JP2021063325A - Fiber treatment agent, fiber bundle, fiber product, fiber intermediate substrate and composite material - Google Patents

Abstract

To provide a fiber treatment agent that is high in matrix resin permeability and can produce a high-strength composite material.SOLUTION: A fiber treatment agent contains a compound (A) having a polycyclic aromatic skeleton and a C2-4 oxyalkylene group. Preferably the fiber treatment agent further contains a compound (B). In the fiber treatment agent described in Claim 1, the compound (B) is at least one selected from the group consisting of polyester (B1), polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), a polyether compound (B5), a polyamide resin (B6) and a polyolefin resin (B7).SELECTED DRAWING: None

Description

The present invention relates to fiber treatment agents, fiber bundles, textile products, fiber intermediate substrates and composite materials.

Composite materials of various matrix resins and carbon fibers and the like are widely used in the fields of sports equipment, leisure goods, aircraft and the like.
Thermosetting resins such as epoxy resins, vinyl ester resins, and unsaturated polyester resins have been used as matrix resins for a long time, but in recent years, thermoplastic resins have also been used from the viewpoints of heat resistance and shortening of processing time. However, when a thermoplastic resin is used as the matrix resin, there is a problem that impregnation of the thermoplastic resin between the carbon fibers occurs poorly, a large number of voids are generated in the composite material, and the strength of the composite material is lowered.
To solve this problem, for example, measures have been taken such as a method of opening a carbon fiber bundle once and impregnating the opened carbon fiber bundle with a thermoplastic resin (for example, Patent Document 1).

However, there is a problem that the strength of the composite material is still low because the impregnation property of the highly viscous thermoplastic resin is not sufficient only through the fiber opening step as in Patent Document 1.

Japanese Unexamined Patent Publication No. 2005-29912

An object of the present invention is to provide a processing agent for fibers capable of producing a composite material having high permeability of a matrix resin and high strength.

The present inventor has arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention is a treatment agent for fibers containing a compound (A) having a polycyclic aromatic skeleton and an oxyalkylene group having 2 to 4 carbon atoms; carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers and minerals. A fiber bundle formed by treating at least one fiber selected from the group consisting of fibers with the fiber treatment agent; a fiber product composed of the fiber bundle; a composite material containing the fiber bundle and a matrix resin; carbon fiber, Fiber intermediate base material formed by treating a fiber intermediate base material composed of at least one fiber selected from the group consisting of glass fiber, aramid fiber, ceramic fiber, metal fiber and mineral fiber with the fiber treatment agent; It is a composite material containing a base material and a matrix resin.

The fiber treatment agent of the present invention has the effect of being able to produce a composite material having high permeability of the matrix resin and high strength.

<Treatment agent for fibers of the present invention>
The fiber treatment agent of the present invention contains a compound (A) having a polycyclic aromatic skeleton and an oxyalkylene group having 2 to 4 carbon atoms.

Since the treatment agent for fibers of the present invention can bundle fibers, it can be used as a fiber focusing agent (fiber sizing agent). Further, by using the fiber treatment agent of the present invention as a fiber sizing agent, the compound (A) coats the fiber surface and facilitates the penetration of the matrix resin between the fibers when producing a composite material. Can be done. Therefore, the fiber bundle bundled with the fiber treatment agent of the present invention and the fiber product composed of the fiber bundle can obtain a composite material having high permeability of the matrix resin and high strength.
Further, if the fiber intermediate base material (fiber bundle and fiber product) after being sized with the fiber treatment agent of the present invention or another fiber bundling agent is treated with the fiber treatment agent of the present invention, the compound (A) can be obtained. The sized fiber surface can be coated to increase the permeability of the matrix resin, and a high-strength composite material can be produced.
That is, the fiber treatment agent of the present invention can be used as a fiber sizing agent and / or a fiber surface modifier for a fiber intermediate base material.
Here, the fiber intermediate base material means the one before impregnation with the matrix resin, and the fiber bundle {continuous fiber bundle, short fiber bundle (chopped yarn, etc.)}, fiber product {fiber woven fabric (fiber unidirectional woven fabric, etc.) Fiber two-dimensional fabric, fiber three-dimensional fabric, fiber four-dimensional or higher fabric, etc.), fiber knitting, fiber non-woven fabric (felt, mat, paper, etc.), chopped fiber, milled fiber, fiber cloth, etc.} and the like.

When unbound fibers are treated with the treatment agent for fibers of the present invention, the binding properties of the fiber bundles are high, the fiber bundles are easy to handle, and the fiber products composed of these fiber bundles have a matrix between fibers. It is possible to obtain a composite material having high resin permeability, high adhesiveness between fibers and matrix resin in the composite material, and high strength.
Further, when a fiber intermediate base material composed of a fiber bundle bundled with the fiber treatment agent of the present invention or another fiber sizing agent is treated with the fiber treatment agent of the present invention, a matrix between fibers is used. It is possible to obtain a composite material having high resin permeability, high adhesiveness between fibers and matrix resin in the composite material, and high strength.

In compound (A), the polycyclic aromatic skeleton means a skeleton in which two or more aromatic rings are condensed, and includes a skeleton in which 2 to 10 aromatic rings are condensed.
The compound (A) includes a compound in which at least one hydrogen atom of a polycyclic aromatic hydrocarbon or a polycyclic heteroaromatic compound is substituted with a group containing an oxyalkylene group having 2 to 4 carbon atoms.
The polycyclic aromatic hydrocarbons include bicyclic aromatic hydrocarbons (naphthalene, azulene, etc.), tricyclic aromatic hydrocarbons (phenanthrene, anthracene, fluorene, phenalene, acenaphtylene, acenaphthene, etc.), and tetracyclic aromatic hydrocarbons. Hydrocarbons (tetracene, triphenylene, pyrene, chrysene, fluoranthene, etc.), 5-ring aromatic hydrocarbons (picene, perylene, pentaphen, pentacene, benzopyrene, benzofluoranthene, etc.), 6 or more ring aromatic hydrocarbons (colannelenene, etc.) , Coronen, Ovalene, etc.) and the like.
Examples of the polycyclic heteroaromatic compound include bicyclic heteroaromatic compounds (indol, isoindole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, benzothiophene, benzimidazole, naphthylidine, indazole, benzothiazole, benzothiasiazol, thienothiophene). , Pteridine and benzopyran, etc.), and tricyclic aromatic hydrocarbons (acridine, xanthene, carbazole, phenothiazine, benzodithiophene, dithienothiophene, etc.) and the like.
Of these, polycyclic aromatic hydrocarbons are preferable, and naphthalene and anthracene are more preferable, from the viewpoint of the strength of the composite material.

Examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, a 1,2- or 1,3-oxypropylene group and a 1,2-, 1,3-, 1,4- or 2,3-oxybutylene. The group etc. can be mentioned.
Of these, an oxyethylene group and a 1,2- or 1,3-oxypropylene group are preferable, and an oxyethylene group is more preferable, from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers.

As the compound (A), at least one of the hydrogen atoms contained in the polycyclic aromatic hydrocarbon or the polycyclic heteroaromatic compound has the following general formula (from the viewpoint of permeation of the matrix resin and handleability of the fiber treatment agent). The compound (A1) substituted with the group represented by 1) is preferable.
-(CH ₂ ) _n- O (AO) _m- H (1)
In the general formula (1), n is an integer of 0 to 2, A represents an alkylene group having 2 to 4 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and m represents 1 to 100 carbon atoms. It is an integer, and the AO when m is 2 or more may be the same or different.
Among the hydrogen atoms contained in polycyclic aromatic hydrocarbons or polycyclic heteroaromatic compounds, the number of hydrogen atoms substituted with the group represented by the above general formula (1) is for the permeability of the matrix resin and for fibers. From the viewpoint of handleability of the treatment agent, one is preferable.

In the general formula (1), n is an integer of 0 to 2, and 0 is preferable from the viewpoint of the permeability of the matrix resin and the handleability of the fiber treatment agent.
In the general formula (1), A represents an alkylene group having 2 to 4 carbon atoms (hereinafter abbreviated as C), and specifically, an ethylene group, a 1,2- or 1,3-propylene group, 1 , 2-, 1,3- or 1,4-butylene group and the like.
AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and specifically, an ethyleneoxy group, 1,2- or 1,3-propyleneoxy group, 1,2-, 1,3-, 1,4-. Alternatively, 2,3-butyleneoxy group and the like can be mentioned.
As the AO, an ethyleneoxy group and a 1,2- or 1,3-propyleneoxy group are preferable, and an ethyleneoxy group is more preferable, from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers.
m is an integer of 1 to 100, and is preferably 2 to 100, more preferably 3 to 50, from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers.

As the compound (A), at least one of the hydrogen atoms of the compound (A1) is a 1-methylbenzyl group (-CH (CH ₃ )) from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers. It is preferably a compound substituted with −Ph).
As a method for preparing the compound in which the hydrogen atom of the compound (A1) is substituted with a 1-methylbenzyl group, a method of adding styrene to the compound (A1) by a known method, or a method of adding styrene to the compound (A1), or the following polycyclic ring by a known method. Examples thereof include a method of adding styrene to alcohols having an aromatic skeleton (excluding styrene compounds) and then adding AO.
Among the hydrogen atoms contained in the compound (A1), the number of hydrogen atoms substituted with the 1-methylbenzyl group is preferably 1 to 5 from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers. More preferably, it is 1 to 4.

In the present invention, the compound (A) is obtained, for example, by adding an alkylene oxide (hereinafter abbreviated as AO) to a compound having a polycyclic aromatic skeleton and a hydroxyl group by a known method.
Examples of the compound having a polycyclic aromatic skeleton and a hydroxyl group include those having a polycyclic aromatic hydrocarbon skeleton (naphthol, dihydroxynaphthalene, phenanthrene methanol, anthracene methanol, anthrol, hydroxytetracene, hydroxytriphenylene, hydroxypyrene, hydroxycrisen, Those having a polycyclic aromatic heterocyclic skeleton (hydroxypicene, hydroxyperylene, hydroxypentaphen, hydroxypentacene, hydroxybenzopyrene, hydroxycholannelene, hydroxycoronen, hydroxyovalene, styrated naphthol, styrated anthrol, etc.) Hydroxyquinolin, hydroxyisoquinolin, hydroxyquinoxalin, hydroxyaclydin, hydroxyphenanthridin, etc.) and the like, and styrenes thereof and the like can be mentioned.
As the compound having a polycyclic aromatic skeleton and a hydroxyl group, at least one polycyclic aromatic hydrocarbon selected from the group consisting of naphthol, anthrol, styrenated naphthol and styrenated anthrol from the viewpoint of permeability of the matrix resin. Monools having a hydrogen skeleton are preferred.
When the compound having a polycyclic aromatic skeleton and a hydroxyl group is a styrene compound, the degree of styrene formation (the number of moles of styrene per 1 mole of the polycyclic aromatic skeleton) is 1 to 1 from the viewpoint of permeability of the matrix resin. 5 is preferable, and 1 to 4 is more preferable.

Examples of AO include those of C2-4, specifically, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), and 1,3-propylene oxide. And 1,2-, 1,3- or 1,4-butylene oxide (hereinafter, abbreviated as BO) and the like. Two or more of these AOs may be used in combination, and the binding mode in the case of two or more types may be block addition, random addition, or a combination of these.
Of these, EO and PO are preferable, and EO is more preferable, from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers.
The number of moles of AO added is preferably 2 to 100, more preferably 3 to 50, from the viewpoint of handleability of the fiber treatment agent.

The compound (A) of the present invention includes a naphthol AO adduct, an anthrol AO adduct, a styrenated naphthol AO adduct, and a styrenated anthrol AO adduct from the viewpoint of the permeability of the matrix resin and the strength of the composite material. At least one selected from the group consisting of, more preferably at least one selected from the group consisting of an EO adduct of naphthol, an anthrol EO adduct, a styrenated naphthol EO adduct and a styrenated anthrol EO adduct. Is.

The weight ratio of EO units in compound (A) (number of EO units x 44 / number average molecular weight) is preferably 5 to 95% by weight from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers. More preferably, it is 10 to 90% by weight.

The HLB of the compound (A) is preferably 1 to 19 and more preferably 2 to 18 from the viewpoint of the permeability of the matrix resin and the handleability of the treatment agent for fibers.
HLB is an index showing the balance between hydrophilicity and lipophilicity. For example, according to the Griffin method described on page 142 of "Introduction to Surfactants" [published by Sanyo Chemical Industries, Ltd. in 2007, by Takehiko Fujimoto], compounds of compounds are prepared. It can be calculated by the following formula from the ratio of the molecular weight value and the molecular weight value of the hydrophilic group portion.
HLB = 20 × Molecular weight of hydrophilic group portion of compound / Number average molecular weight of compound (A) The HLB of compound (A) can be increased, for example, by increasing the content of EO units in the molecule.

The number average molecular weight of the compound (A) is preferably 190 to 20000, more preferably 230 to 10000, from the viewpoint of the permeability of the matrix resin and the strength of the composite material.
The number average molecular weight is measured by a gel permeation chromatography (hereinafter, GPC) method.
The conditions of GPC used for measuring the number average molecular weight of compound (A) are, for example, the following conditions.
Model: HLC-8220GPC (Liquid Chromatograph 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 (Refractive Index)
Solvent: Tetrahydrofuran Flow rate: 0.6 ml / min Sample concentration: 0.25 wt%
Injection volume: 10 μl
Standard: Polystyrene (manufactured by Tosoh Corporation; TSK STANDARD
POLYSTYRENE

The fiber treatment agent preferably further contains the compound (B) from the viewpoint of the strength of the composite material.
Examples of the compound (B) of the present invention include polyester (B1), polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), a polyether compound (B5), and a polyamide resin. At least one selected from the group consisting of (B6) and a polyolefin resin (B7) is included.
As the compound (B), one type may be used alone, or two or more types may be used in combination.
The (meth) acryloyl means acryloyl and / or methacryloyl, and the (meth) acrylate means acrylate and / or methacrylate.
Further, among the compounds corresponding to (B2), (B3) and (B4), the compound having an ester bond shall not be included in (B1).
Further, among the compounds corresponding to (B3) and (B4), the compound having a urethane bond shall not be included in (B2).
Further, among the compounds corresponding to the compounds (A), (B1) to (B4) and (B6), the compound having a polyether group is not included in (B5).

Examples of the polyester (B1) include a reaction product of a diol and a dicarboxylic acid and / or a carboxylic acid anhydride, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid.
Examples of the diol include C2-30 aliphatic alkanediols (ethylene glycol, propylene glycol, butanediol, neopentyl glycol, etc.), C2-4 AO additions to C2-30 aliphatic alkanediols, and primary alkyldiamines. (Preferably C1 to 20, specifically, methyldiamine, ethyldiamine, propyldiamine, octyldiamine, dodecyldiamine, etc.) AO adduct, divalent phenol {C6 to 20 is preferable, and specifically. Is bisphenol (bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A, etc.), catechol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxy Examples thereof include AO adducts such as biphenyl, dihydroxytetramethylbiphenyl and 9,9'-bis (4-hydroxyphenyl) floorene}. The diol may be used alone or in combination of two or more.
The number of moles of AO added to 1 mol of the aliphatic alkanediol of C2 to 30, a primary alkyldiamine or a divalent phenol is preferably 2 to 100 mol.
Examples of AO include those of C2-4, and specific examples thereof include EO, PO, 1,3-propylene oxide and BO. Two or more of these AOs may be used in combination, and the binding mode in the case of two or more types may be block addition, random addition, or a combination of these.

Examples of the dicarboxylic acid include C2-24 dicarboxylic acids, specifically, C2-24 saturated aliphatic dicarboxylic acids (oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, etc.), C2-24. Examples thereof include unsaturated aliphatic carboxylic acids (malonic acid, fumaric acid, etc.) and C2-24 aromatic dicarboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, etc.).
Examples of the carboxylic acid anhydride include C2-24 carboxylic acid anhydrides (maleic anhydride, phthalic anhydride, etc.) and the like.

As the lactone ring-opening polymer, a lactone (β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc.) such as C3-12 monolactone (one ester group in the ring) is used as a metal. Examples thereof include those obtained by ring-opening polymerization using a catalyst such as an oxide and an organic metal compound.
Examples of the polyhydroxycarboxylic acid include those obtained by dehydration condensation of hydroxycarboxylic acid (glycolic acid, lactic acid, etc.).

The viscosity of the polyester (B1) at 30 ° C. is preferably 10 to 1,000,000 Pa · s, more preferably 20 to 500,000 Pa · s, from the viewpoint of the strength of the composite material.

In the present invention, the viscosity of the polyester (B1) is a complex viscosity, and can be measured by, for example, a viscoelasticity measuring device (for example, ARES manufactured by Leometric Scientific Co., Ltd.). The measurement conditions are shown below.
<Measurement conditions for polyester (B1) viscosity>
Sample fixing jig: 25 mm in diameter Disk distance between gaps: 0.25 mm
Distortion: 1%
Frequency: 1Hz
Temperature: 30 ° C

In polyester (B1), a diol is esterified with a dicarboxylic acid and / or a carboxylic acid anhydride by a known method, a lactone is ring-opened polymerized by a known method, or a hydroxycarboxylic acid is dehydrated and condensed by a known method. Can be obtained by

Examples of the polyurethane (B2) include those derived from a polyol, an organic diisocyanate, and if necessary, a chain extender and / or a cross-linking agent.

Examples of the polyol include 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.). Polyester polyols (polyester glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, C2-4 AO adducts of bisphenols, etc.) and the like can be mentioned.
The chemical formula amount or number average molecular weight of the polyol is preferably 40 to 4000.

Specific examples of the organic diisocyanate include C8-30 aromatic diisocyanates [2,4'-or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), etc. 4,4'-Dibenzyldiisocyanate, 1,3- or 1,4-phenylenediocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, etc.]; C4-30 aliphatic diisocyanate [ethylene diisocyanate, hexamethylene diisocyanate ( HDI), lysine diisocyanate, etc.]; C6 to 30 alicyclic diisocyanate [isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, etc.]; and mixtures of two or more of these.

Polyurethane (B2) can be obtained by reacting a polyol, an organic diisocyanate, and if necessary, a chain extender and / or a cross-linking agent by a known method.

The weight average molecular weight of the polyurethane (B2) (hereinafter abbreviated as Mw) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, from the viewpoint of focusing property.
Mw of (B2) can be measured by the gel permeation chromatography (GPC) method under the following measurement conditions.
<Mw measurement condition of (B2)>
Equipment: "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: "Guardcolumn α" + "TSKgel α-M" [both manufactured by Tosoh Corporation]
Sample solution: 0.125% by weight dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

The urethane group concentration of the polyurethane (B2) is preferably 0.1 to 20 mmol / g, more preferably 0.5 to 5 mmol / g, based on the weight of (B2) from the viewpoint of focusing property.

Examples of the compound having an epoxy group (B3) include compounds having one or two or more epoxy groups in one molecule, and specifically, glycidyl ether, diglycidyl ester, diglycidyl amine and the like. An alicyclic die epoxide and the like can be mentioned.

Examples of the glycidyl ether include diglycidyl ether of dihydric phenol, glycidyl ether of monohydric alcohol, and diglycidyl ether of dihydric alcohol.

Examples of the diglycidyl ether of divalent phenol include a condensate (including a polycondensate) of divalent phenol of C6 to 30 and epichlorohydrin having both ends being glycidyl ether. Examples of C6 to 30 divalent phenols include bisphenols (bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A, etc.), catechol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, and dihydroxybiphenyl. Examples thereof include octachloro-4,4'-dihydroxybiphenyl, dihydroxytetramethylbiphenyl and 9,9'-bis (4-hydroxyphenyl) fluorolene.

Examples of the glycidyl ether of the monohydric alcohol include a condensate of the monohydric alcohols C1 to 30 and epichlorohydrin having a glycidyl ether at the end. Examples of C1-30 monohydric alcohols include methanol, ethanol, butanol, hexanol, cyclohexanol, octanol, dodecyl alcohol, tetradecyl alcohol, stearyl alcohol, icosyl alcohol, behenyl alcohol, tetracosyl alcohol and triacontyl alcohol. Can be mentioned.

Examples of the diglycidyl ether of the dihydric alcohol include a condensate (including a polycondensate) of a dihydric alcohol of C2 to 100 and epichlorohydrin, in which both ends are glycidyl ethers. Examples of the dihydric alcohol of C2 to 100 include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, and polyethylene glycol having a number average molecular weight (hereinafter abbreviated as Mn) of 106 to 1932. , Mn = 134 to 5818 polypropylene glycol, Mn = 162 to 1818 polytetramethylene ether glycol and bisphenol A alkylene oxide (1 to 21 mol) adduct having 2 to 4 carbon atoms.

Regarding the above diglycidyl ether (diglycidyl ether of dihydric phenol and diglycidyl ether of dihydric alcohol), the molar ratio of the dihydric phenol unit or dihydric alcohol unit contained in the diglycidyl ether to the epichlorohydrin unit {(2). The number of moles of the valent phenol unit or the dihydric alcohol unit) :( the number of moles of the epichlorohydrin unit)} is n: n + 1. n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. The diglycidyl ether may be a mixture of n = 1 to 10 (mixtures having different degrees of polycondensation, etc.).

Examples of the diglycidyl ester include a diglycidyl ester of an aromatic dicarboxylic acid having 8 to 20 carbon atoms and a diglycidyl ester of an aliphatic dicarboxylic acid having 2 to 20 carbon atoms.

The diglycidyl ester of an aromatic dicarboxylic acid having 8 to 20 carbon atoms is a condensate (including a polycondensate) of an aromatic dicarboxylic acid having 8 to 20 carbon atoms and epichlorohydrin, and has two glycidyl groups. Things etc. can be mentioned.
Examples of the aromatic dicarboxylic acid having 8 to 20 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, phenylglutaric acid, phenyladipic acid, biphenyldicarboxylic acid and naphthalenedicarboxylic acid. Can be mentioned.

The diglycidyl ester of an aliphatic dicarboxylic acid having 2 to 20 carbon atoms is a condensate (including a polycondensate) of an aliphatic dicarboxylic acid having 2 to 20 carbon atoms and epichlorohydrin, and has two glycidyl groups. Things etc. can be mentioned.
Examples of aliphatic dicarboxylic acids having 2 to 20 carbon atoms include oxalic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, tetradecanoic acid, Hexadecanoic acid, octadecanoic acid, icosanniic acid and the like can be mentioned.

In the diglycidyl ester, the molar ratio of the aromatic dicarboxylic acid unit or the aliphatic dicarboxylic acid unit to the epichlorohydrin unit {(the number of moles of the aromatic dicarboxylic acid unit or the aliphatic dicarboxylic acid unit): (the number of moles of the epichlorohydrin unit)} Is n: n + 1. n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. The diglycidyl ester may be a mixture of n = 1-10.

The diglycidyl amine is an N-glycidyl product (N, N-diglycidyl aniline and N, N) obtained by reacting an aromatic amine having 2 to 4 active hydrogen atoms with 6 to 20 carbon atoms and epichlorohydrin. − Diglycidyl toluidine, etc.) and the like.
Examples of the aromatic amine having 6 to 20 carbon atoms and 2 to 4 active hydrogen atoms include aniline, phenylenediamine, tolylenediamine and toluidine.
The active hydrogen atom means a highly reactive hydrogen atom bonded to an atom having a high degree of electrical negativeness (oxygen, nitrogen, etc.), and the active hydrogen atom of an aromatic amine is a hydrogen atom bonded to a nitrogen atom. ..

In diglycidylamine, the molar ratio of the aromatic amine unit to the epichlorohydrin unit {(the number of moles of the aromatic amine unit) :( the number of moles of the epichlorohydrin unit)} is n: n + 1. n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. The diglycidyl amine may be a mixture of n = 1-10.

As the alicyclic diepoxide, an alicyclic epoxide having 6 to 50 carbon atoms and two epoxy groups [vinylcyclohexene dioxide, limonendioxide, dicyclopentadienedioxide, bis (2,3-epoxycyclopentyl) ether) , Ethylene glycol bisepoxy dicyclopentyl ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, etc.] and the like.
Of these, diglycidyl ether is preferable from the viewpoint of molded body strength and the like, more preferably diglycidyl ether of dihydric phenol, particularly preferably diglycidyl ether of bisphenol, and most preferably diglycidyl ether of bisphenol A (bisphenol A). Type epoxy resin).

Examples of the compound (B3) having an epoxy group include bisphenol A type epoxy resins (trade names jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, etc., manufactured by Mitsubishi Chemical Corporation, Nippon Steel & Sumikin Chemical Co., Ltd. Product names made by Epototo YD-128, Epototo YD-134, Epototo YD-011, Epototo YD-012, Epototo YD-013, Epototo YD-014, Epototo YD-017, Epototo YD-019, Epototo YD-020G Etc.), Bisphenol F type epoxy resin (trade names jER806, jER807, jER4004P, jER4005P, jER4007P, jER4010P manufactured by Mitsubishi Chemical Co., Ltd., trade names Epototo YDF-170, Epototo YDF-2001, Epototo YDF manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -2004, Epototo YDF-2005RD, DIC's trade name EPICLON830, EPICLON835, EPICLONEXA-830CRP, etc.), acrylic, styrene epoxy resin (Nippon Oil Co., Ltd.'s trade name Marproof G-0105SA, Marproof G-0130SP) , Marproof G-0150M, Marproof G-025SP, Marproof G-1005S, Marproof G-1005SA, Marproof G-1010S, Marproof G-2050M, Marproof G-01100, Marproof G-017581), Amin-type epoxy resin (trade name Sumiepoxy ELM120, Sumiepoxy ELM100, Sumiepoxy ELM434, Sumiepoxy ELM434HV, DIC Co., Ltd., Epicron 430-L, Epicron 430, Nippon Steel & Sumikin Chemical Co., Ltd. YH434, Epoxy YH434L, trade name Araldite MY720 manufactured by HUNTSMAN, trade name jER604) manufactured by Mitsubishi Chemical Co., Ltd., etc. are commercially available.

The epoxy equivalent (g / eq) of the compound (B3) having an epoxy group is preferably 100 to 5000, more preferably 150 to 4000, from the viewpoint of the strength of the composite material.
Here, the epoxy equivalent is a value measured in accordance with JIS K 7236.

Examples of the compound (B4) having a (meth) acryloyl group include (meth) acrylate obtained by reacting the epoxy group of the compound (B3) having an epoxy group with (meth) acrylic acid by a known method. Examples thereof include acrylate-modified thermoplastic resins.
As the (meth) acrylate-modified thermoplastic resin, a modified product obtained by modifying the hydroxyl group of a thermoplastic resin having an alcoholic hydroxyl group {polyurethane, polyester, polyether (polyurethane glycol, polyethylene glycol, etc.)} with (meth) acrylic acid is used. Included are polyurethane (di / mono) (meth) acrylates, polyester (di / mono) (meth) acrylates, polyether (di / mono) (meth) acrylates and the like. The (di / mono-) (meth) acrylate means a di (meth) acrylate and / or a mono (meth) acrylate.

In the compound (B4) having a (meth) acryloyl group, the (meth) acryloyl group equivalent (g / eq) is preferably 100 to 5000, more preferably 150 to 4000, from the viewpoint of the strength of the composite material.
Here, the (meth) acrylic equivalent means a value obtained by dividing the molecular weight of (B4) by the number of (meth) acryloyl groups in one molecule.

Examples of the polyether compound (B5) include AO adducts to compounds having an active hydrogen group having 1 to 20 carbon atoms, excluding compound (A).
The active hydrogen group means a group having a highly reactive hydrogen atom bonded to an atom having a high electronegativity (oxygen, nitrogen, etc.), and examples thereof include a hydroxyl group, an amino group, a carboxy group, a thiol group, and a phosphoric acid. Be done.
Examples of the compound having an active hydrogen group having 1 to 20 carbon atoms include an aliphatic alkanediol having 2 to 30 carbon atoms exemplified in polyester (B1), a primary alkylamine and a divalent phenol. In addition, as compounds other than the above, monohydric alcohols having 2 to 30 carbon atoms (methanol, ethanol, icosanol, cyclohexanol, oleyl alcohol, etc.), alcohols having one aromatic ring, and styrene alcohols having one aromatic ring. Alcohols having two or more compounds and aromatic rings can be used.
Among the polyether compounds (B5), preferred ones are AO adducts of dihydric phenol (bisphenol A, bisphenol S, etc.), AO adducts of alkyl (preferably alkyl groups having 9 to 15 carbon atoms), and aroma. Alcohol having one ring having a phenolic hydroxyl group but having an AO adduct of a styrene compound (styrene phenol, styrene cresol, etc.), and alcohol having two or more aromatic rings having a phenolic hydroxyl group ( AO adducts of (stylized cumylphenol, etc.), sulfate ester salts of the above-mentioned alkylphenol AO adducts, and stylistized products of alcohols having one aromatic ring having phenolic hydroxyl groups (styrated phenol and styled cresol). Etc.), sulfate ester of AO adduct, sulfate ester of AO adduct of alcohol having two or more aromatic rings and having a phenolic hydroxyl group (cumylphenol, styrenated cumylphenol, etc.), and a mixture thereof. Of the alcohols having one aromatic ring, those having a phenolic hydroxyl group are AO adducts of styrenates (such as styrene phenol and styrene cresol), and alcohols having two or more aromatic rings are more preferable. Among them, AO adducts of those having a phenolic hydroxyl group (cumylphenol, styrenated cumylphenol, etc.), and stylistized products of alcohols having one aromatic ring having a phenolic hydroxyl group (styrated phenol and styrenated). Sulfate ester of AO adduct of cresol etc.), Sulfate ester of AO adduct of alcohol having two or more aromatic rings and having phenolic hydroxyl group (cumylphenol, styrenated cumylphenol, etc.) and these It is a mixture.

The number of moles of AO added in the polyether compound (B5) is preferably 10 to 100 moles from the viewpoint of water solubility, emulsifying property, fibrillation property and focusing property.
In the polyether (B5), specific examples of AO include EO, PO, 1,3-propylene oxide and BO. Two or more of these AOs may be used in combination, and the binding mode in the case of two or more types may be block addition, random addition, or a combination of these.

In the polyether (B5), EO and PO are preferable as the AO from the viewpoint of emulsion stability.
The weight ratio of EO to PO (EO / PO) is preferably 30/70 to 100/0 from the viewpoint of emulsion stability.

The number average molecular weight of the polyether compound (B5) is preferably 1000 to 200,000, more preferably 2000 to 100,000 from the viewpoint of focusing property.

Examples of the polyamide resin (B6) include aliphatic polyamides such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 46 and nylon 610, and aromatic polyamides such as polyhexamethylene terephthalamide and polyhexamethylene isophthalamide. Be done.
In order to improve the adhesiveness between the sizing agent and the matrix resin and to facilitate the waterification of the polyamide resin, those having a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component introduced into the molecule are preferable.

A modified polyamide resin in which a hydrophilic group such as a polyalkylene oxide chain is introduced into the molecule can be produced by a known method. For example, it can be produced by copolymerizing a component obtained by modifying a part or all of polyethylene glycol or polypropylene glycol to diamine and a component obtained by modifying a part or all of polyethylene glycol or polypropylene glycol to dicarboxylic acid.

The polyolefin resin (B7) includes a polymer of an olefin-based monomer (including those having 2 to 36 carbon atoms, specifically, ethylene, propylene, 1-butene, 2-butene, butadiene, etc.). Modification by copolymerizing a monomer having a carboxyl group copolymerizable with an olefin-based monomer from the viewpoint of improving the adhesiveness between the fiber sizing agent composition and the matrix resin and from the viewpoint of facilitating mixing of the polyolefin resin with an aqueous medium. Polyolefin resins are preferred.

Examples of the monomer having a carboxyl group include those having 3 to 20 carbon atoms, and specific examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and fumaric acid. Be done. These may be used alone or in combination of two or more.

The modified polyolefin resin can be produced by a known method. For example, it can be produced by a method such as kneading a polyolefin resin with maleic anhydride at a high temperature in the presence of a peroxide.

Among these, polyester (B1), polyurethane (B2), compound having an epoxy group (B3), compound having a (meth) acryloyl group (B4) and a polyether compound (B5) are selected from the viewpoint of the strength of the composite material. Preferred and even more preferred are polyester (B1), polyurethane (B2) and the polyether compound (B5).

The weight ratio [(A) / (B)] of the compound (A) to the compound (B) is 95/5 to 5/95 from the viewpoint of the permeability of the matrix resin, the strength of the composite material, and the focusing property. It is preferable, more preferably 90/10 to 10/90, and particularly preferably 80/20 to 20/80.

The treatment agent for fibers of the present invention may contain other additives and the like in addition to the compound (A) and the compound (B).

Examples of other additives include smoothing agents, preservatives, antioxidants and the like.
As smoothing agents, higher fatty acids (fatty acids having 6 to 30 carbon atoms) alkyl (alkyls having 1 to 24 carbon atoms) esters (methyl stearate, ethyl stearate, propl stearate, butyl stearate, octyl stearate and stearyl) (Stearate, etc.), higher fatty acids (fatty acids having 6 to 30 carbon atoms) (myristic acid, palmitic acid, stearic acid, etc.), natural fats and oils (palm oil, beef fat, olive oil, rapeseed oil, etc.), liquid paraffin, and the like.
Examples of the preservative include benzoic acid, salicylic acid, sorbic acid, quaternary ammonium salt and imidazole.
Examples of the antioxidant include phenol (2,6-di-t-butyl-p-cresol, etc.), thiodipropionate (dilauryl 3,3'-thiodipropionate, etc.) and phosphite (triphenylphosphine, etc.). ) Etc. can be mentioned.

The contents of the compound (A), the compound (B) and other additives in the processing agent for fibers of the present invention are as follows.
The weight ratio of the compound (A) is the evaporation residue when heated at 105 ° C. according to JIS K0067 (1992) of the fiber treatment agent from the viewpoint of the permeability of the matrix resin, the strength of the composite material and the focusing property (the following). Based on the weight of the evaporation residue), it is preferably 3 to 95% by weight, more preferably 5 to 90% by weight, and particularly preferably 10 to 80% by weight.
The weight ratio of the compound (B) is preferably 3 to 95% by weight, more preferably 3 to 95% by weight, based on the weight of the evaporation residue of the fiber treatment agent from the viewpoint of the permeability of the matrix resin, the strength of the composite material and the focusing property. It is 5 to 90% by weight, particularly preferably 10 to 80% by weight.
The weight ratio of the smoothing agent, the preservative and the antioxidant as other additives is preferably 0.01 to 20 based on the weight of the evaporation residue of the fiber treatment agent from the viewpoint of fluidity and stability over time. By weight%, more preferably 0.05 to 15% by weight, particularly preferably 0.1 to 10% by weight.

The contents of the compound (A), the compound (B) and other additives when the treatment agent for fibers of the present invention is used as a sizing agent for fibers are as follows.
The weight ratio of the compound (A) is preferably based on the weight of the evaporation residue of the fiber treatment agent (the same applies to the following evaporation residue) from the viewpoint of the permeability of the matrix resin, the strength of the composite material and the focusing property. Is 5 to 95% by weight, more preferably 10 to 90% by weight, and particularly preferably 20 to 80% by weight.
The weight ratio of the compound (B) is preferably 5 to 95% by weight, more preferably 5 to 95% by weight, based on the weight of the evaporation residue of the fiber treatment agent from the viewpoint of the permeability of the matrix resin, the strength of the composite material and the focusing property. It is 10 to 90% by weight, particularly preferably 20 to 80% by weight.
The weight ratio of the smoothing agent, the preservative and the antioxidant as other additives is preferably 0.01 to 20 based on the weight of the evaporation residue of the fiber treatment agent from the viewpoint of fluidity and stability over time. By weight%, more preferably 0.05 to 15% by weight, particularly preferably 0.1 to 10% by weight.

The contents of the compound (A), the compound (B) and other additives when the treatment agent for fibers of the present invention is used as a fiber surface modifier for a fiber intermediate base material are as follows.
The weight ratio of the compound (A) is preferably 5 to 5 based on the weight of the evaporation residue of the fiber treatment agent (the same applies to the following evaporation residue) from the viewpoint of the permeability of the matrix resin and the strength of the composite material. It is 95% by weight, more preferably 10 to 90% by weight, and particularly preferably 20 to 80% by weight.
The weight ratio of the compound (B) is preferably 5 to 95% by weight, more preferably 10 to 90, based on the weight of the evaporation residue of the fiber treatment agent from the viewpoint of the permeability of the matrix resin and the strength of the composite material. By weight%, particularly preferably 20-80% by weight.
The weight ratio of the smoothing agent, the preservative and the antioxidant as other additives is preferably 0.01 to 20 based on the weight of the evaporation residue of the fiber treatment agent from the viewpoint of fluidity and stability over time. By weight%, more preferably 0.05 to 15% by weight, particularly preferably 0.1 to 10% by weight.

The fiber treatment agent of the present invention preferably contains an aqueous medium so as to be in the form of an aqueous solution, an aqueous emulsion, or an aqueous suspension.
When an aqueous medium is contained, the solid content contained in the fiber treatment agent can be easily attached to the fiber or the fiber intermediate base material in an appropriate amount, so that the strength of the composite material (molded article) is excellent.
As the aqueous medium, a known aqueous medium or the like can be used. Specifically, water and a hydrophilic organic solvent {monohydric alcohol having 1 to 4 carbon atoms (methanol, ethanol, isopropanol, etc.), carbon number 3 ~ 6 Ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, etc.), glycols with 2 to 6 carbon atoms (ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, etc.) and their monoalkyl (1-2 carbon atoms) ethers. , Dimethylformamide, and alkyl esters of acetate having 3 to 5 carbon atoms (methyl acetate, ethyl acetate, etc.), etc.}.
These may be used in combination of two or more. Of these, from the viewpoint of safety and the like, water and a mixed solvent of hydrophilic organic solvent and water are preferable, and water is more preferable.

From the viewpoint of cost and the like, the fiber treatment agent of the present invention preferably has a high concentration during distribution and a low concentration during use (during treatment of fibers and / or fiber intermediate base material). That is, the fiber intermediate base material (fiber bundle and fiber) that gives excellent molded body strength by reducing the transportation cost, storage cost, etc. by distributing at a high concentration and treating the fiber or fiber intermediate base material at a low concentration. Product) can be manufactured.
The weight ratio of the evaporation residue in the fiber treatment agent at a high concentration is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, from the viewpoint of storage stability and the like.
The weight ratio of the evaporation residue in the fiber treatment agent at a low concentration is preferably 0.5 to 15 weight from the viewpoint of making the amount of the fiber treatment agent adhered to the fiber or the fiber intermediate base material appropriate. %, More preferably 1 to 10% by weight.

The fiber treatment agent of the present invention can be produced by mixing compound (A) and, if necessary, compound (B), an aqueous medium, and other additives in any order.

There is no limitation on the mixing device, dissolving device and emulsifying / dispersing device used for producing the processing agent for fibers of the present invention, and the stirring blade (blade shape: chi type and three-stage paddle, etc.), Nauter mixer, ribbon mixer, conical blender, etc. A mortar mixer, a universal mixer (universal mixing stirrer 5DM-L, manufactured by Sanei Seisakusho Co., Ltd., etc.), a Henschel mixer, etc. can be used.

Known fibers such as glass fiber, carbon fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber (including slug fiber) and rock fiber (International Publication No. 2003) can be applied to the fiber treatment agent of the present invention. / 47830, etc.), and at least one selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, and mineral fibers from the viewpoint of molded body strength. It is a fiber, more preferably a carbon fiber. Two or more of these fibers may be used in combination.

<Fasciculation of the present invention>
The fiber bundle of the present invention is obtained by treating at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber and mineral fiber with the above-mentioned fiber treatment agent ( It is a fiber bundle (a bundle of about 3,000 to 50,000 fibers).

Examples of the treatment method when the treatment agent for fibers of the present invention is used as a sizing agent for fibers for the purpose of bundling fibers include a spray method and a dipping method.
When treating the fibers, the amount (% by weight) of the evaporation residue contained in the fiber treatment agent attached to the fibers is preferably 0.05 to 5% by weight, more preferably 0. It is 2 to 2.5% by weight. Within this range, the strength of the molded product is further excellent.

<Textile product of the present invention>
The textile product of the present invention comprises a fiber bundle treated (focused) with the treatment agent for fibers of the present invention, and includes a fiber product obtained by processing the fiber bundle, and is a fiber woven fabric (fiber one). Oriented woven fabrics, fiber two-dimensional woven fabrics, fiber three-dimensional woven fabrics, woven fabrics of four or more dimensions of fibers, etc.), fiber knitting, fiber non-woven fabrics (felt, mat, paper, etc.), chopped fibers, milled fibers, fiber fabrics, etc.

<Fiber Intermediate Base Material of the Present Invention>
The fiber intermediate base material of the present invention is the above-mentioned treatment agent for fibers of the present invention, and is a fiber intermediate base material [fiber bundle {continuous fiber bundle, short fiber bundle (chopped yarn, etc.)}, textile product before impregnation with a matrix resin. {Fiber woven fabric (fiber unidirectional woven fabric, fiber two-dimensional woven fabric, fiber three-dimensional woven fabric, fiber four-dimensional or higher woven fabric, etc.), fiber knitting, fiber non-woven fabric (felt, mat and paper, etc.), chopped fiber, milled fiber and fiber Cloths, etc.}, etc.] are included, and examples of the treatment method when treating with a fiber treatment agent include a spray method, a dipping method, and the like.
When treating the fiber intermediate base material, the amount (% by weight) of the evaporation residue contained in the fiber treatment agent attached to the fiber intermediate base material is 0.05 based on the weight of the untreated fiber intermediate base material. It is preferably ~ 5% by weight, more preferably 0.2 to 2.5% by weight. Within this range, the strength of the molded product is further excellent.

<Composite material of the present invention>
The composite material of the present invention is a composite material containing the fiber bundle of the present invention and a matrix resin, and a composite material containing the fiber intermediate base material of the present invention and a matrix resin. The composite material containing the textile product of the present invention and the matrix resin is included in the composite material containing the fiber bundle and the matrix resin of the present invention.
Matrix resins include thermoplastic resins and thermosetting resins.
Thermoplastic resins include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, polyethersulfone, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, acrylic resin, polycarbonate, polyetherimide, and polyetheretherketone. , Polyacetal, polyphenylene oxide, polyphenylene sulfide and the like.
Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, vinyl ester resin and the like. When it is a thermosetting resin, the composite material may contain a catalyst. As the catalyst, known catalysts can be used without limitation, and examples thereof include those described in JP-A-2005-213337 when the thermosetting resin is an epoxy resin.

The weight ratio (matrix resin / fiber intermediate base material) of the matrix resin to the fiber intermediate base material (fiber bundle and fiber product) is preferably 10/90 to 90/10, more preferably 20 from the viewpoint of the strength of the molded product. It is / 80 to 70/30, and particularly preferably 30/70 to 60/40.
When a catalyst is contained, the content of the catalyst is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 1 to 3% by weight, based on the matrix resin.

When the matrix resin is a thermoplastic resin, the composite material of the present invention is thermally melted (melting temperature: 60 to 400) in the fiber intermediate base material of the present invention {for example, textile products (textiles, knitting, non-woven fabrics, etc.)}. A method of impregnating and molding a thermoplastic matrix resin (° C.), the fiber intermediate base material of the present invention (fiber bundle or chopped fiber obtained by cutting the fiber bundle) is put into a molten thermoplastic matrix resin and kneaded. , Can be obtained by injection molding method or the like.
When the matrix resin is a thermosetting resin, the fiber intermediate base material of the present invention is impregnated with the thermosetting resin, heat-molded, and solidified at room temperature to form a molded product. The curing does not have to be complete, but it is preferable that the molded product is cured to the extent that the shape can be maintained. After molding, it may be further heated to be completely cured.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, parts indicate parts by weight.

<Production Example 1> Naphthol EO 4 mol adduct (A-1)
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping cylinder, 144 parts (1 mol part) of β-naphthol “β-naphthol” [manufactured by Mitsui Kagaku Fine Co., Ltd.] and 0.5 part of potassium hydroxide were added. The mixture was charged, replaced with nitrogen, sealed, heated to 100 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 160 ° C., and 176 parts (4 mol parts) of EO was added dropwise over 3 hours while adjusting the pressure to 0.5 MPaG or less, and then aged at 160 ° C. for 3 hours. Next, after cooling to 70 ° C., 10 parts of the adduct treatment agent "Kyoward 600" [manufactured by Kyowa Chemical Industry Co., Ltd.] was added, and the mixture was stirred at 70 ° C. for 1 hour for treatment, and then the adsorption treatment agent was filtered to naphthol. An EO4 molar adduct (A-1) was obtained. {The number average molecular weight of (A-1) is 320, HLB = 11.0}

<Production Example 2> naphthol EO 20 mol adduct (A-2)
In Production Example 1, a naphthol EO 20 mol adduct (A-2) was obtained in the same manner as in Production Example 1 except that "176 parts of EO (4 mol parts)" was changed to "880 parts of EO (20 mol parts)". .. {The number average molecular weight of (A-2) is 1020, HLB = 17.2}

<Production Example 3> Distyrene β-naphthol EO 10 mol adduct (A-3)
144 parts (1 mol part) of β-naphthol and 5 parts of Lewis acid catalyst "Galleon Earth" [Mizusawa Industrial Chemicals Co., Ltd.] were charged in a reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping cylinder. Was replaced with nitrogen gas and the temperature was raised to 90 ° C. 208 parts (2 mol parts) of styrene was added dropwise at the same temperature over 5 hours, and the reaction was further carried out at the same temperature for 5 hours. After cooling the product to 50 ° C., the catalyst was filtered off to obtain a β-naphthol distyrene product {distyrene β-naphthol}.
Next, 352 parts (1 mol part) of the obtained distyreneized β-naphthol and 0.5 part of potassium hydroxide were put into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, and after nitrogen substitution. It was sealed, heated to 100 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 160 ° C., and 440 parts (10 mol parts) of EO was added dropwise over 3 hours while adjusting the pressure to 0.5 MPaG or less, and then aged at 160 ° C. for 3 hours. Next, after cooling to 70 ° C., 10 parts of the adduct treatment agent "Kyoward 600" [manufactured by Kyowa Chemical Industry Co., Ltd.] was added, and the mixture was stirred at 70 ° C. for 1 hour for treatment, and then the adduct treatment agent was filtered to distyrene. A 10 molar adduct of naphthol EO (A-3) was obtained. {The number average molecular weight of (A-3) is 790, HLB = 11.1}

<Production Example 4> Distylated β-naphthol EO 30 mol adduct (A-4)
Distylated β-naphthol EO 30 mol adduct (A-4) in the same manner as in Production Example 1 except that “740 parts (10 mol parts) of EO” was changed to “1320 parts (30 mol parts) of EO” in Production Example 3. ) Was obtained. {The number average molecular weight of (A-4) is 1670, HLB = 15.8}

<Production Example 5> Distylated β-naphthol EO 60 mol adduct (A-5)
Distylated β-naphthol EO 60 mol adduct (A-5) in the same manner as in Production Example 1 except that “740 parts (10 mol parts) of EO” was changed to “2640 parts (60 mol parts) of EO” in Production Example 3. ) Was obtained. {The number average molecular weight of (A-5) is 2290, HLB = 17.6}

<Production Example 6> Anthrol EO 20 mol adduct (A-6)
In Production Example 1, "β-naphthol 144 parts (1 mol part)" was changed to "9-anthrol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] 194 parts (1 mol part)" and "EO176 parts (1 mol part)". Anthrol EO 20 mol adduct (A-6) was obtained in the same manner as in Production Example 1 except that "4 mol parts)" was changed to "EO 880 parts (20 mol parts)". {The number average molecular weight of (A-6) is 1070, HLB = 16.4}

<Production Example 7> Distyreneated anthrol EO 80 mol adduct (A-7)
In Production Example 3, "β-naphthol 144 parts (1 mol part)" was changed to "9-anthrol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] 194 parts (1 mol part)" and "EO440 parts (1 mol part)". A distyreneated anthrol EO 80 mol adduct (A-7) was obtained in the same manner as in Production Example 1 except that "10 mol parts)" was changed to "EO 3520 parts (80 mol parts)". {The number average molecular weight of (A-7) is 3920, HLB = 18.0}

<Comparative Production Example 1> Phenol EO 4 mol adduct (A'-2)
Phenol EO 4 mol adduct (A'-) in the same manner as in Production Example 1 except that "β-naphthol 144 parts (1 mol part)" was changed to "Phenol 94 parts (1 mol part)" in Production Example 1. 2) was obtained. {The number average molecular weight of (A'-2) is 270, HLB = 13.0}

<Production Example 8> Production of polyester (B-1) 142 parts by weight (0.86 mol parts) of terephthalic acid, 163 parts by weight (0.98 mol parts), polyethylene glycol "PEG-1000" [Sanyo Chemical Industries, Ltd. ) 263 parts by weight (0.26 mol parts) of polyethylene glycol "PEG-10000" [manufactured by Sanyo Chemical Industries, Ltd.] 359 parts by weight (0.04 mol parts) and 1.8 parts of tetraisopropoxytitanate In a glass reaction vessel, the pressure was reduced to −0.1 MPa at 225 ° C. under nitrogen flow, and the reaction was carried out for 10 hours while distilling off water to obtain 803 parts by weight of polyester resin (B-1). {The complex viscosity of (B-1) is 800,000 Pa · s}

<Production Example 9> Production of Polyurethane (B-3) EO adduct (number average molecular weight 8000) of polypropylene glycol (number average molecular weight 1750) "New Pole PE-68" in a reaction vessel equipped with a stirrer and temperature control device. [Manufactured by Sanyo Kasei Kogyo Co., Ltd.] 8000 parts by weight was added and substituted with nitrogen. The temperature was raised to 80 ° C. under a dry nitrogen atmosphere, 116 parts by weight of toluene diisocyanate "Coronate T-80" [manufactured by Nippon Polyurethane Industry Co., Ltd.] was added, and then aged at 80 ° C. for 5 hours to obtain polyurethane (B-3). Got {Mw of (B-3) is 25,000, urethane group concentration is 0.16 mmol / g}

<Production Example 10> Production of Polyether Compound (B-6) In Production Example 3, "144 parts (1 mol) of β-naphthol" was changed to "94 parts (1 mol) of phenol" and "Styrene 208". Production example except that "parts (2 mol parts)" was changed to "286 parts (2.75 mol parts) of styrene" and "740 parts (10 mol parts) of EO" was changed to "1320 parts (30 mol parts) of EO". In the same manner as in No. 3, a polyether compound (B-6), which is a styrenated (2.75 mol) phenol EO 30 mol adduct, was obtained. {The number average molecular weight of (B-6) is 1700, HLB = 15.5}

<Examples 1 to 12 and Comparative Examples 1 to 2>
The raw materials of the weights shown in Table 1 are blended, and the fiber treatment agents (X-1) to (X-12) of the present invention and the fiber treatment agents (X'-1) to (X'-) for comparison are blended. 2) was obtained.

The chemical composition of the raw materials of the symbols shown in Table 1 is as follows. The blending amount (part by weight) in Table 1 is shown as the amount of pure content.
(A-1) to (A-7): Obtained in Production Examples 1 to 7 (A'-1): EO6 molar adduct of bisphenol A [trade name "Nieuport BPE-60", Sanyo Chemical Industries, Ltd. Made by company]
(A'-2): Obtained in Comparative Production Example 1 (B-1): Obtained in Production Example 8 (B-2): Polyurethane resin 30% by weight aqueous solution [trade name "Permarin UA-150", Made by Sanyo Chemical Industries, Ltd.]
(B-3): Obtained in Production Example 9 (B-4): Bisphenol A type epoxy resin [trade name "JER1004", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 950 g / eq]
(B-5): 2 mol adduct of bisphenol A diglycidyl ether acrylic acid [trade name "epoxy ester 3000A", manufactured by Kyoeisha Chemical Co., Ltd., (meth) acryloyl equivalent: 242 g / eq]
(B-6): Obtained in Production Example 10 (B-7): Polyamide resin "UBESTA XPA" [manufactured by Ube Industries, Ltd.]
(B-8): Maleic acid-modified polypropylene resin "Youmex 1001" [manufactured by Sanyo Chemical Industries, Ltd.]

<Example 13> Textile treatment agent (X-13)
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping cylinder, 160 parts of the polyamide resin "UBESTA XPA" [manufactured by Ube Industries, Ltd.] (B-7), 40 parts of the polyether compound (B-6), and 700 parts of water was charged and the temperature was raised to 180 ° C. with stirring. After stirring for another hour while keeping the temperature at 180 ° C., the contents were cooled to room temperature. 50 parts of the distyreneated anthrol EO80 mol adduct (A-7) of Production Example 7 was charged, and water was further added to adjust the concentration to obtain an emulsion-like processing agent for fibers having an evaporation residue of 5% by weight.

<Example 14> Textile treatment agent (X-14)
150 parts of maleic acid-modified polypropylene resin (B-8), 40 parts of polyether compound (B-6), 10 parts of diethanolamine and 700 parts of water are charged in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder. The temperature was raised to 180 ° C. with stirring. After stirring for another hour while keeping the temperature at 180 ° C., the contents were cooled to room temperature. 50 parts of the naphthol EO 4 mol adduct (A-1) of Production Example 1 was charged, and water was further added to adjust the concentration to obtain an emulsion-like processing agent for fibers having a solid content of 5% by weight.

Using the fiber treatment agents of Examples and Comparative Examples, the focusing property, the permeability of the matrix resin, and the strength of the composite material were evaluated by the following evaluation methods. The results are shown in Table 1.

〇Use as a sizing agent for fibers <Manufacturing of carbon fiber bundles>
The fiber treatment agents (X-1) to (X-14) obtained in Examples and the comparative fiber treatment agents (X'-1) to (X'-2) having a solid content concentration of 1.5 weight by weight. Untreated carbon fibers (fineness 800tex, number of filaments 12,000) are immersed in a liquid dissolved or dispersed in water so as to be%, impregnated with a fiber treatment agent, and dried with hot air at 180 ° C. for 3 minutes to carbon. A fiber bundle was prepared. The amount (% by weight) of the evaporation residue contained in the fiber treatment agent attached to the fiber was 1.5% by weight based on the weight of the untreated carbon fiber.

<Evaluation of focus>
The focusing property of the carbon fiber bundles obtained above was evaluated according to JIS L1096 (2010) 8.21.1 A method (45 ° cantilever method).
The larger the value (cm), the better the focusing property, and 14 cm or more is preferable.

<Making textiles>
(1) The fiber treatment agents (X-1) to (X-14) obtained in Examples and the comparative fiber treatment agents were dissolved or dispersed in water so that the solid content concentration was 2% by weight. Untreated carbon fibers (fineness 800tex, number of filaments 12,000) were immersed in the liquid to impregnate the fiber treatment agent, and dried with hot air at 180 ° C. for 3 minutes to prepare carbon fiber bundles. The amount (% by weight) of the evaporation residue contained in the fiber treatment agent attached to the fiber was 2% by weight based on the weight of the untreated carbon fiber.
(2) The obtained carbon fiber bundle was woven using a loom (a loom disclosed in Japanese Patent Application Laid-Open No. 2003-253547) to prepare ^{a plain weave and a basis weight of 200 g / m 2.}

<Permeability of matrix resin>
Both sides of the obtained carbon fiber woven fabric were laminated with a polycarbonate resin film "Technoloy C000" [Sumitomo Chemical Co., Ltd.] and compressed at 270 ° C. at a pressure of 2 MPa for 1 minute to obtain a carbon fiber composite material (carbon) having a thickness of 250 μm. Fiber volume content 50%) was obtained.
With respect to the obtained carbon fiber composite material, the cross section of the portion cut in the direction perpendicular to the fiber direction was confirmed with an optical microscope.
Print out a cross-sectional image (magnification 900x) on paper, cut out the resin-impregnated part and the non-impregnated part, weigh each paper, and use the following formula to determine the permeability of the matrix resin. I asked.
Permeability of matrix resin (%) = (weight of resin-impregnated part) / [(weight of resin-impregnated part) + (weight of non-resin-impregnated part)] × 100

<Bending elastic modulus and bending strength of carbon fiber composite material>
Both sides of the obtained carbon fiber woven fabric were laminated with a polycarbonate resin film "Technoloy C000" [Sumitomo Chemical Co., Ltd.] and compressed at 270 ° C. at a pressure of 2 MPa for 3 minutes to obtain a carbon fiber composite material (carbon) having a thickness of 250 μm. Fiber volume content 50%) was obtained.
The flexural modulus and bending strength of the obtained carbon fiber composite material were measured according to JIS K7074.

〇Use as a fiber surface modifier A fiber intermediate base material (fiber woven fabric) treated with a fiber treatment agent is manufactured according to the following "Manufacture of fiber intermediate base material" and replaced with the "obtained carbon fiber woven fabric". The permeability, bending elasticity and bending strength of the matrix resin were measured in the same manner as above except that the "fiber intermediate base material (fiber woven fabric) treated with the fiber treatment agent" was used.
<Manufacturing of fiber intermediate base material>
The fiber treatment agents (X-1) to (X-14) obtained in the examples and the comparative fiber treatment agents (X'-1) to (X'-2) had an evaporation residue of 2% by weight. Soak the carbon fiber woven fabric [trade name "EC3C", made by Taiwan Plastics] in the liquid dissolved or dispersed in water so that the evaporation residue (adhesion amount) is 2% by weight with respect to the carbon fiber woven fabric. It was passed through a nip roll to impregnate the treatment agent and dried with hot air at 200 ° C. for 3 minutes to obtain a fiber intermediate base material (fiber woven fabric) treated with the treatment agent for fibers.

From the results in Table 1, it can be seen that the treatment agent for fibers of the present invention is excellent in the focusing property of carbon fibers. Further, the fiber intermediate base material (woven fabric) produced by using the fiber bundle treated with the fiber treatment agent of the present invention and the fiber intermediate base material (fiber woven fabric) treated with the fiber treatment agent of the present invention are made of a matrix resin. It permeates 85% or more in a short time of 1 minute, and permeates almost to the center, indicating that the matrix resin has high permeability. Further, the composite material produced by using the fiber bundle or the fiber intermediate base material (fiber woven fabric) treated with the fiber treatment agent of the present invention can obtain a composite material having high flexural modulus and bending strength and high strength. I know I can do it.
On the other hand, when the fiber treatment agents of Comparative Examples 1 and 2 are used, it can be seen that the carbon fiber bundling property is inferior, the permeability of the matrix resin is low, and the strength of the obtained composite material is also low.

Since the treatment agent for fibers of the present invention can bundle fibers, it can be used as a fiber focusing agent (fiber sizing agent). Furthermore, fiber intermediate base material [fiber bundle {continuous fiber bundle, short fiber bundle (chopped yarn, etc.)}, textile product {fiber woven fabric (fiber unidirectional woven fabric, fiber two-dimensional woven fabric, fiber three-dimensional woven fabric, fiber four-dimensional or more Textiles, etc.), fiber knitting, fiber non-woven fabrics (felt, mat, paper, etc.), chopped fiber, milled fiber, fiber cloth, etc.}, etc.] can be used as a fiber surface modifier to facilitate the penetration of matrix resin. it can.

Claims (9)

A treatment agent for fibers containing a compound (A) having a polycyclic aromatic skeleton and an oxyalkylene group having 2 to 4 carbon atoms. Further, it is a treatment agent for fibers containing compound (B).
Compound (B) includes polyester (B1), polyurethane (B2), compound having an epoxy group (B3), compound having a (meth) acryloyl group (B4), polyether compound (B5), polyamide resin (B6) and The treatment agent for fibers according to claim 1, which is at least one selected from the group consisting of a polyolefin resin (B7). Claim 1 or claim 1, wherein the compound (A) is an alkylene oxide adduct of a compound having at least one polycyclic aromatic hydrocarbon skeleton selected from the group consisting of naphthol, anthrol, styrenated naphthol and styrenated anthrol. 2. The treatment agent for fibers according to 2. The treatment agent for fibers according to any one of claims 1 to 3, further containing water. At least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber and mineral fiber is treated with the fiber treatment agent according to any one of claims 1 to 4. Fiber bundle. A textile product comprising the fiber bundle according to claim 5. A composite material containing the fiber bundle according to claim 5 and a matrix resin. The fiber intermediate base material composed of at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber and mineral fiber for the fiber according to any one of claims 1 to 4. Fiber intermediate base material treated with a treatment agent. A composite material containing the fiber intermediate base material according to claim 8 and a matrix resin.