阅读说明：本技术 纤维用上浆剂组合物、纤维用上浆剂分散体、纤维用上浆剂溶液、纤维束、纤维产品和复合材料 (Sizing composition for fiber, sizing dispersion for fiber, sizing solution for fiber, fiber bundle, fiber product, and composite material ) 是由 阪口幸矢佳 于 2019-07-26 设计创作，主要内容包括：本发明的目的在于提供能够抑制纤维束的起毛的纤维用上浆剂组合物。本发明的纤维用上浆剂组合物是含有下述通式(1)所表示的脂肪族醇环氧烷加成物(A)以及化合物(B)的纤维用上浆剂组合物,其中,上述(B)为选自由聚酯(B1)、聚氨酯(B2)、具有环氧基的化合物(B3)、具有(甲基)丙烯酰基的化合物(B4)以及除上述脂肪族醇环氧烷加成物(A)以外的聚醚化合物(B5)组成的组中的至少一种。R~1O(AO)_mH(1)[通式(1)中,R~1为具有3个以上甲基的碳原子数8～11的脂肪族烃基；AO为碳原子数2～4的亚烷基氧基；m表示环氧烷的数均加成摩尔数,为3～10的数。]。(The purpose of the present invention is to provide a sizing agent composition for fibers, which can suppress fluffing of fiber bundles. The sizing agent composition for fibers of the present invention comprises an aliphatic alcohol alkylene oxide adduct (a) represented by the following general formula (1) and a compound (B), wherein the compound (B) is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound (B3) having an epoxy group, a compound (B4) having a (meth) acryloyl group, and a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (a). R 1 O(AO) m H (1) [ formula (1) wherein R 1 An aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups; AO represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents a number of 3 to 10 as a number-average addition mole number of alkylene oxide.]。)

1. A sizing agent composition for fibers, which contains an aliphatic alcohol alkylene oxide adduct (A) represented by the following general formula (1) and a compound (B),

the compound (B) is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), and a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (A),

R¹O(AO)_mH (1)

in the general formula (1), R¹An aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups; AO represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents the number of alkylene oxideThe number of the average addition mols is 3 to 10.

2. The sizing composition for fibers according to claim 1, wherein the alkyleneoxy group contained in the aliphatic alcohol alkylene oxide adduct (a) is an ethyleneoxy group.

3. The sizing composition for fibers according to claim 1 or 2, wherein the compound (B) is the polyester (B1) and/or the compound having an epoxy group (B3).

4. A fiber sizing dispersion obtained by dispersing the fiber sizing composition according to any one of claims 1 to 3 in water and/or an organic solvent.

5. A fiber sizing solution obtained by dissolving the fiber sizing composition according to any one of claims 1 to 3 in water and/or an organic solvent.

6. A fiber bundle obtained by treating at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers and slag fibers with the sizing agent composition for fibers according to any one of claims 1 to 3.

7. A fiber bundle comprising:

at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slag fiber;

an aliphatic alcohol alkylene oxide adduct (A) represented by the following general formula (1); and

a fiber bundle of the compound (B'), wherein,

the compound (B') is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (A), a reaction product of a compound having an epoxy group (B3), and a reaction product of a compound having a (meth) acryloyl group (B4),

R¹O(AO)_mH (1)

in the general formula (1), R¹An aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups; AO represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents a number of 3 to 10 as a number-average addition mole number of alkylene oxide.

8. A fibrous product comprising the fiber strand of claim 6 or 7.

9. A composite material comprising the fiber strand of claim 6 or 7 and/or the fiber product of claim 8, and a matrix resin.

Technical Field

The present invention relates to a sizing composition for fibers, a sizing dispersion for fibers, a sizing solution for fibers, a fiber bundle, a fiber product, and a composite material.

Background

Composite materials of various fibers and matrix resins such as unsaturated polyester resins, phenol resins, epoxy resins, and polypropylene resins are widely used in the fields of sporting goods, leisure goods, airplanes, and the like.

As fibers used in these composite materials, fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slag fibers are used. In the processing step of producing the above-mentioned composite material, a sizing agent is usually added to these fibers in order to prevent fuzzing and yarn breakage (patent document 1).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2013/146024

Disclosure of Invention

Problems to be solved by the invention

However, in the sizing step of forming a fiber bundle by applying a sizing agent to fibers, it is required that the sizing agent (sizing agent) penetrates between fibers of the fiber bundle, but in the sizing agent proposed in patent document 1, particularly when the number of fibers of the fiber bundle is large, the sizing agent (sizing agent) cannot sufficiently penetrate between fibers, and therefore, there is a problem that fuzzing and yarn breakage of the fiber bundle cannot be sufficiently suppressed.

The invention aims to provide a sizing agent composition for fibers, which can inhibit fluffing of fiber bundles.

Means for solving the problems

The present inventors have conducted studies to achieve the above object, and as a result, have reached the present invention.

Namely, the present invention relates to: a sizing agent composition for fibers, which comprises an aliphatic alcohol alkylene oxide adduct (A) represented by the following general formula (1) and a compound (B), wherein the compound (B) is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound (B3) having an epoxy group, a compound (B4) having a (meth) acryloyl group, and a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (A); a sizing agent dispersion for fibers, which is obtained by dispersing the sizing agent composition for fibers in water and/or an organic solvent; a fiber sizing agent solution obtained by dissolving the fiber sizing agent composition in water and/or an organic solvent; a fiber bundle obtained by treating at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers and slag fibers with the above fiber sizing composition; a fiber bundle comprising at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers and slag fibers, an aliphatic alcohol alkylene oxide adduct (a) represented by the following general formula (1), and a compound (B '), wherein the compound (B') is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (a), a reaction product of a compound having an epoxy group (B3), and a reaction product of a compound having a (meth) acryloyl group (B4); a fiber product comprising the fiber bundle; a composite material comprising the above fiber bundle and/or the above fiber product and a matrix resin.

R¹O(AO)_mH (1)

[ in the general formula (1), R¹An aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups; AO represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents a number of 3 to 10 as a number-average addition mole number of alkylene oxide.]

ADVANTAGEOUS EFFECTS OF INVENTION

The sizing composition for fibers of the present invention exhibits an effect of suppressing fuzzing of fiber bundles.

Drawings

Fig. 1 is a side view schematically showing the arrangement of carbon fiber bundles in the evaluation of fuzzing.

Detailed Description

The sizing composition for fibers of the present invention contains an aliphatic alcohol alkylene oxide adduct (a) represented by the general formula (1) and a compound (B).

The compound (B) is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), and a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (a).

R in the general formula (1)¹An aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups.

The aliphatic hydrocarbon group having 8 to 11 carbon atoms may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group having 8 to 11 carbon atoms include an aliphatic hydrocarbon group having 3 methyl groups, an aliphatic hydrocarbon group having 4 methyl groups, and an aliphatic hydrocarbon group having 5 or more methyl groups.

Examples of the aliphatic hydrocarbon group having 3 methyl groups include an alkyl group having 3 methyl groups (e.g., 3-methylhept-3-yl, 3, 5-dimethylhex-1-yl, 2-methylnon-3-yl, 6-methylhept-2-yl and 2-methyldec-2-yl), an alkenyl group having 3 methyl groups (e.g., 3, 7-dimethyl-6-octen-1-yl), and a cycloalkyl group having 3 methyl groups (e.g., 4-t-butylcyclohex-1-yl).

Examples of the aliphatic hydrocarbon group having 4 methyl groups include an alkyl group having 4 methyl groups (e.g., 2, 4-dimethylpent-3-yl, 3,5, 5-trimethylhex-1-yl, 2, 6-dimethylhept-4-yl, 2,3, 5-trimethylhex-1-yl, 3,5, 5-trimethylhept-1-yl and 3,5, 5-trimethyloct-1-yl), an alkenyl group having 4 methyl groups (e.g., 3, 7-dimethyl-6-octen-2-yl), and a cycloalkyl group having 4 methyl groups (e.g., 4-tert-butyl-2-methylcyclohex-1-yl).

Examples of the aliphatic hydrocarbon group having 5 or more methyl groups include an alkyl group having 5 methyl groups (such as 2, 2-dimethyl-5-methylhexan-4-yl), an alkenyl group having 5 methyl groups (such as 4,7, 7-trimethyl-5-octen-2-yl), and a cycloalkyl group having 5 methyl groups (such as 4-tert-butyl-2, 6-dimethylcyclohex-1-yl).

Among the aliphatic hydrocarbon groups having 8 to 11 carbon atoms, an alkyl group and an alkenyl group are preferable, and an alkyl group is more preferable.

In addition, in the total aliphatic alcohol alkylene oxide adduct (A) contained in the sizing composition for fiber of the present invention, R is¹The number average number of methyl groups in (1) molecule is preferably 3.5 or more.

When the number average number is 3.5 or more, fuzzing of fiber bundles can be further suppressed when the sizing agent composition for fibers is used. In addition, the impregnation of the fiber sizing composition into the matrix resin described in detail below can be improved.

In addition, the number average number of methyl groups can be determined, for example, by comparing the number of methyl groups in R as a raw material used in the synthesis of (A) (the synthesis method is described in detail below)¹With alcohols having hydroxy groups bonded thereto¹H-NMR measurement and gas chromatography measurement.

R¹If the number of carbon atoms of (2) is less than 8 or the number of carbon atoms is more than 11, it is difficult to sufficiently suppress fuzzing of fiber bundles when the sizing agent composition for fibers is used.

In addition, the process is further inhibitedStarting from the aspect of raising of the fiber bundles, R¹The number of carbon atoms of (2) is preferably 9 or more.

In addition, R is for further suppressing fuzzing of the fiber bundle and for the impregnation with the matrix resin described in detail below¹The number of carbon atoms of (2) is preferably 10 or less.

In the general formula (1), AO is an alkyleneoxy group having 2 to 4 carbon atoms, and specific examples thereof include an oxyethylene group, a1, 2-oxypropylene group or a1, 3-oxypropylene group, and a1, 2-oxybutylene group, a1, 3-oxybutylene group, a 2, 3-oxybutylene group or a1, 4-oxybutylene group.

The aliphatic alcohol alkylene oxide adduct (a) represented by the general formula (1) has m AOs, and the types of the respective AOs may be the same or different.

M in the general formula (1) represents the number average addition mole number of alkylene oxide, and is a number of 3 to 10.

When the number average molar number of addition of the alkylene oxide is less than 3, the fuzz suppression of the fiber bundle is insufficient and the solubility of the sizing composition for fiber in water is insufficient.

When the number-average molar number of addition of the alkylene oxide is more than 10, fuzz suppression of the fiber bundle is insufficient.

In addition, the number-average molar number of addition of the alkylene oxide is preferably 4 or more from the viewpoint of further suppressing fuzzing of the fiber bundle and from the viewpoint of impregnation of the fiber sizing agent composition into the matrix resin described in detail below.

In addition, the number-average molar number of addition of the alkylene oxide is preferably 7 or less from the viewpoint of further suppressing fuzz.

The aliphatic alcohol alkylene oxide adduct (A) in the present invention preferably contains a molecule having 3 to 10 alkyleneoxy groups.

In addition, from the viewpoint of further suppressing fuzzing of fiber bundles and from the viewpoint of impregnation of the fiber sizing agent composition into a matrix resin described in detail below, it is preferable to contain a molecule having 4 or more alkyleneoxy groups.

In addition, from the viewpoint of further suppressing fuzz, it is preferable to contain a molecule having 7 or less alkyleneoxy groups.

Examples of the aliphatic alcohol alkylene oxide adduct (A) in the present invention include ethylene oxide (hereinafter, sometimes abbreviated as EO) adduct, 1, 2-propylene oxide or 1, 3-propylene oxide (hereinafter, sometimes abbreviated as PO) adduct, 1, 2-butylene oxide, 1, 3-butylene oxide, 2, 3-butylene oxide or 1, 4-butylene oxide (hereinafter, sometimes abbreviated as BO) adduct of an aliphatic alcohol having 8 to 11 carbon atoms, random adduct of EO and PO, EO-PO block adduct, PO-EO block adduct, random adduct of EO and BO, EO-BO block adduct and BO-EO block adduct.

Among these, EO adducts and PO-EO block adducts are preferable from the viewpoint of suppressing fuzzing of fiber bundles when the sizing agent composition for fibers is used. Further, the EO single adduct is preferable from the viewpoint of further suppressing fuzzing of the fiber bundle and from the viewpoint of impregnation of the sizing agent composition for fiber with the matrix resin described in detail below.

In addition, from the viewpoint of suppressing fuzzing of fiber bundles and the impregnation of the sizing agent composition for fibers into the matrix resin, the molar ratio of the ethyleneoxy group to the propyleneoxy group in the aliphatic alcohol alkylene oxide adduct (a) [ the number of moles of ethyleneoxy group: the molar number of propyleneoxy groups ] is preferably 100: 0 to 70: 30, more preferably 100: 0 to 80: 20.

The aliphatic alcohol alkylene oxide adduct (A) in the present invention may be used alone or in combination of two or more.

The number average molecular weight of the aliphatic alcohol alkylene oxide adduct (A) in the present invention is preferably 260 to 892, more preferably 300 to 500, from the viewpoint of suppressing fuzzing of fiber bundles.

The number average molecular weight is measured at 40 ℃ by gel permeation chromatography (hereinafter referred to as GPC) using polyethylene oxide as a reference substance.

(measurement by GPC)

The measurement conditions of GPC are as follows.

< measurement conditions of GPC >

Model: HLC-8120 (manufactured by Tosoh corporation)

Column: TSK gel SuperH4000

TSK gel SuperH3000

TSK gel SuperH2000

(both manufactured by Tosoh corporation)

Column temperature: 40 deg.C

A detector: RI (Ri)

Solvent: tetrahydrofuran (THF)

Flow rate: 0.6 ml/min

Sample concentration: 0.25% by weight

Injection amount: 10 μ l

Standard substance: POLYETHYLENE glycol (manufactured by Tosoh corporation; TSK STANDARD POLYETHYLENE OXIDE)

A data processing device: SC-8020 (made by Tosoh corporation)

Examples of the method for producing the aliphatic alcohol alkylene oxide adduct (a) include a method of adding an alkylene oxide (c) having 2 to 4 carbon atoms to an aliphatic alcohol (a) having 8 to 11 carbon atoms using an acidic catalyst (d) and a basic catalyst (e) as catalysts, which will be described later.

Examples of the aliphatic alcohol (a) having 8 to 11 carbon atoms include those having an aliphatic hydrocarbon group as defined above in R¹An alcohol having a hydroxyl group bonded thereto.

Specific examples of the alkylene oxide (c) having 2 to 4 carbon atoms include EO, PO and BO.

As a method for adding the alkylene oxide (c) having 2 to 4 carbon atoms to the aliphatic alcohol (a) having 8 to 11 carbon atoms, a usual method can be used, and from the viewpoint of suppressing an offensive odor, a method of carrying out a reaction in 2 stages as follows is preferable.

An aliphatic alcohol (a) having 9 to 10 carbon atoms is charged into a pressurized reaction vessel, and an alkylene oxide (c) having 2 to 4 carbon atoms [ 0.5 to 5 moles per 1 mole of the aliphatic alcohol (a) ] is blown in the presence of an acidic catalyst (d) to carry out the reaction under normal pressure or under pressure. The reaction temperature is preferably 50-200 ℃, and the reaction time is preferably 2-20 hours.

After the addition reaction of the alkylene oxide (c) is completed, the catalyst is neutralized, treated with an adsorbent to remove the catalyst, and purified, whereby an alkylene oxide adduct (a1) which is a precursor of the aliphatic alcohol alkylene oxide adduct (a) can be obtained.

The alkylene oxide adduct (a1) thus obtained is added with a basic catalyst (e), and the alkylene oxide (c) which may be the same as or different from the above is further subjected to addition reaction by the same method as described above to obtain the aimed aliphatic alcohol alkylene oxide adduct (a).

Examples of the acidic catalyst (d) include a perhalogenated acid (salt), a sulfuric acid (salt), a phosphoric acid (salt), a nitric acid (salt), and a metal salt of a perfluoroalkylsulfonic acid. The metal for forming the salt is not particularly limited, and a metal having a valence of 2 to 3 is preferable.

The metal having a valence of 2 to 3 is Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, Cd, Ti, Hf, Cr, Mo, Mn, Fe, Pd and a rare earth atom, more preferably Mg, Zn, Ca, Sr, Ba, Al, Cu, Cd, Ti, Cr, Fe and a rare earth atom, and particularly preferably Mg, Zn, Al, Ti, Fe and Sc.

Examples of the halogen of the perhalogenated acid (salt) include chlorine, bromine and iodine, and chlorine is preferable.

As the metal salt of perfluoroalkylsulfonic acid, trifluoromethanesulfonic acid salt and pentafluoroethanesulfonic acid salt are preferable. Scandium trifluoromethanesulfonate is more preferable.

The acidic catalyst (d) is preferably a perchlorate or a perfluoroalkylsulfonate of a metal having a valence of 2 to 3, more preferably a perchlorate, a trifluoromethanesulfonate or a pentafluoroethanesulfonate of a metal selected from the group consisting of Mg, Zn and Al, and particularly preferably magnesium perchlorate, zinc perchlorate, aluminum perchlorate or scandium trifluoromethanesulfonate.

In the case of performing the reaction in 2 stages as described above, the amount of the acidic catalyst (d) to be used is preferably 0.001 to 1% by weight based on the weight of the alkylene oxide adduct (a1) from the viewpoints of reaction rate and economy. More preferably 0.003 to 0.8 wt%, particularly preferably 0.005 to 0.5 wt%.

Examples of the basic catalyst (e) include hydroxides or alkoxides of alkali metals or alkaline earth metals (lithium, sodium, potassium, cesium, magnesium, calcium, barium, and the like) (e.g., methoxides, ethoxides, propoxides, and butoxides), tertiary amines (e.g., triethylamine, trimethylamine), quaternary ammonium salts (e.g., tetramethylammonium hydroxide), and the like. Among these, potassium hydroxide, sodium hydroxide, and cesium hydroxide are preferable.

In the case of performing the reaction in 2 stages as described above, the amount of the basic catalyst (e) to be used is preferably 0.0001 to 1% by weight based on the weight of the aliphatic alcohol alkylene oxide adduct (a) from the viewpoints of reaction rate and economy. More preferably 0.001 to 0.5% by weight.

In the sizing composition for fibers of the present invention, the compound (B) is at least one selected from the group consisting of a polyester (B1), a polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), and a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (a).

One compound (B) may be used alone, or two or more compounds may be used in combination.

It is to be noted that (meth) acryloyl means acryloyl and/or methacryloyl, and (meth) acrylate means acrylate and/or methacrylate.

Examples of the polyester (B1) include reaction products of diols with dicarboxylic acids or dicarboxylic anhydrides, lactone ring-opening polymers, and polyhydroxycarboxylic acids.

The diol is preferably an aliphatic alkanediol having 2 to 30 carbon atoms (ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol), an alkylene oxide adduct of an aliphatic alkanediol having 2 to 30 carbon atoms and having 2 to 4 carbon atoms, an alkylene oxide adduct of an alkyl primary amine (preferably having 1 to 20 carbon atoms, specifically methylamine, ethylamine, propylamine, octylamine, dodecylamine, etc.), an alkylene oxide adduct of an aromatic ring-containing dihydric phenol (preferably having 6 to 20 carbon atoms, specifically bisphenol a, bisphenol S, cresol, etc.), or the like. The diols may be used alone or in combination of two or more.

The number of moles of alkylene oxide added is preferably 2 to 100 moles per 1 mole of the diol, the primary alkylamine, or the aromatic ring-containing dihydric phenol.

The dicarboxylic acid includes dicarboxylic acids having 2 to 24 carbon atoms, and specifically includes saturated aliphatic dicarboxylic acids having 2 to 24 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, and the like), unsaturated aliphatic carboxylic acids having 2 to 24 carbon atoms (maleic acid, fumaric acid, and the like), and aromatic dicarboxylic acids having 2 to 24 carbon atoms (phthalic acid, terephthalic acid, isophthalic acid, and the like).

Examples of the dicarboxylic anhydride include dicarboxylic anhydrides having 2 to 24 carbon atoms (e.g., maleic anhydride and phthalic anhydride).

Examples of the lactone ring-opening polymer include polymers obtained by ring-opening polymerization of lactones (β -propiolactone, γ -butyrolactone, δ -valerolactone, and ∈ -caprolactone) such as a C3-12 monolactone (the number of ester groups in the ring is 1) using a catalyst such as a metal oxide or an organic metal compound.

Examples of the polyhydroxycarboxylic acid include those obtained by dehydrating and condensing hydroxycarboxylic acids (e.g., glycolic acid and lactic acid).

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

Examples of the polyol include polyester polyols (polyethylene adipate glycol, polybutylene adipate glycol, neopentyl adipate glycol, polybutylene terephthalate glycol, polycaprolactone glycol, polypentanolide glycol, and polyhexamethylene carbonate glycol); polyether polyols (polyethylene glycol, polypropylene glycol, polyethylene/propylene glycol, polytetramethylene glycol, and alkylene oxide adducts of bisphenols having 2 to 4 carbon atoms).

The number average molecular weight of the polyol is preferably 40 to 4000.

Specific examples of the organic diisocyanate include aromatic diisocyanates having 8 to 30 carbon atoms [2,4 ' -or 4,4 ' -diphenylmethane diisocyanate (MDI), 2, 4-or 2, 6-Toluene Diisocyanate (TDI), 4 ' -dibenzyl diisocyanate, 1, 3-or 1, 4-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, etc. ]; aliphatic diisocyanates having 4 to 30 carbon atoms [ e.g., ethylene diisocyanate, Hexamethylene Diisocyanate (HDI), lysine diisocyanate, etc. ]; alicyclic diisocyanates having 6 to 30 carbon atoms [ isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate, and the like ]; and mixtures of two or more thereof.

Examples of the compound having an epoxy group (B3) include compounds having 1 or 2 or more epoxy groups in 1 molecule, and specific examples thereof include glycidyl ethers, diglycidyl esters, diglycidyl amines, and alicyclic diepoxides.

Examples of the glycidyl ether include diglycidyl ethers of dihydric phenols, glycidyl ethers of monohydric alcohols, and diglycidyl ethers of dihydric alcohols.

Examples of the diglycidyl ether of the dihydric phenol include a condensate (including a polycondensate) of a dihydric phenol having 6 to 30 carbon atoms and epichlorohydrin, and diglycidyl ethers at both ends. Examples of the dihydric phenol having 6 to 30 carbon atoms include bisphenols (e.g., bisphenol F, bisphenol a, bisphenol B, bisphenol AD, bisphenol S, and halogenated bisphenol a), catechin, resorcinol, hydroquinone, 1, 5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4, 4 '-dihydroxybiphenyl, tetramethylbiphenyl, and 9, 9' -bis (4-hydroxyphenyl) fluorene.

Examples of the glycidyl ether of the monohydric alcohol include a condensate of a monohydric alcohol having 1 to 30 carbon atoms and epichlorohydrin, and the glycidyl ether is terminated. Examples of the monohydric alcohol having 1 to 30 carbon atoms include methanol, ethanol, butanol, hexanol, cyclohexanol, octanol, dodecanol, tetradecanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, and triacontanol.

Examples of the diglycidyl ether of a diol include a condensate (including a polycondensate) of a diol having 2 to 100 carbon atoms and epichlorohydrin, and a diglycidyl ether-terminated product thereof. Examples of the dihydric alcohol having 2 to 100 carbon atoms include ethylene glycol, propylene glycol, tetramethylene glycol, 1, 6-hexanediol, neopentyl glycol, polyethylene glycol having a number average molecular weight (hereinafter abbreviated as Mn) of 106 to 1932, polypropylene glycol having Mn of 134 to 5818, polytetramethylene ether glycol having Mn of 162 to 1818, and an alkylene oxide (1 to 21 moles) adduct of bisphenol a having 2 to 4 carbon atoms.

Regarding the above-mentioned diglycidyl ethers (diglycidyl ethers of dihydric phenols and diglycidyl ethers of dihydric alcohols), the molar ratio of the dihydric phenol unit or the dihydric alcohol unit to the epichlorohydrin unit contained in the diglycidyl ethers { (dihydric phenol unit or dihydric alcohol unit): (Epichlorohydrin unit) } is represented by n: n + 1. n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. The diglycidyl ether may be a mixture (e.g., a mixture having a different degree of polycondensation) having n of 1 to 10.

Examples of the diglycidyl ester include diglycidyl esters of aromatic dicarboxylic acids having 8 to 20 carbon atoms and diglycidyl esters of aliphatic dicarboxylic acids having 2 to 20 carbon atoms.

Examples of the diglycidyl ester of an aromatic dicarboxylic acid having 8 to 20 carbon atoms include a product having 2 glycidyl groups as a condensate (including a polycondensate) of an aromatic dicarboxylic acid having 8 to 20 carbon atoms and epichlorohydrin.

Examples of the aromatic dicarboxylic acid having 8 to 20 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, phenylpentanedioic acid, phenyladipic acid, biphenyldicarboxylic acid, and naphthalenedicarboxylic acid.

Examples of the diglycidyl ester of the aliphatic dicarboxylic acid having 2 to 20 carbon atoms include a product having 2 glycidyl groups as a condensate (including a polycondensate) of an aliphatic dicarboxylic acid having 2 to 20 carbon atoms and epichlorohydrin.

Examples of the aliphatic dicarboxylic acid having 2 to 20 carbon atoms include oxalic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.

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

Examples of the diglycidyl amine include N-glycidyl compounds (e.g., N-diglycidyl aniline and N, N-diglycidyl toluidine) obtained by reacting epichlorohydrin with an aromatic amine having 6 to 20 carbon atoms and 2 to 4 active hydrogen atoms.

Examples of the aromatic amine having 6 to 20 carbon atoms and 2 to 4 active hydrogen atoms include aniline, phenylenediamine, toluenediamine, toluidine, and the like.

In the diglycidyl amine, 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, and particularly preferably 1 to 5. The diglycidyl amine may be a mixture of n-1 to 10.

Examples of the alicyclic diepoxide include alicyclic epoxides having 6 to 50 carbon atoms and 2 epoxy groups [ vinylcyclohexene diepoxide, limonene dioxide, dicyclopentadiene dioxide, bis (2, 3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) butylamine, and the like ].

Among these, from the viewpoint of the strength of a molded article of a composite material using the sizing agent composition for fibers, diglycidyl ethers are preferable, diglycidyl ethers of 2-valent aromatic alcohols are more preferable, diglycidyl ethers of bisphenols are particularly preferable, and diglycidyl ethers of bisphenol a (bisphenol a type epoxy resins) are most preferable.

Examples of the compound having a (meth) acryloyl group (B4) include a (meth) acrylate-modified thermoplastic resin and a vinyl ester resin.

The (meth) acrylate-modified thermoplastic resin includes a modified product obtained by modifying hydroxyl groups of thermoplastic resin having alcoholic hydroxyl groups { polyurethane, polyester, polyether (polypropylene glycol, polyethylene glycol, and the like) } with (meth) acrylic acid, and examples thereof include polyurethane (di/mono) (meth) acrylate, polyester (di/mono) (meth) acrylate, and polyether (di/mono) (meth) acrylate. The term "(di/mono) (meth) acrylate" means di (meth) acrylate and/or mono (meth) acrylate.

Examples of the vinyl ester resin include bisphenol epoxy resin (meth) acrylate modified products { terminal (meth) acrylate modified resins obtained by reacting an epoxy group of a bisphenol a epoxy resin with a carboxyl group of (meth) acrylic acid }.

The polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (A) includes alkylene oxide adducts having 2 to 4 carbon atoms of compounds having an active hydrogen group having 1 to 20 carbon atoms and sulfuric acid ester salts thereof.

The active hydrogen group is a group having a highly reactive hydrogen atom bonded to an atom having a large electronegativity (oxygen, nitrogen, and the like), and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a mercapto group, and phosphoric acid.

Examples of the compound having an active hydrogen group and having 1 to 20 carbon atoms include aliphatic alkanediols having 2 to 30 carbon atoms, primary alkylamines, and aromatic ring-containing diphenols exemplified in the description of the polyester (B1). As the compounds other than the above, 1-membered alcohols having 2 to 30 carbon atoms (methanol, ethanol, eicosanol, cyclohexanol and oleyl alcohol), phenol and the like can be used.

Among the polyether compounds (B5), preferred are alkylene oxide adducts of phenols (bisphenol a, bisphenol S, cresol, etc.), alkylene oxide adducts of alkyl (preferably alkyl having 9 to 15 carbon atoms) phenols, alkylene oxide adducts of aralkyl (preferably alkyl having 2 to 10 carbon atoms) phenols (styrenated phenol, styrenated cumylphenol, styrenated cresol, etc.), sulfuric acid ester salts of the alkylene oxide adducts of the aforementioned alkylphenols, sulfuric acid ester salts of the alkylene oxide adducts of the aforementioned aralkyl phenols, and mixtures thereof, and more preferred are alkylene oxide adducts of aralkyl phenols, sulfuric acid ester salts of the alkylene oxide adducts of aralkyl phenols, and mixtures thereof.

The number of moles of alkylene oxide added to the polyether compound (B5) is preferably 2 to 100 moles in view of water solubility and emulsifiability of the sizing agent composition for fibers and fiber opening and sizing properties of fiber bundles treated with the sizing agent composition for fibers.

Among these, from the viewpoint of the strength of the composite material produced using the sizing agent composition for fibers, the polyester (B1), the compound having an epoxy group (B3), and the compound having a (meth) acryloyl group (B4) are preferable, and the polyester (B1) and the compound having an epoxy group (B3) are more preferable.

In addition, from the viewpoint of further improving the strength of a composite material using the sizing agent composition for fibers, the compound (B) is preferably used in combination of the polyester (B1) and the compound having an epoxy group (B3), in combination of the polyester (B1) and the compound having a (meth) acryloyl group (B4), and more preferably used in combination of the polyester (B1) and the compound having an epoxy group (B3).

In addition, from the viewpoint of further suppressing fuzzing of the fiber bundle, it is preferable to further use a polyether compound (B5).

The weight ratio [ (a)/(B) ] of the aliphatic alcohol alkylene oxide adduct (a) to the compound (B) is preferably 0.1/99.9 to 60/40, more preferably 1/99 to 50/50, and particularly preferably 5/95 to 40/60, from the viewpoint of satisfying both the sizing properties of the fiber bundle and the strength of the composite material using the sizing agent composition for fibers.

The sizing composition for fibers of the present invention may contain a surfactant (C) which is a compound other than the aliphatic alcohol alkylene oxide adduct (a) and the compound (B).

When the surfactant (C) is contained, the sizing agent attached to the fibers is easily smoothed, and fluffing of the fiber bundles can be further suppressed.

Further, when the surfactant (C) is contained, it is also preferable in that an aqueous emulsion not containing a large amount of an organic solvent in a sizing agent dispersion for fibers described later can be easily produced.

Examples of the surfactant (C) include surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

Examples of such surfactants include alkylglycosides (e.g., decyl glucoside) and alkylbenzenesulfonates (e.g., sodium dodecylbenzenesulfonate).

The surfactant (C) may be used alone or in combination of two or more.

Among the surfactants (C), anionic surfactants and nonionic surfactants are preferable in terms of ease of preparation of the aqueous emulsion.

Additives may be added to the fiber sizing composition of the present invention as needed. Examples of the additives include a smoothing agent, a preservative, and an antioxidant.

Examples of the smoothing agent include waxes (polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, modified polyethylene, modified polypropylene, etc.), esters of higher fatty acids (having 12 to 24 carbon atoms) and alkyl groups (having 1 to 24 carbon atoms) (methyl stearate, ethyl stearate, propyl stearate, butyl stearate, octyl stearate, stearyl stearate, etc.), higher fatty acids (having 12 to 24 carbon atoms) (myristic acid, palmitic acid, stearic acid, etc.), and the like.

Examples of the preservative include benzoic acids, salicylic acids, sorbic acids, quaternary ammonium salts, imidazoles, and the like.

Examples of the antioxidant include phenols (e.g., 2, 6-di-t-butyl-p-cresol), thiodipropionates (e.g., dilauryl 3, 3' -thiodipropionate), and phosphites (e.g., triphenyl phosphite).

The content of the aliphatic alcohol alkylene oxide adduct (a) is preferably 1% by weight or more, more preferably 5% by weight or more based on the total weight of the sizing composition for fibers, from the viewpoint of sizing properties of fiber bundles and prevention of fuzz.

In addition, the content of the aliphatic alcohol alkylene oxide adduct (a) is preferably 40% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less based on the total weight of the fiber sizing composition, from the viewpoints of the sizing property of the fiber bundle, the prevention of fuzz formation, and the impregnation property of the fiber sizing composition into the matrix resin described below in detail.

The content of the compound (B) is preferably 60% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more based on the total weight of the sizing composition for fibers, from the viewpoint of the strength of the composite material using the sizing composition for fibers.

The content of the compound (B) is preferably 99% by weight or less, and more preferably 95% by weight or less, based on the total weight of the sizing agent composition for fibers, from the viewpoint of suppressing fuzzing of fiber bundles.

When the sizing agent composition for fibers of the present invention contains the polyether compound (B5), the weight ratio of the aliphatic alcohol alkylene oxide adduct (a) to the polyether compound (B5) other than the polyester (B1), the polyurethane (B2), the compound having an epoxy group (B3), and the compound having a (meth) acryloyl group (B4), [ (the weight of a)/(the weight of B5) ], is preferably 5/95 to 60/40, from the viewpoints of suppressing fuzzing of fiber bundles and emulsion stability of the sizing agent composition for fibers.

When the surfactant (C) is used, the content thereof is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, and particularly preferably 2 to 15% by weight based on the total weight of the sizing agent composition for fibers, from the viewpoint of the sizing property of the fiber bundle.

The method for producing the sizing composition for fibers of the present invention is not particularly limited, and examples thereof include a method in which the aliphatic alcohol alkylene oxide adduct (a), the compound (B), and if necessary, the surfactant (C) and other additives are charged into a mixing vessel without any particular limitation on the order of charging, and stirred at preferably 20 to 150 ℃, more preferably 50 to 120 ℃ until uniform.

The fiber sizing composition of the present invention is dispersed in a solvent to form a fiber sizing dispersion.

The fiber sizing agent solution of the present invention is obtained by dissolving the fiber sizing agent of the present invention in a solvent.

By dissolving or dispersing the sizing agent composition for fibers in a solvent, it is easy to make the amount of the sizing agent composition for fibers adhering to the fiber bundle an appropriate amount.

Examples of the solvent include water and an organic solvent.

Examples of the organic solvent include 1-membered alcohols having 1 to 4 carbon atoms (such as methanol, ethanol and isopropanol), ketones having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), glycols having 2 to 6 carbon atoms (such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol), mono-lower alkyl (alkyl having 1 to 4 carbon atoms), ethers thereof, dimethylformamide, aromatic hydrocarbons (such as toluene and xylene), alkyl acetates having 3 to 5 carbon atoms (such as methyl acetate and ethyl acetate), and the like.

The above solvents may be used singly or in combination of two or more. Among the above solvents, from the viewpoint of safety such as ignition, a mixed solvent of water and a water-miscible organic solvent (an organic solvent which can be uniformly mixed when mixed with water at 25 ℃ in a volume ratio of 1: 1) and water is preferable, and water is more preferable.

From the viewpoint of cost and the like, the fiber sizing dispersion and the fiber sizing solution of the present invention are preferably high in concentration when distributed and low in concentration when the fiber bundle is produced. That is, by circulating at a high concentration, transmission cost, storage cost, and the like can be reduced; by treating the fibers at a low concentration, a fiber bundle having both excellent sizing properties and opening properties can be produced.

From the viewpoint of storage stability and the like, the concentration (weight ratio of components other than the solvent) when the fiber sizing dispersion and the fiber sizing solution are at a high concentration is preferably 30 to 80% by weight, and more preferably 40 to 70% by weight.

The concentration of the sizing agent dispersion for fiber and the sizing agent solution for fiber is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight when the concentration is low, from the viewpoint of enabling the amount of the sizing agent for fiber to be attached to an appropriate amount during the production of a fiber bundle.

The method for producing the fiber sizing agent dispersion and the fiber sizing agent solution of the present invention is not particularly limited, and examples thereof include a method in which a solvent is added to the fiber sizing agent composition of the present invention, and the fiber sizing agent composition is dissolved or emulsified and dispersed in the solvent.

From the viewpoint of ease of mixing, the temperature at which the sizing agent composition for fibers is dissolved or emulsified and dispersed in the solvent is preferably 20 to 90 ℃, and more preferably 40 to 90 ℃.

The time for dissolving or emulsifying and dispersing the sizing agent composition for fibers in the solvent is preferably 1 to 20 hours, and more preferably 2 to 10 hours.

In dissolving or emulsifying and dispersing the sizing agent composition for fibers in an aqueous medium, a known mixing apparatus, dissolving apparatus and emulsifying and dispersing apparatus can be used, and specifically, stirring blades (blade shape: paddle type, three-bladed paddle, etc.), a nauta mixer [ manufactured by Hosokawa Micron Co., Ltd., etc. ], a ribbon mixer, a conical mixer, a mortar mixer, a universal mixer [ 5DM-L "[ manufactured by Sanyo Co., Ltd. ] and the like ], a Henschel mixer [ manufactured by Nippon Coke Industrial Co., Ltd., etc. ] and an autoclave can be used.

Examples of fibers to which the sizing composition for fibers, the sizing dispersion for fibers, or the sizing solution for fibers of the present invention can be applied include inorganic fibers (glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, slag fibers, and the like), organic fibers (aramid fibers and the like), and the like. Among these, carbon fibers are preferable in view of the strength of a molded article of a composite material using the sizing agent composition for fibers and fibers.

The fiber bundle of the present invention is a fiber bundle obtained by treating at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers and slag fibers with the above-mentioned sizing agent composition for fibers.

The fiber bundle of the present invention comprises: at least one fiber selected from the group consisting of carbon fiber, glass fiber, aramid fiber, ceramic fiber, metal fiber, mineral fiber and slag fiber;

an aliphatic alcohol alkylene oxide adduct (A) represented by the general formula (1); and

compound (B').

R¹O(AO)_mH (1)

[ in the general formula (1), R¹An aliphatic hydrocarbon group having 8 to 11 carbon atoms and having 3 or more methyl groups; AO represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents a number of 3 to 10 as a number-average addition mole number of alkylene oxide.]

Here, the compound (B') is at least one selected from the group consisting of a reaction product of a polyester (B1), a polyurethane (B2), a compound having an epoxy group (B3), a compound having a (meth) acryloyl group (B4), a polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (a), a compound having an epoxy group (B3), and a compound having a (meth) acryloyl group (B4).

The polyester (B1), the polyurethane (B2), the compound having an epoxy group (B3), the compound having a (meth) acryloyl group (B4), and the polyether compound (B5) other than the aliphatic alcohol alkylene oxide adduct (a) in the compound (B') include the same compounds as the polyester (B1), the polyurethane (B2), the compound having an epoxy group (B3), the compound having a (meth) acryloyl group (B4), and the polyether compound (B5) exemplified in the description of the sizing agent composition for fibers of the present invention, and preferred compounds are the same.

The reaction product of the compound having an epoxy group (B3) and the compound having a (meth) acryloyl group (B4) are compounds obtained by chemical changes of the compound having an epoxy group (B3) and the compound having a (meth) acryloyl group (B4) contained in the sizing agent composition for fibers by heat treatment or the like in the production of the fiber bundle of the present invention.

Examples of the reaction product of the compound having an epoxy group (B3) include a polymer (dimer or more) containing the compound having an epoxy group (B3) as an essential structural unit, a reaction product of the compound having an epoxy group (B3) and carbon fibers, and a reaction product of a polymer containing the compound having an epoxy group (B3) as an essential structural monomer and carbon fibers.

Examples of the reaction product of the compound having a (meth) acryloyl group (B4) include a polymer (dimer or more) containing the compound having a (meth) acryloyl group (B4) as an essential structural monomer.

The content of the aliphatic alcohol alkylene oxide adduct (a) is preferably 0.01 wt% or more, more preferably 0.07 wt% or more based on the weight of the fiber bundle of the present invention, from the viewpoint of sizing property of the fiber bundle and prevention of fuzz.

In addition, the content of the aliphatic alcohol alkylene oxide adduct (a) is preferably 1% by weight or less, more preferably 0.3% by weight or less, and particularly preferably 0.15% by weight or less based on the weight of the fiber bundle of the present invention, from the viewpoints of the sizing property of the fiber bundle, the prevention of fuzz formation, and the impregnation property of the fiber sizing agent composition into the matrix resin described below in detail.

In the case where the fiber bundle of the present invention contains the polyether compound (B5), the weight ratio of the aliphatic alcohol alkylene oxide adduct (a) to the polyether compound (B5) other than the polyester (B1), the polyurethane (B2), the compound having an epoxy group (B3) and the compound having a (meth) acryloyl group (B4), i.e., [ (the weight of a)/(the weight of B5) ], is preferably 5/95 to 60/40, from the viewpoints of suppressing fuzzing of the fiber bundle and emulsion stability of the sizing agent composition for fibers.

When the surfactant (C) is used, the content thereof is preferably 0.001 to 0.9% by weight, more preferably 0.002 to 0.6% by weight, and particularly preferably 0.004 to 0.45% by weight based on the weight of the fiber bundle, from the viewpoint of sizing properties of the fiber bundle.

The method for producing a fiber bundle of the present invention includes a method in which at least one fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, and slag fibers is treated with the fiber sizing composition of the present invention, the fiber sizing dispersion of the present invention, or the fiber sizing solution of the present invention to obtain a fiber bundle.

The fiber bundle of the present invention is preferably formed by bundling 3,000 to 50,000 fibers.

In addition, the fiber bundle of the present invention can sufficiently suppress fuzz even when the number of fibers is large (20,000 or more).

The fiber treatment method includes a spraying method and a dipping method. The amount of the sizing composition for fibers attached to the fibers is preferably 0.05 to 5% by weight, more preferably 0.2 to 2.5% by weight, based on the weight of the fibers. When the amount of the sizing agent composition for fibers attached is within this range, the sizing property is excellent.

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

The composite material of the present invention comprises the fiber bundles of the present invention and/or the fiber product of the present invention and a matrix resin. The composite material of the present invention may contain a catalyst as needed.

In the case where a thermosetting resin described later is contained as the matrix resin, the composite material of the present invention may contain a reaction product of the thermosetting resin and the compound (B') [ the compound (B3) having an epoxy group, the compound (B4) having a (meth) acryloyl group, and the like ] contained in the fiber bundle and the fiber product of the present invention.

Examples of the matrix resin include thermoplastic resins (polypropylene, polyamide, polyethylene terephthalate, polycarbonate, polyphenylene sulfide, etc.) and thermosetting resins [ the compound having an epoxy group (B3), unsaturated polyester resins (resins described in japanese patent No. 3723462, etc.), the vinyl ester resins and phenol resins (resins described in japanese patent No. 3723462, etc.) ].

Examples of the catalyst for the compound having an epoxy group (B3) include a curing agent and a curing accelerator for epoxy resins, which are known (catalysts described in jp 2005-213337 a).

Further, as the catalyst for the unsaturated polyester resin and vinyl ester resin, peroxides (benzoyl peroxide, t-butyl peroxybenzoate, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, 1-di (t-butylperoxy) butane, di (4-t-butylcyclohexyl) peroxydicarbonate, etc.) and azo compounds (azobisisovaleronitrile, etc.) can be mentioned.

In the composite material of the present invention, the weight ratio of the matrix resin to the fiber bundles and/or the fiber product (matrix resin/fiber bundles) is preferably 10/90 to 90/10, more preferably 20/80 to 70/30, and particularly preferably 30/70 to 60/40, from the viewpoint of the strength of the molded body of the composite material.

When the composite material contains a catalyst, the content of the catalyst is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 1 to 3% by weight, based on the matrix resin, from the viewpoint of the strength of the molded article of the composite material.

The composite material can be produced by impregnating a fiber bundle and/or a fiber product with a hot-melt (preferably, a melting temperature: 60 to 350 ℃) matrix resin or a matrix resin diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, or the like). When a solvent is used, the prepreg is preferably dried to remove the solvent.

In the composite material of the present invention, when the matrix resin is a thermoplastic resin, the prepreg can be heat-molded and cured at normal temperature to form a molded body.

In the composite material of the present invention, when the matrix resin is a thermosetting resin, the prepreg can be heat-molded and cured to form a molded body.

These resins are not necessarily completely cured, and are preferably cured to such an extent that the molded article can maintain its shape. After molding, it may be further heated to completely cure it.

The method of thermoforming is not particularly limited, and examples thereof include a filament winding method (a method of winding and thermoforming while applying tension to a rotating mandrel), a press molding method (a method of laminating prepregs and thermoforming), an autoclave method (a method of pressing prepregs into a mold with pressure applied and thermoforming), and a method of mixing chopped fibers or milled fibers with a matrix resin and injection molding.

[ examples ]

The present invention is further illustrated by the following examples, but the present invention is not limited thereto. Hereinafter,% represents% by weight and parts represents parts by weight unless otherwise specified.

Production example 1> [ Synthesis of EO4 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-1) ]

144 parts (1 part by mole) of 3,5, 5-trimethyl-1-hexanol and 1 part (0.002 part by mole) of aluminum perchlorate nonahydrate were charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping flask, and then the vessel was sealed after nitrogen substitution, heated to 70 ℃ and dehydrated under reduced pressure for 1 hour. The reaction mixture was heated to 80 ℃ and EO 88 parts (2 parts by mole) were added dropwise over 10 hours while adjusting the pressure to 0.2MPaG or less, followed by aging at 95 ℃ for 5 hours. Then, the mixture was cooled to 70 ℃ and 10 parts of an adsorbent "Kyoward 600" [ manufactured by Kyowa chemical Co., Ltd ] was charged, the mixture was stirred at 70 ℃ for 1 hour to conduct a treatment, and then the adsorbent was filtered off to obtain an EO 2 molar adduct of 3,5, 5-trimethyl-1-hexanol.

To the EO 2 molar adduct of 3,5, 5-trimethyl-1-hexanol thus obtained was added 0.1 part of potassium hydroxide, and then the mixture was sealed under nitrogen gas, heated to 70 ℃ and dehydrated under reduced pressure for 1 hour. The reaction mixture was heated to 140 ℃ and EO 88 parts (2 parts by mole) was added dropwise over 3 hours while adjusting the pressure to 0.5MPaG or less, followed by aging at 140 ℃ for 2 hours. Then, the mixture was cooled to 70 ℃ and then 10 parts of an adsorbent "Kyoward 600" [ manufactured by Kyowa chemical Co., Ltd ] was charged, the mixture was stirred at 70 ℃ for 1 hour to conduct the treatment, and then the adsorbent was filtered off to obtain an EO4 molar adduct of 3,5, 5-trimethyl-1-hexanol (A-1).

The EO4 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-1) is a compound represented by the general formula (1) R¹Is 3,5, 5-trimethylhex-1-yl (number of methyl groups: 4), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 4.

< production example 2> [ Synthesis of EO6 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-2) ]

An EO6 molar adduct (a-2) of 3,5, 5-trimethyl-1-hexanol was obtained in the same manner as in production example 1, except that 88 parts (2 parts by mol) of EO in the 2 nd addition was changed to 176 parts (4 parts by mol) of EO in production example 1.

The EO6 mol adduct (A-2) of 3,5, 5-trimethyl-1-hexanol is a compound represented by the general formula (1) R¹Is 3,5, 5-trimethylhex-1-yl (number of methyl groups: 4), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 6.

Production example 3> [ Synthesis of EO 8 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-3) ]

An EO 8 molar adduct (a-3) of 3,5, 5-trimethyl-1-hexanol was obtained in the same manner as in production example 1, except that 88 parts (2 parts by mol) of EO in the 2 nd addition was changed to 264 parts (6 parts by mol) of EO in production example 1.

The EO 8 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-3) is a compound represented by the general formula (1) R¹Is 3,5, 5-trimethylhex-1-yl (number of methyl groups: 4), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 8.

Production example 4> [ Synthesis of PO 1 mol EO 3 mol adduct of decyl alcohol (A-4) ]

A pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping flask was charged with 158 parts (1 part by mol) of "decanol" [ produced by KH Neochem corporation ] and 0.5 part (0.009 part by mol) of potassium hydroxide, and the vessel was sealed after nitrogen substitution, heated to 70 ℃ and dehydrated under reduced pressure for 1 hour. The mixture was heated to 160 ℃ and, while adjusting the pressure to 0.5MPaG or less, 58 parts (1 part by mole) of 1, 2-propylene oxide and then 132 parts (3 parts by mole) of EO were added dropwise over a period of 5 hours, followed by aging at 160 ℃ for 2 hours. Then, the mixture was cooled to 70 ℃ and 10 parts of an adsorbent "Kyoward 600" (manufactured by Kyowa Kagaku Co., Ltd.) were charged, and the mixture was stirred at 70 ℃ for 1 hour to conduct the treatment, and then the adsorbent was filtered off to obtain a PO 1 mol EO 3 mol adduct of decanol (A-4).

PO 1 mol EO 3 mol adduct (A-4) of decanol represented by the general formula (1)Compound (I) R¹Is decyl, AO is ethyleneoxy and propyleneoxy, and m (number average molar number of alkylene oxide added) is 4.

By the way of illustration¹The results of H-NMR and gas chromatography analyses of decanol produced by KH Neochem as a raw material were as described above at R¹An alcohol having a hydroxyl group bonded thereto. In addition, R¹Has 10 carbon atoms, R¹The number average number of methyl groups in (1) molecule was 3.5.

< production example 5> [ Synthesis of EO6 mol adduct of decanol (A-5) ]

A pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping flask was charged with 158 parts (1 part by mol) of "decanol" [ produced by KH Neochem corporation ] and 0.5 part (0.009 part by mol) of potassium hydroxide, and the vessel was sealed after nitrogen substitution, heated to 70 ℃ and dehydrated under reduced pressure for 1 hour. The reaction mixture was heated to 160 ℃ and EO 264 parts (6 parts by mole) were added dropwise over 5 hours while adjusting the pressure to 0.5MPaG or less, followed by aging at 160 ℃ for 2 hours. Then, the mixture was cooled to 70 ℃ and 10 parts of an adsorbent "Kyoward 600" (manufactured by Kyowa chemical Co., Ltd.) were charged, and the mixture was stirred at 70 ℃ for 1 hour to obtain an adsorbent, and the adsorbent was filtered off to obtain an EO6 molar adduct of decanol (A-5).

The EO6 mol adduct (A-5) of decanol is a compound represented by the general formula (1) R¹Is decyl, AO is ethyleneoxy, and m (number average molar addition of alkylene oxide) is 6.

In addition, use of¹The results of H-NMR and gas chromatography analyses of decanol produced by KH Neochem as a raw material were as described above at R¹An alcohol having a hydroxyl group bonded thereto. In addition, R¹Has 10 carbon atoms, R¹The number average number of methyl groups in (1) molecule was 3.5.

< production example 6> [ Synthesis of EO6 mol adduct of nonanol (A-6) ]

A nonanol EO6 mol adduct (A-6) was obtained in the same manner as in production example 5 except that 158 parts (1 mol) of "decanol" was changed to "Exxal 9S" [ nonanol, manufactured by Exxon Mobil ]144 parts (1 mol).

EO6 mol adduct of nonanol (A-6) is a compound represented by the general formula (1) R¹Is nonyl, AO is ethyleneoxy, and m (number average molar addition of alkylene oxide) is 6.

In addition, use of¹As a result of analysis of Exxal 9S manufactured by Exxon Mobil as a raw material by H-NMR and gas chromatography, the above-mentioned results were obtained at R¹An alcohol having a hydroxyl group bonded thereto. In addition, R¹Has a carbon number of 9.0, R¹The number average number of methyl groups in (1) molecule was 3.0.

< production example 7> [ Synthesis of EO 10 mol adduct of undecanol (A-7) ]

A10-mole adduct of undecanol (A-7) was obtained in the same manner as in production example 5, except that "decanol" was changed from 158 parts (1 mole) to "Exxal 11S" [ undecanol, produced by Exxon Mobil ]172 parts (1 mole) and EO was changed from 264 parts (6 moles) to 440 parts (10 moles) in production example 5.

The EO 10 mol adduct of undecanol (A-7) is a compound represented by the general formula (1) R¹Is undecyl, AO is ethyleneoxy and m (number average molar addition of alkylene oxides) is 10.

In addition, use of¹As a result of analysis of Exxal 11S manufactured by Exxon Mobil as a raw material by H-NMR and gas chromatography, the above-mentioned results were obtained at R¹An alcohol having a hydroxyl group bonded thereto. In addition, R¹Has 11.0 carbon atoms, R¹The number average number of methyl groups in (1) molecule was 3.7.

< production example 8> [ Synthesis of EO6 mol adduct of undecanol (A-8) ]

An EO6 mol adduct of undecanol (A-8) was obtained in the same manner as in production example 5 except that 158 parts (1 mol) of "decanol" was changed to "Exxal 11S" [ undecanol, manufactured by Exxon Mobil ]172 parts (1 mol).

The EO6 mol adduct of undecanol (A-8) is a compound represented by the general formula (1) R¹Is undecyl, AO is ethyleneoxy, m (number average molar addition of alkylene oxide)Number) is 6.

In addition, use of¹As a result of analysis of Exxal 11S manufactured by Exxon Mobil as a raw material by H-NMR and gas chromatography, the above-mentioned results were obtained at R¹An alcohol having a hydroxyl group bonded thereto. In addition, R¹Has 11.0 carbon atoms, R¹The number average number of methyl groups in (1) molecule was 3.7.

Production example 9> [ Synthesis of EO 10 mol adduct of 6-methyl-2-heptanol (A-9) ]

A 10-mole EO adduct (a-9) of 6-methyl-2-heptanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mole) of "decanol" was changed to 130 parts (1 part by mole) of 6-methyl-2-heptanol, and 264 parts (6 parts by mole) of EO was changed to 440 parts (10 parts by mole) of EO in production example 5.

The EO 10 mol adduct of 6-methyl-2-heptanol (A-9) is a compound represented by the general formula (1) wherein R¹Is 6-methylhept-2-yl (number of methyl groups: 3), AO is ethyleneoxy and m (number average molar addition of alkylene oxides) is 10.

Production example 10> [ Synthesis of EO 5 mol adduct of 6-methyl-2-heptanol (A-10) ]

A 5-mole EO adduct (a-10) of 6-methyl-2-heptanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mole) of "decanol" was changed to 130 parts (1 part by mole) of 6-methyl-2-heptanol, and 264 parts (6 parts by mole) of EO was changed to 220 parts (5 parts by mole) of EO in production example 5.

The EO 5 mol adduct of 6-methyl-2-heptanol (A-10) is a compound represented by the general formula (1) wherein R¹Is 6-methylhept-2-yl (number of methyl groups: 3), AO is ethyleneoxy and m (number average molar number of alkylene oxide added) is 5.

Production example 11> [ Synthesis of EO 3 mol adduct of 6-methyl-2-heptanol (A-11) ]

An EO 3 mol adduct (a-11) of 6-methyl-2-heptanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mol) of "decanol" was changed to 130 parts (1 part by mol) of 6-methyl-2-heptanol, and 264 parts (6 parts by mol) of EO was changed to 132 parts (3 parts by mol) of EO in production example 5.

6-methyl-2-heptanolEO 3 mol (A-11) of (A) is a compound represented by the general formula (1), R¹Is 6-methylhept-2-yl (number of methyl groups: 3), AO is ethyleneoxy and m (number average molar number of alkylene oxide added) is 3.

< production example 12> [ Synthesis of EO 3 mol adduct of nonanol (A-12) ]

A nonanol EO 3 mol adduct (A-12) was obtained in the same manner as in production example 5 except that "decanol" 158 parts (1 mol) was changed to "Exxal 9S" [ nonanol, produced by Exxon Mobil ]144 parts (1 mol), and EO 264 parts (6 mol) was changed to EO 132 parts (3 mol) in production example 5.

EO 3 mol adduct of nonanol (A-12) is a compound represented by the general formula (1) R¹Is nonyl, AO is ethyleneoxy, and m (number average molar addition of alkylene oxide) is 3.

In addition, use of¹As a result of analysis of Exxal 9S manufactured by Exxon Mobil as a raw material by H-NMR and gas chromatography, the above-mentioned results were obtained at R¹An alcohol having a hydroxyl group bonded thereto. In addition, R¹Has a carbon number of 9.0, R¹The number average number of methyl groups in (1) molecule was 3.0.

< production example 13> [ Synthesis of EO 10 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-13) ]

A 10-mole EO adduct (a-13) of 3,5, 5-trimethyl-1-hexanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mole) of "decanol" was changed to 144 parts (1 part by mole) of 3,5, 5-trimethyl-1-hexanol and 264 parts (6 parts by mole) of EO was changed to 440 parts (10 parts by mole) of EO in production example 5.

The EO 10 mol adduct of 3,5, 5-trimethyl-1-hexanol (A-13) is a compound represented by the general formula (1) R¹Is 3,5, 5-trimethylhex-1-yl (number of methyl groups: 4), AO is ethyleneoxy, and m (number average molar addition of alkylene oxide) is 10.

< preparation example 14> [ Synthesis of EO6 mol adduct of β -citronellol (A-14) ]

An EO6 mol adduct of β -citronellol (a-14) was obtained in the same manner as in production example 5, except that 158 parts (1 part by mol) of "decanol" was changed to 156 parts (1 part by mol) of β -citronellol in production example 5.

The EO6 mol adduct of β -citronellol (A-14) is a compound represented by the general formula (1) R¹Is a 3, 7-dimethyl-6-octen-1-yl group (number of methyl groups: 3), AO is an ethyleneoxy group, and m (number-average molar number of added alkylene oxide) is 6.

Production example 15 [ Synthesis of EO6 mol adduct of 4-t-butylcyclohexanol (A-15) ]

An EO6 molar adduct of 4-tert-butylhexanol (A-15) was obtained in the same manner as in production example 5, except that 158 parts (1 part by mol) of "decanol" was changed to 156 parts (1 part by mol) of 4-tert-butylcyclohexanol in production example 5.

The EO6 mol adduct of 4-t-butylhexanol (A-15) is a compound represented by the general formula (1) R¹Is 4-t-butylcyclohex-1-yl (number of methyl groups: 3), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 6.

< comparative production example 1> [ Synthesis of EO 5 mol adduct of 1-hexanol (A' -1) ]

A 5-mole EO adduct (a' -1) of 1-hexanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mole) of "decanol" was changed to 102 parts (1 part by mole) of n-hexanol and 264 parts (6 parts by mole) of EO was changed to 220 parts (5 parts by mole) of EO in production example 5.

The EO 5 mol adduct of 1-hexanol (A' -1) is a compound represented by the following general formula (2), R²Is n-hexyl (number of methyl groups: 1), AO is ethyleneoxy group, and m (number average molar number of addition of alkylene oxide) is 5.

R²O(AO)_mH (2)

[ in the general formula (2), R²Is an aliphatic hydrocarbon group; AO represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents the number average molar addition of alkylene oxide.]

< comparative production example 2> [ Synthesis of PO 2 mol EO 1 mol adduct of 2-ethylhexanol (A' -2) ]

A PO 2 mol EO 1 mol adduct (a' -2) of 2-ethylhexanol was obtained in the same manner as in production example 4 except that 158 parts (1 part by mol) of "decanol" was changed to 130 parts (1 part by mol) of 2-ethylhexanol, 58 parts (1 part by mol) of 1, 2-propylene oxide was changed to 116 parts (2 parts by mol) of 1, 2-propylene oxide, and 132 parts (3 parts by mol) of EO was changed to 44 parts (1 part by mol) of EO in production example 4.

The PO 2 mol EO 1 mol adduct (A' -2) of 2-ethylhexanol is a compound represented by the general formula (2) wherein R is²Is 2-ethylhexyl (number of methyl groups: 2), AO is ethyleneoxy and propyleneoxy, and m (number average molar number of alkylene oxide added) is 3.

< comparative production example 3> [ Synthesis of EO 8 mol adduct of 2-ethylhexanol (A' -3) ]

An EO 8 mol adduct (a' -3) of 2-ethylhexanol was obtained in the same manner as in production example 5 except that 158 parts (1 part by mol) of "decanol" was changed to 130 parts (1 part by mol) of 2-ethylhexanol and 264 parts (6 parts by mol) of EO was changed to 352 parts (8 parts by mol) of EO in production example 5.

The EO 8 molar adduct of 2-ethylhexanol (A' -3) is a compound represented by the general formula (2) R²Is 2-ethylhexyl (number of methyl groups: 2), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 8.

< comparative production example 4> [ Synthesis of EO 7 mol adduct of n-dodecanol (A' -4) ]

An EO 7-mole adduct (a' -4) of n-dodecanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mole) of "decanol" was changed to 186 parts (1 part by mole) of n-dodecanol, and 264 parts (6 parts by mole) of EO was changed to 308 parts (7 parts by mole) of EO in production example 5.

The EO 7 mol adduct of n-dodecanol (A' -4) is a compound represented by the general formula (2) R²Is n-dodecyl (number of methyl groups: 1), AO is ethyleneoxy, and m (number-average molar addition of alkylene oxide) is 7.

< comparative production example 5> [ Synthesis of EO6 mol adduct of 2, 4-dimethyl-3-pentanol (A' -5) ]

An EO6 mol adduct (a' -5) of 2, 4-dimethyl-3-pentanol was obtained in the same manner as in production example 5 except that 158 parts (1 part by mol) of "decanol" was changed to 116 parts (1 part by mol) of 2, 4-dimethyl-3-pentanol in production example 5.

The EO6 mol adduct of 2, 4-dimethyl-3-pentanol (A' -5) is a compound represented by the general formula (2) R²Is a 2, 4-dimethylpent-3-yl group (number of methyl groups: 4), AO is an ethyleneoxy group, and m (number-average molar number of alkylene oxides added) is 6.

< comparative production example 6> [ Synthesis of EO 7 mol adduct of 2,6, 8-trimethyl-4-nonanol (A' -6) ]

A7-mole EO adduct (A' -6) of 2,6, 8-trimethyl-4-nonanol was obtained in the same manner as in production example 5 except that 158 parts (1 part by mole) of "decanol" was changed to 186 parts (1 part by mole) of 2,6, 8-trimethyl-4-nonanol and 264 parts (6 parts by mole) of EO was changed to 308 parts (7 parts by mole) of EO in production example 5.

EO 7 mol adduct of 2,6, 8-trimethyl-4-nonanol (A' -6) is a compound represented by the general formula (2) wherein R²Is 2,6, 8-trimethylnonan-4-yl (number of methyl groups: 5), AO is ethyleneoxy and m (number average molar addition of alkylene oxides) is 7.

< comparative production example 7> [ Synthesis of EO 2 molar adduct of 3,5, 5-trimethyl-1-hexanol (A' -7) ]

A 2-mole EO adduct (a' -7) of 3,5, 5-trimethyl-1-hexanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mole) of "decanol" was changed to 144 parts (1 part by mole) of 3,5, 5-trimethyl-1-hexanol and 264 parts (6 parts by mole) of EO was changed to 88 parts (2 parts by mole) of EO in production example 5.

The EO 2 mol adduct of 3,5, 5-trimethyl-1-hexanol (A' -7) is a compound represented by the general formula (2) wherein R²Is 3,5, 5-trimethylhex-1-yl (number of methyl groups: 4), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 2.

< comparative production example 8> [ Synthesis of EO 11 molar adduct of 3,5, 5-trimethyl-1-hexanol (A' -8) ]

An EO 11 mol adduct (a' -8) of 3,5, 5-trimethyl-1-hexanol was obtained in the same manner as in production example 5, except that 158 parts (1 part by mol) of "decanol" was changed to 144 parts (1 part by mol) of 3,5, 5-trimethyl-1-hexanol and 264 parts (6 parts by mol) of EO was changed to 484 parts (11 parts by mol) in production example 5.

EO of 3,5, 5-trimethyl-1-hexanol11 mol of the adduct (A' -8) is a compound represented by the general formula (2) R²Is 3,5, 5-trimethylhex-1-yl (number of methyl groups: 4), AO is ethyleneoxy, and m (number-average molar number of alkylene oxide added) is 11.

< comparative production example 9> [ Synthesis of PO 7 mol EO 7 mol adduct of isobutanol (A' -9) ]

74 parts (1 part by mol) of isobutanol and 0.5 part of potassium isobutyrate were charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping bottle, the vessel was sealed after being replaced with nitrogen, and then heated to 130 ℃ to drop 406 parts (7 parts by mol) of 1, 2-propylene oxide and then 308 parts (7 parts by mol) of EO over 5 hours while adjusting the pressure to 0.5MPaG or less, and then aged at 160 ℃ for 2 hours. Then, the mixture was cooled to 70 ℃ and then 10 parts of an adsorbent "Kyoward 600" (manufactured by Kyowa chemical Co., Ltd.) were charged and stirred at 70 ℃ for 1 hour to conduct the treatment, and then the adsorbent was filtered off to obtain a PO 7 mol EO 7 mol adduct (A' -9) of isobutanol.

PO 7 mol EO 7 mol adduct of isobutanol (A' -9) is a compound represented by the general formula (2) wherein R²Is isobutyl (number of methyl groups: 2), AO is an ethyleneoxy group and a propyleneoxy group, and m (number-average molar number of addition of alkylene oxide) is 14.

< production example 16: production of EO 40 mol adduct of bisphenol A (b1-1) >

404 parts by weight (1 part by mole) of EO4 mol adduct of bisphenol A "Newpol BPE-40" manufactured by Sanyo chemical industries, Ltd., and 2 parts by weight of potassium hydroxide were charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device and a dropping bottle, and the pressure was set to-0.08 MPa after replacement with nitrogen gas. After heating to 130 ℃ and adjusting the pressure to 0.5MPaG or less, 1584 parts by weight (36 parts by mole) of EO was added dropwise over 6 hours, followed by aging at 130 ℃ for 3 hours. Then, the mixture was cooled to 100 ℃ and then 30 parts by weight of an adsorbent "Kyoward 600" (manufactured by Kyowa chemical Co., Ltd.) were charged and the mixture was stirred at 100 ℃ for 1 hour to conduct the treatment, and then the adsorbent was filtered off to obtain an EO 40 molar adduct of bisphenol A (b 1-1).

< production example 17: production of polyester (B1-1)

In a glass reaction vessel, 316 parts by weight (1 part by mole) of an EO 2 molar adduct of bisphenol A "Newpol BPE-20" [ manufactured by Sanyo chemical industries, Ltd. ] (B1-2), 1761 parts by weight (0.89 part by mole) of an EO 40 molar adduct of bisphenol A (B1-1), 113 parts by weight (0.68 part by mole) of terephthalic acid (a-1) and 5 parts by weight of potassium titanium oxalate were reacted at 230 ℃ under reduced pressure to 0.001MPa for 15 hours, followed by removal of water by distillation to obtain 2177 parts by weight of a polyester (B1-1).

Examples 1 to 22 and comparative examples 1 to 10

An aliphatic alcohol alkylene oxide adduct (A), a polyester (B1-1), an emulsion containing polyurethane (B2-1), a compound having an epoxy group (B3-1), a compound having an epoxy group (B3-2), a compound having a (meth) acryloyl group (B4-1), a polyether compound (B5-1), and a polyether compound (B5-2) in the weight parts described in Table 1 were put into a reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, and a dropping funnel, and after stirring for 5 minutes while heating, water was dropped from the dropping funnel over 1 hour to prepare a dispersion of a sizing composition for fibers having a solid content of 1.5% by weight.

The solid content is the residue obtained by drying 1g of the sample at 130 ℃ for 45 minutes by heating with a circulating air dryer.

As the compound (B) in table 1, the following compounds were used.

(B1-1): polyester produced in production example 17

(B2-1): aqueous dispersion of polyether polyurethane (solid content concentration: 50 wt%), trade name: "Parmarin GA-500", manufactured by Sanyo chemical industries, Ltd

(B3-1): condensate of diglycidyl ether of bisphenol a and epichlorohydrin, trade name: "Jer 834", manufactured by Mitsubishi chemical corporation

(B3-2): condensate of diglycidyl ether of bisphenol a and epichlorohydrin, trade name: "jER 1001", manufactured by Mitsubishi chemical corporation

(B4-1): diacrylate of PEG1000, trade name: "NK ESTERA-1000", manufactured by Newzhongcun chemical Co., Ltd

(B5-1): EO 10 molar adduct of bisphenol a, trade name: "Newpol BPE-100", manufactured by Sanyo chemical industries, Ltd

(B5-2): propylene oxide ethylene oxide adduct of styrenated phenol, trade name: soprophor 796/P, Solvay Nicca, Inc

Carbon fiber bundles for testing were produced by the following methods using the dispersions of the sizing agent compositions for fibers obtained in examples 1 to 22 and comparative examples 1 to 10, and the sizing properties, fuzz formation, and contact angles with epoxy resin of the carbon fiber bundles were evaluated.

< production of carbon fiber bundle for testing >

Untreated carbon fibers (having 48,000 filaments) were immersed in the dispersion of the sizing agent composition for fibers to impregnate the fibers with the sizing agent, and then carbon fibers were taken out from the dispersion of the sizing agent composition for fibers, and the taken-out carbon fibers were hot-air dried at 180 ℃ for 3 minutes to prepare a carbon fiber bundle.

The carbon fiber bundle was produced so that the amount of solid matter contained in the sizing composition for fibers adhering to the fibers (weight% based on the weight of the carbon fibers before impregnation) was 1.5 wt%.

< evaluation of sizing Property >

The sizing properties of the carbon fiber bundles were evaluated in accordance with JIS L1096-20108.21.1A method (45 ℃ cantilever beam method).

The larger the value (cm), the more excellent the sizing property.

The carbon fiber bundle obtained under the treatment conditions was evaluated by using a cantilever beam. The sizing property is preferably 14cm or more.

< evaluation of fuzzing >

Fig. 1 is a side view schematically showing the arrangement of carbon fiber bundles in the evaluation of fuzzing.

First, as shown in fig. 1, the wind-out roll 2 and the wind-up roll 3 are arranged so that the carbon fiber bundle 4 is wound from the wind-out roll 2 onto the wind-up roll 3. Further, 5 stainless steel rods 1 having a smooth surface and a diameter of 10mm were prepared, and each stainless steel rod 1 was arranged as follows: the stainless steel rods 1 are parallel to each other such that the interval therebetween in the horizontal direction (the interval indicated by an arrow α in fig. 1) is 50mm, and the carbon fiber bundles 4 pass through each of the stainless steel rods 1 in a zigzag shape while contacting the same (hereinafter, for convenience, referred to as 1 st to 5 th stainless steel rods 1 in order from the winding-up roller 2 side).

In addition, the configuration is performed in the following manner: the straight line connecting the centers of the 1 st, 3 rd and 5 th stainless steel rods 1 through which the carbon fiber bundles 4 pass and the straight line connecting the centers of the 2 nd and 4 th stainless steel rods 1 through which the carbon fiber bundles 4 pass are parallel to the horizontal plane.

In addition, the configuration is performed in the following manner: before and after passing through the above-described 2 nd to 4 th stainless steel rods 1, a straight line as a traveling direction of the carbon fiber bundle 4 before passing and a straight line as a traveling direction of the carbon fiber bundle 4 after passing form an angle of 120 degrees (for example, a straight line as a traveling direction of the carbon fiber bundle 4 passing between the 1 st and 2 nd stainless steel rods 1 and a straight line as a traveling direction of the carbon fiber bundle 4 passing between the 2 nd and 3 rd stainless steel rods 1 form an angle of 120 degrees).

Carbon fiber bundles 4 are arranged in a zigzag pattern between the stainless steel rods 1, and the carbon fiber bundles 4 are sandwiched between 2 pieces of 10cm × 10cm urethane foam to which a load of 1kg is applied at a position indicated by a reference numeral 5 immediately before the take-up roll 3.

The carbon fiber bundle 4 was wound from the wind-up roll 2 to the wind-up roll 3 at a speed of 1 m/min for 5 minutes with a wind-up tension of 1 kg.

The weight of the pile attached to the 2 pieces of urethane foam described above during this period was measured.

A smaller value indicates that fuzz can be suppressed more.

< contact Angle >

The contact angle of the carbon fiber monofilament with the epoxy resin was measured by the Wilhelmy method.

A contact angle meter K100SF manufactured by KRUSS was used to measure the product name of a condensate of diglycidyl ether of bisphenol F and epichlorohydrin: JeR807, manufactured by Mitsubishi chemical corporation ], dynamic advancing contact angle (25 ℃ C., 1 mm/min).

The smaller the contact angle, the more excellent the impregnation with the matrix resin and the more improved the strength of the fiber product when the epoxy resin is used as the matrix resin.

Industrial applicability

The sizing agent composition for fibers of the present invention can be used as a sizing agent for glass fibers, carbon fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers or slag fibers.

In addition, a prepreg can be obtained by using a fiber bundle or a fiber product obtained by treating the fiber sizing composition of the present invention as a reinforcing fiber and a thermoplastic resin or a thermosetting resin as a matrix resin.

Description of the symbols

1 stainless steel bar

2 unwinding roller

3 winding roller

4 carbon fiber bundle

5 position sandwiched with 2 pieces of urethane foam