JP2020002518A - Sizing agent for fiber, fiber bundle, fiber product, prepreg and molded body - Google Patents

Abstract

To provide a sizing agent for fiber achieving both of openability and bundling property.SOLUTION: There is provided a sizing agent for fiber containing a polymer (A) and a compound (B) other than the polymer (A), in which the polymer (A) is a specific compound having a polyoxyethylene chain with molecular weight of 3,000 to 50,000 and/or a polycaprolactone chain with molecular weight of 3,000 to 50,000, the melting point of the polymer (A) is 25 to 70°C, number average molecular weight of the polymer (A) is 3,000 to 50,000, the compound (B) is at least one kind selected from a group consisting of polyurethane, polyamide, polyester, and a compound having an epoxy group, and weight percentage of the polymer (A) is 1 to 50 wt.% based on weight of a solid component contained by the sizing agent for fiber.SELECTED DRAWING: None

Description

  The present invention relates to a fiber sizing agent, a fiber bundle, a fiber product, a prepreg, and a molded article.

BACKGROUND ART Fiber-reinforced composite materials in which fibers are combined with a matrix resin such as a compound having an epoxy group, an unsaturated polyester, and a phenol resin are widely used in sports, leisure, aerospace, and the like. Organic fibers such as polyamide fibers, aramid fibers, polyethylene fibers and polyester fibers and inorganic fibers such as glass fibers and carbon fibers are used as fibers used in these composite materials.
These fibers are usually manufactured in the form of filaments or tows, and further processed into unidirectionally aligned sheets, tapes, filament windings, woven fabrics, chopped fibers, and the like.
In the processing of such fibers, in order to obtain a high-quality processed product, a property (opening property) in which the fibers are easily thinned and spread without gaps with a weak contact pressure is required.
Here, the conventional fiber sizing agent is usually in the form of an emulsion or a solution, and as the contained resin, polyurethane, polyester, a compound having an epoxy group, and a combination thereof are proposed. For example, in Patent Documents 1 and 2, a condensate of an unsaturated dibasic acid and an alkylene oxide adduct of a bisphenol is used in combination with a compound having an epoxy group. However, the sizing agents containing polyesters described in these patent documents exhibit good sizing properties, but are insufficient with respect to the above-mentioned fiber opening properties.
In addition, the sizing property and the opening property are in a contradictory relationship, and it has been difficult for the conventional sizing agent for fibers to achieve both the opening property and the sizing property at a high level.

Patent No. 2957406 JP-B-57-49675

  An object of the present invention is to provide a sizing agent for fibers that has both openability and sizing property.

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, the present invention relates to a fiber sizing agent containing a polymer (A) and a compound (B) other than the polymer (A),
Wherein the polymer (A) is an alkylene oxide adduct (A1) having 2 to 4 carbon atoms to a compound (a) having 1 to 8 hydroxyl groups in one molecule, polycaprolactone (A2), and the alkylene oxide At least one selected from the group consisting of an adduct (A1) and an ester (A3) of a carboxylic acid,
The polymer (A) has a melting point of 25 to 70 ° C,
The number average molecular weight of the polymer (A) is 3,000 to 50,000,
The polymer (A) has a polyoxyethylene chain having a molecular weight of 3,000 to 50,000 and / or a polycaprolactone chain having a molecular weight of 3,000 to 50,000,
The compound (B) is at least one selected from the group consisting of polyurethane, polyamide, polyester and a compound having an epoxy group;
A fiber sizing agent in which the weight ratio of the polymer (A) is 1 to 50% by weight based on the weight of the solid content contained in the fiber sizing agent; carbon fiber, glass fiber, aramid fiber, ceramic fiber A fiber bundle obtained by treating at least one fiber selected from the group consisting of a metal fiber, a mineral fiber, a rock fiber and a slug fiber with the fiber sizing agent; a fiber product containing the fiber bundle; A prepreg comprising the fibrous product as a reinforcing fiber and a thermoplastic resin (E1) or a thermosetting resin (E2) as a matrix; a molded article obtained by molding the prepreg.

  The fiber bundle treated using the fiber sizing agent of the present invention has an effect of being excellent in opening property and sizing property.

It is a figure showing arrangement of a carbon fiber bundle in evaluation of spreadability.

The fiber sizing agent of the present invention contains a polymer (A) and a compound (B) other than the polymer (A),
Wherein the polymer (A) is an alkylene oxide adduct (A1) having 2 to 4 carbon atoms to a compound (a) having 1 to 8 hydroxyl groups in one molecule, polycaprolactone (A2), and the alkylene oxide At least one selected from the group consisting of an adduct (A1) and an ester (A3) of a carboxylic acid,
The polymer (A) has a melting point of 25 to 70 ° C.,
The number average molecular weight of the polymer (A) is 3,000 to 50,000,
The polymer (A) has a polyoxyethylene chain having a molecular weight of 3,000 to 50,000 and / or a polycaprolactone chain having a molecular weight of 3,000 to 50,000,
The weight ratio of the polymer (A) is 1 to 50% by weight based on the weight of the solid content contained in the fiber sizing agent.

As described above, the polymer (A) includes an alkylene oxide adduct (A1) having 2 to 4 carbon atoms to the compound (a) having 1 to 8 hydroxyl groups in one molecule, polycaprolactone (A2), And at least one selected from the group consisting of the alkylene oxide adduct (A1) and an ester (A3) of a carboxylic acid.
As described later in detail, the polymer (A) is a “polymer” having a number average molecular weight of 3,000 or more and having a group derived from alkylene oxide or caprolactone as a constituent unit.

The compound (a) having 1 to 8 hydroxyl groups in one molecule is preferably a compound having 1 to 20 carbon atoms.
Specifically, alcohols having 1 to 8 carbon atoms having 1 to 20 carbon atoms (methanol, ethanol, propanol, decanol, ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, glycerin, trimethylolpropane, pentane Erythritol and sorbitol), etherified products of 1 to 8 valent alcohols having 1 to 20 carbon atoms [diglycerin and polyglycerin (3 to 6-mer), etc.] and sugars having 1 to 20 carbon atoms (shown Sugar and the like).

  Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, and 1,2-, 1,3-, 1,4- or 2,3-butylene oxide. Is mentioned.

The alkylene oxide adduct (A1) has a polyoxyethylene chain having a molecular weight of 3,000 to 50,000.
When the polymer does not contain a molecule having a polyoxyethylene chain having a molecular weight of 3,000 or more, the convergence deteriorates.
In addition, when a molecule having a polyoxyethylene chain having a molecular weight of 50,000 or less is not contained, the spreadability deteriorates.
In addition, from the viewpoint of coexistence of the convergence property and the opening property, the molecular weight of the polyoxyethylene chain of (A1) is preferably 4,000 to 20,000.

  The above (A1) can be produced by a method of adding an alkylene oxide having 2 to 4 carbon atoms to the compound (a) having 1 to 8 hydroxyl groups in one molecule by a known method.

  Examples of the polycaprolactone (A2) include poly-ε-caprolactone and adducts of caprolactone (such as ε-caprolactone) to the compound (a) having 1 to 8 hydroxyl groups in one molecule. .

The polycaprolactone (A2) has a polycaprolactone chain having a molecular weight of 3,000 to 50,000.
When a molecule having a polycaprolactone chain having a molecular weight of 3,000 or more is not contained, convergence deteriorates.
In addition, when a molecule having a polycaprolactone chain having a molecular weight of 50,000 or less is not contained, the spreadability deteriorates.
Further, from the viewpoint of coexistence of the sizing property and the opening property, the molecular weight of the polycaprolactone chain contained in (A2) is preferably 4,000 to 20,000.

The above-mentioned poly-ε-caprolactone can be produced by a method such as ring-opening polymerization of ε-caprolactone by a known method.
The above-mentioned caprolactone adduct to compound (a) having 1 to 8 hydroxyl groups in one molecule is obtained by adding caprolactone to compound (a) having 1 to 8 hydroxyl groups in one molecule by a known method. For example.

Next, the ester (A3) of the alkylene oxide adduct (A1) and a carboxylic acid will be described.
The carboxylic acid used in the esterification reaction with (A1) is a compound having a carboxy group, specifically, a linear aliphatic carboxylic acid having 2 to 20 carbon atoms, an alicyclic carboxylic acid having 4 to 15 carbon atoms. Examples include acids, aromatic carboxylic acids having 7 to 16 carbon atoms, and polymers having a carboxy group.
Examples of the linear aliphatic carboxylic acid having 2 to 20 carbon atoms include acetic acid, 1-propionic acid, 1-butanoic acid, 1-pentanoic acid, 1-hexanoic acid, 1-heptanoic acid, 1-octanoic acid, and oxalic acid. Acid, malonic acid, dipropylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3-methylglutaric Acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, azelaic acid, sebacin Acid, undecandioic acid, dodecandioic acid, pentadecandioic acid, tetradecandiodic acid, heptadecandioic acid, octadecandioic acid, nonadecandioic acid, eicosandioic acid and the like.
Examples of the alicyclic carboxylic acid having 4 to 15 carbon atoms include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, cyclopropanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Acids, cyclohexene dicarboxylic acid, dicyclohexyl-4,4′-dicarboxylic acid, camphoric acid and the like.
Examples of the aromatic carboxylic acid having 7 to 16 carbon atoms include benzoic acid, naphthalene carboxylic acid, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, naphthalenedicarboxylic acid, and 4,4- Examples include biphenyl dicarboxylic acid, orthophthalic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, and diphenyl sulfone dicarboxylic acid.

  Examples of the polymer having a carboxy group include a polyolefin having a carboxy group, a polycarbonate having a carboxyl group, a polyamide having a carboxyl group, a polyimide having a carboxyl group, and a polyurethane having a carboxyl group. Is a polyolefin having a carboxy group.

  Examples of the polyolefin having a carboxy group include polyolefin having no carboxy group (PA) [polyolefin having no carbon-carbon double bond (hereinafter sometimes abbreviated as “C ＝ C bond”) in the molecule. (PA1) and a polyolefin (PA2) having a CＣC bond in the molecule] modified with a compound (x) having both a C ＝ C bond and a carboxy group in the molecule.

Examples of the olefin constituting the polyolefin (PA1) having no C ＝ C bond in the molecule include C2-30 alkenes.
Examples of the C2-30 alkene include ethylene, propylene, 1- or 2-butene, isobutene, 1-hexene, 1-decene and 1-dodecene.

Examples of the polyolefin (PA1) include (co) polymers containing ethylene units [high, medium or low density polyethylene, and ethylene and C4-30 unsaturated monomers (1-butene, 2-butene and 1-butene). And a propylene unit-containing (co) polymer [polypropylene, and propylene and a C4-30 unsaturated monomer (1-butene, 2-butene, 1-hexene and 1, And a copolymer containing ethylene units and propylene units [propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, propylene / ethylene / 1- Alkene (C = 5-20) copolymer, ethylene / propylene / 1,4-hexadiene copolymer, etc.] and polybutene (poly-1-butene and poly-2-butene) Emissions, etc.) and the like.
Of these, preferred are propylene / ethylene copolymer, propylene / 1-butene copolymer and propylene / ethylene / 1-butene copolymer, and more preferred is propylene / 1-butene copolymer. .
In addition, "propylene / ethylene copolymer" indicates that "propylene" and "ethylene" before and after "/" are copolymerized, and the same description method will be used hereinafter.

The polyolefin (PA1) can be obtained by (co) polymerizing the C2-30 alkene by a known method.
The polyolefin (PA1) is, for example, Tuffmer XM5070 [manufactured by Mitsui Chemicals, Inc.], Tuffmer XM5080 [manufactured by Mitsui Chemicals, Inc.], VESTOPLAST750 (manufactured by Evonik), Versify 3000 [manufactured by Dow Chemical Co., Ltd.], or the like. As can be obtained from the market.

The polyolefin having a C ＝ C bond in the molecule (PA2) preferably has a C ＝ C bond at a molecular terminal.
Further, the number of C ＝ C bonds in the polyolefin (PA2) is preferably from 0.1 to 20 per 1,000 carbons from the viewpoint of copolymerizability with (x) and addition reactivity. The number is more preferably 0.3 to 18, particularly preferably 0.5 to 15.
Here, the number of C ＝ C bonds is an integral value of a peak (4.6 to 4.8 ppm) derived from a double bond obtained from ¹ H-NMR (nuclear magnetic resonance) spectroscopy of polyolefin (PA2). Can be calculated from

  The polyolefin having a C を 持 つ C bond in the molecule (PA2) can be obtained by producing by a known production method such as the following polymerization method and thermal degradation method.

  Examples of the polymerization method include a method of using a diene or the like as a monomer and leaving an unsaturated group in a skeleton.

As the thermal degradation method, the above-mentioned polyolefin (PA1) is continuously or discontinuously applied at a temperature of 300 ° C. or more and 450 ° C. or less for 0.5 to 10 hours in the absence of an organic peroxide under nitrogen aeration. A method of thermal degradation (thermal degradation method 1); and a method of continuous or discontinuous thermal degradation at a temperature of 180 ° C or more and less than 300 ° C for 0.5 to 10 hours in the presence of an organic peroxide ( Thermal degradation method 2) and the like.
In both cases (thermal degradation method 1) and (thermal degradation method 2), a method of continuously thermal degradation is preferable from an industrial viewpoint.
Among these (thermal degradation method 1) and (thermal degradation method 2), the method of (thermal degradation method 1) in which one having a larger number of C ＝ C bonds at the molecular terminals is easily obtained is preferable.

Examples of the compound (x) having both a C ＝ C bond and an acid group in the molecule include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, salts thereof (such as alkali metal salts) and unsaturated dicarboxylic anhydrides. And the like.
Examples of unsaturated monocarboxylic acids include linear aliphatic unsaturated monocarboxylic acids having 3 to 24 carbon atoms (hereinafter may be abbreviated as C) (such as acrylic acid and methacrylic acid), and C7 to C24 alicyclic. Unsaturated monocarboxylic acids (cyclohexenecarboxylic acid, cycloheptenecarboxylic acid, bicycloheptenecarboxylic acid, methyltetrahexenecarboxylic acid, etc.) and C7-24 aromatic unsaturated monocarboxylic acids (4-vinylbenzoic acid, etc.) And the like.
Examples of the unsaturated dicarboxylic acid include C4-24 linear aliphatic unsaturated dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc.), and C8-24 alicyclic unsaturated dicarboxylic acids (cyclo Examples include hexenedicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid, and methyltetrahydrophthalic acid) and C8-24 aromatic unsaturated dicarboxylic acids (such as 4,4'-stilbenedicarboxylic acid).
Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride and citraconic anhydride.

As a preferable method for modifying the polyolefin (PA) having no carboxy group with the above (x), the above (PA) and the above (x) may be modified in the presence of a radical initiator or a radical initiator. And a method of performing an addition reaction in the absence of an agent.
In addition, when the addition is carried out using a radical initiator, it is preferable not to use a radical initiator because (x) suppresses self-polymerization, and even when it is used unavoidably, it is 0.3% by weight based on polyolefin (PA). %.

  The polyolefin having a carboxy group can be obtained from the market as UMEX 1010 [manufactured by Sanyo Chemical Industries, Ltd.] or the like.

The ester (A3) of the alkylene oxide adduct (A1) and the carboxylic acid can be obtained by a known method, for example, by reacting the alkylene oxide adduct (A1) with the carboxylic acid.
The ester (A3) can also be obtained by a transesterification method using an ester of an alcohol and a carboxylic acid other than (A1) and an alkylene oxide adduct (A1).

The melting point of the polymer (A) is 25 to 70 ° C. as described above. When the melting point is lower than 25 ° C., the convergence deteriorates. When the melting point exceeds 70 ° C., the spreadability deteriorates.
In addition, the melting point of the polymer (A) is preferably from 40 to 65 ° C. from the viewpoint of achieving both convergence and openability.
The melting point can be measured by a differential scanning calorimeter (hereinafter, may be abbreviated as DSC) under the following conditions.
Equipment: Q20 DSC [TA Instruments Japan Co., Ltd.]
Measurement conditions: sample amount 5 mg.
(1) The temperature was raised from 30 ° C. to 100 ° C. at a rate of 20 ° C./min, and kept at 100 ° C. for 10 minutes.
(2) Cool from 100 ° C. to −70 ° C. at a cooling rate of −20 ° C./min, and hold at −70 ° C. for 10 minutes.
(3) The temperature is raised from -70 ° C to 100 ° C at a rate of 20 ° C / min.
Analysis method: The minimum value of the DCS curve at the second temperature rise is defined as the melting point.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) of the polymer (A) is 3,000 to 50,000 as described above. When Mn is less than 3,000, the convergence deteriorates, and when Mn exceeds 50,000, the spreadability deteriorates.
Further, from the viewpoint of coexistence of the convergence property and the fiber opening property, the Mn of the polymer (A) is preferably 4,000 to 20,000.
The Mn of the polymer (A) can be measured, for example, by gel permeation chromatography (hereinafter, may be abbreviated as GPC) under the following conditions.
Main unit: HLC-8120 (Tosoh Corporation)
Column: Tosoh Corp. TSKgel α6000, G3000 PWXL
Detector: RI (Refractive Index)
Eluent: 0.5% sodium acetate / water / methanol (70/30 by volume)
Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C
Sample concentration: 0.25% by weight
Injection volume: 200 μl
Standard substance: TSK TANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation
Data processing software: GPC-8020 model II (manufactured by Tosoh Corporation)

As described above, the polymer (A) has a polyoxyethylene chain having a molecular weight of 3,000 to 50,000 and / or a polycaprolactone chain having a molecular weight of 3,000 to 50,000.
The ratio of the total weight of the polyoxyethylene chain having a molecular weight of 3,000 to 50,000 and the polycaprolactone chain having a molecular weight of 3,000 to 50,000 contained in the polymer (A) is determined by the weight of the polymer (A). As a reference, it is preferably 50 to 100% by weight.
The molecular weight of the polyoxyethylene chain of the polymer (A), the molecular weight of the polycaprolactone chain of the polymer (A), and the polyoxyethylene chain having a molecular weight of 3,000 to 50,000 and the molecular weight of 3,000 to 50,000 The ratio of the total weight of the polycaprolactone chains of 000 can also be determined from the weight of each raw material when producing the polymer (A) by the above method.

  As described above, the compound (B) other than the polymer (A) is at least one selected from the group consisting of polyurethane, polyamide, polyester and a compound having an epoxy group.

  As the other compound (B), a compound having a polyester and an epoxy group is preferable from the viewpoint of convergence and strength of a molded article.

  As the polyester, any known polyester may be used, but from the viewpoints of convergence and spreadability, polyester composed of dicarboxylic acid or its anhydride (α) and diol (β) It is preferable that

  Examples of the dicarboxylic acid or anhydride (α) constituting the polyester include aliphatic dicarboxylic acid (α1), aromatic dicarboxylic acid (α2), and acid anhydrides thereof.

  Examples of the aliphatic dicarboxylic acid (α1) include linear saturated aliphatic dicarboxylic acids (α11), linear unsaturated aliphatic dicarboxylic acids (α12), alicyclic dicarboxylic acids (α13), and dimer acids (α14). Can be

  Examples of the linear saturated aliphatic dicarboxylic acid (α11) include linear or branched linear saturated aliphatic dicarboxylic acids having 2 to 22 carbon atoms (oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, ethyl succinic acid, Dimethylmalonic acid, α-methylglutaric acid, β-methylglutaric acid, 2,4-diethylglutaric acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid , Dodecane dicarboxylic acid, tridecane dicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, octadecane dicarboxylic acid, icosane dicarboxylic acid, decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.).

  Examples of the linear unsaturated aliphatic dicarboxylic acid (α12) include linear or branched linear unsaturated aliphatic dicarboxylic acids having 4 to 22 carbon atoms (maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenyl succinic acid, pentane). Decenylsuccinic acid and octadecenylsuccinic acid).

  Examples of the alicyclic dicarboxylic acid (α13) include C7 to C14 alicyclic dicarboxylic acids (1,3- or 1,2-cyclopentanedicarboxylic acid, 1,2-, 1,3- or 1,4 -Cyclohexanedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanediacetic acid and dicyclohexyl-4,4'-dicarboxylic acid).

  Examples of the dimer acid (α14) include a dimer of a chain unsaturated aliphatic carboxylic acid having 8 to 24 carbon atoms (eg, oleic acid, linoleic acid, and linolenic acid).

  Examples of the aromatic dicarboxylic acid (α2) include aromatic dicarboxylic acids having 8 to 14 carbon atoms (terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipate, β-phenyladipic acid, biphenyl-2,2′- or 4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate, potassium 5-sulfoisophthalate, and the like.

  Examples of the anhydride of dicarboxylic acid include the anhydrides of the above (α1) and (α2), for example, succinic anhydride, maleic anhydride and phthalic anhydride.

The dicarboxylic acid and its anhydride (α) may be used alone or in combination of two or more.
Among these, from the viewpoint of convergence, a chain saturated aliphatic dicarboxylic acid (α11), a chain unsaturated aliphatic dicarboxylic acid (α12) and an aromatic dicarboxylic acid (α2) are preferable, and oxalic acid is more preferable. , Malonic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, terephthalic acid, isophthalic acid and phthalic acid, particularly preferred are adipic acid, maleic acid, fumaric acid, terephthalic acid and isophthalic acid. .

  Examples of the diol (β) constituting the polyester include an aliphatic alkanediol and its alkylene oxide (hereinafter, “alkylene oxide” may be abbreviated as “AO”) adduct, alicyclic diol and its AO adduct, AO adducts of primary amines and AO adducts of aromatic ring-containing dihydric phenols are exemplified.

As the aliphatic alkanediol, one having 2 to 16 carbon atoms, specifically, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol Octanediol, decanediol, dodecanediol, hexadecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol.
Examples of the AO adduct of an aliphatic alkanediol include the above-mentioned diol and the above-mentioned compound having 2 to 4 carbon atoms added to AO.
Two or more of these AOs may be used in combination, and in the case of a combination of two or more, the bonding mode may be any of block addition, random addition, and combination thereof.
The number of moles of AO added per molecule of the aliphatic alkanediol is preferably from 1 to 120 mol.

  Examples of the alicyclic diols include those having 4 to 16 carbon atoms, specifically, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A. Examples of AO adducts of alicyclic diols include those in which AO having 2 to 4 carbon atoms is added.

Examples of the primary amine in the AO adduct of the primary amine include primary amines having 1 to 18 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine, dodecylamine and the like. .
Examples of the AO adduct of a primary amine include those obtained by adding AO having 2 to 4 carbon atoms as described above.

Examples of the aromatic ring-containing dihydric phenol in the AO adduct of the aromatic ring-containing dihydric phenol include bisphenol A, bisphenol S, cresol, and hydroquinone.
Examples of the AO adduct of an aromatic ring-containing dihydric phenol include those obtained by adding AO having 2 to 4 carbon atoms as described above.

The diol (β) may be used alone or in combination of two or more.
Among the diols (β), aliphatic alkane diols and their AO adducts, alicyclic diol AO adducts, primary amine AO adducts, and aromatic ring-containing dihydric phenols are preferable from the viewpoint of convergence. AO adducts of aliphatic alkanediols and their AO adducts, and AO adducts of aromatic ring-containing dihydric phenols are more preferred.

The viscosity of the polyester at 100 ° C. is preferably 0.5 to 50 Pa · s, more preferably 1 to 30 Pa · s, and particularly preferably 3 to 20 Pa · s.
When the viscosity is in the range of 0.5 to 50 Pa · s, better convergence and emulsion stability can be obtained. Here, the viscosity of the polyester at 100 ° C. is measured by a Brookfield viscometer (BL type) in accordance with JIS K7117-1: 1999 (corresponding to ISO2555: 1990).

The polyester preferably has a number average molecular weight of 1,000 to 50,000 (hereinafter abbreviated as Mn). When Mn is 1,000 or more, sufficient convergence is obtained, and when Mn is 50,000 or less, affinity for water is high and emulsion stability is excellent.
Note that Mn is measured by GPC. Mn is more preferably from 1,500 to 30,000, particularly preferably from 2,000 to 20,000. Within this range, the convergence and the affinity for water are more excellent.

The conditions of GPC used for measuring Mn of the polyester are, for example, the following conditions.
Model: Alliance (Liquid Chromatograph manufactured by Japan Waters Co., Ltd.)
Column: Guardcolumn Super HL
+ TSK gel Super H4000
+ TSK gel Super H3000
+ TSK gel Super H2000
(All manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI (Refractive Index)
Eluent: tetrahydrofuran Eluent flow rate: 0.6 ml / min Sample concentration: 0.25% by weight
Injection volume: 10 μl
Standard substance: polystyrene (Tosoh Corporation; TSK STANDARD POLYSTYRENE)

As a method for producing a polyester, for example, a dicarboxylic acid or its anhydride (α) and a diol (β) are charged at a predetermined molar ratio, and the mixture is stirred at a reaction temperature of 100 to 250 ° C. and a pressure of −0.1 to 1.2 MPa. And a method of removing water.
The charged molar ratio [(α) / (β)] of the dicarboxylic acid or its anhydride (α) to the diol (β) is preferably from 0.7 to 1 from the viewpoint of improving the convergence, with Mn within the above range. 0.5, more preferably 0.8 to 1.25.

  When producing polyester, it is preferred to add a catalyst in an amount of 0.05 to 0.5% by weight based on the weight of the polyester. Examples of the catalyst include paratoluenesulfonic acid, dibutyltin oxide, tetraisopropoxytitanate and potassium oxalate titanate, and tetraisopropoxytitanate and potassium oxalate are preferred from the viewpoint of reactivity and the effect on the environment. More preferably, potassium oxalate titanate is used.

  Examples of the compound having an epoxy group include diepoxide, phenol novolak epoxy resin, and epoxidized unsaturated fatty acid triglyceride (epoxidized soybean oil, epoxidized rapeseed oil, and the like).

  Examples of the diepoxide include diglycidyl ether, diglycidyl ester, diglycidylamine, and alicyclic diepoxide.

Examples of the diglycidyl ether include diglycidyl ether of a dihydric phenol and diglycidyl ether of a dihydric alcohol.
Examples of the diglycidyl ether of a dihydric phenol include a condensate (including a polycondensate) of a dihydric phenol having 6 to 30 carbon atoms and epichlorohydrin, both of which are glycidyl ethers.
Examples of the dihydric phenol include bisphenol (bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S and halogenated bisphenol A), catechin, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4, Examples include 4'-dihydroxybiphenyl, tetramethylbiphenyl, and 9,9'-bis (4-hydroxyphenyl) fluorene.
Examples of the diglycidyl ether of a dihydric alcohol include a condensate (including a polycondensate) of a diol having 2 to 100 carbon atoms and epichlorohydrin, both of which are glycidyl ethers.
As the dihydric alcohol, ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, neopentyl glycol and bisphenol A are added with AO (1 to 20 mol). Objects and the like.
Examples of the AO include the above-mentioned AO having 2 to 4 carbon atoms.

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

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

Examples of the diglycidylamine include N-glycidyl compounds (N, N-diamine) obtained by reacting an aromatic amine having 6 to 20 carbon atoms and having 2 to 4 active hydrogen atoms (such as aniline and toluidine) with epichlorohydrin. Glycidylaniline and N, N-diglycidyltoluidine).
In the diglycidylamine, the molar ratio of the aromatic amine unit to the epichlorohydrin unit {(aromatic amine unit) :( epichlorohydrin unit)} is represented by n: n + 1. n is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5. Diglycidylamine may be a mixture of n = 1 to 10.

  Examples of the alicyclic diepoxide include alicyclic epoxides having 6 to 50 carbon atoms and having 2 epoxy groups, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, and bis (2,3-epoxycyclopentyl) ether. , Ethylene glycol bisepoxy dicyclopentyl ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine.

  Among these, diglycidyl ether is preferable from the viewpoint of the strength of the molded article, more preferably diglycidyl ether of dihydric aromatic alcohol, particularly preferably diglycidyl ether of bisphenol, and most preferably diglycidyl ether of bisphenol A ( (Bisphenol A type epoxy resin).

Mn of the compound having an epoxy group is preferably from 200 to 10,000, more preferably from 350 to 3,000, particularly preferably from 380 to 2,500. When Mn is within this range, the strength of the molded body is further improved.
The GPC conditions used for measuring the Mn of the compound having an epoxy group are the same as those for measuring the Mn of the polyester.

  The fiber sizing agent of the present invention may contain a surfactant (C) and other additives (D) in addition to the polymer (A) and the compound (B).

The surfactant (C) may be blended for the purpose of emulsifying a mixture of the polymer (A) and the compound (B).
As the surfactant (C), known surfactants such as nonionic surfactants other than the polymer (A), anionic surfactants, cationic surfactants and amphoteric surfactants (JP-A-2006-124877) Gazettes and those described in WO2003 / 37964).
As the surfactant (C), one type may be used alone, or two or more types may be used in combination.
The surfactant (C) specifically includes the following compounds other than the polymer (A).
AO adduct of alkylphenol (C10-20) (Mn500-5,000), arylalkylphenol５ ， styrenated phenol (C14-62), styrenated cumylphenol and styrenated cresol (C15-61) AO adducts (Mn 500 to 5,000), sulfate esters (sodium salt, potassium salt, ammonium salt and alkanolamine salt) of AO adducts (Mn 500 to 5,000) of alkylphenols (C10 to C20) Etc.), sulfate salts of AO adducts (Mn 500-5,000) such as arylalkylphenols {styrenated phenols (14-62 carbon atoms), styrenated cumylphenol and styrenated cresol (15-61 carbon atoms) etc.} And the like.
In the surfactant (C), AO addition means ethylene oxide (hereinafter, “ethylene oxide” may be abbreviated as “EO”) alone, and propylene oxide (hereinafter, “propylene oxide”). Examples thereof include a product obtained by adding EO to at least one of “PO” and butylene oxide (hereinafter “butylene oxide” may be abbreviated to “BO”). When at least one of PO and BO is contained, a random adduct, a block adduct, and a mixed adduct thereof are included.
The method for measuring Mn of the surfactant (C) is the same as the method for measuring Mn of the polymer (A) described above.

  Among the surfactants (C), anionic surfactants and nonionic surfactants other than (A) are preferable, and more preferably an AO adduct of an alkylphenol having an Mn of 3,000 or less and a melting point of less than 25 ° C., Mn 3,000 AO adduct of an arylalkylphenol having a melting point of less than 25 ° C., a sulfate salt of an AO adduct of an alkylphenol having a Mn of 3,000 or less and having a melting point of less than 25 ° C .; Sulfate ester salts of AO adducts and mixtures thereof, particularly preferably AO (EO and PO) adducts of arylalkylphenols having a Mn of 3,000 or less and a melting point of less than 25 ° C and aryls having an Mn of 3,000 or less and a melting point of less than 25 ° C Sulfur of AO (EO and PO) adduct of alkyl phenol Esters salts and mixtures thereof.

Other additives (D) include a leveling agent, a preservative and an antioxidant.
Examples of the leveling agent include wax (polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, modified polyethylene, and modified polypropylene), higher fatty acid (fatty acid having 6 to 30 carbon atoms) alkyl (having alkyl having 1 to 24 carbon atoms) ester (methyl stearate) Rate, ethyl stearate, propyl stearate, butyl stearate, octyl stearate, stearyl stearate, etc.), higher fatty acids (fatty acid having 6 to 30 carbon atoms) (myristic acid, palmitic acid, stearic acid, etc.), natural fats and oils (Coconut oil, beef tallow, olive oil, rapeseed oil, etc.) and liquid paraffin.
Preservatives include benzoic acid, salicylic acid, sorbic acid, quaternary ammonium salts, imidazole and the like.
Examples of antioxidants include phenol (such as 2,6-di-t-butyl-p-cresol), thiodipropionate (such as dilauryl 3,3′-thiodipropionate) and phosphite (such as triphenyl phosphite). ) And the like.

The complex viscosities of the sizing agent for fibers of the present invention are preferably the following values of the complex viscosities measured using a rheometer under the following conditions with respect to the contained solid content, from the viewpoint of fiber opening properties and sizing properties.
Here, the solid content contained in the fiber sizing agent refers to a residue after heating and drying 10 g of the fiber sizing agent with a circulating drier at 130 ° C. for 1 hour.
<Preferred complex viscosity>
The complex viscosity measured under the conditions of 25 ° C., frequency 1 Hz, and strain 0.5% is 800 to 10,000 Pa · s, and measured at 70 ° C., frequency 1 Hz, and strain 0.5%. The obtained complex viscosity is 1 to 4 Pa · s.

The contents of the polymer (A), compound (B), surfactant (C) and other additives (D) in the sizing agent of the present invention are as follows, respectively.
The weight ratio of (A) needs to be 1 to 50% by weight based on the weight of the solid content contained in the fiber sizing agent.
When the weight ratio of (A) is less than 1% by weight, the convergence deteriorates, and when it exceeds 50% by weight, the spreadability deteriorates. The weight ratio of (A) is preferably from 3 to 45% by weight, and more preferably from 5 to 40% by weight, based on the weight of the solid content of the sizing agent for fibers, from the viewpoints of sizing and opening properties. .
The weight ratio of (B) is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably 30 to 80% by weight based on the weight of the solid content of the fiber sizing agent from the viewpoint of sizing properties. 75% by weight.
The weight ratio of (C) is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, based on the weight of the solid content of the fiber sizing agent, from the viewpoint of emulsion stability. Particularly preferably, it is 1 to 30% by weight.
The weight ratio of (D) is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight based on the weight of the solid content of the fiber sizing agent from the viewpoint of fluidity and stability over time. %, Particularly preferably 0.1 to 10% by weight.

The sizing agent for fibers of the present invention preferably contains an aqueous medium so as to form an aqueous solution or an aqueous emulsion.
When the aqueous medium is contained, it is easy to make the amount of solids contained in the fiber sizing agent adhere to the fibers in an appropriate amount, so that a fiber bundle having further excellent strength when formed into a molded article can be obtained.
As the aqueous medium, a known aqueous medium or the like can be used. Specifically, water and a hydrophilic organic solvent [monohydric alcohols having 1 to 4 carbon atoms (such as methanol, ethanol and isopropanol), and 3 carbon atoms] To 6 ketones (such as acetone, ethyl methyl ketone and methyl isobutyl ketone), glycols having 2 to 6 carbon atoms (such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol) and their monoalkyl (1-2 carbon atoms) ethers Dimethylformamide, and alkyl acetates having 3 to 5 carbon atoms (such as methyl acetate and ethyl acetate).
These may be used in combination of two or more. Among these, water and a mixed solvent of a hydrophilic 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 fiber sizing agent of the present invention preferably has a high concentration during distribution and a low concentration during production of the fiber bundle. In other words, by circulating at a high concentration, transportation costs and storage costs are reduced, and by treating fibers at a low concentration, a fiber bundle giving excellent molded article strength can be produced.
The concentration of the high-concentration aqueous solution or emulsion (weight ratio of the solid content to the fiber sizing agent) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, from the viewpoint of storage stability and the like.
On the other hand, the concentration of the low-concentration aqueous solution or emulsion (the weight ratio of the solid content to the sizing agent for fibers) is preferably 0.5 to 15% by weight from the viewpoint of adjusting the amount of the sizing agent attached to the fiber bundle during the production. %, More preferably 1 to 10% by weight.

Examples of the method for producing the fiber sizing agent of the present invention include a method in which the above (A), (B), an aqueous medium, and if necessary, (C) to (D) are mixed in an arbitrary order, and the like. Preferably, a method in which components other than the aqueous medium are mixed in advance and the resulting mixture is charged with an aqueous medium to dissolve or emulsify and disperse.
When two or more compounds (B) are used, one of them may be finally added to and mixed with an aqueous solution or emulsion produced using other components.

The temperature in the case where components other than the aqueous medium are preliminarily mixed is preferably from 20 to 90 ° C, more preferably from 40 to 90 ° C, from the viewpoint of easy mixing, and the same applies to the temperature of the subsequent dissolution or emulsification and dispersion. is there.
The time for the dissolution or emulsification / dispersion is preferably 1 to 20 hours, more preferably 2 to 10 hours.

  There is no limitation on the mixing device, the dissolving device and the emulsifying and dispersing device, and the stirring blade (blade shape: chi type and three-stage paddle, etc.), Nauta mixer, ribbon mixer, conical blender, mortar mixer, universal mixer (universal mixer 5DM) -L, manufactured by Sanei Seisakusho) and Henschel mixer.

  Known fibers such as glass fiber, carbon fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, rock fiber and slug fiber (described in WO2003 / 47830) can be used as the fiber to which the sizing agent of the present invention can be applied. And the like, and from the viewpoint of the strength of the molded product, carbon fibers are preferred. Two or more of these fibers may be used in combination.

  The fiber bundle of the present invention is obtained by treating at least one fiber selected from the group consisting of these fibers with the above-mentioned sizing agent (a fiber bundle in which about 3,000 to 30,000 fibers are bundled).

  Examples of the method for treating fibers include a spray method and a dipping method. The attached amount (% by weight) of the solids contained in the fiber sizing agent to the fiber is preferably 0.05 to 5% by weight, more preferably 0.2 to 5% by weight, based on the weight of the fiber (the weight before the treatment). ~ 2.5% by weight. Within this range, the strength of the molded body is further improved.

  The fiber product of the present invention is obtained by processing the fiber bundle into a fiber product, and includes woven fabric, knitted fabric, nonwoven fabric (felt, mat, paper, etc.), chopped fiber, milled fiber, and the like.

The prepreg of the present invention uses the fiber bundle or the fiber product and a matrix resin. If necessary, a catalyst may be contained. When a catalyst is contained, the molded article strength is further improved. Examples of the matrix resin include a thermoplastic resin (E1) and a thermosetting resin (E2).
Examples of the thermoplastic resin (E1) include thermoplastic resins (polyethylene resin, polypropylene) described in WO2003 / 09015, WO2004 / 067612, JP2926227, JP2616869A, and the like. Resin, polystyrene resin, polyurethane resin, polyamide resin, polyester resin, and acrylic resin).
Examples of the thermosetting resin (E2) include an epoxy resin, a (meth) acrylate-modified resin, and an unsaturated polyester resin (such as those described in Japanese Patent No. 3723462).
In addition, (meth) acrylate means methacrylate and / or acrylate.
One type of matrix resin may be used alone, or two or more types may be used in combination.
The matrix resin is preferably a thermosetting resin (E2), and more preferably an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin (an epoxy resin having an acrylic group and / or a methacryl group added). Examples of the catalyst include known epoxy resin curing agents and curing accelerators (such as those described in JP-A-2005-213337).

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

  The prepreg is prepared by heating and melting a matrix resin (melting temperature: 60 to 150 ° C.) or a matrix resin diluted with a solvent (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and ethyl acetate) into a fiber bundle or a fiber product. It can be manufactured by impregnation. When a solvent is used, it is preferable to dry the prepreg to remove the solvent.

  The molded article of the present invention is obtained by molding the prepreg. When the matrix resin is a thermoplastic resin, a prepreg can be formed by heating and solidifying at room temperature. When the matrix resin is a thermosetting resin, a prepreg can be molded by heating and curing. Although the curing need not be completed, it is preferable that the molded body has been cured to such an extent that its shape can be maintained. After molding, it may be further heated to be completely cured. The method of heat forming is not particularly limited, and examples thereof include a filament winding forming method (a method in which a rotating mandrel is wound while applying tension and heat forming), a press forming method (a method in which prepreg sheets are laminated and heat formed), an autoclave. And a method in which chopped fibers or milled fibers are mixed with a matrix resin and injection-molded.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, parts are parts by weight.

The melting points of (A-1) to (A-6) and (A'-1) to (A'-3) used in the following examples were measured by DSC.
<Measurement method of melting point>
Equipment: Q20 DSC [TA Instruments Japan Co., Ltd.]
Measurement conditions: sample amount 5 mg.
(1) The temperature was raised from 30 ° C. to 100 ° C. at a rate of 20 ° C./min, and kept at 100 ° C. for 10 minutes.
(2) Cool from 100 ° C. to −70 ° C. at a cooling rate of −20 ° C./min, and hold at −70 ° C. for 10 minutes.
(3) The temperature is raised from -70 ° C to 100 ° C at a rate of 20 ° C / min.
Analysis method: The minimum value of the DCS curve at the second temperature rise is defined as the melting point.

The number average molecular weights of (A-1) to (A-6) and (A'-1) to (A'-3) used in the following examples were measured by gel permeation chromatography (hereinafter, GPC) under the following conditions. ).
Main unit: HLC-8120 (Tosoh Corporation)
Column: Tosoh Corp. TSKgel α6000, G3000 PWXL
Detector: RI (Refractive Index)
Eluent: 0.5% sodium acetate / water / methanol (70/30 by volume)
Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C
Sample concentration: 0.25% by weight
Injection volume: 200 μl
Standard substance: TSK TANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation
Data processing software: GPC-8020 model II (manufactured by Tosoh Corporation)

Production Example 1 [Production of polymer (A-4)]
485 parts of EO adduct of bisphenol A (trade name "Newpol BPE-40", manufactured by Sanyo Chemical Industries, Ltd.) in which 4 mol parts of EO is added to 1 mol part of bisphenol A, 485 parts of terephthalic acid (alcohol / acid = (6/5 molar ratio) and 0.5 parts of tetraisopropoxytitanate were reacted in a glass reactor at 170 ° C. for 10 hours while distilling off water under a stream of nitrogen. 470 parts of polyoxyethylene glycol [trade name “PEG-10000”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 11,000] is further added thereto, and the pressure is reduced to −0.1 MPa at 180 ° C. to distill off water. While the reaction was carried out for 10 hours (ester exchange reaction), 1,000 parts of a polymer (A-4) as a polyester resin was obtained.
The melting point of (A-4) was 60 ° C., and the number average molecular weight of (A-4) was 4,500.

Production Example 2 [Production of polymer (A-6)]
In a SUS pressure-resistant reaction vessel equipped with a thermometer, a stirrer, and a vacuum line, 200 parts of acid-modified polypropylene [trade name "UMEX 1010", manufactured by Sanyo Chemical Industries, Ltd.], polyoxyethylene glycol [trade name "PEG-4000E" 800 parts by Sanyo Kasei Kogyo Co., Ltd., number average molecular weight 3,850], and reacted at 180 ° C. for 10 hours while reducing the pressure to −0.1 MPa to obtain 1,000 parts of a polymer (A-6). Was.
The melting point of (A-6) was 60 ° C, and the number average molecular weight of (A-6) was 6,700.

Comparative Production Example 1 [Production of polymer (A'-2)]
In Production Example 1, polyoxyethylene glycol [trade name "PEG-10000", manufactured by Sanyo Chemical Industry Co., Ltd., molecular weight 10,000] was replaced with polyoxyethylene glycol [trade name "PEG-2000", Sanyo Chemical Industry Co., Ltd.] ) And the number average molecular weight was changed to 2,000] to obtain 1,000 parts of a polymer (A'-2) as a comparative polyester resin.
The melting point of (A′-2) was 51 ° C., and the number average molecular weight of (A′-2) was 2,600.

Comparative Production Example 2 [Production of polymer (A'-3)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping cylinder, 222 parts of (higher alcohol having 14 to 15 carbon atoms [trade name “Neodol 45”, manufactured by Shell Chemicals Japan KK, number average molecular weight 222]] (1 mol part) and 0.5 part (0.009 mol part) of potassium hydroxide were charged, and the flask was purged with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. After warming, 1716 parts (39 mole parts) of EO was added dropwise over 5 hours while adjusting the pressure to 0.5 MPaG or less, and the mixture was aged at 160 ° C. for 2 hours. 10 parts of "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) are charged, and the mixture is stirred at 70 ° C. for 1 hour and treated. Then, the adsorption treating agent is filtered and 39 moles of EO of alcohol having 14 to 15 carbon atoms is added. Object (A'-3) Obtained.
The melting point of (A′-3) was 52 ° C., and the number average molecular weight of (A′-3) was 1930.

Production Example 3 [Production of polyester (B-1)]
EO adduct of bisphenol A (trade name "Newpol BPE-20", manufactured by Sanyo Chemical Industries, Ltd.) in which 2 mol parts of EO is added to 1 mol part of bisphenol A, 316 parts, fumaric acid 154 parts (alcohol / acid = (3/4 molar ratio) and 0.3 part of tetraisopropoxytitanate were reacted in a glass reaction vessel for 10 hours while distilling off water at 170 ° C. under a stream of nitrogen to obtain 400 parts of polyester (B-1). .

<Examples 1 to 7, Comparative Examples 1 to 5>
Raw materials other than water in the number of parts described in Table 1 were uniformly dissolved in a universal mixer [universal mixing stirrer, manufactured by Sanei Seisakusho] for 30 minutes while controlling the temperature at 60 ° C., and water was added thereto for 6 hours. The fiber sizing agents (X-1) to (X-7) and the fiber sizing agents (X'-1) to (X'-5) for comparison having a concentration of 40% by weight were added. 2500 parts were each obtained.

The abbreviations in Table 1 represent the following compositions.
(A-1): polyoxyethylene glycol [trade name “PEG-10000”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 11,000, melting point: 59 ° C.]
(A-2): polyoxyethylene glycol [trade name “PEG-20,000”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 20,000, melting point: 60 ° C.]
(A-3): polyoxyethylene glycol [trade name “PEG-6000P”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 8,600, melting point: 59 ° C.]
(A-5): poly-ε-caprolactone [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., number average molecular weight: 10,000, melting point: 60 ° C]
(A′-1): polyoxyethylene glycol [trade name “PEG-2000”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 2,000, melting point: 51 ° C.]
(B-2): Bisphenol A type epoxy resin [trade name “JER1001”, manufactured by Mitsubishi Chemical Corporation]
(B-3): bisphenol A type epoxy resin [trade name “JER828”, manufactured by Mitsubishi Chemical Corporation]
(B-4): bisphenol F type epoxy resin [trade name “JER807”, manufactured by Mitsubishi Chemical Corporation]
(C-1): Styrenated phenol EO / PO adduct [trade name “STP-200”, manufactured by Sanyo Chemical Industries, Ltd., melting point: less than 25 ° C.]

<Measurement of complex viscosity of solids contained in fiber sizing agent>
10 g of the fiber sizing agents (X-1) to (X-7) and the fiber sizing agents (X'-1) to (X'-5) for comparison are placed in an aluminum cup and circulated at 130 ° C. The water was evaporated over 1 hour by a machine to obtain 4 g of a solid content of the fiber sizing agent.
Using a rheometer [MODULAR COMPACT RHEOMETER (PHYSICA MCR302), manufactured by Anton-Paar], at 25 ° C. or 70 ° C., at a frequency of 1 Hz and a strain of 0.5%, the complex of each solid content of the fiber sizing agent is changed. The viscosity (Pa · s) was measured. The results are shown in Table 1.

<Evaluation of carbon fiber bundle>
The sizing agent for fibers (X-1) to (X-7) and the sizing agent for fibers (X'-1) to (X'-5) for comparison are the weight of the solid content of the sizing agent for fibers. Diluted with water to 1.5%, immersed carbon fiber (800 tex fineness, 12,000 filaments, weight listed in Table 1), impregnated with sizing agent, and dried with hot air at 150 ° C for 3 minutes The carbon fiber bundles (weights described in Table 1) obtained by the evaluation were evaluated for openability and bunching properties according to the following methods, and the results are shown in Table 1.

<Evaluation of spreadability>
Five stainless steel rods having a smooth surface and heated to 70 ° C. and having a diameter of 10 mm are parallelly arranged so that the horizontal distance between the stainless steel rods is 50 mm, and zigzag while the carbon fiber bundle is in contact with the stainless steel rods. It was arranged to pass through (FIG. 1). The straight line connecting the centers of the stainless steel rods through which the carbon fiber bundle passes first, third and fifth, and the straight line connecting the centers of the stainless steel rods through which the carbon fiber bundle passes second and fourth are defined as a horizontal plane. They were arranged so as to be parallel. Further, before and after the passage of the second to fourth stainless steel rods, the straight line that is the traveling direction of the carbon fiber bundle before passing and the straight line that is the traveling direction of the carbon fiber bundle after passing are formed at an angle of 120 degrees. (For example, a straight line which is a traveling direction of a carbon fiber bundle passing between the first and second stainless steel rods, and a carbon fiber bundle passing between the second and third stainless steel rods) Are arranged so that an angle of 120 degrees is formed with a straight line which is the traveling direction of (1).
The carbon fiber bundle treated with each sizing agent is zigzag between the stainless steel bars, and the carbon fiber bundle is transferred from the unwinding roll to the winding roll at a tension of 1000 g between the winding roll and the unwinding roll at a speed of 3 m / min. The spread width (mm) of the carbon fiber bundle after winding and passing through five stainless steel rods was measured {using a yarn running test device manufactured by Asano Machinery Co., Ltd.}. The larger the numerical value, the more excellent the spreadability was, and the evaluation was made according to the following criteria.
◎: 8 mm or more ○: 7 mm or more and less than 8 mm △: 6 mm or more and less than 7 mm ×: less than 6 mm

<Evaluation of convergence>
The sizing properties of the carbon fiber bundles treated with each sizing agent were evaluated according to JIS L1096-2010 (8.21.1A method, 45-degree cantilever method). The larger the value, the better the convergence, and the evaluation was made according to the following criteria.
◎: 17.0 cm or more ○: 16.5 cm or more and less than 17.0 cm △: 16.0 cm or more and less than 16.5 cm ×: less than 16.0 cm

As is clear from the results in Table 1, the carbon fiber bundle treated with the fiber sizing agent of the present invention has excellent bundle opening properties while having excellent fiber opening properties.
On the other hand, instead of the polymer (A), a comparison was made containing (A ′) having neither a polyoxyethylene chain having a molecular weight of 3,000 to 50,000 nor a polycaprolactone chain having a molecular weight of 3,000 to 50,000. Carbon fiber bundles (Comparative Examples 1 to 4) treated with a fiber sizing agent for fibers do not have both openability and sizing properties.
Further, the carbon fiber bundle treated with the comparative fiber sizing agent containing neither the polymer (A) nor (A ′) (Comparative Example 5) cannot achieve both the opening property and the sizing property.

The fiber sizing agent of the present invention can be used as a sizing agent for glass fiber, carbon fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, rock fiber or slug fiber.
Further, a prepreg can be obtained by using a fiber bundle or a fiber product obtained by treating with the fiber sizing agent of the present invention as a reinforcing fiber and using a thermoplastic resin or a thermosetting resin as a matrix.

1. Stainless steel rod2. Unwinding roll3. Take-up roll 4. 4. carbon fiber bundle Measurement position of spreadability

Claims (6)

A fiber sizing agent containing a polymer (A) and a compound (B) other than the polymer (A),
Wherein the polymer (A) is an alkylene oxide adduct (A1) having 2 to 4 carbon atoms to a compound (a) having 1 to 8 hydroxyl groups in one molecule, polycaprolactone (A2), and the alkylene oxide At least one selected from the group consisting of an adduct (A1) and an ester (A3) of a carboxylic acid,
The polymer (A) has a melting point of 25 to 70 ° C,
The number average molecular weight of the polymer (A) is 3,000 to 50,000,
The polymer (A) has a polyoxyethylene chain having a molecular weight of 3,000 to 50,000 and / or a polycaprolactone chain having a molecular weight of 3,000 to 50,000,
The compound (B) is at least one selected from the group consisting of polyurethane, polyamide, polyester and a compound having an epoxy group;
A sizing agent for fibers, wherein the weight ratio of the polymer (A) is 1 to 50% by weight based on the weight of solids contained in the sizing agent for fibers.   The sizing agent for fibers according to claim 1, wherein the compound (B) is a compound having a polyester and / or an epoxy group.   At least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber, rock fiber and slug fiber is treated with the fiber sizing agent according to claim 1 or 2. Fiber bundle.   A fiber product containing the fiber bundle according to claim 3.   A prepreg comprising the fiber bundle according to claim 3 or the fiber product according to claim 4 as a reinforcing fiber, and a thermoplastic resin (E1) or a thermosetting resin (E2) as a matrix. A molded article obtained by molding the prepreg according to claim 5.

Images