JP7429827B1 - Sizing agents for textiles and their uses - Google Patents

Abstract

The present invention provides a sizing agent that improves the wettability of a matrix resin to a fiber strand, a fiber strand using the same, and a fiber-reinforced composite material. Solution: A compound containing a compound (A) and an acetylene compound (B), wherein the compound (A) is at least one selected from a thermosetting resin (A1), a thermoplastic resin (A2), and a rubber (A3). A sizing agent for fibers, wherein the weight ratio ((B)/(A)) of the acetylene compound (B) to the compound (A) is 0.0005 to 0.13.

Description

The present invention relates to a sizing agent for fibers and its uses. In particular, the present invention relates to a fiber sizing agent, fiber strands and fiber reinforced composite materials using the same.

BACKGROUND OF THE INVENTION Fiber-reinforced composite materials, which are plastic materials (called matrix resins) reinforced with various synthetic fibers, are widely used in automobiles, aerospace, sports and leisure, and general industrial applications. Examples of the fibers used in these composite materials include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as aramid fibers, polyamide fibers, and polyethylene fibers. These various synthetic fibers are usually manufactured in the form of filaments, which are then processed into sheet-like intermediate materials called unidirectional prepregs by hot-melt or drum winding methods, processed into sheet-like intermediate materials by filament winding methods, or in some cases, fabricated into fabrics. Alternatively, it is used as a reinforcing fiber after undergoing various high-order processing steps, such as being processed into a chopped fiber shape.

Epoxy resins are widely used as matrix resins for fiber reinforced composite materials. In addition to epoxy resins, unsaturated polyester resins, vinyl ester resins, acrylic resins, and the like are used as radical polymerization matrix resins.
In order to improve the mechanical strength of fiber-reinforced composite materials, the wettability and adhesion between the matrix resin and the fibers are important. Sizing agents (for example, Patent Documents 1, 2, etc.) that improve the sizing agent have been proposed.

However, although the sizing agents described in Patent Document 1 and Patent Document 2 improve the wettability and adhesion of fibers and epoxy resins and radical polymerization matrix resins, it is difficult to achieve both, and it is difficult to achieve both the It was not possible to satisfy the physical properties of the composite material. Furthermore, some fibers have low elongation and are brittle. These fibers to which conventional sizing agents have been applied are subject to mechanical friction during the processing process, which may cause problems such as fluffing, fiber breakage, and lack of cohesiveness.
Therefore, in the field of fiber-reinforced composite materials, it is possible to improve the wettability of fibers and matrix resin and to firmly bond them, suppressing fuzz of fiber strands and improving cohesiveness, and further improving long-term storage stability. The development of an excellent sizing agent is desired.

Japanese Patent Publication No. 53-52796 Japanese Patent Application Publication No. 06-173170

In view of this conventional technical background, an object of the present invention is to provide a fiber sizing agent that improves the wettability of a matrix resin to a fiber strand, a fiber sizing agent using the same, and a fiber reinforced composite material.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved with a fiber sizing agent containing a specific compound (A) and a specific compound (B) in a specific ratio. I found it.
That is, the sizing agent for fibers of the present invention includes the following embodiments.
<1> A fiber sizing agent containing a compound (A) and an acetylene compound (B), wherein the compound (A) is a thermosetting resin (A1), a thermoplastic resin (A2), and a rubber (A3). ), and the weight ratio of the acetylene compound (B) to the compound (A) ((B)/(A)) is 0.0005 to 0.13. .

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して炭素数１～８のアルキル基である。）

（式（２）中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立して炭素数１～８のアルキル基である。）

（式（３）中、Ｒ^１及びＲ^２は、それぞれ独立して炭素数１～８のアルキル基である。Ｒ^７は水素原子、または炭素数１～５のアルキル基である。ＡＯは炭素数２～４のオキシアルキレン基を示す。ｎは１～５０の数である。）

（式（４）中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立して炭素数１～８のアルキル基である。Ｒ^７は水素原子、または炭素数１～５のアルキル基である。なお、式（４）における複数のＲ^７は、同一であってもよく異なっていてもよい。ＡＯは炭素数２～４のオキシアルキレン基を示す。ｍ、ｎはそれぞれ独立して１～５０の数である。）
＜７＞繊維ストランドに対して、前記＜１＞～＜６＞のいずれかに記載の繊維用サイジング剤を付着させた、サイジング剤付着繊維ストランド。
＜８＞マトリックス樹脂と、前記＜７＞に記載のサイジング剤付着繊維ストランドとを含む、繊維強化複合材料。
＜９＞前記マトリックス樹脂が熱硬化性樹脂及び熱可塑性樹脂から選ばれる少なくとも１種である、前記＜８＞に記載の繊維強化複合材料。 <2> The thermosetting resin (A1) is at least one selected from epoxy resin (A1-1), vinyl ester resin (A1-2), and unsaturated polyester resin (A1-3), and The plastic resin (A2) is at least one selected from aromatic polyurethane resin (A2-1), saturated polyester resin (A2-2), and polyolefin resin (A2-3), and the rubber (A3) is The fiber sizing agent according to <1> above, which is at least one selected from silicone rubber (A3-1) and diene rubber (A3-2).
<3> Further contains a nonionic compound (C), and the weight ratio ((B)/(C)) of the acetylene compound (B) to the nonionic compound (C) is 0.001 to 0. 5, the fiber sizing agent according to <1> or <2> above.
<4> The fiber sizing agent according to <3>, wherein the nonionic compound (C) has a weight average molecular weight of 1,000 to 20,000.
<5> The acetylene compound (B) is selected from acetylene alcohol (B1), acetylene diol (B2), a compound obtained by adding alkylene oxide to acetylene alcohol (B3), and a compound obtained by adding alkylene oxide to acetylene diol (B4) The fiber sizing agent according to any one of <1> to <4>, which is at least one selected from the above.
<6> The acetylene alcohol (B1) is a compound represented by the following general formula (1), the acetylene diol (B2) is a compound represented by the following general formula (2), and the acetylene alcohol contains an alkylene The compound (B3) to which an oxide is added is a compound represented by the following general formula (3), and the compound (B4) to which an alkylene oxide is added to the acetylene diol is a compound represented by the following general formula (4). , the fiber sizing agent according to <5> above.

(In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms.)

(In formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 8 carbon atoms.)

(In formula (3), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms. R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. AO is a carbon It represents an oxyalkylene group of 2 to 4. n is a number of 1 to 50.)

(In formula (4), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 8 carbon atoms. R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In addition, a plurality of R ⁷ 's in formula (4) may be the same or different. AO represents an oxyalkylene group having 2 to 4 carbon atoms. m and n each independently represent It is a number from 1 to 50.)
<7> A sizing agent-attached fiber strand, in which the fiber sizing agent according to any one of <1> to <6> is adhered to the fiber strand.
<8> A fiber-reinforced composite material comprising a matrix resin and the sizing agent-attached fiber strand according to <7> above.
<9> The fiber reinforced composite material according to <8>, wherein the matrix resin is at least one selected from thermosetting resins and thermoplastic resins.

The sizing agent for fibers of the present invention can uniformly apply the sizing agent to the fibers. Moreover, it is possible to impart excellent wettability and adhesiveness to the matrix resin to the fibers. Furthermore, it is possible to suppress fiber fuzz and provide high cohesiveness. By using the fiber strands of the present invention, fiber-reinforced composite materials with excellent physical properties can be obtained.

Each component of the fiber sizing agent of the present invention will be explained in detail.
[Compound (A)]
The fiber sizing agent of the present invention contains compound (A). Compound (A) is at least one selected from thermosetting resins (A1), thermoplastic resins (A2), and rubbers (A3). The compound (A) may be used alone or in combination of two or more.
The reason why the wettability of the matrix resin is improved by the fiber sizing agent of the present invention containing at least one selected from curable resin (A1), thermoplastic resin (A2) and rubber (A3) is that the compound (A ) uniformly covers the fiber surface, imparting appropriate polarity to the entire fiber surface and improving affinity with the matrix resin.

As the thermosetting resin (A1), epoxy resin (A1-1), vinyl ester resin (A1-2), unsaturated polyester resin (A1-3), and phenol resin (A1-4) can be used in terms of achieving the effects of the present invention. Among these, at least one selected from epoxy resin (A1-1), vinyl ester resin (A1-2) and unsaturated polyester resin (A1-3) is preferred, and epoxy resin (A1-1) and unsaturated polyester resins (A1-3), which is more preferable since the effects of the present invention are more effectively achieved. These resins may be used alone or in combination of two or more.

The thermoplastic resin (A2) is preferably at least one selected from aromatic polyurethane resins (A2-1), saturated polyester resins (A2-2), and polyolefin resins (A2-3) in terms of achieving the effects of the present invention. , aromatic polyurethane resin (A2-1), saturated polyester resin (A2-2), and polyolefin resin (A2-3). At least one selected from A2-3) is more preferable in that it more effectively exhibits the effects of the present application. Two or more of these resins may be used in combination.

As the rubber (A3), at least one kind selected from silicone rubber (A3-1) and diene rubber (A3-2) is preferable in terms of producing the effects of the present application, and among these, diene rubber (A3-2) is preferable. It is more preferable if it exists because the effect of the present invention is more effectively achieved. Two or more of these resins may be used in combination.

[Epoxy resin (A1-1)]
The epoxy resin (A1-1) is a compound having two or more reactive epoxy groups in its molecular structure. Typical examples of epoxy resins include glycidyl ether types obtained from epichlorohydrin and active hydrogen compounds, and other types include glycidyl ester types, glycidyl amine types, and alicyclic types. The epoxy resin may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin (A1-1) is preferably 100 to 1500 g/eq. When the epoxy equivalent is within the above range, it is possible to achieve both suppression of deterioration of the fiber strand over time and adhesion to the matrix resin. The upper limit of the epoxy equivalent is more preferably 1000 g/eq, still more preferably 800 g/eq, particularly preferably 700 g/eq. On the other hand, the lower limit of the epoxy equivalent is more preferably 120 g/eq, still more preferably 150 g/eq, particularly preferably 170 g/eq. Further, for example, 120 g/eq to 1000 g/eq is more preferable, 150 g/eq to 800 g/eq is even more preferable, and 170 g/eq to 700 g/eq is particularly preferable. Incidentally, the epoxy equivalent refers to one based on JIS-K7236.

The weight average molecular weight of the epoxy resin (A1-1) is preferably 100 to 10,000 in terms of good heat resistance. The lower limit of the average molecular weight is more preferably 150, still more preferably 200. On the other hand, the upper limit of the average molecular weight is more preferably 8,000, and still more preferably 7,000. Further, for example, 150 to 8,000 is more preferable, and even more preferably 200 to 7,000. The weight average molecular weight is determined by the method described in Examples.

The epoxy resin (A1-1) is preferably an aromatic epoxy resin having an aromatic ring in its molecular structure from the viewpoint of improving the wettability of the matrix resin.
The above aromatic epoxy resins include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, and pyrocatechol; dihydroxynaphthalene, biphenol, bisphenol F, bisphenol A, phenol novolac, orthocresol novolac, resorcinol novolac, Examples include polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol F novolac, bisphenol A novolac, dicyclopentadiene-modified phenol, triphenylmethane, and tetraphenylethane.

（式（５）中、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立して、水素原子又はメチル基である。）
ｐは０～３０の整数であり、マトリックス樹脂の濡れ性が向上する観点から、０～２０が好ましく、０～１０がさらに好ましい。 Among these aromatic epoxy resins, compounds represented by the following general formula (5) are preferred from the viewpoint of the effects of the present application.

(In formula (5), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group.)
p is an integer from 0 to 30, preferably from 0 to 20, more preferably from 0 to 10, from the viewpoint of improving the wettability of the matrix resin.

The method for producing the above-mentioned epoxy resin (A1-1) is not particularly limited, and any known method can be employed. Moreover, the above-mentioned epoxy resins are generally commercially available, and these commercially available epoxy resins can be used in the sizing agent for carbon fibers of the present invention.

[Vinyl ester resin (A1-2)]
The vinyl ester resin (A1-2) is a compound having at least one type selected from vinyl ester groups, acrylate groups, and methacrylate groups. One type or two or more types of vinyl ester resins (A1-2) may be used. In addition, a vinyl ester group represents a group represented by "CH2=CHOCO-", an acrylate group represents a group represented by "CH2=CHCOO-", and a methacrylate group represents a group represented by "CH2=CCH3COO-". shall indicate the group.

Examples of the vinyl ester resin (A1-2) include alkyl (meth)acrylate, alkoxypolyalkylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy Alkyl (meth)acrylic ester, dialkylaminoethyl (meth)acrylic ester, glycidyl (meth)acrylate, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, polyalkylene glycol di(meth)acrylate, alkanediol di(meth)acrylate, ) acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A (meth)acrylic acid ester, alkylene oxide-added bisphenol A (meth)acrylic acid ester, bisphenol A diglycidyl ether (meth)acrylic acid adduct, alkylene oxide-adducted bisphenol A diglycidyl ether (meth)acrylic acid adduct, trimethylolpropane tri(meth)acrylate, glycidyl (meth)acrylate , phenoxyalkyl (meth)acrylic ester, phenoxypolyalkylene glycol (meth)acrylic ester, 2-hydroxy-3 phenoxypropanol (meth)acrylic ester, polyalkylene glycol nonylphenyl ether (meth)acrylic ester, 2- (meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentyl glycol (meth)acrylic acid benzoate , alkylene oxide addition trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate Examples include acrylate hexamethylene diisocyanate urethane prepolymer.

Among these, the vinyl ester resin (A1-2) preferably contains at least one kind selected from an oxyalkylene group and an aryl group, and more preferably contains an aryl group, in terms of excellent adhesiveness with the matrix resin. . Specifically, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, polyalkylene glycol di(meth)acrylate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2- Hydroxyethyl-phthalic acid, neopentyl glycol (meth)acrylic acid benzoate, bisphenol A (meth)acrylic acid ester, alkylene oxide addition bisphenol A (meth)acrylic ester, bisphenol A diglycidyl ether (meth)acrylic acid addition polyalkylene glycol di(meth)acrylate, bisphenol A (meth)acrylic ester, alkylene oxide-added bisphenol A (meth)acrylic ester, Bisphenol A diglycidyl ether (meth)acrylic acid adducts, alkylene oxide-added bisphenol A diglycidyl ether (meth)acrylic acid adducts are more preferred, and bisphenol A (meth)acrylic acid esters, alkylene oxide-added bisphenol A (meth)acrylic acids Particularly preferred are acid esters, bisphenol A diglycidyl ether (meth)acrylic acid adducts, and alkylene oxide adducts of bisphenol A diglycidyl ether (meth)acrylic acid adducts.

[Unsaturated polyester resin (A1-3)]
The unsaturated polyester resin (A1-3) is not particularly limited as long as it is a polyester resin having a carbon-carbon double bond and is other than the vinyl ester resin (A1-2), but for example, α , an unsaturated polyester obtained by reacting an acid component containing a β-unsaturated dicarboxylic acid with an alcohol. Examples of α,β-unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, and derivatives of these acid anhydrides, and two or more of these may be used in combination. In addition, if necessary, saturated dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid as well as acid anhydrides of these acids may be added as acid components other than α,β-unsaturated dicarboxylic acids. The derivatives may also be used in combination with α,β-unsaturated dicarboxylic acids. Examples of the alcohol include aliphatic glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , alicyclic diols such as cyclopentanediol and cyclohexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide (1 to 100 mol) adducts, aromatic diols such as xylene glycol, polyhydric diols such as trimethylolpropane, pentaerythritol, etc. Examples include alcohol, and two or more of these may be used in combination.

Among the unsaturated polyester resins (A1-3), aromatic unsaturated polyester resins are preferred because they have excellent adhesion to matrix resins. Among aromatic unsaturated polyester resins, condensates of fumaric acid or maleic acid with ethylene oxide (hereinafter abbreviated as EO) adducts of bisphenol A, propylene oxide (hereinafter referred to as PO) adducts of fumaric acid or maleic acid and bisphenol A, etc. ) adducts, and condensates of fumaric acid or maleic acid with EO and PO adducts of bisphenol A (the addition of EO and PO may be random or block) are more preferred.

The weight average molecular weight of the unsaturated polyester resin (A1-3) is preferably 1,000 to 12,000 in terms of good heat resistance. The upper limit of the weight average molecular weight is more preferably 8,000, and even more preferably 7,000. On the other hand, the lower limit of the weight average molecular weight is more preferably 1,500, and even more preferably 2,000. Further, for example, it is more preferably 1,500 to 8,000, and even more preferably 2,000 to 7,000. The acid value is preferably 5 or less. The weight average molecular weight is determined by the method described in Examples.

[Phenol resin (A1-4)]
Examples of phenolic resins include resins obtained by condensing phenols such as phenol, cresol, xylenol, t-butylphenol, nonylphenol, cashew oil, lignin, resorcinol, and catechol with aldehydes such as formaldehyde, acetaldehyde, and furfural. Examples include novolac resins and resol resins. Novolak resin is obtained by reacting phenol and formaldehyde in the same amount or in excess of phenol in the presence of an acid catalyst such as oxalic acid. The resol resin is obtained by reacting phenol and formaldehyde in the same amount or in excess of formaldehyde in the presence of a basic catalyst such as sodium hydroxide, ammonia or an organic amine.

[Aromatic polyurethane resin (A2-1)]
The aromatic polyurethane resin (A2-1) can be obtained by reacting polyisocyanates and polyols with a chain extender if necessary, and at least one of the polyisocyanates and polyols is aromatic. This includes group-based compounds.

Examples of polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate; Examples include aromatic diisocyanates such as diisocyanate and diphenylmethane-4,4'-diisocyanate, and araliphatic diisocyanates such as xylylene diisocyanate. As the polyisocyanates, compounds in which an alkyl group (for example, a methyl group) is substituted in the main chain or ring may be used.

Examples of polyols include polyester diols (aliphatic dicarboxylic acid components having 4 to 12 carbon atoms such as fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid; phthalic acid, terephthalic acid, and isophthalic acid) Aromatic dicarboxylic acid components such as acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, phthalic anhydride; ethylene glycol, propylene glycol, butanediol, neopentyl C2-12 aliphatic diol components such as glycol; polyester diols obtained from C4-12 lactone components such as ε-caprolactone, etc.), polyether diols (polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene blocks) copolymers, polyoxytetramethylene glycol, bisphenol A-alkylene oxide adducts, etc.), polyester ether diols (polyester diols using the above polyether diol as part of the diol component), and the like.

Furthermore, examples of the chain extender include alkylene diols having 2 to 10 carbon atoms such as ethylene glycol and propylene glycol, as well as diamines. Examples of diamines include those having 2 to 10 carbon atoms, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,7-diaminoheptane, and 1,8-diaminooctane. Aliphatic diamines such as linear or branched polyalkylene polyamines such as linear or branched alkylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and dipropylene triamine; isophorone diamine, bis(4- Examples include alicyclic diamines such as amino-3-methylcyclohexyl)methane and bis(aminomethyl)cyclohexane; aromatic diamines such as phenylenediamine, xylylenediamine, and diaminodiphenylmethane.

Among the aromatic polyurethane resins (A2-1), aromatic polyester polyurethane resins are more preferable because they can achieve both heat resistance and adhesion to the matrix resin.

[Saturated polyester resin (A2-2)]
Examples of the saturated polyester resin (A2-2) include aliphatic polyester resins and aromatic polyester resins. As the saturated polyester resin, a polyalkylene arylate resin or an aromatic polyester resin is preferable, and an aromatic polyester resin is more preferable, since both heat resistance and adhesiveness with the matrix resin can be achieved.
Examples of aromatic polyester resins include polyalkylene terephthalates with 2 to 4 carbon atoms such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyalkylene naphthalates with 2 to 4 carbon atoms corresponding to these polyalkylene terephthalates (e.g. , polyethylene naphthalate, etc.); 1,4-cyclohexyl dimethylene terephthalate (PCT)). The aromatic polyester resin may be a copolyester containing alkylene arylate units as a main component (for example, 50% by weight or more), and the copolymerization component includes carbon such as ethylene glycol, propylene glycol, butanediol, hexanediol, etc. Examples include alkylene glycols having 2 to 6 carbon atoms, polyoxyalkylene glycols having 2 to 4 carbon atoms, asymmetric aromatic dicarboxylic acids such as phthalic acid and isophthalic acid or their acid anhydrides, and aliphatic dicarboxylic acids such as adipic acid. Furthermore, a branched structure may be introduced into the linear polyester using a small amount of polyol and/or polycarboxylic acid.

Furthermore, a modified polyester resin modified with a modifying compound (for example, an aromatic polyester resin having at least one selected from an amino group and an oxyalkylene group) may be used. Examples of modified compounds include polyamines (ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, etc.). Aliphatic diamines such as linear or branched alkylene diamines of about 2 to 10; alicyclic diamines such as isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, bis(aminomethyl)cyclohexane, etc. For example, aromatic diamines such as phenylene diamine, xylylene diamine, diaminodiphenylmethane; etc.), polyols (for example, (poly)oxyethylene glycol, (poly)oxytrimethylene glycol, (poly)oxypropylene glycol, ( Examples include (poly)oxyalkylene glycols having 2 to 4 carbon atoms such as poly(oxytetramethylene glycol). Modification can be carried out, for example, by heating and mixing a polyester resin and a modified compound and performing amidation, esterification, or transesterification.

The weight average molecular weight of the saturated polyester resin (A2-2) is preferably 3,000 to 20,000 in terms of good heat resistance. The upper limit of the weight average molecular weight is more preferably 19,000, and even more preferably 18,000. On the other hand, the lower limit of the weight average molecular weight is more preferably 6,000, and even more preferably 7,000. Further, for example, it is more preferably 6,000 to 19,000, and even more preferably 7,000 to 18,000. The weight average molecular weight is determined by the method described in Examples.

[Polyolefin resin (A2-3)]
Examples of the polyolefin resin (A2-3) include copolymers of olefin monomers and monomers such as unsaturated carboxylic acids that are copolymerizable with the olefin monomers, and can be produced by known methods. The polyolefin resin may be a random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid, or a graft copolymer obtained by grafting an unsaturated carboxylic acid onto an olefin monomer. One type or two or more types of polyolefin resins may be used.

Examples of olefinic monomers include ethylene, propylene, and 1-butene. These can be used alone or in combination of two or more. Examples of monomers copolymerizable with olefinic monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and fumaric acid. These can be used alone or in combination of two or more.

The copolymerization ratio of the above-mentioned olefin monomer and a monomer copolymerizable with the olefin monomer is determined based on the total weight of the copolymer being 100% by weight in order to improve the adhesion with the matrix resin. Preferably 80 to 99.5% by weight of the monomer, 0.5 to 20% by weight of the monomer copolymerizable with the olefinic monomer, 90 to 99% by weight of the olefinic monomer, and the monomer copolymerizable with the olefinic monomer 1 It is more preferably from 10% by weight to 95% to 98% by weight of the olefinic monomer, and particularly preferably from 2% to 5% by weight of the monomer copolymerizable with the olefinic monomer.

In addition, in the polyolefin resin (A2-3), it is preferable that the modified group such as a carboxyl group introduced by copolymerization is neutralized with a basic compound, since the storage stability of the emulsion is improved. Examples of basic compounds include metal salts such as sodium hydroxide and potassium hydroxide; ammonia; laurylamine, ethylenediamine, trimethylamine, dimethylethanolamine, dibutylethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, Examples include amines such as dipropanolamine and monobutanolamine. Among these, amines are more preferred, and diethanolamine is particularly preferred.

The weight average molecular weight of the polyolefin resin (A2-3) is preferably 5,000 to 200,000 in terms of good heat resistance. The upper limit of the weight average molecular weight is more preferably 150,000, and even more preferably 130,000. On the other hand, the lower limit of the weight average molecular weight is more preferably 6,000, and even more preferably 7,000. Further, for example, it is more preferably 6,000 to 150,000, and even more preferably 7,000 to 130,000. The weight average molecular weight is determined by the method described in Examples.

[Silicone rubber (A3-1)]
Examples of the silicone rubber include addition-type silicone resins, self-crosslinking silicone resins, silicone rubber film-forming silicone resin components, and silicone rubber powders, and those that form a film by heating, reaction, etc. are preferable. One type or two or more types of silicone rubber may be used.
Examples of addition type silicone resins include room temperature curable silicone rubber (RTV silicone rubber), low temperature curable silicone rubber (LTV silicone rubber), and silicone resin components of O/W type emulsions in which reactive silicone is emulsified with an emulsifier. Can be mentioned. Among these, in order to further express the effects of the present invention, an aqueous dispersion of room temperature curable silicone rubber (RTV silicone rubber) or a silicone resin emulsified with reactive silicone is preferable, and the aqueous dispersion is dried. It is more preferable that a silicone rubber film can be formed by doing so.

[Diene rubber (A3-2)]
The diene rubber (A3-2) is not particularly limited as long as it is a polymer containing a polymerizable monomer having a conjugated diene structure as a constituent unit, and the polymerizable monomer having a conjugated diene structure includes: For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, etc. Can be mentioned.

Specific examples of the diene rubber (A3-1) include butadiene polymer, isoprene polymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, and acrylonitrile-butadiene-isoprene copolymer. Coalescence, methacrylonitrile-butadiene copolymer, methacrylonitrile-isoprene copolymer, methacrylonitrile-butadiene-isoprene copolymer, athacrylonitrile-methacrylonitrile-butadiene copolymer, acrylonitrile-butadiene-methyl acrylate Copolymer, acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-n-butyl acrylate copolymer, acrylonitrile-butadiene-n-butyl acrylate-itaconate monopolymer Examples include n-butyl copolymers. Among these, styrene-butadiene copolymer is preferred because it has excellent heat resistance. An aqueous dispersion may be used as the diene rubber, and a film may be formed by drying the aqueous dispersion.

[Acetylene compound (B)]
The sizing agent for carbon fibers of the present invention contains an acetylene compound (B). It is speculated that by using the compound (A) and the acetylene compound (B) together, the wettability of the matrix resin can be improved by lowering the surface tension and increasing the affinity between the matrix resin and the fiber surface. .
When using only other surfactants without using the acetylene compound (B), even when using only the compound (A), there is an effect of lowering the surface tension, but the matrix resin and fiber It is assumed that the wettability of the matrix resin is not sufficient due to insufficient affinity with the surface.
Note that the acetylene compound refers to a compound having an acetylene group and a hydrophilic group such as a hydroxyl group in its molecular structure. The acetylene compound (B) may be used alone or in combination of two or more.

The acetylene compound (B) is preferably an acetylene surfactant, and includes acetylene alcohol (B1), acetylene diol (B2), a compound obtained by adding an alkylene oxide to acetylene alcohol (B3), and a compound having an alkylene oxide added to acetylene diol. More preferably, it is at least one selected from the compounds (B4). Among these, the compound (B3) in which alkylene oxide is added to acetylene alcohol and the compound (B4) in which alkylene oxide is added to acetylene diol are preferred, and the compound (B4) in which alkylene oxide is added to acetylene diol is more preferred.

Acetylene alcohol (B1) is a compound having an acetylene group and one hydroxyl group in its molecular structure.
The acetylene alcohol (B1) is preferably a compound represented by the above general formula (1).

Acetylene diol (B2) is a compound having an acetylene group and two hydroxyl groups in its molecular structure.
The acetylene diol (B2) is preferably a compound represented by the above general formula (2).

The compound (B3) in which alkylene oxide is added to acetylene alcohol is a compound in which alkylene oxide is added to the hydroxyl group of acetylene alcohol.
The compound (B3) obtained by adding alkylene oxide to acetylene alcohol is preferably a compound represented by the above general formula (3).

The compound (B4) in which alkylene oxide is added to acetylene diol is a compound in which alkylene oxide is added to at least one of the hydroxyl groups of acetylene diol.
The compound (B4) obtained by adding alkylene oxide to acetylene diol is preferably a compound represented by the above general formula (4).

In formulas (1) and (3), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear or may have a branched structure. The alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 5 carbon atoms.
In formulas (2) and (4), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear or may have a branched structure. The alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 5 carbon atoms.

In formulas (3) and (4), R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 to 2 carbon atoms.
In formulas (3) and (4), AO represents an oxyalkylene group having 2 to 4 carbon atoms. That is, it represents an oxyethylene group, an oxypropylene group, or an oxybutylene group. As the oxyalkylene group, an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable. The number of AOs constituting (AO) _n or (AO) _m may be one, or two or more. In the case of two or more types, any of block adducts, alternating adducts, and random adducts may be used.

In formula (3), n is a number from 1 to 50. n is preferably 1 to 45, more preferably 1 to 40, even more preferably 1 to 35.
In formula (4), m and n are each independently a number from 1 to 50. m and n are each independently preferably from 1 to 45, more preferably from 1 to 40, even more preferably from 1 to 35.

The HLB of the acetylene compound (B) is preferably 4 to 25 from the viewpoint of emulsifying properties. The upper limit of the HLB is more preferably 20, and still more preferably 18. On the other hand, the lower limit of the HLB is more preferably 5, and still more preferably 6. The HLB in the present invention can be determined experimentally by the atlas method proposed by Griffin et al.

The acetylene compound (B) is a known compound and can be easily produced by a known method. For example, such a compound can be obtained by a method called the Reppe reaction, in which acetylene is reacted with a ketone or aldehyde under pressure in the presence of a catalyst such as an alkali or a metal compound.
In addition, the above compound (B3) or compound (B4) can be prepared by adding an alkylene oxide (e.g. ethylene oxide and/or propylene oxide) to acetylene alcohol (B1) or acetylene diol (B2), respectively, and adding a catalyst such as an alkali or a metal compound. It can be obtained by addition polymerization in the presence of

[Nonionic compound (C)]
The sizing agent for fibers of the present invention preferably contains a nonionic compound (C) because it improves the wettability of the matrix resin. The nonionic compound (C) is a compound other than the compound (A) and the acetylene compound (B), and is preferably a nonionic surfactant.

Examples of the compound (C) include polyoxyalkylene alkenyl ethers such as polyoxyalkylene alkyl ether and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl ether, etc. Polyoxyalkylene alkylphenyl ether; polyoxyethylene tristyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene Polyoxyalkylene alkylaryl phenyl ether such as benzyl phenyl ether; polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristyrate, polyoxyethylene dilaurate, polyoxyethylene dilaurate polyoxyalkylene fatty acid esters such as esters, polyoxyethylene dimyristyrate, and polyoxyethylene distearate; sorbitan esters such as sorbitan monopalmitate and sorbitan monooleate; polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan mono Polyoxyalkylene sorbitan fatty acid esters such as oleates; glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, and glycerin monopalmitate; polyoxyalkylene sorbitol fatty acid esters; sucrose fatty acid esters; Oxyalkylene castor oil ether; polyoxyalkylene hydrogenated castor oil ether such as polyoxyethylene hydrogenated castor oil ether; oxyethylene-oxypropylene block or random copolymer; terminal sucrose etherified product of oxyethylene-oxypropylene block or random copolymer; etc. can be mentioned. Compound (C) is preferably a surfactant since it provides good emulsifying properties.

The weight average molecular weight of the compound (C) is preferably 1,000 to 20,000 from the viewpoint of achieving the effects of the present application. The upper limit of the weight average molecular weight is more preferably 18,000, still more preferably 17,000, particularly preferably 16,000. On the other hand, the lower limit of the weight average molecular weight is more preferably 1,500, still more preferably 1,800, particularly preferably 2,000. Further, for example, it is more preferably from 1,500 to 18,000, even more preferably from 1,800 to 17,000, and particularly preferably from 2,000 to 16,000. The weight average molecular weight is determined by the method described in Examples.

The oxyethylene-oxypropylene block or random copolymer is preferably a block copolymer from the viewpoint of achieving the effects of the present invention.
The average number of added moles of oxyethylene groups constituting the oxyethylene-oxypropylene block or random copolymer is preferably 10 to 500 from the viewpoint of achieving the effects of the present invention. The upper limit of the average number of added moles is more preferably 450, still more preferably 400. On the other hand, the lower limit of the average number of moles added is more preferably 30, still more preferably 50. Further, for example, it is more preferably 30 to 450, and even more preferably 50 to 400.

The oxyethylene-oxypropylene block or random copolymer preferably has an average number of added moles of oxypropylene groups of 1 to 100 from the viewpoint of achieving the effects of the present invention. The upper limit of the average number of added moles is more preferably 80, still more preferably 70, particularly preferably 60. On the other hand, the lower limit of the average number of moles added is more preferably 5, still more preferably 10, particularly preferably 15. Further, for example, the number is more preferably 5 to 80, even more preferably 10 to 70, and particularly preferably 15 to 60.

[Sizing agent for textiles]
The fiber sizing agent of the present invention contains a compound (A) and an acetylene compound (B), and the weight ratio ((B)/(A)) of the acetylene compound (B) to the compound (A) is 0. It is .0005 to 0.13. Incidentally, the weight of the compound (A) and the acetylene compound (B) refers to the weight of each component in the nonvolatile content contained in the sizing agent of the present invention.
The reason why the wettability of the matrix resin is improved by including the compound (A) and the acetylene compound (B) in a specific ratio is thought to be that the compatibility between the compound (A) and the acetylene compound (B) is improved. ing. When the ratio ((B)/(A)) is less than 0.0005, the wettability of the matrix resin is insufficient, and when it exceeds 0.13, the adhesiveness with the matrix resin is insufficient.
From the viewpoint of improving the wettability of the matrix resin, the upper limit of ((B)/(A)) is preferably 0.125, more preferably 0.12, further preferably 0.115, and particularly 0.11. Preferably, 0.10 is most preferred. On the other hand, the lower limit of ((B)/(A)) is preferably 0.001, more preferably 0.005, even more preferably 0.007, particularly preferably 0.01, and most preferably 0.012. Further, for example, it is preferably 0.001 to 0.125, more preferably 0.005 to 0.12, and even more preferably 0.007 to 0.115.

When the fiber sizing agent of the present invention contains a nonionic compound (C), from the viewpoint of improving adhesiveness with the matrix resin, the weight ratio of the acetylene compound (B) to the nonionic compound (C) is ((B)/(C)) is preferably 0.001 to 0.5. Incidentally, the weight of the acetylene compound (B) and the nonionic compound (C) refers to the weight of each component in the nonvolatile content contained in the sizing agent of the present invention.
The upper limit of the weight ratio is more preferably 0.4, still more preferably 0.3, particularly preferably 0.2. On the other hand, the lower limit of the weight ratio is more preferably 0.02, still more preferably 0.03, particularly preferably 0.05. Further, for example, 0.02 to 0.4 is more preferable, and 0.03 to 0.3 is even more preferable,

When the fiber sizing agent of the present invention contains a nonionic compound (C), from the viewpoint of wettability and adhesiveness of the matrix resin, the acetylene sizing agent for fibers of the present invention The weight ratio ((B)/((A)+(C))) of the system compound (B) is preferably 0.005 to 0.5. Note that the weights of the compound (A), the acetylene compound (B), and the nonionic compound (C) refer to the weight of each component in the nonvolatile content contained in the sizing agent of the present invention.
The upper limit of the weight ratio is more preferably 0.4, still more preferably 0.3, particularly preferably 0.2. On the other hand, the lower limit of the weight ratio is more preferably 0.007, still more preferably 0.009, particularly preferably 0.01. Further, for example, it is more preferably from 0.007 to 0.4, even more preferably from 0.009 to 0.3, and particularly preferably from 0.01 to 0.2.

The weight proportion of the compound (A) in the nonvolatile content of the fiber sizing agent of the present invention is preferably 20% to 99% by weight from the viewpoint of cohesiveness and adhesiveness. The upper limit of the weight ratio is more preferably 98% by weight, still more preferably 97% by weight, particularly preferably 95% by weight. On the other hand, the lower limit of the weight ratio is more preferably 25% by weight, still more preferably 30% by weight, particularly preferably 40% by weight, and most preferably 50% by weight. Further, for example, it is more preferably 25% to 98% by weight, even more preferably 30% to 97% by weight, and particularly preferably 40% to 95% by weight.

The weight proportion of the acetylene compound (B) in the nonvolatile content of the fiber sizing agent of the present invention is preferably 0.05% to 10% by weight from the viewpoint of wettability with the matrix resin. The upper limit of the weight ratio is more preferably 9% by weight, still more preferably 8% by weight, particularly preferably 7% by weight. On the other hand, the lower limit of the weight ratio is more preferably 0.06% by weight, still more preferably 0.08% by weight, particularly preferably 0.1% by weight. Further, for example, it is more preferably 0.06% to 9% by weight, even more preferably 0.08% to 8% by weight, and particularly preferably 0.1% to 7% by weight.

There are no particular limitations on the method for producing the sizing agent of the present invention, and any known method can be employed. A method of making an aqueous solution, emulsion or aqueous dispersion by adding each component constituting a sizing agent into water under stirring, and a method of making an aqueous solution, emulsion or aqueous dispersion when producing each component constituting a sizing agent. A method in which each component constituting the sizing agent is added to water containing a surfactant under stirring to emulsify or disperse the component, and each component constituting the sizing agent is mixed into an emulsified dispersion liquid that has been emulsified and dispersed in advance. Method: After mixing the components constituting the sizing agent and heating the resulting mixture above the softening point, water is gradually added while applying mechanical shearing force using a homogenizer, homomixer, ball mill, etc. Examples include a method of phase inversion emulsification, and a method of mixing emulsified dispersion with an emulsified dispersion in an oil bath in which a sizing agent is applied.

The sizing agent of the present invention is preferably self-emulsified and/or emulsified and dispersed in water. The average particle diameter when the sizing agent is self-emulsified and/or emulsified and dispersed in water is not particularly limited, but from the viewpoint of storage stability, it is preferably 10 μm or less, more preferably 0.01 to 1 μm, and 0. More preferably, the thickness is from .01 to 0.5 μm. Note that the average particle diameter as used in the present invention refers to the arithmetic mean diameter measured with a laser diffraction/scattering particle size distribution analyzer (Horiba LA-920).

[Fiber strand]
The fiber strand of the present invention is obtained by adhering the above-mentioned fiber sizing agent to a raw material synthetic fiber strand, and can be suitably used as a reinforcing fiber for reinforcing a thermosetting resin or a thermoplastic matrix resin. .

The method for producing a fiber strand of the present invention includes a sizing treatment step of attaching the above-described fiber sizing agent to a raw synthetic fiber strand and drying the resulting deposit.
There are no particular limitations on the method of attaching the fiber sizing agent to raw synthetic fiber strands to obtain deposits, but the fiber sizing agent can be applied to raw synthetic fiber strands by kiss roller method, roller dipping method, spray method, or other known methods. Any method may be used as long as it is attached to the fiber strands. Among these methods, the roller dipping method is preferred because it allows the fiber sizing agent to be uniformly attached to the raw synthetic fiber strand.
There is no particular limitation on the method of drying the obtained deposit, and for example, it can be dried by heating with a heated roller, hot air, hot plate, or the like.

In addition, when attaching the fiber sizing agent of the present invention to the raw synthetic fiber strand, it may be applied after all the constituent components of the fiber sizing agent are mixed, or the constituent components may be attached separately in two or more stages. You may let them. In addition, thermosetting resins such as epoxy resins, vinyl ester resins, unsaturated polyester resins, and phenol resins, as well as polyolefin resins, nylon resins, polycarbonate resins, polyester resins, and polyacetal resins may also be used within the range that does not impede the effects of the present invention. Thermoplastic resins such as ABS resins, phenoxy resins, polymethyl methacrylate resins, polyphenylene sulfide resins, polyetherimide resins, and polyetherketone resins may be attached to the raw synthetic fiber strands.

The fiber strands of the present invention can be used as reinforcing fibers for composite materials using various thermosetting resins or various thermoplastic resins as matrix resins, and can be used in the form of continuous fibers or cut into predetermined lengths. It may be in the same state.

The amount of non-volatile content of the fiber sizing agent attached to the raw synthetic fiber strand can be selected as appropriate, and may be the amount necessary for the synthetic fiber strand to have the desired function, but the amount attached to the raw synthetic fiber strand may vary depending on the raw material synthetic fiber strand. The amount is preferably 0.1 to 20% by weight. In the synthetic fiber strand in the form of continuous fibers, the amount of adhesion is more preferably 0.1 to 10% by weight, and even more preferably 0.5 to 5% by weight, based on the raw synthetic fiber strand. Further, in the case of a strand cut into a predetermined length, the content is more preferably 0.5 to 20% by weight, and even more preferably 1 to 10% by weight.

When the amount of the fiber sizing agent attached is small, it is difficult to obtain the effects of the present invention regarding wettability with the matrix resin, and the cohesiveness of the synthetic fiber strands may be insufficient, resulting in poor handling properties. Furthermore, if the amount of the fiber sizing agent deposited is too large, the synthetic fiber strands may become too rigid, resulting in poor resin impregnation during composite molding, which is not preferable.

The synthetic fibers of the (raw material) synthetic fiber strands to which the fiber sizing agent of the present invention can be applied include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, aramid fibers, polyethylene fibers, polyethylene terephthalate fibers, and polybutylene terephthalate fibers. Examples include various organic fibers such as fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber, and polyketone fiber. From the viewpoint of physical properties of the resulting fiber-reinforced composite material, carbon fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber and polyketone fibers are preferred, and carbon fibers are more preferred.

[Fiber-reinforced composite material]
The fiber reinforced composite material of the present invention contains a thermosetting matrix resin or a thermoplastic matrix resin and the aforementioned fiber strands. Since the fiber strands are treated with the fiber sizing agent of the present invention, the fiber strands have good affinity with the thermoplastic matrix resin, resulting in a fiber reinforced composite material with excellent adhesive properties.
The fiber reinforced composite material of the present invention contains a matrix resin and the aforementioned fiber strands. The fiber strands are treated with the sizing agent of the present invention, and the sizing agent is uniformly adhered to the fiber strands, resulting in good compatibility with the fiber strands and the matrix resin, resulting in a fiber-reinforced composite material with excellent adhesive properties. Furthermore, thermal decomposition of the sizing agent during high-temperature treatment can be suppressed, and inhibition of adhesion to the matrix resin due to thermal decomposition can be suppressed. Here, the matrix resin refers to a matrix resin made of a thermosetting resin or a thermoplastic resin, and may contain one or more types. The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, phenol resins, unsaturated polyester resins, vinyl ester resins, cyanate ester resins, polyimide resins, and the like. Thermoplastic resins are not particularly limited, and include polyolefin resins, polyamide resins, polycarbonate resins, polyester resins, polyacetal resins, ABS resins, phenoxy resins, polymethyl methacrylate resins, polyphenylene sulfide resins, polyetherimide resins, and polyester resins. Examples include ether ketone resin. Among these, thermosetting resins are preferred, and epoxy resins and vinyl ester resins are more preferred, since the sizing agent of the present invention has a higher effect of improving adhesiveness.

Part or all of these matrix resins may be modified for the purpose of further improving adhesiveness with fiber strands.
The method for producing the fiber-reinforced composite material is not particularly limited, and known methods such as compound injection molding using chopped fibers, long fiber pellets, etc., press molding using UD sheets, textile sheets, etc., and other filament winding molding can be employed.
The content of synthetic fiber strands in the fiber-reinforced composite material is not particularly limited, and may be selected depending on the type and form of the fibers, the type of thermoplastic matrix resin, etc.; It is preferably 5 to 70% by weight, more preferably 20 to 60% by weight.

Hereinafter, the present invention will be specifically explained with reference to Examples, but it is not limited to the Examples described herein. Note that percentages (%) and parts shown in the following examples indicate "% by weight" and "parts by weight" unless otherwise specified. Measurement of each characteristic value was performed based on the method shown below.

<Permeability evaluation>
Permeability was evaluated using the following felt sedimentation test.
Orifelt S20 (No. 103) manufactured by Nikke Co., Ltd., cut into 2 cm x 2 cm, was floated on 100 mL of each sizing agent diluted with water to a nonvolatile content concentration of 1%, and the time (seconds) until it settled was measured. , the permeability was evaluated. Temperature: 23℃. The shorter the time until sedimentation, the better the permeability.
The indicators are as follows, and ◎ and ○ are considered passing.
Very good (◎): 90 seconds or less Good (○): More than 90 seconds and less than 180 seconds Slightly poor (△): More than 180 seconds and less than 300 seconds Poor (×): More than 300 seconds

<Adhesion rate of treatment agent>
Approximately 10 g of fibers coated with the sizing agent composition were placed in a Soxhlet extractor, extracted with methyl ethyl ketone for 2 hours, and calculated from the difference in weight of the fibers before and after extraction.

<Method for producing matrix resin drops>
Epoxy resin: A drop of matrix resin adjusted to 100 parts by weight of epoxy resin jER828 (manufactured by Mitsubishi Chemical Corporation) and 3 parts by weight of DICY (manufactured by Mitsubishi Chemical Corporation) was formed on a carbon fiber filament, and heated at 80°C for 1 hour. , and was cured by heating at 150° C. for 3 hours.
Polyamide resin: Polyamide resin T-663 (manufactured by Toyobo Co., Ltd.) was melted on a composite material interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.), and a drop was formed on a carbon fiber filament.

<Wettability of matrix resin>
The wettability of each matrix resin was evaluated using a composite material interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.). Carbon fiber filaments were taken out from the carbon fiber strands obtained in Examples and Comparative Examples and set in a sample holder. Drops of the above matrix resin were formed on a carbon fiber filament, 20 drops with a drop diameter in the drawing direction in the range of 100 to 120 μm were selected, and the contact angle with respect to the carbon fiber filament was measured, and the average value was obtained. The wettability of each matrix resin was evaluated according to the following criteria by comparison with the contact angle obtained in the same manner using carbon fiber filaments taken out from carbon fiber strands that were not treated with the sizing agent, and ◎ and 〇 were evaluated as passing.
◎: The contact angle is 2° or more smaller than the contact angle of the sizing agent-untreated carbon fiber.
○: The contact angle is 1° or more smaller than the contact angle of sizing agent-untreated carbon fiber.
△: Almost the same as the contact angle of untreated carbon fiber (difference in contact angle is less than ±1°)
×: The contact angle is 1° or more larger than that of the sizing agent-untreated carbon fiber.

<Adhesiveness>
Adhesion was evaluated by the microdroplet method using a composite material interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.).
Carbon fiber filaments were taken out from the carbon fiber strands obtained in Examples and Comparative Examples and set in a sample holder. A drop of each matrix resin was formed on a carbon fiber filament to obtain a sample for measurement. The measurement sample was set in the device, the drop was sandwiched between the device blades, the carbon fiber filament was run on the device at a speed of 0.06 mm/min, and the maximum pulling load F when pulling the drop from the carbon fiber filament was measured.
The interfacial shear strength τ was calculated using the following formula, and the adhesion between the carbon fiber filament and the matrix resin was evaluated. The above-mentioned epoxy resin and polyamide resin were used as the matrix resin. Each matrix resin drop was produced by the method shown above.
Interfacial shear strength τ (unit: MPa) = F/πdl
(F: Maximum pullout load d: Carbon fiber filament diameter l: Particle diameter in the drop pullout direction)

<Abrasion resistance>
Using a TM-type friction binding force tester TM-200 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the results obtained in Examples and Comparative Examples were measured using a tension of 50 g through three mirror-plated stainless steel needles arranged in a zigzag pattern. The carbon fiber strand thus obtained was rubbed 1000 times (reciprocating speed 300 times/min), and the state of fluff on the carbon fiber strand was visually judged according to the following criteria, and ◎ and 〇 were judged as passing.
◎: No fluff was observed as before rubbing.
○: Although some fuzz was observed, it was at a level that caused no practical problems.
△: Much fluff was observed, and some thread breakage was also observed.
×: Very many fluffs and single yarn breakages were observed.

<Convergence>
Carbon fibers sized with each sizing agent (diluted to 3% with water, target adhesion rate 1%) were visually evaluated to see if they would loosen when 10 pieces of 5mm length were cut out using a cutter knife. Judgment was made based on the following evaluation criteria, and ◎ and ○ were judged as passing.
◎: Less than 2 lines can be loosened ○: 3 to 4 lines can be loosened △: 5 to 7 lines can be loosened ×: 8 or more lines can be loosened

<Weight average molecular weight and number average molecular weight>
In the present invention, the weight average molecular weight and number average molecular weight refer to values measured by the gel permeation chromatography (GPC) measurement method described below and converted to polystyrene.
(GPC measurement conditions)
Equipment: Equipment name “HPLC LC-6A SYSTEM” (manufactured by SHIMAZU)
Column: "KF-800P (10mm x 4.6mmφ)", "KF-804 (300mm x 8mmφ)", "KF-802.5 (300mm x 8mmφ)", "KF-801 (300mm x 8mmφ)" ( The above are manufactured by SHODEX)
Mobile phase: Tetrahydrofuran (THF)
Flow rate: 1.0ml/min
Sample amount: 100 μl (100 times dilution)
Column temperature: 50℃
Calibration curve creation standard material: polystyrene (PSt)

The compounds used in the examples are as follows.
a1-1: jER828/jER1001 = 50/50 (weight ratio) (epoxy resin mixture manufactured by Mitsubishi Chemical Corporation)
a1-2: Vinyl ester resin (bisphenol A diglycidyl ether acrylic acid adduct)
a1-3: Unsaturated polyester resin (synthesis example a1-3 below)
a1-4: jER807/jER4005P = 50/50 (weight ratio) (epoxy resin mixture manufactured by Mitsubishi Chemical Corporation)
a1-5: Vinyl ester resin (trimethylolpropane trimethacrylate)
a1-6: Unsaturated polyester resin (synthesis example a1-6 below)
a2-1: Aromatic polyurethane resin (synthesis example a2-1 below)
a2-2: Saturated polyester resin (synthesis example a2-2 below)
a2-3: Polyolefin resin (maleic anhydride modified polypropylene resin (propylene/maleic anhydride graft copolymerization ratio (wt%): 95/5, weight average molecular weight: 30000))
a2-4: Aromatic polyurethane resin (synthesis example a2-4 below)
a2-5: Saturated polyester resin (synthesis example a2-5 below)
a2-6: Polyolefin resin (maleic anhydride modified polypropylene resin (propylene/maleic anhydride graft copolymerization ratio (wt%): 85/15, weight average molecular weight: 37000))
a3-1: KM-9749 (manufactured by Shin-Etsu Chemical Co., Ltd.)
a3-2: SBL0533 (manufactured by Eneos Materials Co., Ltd.)
a3-3: KM-2002-L-1 (manufactured by Shin-Etsu Chemical Co., Ltd.)
a3-4: SBL0548 (manufactured by Eneos Materials Co., Ltd.)
a'4: isooctyl stearate b1: 20 mole ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol b2: 2,4,7,9-tetramethyl- 5-mol ethylene oxide adduct of 5-decyne-4,7-diol b3: 3,6-dimethyl-4-octyne-3,6-diol b4: 2,4,7,9-tetramethyl-5-decyne- 4,7-diol c1: POEO block polyether (PO/EO=20/80) (Mw15500)
c2: POEO block polyether (PO/EO=50/50) (Mw4500)
In addition, a1-1, a1-2, a1-3, a1-4, a1-5, a1-6, a2-3, a2-6, a'4, b3 and b4 were non-self-emulsifying components. .

(Synthesis example a1-3)
0.9 mol of maleic anhydride and 1.0 mol of an adduct of 4 mol of ethylene oxide of bisphenol A were reacted at 140° C. for 5 hours to obtain an unsaturated polyester resin (a1-3) with an acid value of 2.5. The weight average molecular weight (Mw) was 5051, and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) was 1.6.

(Synthesis example a1-6)
0.8 mol of maleic anhydride and 1.0 mol of an adduct of 2 mol of ethylene oxide of bisphenol A were reacted at 140° C. for 3 hours to obtain an unsaturated polyester (a1-6) with an acid value of 3.5. The weight average molecular weight (Mw) was 1626, and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) was 1.7.

(Synthesis example a2-1)
498 parts of terephthalic acid, 332 parts of isophthalic acid, 248 parts of ethylene glycol, 106 parts of diethylene glycol, 45 parts of tetramethylene glycol, and 0.2 parts of dibutyltin oxide were charged into a reactor under nitrogen gas, and the mixture was heated at 190 to 240°C. The esterification reaction was carried out for 10 hours to obtain an aromatic polyester polyol. Next, 1000 parts of the obtained aromatic polyester polyol was dehydrated under reduced pressure at 120°C, and after cooling to 80°C, 680 parts of methyl ethyl ketone was charged and dissolved with stirring. Subsequently, 218 parts of isophorone diisocyanate and 67 parts of 2,2-dimethylolpropionic acid as a chain extender were charged, and a urethane reaction was carried out at 70°C for 12 hours. After the reaction was completed, it was cooled to 40°C, and 97 parts of 13.6% aqueous ammonia was added to neutralize it, followed by vacuum treatment at 65°C to distill off the methyl ethyl ketone, and the aromatic polyurethane resin (a2-1) was obtained. Obtained.

(Synthesis example a2-4)
332 parts of terephthalic acid, 332 parts of isophthalic acid, 146 parts of adipic acid, 258 parts of ethylene glycol, 106 parts of diethylene glycol, 52 parts of neopentyl glycol and 0.2 parts of dibutyltin oxide were charged into a reactor under nitrogen gas. Esterification reaction was carried out at 190 to 240°C for 10 hours to obtain an aromatic polyester polyol. Next, 1000 parts of the obtained aromatic polyester polyol was dehydrated under reduced pressure at 120°C, and after cooling to 80°C, 680 parts of methyl ethyl ketone was charged and dissolved with stirring. Subsequently, 160 parts of hexamethylene diisocyanate and 67 parts of 2,2-dimethylolpropionic acid as a chain extender were charged, and a urethane reaction was carried out at 70°C for 12 hours. After the reaction was completed, the mixture was cooled to 40°C, neutralized by adding 97 parts of 13.6% aqueous ammonia, and then treated under reduced pressure at 65°C to distill off the methyl ethyl ketone to obtain the aromatic polyurethane resin (a2-4). Obtained.

(Synthesis example a2-2)
950 parts of dimethyl isophthalate, 1000 parts of diethylene glycol, 0.5 parts of zinc acetate and 0.5 parts of antimony trioxide were charged into a reactor under nitrogen gas, and a transesterification reaction was carried out at 140 to 220°C for 3 hours. . Next, 30 parts of 5-sodium sulfoisophthalic acid was added and an esterification reaction was carried out at 220 to 260°C for 1 hour, followed by a polycondensation reaction at 240 to 270°C for 2 hours under reduced pressure. -2) was obtained.

(Synthesis example a2-5)
In a reactor filled with nitrogen gas, 475 parts of dimethyl isophthalate, 475 parts of dimethyl terephthalate, 1000 parts of diethylene glycol, 0.5 part of zinc acetate and 0.5 part of antimony trioxide were charged, and the ester was heated at 140 to 220°C for 3 hours. An exchange reaction was performed. Next, 30 parts of 5-sodium sulfoisophthalic acid was added, an esterification reaction was performed at 220 to 260°C for 1 hour, a polycondensation reaction was performed at 240 to 270°C for 2 hours under reduced pressure, and 240 to 270 parts of 5-sodium sulfoisophthalic acid was added. A polycondensation reaction was carried out at °C under reduced pressure for 2 hours to obtain a saturated polyester resin (a2-5).

(Manufacture of sizing agent for textiles)
(Example 1)
75 parts by weight of epoxy resin mixture a1-1 as a non-self-emulsifying component, 10 parts by weight of c1 and 10 parts by weight of c2 as emulsifiers were charged into an emulsifying device, and stirring sewage was gradually added to phase inversion emulsification to produce a homogeneous emulsifier. An aqueous dispersion of non-self-emulsifying components was obtained. Thereafter, 5 parts by weight of b1 as the remaining components other than the non-self-emulsifying component and the emulsifier were mixed into the water dispersion to obtain a sizing agent with a non-volatile content concentration of 40% by weight.

(Examples 2 to 39 and Comparative Examples 1 to 14)
A component selected from a1-1, a1-2, a1-3, a1-4, a1-5, a1-6, a2-3, a2-6, a'4, b3 and b4 as a non-self-emulsifying component. , a component selected from c1 and c2 as an emulsifier, and a2-1, a2-2, a2-4, a2-5, a3-1, a3-2, a3 as a non-self-emulsifying component and the remaining components other than the emulsifier. A sizing agent was obtained in the same manner as in Example 1, except that the components selected from -3, a3-4, b1 and b2 were changed to the nonvolatile compositions shown in Tables 1 to 6, respectively. The numerical values listed in the table indicate the weight proportion of each component (in the case of an aqueous dispersion, the nonvolatile content) in the nonvolatile content of the sizing agent.

(Manufacture of fiber strands with sizing agent attached)
The obtained sizing agent was diluted with water to prepare a sizing agent diluted solution having a nonvolatile content concentration of 3% by weight.
Next, a sizing agent-untreated carbon fiber strand (fineness: 800 tex, number of filaments: 12,000) was dipped and impregnated in the prepared sizing agent diluted solution by the Dip Nip method, and then dried with hot air at 105° C. for 15 minutes to undergo the sizing agent treatment. A carbon fiber strand was obtained. Using the obtained sizing agent-treated carbon fiber strands, permeability, adhesion rate of the treatment agent, wettability of the matrix resin, adhesiveness, abrasion resistance, and cohesiveness were evaluated by the methods described above.

As is clear from Tables 1 to 4, the sizing agents of Examples contain the compound (A) and the acetylene compound (B), and the weight ratio of the compound (B) to the compound (A) ((B) /(A)) is 0.0005 to 0.13, it provides fibers with excellent wettability with matrix resin and can be suitably used as a sizing agent.
On the other hand, as shown in Tables 5 and 6, the sizing agents of the comparative examples do not contain the compound (B) (Comparative Examples 1 to 3), and do not contain the compound (A) (Comparative Examples 4, 11, 14). ), (B)/(A) is not within the range of 0.0005 to 0.13 (Comparative Examples 5 to 10, 12, 13). As a result of the evaluation, Comparative Examples 1 to 3, 5, 7, 9, 12, and 14 had insufficient wettability with the matrix resin, and Comparative Examples 4, 6, 8, 10, 11, and 13 had insufficient wettability with the matrix resin. Although the treatment agents have good properties, they do not meet the requirements as a sizing agent due to insufficient cohesiveness. Therefore, the treatment agents of all comparative examples cannot be used as fiber sizing agents to improve the wettability of the matrix resin to the fiber strands. Therefore, the problem of the present application cannot be solved.

Possibility of industrial use

Fiber-reinforced composite materials, in which matrix resin is reinforced with reinforcing fibers, are used in automobiles, aerospace, aerospace, sports and leisure, general industrial applications, etc. Examples of reinforcing fibers include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as aramid fibers, polyamide fibers, and polyethylene fibers.

Claims (8)

A fiber sizing agent containing a compound (A) and an acetylene compound (B),
The compound (A) is at least one selected from thermosetting resin (A1), thermoplastic resin (A2) and rubber (A3),
The weight ratio ((B)/(A)) of the acetylene compound (B) to the compound (A ) is 0.0005 to 0.13,
The thermosetting resin (A1) is at least one selected from epoxy resin (A1-1), vinyl ester resin (A1-2) and unsaturated polyester resin (A1-3),
The thermoplastic resin (A2) is at least one selected from aromatic polyurethane resin (A2-1), saturated polyester resin (A2-2), and polyolefin resin (A2-3),
The rubber (A3) is at least one selected from silicone rubber (A3-1) and diene rubber (A3-2),
A sizing agent for fibers, wherein the epoxy resin (A1-1) is an aromatic epoxy resin . A sizing agent for fibers containing a compound (A) and an acetylene compound (B),
The compound (A) is at least one selected from thermosetting resin (A1), thermoplastic resin (A2) and rubber (A3),
The weight ratio ((B)/(A)) of the acetylene compound (B) to the compound (A) is 0.0005 to 0.13,
It further contains a nonionic compound (C), and the weight ratio ((B)/(C)) of the acetylene compound (B) to the nonionic compound (C) is 0.001 to 0.5. , sizing agent for textiles. The fiber sizing agent according to claim 1 , further comprising a nonionic compound (C), wherein the nonionic compound (C) has a weight average molecular weight of 1,000 to 20,000. The acetylene compound (B) is at least selected from acetylene alcohol (B1), acetylene diol (B2), a compound obtained by adding alkylene oxide to acetylene alcohol (B3), and a compound obtained by adding alkylene oxide to acetylene diol (B4). The fiber sizing agent according to claim 1 , which is one type. The acetylene alcohol (B1) is a compound represented by the following general formula (1), the acetylene diol (B2) is a compound represented by the following general formula (2), and alkylene oxide is added to the acetylene alcohol. The compound (B3) is a compound represented by the following general formula (3), and the compound (B4) obtained by adding alkylene oxide to the acetylene diol is a compound represented by the following general formula (4). 4. The fiber sizing agent according to item 4 .

(In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms.)

(In formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 8 carbon atoms.)

(In formula (3), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms. R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. AO is a carbon It represents an oxyalkylene group of 2 to 4. n is a number of 1 to 50.)

(In formula (4), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 8 carbon atoms. R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In addition, a plurality of R ⁷ 's in formula (4) may be the same or different. AO represents an oxyalkylene group having 2 to 4 carbon atoms. m and n each independently represent It is a number from 1 to 50.) A sizing agent-attached fiber strand, wherein the fiber sizing agent according to any one of claims 1 to 5 is attached to the fiber strand. A fiber-reinforced composite material comprising a matrix resin and the sizing agent-attached fiber strand according to claim 6 . The fiber reinforced composite material according to claim 7 , wherein the matrix resin is at least one selected from thermosetting resins and thermoplastic resins.