nitric acid (salts), perfluoroalkylsulfonic acid metal salts, and the like. The metal used to form the salt is not particularly limited, but divalent to trivalent metals are preferred. Divalent to trivalent metals include Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, Cd, Ti, Hf, Cr, Mo, Mn, Fe, Pd and rare earth atoms, and more preferred. are Mg, Zn, Ca, Sr, Ba, Al, Cu, Cd, Ti, Cr, Fe and rare earth atoms, particularly preferred are Mg, Zn, Al, Ti, Fe, Sc.
Halogen in the perhalogen acid (salt) includes chlorine, bromine and iodine, with chlorine being preferred. As the perfluoroalkylsulfonic acid metal salt, trifluoromethanesulfonate and pentafluoroethanesulfonate are preferable. More preferred is scandium triflate.
Preferred as acidic catalysts are perchlorates of divalent to trivalent metals and perfluoroalkylsulfonic acid metal salts, and more preferred are perchlorates of metals selected from Mg, Zn and Al, trifluoro romethanesulfonates and pentafluoroethanesulfonates, particularly preferred are magnesium perchlorate, zinc perchlorate, aluminum perchlorate and scandium triflate.
When the reaction is carried out in two stages as described above, the amount of the acidic catalyst used is based on the weight of the alkylene oxide adduct [precursor of the compound of general formula (1)] from the viewpoint of reaction rate and economy. , 0.001 to 1% by weight. More preferably 0.003 to 0.8% by weight, particularly preferably 0.005 to 0.5% by weight.

Alkali catalysts include hydroxides or alkoxides (methoxide, ethoxide, propoxide, butoxide, etc.) of alkali metals or alkaline earth metals (lithium, sodium, potassium, cesium, magnesium, calcium, barium, etc.), tertiary amines ( triethylamine, trimethylamine, etc.) and quaternary ammonium salts (tetramethylammonium hydroxide, etc.). Among these, potassium hydroxide, sodium hydroxide and cesium hydroxide are preferred.
When reacting in two stages as described above, the amount of alkali catalyst used is, from the viewpoint of reaction rate and economy, based on the weight of the aliphatic alcohol alkylene oxide adduct [compound of general formula (1)], 0.0001 to 1% by weight is preferred. More preferably, it is 0.001 to 0.5% by weight.

In the present invention, the HLB (Hydrophile-Lipophile Balance) value of the nonionic surfactant (B) is 11-15. When the HLB value of the nonionic surfactant (B) is from 11 to 15, it is possible to provide a fiber sizing agent composition that suppresses fluffing and has excellent fiber opening properties. If the HLB value of the nonionic surfactant (B) is less than 11 or more than 15, the anti-fluffing effect may be insufficient. The HLB value of the nonionic surfactant (B) is preferably 11.3-13.5.

In the present invention, the HLB value is a numerical value representing the balance between hydrophilicity and lipophilicity, and in the case of a single compound, it is obtained from the following formula (2) (see "Synthesis of Surfactants and Their Applications", 501, published by Maki Shoten, 1957; "Introduction to Surfactants", pp. 212-213, published by Sanyo Chemical Industry, 2007, etc.).
HLB value = 10 x (inorganic/organic) (2)
In formula (2), the parenthesis indicates the ratio of the inorganic and organic properties of the organic compound, and the ratio can be calculated from the values described in the above literature.

The HLB value of the nonionic surfactant (B) can be adjusted by adjusting the type and blending amount of the surfactant used. In the present invention, as the nonionic surfactant (B), one containing at least one aromatic nonionic surfactant (B1) and one aliphatic nonionic surfactant (B2) is used. Use a surfactant. When preparing the nonionic surfactant (B) using two or more surfactants, the HLB value of the nonionic surfactant (B) can be calculated by weighted average. For example, the nonionic surfactant (B) is an aromatic nonionic surfactant (B1) with an HLB value h1 of M1 parts by weight and an aliphatic nonionic surfactant (B2) with an HLB value of h2 by M2 parts by weight. When part is included, the HLB value of the nonionic surfactant (B) can be calculated by the following formula.
HLB value of nonionic surfactant (B) = (h1 × M1 + h2 × M2) / (M1 + M2)

The content of the nonionic surfactant (B) in the fiber sizing agent composition of the present invention is 5 to 90% by weight based on the weight of the solid content of the fiber sizing agent composition from the viewpoint of suppressing fluffing. Preferably.

In the present invention, the ratio (W1/W2) of the weight W1 of the aromatic nonionic surfactant (B1) to the weight W2 of the aliphatic nonionic surfactant (B2) is preferably 20/W2 from the viewpoint of storage stability. 80 to 90/10, more preferably 50/50 to 85/15.

In the fiber sizing agent composition of the present invention, components other than the polyether-containing compound (A) and the nonionic surfactant (B) are further selected from the group consisting of epoxy resins, vinyl ester resins and unsaturated polyester resins. preferably contains at least one resin (C).

Epoxy resins include diepoxides, phenolic novolac type epoxy resins, and epoxidized unsaturated fatty acid triglycerides (epoxidized soybean oil, epoxidized rapeseed oil, etc.) and the like.

The diepoxides include diglycidyl ethers, diglycidyl esters, diglycidyl amines and alicyclic diepoxides.

Diglycidyl ethers include diglycidyl ethers of dihydric phenols and diglycidyl ethers of dihydric alcohols. Examples of diglycidyl ethers of dihydric phenols include condensates (including polycondensates) of dihydric phenols having 6 to 30 carbon atoms and epichlorohydrin having glycidyl ethers at both ends. Examples of dihydric phenol include bisphenol (bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S and halogenated bisphenol A), catechin, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4, 4'-dihydroxybiphenyl, tetramethylbiphenyl, 9,9'-bis(4-hydroxyphenyl)fluorene and the like. Diglycidyl ethers of dihydric alcohols include condensates (including polycondensates) of diols having 2 to 100 carbon atoms and epichlorohydrin having glycidyl ethers at both ends. Dihydric alcohols include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, neopentyl glycol and AO (1 to 20 mol) addition of bisphenol A. things, etc. AO includes the above-mentioned AO having 2 to 4 carbon atoms.

The molar ratio of the dihydric phenol unit or dihydric alcohol unit contained in the diglycidyl ether and the epichlorohydrin unit {(dihydric phenol unit or dihydric alcohol unit):(epichlorohydrin unit)} is represented by n:n+1. . n is preferably 1-10, more preferably 1-8, particularly preferably 1-5. The diglycidyl ether may be a mixture of n=1 to 10 (such as a mixture with different degrees of polycondensation).

Examples of diglycidyl esters include diglycidyl esters of aromatic dicarboxylic acids and diglycidyl esters of aliphatic dicarboxylic acids. Examples of diglycidyl esters of aromatic dicarboxylic acids include condensates (including polycondensates) of aromatic dicarboxylic acids and epichlorohydrin having two glycidyl groups. Examples of diglycidyl esters of aliphatic dicarboxylic acids include aromatic nucleus water additives of aromatic dicarboxylic acids (hexahydrophthalic acid and 4-cyclohexene-1,2-dicarboxylic acid, etc.) or linear or branched aliphatic dicarboxylic acids ( adipic acid, 2,2-dimethylpropanedicarboxylic acid, etc.) and epichlorohydrin (including polycondensates), which have two glycidyl groups. In the diglycidyl ester, the molar ratio of the aromatic dicarboxylic acid unit or aliphatic dicarboxylic acid unit to the epichlorohydrin unit {(aromatic dicarboxylic acid unit or aliphatic dicarboxylic acid unit):(epichlorohydrin unit)} is n:n+1. expressed. n is preferably 1-10, more preferably 1-8, particularly preferably 1-5. The diglycidyl esters may be mixtures of n=1-10.

Examples of diglycidylamines include N-glycidyl compounds (N,N-di glycidylaniline and N,N-diglycidyltoluidine, etc.). In diglycidylamine, the molar ratio of aromatic amine units to epichlorohydrin units {(aromatic amine units):(epichlorohydrin units)} is expressed as n:n+1. n is preferably 1-10, more preferably 1-8, particularly preferably 1-5. The diglycidylamines may be mixtures where n=1-10.

The alicyclic diepoxides include alicyclic epoxides having 6 to 50 carbon atoms and 2 epoxy groups {vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl) ether , ethylene glycol bisepoxydicyclopentyl ether, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate and bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine}.

Moreover, as an epoxy resin, you may use what is marketed. Commercially available epoxy resins include jER834 [manufactured by Mitsubishi Chemical Corporation] and jER1001 [manufactured by Mitsubishi Chemical Corporation] (both of which are condensates of diglycidyl ether of bisphenol A and epichlorohydrin).

The epoxy resin is preferably a diglycidyl ether or a condensate of diglycidyl ether and epichlorohydrin, more preferably a condensate of diglycidyl ether of dihydric phenol and epichlorohydrin, particularly preferably a diglycidyl ether of bisphenol A. It is a condensate (bisphenol A type epoxy resin) with epichlorohydrin.

As the vinyl ester resin, a bisphenol-type epoxy resin (meth)acrylate-modified product {such as a terminal (meth)acrylate-modified resin obtained by reacting an epoxy group of a bisphenol A-type epoxy resin with a carboxyl group of (meth)acrylic acid}. etc. A commercially available resin can be used as the vinyl ester resin. Examples of commercially available resins include Epoxy Ester 3000A [manufactured by Kyoeisha Chemical Co., Ltd.] (2 mol acrylic acid adduct of bisphenol A diglycidyl ether).

The unsaturated polyester resin is a polyester resin other than the ester compound (A1). Unsaturated polyester resins include unsaturated dibasic acids (maleic anhydride, fumaric acid, iataconic acid, etc.) or saturated dibasic acids (phthalic anhydride, isophthalic acid, hetic acid, adipic acid, etc.) and glycols (ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, neopentyl glycol, etc.), and further crosslinked with polymerizable monomers such as styrene, chlorostyrene, t-butylstyrene, and methyl methacrylate. things, etc.

As the resin (C), one type may be used, or two or more types may be used. The resin (C) is preferably an epoxy resin, more preferably a condensate of diglycidyl ether of bisphenol A and epichlorohydrin, from the viewpoint of excellent cohesiveness.

The content of the resin (C) in the fiber sizing agent composition of the present invention is from 0 to 60% by weight is preferred, and 5 to 60% by weight is more preferred.

The fiber sizing agent composition of the present invention may contain components other than the aliphatic alcohol alkylene oxide adduct (A), the nonionic surfactant (B) and the resin (C). Other components include surfactants (D) other than nonionic surfactants and additives (E).

Other surfactants (D) than nonionic surfactants include cationic surfactants, anionic surfactants and amphoteric surfactants.
Examples of cationic surfactants include quaternary ammonium salt type [tetraalkyl (C 1-30) ammonium salts (lauryltrimethylammonium chloride, didecyldimethylammonium chloride and stearyltrimethylammonium bromide, etc.); 2-4) Trialkyl (C 1-30) ammonium salts (polyoxyethylene trimethylammonium chloride, etc.)] and amine salt type [aliphatic higher (C 12-60) amines (laurylamine, stearylamine, etc.) ); and inorganic or organic acid salts such as EO adducts of aliphatic amines (having 1 to 30 carbon atoms)].

Examples of anionic surfactants include carboxylic acids (saturated or unsaturated fatty acids having 8 to 22 carbon atoms) or salts thereof (salts of sodium, potassium, ammonium, alkanolamine, etc.), sulfate ester salts [higher alcohols (having 8 to 18) Sulfuric acid ester salt, etc.], higher alkyl ether sulfate salt [sulfuric acid ester salt of EO (1 to 10 mol) adduct of fatty alcohol having 8 to 18 carbon atoms, etc.], sulfonate [alkyl (1 carbon to 20) benzenesulfonates, alkyl (C 1-20) naphthalene sulfonates, dialkyl sulfosuccinate (C 1-20) esters, and α-olefin (C 12-18) sulfonates] and Phosphate ester salts [higher alcohol (C 8-60) phosphate ester salts and higher alcohol (C 8-60) EO adduct phosphate ester salts] and the like.

Amphoteric surfactants include amino acid-type amphoteric surfactants [higher alkylamine (C12-18) sodium propionate, etc.], betaine-type amphoteric surfactants [alkyl (C12-18) dimethylbetaine, etc.]. , Sulfate-type amphoteric surfactant [higher alkyl (C8-18) amine sulfate sodium salt, hydroxyethylimidazoline sulfate sodium salt, etc.], sulfonate-type amphoteric surfactant [pentadecyl sulfotaurine, imidazoline sulfonic acid, etc.] and phosphate ester-type amphoteric surfactants [phosphate amine salts of glycerin higher fatty acid (C8-22) esters] and the like.

As the other surfactant (D), an anionic surfactant is preferable, and a sulfate ester salt of an AO adduct of alkylphenol, a sulfate ester salt of an AO adduct of arylalkylphenol, and a mixture thereof are more preferable.

The content of the other surfactant (D) in the sizing agent composition for fibers of the present invention, from the viewpoint of excellent storage stability and sizing properties, is equal to 0 to 15% by weight is preferred, and 0 to 10% by weight is more preferred.

Additives (E) include smoothing agents, preservatives, antioxidants, and the like.
Smoothing agents include waxes (polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, modified polyethylene, modified polypropylene, etc.), higher fatty acid alkyl (C 1-24) esters (methyl stearate, ethyl stearate, prople stearate). latex, butyl stearate, octyl stearate, stearyl stearate, etc.), higher fatty acids (myristic acid, palmitic acid, stearic acid, etc.), natural oils and fats (coconut oil, beef tallow, olive oil, rapeseed oil, etc.), and liquid paraffin. be done.
Examples of antiseptics include benzoic acids, salicylic acids, sorbic acids, quaternary ammonium salts, imidazoles, and the like.
Antioxidants include phenols (2,6-di-t-butyl-p-cresol, etc.), thiodipropionates (dilauryl 3,3'-thiodipropionate, etc.) and phosphites (triphenyl phosphite, etc.).

The content of the additive (E) in the sizing agent composition for fibers of the present invention is 0 based on the weight of the solid content contained in the sizing agent composition for fibers, from the viewpoint of excellent storage stability and sizing properties. ~5% by weight is preferred, and 0-2% by weight is more preferred.

The method for producing the fiber sizing agent composition of the present invention is not particularly limited. For example, the surfactant (D) and the additive (E) are added and stirred at a temperature of preferably 20 to 150° C., more preferably 50 to 120° C. until uniform. The order in which the components [(A) to (E)] constituting the composition are added is not particularly limited.

The sizing agent composition for fibers of the present invention has a viscosity at 100°C of 200 mPa·s to 2000 mPa·s and a viscosity at 60°C of 3,000 mPa·s to 20,000 mPa·s. When the viscosity at 100° C. and the viscosity at 60° C. are within the above ranges, it is possible to provide a fiber sizing agent composition that suppresses fluffing and has excellent fiber opening properties.
If the viscosity of the fiber sizing agent composition at 100° C. is less than 200 mPa, the effect of suppressing fluffing may be insufficient, and if the viscosity exceeds 2000 mPa, the spreadability may be insufficient. If the viscosity of the fiber sizing agent composition at 60° C. is less than 3000 mPa, the effect of suppressing fluffing may be insufficient, and if the viscosity exceeds 2000 mPa, the spreadability may be insufficient.
The viscosity at 100° C. and the viscosity at 60° C. of the fiber sizing agent composition are measured using a Brookfield viscometer (BL type) in accordance with JIS K7117-1:1999 (corresponding to ISO2555:1990). be able to.

From the standpoint of excellent anti-fluffing effect and excellent fiber opening property, the viscosity of the fiber sizing agent composition at 100° C. is preferably 300 mPa·s to 1800 mPa·s, more preferably 400 mPa·s to 1500 mPa·s. is.
From the standpoint of excellent anti-fluffing effect and excellent fiber opening property, the viscosity of the fiber sizing agent composition at 60° C. is preferably 4000 mPa·s to 19,000 mPa·s, more preferably 4500 mPa·s to 18 , 500 mPa·s.

A sizing agent composition for fibers comprises a polyether-containing compound (A) having a polyoxyethylene group consisting of 2 to 60 consecutive oxyethylene groups and a nonionic surfactant (B) having an HLB value of 11 to 15. and the nonionic surfactant (B) contains at least one aromatic nonionic surfactant (B1) and one aliphatic nonionic surfactant (B2), thereby providing a fiber sizing agent The composition can have a viscosity at 100° C. of 200 mPa·s to 2000 mPa·s and a viscosity at 60° C. of 3,000 mPa·s to 20,000 mPa·s.
From the viewpoint that the viscosity of the fiber sizing agent composition at the above temperature can be adjusted to the above range, the fiber sizing agent composition contains a polyether-containing compound (A) containing a dicarboxylic acid or its anhydride (a1) and a diol ( An aspect that is an ester compound (A1) obtained by reacting a2), the ratio of the weight W1 of the aromatic nonionic surfactant (B1) to the weight W2 of the aliphatic nonionic surfactant (B2) (W1/W2) is 40/60 to 90/10, an aspect in which the aliphatic nonionic surfactant (B2) is a compound represented by the general formula (1), or a combination of these aspects is preferred.

<Fiber sizing agent solution>
The fiber sizing agent solution of the present invention is obtained by dissolving or dispersing the fiber sizing agent composition of the present invention in water and/or an organic solvent. Water and organic solvents are also referred to as "solvents".
By dissolving or dispersing the fiber sizing agent composition of the present invention in a solvent, it becomes easy to make the amount of the fiber sizing agent composition adhered to the fiber bundles appropriate.

Examples of solvents include water and organic solvents.
Examples of organic solvents include monohydric alcohols having 1 to 4 carbon atoms (methanol, ethanol, isopropanol, etc.), ketones having 3 to 6 carbon atoms (acetone, ethyl methyl ketone, methyl isobutyl ketone, etc.), and 2 to 4 carbon atoms. 6 glycol (ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol, etc.), its mono-lower alkyl (alkyl has 1 to 4 carbon atoms) ether, dimethylformamide, aromatic hydrocarbon (toluene, xylene, etc.), carbon number 3 to 5 acetic acid alkyl esters (methyl acetate, ethyl acetate, etc.) and the like.
One of the above solvents may be used alone, or two or more thereof may be used in combination. Among the above solvents, water and water-miscible organic solvents (at 25 ° C., when mixed with water at a volume ratio of 1:1, are uniformly mixed from the viewpoint of safety against fire, etc.) organic solvent) and water, more preferably water.

From the viewpoint of cost and the like, the fiber sizing agent solution of the present invention preferably has a high concentration during distribution and a low concentration during production of the fiber bundle. That is, by distributing the fiber at a high concentration, transportation costs, storage costs, etc. can be reduced, and by processing the fibers at a low concentration, it is possible to produce a fiber bundle that achieves both excellent bundling and opening properties.
When the fiber sizing agent solution has a high concentration, the concentration (weight ratio of components other than the solvent) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, from the viewpoint of storage stability and the like. be.
When the concentration of the fiber sizing agent solution is low, the concentration is preferably 0.5 to 15% by weight from the viewpoint that the adhesion amount of the fiber sizing agent can be made appropriate during the production of the fiber bundle. More preferably 1 to 10% by weight.

The method for producing the fiber sizing agent solution of the present invention is not particularly limited, but for example, a solvent is added to the fiber sizing agent composition of the present invention to dissolve or emulsify the fiber sizing agent composition in the solvent. There is a method to make
The temperature at which the fiber sizing agent composition is dissolved or emulsified and dispersed in the solvent is preferably 20 to 90°C, more preferably 40 to 90°C, from the viewpoint of ease of mixing. The time for dissolving or emulsifying and dispersing the fiber sizing agent composition in the solvent is preferably 1 to 20 hours, more preferably 1 to 10 hours.
When dissolving or emulsifying and dispersing the fiber sizing agent composition in a solvent, known mixing devices, dissolving devices and emulsifying and dispersing devices can be used. and three-stage paddle, etc.), Nauta Mixer [manufactured by Hosokawa Micron Corporation, etc.], ribbon mixer, conical blender, mortar mixer, universal mixer {universal mixer "5DM-L" [manufactured by Sanei Seisakusho Co., Ltd.], etc. }, a Henschel mixer [Nippon Coke Kogyo Co., Ltd.], an autoclave, and the like can be used.

Fibers to which the fiber sizing agent composition or fiber sizing agent solution of the present invention can be applied include inorganic fibers (carbon fibers, glass fibers, ceramic fibers, metal fibers, mineral fibers, slag fibers, etc.) and organic fibers (aramid fibers, etc.). etc.). Among these, carbon fiber is preferable from the viewpoint of the strength of the molded article of the composite material using the fiber sizing agent composition and the fiber.

<Fiber bundle>
In the fiber bundle of the present invention, at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slag fiber is mixed with the fiber sizing agent composition of the present invention. It is a fiber bundle formed by processing.

As a method for producing the fiber bundle of the present invention, at least one kind of fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slag fiber is mixed with the fiber bundle of the present invention. and a method of obtaining a fiber bundle by treatment with the agent composition or the fiber sizing agent solution of the present invention.
The fiber bundle of the present invention preferably has 3,000 to 50,000 fibers bundled together. The sizing agent composition for fibers of the present invention or the sizing agent solution for fibers of the present invention can sufficiently suppress fluffing even when the number of fibers in the fiber bundle is large (20,000 or more).

Methods of treating fibers include spraying and dipping. The amount of the fiber sizing agent composition deposited on the fibers is preferably 0.05 to 5% by weight, more preferably 0.2 to 2.5% by weight, based on the weight of the fibers. When the adhesion amount of the fiber sizing agent composition is within this range, the sizing property is excellent.

<Textile products>
The textile product of the present invention contains the fiber bundle of the present invention. Textile products include textile products obtained by processing the fiber bundle of the present invention, including woven fabrics, knitted fabrics, non-woven fabrics (felt, mat, paper, etc.), chopped fibers, milled fibers, and the like.

<Composite material>
The composite material of the present invention contains the fiber bundle of the present invention and/or the fiber product of the present invention, and a matrix resin. The composite material of the present invention may contain a catalyst if necessary.
When the matrix resin contains a thermosetting resin, which will be described later, the composite material of the present invention contains the thermosetting resin and a component contained in the fiber bundle and fiber product of the present invention (for example, [epoxy resin used as resin (C) etc.]) may be contained.

As matrix resins, thermoplastic resins (polypropylene, polyamide, polyethylene terephthalate, polycarbonate, polyphenylene sulfide, etc.) and thermosetting resins [similar to the epoxy resins, unsaturated polyester resins and vinyl ester resins described in component (C) , and phenolic resins (such as those described in Japanese Patent No. 3723462)] and the like.

Examples of catalysts for epoxy resins include known curing agents and curing accelerators for epoxy resins (such as those described in JP-A-2005-213337). As catalysts for unsaturated polyester resins and vinyl ester resins, peroxides (benzoyl peroxide, t-butyl perbenzoate, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, 1,1-di(t- butylperoxy)butane, di(4-t-butylcyclohexyl)peroxydicarbonate, etc.) and azo compounds (azobisisovaleronitrile, etc.).

In the composite material of the present invention, the weight ratio of the matrix resin to the fiber bundle (matrix resin/fiber bundle) is preferably from 10/90 to 90/10 from the viewpoint of the strength of the molded article of the composite material. It is preferably 20/80 to 70/30, particularly preferably 30/70 to 60/40.
When the composite material contains a catalyst, the content ratio of the catalyst is preferably 0.01 to 10% by weight, more preferably 0.1%, based on the matrix resin, from the viewpoint of the strength of the molded article of the composite material. to 5% by weight, particularly preferably 1 to 3% by weight.

The composite material is a matrix resin that has been thermally melted (preferred melting temperature: 60 to 350 ° C.) or diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, etc.), fiber bundles and / Alternatively, it can be produced by impregnating a textile product. If a solvent is used, it is preferred to dry the prepreg to remove the solvent.

In the composite material of the present invention, when the matrix resin is a thermoplastic resin, the prepreg can be heat-molded and solidified at room temperature to form a molded body.
In the composite material of the present invention, when the matrix resin is a thermosetting resin, the prepreg can be heat-molded and cured to form a molded body.
These resins do not need to be completely cured, but are preferably cured to such an extent that the molded article can maintain its shape. After molding, it may be further heated for complete curing.
The method of thermoforming is not particularly limited, and includes a filament winding molding method (a method of winding while applying tension to a rotating mandrel and thermoforming), a press molding method (a method of laminating prepreg sheets and thermoforming), an autoclave method ( a method of heat-molding a prepreg sheet by applying pressure to a mold; and a method of injection-molding a mixture of chopped fibers or milled fibers with a matrix resin.

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. Hereinafter, unless otherwise specified, % means % by weight, and part means part by weight.

<Production Example 1: Production of EO 16 mol adduct (a2-5) of bisphenol A>
228 parts (1 mol part) of bisphenol A, 200 parts of toluene and 2 parts of potassium hydroxide were charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping cylinder, and the pressure was adjusted to -0.08 MPa. The temperature was raised to 130° C., and 704 parts by weight (16 mol parts) of EO was added dropwise over 6 hours while adjusting the pressure to 0.5 MPaG or less, followed by aging at 130° C. for 3 hours. Next, after cooling to 100°C, 30 parts by weight of the adsorption treatment agent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after stirring at 100°C for 1 hour for treatment, the adsorption treatment agent was filtered, An EO 16 mol adduct of bisphenol A (a2-5) was obtained. (a2-5) had two polyoxyethylene groups, and the number of oxyethylene groups per one (poly)oxyethylene group was eight.

<Production Example 2: Production of polyethylene glycol (a2-6)>
62 parts (1 mol part) of ethylene glycol and 1 part of potassium hydroxide were charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping cylinder, and the pressure was adjusted to -0.08 MPa. The temperature was raised to 100° C., and 176 parts by weight (4 mol parts) of EO was added dropwise over 6 hours while adjusting the pressure to 0.5 MPaG or less, followed by aging at 100° C. for 3 hours. Next, 30 parts by weight of the adsorption treatment agent "Kyoward 600" [manufactured by Kyowa Chemical Industry Co., Ltd.] was added and stirred at 100 ° C. for 1 hour. ). (a2-6) had one polyoxyethylene group, and the number of oxyethylene groups per one (poly)oxyethylene group was five.

<Production Example 3: Production of 40 mol EO adduct of bisphenol A (a2-7)>
In Production Example 1, except that 200 parts of toluene was changed to 400 parts of toluene and 704 parts of EO was changed to 1760 parts (40 mol parts) of EO, in the same manner as in Production Example 1, the 40 mol EO adduct of bisphenol A (a2 -7) was obtained. (a2-7) had two polyoxyethylene groups, and the number of oxyethylene groups per (poly)oxyethylene group was 20.

<Production Example 4: Production of 80 mol EO adduct of bisphenol A (a2-8)>
In Production Example 1, except that 200 parts of toluene was changed to 1000 parts of toluene and 704 parts of EO was changed to 3520 parts (80 mol parts) of EO, in the same manner as in Production Example 1, an 80 mol EO adduct of bisphenol A (a2 -8) was obtained. (a2-8) had two polyoxyethylene groups, and the number of oxyethylene groups per (poly)oxyethylene group was 40.

<Production Example 5: Production of EO 120 mol adduct (a2-9) of bisphenol A>
In Production Example 1, except that 200 parts of toluene was changed to 1500 parts of toluene and 704 parts of EO was changed to 5280 parts (120 mol parts) of EO, in the same manner as in Production Example 1, an adduct of bisphenol A with 120 mol of EO (a2 -9) was obtained. (a2-9) had two polyoxyethylene groups, and the number of oxyethylene groups per (poly)oxyethylene group was 60.

<Production Example 6: Production of polyether-containing compound (A-1)>
EO 2 mol adduct of bisphenol A (the number of oxyethylene groups per hydroxyl group is 1) "Newpol BPE-20" [manufactured by Sanyo Chemical Industries Co., Ltd.] (a2-2) 632 parts (2 mol parts) , EO 40 mol adduct of bisphenol A (a2-7) 795 parts (0.40 mol parts), terephthalic acid (a1-1) 498 parts (3 mol parts) and potassium oxalate titanate 3 parts, a glass reaction vessel The pressure was reduced to 0.001 MPa at a medium temperature of 230° C., and the reaction was continued for 15 hours while distilling off water to obtain a polyether-containing compound (A-1) having a number average molecular weight (Mn) of 1,850. The compound is a compound having an ester group (ester compound).

<Production Examples 7 to 18 and Comparative Production Example 1: Production of polyether-containing compounds (A-2) to (A-13) and polyether-containing compound (A'-1)>
In Production Example 6, polyether-containing in the same manner as in Production Example 6 except that the type and amount of the dicarboxylic acid or its anhydride (a1) used and the type and amount of the diol (a2) were as shown in Table 1. Compounds (A-2) to (A-13) and polyether-containing compound (A'-1) were obtained. These compounds are compounds having an ester group (ester compounds).

<Production Example 19: Production of polyether-containing compound (A-14)>
Polypropylene glycol "PP-1000" [manufactured by Sanyo Chemical Industries Co., Ltd.] 1000 parts by weight (1 mol part), potassium hydroxide (manufactured by Toagosei Co., Ltd.) ) was charged, and after purging with nitrogen, vacuum dehydration was performed at 120° C. for 60 minutes to reduce the water content to 0.1 wt % or less. Then, 3000 parts by weight (68 mol parts) of EO was pressurized at 105 to 130° C. over 3 hours and reacted at the same temperature to obtain an EO adduct of polypropylene glycol [having two polyoxyethylene groups, (poly ) 34 oxyethylene groups per oxyethylene group]. After the volatile content became 0.1% or less, 3000 parts by weight (51.7 mol parts) of PO was injected over 3 hours and reacted at the same temperature. After the volatile content became 0.1% or less, 3000 parts by weight (68 mol parts) of EO were further pressurized over 3 hours and reacted at the same temperature until the volatile content became 0.1% or less.
Water and an alkali adsorbent (Kyoward 600, manufactured by Kyowa Chemical Industry Co., Ltd.) are added to the resulting reaction product, filtered, and then dehydrated by heating to obtain a polyether-containing compound (A-14) having a number average molecular weight of 10,000. ) (polyether diol) was obtained. The polyether-containing compound (A-14) had 4 polyoxyethylene groups, and the number of oxyethylene groups per (poly)oxyethylene group was 34.

<Production Example 20: Production of polyether-containing compound (A-15)>
1896 parts (6 mol parts) of (a2-2) and 1988 parts (1 mol part) of (a2-7) were charged into a reaction vessel equipped with a stirrer and a heating/cooling device, and stirred at 30°C until uniform. After that, diphenylmethane diisocyanate "Millionate MT" [manufactured by Tosoh Corporation] 1500 parts (6 mol parts) was charged, heated to 80 ° C. and stirred for 10 hours to cause a urethanization reaction, containing a polyether having a number average molecular weight of 5100 A compound (A-15) (urethane compound) was obtained.

Materials used in the production of polyether-containing compounds (A-1) to (A-15) and polyether-containing compound (A'-1) are as follows.
<Dicarboxylic acid or its anhydride (a1)>
(a1-1): terephthalic acid (a1-2): fumaric acid <diol (a2)>
(a2-1): PO3 molar adduct of bisphenol A [the number of oxyethylene groups in one molecule is 0, that is, the number of oxyethylene groups per (poly)oxyethylene group is 0, trade name: "New Pole BP-3P", manufactured by Sanyo Chemical Industries Co., Ltd.]
(a2-2): EO 2 mol adduct of bisphenol A [the number of oxyethylene groups per (poly)oxyethylene group is 1, trade name: "Newpol BPE-20", Sanyo Chemical Industry Co., Ltd. made]
(a2-3): Polyethylene glycol [manufactured by Sanyo Chemical Industries, Ltd., trade name “PEG-4000S”, number of oxyethylene groups per (poly)oxyethylene group is 90]
(a2-4): EO 4 mole adduct of bisphenol A (the number of oxyethylene groups per (poly)oxyethylene group is 2), trade name: "Newpol BPE-40", Sanyo Chemical Industry Co., Ltd. ) Product (a2-5): EO 16 mol adduct of bisphenol A produced in Production Example 1 (the number of oxyethylene groups per (poly)oxyethylene group is 8)
(a2-6): Polyethylene glycol produced in Production Example 2 [5 oxyethylene groups per (poly)oxyethylene group]
(a2-7): 40 mol EO adduct of bisphenol A produced in Production Example 3 [the number of oxyethylene groups per (poly)oxyethylene group is 20]
(a2-8): 80 mol EO adduct of bisphenol A produced in Production Example 4 [the number of oxyethylene groups per (poly)oxyethylene group is 40]
(a2-9): EO 120 mol adduct of bisphenol A produced in Production Example 5 [the number of oxyethylene groups per (poly)oxyethylene group is 60]
(a2-10): Polyethylene glycol [manufactured by Sanyo Chemical Industries, Ltd., trade name “PEG-2000”, number of oxyethylene groups per (poly)oxyethylene group is 45]

<Production Example 21: Production of EO4 mol adduct (B2-1) of 3,5,5-trimethyl-1-hexanol>
144 parts (1 mol part) of 3,5,5-trimethyl-1-hexanol and 1 part of aluminum perchlorate nonahydrate (0.1 mol part) were added to a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping cylinder. 002 mol parts) was put in, and after purging with nitrogen, the inside was sealed, the temperature was raised to 70° C., and dehydration was performed under reduced pressure for 1 hour. The temperature was raised to 80° C., and 88 parts (2 mol parts) of ethylene oxide was added dropwise over 10 hours while adjusting the pressure to 0.2 MPaG or less, followed by aging at 95° C. for 5 hours. Next, after cooling to 70°C, 10 parts of the adsorption treatment agent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 70°C for 1 hour for treatment. , 5,5-trimethyl-1-hexanol with EO 2 molar adduct was obtained.
After adding 0.1 part of potassium hydroxide to the resulting EO 2 mol adduct of 3,5,5-trimethyl-1-hexanol, the mixture was replaced with nitrogen, sealed, heated to 70° C., and dehydrated under reduced pressure for 1 hour. did The temperature was raised to 140 ° C., and 88 parts (2 mol parts) of ethylene oxide was added dropwise over 3 hours while adjusting the pressure to 0.5 MPaG or less, and then aged at 140 ° C. for 2 hours (second EO addition). Next, after cooling to 70°C, 10 parts of the adsorption treatment agent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 70°C for 1 hour for treatment. , 5,5-trimethyl-1-hexanol to give an EO 4 mole adduct (B2-1).
EO4 mol adduct (B2-1) of 3,5,5-trimethyl-1-hexanol is a compound represented by general formula (1), wherein R ¹ is 3,5,5-trimethylhexane-1- AO was an ^ethyleneoxy group and m was 4.

<Production Example 22: Production of 6 mol EO adduct (B2-2) of 3,5,5-trimethyl-1-hexanol>
In Production Example 21, 3,5,5-trimethyl An EO 6 mol adduct (B2-2) of -1-hexanol was obtained.
EO6 mol adduct (B2-2) of 3,5,5-trimethyl-1-hexanol is a compound represented by general formula (1), wherein R ¹ is 3,5,5-trimethylhexane-1- AO was an ^ethyleneoxy group and m was 6.

<Production Example 23: Production of decanol-EO6 mol adduct (B2-3)>
158 parts (1 mol part) of "Decanol" [manufactured by KH Neochem Co., Ltd.] and 0.5 parts (0.009 mol part) of potassium hydroxide are added to a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping cylinder. ) was put thereinto, and after purging with nitrogen, the inside was sealed, the temperature was raised to 70° C., and dehydration was performed under reduced pressure for 1 hour. The temperature was raised to 160° C., and 264 parts (6 mol parts) of EO was added dropwise over 5 hours while adjusting the pressure to 0.5 MPaG or less, followed by aging at 160° C. for 2 hours. Next, after cooling to 70°C, 10 parts of the adsorption treatment agent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after stirring at 70°C for 1 hour for treatment, the adsorption treatment agent was filtered and decanol was added. to obtain an EO 6 molar adduct (B2-3) of
Decanol manufactured by KH Neochem Co., Ltd., which is a raw material compound used in this production example, was analyzed by ¹ H-NMR and gas chromatography, and a hydroxyl group was bonded to the decyl group (aliphatic hydrocarbon group having 10 carbon atoms). It was confirmed that it was an alcohol and that the number of methyl groups in R ¹ per molecule of the compound was 3.5.
Therefore, the decanol-EO5 mol adduct (B2-3) obtained in this production example is a compound represented by the general formula (1), where R ¹ is a decyl group (the methyl group in R ¹ is 3.5 ), AO is an ethyleneoxy group, and m is 6.

<Production Example 24: Production of EO 5 mole adduct (B2-4) of 6-methyl-2-heptanol>
In Production Example 23, 130 parts (1 mol part) of 6-methyl-2-heptanol was used instead of 158 parts (1 mol part) of "decanol", and 264 parts (6 mol parts) of EO were replaced with 220 parts of EO ( EO 5 mol adduct (B2-4) of 6-methyl-2-heptanol was obtained in the same manner as in Production Example 23, except that the amount was changed to 5 mol parts).
The EO5 molar adduct of 6-methyl-2-heptanol (B2-4) is a compound represented ^by the general formula (1), where R ¹ is a 6-methylheptan-2-yl group (methyl 3), AO was an ethyleneoxy group, and m was 5.

<Production Example 25: Production of 2 mol EO adduct (B2-5) of 3,5,5-trimethyl-1-hexanol>
In Production Example 23, 144 parts (1 mol part) of 3,5,5-trimethyl-1-hexanol was used instead of 158 parts (1 mol part) of "decanol", and 264 parts (6 mol parts) of EO were used. A 2 mol EO adduct (B2-5) of 3,5,5-trimethyl-1-hexanol was obtained in the same manner as in Production Example 23, except that EO was changed to 88 parts (2 mol parts).
EO2 molar adduct (B2-5) of 3,5,5-trimethyl-1-hexanol is a compound represented by general formula (1), wherein R ¹ is 3,5,5-trimethylhexane-1- AO was an ^ethyleneoxy group and m was 2.

<Comparative Production Example 2: Production of polyether-containing compound (A'-2)]
In Production Example 20, 2400 parts of (a2-1) were used in place of 1896 parts of (a2-2), 2000 parts of (a2-11) were used in place of 1988 parts of (a2-7), and A polyether-containing compound (A'-2) (urethane compound) having a number average molecular weight of 5,200 was obtained in the same manner as in Production Example 20, except that 1,500 parts of diphenylmethane diisocyanate was changed to 1,375 parts.

<Examples 1 to 21 and Comparative Examples 1 to 11>
In a reaction vessel equipped with a stirrer, a heating and cooling device, a thermometer and a dropping funnel, polyether-containing compound (A), aromatic nonionic surfactant (B1), aromatic nonionic surfactant (B1), Aliphatic nonionic surfactant (B1) and resin (C) were added and stirred for 5 minutes while heating to obtain a fiber sizing agent composition. A portion of the fiber sizing agent composition was subjected to viscosity measurement.
Next, water is added dropwise to the fiber sizing agent composition from a dropping funnel over 1 hour to obtain a fiber sizing agent solution (X-1), which is a dispersion of the fiber sizing agent composition having a solid content concentration of 40%. ~ (X-21), (X'-1) ~ (X'-11) were produced. Here, the solid content is the residue after heating and drying 1 g of the sample at 130° C. for 45 minutes in a circulating dryer.

The materials used in the production of fiber sizing agent solutions in Examples and Comparative Examples are as follows.
<Polyether-containing compound (A)>
(A-1) to (A-13): ester compounds produced in Production Examples 6 to 18 (A-14): polyether diol produced in Production Example 19 (A-15): urethane produced in Production Example 20 Compound <comparative polyether-containing compound>
(A'-1): Ester compound (A'-2) produced in Comparative Production Example 1: Urethane compound (A'-3) produced in Comparative Production Example 2: Polyethylene glycol (polyoxyethylene group in one molecule and the polyoxyethylene group consists of 227 consecutive oxyethylene groups) [trade name: “PEG-10000”, manufactured by Sanyo Chemical Industries Co., Ltd.]
(A'-4): Block polymer of polyoxyethylene and polyoxypropylene (the number of oxyethylene groups per polyoxyethylene group is 80) [trade name: "Newpol PE-78", Sanyo Kasei manufactured by Kogyo Co., Ltd.]
<Aromatic nonionic surfactant (B1)>
(B1-1): Propylene oxide ethylene oxide adduct of styrenated phenol [trade name: “Soprophor 796/P” manufactured by Solvay Nikka Co., Ltd.; mole]
(B1-2): Propylene oxide ethylene oxide adduct of styrenated phenol [trade name: “Soprophor TSP/724” manufactured by Solvay Nikka Co., Ltd., HLB value is 11.9]
(B1-3): Propylene oxide ethylene oxide adduct of styrenated phenol [trade name: “Soprophor TSP/461” manufactured by Solvay Nikka Co., Ltd., HLB value is 9.2]
<Aliphatic nonionic surfactant (B2)>
(B2-1): EO 4 mole adduct of 3,5,5-trimethyl-1-hexanol produced in Production Example 21 (B2-2): 3,5,5-trimethyl-1- produced in Production Example 22 EO 6 mol adduct of hexanol (B2-3): EO 6 mol adduct of decanol produced in Production Example 23 (B2-4): EO 5 mol adduct of 6-methyl-2-heptanol produced in Production Example 24 (B2 -5): EO 2 mol adduct of 3,5,5-trimethyl-1-hexanol produced in Production Example 25 <Resin (C)>
(C-1): Epoxy resin [condensation product of bisphenol A diglycidyl ether and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation, trade name: "jER834"]
(C-2): Epoxy resin [condensation product of bisphenol A diglycidyl ether and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation, trade name: "jER1001"]
(C-3): Vinyl ester resin [2 mol acrylic acid adduct of bisphenol A diglycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd., trade name “Epoxy Ester 3000A”]

The viscosities at 60° C. and 100° C. of the fiber sizing agent compositions of Examples 1 to 21 and Comparative Examples 1 to 11, and the fiber sizing agent solutions obtained in Examples 1 to 21 and Comparative Examples 1 to 11 The storage stability of (X-1) to (X-21) and (X'-1) to (X'-11), and the fiber sizing agent solutions (X-1) to (X-21), The bundling properties, fiber opening properties and fluffiness of the carbon fiber bundles produced using (X'-1) to (X'-11) were evaluated by the following methods. Results are shown in Tables 2 and 3.

[Viscosity measurement of fiber sizing agent composition]
The viscosity at 60° C. and the viscosity at 100° C. of the fiber sizing agent compositions of Examples 1 to 21 and Comparative Examples 1 to 11 were measured twice under the following conditions, and the average value was calculated.
(Viscosity measurement conditions)
Measuring equipment: BL type viscometer (manufactured by Toki Sangyo Co., Ltd.)
Rotor speed: 60 rpm (viscosity less than 10 Pa s)
6 rpm (viscosity of 10 Pa·s or more)
Measurement temperature: 100°C and 60°C
Rotor: No. 4

[Evaluation Test of Fiber Sizing Agent Solution]
<Production of carbon fiber bundle for evaluation test>
Water was added to the fiber sizing agent solutions obtained in Examples and Comparative Examples so that the solid content concentration was 1.5% to form a dispersion, and untreated carbon fibers (24,000 filaments) were immersed. was impregnated with a dispersion of the sizing agent composition for fibers. After that, the carbon fibers were taken out from the dispersion of the fiber sizing agent composition and dried with hot air at 180° C. for 3 minutes to obtain a carbon fiber bundle. The carbon fiber bundles were produced such that the amount of the solid content adhered to the fibers (percentage based on the weight of the carbon fibers before immersion) in the dispersion of the fiber sizing agent composition was 1.5%. The carbon fiber bundle was subjected to an evaluation test for bundling property, fiber opening property and fluffiness.

<Convergence evaluation test>
Using a carbon fiber bundle for testing, the convergence was evaluated according to JIS L1096-2010 8.21.1 A method (45° cantilever method). A cantilever was used to evaluate the carbon fiber bundle obtained under the treatment conditions specified by JIS. A larger measured value (cm) means better convergence. The convergence value measured by this evaluation method is preferably 14 cm or more.

<Evaluation test for openability>
A roll was prepared by winding the carbon fiber bundle for the above test, and an evaluation test of opening property was performed by the following method.
(1) Description of Apparatus for Evaluation As shown in FIG. The carbon fiber bundles 4 were arranged parallel to each other with a horizontal interval of 50 mm, and the carbon fiber bundles 4 passed through the stainless steel rods 1A, 1B, 1C, 1D and 1E in a zigzag manner while being in contact with them. The horizontal direction is the direction indicated by the arrows indicated by XX' in the drawing, and is the direction parallel to the horizontal plane HL.
A straight line connecting the centers of the stainless steel rods 1A, 1C and 1E through which the carbon fiber bundles 4 pass the first, third and fifth, and the stainless steel rod 1B and the stainless steel rod 1B through which the carbon fiber bundles 4 pass the second and fourth. A straight line connecting the centers of 1D was arranged so as to be parallel to the horizontal plane. Before and after the passage of the second to fourth stainless steel rods 1B and 1D, the straight line in the traveling direction of the carbon fiber bundles before passing and the straight line in the traveling direction of the carbon fiber bundles after passing are 120 degrees. (for example, a straight line parallel to the traveling direction of the carbon fiber bundle passing between the first stainless steel rod 1A and the second stainless steel rod 1B, and the second stainless steel rods 1B and 3 The angle formed by the traveling direction of the carbon fiber bundle passing between the second stainless steel rod 1C and a straight line parallel thereto forms an angle of 120 degrees).
(2) Measurement of spread width of carbon fiber bundle Two unwinding rolls around which carbon fiber bundles for testing are wound are prepared, and the carbon fiber bundle 4 unwound from the two unwinding rolls 2A and 2B is Zigzag between the rods 1A, 1B, 1C, 1D, and 1E, set the tension between the winding roll 3 and the unwinding rolls 2A and 2B to 14.7 N (1500 gf), and speed 3 m / min, each carbon fiber bundle is wound up from the unwinding rolls 2A, 2B to the winding roll 3. The winding of the carbon fiber bundle is carried out by superimposing two carbon fiber bundles 4 drawn out from two unwinding rolls 2A and 2B on the first stainless steel rod 1A exactly vertically, followed by five stainless steel rods 1A and 1B. , 1C, 1D, 1E. The spreadability was evaluated by measuring the spreading width (cm) of the carbon fiber bundle 4 in the area 5 up to the take-up roll 3 after passing through five stainless steel rods. The spread width of the carbon fiber bundle was measured using a yarn running tester manufactured by Asano Kikai Seisakusho Co., Ltd. The spreading width of the carbon fiber bundle measured under these conditions is preferably 2 cm or more.

<Fluff evaluation test>
(1) Description of Apparatus for Evaluation As shown in FIG. The carbon fiber bundles 4 were arranged parallel to each other with a horizontal interval of 50 mm, and the carbon fiber bundles 4 passed through the stainless steel rods 1A, 1B, 1C, 1D and 1E in a zigzag manner while being in contact with them. The horizontal direction is the direction indicated by the arrows indicated by XX' in the drawing, and is the direction parallel to the horizontal plane HL.
A straight line connecting the centers of the stainless steel rods 1A, 1C and 1E through which the carbon fiber bundles 4 pass the first, third and fifth, and the stainless steel rod 1B and the stainless steel rod 1B through which the carbon fiber bundles 4 pass the second and fourth. A straight line connecting the centers of 1D was arranged so as to be parallel to the horizontal plane. Before and after the passage of the second to fourth stainless steel rods 1B and 1D, the straight line in the traveling direction of the carbon fiber bundles before passing and the straight line in the traveling direction of the carbon fiber bundles after passing are 120 degrees. (for example, a straight line parallel to the traveling direction of the carbon fiber bundle passing between the first stainless steel rod 1A and the second stainless steel rod 1B, and the second stainless steel rods 1B and 3 The angle formed by the traveling direction of the carbon fiber bundle passing between the second stainless steel rod 1C and a straight line parallel thereto forms an angle of 120 degrees).
The unwinding roll 2 and the winding roll 3 were set to rotate in the direction of the arrow drawn near each roll.
(2) Measurement of fluff weight The carbon fiber bundle 4 is zigzag between the stainless steel rods 1A, 1B, 1C, 1D, and 1E, and after passing through the stainless steel rod 1E, the area immediately before being wound on the winding roll 3 (winding In the region 5A) 10 cm upstream from the winding start point 3A of the take-up roll 3, the carbon fiber bundle 4 is made of two square urethane foam sheets of 10 cm × 10 cm under a load of 1 kg, and the thickness of the fiber bundle is It was sandwiched from the direction (vertical direction in the drawing). In this example, since the carbon fiber bundle is conveyed from the unwinding roll 2 to the winding roll 3, the "upstream side" means the upstream in the conveying direction, that is, the unwinding roll 2 side.
The unit fiber bundle 4 is wound while being sandwiched between urethane foams. The unwinding tension is set to 9.8 N (1 kgf), and the carbon fiber bundle 4 is spun at a speed of 1 m/min for 5 minutes. It was wound up from the unwinding roll 2 to the winding roll 3. During this time, the weight of fluff adhering to the two urethane foam sheets was measured. A smaller numerical value indicates that fluffing can be suppressed.

<Evaluation of storage stability (5°C)>
30 g of the fiber sizing agent solutions (X-1) to (X-21) and (X'-1) to (X'-11) produced in Examples and Comparative Examples, a screw tube [50 mL (barrel diameter 35 mm x height 78 mm)] and stored at 5°C for 14 days. The median diameter (μm) before and after storage was measured, and the storage stability at 5° C. was calculated by the following formula (2) using the measurement results.
The storage stability at 5°C was evaluated according to the following criteria.
Storage stability at 5°C (%) = 100 x (median diameter after storage)/(median diameter before storage) (2)
(Evaluation criteria)
A: Less than 110% B: 110% or more and less than 115% C: 115% or more and less than 120% D: 120% or more

<Evaluation of storage stability (40°C)>
30 g of the fiber sizing agent solutions (X-1) to (X-21) and (X'-1) to (X'-11) produced in Examples and Comparative Examples, a screw tube [50 mL (barrel diameter 35 mm x height 78 mm)] and stored at 40°C for 14 days. The median diameter (μm) before and after storage was measured, and the storage stability at 40° C. was calculated by the following formula (3) using the measurement results.
The storage stability at 40°C was evaluated according to the following criteria.
Storage stability at 40°C (%) = 100 x (median diameter after storage)/(median diameter before storage) (3)
(Evaluation criteria)
A: Less than 110% B: 110% or more and less than 115% C: 115% or more and less than 120% D: 120% or more

As shown in Tables 2 and 3, it was found that the use of the fiber sizing agent solutions of Examples can suppress fluffing and improve the bundling and opening properties.
The fiber sizing agent composition constituting the fiber sizing agent solution of the above example comprises the polyether-containing compound (A) defined in the present invention, the aromatic nonionic surfactant (B1) and the aliphatic nonionic interface and a nonionic surfactant (B) containing at least one active agent (B2), and the HLB of the nonionic surfactant is 11-15. The fiber sizing agent solution of the above example is a sizing agent composition having a viscosity of 200 to 2,000 mPa·s at 100°C and a viscosity of 3,000 to 20,000 mPa·s at 60°C. is dissolved or dispersed in water. Therefore, according to the present invention, it is possible to provide a fiber sizing agent that suppresses fluffing and has excellent fiber opening properties.

1A, 1B, 1C, 1D, 1E... Stainless steel rods 2, 2A, 2B... Unwinding roll 3... Winding roll 3A... Winding start point 4... Carbon fiber bundle 5... Winding after passing through five stainless steel bars Area 5A up to the roll... Area 10 cm upstream from 3A HL... Horizontal plane

Claims (9)

A fiber sizing agent composition containing a polyether-containing compound (A) and a nonionic surfactant (B),
The polyether-containing compound (A) is at least one compound selected from the group consisting of the ester compound (A1), the urethane compound (A2) and the polyether diol (A3), and has two or more It has one or more polyoxyethylene groups consisting of continuous oxyethylene groups, and the number of oxyethylene groups per polyoxyethylene group is 2 to 60,
The nonionic surfactant (B) is a compound other than the polyether-containing compound (A), and contains at least one aromatic nonionic surfactant (B1) and at least one aliphatic nonionic surfactant (B2). , the HLB value of the nonionic surfactant (B) is 11 to 15, and the ratio of the weight W1 of the aromatic nonionic surfactant (B1) to the weight W2 of the aliphatic nonionic surfactant (B2) (W1 /W2) is 20/80 to 90/10,
The fiber sizing agent composition has a viscosity of 200 to 2,000 mPa·s at 100°C and a viscosity of 3,000 to 20,000 mPa·s at 60°C. . The polyether-containing compound (A) contains an ester compound obtained by reacting a dicarboxylic acid or its anhydride (a1) and a diol (a2),
The diol (a2) has at least one polyoxyethylene group consisting of two or more continuous oxyethylene groups in one molecule, and the number of oxyethylene groups per polyoxyethylene group is from 2 to The fiber sizing agent composition according to claim 1, comprising 60 diols. The fiber sizing agent composition according to claim 1 or 2, wherein the aliphatic nonionic surfactant (B2) is a compound represented by the following general formula (1).
R ¹ O(AO) _m H (1)
[In general formula (1), R ¹ is an aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups; AO is an alkyleneoxy group having 2 to 4 carbon atoms; ~10 numbers. ] The fiber sizing agent composition according to any one of claims 1 to 3 , further comprising at least one resin (C) selected from the group consisting of epoxy resins, vinyl ester resins and unsaturated polyester resins. A fiber sizing agent solution obtained by dissolving or dispersing the fiber sizing agent composition according to any one of claims 1 to 4 in water and/or an organic solvent. At least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slag fiber is combined with the fiber sizing agent according to any one of claims 1 to 4 . A fiber bundle treated with the composition. A textile product comprising the fiber bundle according to claim 6 . A composite material comprising the fiber bundle according to claim 6 and a matrix resin. A composite material comprising the fiber product according to claim 7 and a matrix resin.

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