JP2016223033A - Treatment agent for ceramic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment agent for ceramic fiber without reduction of process passage property by breakage of a fiber bundle during the process.SOLUTION: There is provided a treatment agent for ceramic fiber containing a polyester resin (A) having critical surface tension of 40 mN/m or less, where the polyester resin (A) is a polyester resin (A) obtained by reacting a diol which is an ethylene oxide addition product having average addition molar number of ethylene oxide of 4 to 400 mol.SELECTED DRAWING: None

Description

  The present invention relates to a treating agent for ceramic fibers. More specifically, the present invention relates to a treating agent for ceramic fibers used for a resin or a ceramic composite material.

  Composite materials of matrix resins such as unsaturated polyester resins, phenol resins, and epoxy resins and various fibers are widely used in the fields of building materials, sports equipment, leisure goods, aircraft, and the like. In addition, ceramic composites reinforced with inorganic fibers are being developed as next-generation heat-resistant materials because of their excellent heat resistance and damage tolerance not found in single-phase ceramics.

  Ceramic fibers, which are one of the fibers used for these materials, are used as bundles (fiber bundles) with a sizing agent or the like. A resin such as polyethylene oxide is used as a sizing agent for ceramic fibers (Patent Document 1).

JP 2011-157632 A

In the treatment agent proposed in Patent Document 1, since the fiber bundle becomes hard, there is a problem that the fiber bundle is broken in the middle of the process and the process passability is lowered.
The objective of this invention is providing the processing agent for ceramic fibers by which a fiber bundle fractures | ruptures in the middle of a process and process permeability does not fall.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a treating agent for a ceramic fiber containing a polyester resin (A) having a critical surface tension of 40 mN / m or less, wherein the polyester resin (A) has an average added mole number of ethylene oxide of 4. It is the processing agent for ceramic fibers which is a polyester resin (A) obtained by making diol which is -400 mol ethylene oxide adduct react.

  The treatment agent for ceramic fibers of the present invention has an effect of excellent process passability because the fiber bundle is not easily broken during the process.

  The processing agent for ceramic fibers of the present invention contains a polyester resin (A) having a critical surface tension of 40 mN / m or less.

The critical surface tension of the polyester resin (A) contained in the ceramic fiber treating agent of the present invention is 40 mN / m or less, preferably 15 to 40 mN / m, and more preferably 25 to 37 mN / m. If the critical surface tension of the polyester (A) exceeds 40 mN / m, the wetting between the fiber treating agent and the ceramic fiber is poor, so that a large amount of treating agent is required and process passability is lowered.
<Measurement method of critical surface tension of high viscosity sample>
The critical surface tension of the polyester resin (A) contained in the ceramic fiber treating agent of the present invention can be measured using a fully automatic contact angle meter (PD-W, manufactured by Kyowa Interface Science Co., Ltd.).
(1) A mixed solution in which ethanol concentration is 0 mol%, 2 mol%, 4 mol%, 10 mol%, 20 mol%, 40 mol%, 60 mol%, and 100 mol% in a mixed solution of ethanol and water is prepared.
(2) A sample is applied on a glass plate (for example, length 76 mm × width 26 mm × thickness 1 mm), the aqueous medium or the like is removed by drying, and a sample of a dry film (thickness about 0.1 mm) is prepared.
(3) The above-mentioned fully automatic contact angle meter is set to the contact angle measurement mode, and the liquid mixture prepared in (1) is dropped on the dry film prepared in (2), and the contact angle is measured 10 times at 25 ± 1 ° C. And obtain the average value.
(4) The surface tension of the mixed solution prepared in (1) is measured by the above-described hanging drop method.
The x-axis is plotted as the surface tension of the liquid mixture prepared in (1), and the y-axis is plotted as the cosine of the average value of the contact angle when the liquid mixture prepared in (1) is dropped. Extrapolating the approximate straight line of this plot, the cosine of the contact angle is 1

The polyester resin (A) in the present invention is obtained by reacting a diol having an ethylene oxide adduct having an average addition mole number of ethylene oxide of 4 to 400 mol.
When the average added mole number of ethylene oxide is less than 4 moles, the crystallinity of the polyester resin becomes high, and the bundle property of the fiber bundle becomes too high. When the average added mole number of ethylene oxide exceeds 400 moles, the processability of the fiber bundle is lowered.
The diol contained in the polyester resin (A) can be used alone or in combination of two or more, but at least one of the one or two or more diols used is an average addition of ethylene oxide. The diol is an ethylene oxide adduct having a mole number of 4 to 400 moles, preferably 30 to 200 moles, and more preferably 40 to 120 moles.
The average added mole number may be an integer or a small number.
Ethylene oxide can be used in combination with 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, and 1,4-butylene oxide (hereinafter abbreviated as BO).
In the case of using two or more kinds in combination, any of block addition, random addition and combinations thereof may be used. The number of moles of AO added per molecule of aliphatic alkanediol is preferably 1 to 120 moles.

Examples of the diol that is an ethylene oxide adduct having an average addition mole number of ethylene oxide of 4 to 400 mol include aliphatic alkane diol, alicyclic diol, primary amine, and aromatic ring-containing divalent phenol.
The polyester resin (A) may contain a diol other than a diol that is an ethylene oxide adduct having an average addition mole number of ethylene oxide of 4 to 400 mol.

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.
Among ethylene glycol AO adducts, ethylene oxide adducts having an average addition mole number of ethylene oxide of 4 to 400 mol include, specifically, ethylene glycol EO 10 mol adduct, ethylene glycol EO 50 mol adduct. EO 100 mol adduct of ethylene glycol, EO 150 mol adduct of ethylene glycol, PO1 mol EO10 mol random adduct of ethylene glycol and EO 100 mol PO10 mol block adduct of ethylene glycol.
Among the AO adducts of aliphatic alkanediol having 3 to 4 carbon atoms, as an ethylene oxide adduct having an average addition mole number of ethylene oxide of 2 to 200, specifically, an EO 9 mol adduct of propylene glycol, Examples include a PO 1.3 mol EO 9 mol block adduct of propylene glycol, a PO 1.3 mol EO 22 mol block adduct of propylene glycol, and a BO 1.3 mol EO 22 mol random adduct of butylene glycol.

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

  Examples of the primary amine in the AO adduct of primary amine include primary amines having 1 to 18 carbon atoms such as methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine, and dodecylamine. As the alkylene oxide adduct of primary amine, there can be mentioned those obtained by adding AO having 2 to 4 carbon atoms.

Examples of the aromatic ring-containing divalent phenol in the AO adduct of the aromatic ring-containing divalent phenol include bisphenol A, bisphenol S, cresol, and hydroquinone.
Among the AO adducts of aromatic ring-containing divalent phenol, primary amine, alkane diol having 5 to 16 carbon atoms or alicyclic diol, having ethylene oxide having an average added mole number of 4 to 400 mol, Specifically, EO 4 mol adduct of bisphenol S, EO 20 mol adduct of bisphenol F, EO 60 mol adduct of bisphenol A, EO 150 mol BO 5 mol block adduct of bisphenol A and EO 300 mol PO10 mol random adduct of bisphenol A , Laurylamine EO 20 mol adduct, decanediol EO 60 mol adduct, 1,4-cyclohexanediol EO 60 mol adduct, and the like.

  Among these, from the viewpoint of processability of fiber bundles, aliphatic alkanediols and their AO adducts, AO adducts of alicyclic diols, AO adducts of primary amines, and AO additions of aromatic ring-containing dihydric phenols Products are preferred, and aliphatic alkanediols and their AO adducts, and AO adducts of aromatic ring-containing dihydric phenols are more preferred.

  Among diols which are ethylene oxide adducts having an average addition mole number of ethylene oxide of 4 to 400 mol, from the viewpoint of processability of the fiber bundle, EO30 to 120 mol adduct of bisphenol A and / or EO30 of ethylene glycol. A ~ 120 molar adduct is preferred.

  In the treating agent for ceramic fibers of the present invention, ethylene oxide having an average added mole number of ethylene oxide of 4 to 400 moles is preferably based on the weight of the polyester resin (A) from the viewpoint of processability of the fiber bundle. Is from 10 to 60% by weight, more preferably from 20 to 50% by weight.

The polyester resin (A) in the present invention may be a product obtained by reacting a dibasic acid with a diol, which is an ethylene oxide adduct having an average addition mole number of ethylene oxide of 4 to 400 mol.
Examples of the dibasic acid include dicarboxylic acids having 2 to 24 carbon atoms, specifically, saturated aliphatic dicarboxylic acids having 2 to 24 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, etc. ), Unsaturated aliphatic carboxylic acids having 2 to 24 carbon atoms (maleic acid, fumaric acid and the like), aromatic dicarboxylic acids having 2 to 24 carbon atoms (phthalic acid, terephthalic acid, isophthalic acid and the like), and 2 to 24 carbon atoms. And dicarboxylic anhydrides (such as maleic anhydride and phthalic anhydride).

The polyester resin (A) in the present invention preferably has a number average molecular weight (hereinafter abbreviated as Mn) of 1,000 to 100,000. When Mn is 1,000 to 100,000, appropriate convergence can be expressed. Mn is measured by a gel permeation chromatography (hereinafter referred to as GPC) method. Mn is more preferably 2,000 to 30,000, particularly preferably 3,000 to 20,000. Within this range, the convergence is further improved.
The conditions of GPC used for the measurement of Mn of the polyester resin (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% by weight
Injection volume: 10 μl
Standard: Polystyrene (Tosoh Corporation; TSK STANDARD
POLYSTYRENE

  As a method for producing the polyester resin (A), for example, dicarboxylic acid or its anhydride and diol are charged at a predetermined molar ratio, and the reaction temperature is 100 to 250 ° C. and the pressure is −0.1 to 1.2 MPa. The method of distilling water off is mentioned.

  As a method for producing the polyester resin (A), 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, tetraisopropoxy titanate and potassium oxalate titanate, and tetraisopropoxy titanate and potassium oxalate titanate are preferable from the viewpoint of reactivity and environmental impact. More preferred is potassium oxalate titanate.

The processing agent for ceramic fibers of the present invention contains at least one of a resin (B) other than the polyester resin (A), a surfactant (C) and other additives (D) in addition to the polyester resin (A). May be.
When the resin (B) other than the polyester resin (A) is contained, since the affinity with the matrix resin is improved when the resin composite material is prepared using the ceramic fiber bundle, the strength of the resin composite material is excellent. In addition, when the surfactant (C) is contained, the bundling agent attached to the inorganic fibers tends to be smooth, so that the scratch resistance of the inorganic fiber bundle is further improved.

  Resins (B) other than the polyester resin (A) include thermoplastic resins such as polyethylene resins, polypropylene resins, polystyrene resins, polyurethane resins, polyamide resins and acrylic resins, epoxy resins, (meth) acrylate modified resins and unsaturated polyesters. Examples thereof include thermosetting resins such as resins.

  Examples of the polyurethane resin include those derived from a polymer polyol, an organic diisocyanate, and, if necessary, a chain extender and / or a crosslinking agent.

  Examples of the polymer polyol include polyester polyol (for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, polycaprolactone diol, polyvalerolactone diol, and polyhexamethylene carbonate. Diol etc.); polyether polyol [polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene oxypropylene glycol, polyoxytetramethylene glycol, bisphenol alkylene oxide adducts of 2 to 4 carbon atoms, etc.] It is done.

  Specific examples of the organic diisocyanate include, for example, 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4′-dibenzyl diisocyanate. , 1,3- or 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate and other aromatic diisocyanates; ethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate and other aliphatic diisocyanates; isophorone And alicyclic diisocyanates such as diisocyanate (IPDI) and 4,4′-dicyclohexylmethane diisocyanate; and mixtures of two or more thereof.

  Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, polyalkylene glycol Epoxidized epoxy resin, polyurethane-based epoxy resin, glycidylated aliphatic alcohol, and the like.

  (Meth) acrylate-modified resins include (meth) acrylate-modified thermoplastic resins and vinyl ester resins. Examples of the (meth) acrylate-modified thermoplastic resin include modified products in which the hydroxyl group of a thermoplastic resin {polyurethane, polyester, polyether (polypropylene glycol, polyethylene glycol, etc.) having an alcoholic hydroxyl group is modified with (meth) acrylic acid. Examples include polyurethane (di- / mono-) (meth) acrylate, polyester (di- / mono-) (meth) acrylate, and polyether (di- / mono-) (meth) acrylate. In addition, (di- / mono-) (meth) acrylate means di (meth) acrylate and mono (meth) acrylate.

  As vinyl ester resin, bisphenol type epoxy resin (meth) acrylate modified product {terminal (meth) acrylate modified resin obtained by reaction of epoxy group of bisphenol A type epoxy resin and carboxyl group of (meth) acrylic acid, etc.} Etc.

As unsaturated polyester resin, what melt | dissolved the unsaturated polyester obtained by making the acid component and alcohol which contain (alpha), (beta) -unsaturated dicarboxylic acid react in a polymerizable unsaturated monomer is mentioned. Examples of the α, β-unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like, derivatives of these acid anhydrides and the like, and these may be used in combination of two or more. In addition, as necessary, as an acidic component other than α, β-unsaturated dicarboxylic acid, saturated dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, and acid anhydrides thereof, etc. The derivative may be used in combination with an α, β-unsaturated dicarboxylic acid. Examples of the alcohol include aliphatic glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, cyclohexane Alicyclic diols such as pentanediol and cyclohexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide (1 to 100 mol) adducts, aromatic diols such as xylene glycol, polyhydric alcohols such as trimethylolpropane and pentaerythritol, etc. These may be used in combination of two or more thereof.
Specific examples include, for example, a condensate of fumaric acid or maleic acid and an ethylene oxide adduct of bisphenol A, a condensate of fumaric acid or maleic acid and a propylene oxide adduct of bisphenol A, and fumaric acid or maleic acid and bisphenol. A condensate of A with an ethylene oxide propylene oxide adduct (which may be random or block) is included, and these condensates may be dissolved in a monomer such as styrene as necessary.

  The Mn of the resin (B) other than the polyester resin (A) is preferably 200 to 10,000, more preferably 350 to 3,000, and particularly preferably 380 to 2,500. When Mn is within this range, the strength of the resin composite material and the removability of the treating agent of the ceramic composite material are excellent.

Of the resins (B) other than the polyester resin (A), polyurethane resin, polyamide resin and thermosetting resin are preferable from the viewpoint of resin composite material strength and the like, more preferably polyurethane resin, epoxy resin and (meth) acrylate modified. A resin, particularly preferably an epoxy resin.
Examples of the epoxy resin include diglycidyl ether of bisphenol A (bisphenol A type epoxy resin).

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

  Nonionic surfactants include, for example, alkylene oxide [2 to 4 carbon atoms; ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, and combinations of two or more thereof, and the following surfactants. (Same in description of (C))] addition type nonionic surfactant [for example, alkylene oxide adduct of higher alcohol (carbon number 8-18) or higher fatty acid (carbon number 12-24) [weight average molecular weight (hereinafter referred to as Mw) Abbreviation) = 158-20,000]; alkylene of alkylphenol (carbon number 10-20), styrenated phenol (carbon number 14-62), styrenated cumylphenol or styrenated cresol (carbon number 15-61) Oxide adduct (Mw 500-5,000) or polyalkylene glycol (M 150 to 6,000) reacted with higher fatty acid; polyvalent (divalent to octavalent or higher) alcohol (C2-C32, for example, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitan, etc.) Alkylene oxide adduct (Mw 350 to 10,000) of an esterified product obtained by reacting with a higher fatty acid (12 to 24 carbon atoms such as lauric acid or stearic acid); higher alkylene oxide adduct of higher fatty acid amide (Mw 200 to 30,000); polyvalent (divalent to octavalent or higher) alcohol alkyl (carbon number 8 to 60) ether alkylene oxide adduct (Mw 220 to 30,000) and the like], and polyvalent (divalent to 8) Valence or higher) alcohol (carbon number 2 to 32) type nonionic surfactant [polyvalent alcohol Fatty acids (8 to 36 carbon atoms) esters, polyhydric alcohol alkyl (7-32 carbon atoms) ether, fatty acids (8 to 32 carbon atoms) alkanolamide, etc.) and the like.

  Examples of the anionic surfactant include carboxylic acids (saturated or unsaturated fatty acids having 8 to 22 carbon atoms) or salts thereof (salts such as sodium, potassium, ammonium and alkanolamine), aliphatic alcohols having 8 to 16 carbon atoms. A carboxymethylated salt of an aliphatic alcohol ether carboxylic acid having 8 to 24 carbon atoms (for example, carboxy of an alkylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms) Methylated products, etc.), sulfate esters [higher alcohol sulfate esters (sulfate esters of fatty acid alcohols having 8 to 18 carbon atoms)], higher alkyl ether sulfate salts [ethylene oxide of fatty acid alcohols of 8 to 18 carbon atoms ( 1 to 10 mol) adduct sulfate salt], sulfated oil (natural unsaturation) Fat or unsaturated wax that has been neutralized by sulfation), sulfated fatty acid ester (sulfurized and neutralized lower alcohol ester of unsaturated fatty acid), sulfated olefin (olefin having 12 to 18 carbon atoms) And sulfonates [alkylbenzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diester, α-olefin (carbon number 12 to 18) sulfonate, Igepon T type, etc.] and phosphorus Acid ester salt [higher alcohol (carbon number 8 to 60) phosphate ester salt, higher alcohol (carbon number 8 to 60) ethylene oxide adduct phosphate ester salt, alkyl (carbon number 8 to 60) phenol ethylene oxide adduct phosphoric acid Ester salts, etc.], alkylenephenols of alkylphenols (10-20 carbon atoms) Sulfate adducts (sodium salt, potassium salt, ammonium salt, alkanolamine salt, etc.), arylalkylphenol [styrenated phenol (carbon number 14-62), styrenated cumylphenol and Examples thereof include a sulfate ester salt of an alkylene oxide adduct (Mw 500 to 5,000) of styrenated cresol (carbon number 15 to 61) or the like].

  Examples of cationic surfactants include quaternary ammonium salt types [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.], amine salt types [stearin Acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Examples of amphoteric surfactants include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylbetaine, lauryldimethylbetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxysulfobetaine. And lauroylamidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl phosphate sodium, etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate etc.].

  Of the surfactants (C), preferred are anionic surfactants, nonionic surfactants, and mixtures of anionic surfactants and nonionic surfactants, and more preferred are alkylene oxide adducts of alkylphenols, aryls. Alkylene oxide alkylene oxide adduct, alkylphenol alkylene oxide adduct sulfate, arylalkylphenol alkylene oxide adduct sulfate, and mixtures thereof, particularly preferred are arylalkylphenol alkylene oxides (ethylene oxide and Propylene oxide) adducts and sulfuric acid ester salts of alkylene oxides (ethylene oxide and propylene oxide) adducts of arylalkylphenols and these It is a compound.

Examples of the other additive (D) 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).

The contents of the polyester resin (A), the resin (B) other than the polyester resin (A), the surfactant (C), and other additives (D) in the sizing agent of the present invention are as follows.
The content of (A) is preferably 2 to 100% by weight, more preferably 5 to 95% by weight, based on the total weight of (A), (B), (C) and (D). Particularly preferred is 10 to 90% by weight.
The content when (B) is used is preferably 5 to 70% by weight, more preferably 10 to 55%, based on the total weight of (A), (B), (C) and (D). % By weight, particularly preferably 15 to 40% by weight.
When (C) is used, its content is preferably 0.5 to 20% by weight, more preferably 1 based on the total weight of (A), (B), (C) and (D). -15% by weight, particularly preferably 2-10% by weight.
When (D) is used, its content is preferably 10 to 60% by weight, more preferably 20 to 55, based on the total weight of (A), (B), (C) and (D). % By weight, particularly preferably 30 to 50% by weight.

The ceramic fiber treatment agent dispersion of the present invention is preferably formed by dispersing the ceramic fiber treatment agent of the present invention in a solvent.
Moreover, it is preferable that the processing agent solution for ceramic fibers of this invention dissolves the processing agent for ceramic fibers of this invention in a solvent.
By dissolving or dispersing the treating agent for ceramic fibers in a solvent, it becomes easy to adjust the amount of the treating agent for ceramic fibers attached to the fiber bundle to an appropriate amount.
Examples of the solvent include known solvents such as water and organic solvents [lower alcohols having 1 to 4 carbon atoms (methanol, ethanol, isopropanol, etc.), ketones having 3 to 6 carbon atoms (acetone, ethyl methyl ketone, methyl isobutyl ketone, etc.) ), Glycols having 2 to 6 carbon atoms (ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, etc.) and their monoalkyl (1 to 2 carbon atoms) ethers, dimethylformamide and alkyl esters of 3 to 5 carbon atoms (acetic acid Methyl and ethyl acetate) and the like. Two or more of these may be used in combination. Among these, water and a mixed solvent of an organic solvent and water are preferable from the viewpoint of safety and the like, and water is more preferable.

From the viewpoint of cost and the like, the treatment agent dispersion for ceramic fibers of the present invention preferably has a high concentration during distribution. That is, it is possible to reduce transportation costs, storage costs, etc. by distributing them at a high concentration.
The concentration (content ratio of components other than the aqueous medium) when the treating agent dispersion for ceramic fibers is high is preferably 30 to 80% by weight, more preferably 40 to 70, from the viewpoint of storage stability and the like. % By weight.

The method for producing the ceramic fiber treating agent dispersion of the present invention is not particularly limited. For example, a solvent is added to the ceramic fiber treating agent of the present invention obtained by the above-described method to produce a fiber sizing agent composition. Can be dissolved or emulsified and dispersed in a solvent.
The temperature at which the ceramic fiber treatment agent 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 ease of mixing.
The time for dissolving or emulsifying and dispersing the ceramic fiber treating agent in the solvent is preferably 1 to 20 hours, and more preferably 2 to 10 hours.
When the ceramic fiber treating agent is dissolved or emulsified and dispersed in a solvent, known mixing devices, dissolving devices and emulsifying and dispersing devices can be used. Specifically, stirring blades (blade shape: chi-shaped and Three-stage paddles, etc.), Nauta mixer [manufactured by Hosokawa Micron Co., Ltd.], ribbon mixer, conical blender, mortar mixer, universal mixer {universal mixing stirrer "5DM-L" [manufactured by Sanei Seisakusho] etc.] and Henschel mixer [Nippon Coke Industry Co., Ltd.] etc. can be used.

  Examples of the ceramic fiber of the present invention include oxide ceramics and non-oxide ceramics.

  Specific examples of oxide ceramics include aluminum, magnesium, silicon, yttrium, indium, uranium, calcium, scandium, tantalum, niobium, neodymium, lanthanum, ruthenium, rhodium, beryllium, titanium, tin, strontium, barium, zinc, zirconium. And oxides of elements such as iron and complex oxides of these metals.

Specific examples of non-oxide ceramics include carbides, nitrides and borides. Specific examples of the carbide include carbides of elements such as silicon, titanium, zirconium, aluminum, uranium, tungsten, tantalum, hafnium, boron, iron, and manganese, and composite carbides of these elements. Examples of this composite carbide include inorganic substances obtained by heating and baking polytitanocarbosilane or polyzirconocarbosilane.
Specific examples of nitrides include nitrides of elements such as silicon, boron, aluminum, magnesium, and molybdenum, composite oxides of these elements, and sialon.
Specific examples of borides include borides of elements such as titanium, yttrium, and lanthanum, and platinum boride lanthanoids such as CeCoB ₂ , CeCo ₄ B ₄ , and ErRh ₄ B ₄ .

  Among these, from the viewpoint of the strength of the molded body, non-oxide ceramic fibers are preferable, and silicon carbide fibers are more preferable. Two or more of these fibers may be used in combination.

  The ceramic fiber bundle of the present invention is a fiber bundle in which about 100 to 30,000 fibers are bundled, and at least one kind of fiber selected from the group consisting of these fibers is used as the ceramic fiber treatment agent or ceramic fiber. It is obtained by treating with a treating agent dispersion.

  Examples of the method for treating the ceramic fiber bundle include a spray method or a dipping method. The adhesion amount of the treating agent for ceramic fiber on 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. Within this range, the processability of the fiber bundle is excellent.

  The ceramic fiber bundle of the present invention is characterized in that the fiber bundle treated with the ceramic fiber treatment agent or ceramic fiber treatment dispersion of the present invention is a reinforcing fiber, and a resin or ceramic is a matrix as described above. To do. There is no restriction | limiting in particular in the form of this ceramic fiber bundle, Two-dimensional or three-dimensional textiles, such as a plain weave and a satin weave, a unidirectional sheet-like thing, or those laminated bodies may be sufficient.

A ceramic fiber bundle made of a matrix resin is manufactured through a resin composite intermediate.
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. Of the matrix resins, preferred are thermosetting resins, more preferred are epoxy resins, unsaturated polyester resins and vinyl ester resins, and particularly preferred are epoxy resins.

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

  The weight ratio of the matrix resin to the ceramic fiber bundle (matrix resin / fiber bundle) is not particularly limited, but is preferably 10/90 to 90/10, and more preferably 20/90, from the viewpoint of the strength of the molded body. It is 80-70 / 30, Most preferably, it is 30 / 70-60 / 40. When the catalyst is contained, 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. Especially preferably, it is 1-3 weight%.

  The resin composite intermediate is a matrix resin that is melted by heat (melting temperature: 60 to 150 ° C.) or a matrix resin that is diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, etc.) into the fiber bundle. It can be produced by impregnation. When a solvent is used, it is preferable to dry the prepreg and remove the solvent.

  The ceramic fiber bundle of the present invention is obtained by molding the resin composite intermediate. 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.

  There are no particular restrictions on the method of compositing the ceramic composite material comprising the ceramic matrix. However, after the preform woven with fibers is coated with boron nitride or carbon as the interface layer, the precursor polymer of the ceramic, eg, polycarbohydrate, is coated. Impregnating a polymer impregnation / firing method in which silane, polymetallocarbosilane, polysilazane, etc. are dissolved in a solvent such as xylene, impregnated and dried, and then heated and fired to form a composite, slurry of matrix raw material powder, A method of pressure sintering at high temperature by hot pressing, etc., a sol-gel method using matrix element alkoxide as a raw material, a chemical vapor deposition method in which a matrix is formed by reaction of reaction gas at high temperature, and impregnating molten metal at high temperature A reactive sintering method for converting to ceramics by reaction can be used. There is also a method in which a part of the matrix is formed by chemical vapor deposition and then the remaining space is densified by reaction sintering or polymer impregnation / firing.

  As the ceramic matrix, oxide ceramics, non-oxide ceramics, glass, crystallized glass, a mixture thereof, and those obtained by dispersing particles of these ceramics are preferable.

  Specific examples of oxide ceramics include aluminum, magnesium, silicon, yttrium, indium, uranium, calcium, scandium, tantalum, niobium, neodymium, lanthanum, ruthenium, rhodium, beryllium, titanium, tin, strontium, barium, zinc, zirconium. And oxides of elements such as iron and complex oxides of these metals.

  Specific examples of non-oxide ceramics include carbides, nitrides and borides. Specific examples of the carbide include carbides of elements such as silicon, titanium, zirconium, aluminum, uranium, tungsten, tantalum, hafnium, boron, iron, and manganese, and composite carbides of these elements. Examples of this composite carbide include inorganic substances obtained by heating and baking polytitanocarbosilane or polyzirconocarbosilane.

Specific examples of nitrides include nitrides of elements such as silicon, boron, aluminum, magnesium, and molybdenum, composite oxides of these elements, and sialon. Specific examples of borides include borides of elements such as titanium, yttrium, and lanthanum, and platinum boride lanthanoids such as CeCoB ₂ , CeCo ₄ B ₄ , and ErRh ₄ B ₄ .

Specific examples of the glass include amorphous glass such as silicate glass, phosphate glass, and borate glass. Examples of the crystallized glass, the main crystal phase is β- Supujumen _{LiO 2} -Al2O ₃ -MgO-SiO 2 based glass and _{LiO 2 -Al 2 O 3 -MgO-} SiO 2 -Nb 2 O 5 -based glass the main crystal phase is cordierite _MgO-Al 2 O 3 -SiO ₂ based glass, the main crystal phase is barium male solid light _BaO-MgO-Al 2 O 3 -SiO ₂ based glass, the main crystalline phase is mullite or Examples include BaO—Al ₂ O ₃ —SiO ₂ -based glass that is hexacelsian, and CaO—Al ₂ O ₃ —SiO ₂ -based glass whose main crystal phase is anorthite. The crystal phase of these crystallized glasses may contain cristobalite. Examples of the ceramic in the present invention include solid solutions of the various ceramics described above.

  As a specific example of the particle dispersion strengthening of ceramic, an inorganic material selected from silicon nitride, silicon carbide, zirconium oxide, magnesium oxide, potassium titanate, magnesium borate, zinc oxide, titanium boride and mullite in the above ceramic matrix. Examples thereof include a ceramic in which 0.1 to 60% by volume of spherical particles, polyhedral particles, plate-like particles, rod-like particles, and whiskers are uniformly dispersed. The particle size of spherical particles and polyhedral particles is 0.1 μm to 1 mm, and the aspect ratio of plate-like particles, rod-like particles and whiskers is generally 1.5 to 1000.

  The weight ratio of the ceramic matrix to the fiber bundle (ceramic matrix / fiber bundle) is not particularly limited, but is preferably 10/90 to 50/50, more preferably 20/80, from the viewpoint of the strength of the molded body. ~ 40/60.

EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention further, this invention is not limited to these.
<Production Example 1 Production of bisphenol A EO 60 mol adduct (a-1)>
Into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 228 parts by weight of bisphenol A (1 part by mole), 400 parts by weight of toluene, 2 parts by weight of potassium hydroxide were added, and the atmosphere was replaced with nitrogen. The temperature was raised to 100 ° C., and 2640 parts by weight (60 mol parts) of EO were 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. The EO 60 mol adduct (a-1) of bisphenol A was obtained.

<Production Example 1 Production of Polyester Resin (A-1)>
Bisphenol A ethylene oxide 2-mole adduct "New Pole BPE-20" [manufactured by Sanyo Chemical Industries, Ltd.] 316 parts by weight (1 mole part), terephthalic acid 142 parts by weight (0.86 mole part) and titanium oxalate 3 parts by weight of potassium acid was reacted in a glass reaction vessel under reduced pressure at 230 ° C. to 0.001 MPa for 15 hours while distilling off water. Further, 263 parts by weight (0.39 parts by mole) of bisphenol A ethylene oxide 10 mole adduct “New Pole BPE-100” (manufactured by Sanyo Chemical Industries, Ltd.) was added to the reaction mixture at 150 ° C. and normal pressure for 2 hours. The reaction was carried out to obtain 690 parts by weight of (A-1). The content of ethylene oxide in (A-1) is 25% by weight, and the number average molecular weight of (A-1) is 1300.

<Production Example 2 Production of Polyester Resin (A-2)>
Bisphenol A ethylene oxide 10 mol adduct “New Pole BPE-100” [manufactured by Sanyo Chemical Industries, Ltd.] 263 parts by weight (0.39 mol parts) bisphenol A EO 60 mol adduct (a-1) 263 wts 690 parts by weight of (A-2) was obtained in the same manner as in Example 1 except that the amount was changed to 0.09 parts by weight (0.09 mole part). The content of ethylene oxide in (A-2) is 35% by weight, and the number average molecular weight of (A-2) is 3000.

<Production Example 3 Production of Polyester Resin (A-3)>
Bisphenol A ethylene oxide 10 mol adduct "New Pole BPE-100" [manufactured by Sanyo Chemical Industries Ltd.] 263 parts by weight (0.39 mol parts) polyoxyethylene glycol "PEG1000" [manufactured by Sanyo Chemical Industries Ltd. 690 parts by weight of (A-3) were obtained in the same manner as in Example 1 except that the amount was changed to 381 parts by weight (0.26 parts by mole). The content of ethylene oxide in (A-3) is 38% by weight, and the number average molecular weight is 1700.

<Production Example 4 Production of Polyester Resin (A-4)>
Bisphenol A ethylene oxide 10 mol adduct "New Pole BPE-100" [manufactured by Sanyo Chemical Industries Ltd.] 263 parts by weight (0.39 mol parts) polyoxyethylene glycol "PEG10000" [Sanyo Kasei Kogyo Co., Ltd. [Product]] 800 parts by weight of (A-4) was obtained in the same manner as in Example 1, except that the amount was changed to 359 parts by weight (0.04 mole part, 226 moles of ethylene oxide adduct). The content of ethylene oxide in (A-4) is 45% by weight, and the number average molecular weight of (A-4) is 15000.

<Production Example 5 Production of Polyester Resin (A-5)>
142 parts by weight (0.86 parts by mole) of terephthalic acid, 162 parts by weight (0.98 parts by mole), and 10 mol of bisphenol A ethylene oxide adduct “New Pole BPE-100” [manufactured by Sanyo Chemical Industries, Ltd.] 263 Implemented except changing the weight part (0.39 mol part) to 359 parts by weight (0.02 mol part) of EO adduct "New Pole PE-108" (manufactured by Sanyo Chemical Industries, Ltd.) of polyoxypropylene glycol In the same manner as in Example 1, 800 parts by weight of (A-5) was obtained. The content of ethylene oxide in (A-5) is 36% by weight, and the number average molecular weight of (A-5) is 20000.

<Comparative Production Example 1 Production of Polyester Resin (A′-1)>
Bisphenol A ethylene oxide 2-mole adduct "New Pole BPE-20" [manufactured by Sanyo Chemical Industries, Ltd.] 316 parts by weight (1 mole part), terephthalic acid 142 parts by weight (0.86 mole part) and titanium oxalate 3 parts by weight of potassium acid was reduced to 0.001 MPa at 230 ° C. in a glass reaction vessel and reacted for 15 hours while distilling off water to obtain 430 parts by weight of (A′-1). The content of ethioxide in (A′-1) is 0% by weight, and the number average molecular weight is 3000.

<Examples 1-10 and Comparative Examples 1-2>
After mixing each raw material of Table 1, and obtaining the processing agent for ceramic fibers, water or an organic solvent is added to this, and the whole is made 100 weight part, The processing agent dispersion for ceramic fibers and ceramic fiber Treatment solution (Examples 1 to 10 and Comparative Examples 1 to 2).
In addition, each component used for the Example is as follows.
PEG2000: “PEG-2000”, “Sanyo Chemical Industries, Ltd.”
Surfactant: Propylene oxide / ethylene oxide adduct of styrenated phenol “Soprophor 796 / P” [manufactured by Rhodia Nippon Co., Ltd.]

About Examples 1-10 and Comparative Examples 1-2, the critical surface tension of polyester resin (A), the bundling property of the processing agent for ceramic fibers, and process passability were evaluated, and the results are shown in Table 1.
<Evaluation of critical surface tension>
The test sample was coated on a glass plate (length 76 mm × width 26 mm × thickness 1 mm) to prepare a sample with a coating (thickness about 0.1 mm).
About the obtained test sample, the surface tension of the surface of the test sample is known in an atmosphere of 23 ° C. and 50% RH using an image processing type / solid-liquid interface analysis system (Dropmaster 500 manufactured by Kyowa Interface Science Co., Ltd.). A wet tension test mixture (ethanol / water) was added dropwise, and the contact angle was measured. The measurement was performed on five test samples, and the average value was obtained. The points (five or more) obtained from cos θ (Y axis) calculated from the contact angle θ and the surface tension (X axis) of the test liquid mixture are plotted on the XY coordinates, and the minimum of these points is plotted. The surface tension (X axis) corresponding to the intersection of the straight line obtained by the square method and cos θ = 1 was defined as the critical surface tension (mN / m).
<Evaluation of convergence>
It was obtained by diluting an aqueous dispersion for fiber treatment with water, immersing silicon carbide fibers (average diameter 7.5 μm, number of filaments 1600) to impregnate the treatment agent, and drying with hot air at 190 ° C. for 3 minutes. A carbon fiber bundle was prepared.
The obtained 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.
<Evaluation of process passability>
When the numerical value of convergence is less than 10 cm, Δ, 10-20 cm is indicated by ◯, and the case where it is larger than 20 cm is indicated by ×. ○ is a preferred range in the present invention.

  As can be seen from Table 1, the fiber bundle obtained by treating with the ceramic fiber treating agent of the present invention exhibits excellent process passability.

By using the ceramic fiber treating agent of the present invention, a ceramic fiber bundle can be produced efficiently. In addition, the composite material using the fiber bundle obtained by treating with the ceramic fiber treating agent of the present invention as a reinforcing fiber is suitably used in the fields of civil engineering / architecture, gas turbines, engine members, sports equipment, aerospace, and the like. it can.

Claims (9)

  A processing agent for ceramic fibers containing a polyester resin (A) having a critical surface tension of 40 mN / m or less, wherein the polyester resin (A) is an ethylene oxide having an average added mole number of ethylene oxide of 4 to 400 mol. The processing agent for ceramic fibers which is a polyester resin (A) obtained by making the diol which is an adduct react.   The processing agent for ceramic fibers according to claim 1, wherein the content of the ethylene oxide in the polyester resin (A) is 10 to 60% by weight based on the weight of the polyester resin (A).   The processing agent for ceramic fibers according to claim 1 or 2, wherein the polyester resin (A) is a polyester resin (A) obtained by reacting bisphenol A and / or an ethylene oxide adduct of ethylene glycol.   The number average molecular weight of the said polyester resin (A) is 1,000-100,000, The processing agent for ceramic fibers in any one of Claims 1-3.   Furthermore, the processing agent for ceramic fibers in any one of Claims 1-4 containing 1 or more types of resin chosen from the group which consists of a polyurethane resin, a polyamide resin, an epoxy resin, a (meth) acrylate modified resin, and unsaturated polyester. .   The processing agent dispersion for ceramic fibers formed by disperse | distributing the processing agent for ceramic fibers in any one of Claims 1-5 in water or an organic solvent.   The processing agent solution for ceramic fibers formed by melt | dissolving the processing agent for ceramic fibers in any one of Claims 1-5 in water or an organic solvent.   A ceramic fiber bundle obtained by treating ceramic fibers with the sizing agent dispersion for ceramic fibers according to claim 6 or the sizing agent solution for ceramic fibers according to claim 7.   A composite material obtained by treating a resin or ceramic with the ceramic fiber bundle according to claim 8.