JP2018090927A - Sizing agent composition for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sizing agent composition for a fiber that can afford both excellent bundling property and openability in a fiber bundle and can impart excellent strength to a fiber-reinforced composite material.SOLUTION: A sizing agent composition for a fiber including a polyester resin (A) and a polyether-based polymer (B) is provided. The polyester resin (A) is a polyester of a carboxylic acid component (a) and a diol component (b) including an alkylene oxide adduct (b1), and the polyether-based polymer (B) is a polyurethane resin (B1) produced by reacting a polyether diol (c) having HLB of 10 to 20 with a diisocyanate (d1) and/or a polycarbonate resin (B2) produced by reacting a polyether diol (c) having HLB of 10 to 20 with a dialkyl carbonate (d2) or an alkylene carbonate (d3).SELECTED DRAWING: None

Description

  The present invention relates to a sizing agent for fibers. More particularly, the present invention relates to a sizing agent for fibers used in fiber reinforced composite materials.

Composite materials of various fibers such as aramid fiber, glass fiber and carbon fiber and matrix resin such as unsaturated polyester resin, phenol resin and epoxy resin are widely used in the fields of building materials, sports equipment, leisure goods and aircraft, etc. ing. These fibers are usually provided with a sizing agent in order to prevent fuzz and yarn breakage in the processing step.

In recent years, there has been a demand for further increasing the strength of composite materials in order to develop them in various applications. For this reason, developments have been made to enhance the function of the sizing agent and improve the strength of the composite material.
For example, a sizing agent (Patent Document 1) containing a specific polyester resin, a sizing agent composed of a liquid and solid epoxy resin, a water-soluble polyurethane resin and a stearic acid ester (Patent Document 2) can be mentioned.

JP 2009-1954 A Japanese Patent Laid-Open No. 09-250087

By the way, in general, the sizing property and the opening property of the fiber depend on the viscosity of the sizing agent and are contradictory performances. When the viscosity of the sizing agent is high, the sizing property is high and the handling property of the fiber is good. However, since the opening property is low, the impregnation property of the resin is inferior. Although the impregnation property is excellent, the handling property of the fiber is inferior due to the low convergence.
In that respect, the bundling agents proposed in Patent Documents 1 and 2 have a problem that the fiber bundling property and the fiber spreading property are insufficient, and as a result, the strength of the composite material is not sufficient.

It is an object of the present invention to provide a fiber sizing agent composition that has both excellent bundling and fiber opening properties in a fiber bundle and can impart excellent strength to a fiber-reinforced composite material.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention is a fiber sizing agent composition comprising a polyester resin (A) and a polyether polymer (B), wherein the polyester resin (A) comprises a carboxylic acid component (a) and an alkylene oxide addition. Polyurethane obtained by reacting a polyether diol (c) having a HLB of 10 to 20 with a diisocyanate (d1), which is a polyester with a diol component (b) containing a product (b1) Resin (B1) and / or polycarbonate resin (B2) obtained by reacting polyether diol (c) having an HLB of 10 to 20 with dialkyl carbonate (d2) or alkylene carbonate (d3), a sizing agent for fibers Weight ratio (A) / (B of polyester resin (A) and polyether polymer (B) in the composition 50/50 to 99.5 / 0.5 fiber sizing agent composition; a fiber sizing agent dispersion in which the fiber sizing agent composition is dispersed in water or an organic solvent; A fiber sizing agent solution in which the composition is dissolved in water or an organic solvent; a fiber bundle obtained by treating fibers with the fiber sizing agent; and a fiber product comprising the fiber bundle.

The sizing agent composition for fibers of the present invention gives good sizing properties and spreadability to fiber bundles, and a composite material using these has the effect of being excellent in strength. Furthermore, there is little fuzzing and the resin impregnation is good.

The fiber sizing agent composition of the present invention contains a polyester resin (A) and a polyether-based polymer (B) as essential components. This polyester resin (A) is a polyester of a carboxylic acid component (a) and a diol component (b) containing an alkylene oxide adduct (b1). On the other hand, the polyether polymer (B) is a polyurethane resin (B1) and / or a polycarbonate resin (B2). The polyurethane resin (B1) is a polyether diol (c) having an HLB of 10 to 20 and a diisocyanate (d1). Is a polyurethane resin obtained by reacting The polycarbonate resin (B2) is a polycarbonate resin obtained by reacting a polyether diol (c) having an HLB of 10 to 20 with a dialkyl carbonate (d2) or an alkylene carbonate (d3).
The weight ratio (A) / (B) of the polyester resin (A) and the polyether polymer (B) in the fiber sizing agent composition is 50/50 to 99.5 / 0.5.

The polyester resin (A) of the present invention is a polyester of a carboxylic acid component (a) and a diol component (b) containing an alkylene oxide adduct (b1).

  Examples of the carboxylic acid component (a) include aliphatic saturated dicarboxylic acids, aliphatic unsaturated dicarboxylic acids, alicyclic dicarboxylic acids, dimer acids, aromatic dicarboxylic acids; and their anhydrides or esters with lower alcohols. Can be mentioned.

  Examples of the aliphatic saturated dicarboxylic acid include linear or branched aliphatic saturated dicarboxylic acids having 2 to 22 carbon atoms (oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, ethyl succinic acid, dimethyl malonic 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, icosane dicarboxylic acid, decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.).

  Examples of the aliphatic unsaturated dicarboxylic acid include linear or branched aliphatic unsaturated dicarboxylic acids having 4 to 22 carbon atoms (maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenyl succinic acid, pentadecenyl succinic acid and octadecyl succinic acid). Decenyl succinic acid, etc.).

  Examples of the alicyclic dicarboxylic acid include 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. Acid, 1,2-, 1,3- or 1,4-cyclohexanediacetic acid and dicyclohexyl-4,4′-dicarboxylic acid) and the like.

  Examples of the dimer acid include dimers of chain unsaturated carboxylic acids having 8 to 24 carbon atoms (such as oleic acid, linoleic acid, and linolenic acid).

  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).

Examples of carboxylic acid anhydrides include the above dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride.
Examples of the ester of a carboxylic acid and a lower alcohol include esters of the above dicarboxylic acid with a lower alcohol (methanol, ethanol, etc.), such as sodium dimethyl-5-sulfonate, isophthalate.

  The carboxylic acid component (a) may be used alone or in combination of two or more. Of these, chain saturated dicarboxylic acid, chain unsaturated dicarboxylic acid and aromatic dicarboxylic acid are preferable from the viewpoint of convergence, and oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, maleic acid are more preferable. , Fumaric acid, terephthalic acid, isophthalic acid, phthalic acid and combinations of two or more thereof, particularly preferably adipic acid, maleic acid, fumaric acid, terephthalic acid, isophthalic acid and two or more of these It is a combined use.

Examples of the diol component (b) include aliphatic alkane diols, alicyclic diols, aromatic ring-containing divalent phenols, and alkylene oxide adducts (b1).

  Aliphatic alkanediols having 2 to 16 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Examples include decanediol, dodecanediol, hexadecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.

  Examples of the alicyclic diol include those having 4 to 16 carbon atoms, such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

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

The alkylene oxide adduct (b1) may be abbreviated as AO to an aliphatic alkanediol, an alicyclic diol, an aromatic ring-containing dihydric phenol, and a primary amine. ) Is added.

Examples of the AO adduct of aliphatic alkanediol include compounds obtained by adding AO having 2 to 4 carbon atoms to the aliphatic alkanediol. As AO having 2 to 4 carbon atoms, ethylene oxide (hereinafter, “ethylene oxide” may be abbreviated as EO), 1,2-propylene oxide (hereinafter, “propylene oxide” may be abbreviated as PO). And 1,2-butylene oxide and 1,4-butylene oxide. Two or more kinds of these AOs may be used in combination, and the combination mode in the case of using two or more kinds may be any of block addition, random addition, and combination thereof.

Examples of the AO adduct of alicyclic diol include compounds obtained by adding AO having 2 to 4 carbon atoms to the diol.

Examples of the AO adduct of an aromatic ring-containing dihydric phenol include compounds obtained by adding AO having 2 to 4 carbon atoms to the above phenol.

  Examples of the primary amine in the AO adduct of primary amine include primary amines having 1 to 22 carbon atoms such as methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine, and dodecylamine. Examples of the primary amine AO adduct include compounds in which AO having 2 to 4 carbon atoms is added to the amine.

  Among the diol components (b), the alkylene oxide adduct (b1) is preferable from the viewpoint of achieving both convergence and spreadability, and more preferable is an AO adduct of an aliphatic alkanediol, an aromatic ring. AO adduct of contained dihydric phenol and a combination of two or more of these.

  Of the alkylene oxide adduct (b1), a diol (b11) having 4 to 500 oxyethylene groups is preferable from the viewpoint of emulsion stability of the sizing agent, and EO of bisphenol A is particularly preferable. It is an EO adduct of an adduct and / or an alkylene glycol having 2 to 6 carbon atoms.

  Examples of the diol (b11) having 4 to 500 oxyethylene groups include the following.

  Among the AO adducts of aliphatic alkanediols, EO is added in an amount of 4 to 500, specifically, ethylene glycol EO 4 mol adduct, ethylene glycol EO 23 mol adduct, ethylene glycol EO 90 mol addition. EO 200 mol adduct of ethylene glycol, EO 500 mol adduct of ethylene glycol, EO 5 mol adduct of propylene glycol, PO2 mol of propylene glycol / EO 20 mol adduct (block adduct), PO2 mol of propylene glycol / 100 mol of EO Adduct (block adduct), propylene glycol PO2 mol / EO 500 mol adduct (random adduct), 1,4-butanediol EO 100 mol adduct, 1,6-hexanediol EO 100 mol adduct, octanediol EO 00 mol adduct, decanediol EO100 mole adduct, dodecanediol EO100 mole adduct, hexadecane diol EO100 mol adduct of neopentyl glycol EO100 mole adducts.

  Among the AO adducts of aromatic ring-containing dihydric phenol, primary amine or alicyclic diol, EO is added in an amount of 4 to 500, specifically, EO 10 mol adduct of bisphenol A, bisphenol A EO 50 mol adduct, bisphenol A EO 200 mol adduct and bisphenol A EO 500 mol adduct, dodecylamine EO 10 mol adduct, dodecylamine EO 50 mol adduct, hydrogenated bisphenol A EO 4 mol adduct and bisphenol A EO 50 mol adduct and the like can be mentioned.

  Among the diols (b11) having 4 to 500 oxyethylene groups, preferred are an EO adduct of bisphenol A and / or an EO adduct of ethylene glycol from the viewpoint of suppressing fluffing of the fiber bundle.

The ester group concentration in the polyester resin (A) is preferably 10 mmol / g or less, more preferably 5 mmol / g or less, based on the weight of the polyester resin (A). When the ester group concentration is too high, the viscosity of the polyester resin (A) becomes high and the fluff of the fiber bundle increases.
Although the minimum of the ester group density | concentration in a polyester resin (A) is not specifically limited, Based on the weight of the said polyester resin (A), it is preferable that it is 0.5 mmol / g or more.
The ester group concentration can be determined, for example, by NMR measurement.

  As a method for producing the polyester resin (A), for example, the carboxylic acid component (a) and the diol component (b) are charged in a predetermined molar ratio, the reaction temperature is 100 to 250 ° C., and the pressure is −0.1 to 1.2 MPa. The method of distilling water off with stirring is mentioned. The diol component (b) may be further added to the reaction mixture for reaction.

  When the polyester resin (A) is produced, it is preferable to add 0.05 to 0.5% by weight of a catalyst based on the weight of the polyester resin (A). Examples of the catalyst include p-toluenesulfonic acid, dibutyltin oxide, tetraisopropoxytitanate and potassium oxalate titanate, and tetraisopropoxytitanate and potassium oxalate titanate are preferable from the viewpoint of reactivity and environmental impact. .

The fiber sizing agent composition of the present invention comprises a polyether polymer (B).
This polyether polymer (B) is a polyurethane resin (B1) obtained by reacting a polyether diol (c) having an HLB of 10 to 20 and a diisocyanate (d1), and / or a polyether having an HLB of 10 to 20. Polycarbonate resin (B2) obtained by reacting diol (c) with dialkyl carbonate (d2) or alkylene carbonate (d3).

The polyurethane resin (B1) is obtained by reacting a polyether diol (c) and a diisocyanate (d1), and the polyether diol (c) has an HLB of 10-20.
In this specification, HLB is a value determined by the Griffin method. The HLB of the polyether diol (c) is 10 to 20, preferably 11 to 20, and more preferably 12 to 20. When HLB is less than 10, the strength of the composite material decreases.

The polyether diol (c) is the same as the alkylene oxide adduct (b1) described in the polyester resin (A), and includes an AO adduct of an aliphatic alkanediol, an AO adduct of an alicyclic diol, Examples include AO adducts of secondary amines and AO adducts of aromatic ring-containing dihydric phenols.
Specific examples include polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol polymer, cyclohexanediol EO adduct, butylamine EO adduct, and bisphenol A EO adduct.

The number average molecular weight of the polyether diol (c) is not particularly limited, but 600 to 30,000 is preferable from the viewpoint of the strength of the composite material.
If the number average molecular weight is too low, the urethane group content tends to be high, and it is difficult to achieve both convergence and openability, which is not preferable. If the number average molecular weight is too high, the impregnation property of the matrix resin is deteriorated.

Examples of the diisocyanate (d1) include aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and dodecamethylene diisocyanate.

  Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

  Examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate, and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

  Aromatic diisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) and 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI). Etc.

  Of these diisocyanates (d1), araliphatic diisocyanates and aromatic diisocyanates are preferable, and aromatic diisocyanates are more preferable, from the viewpoint of fiber bundle convergence. Specifically, XDI, TDI, MDI, and the like.

The polyurethane resin (B1) is obtained by reacting the polyether diol (c) and the diisocyanate (d1), and its production method is not particularly limited. For example, in the presence of an organic solvent in a batch reactor equipped with a stirrer or A method in which polyether diol (c) and diisocyanate (d1) are mixed and reacted in a single shot in the absence thereof.
The equivalent ratio of the polyether diol (c) and the diisocyanate (d1) is not particularly limited, but it is preferable that the equivalent of the isocyanate group does not become excessive. When the isocyanate group equivalent is excessive, use a reaction terminator such as C1-C20 monoalcohols (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.) It is preferable to do.

Although the number average molecular weight of a polyurethane resin (B1) is not specifically limited, 2000-500,000 are preferable from a viewpoint of the intensity | strength of a composite material. When the number average molecular weight is too low, there is no effect of increasing the strength of the composite material, and a useful component of the sizing agent is diluted, which is not preferable. When the number average molecular weight is too high, the viscosity of the sizing agent becomes high, so that the openability becomes low, and as a result, the strength of the composite material does not increase.

The polycarbonate resin (B2) is obtained by reacting a polyether diol (c) having an HLB of 10 to 20 with a dialkyl carbonate (d2) or an alkylene carbonate (d3).
The polyether diol (c) is the same as the alkylene oxide adduct (b1) described in the polyester resin (A), and the preferred range is also the same.

Examples of the dialkyl carbonate (d2) include carbonates having an alkyl group having 1 to 20 carbon atoms. Examples thereof include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-propyl carbonate, di-isopropyl carbonate, di-n-butyl carbonate, di-isobutyl carbonate, di-t-butyl carbonate, and dioctyl carbonate.
Examples of the alkylene carbonate (d3) include carbonates having a C 2-6 alkylene group forming a ring. Examples thereof include ethylene carbonate and propylene carbonate.
Among these, preferred are dialkyl carbonates having an alkyl group having 1 to 4 carbon atoms, and more preferred is dimethyl carbonate. The smaller the number of carbon atoms in the alkyl group, the lower the boiling point of the by-produced alcohol.

The manufacturing method of polycarbonate resin (B2) is as follows.

  Although there is no restriction | limiting of the usage-amount of dialkyl carbonate (d2) or alkylene carbonate (d3), The input molar ratio of (c): [(d2) + (d3)] is preferably 1: 9 to 3: 1. 4 to 2: 1 is more preferable. When the amount of (d2) or (d3) used is small, the number average molecular weight of the polycarbonate resin (B2) cannot be increased. On the other hand, when the amount of (d2) or (d3) used is too large, the molecular weight of the polycarbonate resin (B2) is too small.

You may use a catalyst for manufacture of polycarbonate resin (B2). Examples of the catalyst used include alkali metals and amine compounds.
Examples of alkali metals include alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal alkoxides, alkali metals and alkaline earths. Examples include simple metals, and alkali metal and alkaline earth metal carbonates.
Examples of amine compounds include tertiary amines and ordinary quaternary ammonium salts. Examples of the tertiary amine include N, N-dimethylethanamine, N-methyl-N-ethylethanamine, triethylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, and 1,8-diazabicyclo [ 5,4,0] undec-7-ene and the like. Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetramethylammonium / 6 fluorophosphate, and quaternary salts of pyridines.

Two or more of these catalysts can be used in combination. Among these, preferred are alkali metals, more preferred are alkali metals derived from sodium and potassium metals, and most preferred are sodium hydroxide and potassium hydroxide. The input amount of the catalyst (D) is usually 0.01 to 5% by weight, preferably 0.05 to 1% by weight, based on the weight of the polyether diol (c).
When the catalyst needs to be separated, a separation / purification operation such as a precipitation / filtration operation with a carbonate or an adsorption filtration treatment operation with an adsorbent may be performed. When separation of the catalyst is not necessary, the separation / purification operation may not be performed.

In the production of the polycarbonate resin (B2), a solvent can be used as necessary. Solvents include ethers (tetrahydrofuran, 1,4-dioxane, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (normal hexane, normal nonane, cyclohexane, cyclohexene, etc.) and aromatics. Hydrocarbons (benzene, toluene, ethylbenzene, xylene, styrene, etc.) are preferred. The amount of the solvent used is usually 100% by weight or less, preferably 10% by weight or less, more preferably no solvent, based on the weight of the polyether diol (c).

The order in which the polyether diol (c), the dialkyl carbonate (d2) and / or the alkylene carbonate (d3) is added during the production of the polycarbonate resin (B2) is not particularly limited. The charging method of (d2) and / or (d3) may be batch charging or split charging.

The temperature at which the polyether diol (c) is reacted with the dialkyl carbonate (d2) or the alkylene carbonate (d3) is usually 20 to 250 ° C., preferably 40 to 180 ° C., more preferably 65 to 135 ° C. If it is less than 20 degreeC, the viscosity of a reaction system is high and handling property is bad. If the temperature exceeds 250 ° C., the polyether polymer (P) is thermally decomposed, resulting in a problem that a high molecular weight product cannot be obtained.

The number average molecular weight of the polycarbonate resin (B2) is not particularly limited, but is preferably 2,000 to 500,000 from the viewpoint of the strength of the composite material. When the number average molecular weight is too low, there is no effect of increasing the strength of the composite material, and a useful component of the sizing agent is diluted, which is not preferable. When the number average molecular weight is too high, the viscosity of the sizing agent becomes high, so that the openability becomes low, and as a result, the strength of the composite material does not increase.

The fiber sizing agent composition of the present invention comprises a polyester resin (A) and a polyether polymer (B), and the weight ratio (A) / (B) of the polyester resin (A) and the polyether polymer (B). Is 50/50 to 99.5 / 0.5, preferably 55/45 to 99/1, and more preferably 60/40 to 95/5.
When the polyester resin (A) is less than 50, generation of fluff increases, which is not preferable. When the polyether-based polymer (B) is less than 0.5, it is not preferable because the convergence property and the fiber-opening property are not compatible and the strength of the composite material does not increase.

In addition to the polyester resin (A) and the polyether polymer (B), the fiber sizing agent composition of the present invention includes a resin (C) other than the polyester resin (A) and the polyurethane resin (B1), a surfactant (D ) And other additives (E).

  When the fiber sizing agent composition of the present invention contains the resin (C), the impregnation property of the matrix resin into the fiber bundle is improved, and thus the strength of the composite material is excellent. Moreover, when the sizing agent composition for fibers of the present invention contains a surfactant (D), the sizing agent attached to the inorganic fibers tends to be smooth, so that the scratch resistance of the inorganic fiber bundle is further improved, and an organic solvent is used. It is easy to produce an aqueous emulsion that does not contain a large amount.

Examples of the resin (C) other than the polyester resin (A) include epoxy resins, polyurethane resins other than the polyurethane resin (B1), thermosetting resins such as (meth) acrylate-modified resins and unsaturated polyester resins, and polyamide resins ( Examples thereof include thermoplastic resins such as polyester resins other than (meth) acrylate resins and polyester resins (A), polyethylene resins, polypropylene resins, and polystyrene resins.
Two or more of these may be used in combination. In addition, (meth) acrylate means an acrylate and a methacrylate. In addition, the polyester resin other than the polyester resins (A) and (A) does not include an unsaturated polyester resin.

  Among the resins (C), from the viewpoint of the strength of the composite material, etc., other than epoxy resin, polyurethane resin other than polyurethane resin (B1), (meth) acrylate resin, unsaturated polyester resin, polyamide resin, and other than polyester resin (A) Polyester resins are preferred, epoxy resins, polyurethane resins, (meth) acrylate resins and unsaturated polyester resins are more preferred, and epoxy resins are particularly preferred.

  When using the resin (C), the content thereof is preferably 1 to 90% by weight, more preferably 5 to 5% from the viewpoint of the impregnating property of the matrix resin, based on the total weight of the sizing agent composition for fibers. 80% by weight, more preferably 10 to 75% by weight, and particularly preferably 10 to 50% by weight.

  Examples of the surfactant (D) include surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Two or more of these may be used in combination.

  Of the surfactants (D), anionic surfactants, nonionic surfactants, and mixtures of anionic surfactants and nonionic surfactants are preferred, and AO adducts of alkylphenols, arylalkylphenols are more preferred. AO adduct of (styrenated phenol, styrenated cumylphenol or styrenated cresol), sulfate ester salt of alkylphenol AO adduct, sulfate ester salt of arylalkylphenol AO adduct, and mixtures thereof are particularly preferable. Are arylalkylphenol AO adducts, sulfate esters of arylalkylphenol AO adducts, and mixtures thereof.

  When the surfactant (D) is used, the content thereof is preferably 0.5 to 20% by weight based on the total weight of the fiber sizing agent composition, from the viewpoint of the sizing property of the fiber bundle, Preferably it is 1 to 15 weight%, Most preferably, it is 2 to 10 weight%.

An additive may be added to the fiber sizing agent composition of the present invention as necessary, and examples thereof include a smoothing agent, a preservative, and an antioxidant.
Examples of the smoothing agent include waxes (polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, modified polyethylene, modified polypropylene, etc.), higher fatty acid alkyl (1 to 24 carbon atoms) esters (methyl stearate, ethyl stearate, and propylene stearate). Rate, butyl stearate, octyl stearate, stearyl stearate), higher fatty acids (myristic acid, palmitic acid, stearic acid) and the like.
Examples of the preservative include benzoic acids, salicylic acids, sorbic acids, quaternary ammonium salts imidazoles and the like.
Antioxidants include phenols (such as 2,6-di-t-butyl-p-cresol), thiodipropionates (such as dilauryl 3,3′-thiodipropionate), and phosphites (triphenyl). Phosphite).

  Although there is no restriction | limiting in particular in the manufacturing method of the sizing agent composition for fibers of this invention, For example, a polyester container (A) and a reactive compound (B) and, if needed, resin (C), surface active in a mixing container The agent (D) and other additives are added to the charging order without any particular limitation, and preferably 20 to 150 ° C., more preferably 50 to 120 ° C., stirring until the mixture is uniform. .

The fiber sizing agent dispersion of the present invention is preferably formed by dispersing the fiber sizing agent composition of the present invention in a solvent.
The fiber sizing agent solution of the present invention is preferably formed by dissolving the fiber sizing agent of the present invention in a solvent.
By dissolving or dispersing the fiber sizing agent composition in a solvent, the amount of the fiber sizing agent composition attached to the fiber bundle can be easily adjusted to an appropriate amount.

Examples of the solvent include water and known organic solvents.
Examples of the organic solvent include lower alcohols having 1 to 4 carbon atoms (such as methanol, ethanol, and isopropanol), ketones having 3 to 6 carbon atoms (such as acetone, ethyl methyl ketone, and methyl isobutyl ketone), and those having 2 to 6 carbon atoms. Glycol (ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, etc.), mono-lower alkyl ethers thereof, dimethylformamide, aromatic hydrocarbons (toluene, xylene), alkyl esters of 3 to 5 carbon atoms (methyl acetate and ethyl acetate) Etc.).
Two or more of these may be used in combination. Of the above solvents, water and a mixed solvent of a water-miscible organic solvent and water are preferable from the viewpoint of safety such as fire, and water is more preferable.

The sizing agent dispersion for fibers and the sizing agent solution for fibers of the present invention preferably have a high concentration during distribution and a low concentration during the production of fiber bundles from the viewpoint of cost and the like. That is, a fiber bundle that has both excellent convergence and spreadability can be produced by reducing the transportation cost and storage cost by distributing at a high concentration and treating the fiber at a low concentration.
The concentration (content ratio of components other than the solvent) when the sizing agent dispersion for fibers and the sizing agent solution for fibers are high is preferably 30 to 80% by weight, more preferably from the viewpoint of storage stability and the like. Is 40 to 70% by weight.
The concentration when the sizing agent dispersion for fibers and the sizing agent solution for fibers is low is preferably 0.5 from the viewpoint that the amount of the sizing agent for fibers can be adjusted to an appropriate amount when the fiber bundle is produced. -15% by weight, more preferably 1-10% by weight.

Although there is no particular limitation on the method for producing the fiber sizing agent dispersion and the fiber sizing agent solution of the present invention, for example, a solvent is added to the fiber sizing agent composition of the present invention obtained by the above method, Examples thereof include a method of dissolving or emulsifying and dispersing the fiber sizing agent composition in a solvent.
The temperature at which the fiber sizing agent composition is dissolved or emulsified and dispersed in a solvent is preferably 20 to 90 ° C, more preferably 40 to 90 ° C, from the viewpoint of easy mixing.
The time for dissolving or emulsifying and dispersing the fiber sizing agent composition in a solvent is preferably 1 to 20 hours, and more preferably 2 to 10 hours.
When the sizing agent composition for fibers is dissolved or emulsified and dispersed in an aqueous medium, a known mixing device, dissolving device and emulsifying and dispersing device can be used. Specifically, a stirring blade (blade shape: Type, three-stage paddle, etc.), Nauta mixer [made by Hosokawa Micron Co., Ltd.], ribbon mixer, conical blender, mortar mixer, universal mixer {universal mixing stirrer "5DM-L" [manufactured by Sanei Seisakusho] Etc.}, Henschel mixer [Nippon Coke Kogyo Co., Ltd.], autoclave, etc. can be used.

  Examples of fibers to which the fiber sizing agent composition, fiber sizing agent dispersion or fiber sizing agent solution of the present invention can be applied include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, and slug fibers. And organic fibers such as aramid fibers, and carbon fibers are preferred from the viewpoint of the strength of the molded body.

In the method for producing a 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 slug fiber is used as the fiber sizing agent. A fiber bundle is obtained by treatment with the composition, or a fiber sizing agent dispersion in which the sizing agent composition is dispersed or a fiber sizing agent solution in which the sizing agent composition is dissolved.
The resulting fiber bundle is preferably bundled with about 3,000 to 50,000 fibers.

  Examples of the fiber processing method include a spray method and a dipping method. The adhesion amount of the fiber sizing agent composition onto the fiber is preferably 0.05 to 5% by weight, more preferably 0.2 to 2.5% by weight, based on the weight of the fiber. When the amount of the sizing agent composition for fibers is in this range, the sizing property is excellent.

  The fiber product of the present invention comprises the fiber bundle treated with the fiber sizing agent composition, the fiber sizing agent dispersion or the fiber sizing agent solution and the matrix resin as described above. The textile product of the present invention may contain a catalyst, if necessary.

  Examples of the matrix resin include thermoplastic resins such as polypropylene, polyamide, polyethylene terephthalate, polycarbonate, and polyphenylene sulfide, and thermosetting resins such as epoxy resins, unsaturated polyester resins, vinyl ester resins, and phenol resins.

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

  In the fiber product of the present invention, the weight ratio of the matrix resin to the fiber bundle (matrix resin / fiber bundle) is preferably 10/90 to 90/10, more preferably 20 / It is 80-70 / 30, Most preferably, it is 30 / 70-60 / 40. When the fiber product contains a catalyst, the content of the catalyst is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight with respect to the matrix resin from the viewpoint of the strength of the molded body and the like. And particularly preferably 1 to 3% by weight.

  For fiber products, the fiber bundle is impregnated with a matrix resin that has been melted hot (melting temperature: 60 to 350 ° C.) or a matrix resin that has been diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, etc.). Can be manufactured. When a solvent is used, it is preferable to dry the prepreg and remove the solvent.

  A fiber-reinforced composite material can be obtained by molding the fiber product of the present invention. When the matrix resin is a thermoplastic resin, the prepreg can be formed by heating and solidifying at room temperature. When the matrix resin is a thermosetting resin, the prepreg can be formed by heating and curing. Curing does not need to be completed, but it is preferable that the molded body is cured to such an extent that the shape can be maintained. After molding, it may be further heated to be completely cured. The method of heat forming is not particularly limited. For example, a filament winding forming method (a method in which a rotating mandrel is wound while being tensioned and heat forming), a press forming method (a method in which prepreg sheets are laminated and heat forming), an autoclave method (Method of heat-pressing a prepreg sheet by applying pressure to the mold) and a method of injection-molding by mixing chopped fiber or milled fiber with a matrix resin.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1 Production of bisphenol A EO 30 mol adduct (b-1) and (c-1)>
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, an EO4 molar adduct of bisphenol A “New Pole BPE-40” [manufactured by Sanyo Chemical Industries, Ltd.] 404 parts by weight (1 molar part), and 2 parts by weight of potassium hydroxide was added, and after replacing with nitrogen, the pressure was -0.08 MPa. The temperature was raised to 130 ° C., and 1144 parts by weight (26 mol parts) of EO was added dropwise over 6 hours while adjusting the pressure to be 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 an adsorption treatment agent “KYOWARD 600” [manufactured by Kyowa Chemical Industry Co., Ltd.] is added, and the mixture is stirred for 1 hour at 100 ° C., and then the adsorption treatment agent is filtered. An EO 30 mol adduct (b-1) of bisphenol A was obtained. Since this HLB was 17.0, it is also used as (c-1).

<Production Example 2 Production of bisphenol A EO3 molar adduct (b-2)>
Into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping cylinder, 228 parts by weight (1 mole part) of bisphenol A, 400 parts by weight of toluene, and 2 parts by weight of potassium hydroxide were charged and purged with nitrogen. The temperature was raised to 100 ° C., and 132 parts by weight (3 mol parts) of EO was added dropwise over 6 hours while adjusting the pressure to be 0.5 MPaG or less, and then aged at 120 ° C. for 3 hours to reach −0.1 MPa. The toluene was removed. Next, after cooling to 100 ° C., 30 parts by weight of an adsorption treatment agent “KYOWARD 600” [manufactured by Kyowa Chemical Industry Co., Ltd.] is added, and the mixture is stirred for 1 hour at 100 ° C., and then the adsorption treatment agent is filtered. An EO3 molar adduct (b-2) of bisphenol A was obtained.

<Production Example 3 Production of Polyester Resin (A-1)>
EO2 molar adduct of bisphenol A (b-3) “New Pole BPE-20” [manufactured by Sanyo Chemical Industries, Ltd.] 316 parts by weight (1 part by mole), 142 parts by weight of terephthalic acid (a-1) (0. 86 mol parts) and 3 parts by weight of potassium oxalate titanate were reacted in a glass reactor at 230 ° C. to 0.001 MPa for 15 hours while distilling off water. Further, 263 parts by weight (0.26 mole part) of polyoxyethylene glycol (b-4) “PEG-1000” [manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 1000] was added to the reaction mixture at 150 ° C. under normal pressure. For 2 hours to obtain 690 parts by weight of a polyester resin (A-1). The ester group concentration of (A-1) was 2.5 mmol / g.

<Production Example 4 Production of Polyester Resin (A-2)>
In Production Example 3, 142 parts by weight (0.86 mol part) of terephthalic acid (a-1) was changed to 163 parts by weight (0.98 mol part), and polyoxyethylene glycol (b-4) was changed to polyoxyethylene glycol ( b-5) “PEG-10000” [manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 11000] 359 parts by weight (0.04 mol part), except that the polyester resin (A -2) 803 parts by weight were obtained. The ester group concentration of (A-2) was 2.4 mmol / g.

<Production Example 5 Production of Polyester Resin (A-3)>
EO6 mol adduct of bisphenol A (b-6) “New Pole BPE-60” [manufactured by Sanyo Chemical Industries, Ltd.] 492 parts by weight (1 mol part), fumaric acid (a-2) 108 parts by weight (0. 93 mol parts) and 3 parts by weight of potassium oxalate titanate were reacted in a glass reactor at 230 ° C. to 0.001 MPa for 15 hours while distilling off water. To the reaction mixture, polyoxyethylene glycol (b-7) “PEG-2000” [manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 2000] 480 parts by weight (0.24 mole part) was added, and atmospheric pressure at 150 ° C. For 2 hours to obtain 1046 parts by weight of a polyester resin (A-3). The ester group concentration of (A-3) was 1.8 mmol / g.

<Production Example 6 Production of Polyester Resin (A-4)>
PO3 mol adduct of bisphenol A (b-8) “New Pole BP-3P” [manufactured by Sanyo Chemical Industries, Ltd.] 402 parts by weight (1 mole part), 156 parts by weight of terephthalic acid (a-1) (0. 94 mol parts) and 3 parts by weight of potassium oxalate titanate were reacted in a glass reaction vessel under reduced pressure at 230 ° C. to 0.001 MPa for 15 hours while distilling off water. Further, 222 parts by weight (0.14 mol) of bisphenol A EO 30 mol adduct (b-1) obtained in Production Example 1 was added to the reaction mixture, and the mixture was reacted at 150 ° C. under normal pressure for 2 hours. A-4) 745 parts by weight were obtained. The ester group concentration of (A-4) was 2.5 mmol / g.

<Production Example 7 Production of Polyester Resin (A-5)>
EO2 molar adduct of bisphenol A (b-3) “New Pole BPE-20” [manufactured by Sanyo Chemical Industries, Ltd.] 316 parts by weight (1 mole part), 163 parts by weight of terephthalic acid (a-1) (0. 98 mol parts) and 3 parts by weight of potassium oxalate titanate were reacted in a glass reaction vessel at 230 ° C. to 0.001 MPa and reacted for 15 hours while distilling off water. The reaction mixture was further added with a polyoxypropylene glycol (number average molecular weight 3,250) 290 mol adduct (b-8) “New Pole PE-108” [manufactured by Sanyo Chemical Industries, Ltd.] 359 parts by weight (0.02 mol) Part) was added and reacted at 150 ° C. under normal pressure for 2 hours to obtain 551 parts by weight of a polyester resin (A-5). The ester group concentration of (A-5) was 2.4 mmol / g.

<Production Example 7 Production of Polyester Resin (A-6)>
360 parts by weight (1 mole part) of an EO3 mole adduct of bisphenol A (b-2), 107 parts by weight (0.92 mole part) of fumaric acid (a-2) and 3 parts by weight of potassium oxalate titanate In the reaction vessel, the pressure was reduced to 0.001 MPa at 230 ° C., and the reaction was carried out for 15 hours while distilling off water. To the reaction mixture, bisphenol A EO 10 mol adduct (b-9) “New Pole BPE-100” [manufactured by Sanyo Chemical Industries Co., Ltd.] 117 parts by weight (0.17 mol part) was added and atmospheric pressure at 150 ° C. For 2 hours to obtain 800 parts by weight of a polyester resin (A-6). The ester group concentration of (A-6) was 3.4 mmol / g.

<Production Example 8 Production of hexanediol EO 30 mol adduct (c-2)>
Into a reaction vessel equipped with a stirrer and a heating / cooling apparatus, 118 parts by weight (1 mole part) of 1,6-hexanediol [manufactured by Wako Pure Chemical Industries, Ltd.] and 2 parts by weight of potassium hydroxide were added, and nitrogen was added. After replacement, the pressure was -0.08 MPaG. The temperature was raised to 130 ° C., 1320 parts by weight (26 mol parts) of EO was added dropwise over 6 hours while adjusting the pressure to be 0.5 MPaG or less, and then aged at 130 ° C. for 3 hours. Next, after cooling to 100 ° C., 30 parts by weight of an adsorption treatment agent “KYOWARD 600” [manufactured by Kyowa Chemical Industry Co., Ltd.] is added, and the mixture is stirred for 1 hour at 100 ° C., and then the adsorption treatment agent is filtered. An EO 30 mol adduct (c-2) of hexanediol was obtained. The HLB of (c-2) was 18.4.

<Production Example 9 Production of Polyurethane Resin (B1-1)>
In a reaction vessel equipped with a stirrer and a temperature controller, polyoxyethylene glycol (c-3) “PEG-1000” having a HLB of 20 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 1000) 100 parts by weight (0 .1 mol part) was added and the atmosphere was replaced with nitrogen. The temperature was raised to 80 ° C. in a dry nitrogen atmosphere, and toluene diisocyanate (d1-1) “Coronate T-80” [manufactured by Nippon Polyurethane Industry Co., Ltd.] (hereinafter abbreviated as TDI) 15.66 parts by weight (0.09 mol) Part) was aged at 80 ° C. for 5 hours to obtain a polyurethane resin (B1-1).

<Production Example 10 Production of Polyurethane Resin (B1-2)>
In a reaction vessel similar to Production Example 9, polyoxyethylene glycol (c-4) “PEG-10000” having an HLB of 20 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 11000) 100 parts by weight (0.01 Mol part) was added and the atmosphere was replaced with nitrogen. The temperature was raised to 85 ° C. in a dry nitrogen atmosphere, and 1.392 parts by weight (0.008 mol part) of TDI (d1-1) was added, followed by aging at 85 ° C. for 5 hours to obtain a polyurethane resin (B1-2). Obtained.

<Production Example 11 Production of Polyurethane Resin (B1-3)>
In Production Example 10, polyoxyethylene glycol (c-4) is polyoxyethylene glycol (c-5) having a HLB of 20 “PEG-20000” [manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 20000] 200 weight Part 10 (0.01 mole part) and Production Example 10 except that 1.392 parts by weight (0.008 mole part) of TDI (d1-1) was changed to 1.305 parts by weight (0.008 mole part). Similarly, a polyurethane resin (B1-3) was obtained.

<Production Example 12 Production of Polyurethane Resin (B1-4)>
In Production Example 10, polyoxyethylene glycol (c-4) is a polyoxyethylene polyoxypropylene glock polymer (c-6) “New Pole PE-68” having an HLB of 15.6 [manufactured by Sanyo Chemical Industries, Ltd.] Production Example, except that 80 parts by weight (0.01 mol part) and 1.392 parts by weight (0.008 mol part) of TDI (d1-1) were changed to 1.305 parts by weight (0.008 mol part) In the same manner as in Example 10, a polyurethane resin (B1-4) was obtained.

<Production Example 13 Production of Polyurethane Resin (B1-5)>
In Production Example 10, polyoxyethylene glycol (c-4) is a polyoxyethylene polyoxypropylene glock polymer (c-7) “New Det PE-85” with an HLB of 10.2 [manufactured by Sanyo Chemical Industries, Ltd.] To 464 parts by weight (0.1 mol part), TDI (d1-1) is 4,4′-diphenylmethane diisocyanate (d1-2) “Millionate MT” [manufactured by Nippon Polyurethane Co., Ltd.] 22.2 parts by weight (0 0.09 mol part), a polyurethane resin (B1-5) was obtained in the same manner as in Production Example 10, except that

<Production Example 14 Production of Polyurethane Resin (B1-6)>
In Production Example 10, polyoxyethylene glycol (c-4) was added to 155 parts by weight (0.1 mole part) of EO 30 mol adduct (c-1) of bisphenol A having an HLB of 17.0 obtained in Production Example 1. In the same manner as in Production Example 10, except that TDI (d1-1) was changed to 22.1 parts by weight (0.095 mol part) of isophorone diisocyanate (d1-3) “Desmodur I” [manufactured by Sumitomo Bayer Urethane] A polyurethane resin (B1-6) was obtained.

<Production Example 15 Production of Polyurethane Resin (B1-7)>
In Production Example 10, polyoxyethylene glycol (c-4) was added to 144 parts by weight (0.1 mole part) of EO 30 mol adduct (c-2) of hexanediol having an HLB of 18.4 obtained in Production Example 8. , TDI (d1-1) 1.392 parts by weight (0.008 mole part) was changed to 16.5 parts by weight (0.095 mole part) in the same manner as in Production Example 10 except that polyurethane resin (B1- 7) was obtained.

<Production Example 16 Production of Polycarbonate Resin (B2-1)>
In a reaction vessel equipped with a stirrer and a temperature controller, polyoxyethylene glycol (c-3) “PEG-1000” having an HLB of 20 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 1000) 100 parts by weight (0. 1 mol part) and 0.2 part by weight (0.0036 mol part) of potassium hydroxide were added, and the atmosphere was replaced with nitrogen. The temperature was raised to 85 ° C. in a dry nitrogen atmosphere, 9 parts by weight (0.1 mol part) of dimethyl carbonate (d2-1) “DMC” [manufactured by Sankyo Chemical Co., Ltd.] was added, and then the volatile content at 85 ° C. The reaction was allowed to proceed for 5 hours while removing the temperature and aged at 130 ° C. for 3 hours. The obtained crude polycarbonate was subjected to adsorption filtration treatment with an adsorbent to obtain a polycarbonate resin (B2-1).

<Production Example 17 Production of Polycarbonate Resin (B2-2)>
In Production Example 16, polyoxyethylene glycol (c-3) is polyoxyethylene glycol (c-4) “PEG-10000” having an HLB of 20 [manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 11000] 100 parts by weight The polycarbonate resin (B2-2) was prepared in the same manner as in Production Example 16 except that the dimethyl carbonate (d2-1) was changed to 0.9 parts by weight (0.01 parts by mole). Obtained.

<Production Example 18 Production of Polycarbonate Resin (B2-3)>
In Production Example 16, polyoxyethylene glycol (c-3) is polyoxyethylene glycol (c-5) “PEG-20000” having a HLB of 20 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 20000) 200 parts by weight The polycarbonate resin (B2-3) was prepared in the same manner as in Production Example 16 except that the dimethyl carbonate (d2-1) was changed to 0.9 parts by weight (0.01 mol parts). Obtained.

<Production Example 19 Production of Polycarbonate Resin (B2-4)>
In Production Example 16, polyoxyethylene glycol (c-3) is a polyoxyethylene polyoxypropylene glock polymer (c-6) “New Pole PE-68” with an HLB of 15.6 [manufactured by Sanyo Chemical Industries, Ltd.] Except that 80 parts by weight (0.01 mole part) and dimethyl carbonate (d2-1) were changed to 0.9 parts by weight (0.01 mole part), polycarbonate resin (B2- 4) was obtained.

<Production Example 20 Production of Polycarbonate Resin (B2-5)>
In Production Example 16, polyoxyethylene glycol (c-3) is a polyoxyethylene polyoxypropylene glock polymer (c-7) “New Det PE-85” having an HLB of 10.2 [manufactured by Sanyo Chemical Industries, Ltd.] Except for changing dimethyl carbonate (d2-1) to 4.5 parts by weight (0.05 mol parts) to 232 parts by weight (0.05 mol parts), polycarbonate resin (B2- 5) was obtained.

<Production Example 21 Production of Polycarbonate Resin (B2-6)>
Production Example 16 except that polyoxyethylene glycol (c-3) was changed to 155 parts by weight (0.1 mol part) of EO 30 mol adduct of bisphenol A having an HLB of 17.0 (c-1) in Production Example 16. In the same manner as in 16, a polycarbonate resin (B2-6) was obtained.

<Production Example 22 Production of Polycarbonate Resin (B2-7)>
In Production Example 16, polyoxyethylene glycol (c-3) was added to 144 parts by weight (0.1 mole part) of EO 30 mol adduct (c-2) of hexanediol having an HLB of 18.4 obtained in Production Example 8. Except having changed, it carried out similarly to manufacture example 16, and obtained polycarbonate resin (B2-7).

<Production of Comparative Production Example 1 Polyurethane Resin (B′1-1)>
In Production Example 10, polyoxyethylene glycol (c-4) is polyoxypropylene glycol (c′-1) “New Paul PP-4000” (manufactured by Sanyo Chemical Industries, Ltd.) having an HLB of 0, 200 parts by weight (0 0.05 mol part) and polyurethane resin (B′1-1) was obtained in the same manner as in Production Example 10 except that TDI (d1-1) was changed to 6.5 parts by weight (0.038 mol part). It was.

<Comparative Production Example 2 Production of Polyurethane Resin (B′1-2)>
In Production Example 10, polyoxyethylene glycol (c-4) was added to EO of glycerin (c′-2), a trivalent alcohol with HLB of 16.9, “New Pole GP-600” [Sanyo Chemical Industries, Ltd. )]] 60 parts by weight (0.1 mol parts), except that TDI (d1-1) was changed to 17.4 parts by weight (0.1 mol parts), a polyurethane resin ( B′1-2) was obtained.

<Comparative Production Example 3 Production of Polyurethane Resin (B′1-3)>
In Production Example 10, polyoxyethylene glycol (c-4) is a polyoxyethylene polyoxypropylene glock polymer (c-6) “New Pole PE-34” with an HLB of 8.2 [manufactured by Sanyo Chemical Industries, Ltd.] A polyurethane resin (B′1) was prepared in the same manner as in Production Example 10 except that 170 parts by weight (0.1 mole part) and TDI (d1-1) were changed to 15.7 parts by weight (0.09 mole part). -2) was obtained.

<Comparative Production Example 4 Production of Polycarbonate Resin (B′2-1)>
In Production Example 16, polyoxyethylene glycol (c-3) is polyoxypropylene glycol (c′-1) “New Paul PP-4000” (manufactured by Sanyo Chemical Industries, Ltd.) having an HLB of 0, 200 parts by weight (0 0.05 parts by weight), 9 parts by weight (0.1 parts by mole) of dimethyl carbonate (d2-1) “DMC” [manufactured by Sankyo Chemical Co., Ltd.] to 4.5 parts by weight (0.05 parts by mole) Except having changed, it carried out similarly to manufacture example 16, and obtained polycarbonate resin (B'2-1).

<Comparative Production Example 5 Production of Polycarbonate Resin (B'2-2)>
In Production Example 16, polyoxyethylene glycol (c-3) was added as an EO adduct of glycerin (c′-2), which is a trihydric alcohol with an HLB of 16.9, “New Pole GP-600” [Sanyo Chemical Industries, Ltd. )] A polycarbonate resin (B′2-2) was obtained in the same manner as in Production Example 16 except that the amount was changed to 60 parts by weight (0.1 mol part).

<Comparative Production Example 5 Production of Polycarbonate Resin (B′2-3)>
In Production Example 16, polyoxyethylene glycol (c-3) is a polyoxyethylene polyoxypropylene glock polymer (c-6) having a HLB of 8.2, “New Pole PE-34” [manufactured by Sanyo Chemical Industries, Ltd.] Except having changed to 170 weight part (0.1 mol part), it carried out similarly to manufacture example 16, and obtained polycarbonate resin (B'2-3).

Fiber sizing agent compositions having parts by weight shown in Tables 1 and 2 were prepared.
This fiber sizing agent composition and N, N-dimethylformamide (DMF) were mixed, and a solution of fiber sizing agent composition having a solid content concentration of 1.5% by weight (Examples 1 to 19 and Comparative Examples 1 to 9). ) Was produced.

In addition, each component used for the Example and comparative example other than having described in the manufacture example and the comparative manufacture example is as follows.
(A′-1): Polylactic acid “RESOMER R202S” (manufactured by Aldrich). The ester group concentration is 13.6 mmol / g
(C-1): Diglycidyl ether of bisphenol A “JER834” [Mitsubishi Chemical Corporation]
(C-2): Diglycidyl ether of phenol novolac “JER152” [Mitsubishi Chemical Corporation]
(C-3): N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane “Araldite MY721” [manufactured by Harzman Advanced Materials]
(C-4): Polyoxyalkylene diglycidyl ether “Denacol EX-946L” [manufactured by Nagase ChemteX Corporation]
(C-5): Urethane-modified epoxy “Adeka Resin EPU-6” [manufactured by ADEKA Corporation]
(D-1): Propylene oxide / ethylene oxide adduct of styrenated phenol “Soprophor 796 / P” [manufactured by Solvay Nikka Co., Ltd.]

Using the aqueous dispersions of Examples 1 to 19 and Comparative Examples 1 to 9, the following evaluation methods were used to evaluate the carbon fiber bundle focusing property, the fiber opening property, and the composite material strength.

<Evaluation of convergence>
An untreated carbon fiber (fineness: 800 tex, number of filaments: 12,000) is immersed in a solution of a fiber sizing agent composition having a solid content concentration of 1.5% by weight to impregnate the sizing agent, and hot air is blown at 160 ° C. for 3 minutes. A carbon fiber bundle was produced by drying.
The convergence property of the obtained carbon fiber bundle was evaluated according to JIS L1096-1999 8.19.1 A method (45 ° cantilever method). The larger the value, the better the convergence.
The convergence value obtained by evaluating the carbon fiber bundle obtained under these treatment conditions with a cantilever is generally preferably 13 cm or more.
In addition, since the sizing agent composition of Comparative Examples 5 and 8 did not dissolve the polyether polymer in DMF, the sizing agent composition for fibers could not be uniformly applied to the carbon fiber, and the sizing property could be evaluated. There wasn't.

<Evaluation of spreadability>
Using a yarn traveling test apparatus manufactured by Asano Machinery Works, the following conditions were used.
Five stainless steel rods having a smooth surface with a diameter of 10 mm were arranged in a zigzag so that the carbon fiber bundle yarns passed in contact at an angle of 120 degrees in parallel at intervals of 50 mm. When the above-mentioned treated carbon fiber bundle is zigzag between the stainless steel bars and passed at a speed of 3 m / min while adding an initial tension of 1,000 g, the spread width (mm ) Was measured.
In general, the spread width of the carbon fiber bundle measured under these conditions is preferably 8 mm or more.
In addition, since the sizing agent composition of Comparative Examples 5 and 8 did not dissolve the polyether polymer in DMF, the sizing agent composition for fibers could not be uniformly applied to the carbon fiber, and the fiber opening property was evaluated. could not.

<Strength evaluation of composite material>

The above-mentioned treated carbon fiber bundles are aligned in one direction and put into a mold, and a resin prepared by adding bisphenol A type diglycidyl ether (epoxy equivalent 190) / BF3 monoethylamine salt = 100/3 parts is added thereto. Impregnate in vacuum. At this time, the amount of the carbon fiber bundle is adjusted so that the volume content of the fiber is 60%. After impregnation, it is cured under pressure at 150 ° C. for 1 hour, and further cured at 140 ° C. for 4 hours. The strength of the test piece having a thickness of 2.5 mm and a width of 6.0 mm thus obtained was measured according to ASTM D-2344. In general, the strength of the carbon fiber bundle measured under these conditions is preferably 8 MPa or more.
In addition, since the sizing agent composition of Comparative Examples 5 and 8 did not dissolve the polyether polymer in DMF, the sizing agent composition for fibers could not be uniformly applied to the carbon fiber, and the strength evaluation could not be performed. .

The carbon fibers treated with the aqueous dispersion using the sizing agent compositions of Examples 1 to 19 of the present invention showed good results in any evaluation of the sizing property, the fiber opening property, and the strength of the composite material.
On the other hand, the thing which does not contain a polyether polymer (B) like the comparative example 1 has low intensity | strength. The comparative example 2 which does not contain a polyester resin (A) and the comparative example 3 using polylactic acid have low openability and strength. Those containing a polyether-based polymer composed of a polyether diol having an HLB of less than 10 as in Comparative Examples 4, 6, 7, and 9 are slightly deficient in opening properties and low in strength. As in Comparative Examples 5 and 8, since the polyether-based polymer composed of polyether triol is insoluble in the solvent, it cannot be applied to the carbon fiber.

Since the fiber reinforced composite material obtained from the fiber bundle and the matrix resin produced using the fiber sizing agent composition of the present invention has a very high strength, various civil engineering / building materials, materials for transportation equipment, It can be suitably used as a sporting goods material, a power generator material and the like.

Claims (8)

  A fiber sizing agent composition comprising a polyester resin (A) and a polyether polymer (B), wherein the polyester resin (A) comprises a carboxylic acid component (a) and an alkylene oxide adduct (b1). Polyurethane resin (B1), which is a polyester with a diol component (b), wherein the polyether polymer (B) is obtained by reacting a polyether diol (c) having an HLB of 10 to 20 and a diisocyanate (d1), and Polyester resin in fiber sizing agent composition, which is a polycarbonate resin (B2) obtained by reacting polyether diol (c) with HLB of 10 to 20 and dialkyl carbonate (d2) or alkylene carbonate (d3) The weight ratio (A) / (B) between (A) and the polyether polymer (B) is 50/50 to 99.99. Fiber sizing composition is /0.5.   The sizing agent composition for fibers according to claim 1, wherein the ester group concentration in the polyester resin (A) is 10 mmol / g or less based on the weight of the polyester resin (A).   The sizing agent composition for fibers according to claim 1 or 2, wherein the alkylene oxide adduct (b1) contains a diol (b11) having 4 to 500 oxyethylene groups.   The sizing agent composition for fibers according to any one of claims 1 to 3, wherein the alkylene oxide adduct (b1) is an ethylene oxide adduct of bisphenol A and / or an ethylene oxide adduct of alkylene glycol having 2 to 6 carbon atoms. .   A fiber sizing agent dispersion, wherein the fiber sizing agent composition according to claim 1 is dispersed in water or an organic solvent.   A fiber sizing agent solution obtained by dissolving the fiber sizing agent composition according to claim 1 in water or an organic solvent.   The fiber sizing agent composition according to any one of claims 1 to 4, wherein at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, and slug fiber is used. A fiber bundle that is processed.   A fiber product comprising the fiber bundle according to claim 7.