JP2013116998A - Substrate for molding, molding material, and carbon fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sizing agent coated carbon fiber cloth that excels in interfacial adhesion of a carbon fiber and a thermosetting resin, and can obtain a molding excellent in a dynamic property.SOLUTION: A substrate for molding uses a carbon fiber that is applied with a sizing agent including the following components (A) and (B), wherein the form of the substrate for molding is a woven fabric or a braided string. The component (A) is an epoxy compound that has two or more epoxy groups or two or more functional groups. The component (B) is 0.1-25 parts by mass of one or more compounds selected from the group consisting of a tertiary amine compound, a tertiary amine salt, a quarternary ammonium salt, a quarternary phosphonium salt, and a phosphine compound based on 100 parts by mass of the component (A).

Description

  The present invention relates to a molding substrate, molding material, and carbon fiber reinforced composite material suitably used for aircraft members, spacecraft members, automobile members, ship members, and the like.

  Since carbon fiber is lightweight and has excellent strength and elastic modulus, many composite materials combined with various matrix resins are used for aircraft members, spacecraft members, automobile members, ship members, civil engineering and building materials, and sporting goods. Used in the field. In a composite material using carbon fibers, in order to make use of the excellent characteristics of carbon fibers, it is important that the adhesion between the carbon fibers and the matrix resin is excellent.

  In order to improve the adhesion between the carbon fiber and the matrix resin, a method of introducing an oxygen-containing functional group on the surface of the carbon fiber is usually performed by subjecting the carbon fiber to oxidation treatment such as gas phase oxidation or liquid phase oxidation. . For example, a method of improving the interlaminar shear strength, which is an index of adhesiveness, by subjecting carbon fibers to electrolytic treatment has been proposed (see Patent Document 1). However, in recent years, as the level of required properties for composite materials has improved, the adhesion that can be achieved by such oxidation treatment alone is becoming insufficient.

  On the other hand, since carbon fiber is brittle and has poor convergence and friction resistance, fluff and yarn breakage are likely to occur in the high-order processing step. For this reason, the method of apply | coating to carbon fiber is proposed (refer patent document 2 and 3).

  For example, a method of applying diglycidyl ether of bisphenol A as a sizing agent to carbon fibers has been proposed (see Patent Documents 2 and 3). In addition, a method of applying a polyalkylene oxide adduct of bisphenol A as a sizing agent to carbon fibers has been proposed (see Patent Documents 4 and 5). Moreover, the method of apply | coating what added the epoxy group to the polyalkylene oxide addition product of bisphenol A as a sizing agent to carbon fiber is proposed (refer patent documents 6 and 7). Furthermore, a method of applying an epoxy adduct of polyalkylene glycol as a sizing agent to carbon fibers has been proposed (see Patent Documents 8, 9 and 10).

  Separately, a method of applying a urethane compound having an epoxy group and a quaternary ammonium salt as a sizing agent to carbon fibers has been proposed (see Patent Document 11). Even with this proposed method, the convergence and friction resistance are improved, but the adhesion between the carbon fiber and the matrix resin cannot be improved.

  According to these methods, it is known that the converging property and friction resistance of the carbon fiber are improved. However, these conventional proposals do not have a technical idea of positively improving the adhesion between the carbon fiber and the matrix resin by using a sizing agent, and actually greatly improve the adhesion between the carbon fiber and the matrix resin. I couldn't.

  On the other hand, a method of applying a specific sizing agent to carbon fibers has been performed for the purpose of improving the impregnation property of the matrix resin into the carbon fibers.

  For example, a method of applying a cationic surfactant having a surface tension of 40 mN / m or less and a viscosity at 80 ° C. of 200 mPa · s or less as a sizing agent to carbon fibers has been proposed (see Patent Document 12). Further, a method of applying an epoxy resin, a water-soluble polyurethane resin, and a polyether resin as sizing agents to carbon fibers has been proposed (see Patent Document 13). According to these methods, it has been recognized that the carbon fiber is easily bundled and the matrix resin is impregnated into the carbon fiber. However, these conventional proposals do not have a technical idea of positively improving the adhesion between the carbon fiber and the matrix resin by using the sizing agent, and the adhesion between the carbon fiber and the matrix resin is actually greatly improved. I couldn't make it.

  As described above, the sizing agent is conventionally used as a so-called paste agent for the purpose of improving the high-order workability and for the purpose of improving the impregnation property of the matrix resin into the carbon fiber. There has been almost no investigation to improve the adhesiveness. Moreover, even in the studied examples, the effect of improving the adhesiveness is insufficient, or the effect is limited only in combination with a special carbon fiber.

  For example, a method of applying N, N, N ′, N′-tetraglycidylmetaxylylenediamine as a sizing agent to carbon fibers has been proposed (see Patent Document 14). However, this proposed method shows that the interlaminar shear strength, which is an index of adhesion, is improved as compared with the case where glycidyl ether of bisphenol A is used, but the effect of improving adhesion is still insufficient. Met. In addition, N, N, N ′, N′-tetraglycidylmetaxylylenediamine used in this proposal contains an aliphatic tertiary amine in the skeleton and has nucleophilicity. In particular, there is a problem that the carbon fiber bundle becomes hard and the high-order workability is lowered.

Further, a method has been proposed in which a mixture of a vinyl compound monomer having a glycidyl group and an amine curing agent for epoxy resin is applied to carbon fibers as a sizing agent (see Patent Document 15). However, although this proposed method has been shown to improve the interlaminar shear strength, which is an index of adhesion, compared with the case where no amine curing agent is used, the effect of improving adhesion is still insufficient. It was. In addition, the glycidyl group and amine curing agent react with each other in the drying process of the sizing agent to increase the molecular weight. As a result, the carbon fiber bundle becomes hard and the high-order workability decreases, and the gaps between the carbon fibers become narrower and the resin. There was a problem that the impregnation property of the resin deteriorated.
Another method using a sizing agent in which an epoxy compound and an amine curing agent are used in combination has been proposed (see Patent Document 16). However, according to this proposal, the handling property and impregnation property of the fiber bundle are improved, but the adhesion between the carbon fiber and the epoxy matrix resin is inhibited by the film formation of the high molecular weight sizing agent on the carbon fiber surface. There was a case.
Furthermore, a method of applying an amine compound to carbon fibers has been proposed (see Patent Document 17). However, although the proposed method shows that the interlaminar shear strength, which is an index of adhesion, is improved as compared with the case where nothing is applied, the effect of improving adhesion is still insufficient. In this proposal, there is no detailed description of the adhesion improvement mechanism, but it is presumed that it is roughly the following mechanism. That is, in this proposal, diethylenetriamine containing a primary amino group, xylenediamine, piperidine containing a secondary amino group, and imidazole are used as amine compounds. It is considered that the active hydrogen acts on the epoxy matrix resin and accelerates the curing reaction. For example, the hydroxyl group formed by the reaction of the epoxy matrix and the amine compound, the carboxyl group on the carbon fiber surface, the hydroxyl group, etc. It is thought that the adhesion is improved by forming an action. However, as described above, the result of improvement in adhesion is still insufficient with this proposal, and it cannot be said that the demands for composite materials in recent years are satisfied.

  Furthermore, as another example using an amine compound as a sizing agent, a method using a thermosetting resin and a cured product of an amine compound has been proposed (see Patent Document 18). In this proposal, m-xylenediamine containing a primary amino group and piperazine containing a secondary amino group are used as an amine compound. The purpose of this proposal is to improve the convergence and handling of the carbon fiber bundle by actively reacting the active hydrogen contained in the amine compound with a thermosetting resin represented by an epoxy resin to produce a cured product. Met. This carbon fiber bundle was limited to chopped applications, and the mechanical properties related to the adhesiveness of the molded product after melt-kneading with a thermoplastic resin were still insufficient.

  Further, carbon fibers having surface oxygen concentration O / C, surface hydroxyl group concentration and carboxyl group concentration within specific ranges are used, and an aliphatic compound having a plurality of epoxy groups is applied to the carbon fiber as a sizing agent. A method has been proposed (see Patent Document 19). However, this proposed method has been shown to improve EDS, which is an index of adhesion, but the effect of improving the adhesion between the carbon fiber and the matrix resin is still insufficient, and adhesion The improvement effect was limited to be manifested only when combined with special carbon fibers.

Japanese Patent Laid-Open No. 04-361619 US Pat. No. 3,957,716 JP-A-57-171767 JP 07-009444 A JP 2000-336577 A JP 61-028074 A Japanese Patent Laid-Open No. 01-272867 JP-A-57-128266 U.S. Pat. No. 4,555,446 JP 62-033872 A U.S. Pat. No. 4,496,671 JP 2010-31424 A JP-A-2005-320641 JP 52-059794 A JP-A-52-045673 JP 2005-146429 A JP-A-52-045672 JP 09-217281 A US Pat. No. 5,691,055

  Accordingly, an object of the present invention is to provide a molding substrate, a molding material, and a carbon fiber reinforced composite material that are excellent in interfacial adhesion between carbon fibers and a matrix resin and have high mechanical properties in view of the problems in the above-described prior art. It is to provide.

  The sizing agent includes (A) a specific epoxy compound and (B) a specific tertiary amine compound and / or tertiary amine salt, quaternary ammonium salt, quaternary phosphonisum salt and / or phosphine compound, When a sizing agent containing a specific ratio is applied to carbon fiber and heat-treated at a specific temperature, the adhesion between the carbon fiber and the matrix resin can be improved, thereby finding that the mechanical properties of the carbon fiber reinforced composite material can be improved. The present invention has been conceived.

That is, the present invention is a molding base material using carbon fiber to which a sizing agent containing the following components (A) and (B) is applied, and the form thereof is a woven fabric or a braid. To do.
Component (A): Epoxy compound (A1) having two or more epoxy groups, and / or one or more epoxy groups, a hydroxyl group, an amide group, an imide group, a urethane group, a urea group, a sulfonyl group, and a sulfo group Epoxy compound (A2) having at least one functional group selected from
Component (B): 0.1 to 25 parts by mass of at least one reaction accelerator selected from the group consisting of the following [a], [b] and [c] with respect to 100 parts by mass of component (A)
[A] A tertiary amine compound and / or a tertiary amine salt (B1) having a molecular weight of 100 g / mol or more, which is used as at least the component (B)
[B] At least the following general formula (I) used as component (B)

（式中、Ｒ_１〜Ｒ_４は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい）、または一般式（ＩＩ）

(Wherein R _{1 to} R ₄ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- Optionally substituted by O-, -O-CO- or -CO-O-), or general formula (II)

（式中、Ｒ_５は、炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。Ｒ_６とＲ_７は、それぞれ水素、または炭素数１〜８の炭化水素基を表し、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。）のいずれかで示されるカチオン部位を有する４級アンモニウム塩（Ｂ２）

(In the formula, R ₅ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group represents —O—, — R ₆ and R ₇ each independently represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and CH ₂ group in the hydrocarbon group may be substituted by O—CO— or —CO—O—. May be substituted by —O—, —O—CO— or —CO—O—.) A quaternary ammonium salt (B2) having a cation moiety

  [C] Quaternary phosphonium salt and / or phosphine compound (B3) used as at least component (B)

  According to a preferred aspect of the molding substrate of the present invention, in the above invention, the tertiary amine compound and / or tertiary amine salt having the molecular weight of (B1) of [a] of 100 g / mol or more is represented by the following general formula: (III)

（式中、Ｒ_８は炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。Ｒ_９は、炭素数２〜２２のアルキレン基、炭素数２〜２２のアルケニレン基、または炭素数２〜２２のアルキニレン基のいずれかを表す。Ｒ_１０は、水素または炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。または、Ｒ_８とＲ_１０は結合して炭素数２〜１１のアルキレン基を形成してもよい）、一般式（ＩＶ）

(In the formula, R ₈ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group represents —O—, —O, R ₉ may be any one of an alkylene group having 2 to 22 carbon atoms, an alkenylene group having 2 to 22 carbon atoms, or an alkynylene group having 2 to 22 carbon atoms, which may be substituted with —CO— or —CO—O—. R ₁₀ represents hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is —O— , -O-CO- or -CO-O-, or R ₈ and R ₁₀ may combine to form an alkylene group having 2 to 11 carbon atoms), a general formula ( IV)

（式中、Ｒ_１１〜Ｒ_１４は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい）、一般式（Ｖ）

(In the formula, each of R _{11 to} R ₁₄ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- Optionally substituted by O-, -O-CO- or -CO-O-), general formula (V)

（式中、Ｒ_１５〜Ｒ_２０は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。Ｒ_２１は、水酸基または炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい）、一般式（ＶＩ）

(Wherein R _{15 to} R ₂₀ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O-, -O-CO- or -CO-O- R ₂₁ represents a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group has a hydroxyl group. And the CH ₂ group in the hydrocarbon group may be substituted by —O—, —O—CO— or —CO—O—), the general formula (VI)

（式中、Ｒ_２２〜Ｒ_２４は、それぞれ炭素数１〜８の炭化水素基を表し、該炭化水素基は水酸基を有していてもよい）、一般式（ＶＩＩ）

(Wherein R _{22 to} R ₂₄ each represent a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may have a hydroxyl group), general formula (VII)

（式中、Ｒ_２５は、炭素数１〜８の炭化水素基を表し、該炭化水素基は水酸基を有していてもよい）、または一般式（ＶＩＩＩ）

(Wherein R ₂₅ represents a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may have a hydroxyl group), or general formula (VIII)

（式中、Ｒ_２６〜Ｒ_２８は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。さらに、Ｒ_２６〜Ｒ_２８のいずれかに、次の一般式（ＩＸ）または（Ｘ）で示される１以上の分岐構造を有し、かつ少なくとも１以上の水酸基を含む）であることを特徴とする。

(In the formula, each of R _{26 to} R ₂₈ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O—, —O—CO— or —CO—O—, and any one of R _{26 to} R _{28 represented} by the following general formula (IX) or (X) And having at least one hydroxyl group).

（式中、Ｒ_２９、Ｒ_３０は、それぞれ炭素数１〜２０の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。但し、Ｒ_２９とＲ_３０の炭素数の合算値が２１以下である。）

(Wherein R ₂₉ and R ₃₀ each represent a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O-, -O-CO- or -CO-O-, provided that the total number of carbon atoms of R ₂₉ and R ₃₀ is 21 or less.)

（式中、Ｒ_３１〜Ｒ_３３は、それぞれ水酸基または炭素数１〜１９の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。但し、Ｒ_３１とＲ_３２とＲ_３３の炭素数の合算値が２１以下である。）

(Wherein R _{31 to} R ₃₃ each represent a hydroxyl group or a hydrocarbon group having 1 to 19 carbon atoms, the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is , -O-, -O-CO- or -CO-O-, provided that the total number of carbon atoms of R ₃₁ , R ₃₂ and R ₃₃ is 21 or less.)

  According to a preferred aspect of the molding substrate of the present invention, in the above invention, the compound represented by the general formula (III) is 1,5-diazabicyclo [4,3,0] -5-nonene or a compound thereof. It is a salt or 1,8-diazabicyclo [5,4,0] -7-undecene or a salt thereof.

According to a preferred embodiment of the molding substrate of the present invention, in the above invention, in the compound represented by the general formula _(VIII), at least two of R 26 _{to R 28,} the general formula (IX) or general A branched structure represented by the formula (X) is included.

  According to a preferred aspect of the molding substrate of the present invention, in the above invention, the compound represented by the general formula (VIII) is triisopropanolamine or a salt thereof.

According to a preferred embodiment of the molding substrate of the present invention, in the above invention, in the general formula [b] (I), R 3 and R ₄ are each a hydrocarbon group having 2 to 22 carbon atoms The hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group may be substituted by —O—, —O—CO— or —CO—O—. It is characterized by.

  According to a preferred aspect of the molding substrate of the present invention, in the above invention, the anion portion of the quaternary ammonium salt having the cation portion (B2) of [b] is a halogen ion.

  According to a preferred aspect of the molding substrate of the present invention, in the above invention, the (B3) quaternary phosphonium salt and / or phosphine compound of the above [c] is represented by the following general formula (XI):

（式中、Ｒ_３４〜Ｒ_３７は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい）で示されるカチオン部位を有する４級ホスホニウム塩、または一般式（ＸＩＩ）

(In the formula, each of R _{34 to} R ₃₇ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- A quaternary phosphonium salt having a cation moiety represented by the formula (XII), which may be substituted by O—, —O—CO— or —CO—O—

（式中、Ｒ_３８〜Ｒ_４０は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい）で示されるホスフィン化合物から選択される１つ以上であることを特徴とする。

(Wherein R _{38 to} R ₄₀ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be one or more selected from phosphine compounds represented by the formula (which may be substituted by O—, —O—CO— or —CO—O—).

  Moreover, according to the preferable aspect of the base material for shaping | molding of this invention, in the said invention, the epoxy equivalent of (A) component is less than 360 g / mol, It is characterized by the above-mentioned.

  Moreover, according to the preferable aspect of the base material for shaping | molding of this invention, in the said invention, (A) component is an epoxy compound which has a 3 or more epoxy group, It is characterized by the above-mentioned.

  Moreover, according to the preferable aspect of the base material for shaping | molding of this invention, in the said invention, (A) component contains an aromatic ring in a molecule | numerator, It is characterized by the above-mentioned.

  According to a preferred aspect of the molding substrate of the present invention, in the above invention, the component (A1) is any one of a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and tetraglycidyl diaminodiphenylmethane. And

  Moreover, according to the preferable aspect of the base material for shaping | molding of this invention, in the said invention, the surface oxygen concentration O / C measured by the X ray photoelectron spectroscopy of carbon fiber is 0.05-0.5. It is characterized by.

  Moreover, according to the preferable aspect of the base material for shaping | molding of this invention, after carbon fiber is liquid phase electrolytically oxidized in alkaline electrolyte, or after liquid phase electrolytic oxidation in acidic electrolyte in the said invention. Subsequently, the substrate is washed with an alkaline aqueous solution.

  According to a preferred aspect of the molding material of the present invention, the molding substrate according to any one of the above and a thermosetting resin or a thermoplastic resin are combined.

  Moreover, according to the preferable aspect of the carbon fiber reinforced composite material of this invention, it shape | molds the molding material as described above, It is characterized by the above-mentioned.

  According to the present invention, in (A) a sizing agent containing a specific epoxy compound as a main component, (B) a specific tertiary amine compound and / or a tertiary amine salt, a quaternary ammonium salt, a quaternary phosphonisum salt, and / or Alternatively, when a specific amount of a phosphine compound is blended and heat treatment is performed under specific conditions, the epoxy compound and an oxygen-containing functional group originally contained on the carbon fiber surface, or a carboxyl group introduced by oxidation treatment Further, formation of a covalent bond is promoted between oxygen and a functional group containing oxygen such as a hydroxyl group, and a molding substrate, molding material, and carbon fiber reinforced composite material can be obtained that have significantly improved adhesion to the matrix resin.

  Hereinafter, in more detail, the shaping | molding base material concerning this invention, the shaping | molding material using this shaping | molding base material, and the form for implementing the carbon fiber reinforced composite material formed by shape | molding this shaping | molding material are demonstrated. The present invention is a forming base material using carbon fibers to which a sizing agent containing the following components (A) and (B) is applied, the form of which is a woven fabric or braid. First, the carbon fiber formed by applying a sizing agent containing the components (A) and (B) will be described.

  The component (A) used in the present invention is (A1) a compound having two or more epoxy groups in the molecule, and / or (A2) one or more epoxy groups, hydroxyl group, amide group in the molecule. An epoxy compound having at least one functional group selected from imide group, urethane group, urea group, sulfonyl group, and sulfo group.

  The component (B) used in the present invention is (B1) a tertiary amine compound and / or tertiary amine salt having a molecular weight of 100 g / mol or more, (B2) general formula (I)

（式中、Ｒ_１〜Ｒ_４は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい）、または一般式（ＩＩ）

(Wherein R _{1 to} R ₄ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- Optionally substituted by O-, -O-CO- or -CO-O-), or general formula (II)

（式中、Ｒ_５は、炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。Ｒ_６とＲ_７は、それぞれ水素、または炭素数１〜８の炭化水素基を表し、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。）のいずれかで示されるカチオン部位を有する４級アンモニウム塩、（Ｂ３）４級ホスホニウム塩および／またはホスフィン化合物から選択される少なくとも１種の化合物をさす。

(In the formula, R ₅ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group represents —O—, — R ₆ and R ₇ each independently represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and CH ₂ group in the hydrocarbon group may be substituted by O—CO— or —CO—O—. May be substituted by -O-, -O-CO- or -CO-O-)), (B3) a quaternary phosphonium salt and / or Or it refers to at least one compound selected from phosphine compounds.

  In this invention, (A) component and (B) component are at least 1 sort (B) component selected from said (B1), (B2), (B3) with respect to 100 mass parts of (A) component. It is preferable to use a sizing agent obtained by blending 0.1 to 25 parts by mass of

  The mechanism by which the adhesiveness is improved by applying a sizing agent containing a specific amount of the component (A) and the component (B) to the carbon fiber and performing a heat treatment at 160 to 260 ° C. for 30 seconds to 600 seconds is not certain. First, the component (B) acts on oxygen-containing functional groups such as carboxyl groups and hydroxyl groups of the carbon fibers used in the present invention, and after drawing out hydrogen ions contained in these functional groups to anionize, this anionization It is considered that the functional group and the epoxy group contained in the component (A) undergo a nucleophilic reaction. This forms a strong bond between the carbon fiber used in the present invention and the epoxy group in the sizing agent. On the other hand, in relation to the matrix resin, each of (A1) and (A2) will be described as follows.

  In the case of (A1), it is considered that the remaining epoxy groups not participating in the covalent bond with the carbon fiber used in the present invention react with the matrix resin-containing functional group to form a covalent bond, or form a hydrogen bond. It is done. In particular, when the matrix resin is an epoxy resin, it is considered that a strong interface can be formed by the reaction between the epoxy group of (A1) and the epoxy group of the matrix resin, or the reaction via the amine curing agent contained in the epoxy resin. . The structure (A1) preferably contains one or more unsaturated groups. When the matrix resin is a radical polymerization resin such as an unsaturated polyester resin or vinyl ester resin, the unsaturation of (A1) It is possible to form a strong interface by radical reaction between the group and the unsaturated group of the matrix resin.

  In the case of (A2), the epoxy group of (A2) forms a covalent bond with an oxygen-containing functional group such as a carboxyl group and a hydroxyl group of the carbon fiber used in the present invention, but the remaining functional groups are a hydroxyl group and an amide group. , An imide group, a urethane group, a urea group, a sulfonyl group, or a sulfo group is considered to form an interaction such as a covalent bond or a hydrogen bond depending on the matrix resin. If the matrix resin is an epoxy resin, the hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group of (A2) reacts with the epoxy group of the matrix resin or the amine curing agent and the epoxy group. It is considered that a strong interface can be formed by the interaction with the hydroxyl group thus formed. Further, if the matrix resin is a thermoplastic resin typified by polyamide, polyester and acid-modified polyolefin, (A2) hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group It is considered that a strong interface can be formed by the interaction with amide groups, ester groups, acid anhydride groups, carboxyl groups such as terminals, hydroxyl groups, and amino groups contained in these matrix resins.

  That is, in the case of (A1), the remaining epoxy group not involved in the covalent bond with the carbon fiber is the hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group in the case of (A2). It is considered to have a function corresponding to the group.

  In the present invention, the epoxy equivalent of the (A) epoxy compound is preferably less than 360 g / mol, more preferably less than 270 g / mol, and even more preferably less than 180 g / mol. When the epoxy equivalent is less than 360 g / mol, covalent bonds are formed at a high density, and the adhesion between the carbon fiber and the matrix resin is further improved. There is no particular lower limit of the epoxy equivalent, but the adhesiveness may be saturated at less than 90 g / mol.

  In the present invention, the (A) epoxy compound is preferably an epoxy resin having 3 or more epoxy groups, and more preferably an epoxy resin having 4 or more epoxy groups. (A) When the epoxy compound is an epoxy resin having three or more epoxy groups in the molecule, even when one epoxy group forms a covalent bond with an oxygen-containing functional group on the surface of the carbon fiber, the remaining two One or more epoxy groups can form a covalent bond or a hydrogen bond with the matrix resin, and the adhesion is further improved. There is no particular upper limit on the number of epoxy groups, but if it is 10 or more, the adhesiveness may be saturated.

  In the present invention, the (A) epoxy compound is preferably an epoxy resin having 3 or more types of two or more functional groups, and more preferably an epoxy resin having 4 or more types of 2 or more functional groups. The functional group possessed by the epoxy compound is preferably selected from a hydroxyl group, an amide group, an imide group, a urethane group, a urea group, a sulfonyl group, or a sulfo group in addition to the epoxy group. (A) When the epoxy compound is an epoxy resin having three or more epoxy groups or other functional groups in the molecule, one epoxy group forms a covalent bond with an oxygen-containing functional group on the carbon fiber surface However, the remaining two or more epoxy groups or other functional groups can form a covalent bond or a hydrogen bond with the matrix resin, and the adhesion is further improved. There is no particular upper limit on the number of epoxy groups, but if it is 10 or more, the adhesiveness may be saturated.

  In the present invention, the (A) epoxy compound preferably has one or more aromatic rings in the molecule, and more preferably has two or more aromatic rings. In a fiber-reinforced composite material composed of carbon fibers and a matrix resin, a so-called interface layer in the vicinity of the carbon fibers may be affected by the carbon fibers or the sizing agent and have different characteristics from the matrix resin. (A) When the epoxy compound has one or more aromatic rings, a rigid interface layer is formed, the stress transmission ability between the carbon fiber and the matrix resin is improved, and the fiber reinforced composite material has a 0 ° tensile strength, etc. Mechanical properties are improved. There is no particular upper limit on the number of aromatic rings, but if it is 10 or more, the mechanical properties may be saturated.

  In the present invention, the (A1) epoxy compound is preferably a phenol novolac epoxy resin, a cresol novolac epoxy resin, or tetraglycidyldiaminodiphenylmethane. These epoxy resins have a large number of epoxy groups, a small epoxy equivalent, and have two or more aromatic rings. In addition to improving the adhesion between carbon fiber and matrix resin, fiber reinforced composite materials Improve mechanical properties such as 0 ° tensile strength. The bifunctional or higher functional epoxy resin is more preferably a phenol novolac type epoxy resin and a cresol novolac type epoxy resin.

  In the present invention, (A1) specific examples of the epoxy compound having two or more epoxy groups include, for example, a glycidyl ether type epoxy resin derived from a polyol, and a glycidyl amine type epoxy derived from an amine having a plurality of active hydrogens. Examples thereof include a resin, a glycidyl ester type epoxy resin derived from polycarboxylic acid, and an epoxy resin obtained by oxidizing a compound having a plurality of double bonds in the molecule.

  Examples of the glycidyl ether type epoxy resin include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetrabromobisphenol A, phenol novolac, cresol novolac, hydroquinone, resorcinol, 4,4′-dihydroxy-3,3 ′, 5. , 5'-tetramethylbiphenyl, 1,6-dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene, tris (p-hydroxyphenyl) methane, and tetrakis (p-hydroxyphenyl) ethane and epichlorohydride The glycidyl ether type epoxy resin obtained by reaction with phosphorus is mentioned. Further, as glycidyl ether type epoxy resins, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, trimethylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, polybutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4 -Cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, glycerol, diglycerol, polyglycerol, trimethylolpropane, penta Risuritoru, sorbitol, and arabitol and a glycidyl ether type epoxy resin obtained by reaction of epichlorohydrin are also exemplified. Examples of the glycidyl ether type epoxy resin include a glycidyl ether type epoxy resin having a dicyclopentadiene skeleton and a glycidyl ether type epoxy resin having a biphenyl aralkyl skeleton.

  Examples of the glycidylamine type epoxy resin include N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, 1,3-bis (aminomethyl) cyclohexane, m-xylylenediamine, m-phenylenediamine, Examples include 4,4′-diaminodiphenylmethane and 9,9-bis (4-aminophenyl) fluorene.

  Furthermore, for example, as a glycidylamine type epoxy resin, both the hydroxyl group and amino group of aminophenols of m-aminophenol, p-aminophenol, and 4-amino-3-methylphenol are reacted with epichlorohydrin. And epoxy resin obtained.

  Examples of the glycidyl ester type epoxy resin include glycidyl ester type epoxy resins obtained by reacting phthalic acid, terephthalic acid, hexahydrophthalic acid, and dimer acid with epichlorohydrin.

  Examples of the epoxy resin obtained by oxidizing a compound having a plurality of double bonds in the molecule include an epoxy resin having an epoxycyclohexane ring in the molecule. Furthermore, the epoxy resin includes epoxidized soybean oil.

  In addition to these epoxy resins, (A1) epoxy compounds used in the present invention include epoxy resins such as triglycidyl isocyanurate. Furthermore, the epoxy resin synthesize | combined from the epoxy resin mentioned above as a raw material, for example, the epoxy resin synthesize | combined by the oxazolidone ring formation reaction from bisphenol A diglycidyl ether and tolylene diisocyanate is mentioned.

  In the present invention, (A2) an epoxy compound having one or more epoxy groups and at least one functional group selected from a hydroxyl group, an amide group, an imide group, a urethane group, a urea group, a sulfonyl group, and a sulfo group Specific examples of the compound include, for example, a compound having an epoxy group and a hydroxyl group, a compound having an epoxy group and an amide group, a compound having an epoxy group and an imide group, a compound having an epoxy group and a urethane group, and a compound having an epoxy group and a urea group , A compound having an epoxy group and a sulfonyl group, and a compound having an epoxy group and a sulfo group.

  Examples of the compound having an epoxy group and a hydroxyl group include sorbitol-type polyglycidyl ether and glycerol-type polyglycidyl ether. Specifically, Denacol (registered trademark) EX-611, EX-612, EX-614, EX -614B, EX-622, EX-512, EX-521, EX-421, EX-313, EX-314 and EX-321 (manufactured by Nagase ChemteX Corporation).

  Examples of the compound having an epoxy group and an amide group include glycidyl benzamide and amide-modified epoxy resin. The amide-modified epoxy can be obtained by reacting an epoxy group of an epoxy resin having two or more epoxy groups with a carboxyl group of a dicarboxylic acid amide.

  Examples of the compound having an epoxy group and an imide group include glycidyl phthalimide. Specifically, Denacol (trademark registration) EX-731 (made by Nagase ChemteX Corporation) etc. are mentioned.

  Examples of the compound having an epoxy group and a urethane group include a urethane-modified epoxy resin. Specifically, Adeka Resin (registered trademark) EPU-78-13S, EPU-6, EPU-11, EPU-15, EPU- 16A, EPU-16N, EPU-17T-6, EPU-1348, EPU-1395 (manufactured by ADEKA Corporation) and the like. Alternatively, by reacting the terminal hydroxyl group of the polyethylene oxide monoalkyl ether with a polyvalent isocyanate equivalent to the amount of the hydroxyl group, and then reacting the isocyanate residue of the obtained reaction product with the hydroxyl group in the polyvalent epoxy resin. Can be obtained. Here, as the polyvalent isocyanate used, 2,4-tolylene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, triphenylmethane triisocyanate and biphenyl-2, Examples include 4,4′-triisocyanate.

  Examples of the compound having an epoxy group and a urea group include a urea-modified epoxy resin. The urea-modified epoxy can be obtained by reacting the epoxy group of an epoxy resin having two or more epoxy groups with the carboxyl group of the dicarboxylic acid urea.

  Examples of the compound having an epoxy group and a sulfonyl group include bisphenol S-type epoxy.

  Examples of the compound having an epoxy group and a sulfo group include glycidyl p-toluenesulfonate and glycidyl 3-nitrobenzenesulfonate.

  Hereinafter, (B1) to (B3) of the component (B) will be described in order.

  The (B1) tertiary amine compound and / or tertiary amine salt having a molecular weight of 100 g / mol or more used in the present invention is blended in an amount of 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) epoxy compound. Is required, preferably 0.5 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 2 to 8 parts by mass. When the blending amount is less than 0.1 part by mass, the formation of a covalent bond between (A) the epoxy compound and the oxygen-containing functional group on the surface of the carbon fiber is not promoted, and the adhesion between the carbon fiber and the matrix resin is poor. It will be enough. On the other hand, when the blending amount exceeds 25 parts by mass, (B1) covers the carbon fiber surface, the covalent bond formation is inhibited, and the adhesion between the carbon fiber and the matrix resin becomes insufficient.

  The tertiary amine compound and / or tertiary amine salt (B1) having a molecular weight of 100 g / mol or more used in the present invention needs to have a molecular weight of 100 g / mol or more, and the molecular weight is 100 to 400 g. It is preferably within the range of / mol, more preferably within the range of 100 to 300 g / mol, and even more preferably within the range of 100 to 200 g / mol. When the molecular weight is 100 g / mol or more, volatilization is suppressed even during the heat treatment, and a large effect of improving adhesiveness can be obtained even with a small amount. On the other hand, when the molecular weight is 400 g / mol or less, the ratio of active sites in the molecule is high, and a large adhesion improvement effect can be obtained even with a small amount.

  The tertiary amine compound used in the present invention refers to a compound having a tertiary amino group in the molecule. The tertiary amine salt used in the present invention refers to a salt obtained by neutralizing a compound having a tertiary amino group with a proton donor. Here, the proton donor means a compound having active hydrogen that can be donated as a proton to a compound having a tertiary amino group. The active hydrogen refers to a hydrogen atom that is donated as a proton to a basic compound.

  Examples of proton donors include inorganic acids, carboxylic acids, organic acids such as sulfonic acids and phenols, alcohols, mercaptans, and 1,3-dicarbonyl compounds.

  Specific examples of inorganic acids include sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, and amidosulfuric acid. Is mentioned. Of these, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid are preferably used.

  The carboxylic acids are classified into aliphatic polycarboxylic acids, aromatic polycarboxylic acids, S-containing polycarboxylic acids, aliphatic hydroxycarboxylic acids, aromatic hydroxycarboxylic acids, aliphatic monocarboxylic acids, and aromatic monocarboxylic acids, The following compounds are mentioned.

  Specific examples of the aliphatic polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, azelaic acid, sebacic acid, undencanic acid, dodecanedioic acid, tridecanedioic acid, Tetradecanedioic acid, pentadecanedioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid, hexylmalonic acid, dimethylmalonic acid, diethylmalonic acid, methylpropylmalonic acid, methylbutylmalonic acid, Ethylpropylmalonic acid, dipropylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-methyl-3- Ethyl glutaric acid, 3,3-diethyl glutaric acid, 3,3-dimethyl glutar Examples include acid, 3-methyladipic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid.

  Specific examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

  Specific examples of the S-containing polycarboxylic acid include thiodipropionic acid.

  Specific examples of the aliphatic hydroxycarboxylic acid include glycolic acid, lactic acid, tartaric acid and castor oil fatty acid.

  Specific examples of the aromatic hydroxycarboxylic acid include salicylic acid, mandelic acid, 4-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid. Can be mentioned.

  Specific examples of the aliphatic monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, octylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid, Examples include behenic acid, undecanoic acid, acrylic acid, methacrylic acid, crotonic acid, and oleic acid.

  Specific examples of the aromatic monocarboxylic acid include benzoic acid, cinnamic acid, naphthoic acid, toluic acid, ethyl benzoic acid, propyl benzoic acid, isopropyl benzoic acid, butyl benzoic acid, isobutyl benzoic acid, sec-butyl benzoic acid, Tertiary butyl benzoic acid, methoxy benzoic acid, ethoxy benzoic acid, propoxy benzoic acid, isopropoxy benzoic acid, butoxy benzoic acid, isobutoxy benzoic acid, second butoxy benzoic acid, tertiary butoxy benzoic acid, amino benzoic acid, N-methyl Aminobenzoic acid, N-ethylaminobenzoic acid, N-propylaminobenzoic acid, N-isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid, N-secondary butylaminobenzoic acid, N- Tertiary butylaminobenzoic acid, N, N-dimethylaminobenzoic acid, N, N-die Arylamino benzoic acid, and nitrobenzoic acid and fluorosilicone benzoate.

  Of the above carboxylic acids, aromatic polycarboxylic acids, aliphatic monocarboxylic acids, and aromatic carboxylic acids are preferably used. Specifically, phthalic acid, formic acid, and octylic acid are preferably used.

  The sulfonic acid can be classified into aliphatic sulfonic acid and aromatic sulfonic acid, and examples thereof include the following compounds.

  Among the aliphatic sulfonic acids, specific examples of monovalent saturated aliphatic sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropylsulfonic acid, butanesulfonic acid, isobutylsulfonic acid, tert-butylsulfonic acid. , Pentanesulfonic acid, isopentylsulfonic acid, hexanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, undecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, tetradecanesulfonic acid, n-octylsulfonic acid, dodecylsulfonic acid and cetyl A sulfonic acid etc. are mentioned.

  The aliphatic sulfonic acid may be an unsaturated aliphatic sulfonic acid, and specific examples of the unsaturated aliphatic sulfonic acid include ethylene sulfonic acid and 1-propene-1-sulfonic acid.

  Among aliphatic sulfonic acids, specific examples of divalent or higher aliphatic sulfonic acids include methionic acid, 1,1-ethanedisulfonic acid, 1,2-ethanedisulfonic acid, 1,1-propanedisulfonic acid, 1, Examples thereof include 3-propanedisulfonic acid and polyvinyl sulfonic acid.

  The aliphatic sulfonic acid may be an oxyaliphatic sulfonic acid having a hydroxyl group, and specific examples of the oxyaliphatic sulfonic acid include isethionic acid and 3-oxy-propanesulfonic acid.

  The aliphatic sulfonic acid may be a sulfoaliphatic carboxylic acid, and specific examples of the sulfoaliphatic carboxylic acid include sulfoacetic acid and sulfosuccinic acid.

  The aliphatic sulfonic acid may be a sulfoaliphatic carboxylic acid ester, and specific examples of the sulfoaliphatic carboxylic acid ester include di (2-ethylhexyl) sulfosuccinic acid.

  The aliphatic sulfonic acid may be fluorosulfonic acid, and specific examples of the fluorosulfonic acid include trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluoroisopropylsulfonic acid, perfluorobutanesulfonic acid. Acid, perfluoroisobutylsulfonic acid, perfluoro-tert-butylsulfonic acid, perfluoropentanesulfonic acid, perfluoroisopentylsulfonic acid, perfluorohexanesulfonic acid, perfluorononanesulfonic acid, perfluorodecanesulfonic acid, perfluoro Undecanesulfonic acid, perfluorododecanesulfonic acid, perfluorotridecanesulfonic acid, perfluorotetradecanesulfonic acid, perfluoro-n-octylsulfonic acid, perfluoro Dodecyl sulfonic acid and perfluorosulfonic cetyl sulfonic acid.

  Among aromatic sulfonic acids, specific examples of monovalent aromatic sulfonic acids include benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, o-xylene-4-sulfonic acid. M-xylene-4-sulfonic acid, 4-ethylbenzenesulfonic acid, 4-propylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-dodecylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, 2-methyl-5- Examples include isopropylbenzenesulfonic acid, 2-naphthalenesulfonic acid, butylnaphthalenesulfonic acid, t-butylnaphthalenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, benzylsulfonic acid, and phenylethanesulfonic acid.

  Among aromatic sulfonic acids, specific examples of di- or higher valent aromatic sulfonic acids include m-benzenedisulfonic acid, 1,4-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid. 2,6-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 1,3,6-naphthalenetrisulfonic acid, sulfonated polystyrene, and the like.

  The aromatic sulfonic acid may be an oxyaromatic sulfonic acid. Specific examples of the oxyaromatic sulfonic acid include phenol-2-sulfonic acid, phenol-3-sulfonic acid, phenol-4-sulfonic acid, anisole- o-sulfonic acid, anisole-m-sulfonic acid, phenetol-o-sulfonic acid, phenetol-m-sulfonic acid, phenol-2,4-disulfonic acid, phenol-2,4,6-trisulfonic acid, anisole-2 , 4-disulfonic acid, phenetole-2,5-disulfonic acid, 2-oxytoluene-4-sulfonic acid, pyrocatechin-4-sulfonic acid, veratrol-4-sulfonic acid, resorcin-4-sulfonic acid, 2-oxy -1-methoxybenzene-4-sulfonic acid, 1,2-dioxybenzene-3,5-disulfonic acid, reso Shin-4,6-disulfonic acid, hydroquinone sulfonic acid, hydroquinone-2,5-disulfonic acid and 1,2,3-oxybenzene-4-sulfonic acid and the like.

  The aromatic sulfonic acid may be a sulfoaromatic carboxylic acid. Specific examples of the sulfoaromatic carboxylic acid include o-sulfobenzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, and 2,4-disulfo. Benzoic acid, 3-sulfophthalic acid, 3,5-disulfophthalic acid, 4-sulfoisophthalic acid, 2-sulfoterephthalic acid, 2-methyl-4-sulfobenzoic acid, 2-methyl-3,5-disulfobenzoic acid, 4 -Propyl-3-sulfobenzoic acid, 2,4,6-trimethyl-3-sulfobenzoic acid, 2-methyl-5-sulfoterephthalic acid, 5-sulfosalicylic acid and 3-oxy-4-sulfobenzoic acid It is done.

  The aromatic sulfonic acid may be a thioaromatic sulfonic acid. Specific examples of the thioaromatic sulfonic acid include thiophenol sulfonic acid, thioanisole-4-sulfonic acid, and thiophenetol-4-sulfonic acid. Can be mentioned.

  Among the aromatic sulfonic acids, specific examples having other functional groups include benzaldehyde-o-sulfonic acid, benzaldehyde-2,4-disulfonic acid, acetophenone-o-sulfonic acid, acetophenone-2,4-disulfonic acid, benzophenone. -O-sulfonic acid, benzophenone-3,3'-disulfonic acid, 4-aminophenol-3-sulfonic acid, anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1,5-disulfonic acid, anthraquinone Examples include -1,8-disulfonic acid, anthraquinone-2,6-disulfonic acid, and 2-methylanthraquinone-1-sulfonic acid.

  Among the above sulfonic acids, monovalent aromatic sulfonic acid is preferably used, and specifically, benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid and m-toluenesulfonic acid are preferably used.

  Specific examples of phenols containing one active hydrogen per molecule include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, and tert-butylphenol. Cyclohexylphenol, dimethylphenol, methyl-tert-butylphenol, di-tert-butylphenol, chlorophenol, bromophenol, nitrophenol, methoxyphenol, and methyl salicylate.

  Specific examples of phenols containing two active hydrogens in one molecule include hydroquinone, resorcinol, catechol, methylhydroquinone, tert-butylhydroquinone, benzylhydroquinone, phenylhydroquinone, dimethylhydroquinone, methyl-tert-butylhydroquinone, di- -Tert-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, methylresorcinol, tert-butylresorcinol, benzylresorcinol, phenylresorcinol, dimethylresorcinol, methyl-tert-butylresorcinol, di-tert-butylresorcinol, trimethylresorcinol, methoxyresorcinol, methyl Catechol, tert-butylcatechol, benzylcatechol, phenylcatechol , Dimethylcatechol, methyl-tert-butylcatechol, di-tert-butylcatechol, trimethylcatechol, methoxycatechol, biphenol, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl, 4 Biphenols such as 4,4′-dihydroxy-3,3 ′, 5,5′-tetra-tert-butylbiphenyl, bisphenol A, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbisphenol A, 4,4′-dihydroxy-3,3 ′, 5,5′-tetra-tert-butylbisphenol A, bisphenol F, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbisphenol F, 4,4′-dihydroxy-3,3 ′, 5,5′-tetra-tert-butylbispheno F, bisphenol AD, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbisphenol AD, 4,4′-dihydroxy-3,3 ′, 5,5′-tetra-tert-butyl Bisphenol AD is mentioned.

Further, as phenols containing two active hydrogens in one molecule, the following structural formula (XIII),

Structural formula (XIV),

Structural formula (XV),

Structural formula (XVI),

Structural formula (XVII),

Structural formula (XVIII),

Or structural formula (XIX)

Bisphenols represented by terpene phenol, structural formula (XX)

で示される化合物等が挙げられる。１分子中に３個の活性水素を含むフェノール類の具体例としては、トリヒドロキシベンゼンおよびトリス（ｐ−ヒドロキシフェニル）メタン等が挙げられる。１分子中に４個の活性水素を含むフェノール類の具体例として、テトラキス（ｐ−ヒドロキシフェニル）エタン等が挙げられる。また、それ以外の具体例として、フェノール、アルキルフェノールおよびハロゲン化フェノール等とホルムアルデヒドとの反応により得られるフェノールノボラックが挙げられる。 Structural formula (XXI)

And the like. Specific examples of phenols containing three active hydrogens in one molecule include trihydroxybenzene and tris (p-hydroxyphenyl) methane. Specific examples of phenols containing 4 active hydrogens in one molecule include tetrakis (p-hydroxyphenyl) ethane. Other specific examples include phenol novolac obtained by reaction of phenol, alkylphenol, halogenated phenol, and the like with formaldehyde.

  Of the above phenols, phenol and phenol novolac are preferably used.

  Examples of alcohols include those containing two hydroxyl groups in one molecule, such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,1-dimethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4- Pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dodecahydrobisphenol A, structural formula (XXII)

で表されるビスフェノールＡのエチレンオキサイド付加物、構造式（ＸＸＩＩＩ）

An ethylene oxide adduct of bisphenol A represented by the structural formula (XXIII)

で表されるビスフェノールＡのプロピレンオキサイド付加物、構造式（ＸＸＩＶ）

A propylene oxide adduct of bisphenol A represented by the structural formula (XXIV)

で表されるドデカヒドロビスフェノールＡのエチレンオキサイド付加物、構造式（ＸＸＶ）

An ethylene oxide adduct of dodecahydrobisphenol A represented by the structural formula (XXV)

で表されるドデカヒドロビスフェノールＡのプロピレンオキサイド付加物、グリセリン、トリメチロールエタンおよびトリメチロールプロパン等が挙げられる。また、１分子中に４個の水酸基を含むアルコール類の具体例としては、ペンタエリスリトール等が挙げられる。

And propylene oxide adducts of dodecahydrobisphenol A, glycerin, trimethylolethane, and trimethylolpropane. In addition, specific examples of alcohols containing four hydroxyl groups in one molecule include pentaerythritol.

  Examples of mercaptans include mercaptans containing one active hydrogen in one molecule. For example, methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-methyl -1-propanethiol, 2-butanethiol, 2-methyl-2-propanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, benzyl mercaptan, Examples include benzene thiol, toluene thiol, chlorobenzene thiol, bromobenzene thiol, nitrobenzene thiol and methoxybenzene thiol.

  Specific examples of mercaptans containing two active hydrogens in one molecule include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 2,2 '-Oxydiethanethiol, 1,6-hexanedithiol, 1,2-cyclohexanedithiol, 1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol and 1 , 4-benzenethiol and the like.

  Examples of 1,3-dicarbonyl compounds include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3,5-heptanedione, 4 , 6-nonanedione, 2,6-dimethyl-3,5-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, 1,3- Diphenyl-1,3-propanedione, 1,3-cyclopentanedione, 2-methyl-1,3-cyclopentanedione, 2-ethyl-1,3-cyclopentanedione, 1,3-cyclohexanedione, 2- Examples include methyl-1,3-cyclohexanedione, 2-ethyl-cyclohexanedione, 1,3-indandione, ethyl acetoacetate and diethyl malonate.

  The tertiary amine compound and / or tertiary amine salt (B1) having a molecular weight of 100 g / mol or more used in the present invention has the following general formula (III)

(In the formula, R ₈ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group represents —O—, —O, R ₉ may be any one of an alkylene group having 2 to 22 carbon atoms, an alkenylene group having 2 to 22 carbon atoms, or an alkynylene group having 2 to 22 carbon atoms, which may be substituted with —CO— or —CO—O—. R ₁₀ represents hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is —O— , -O-CO- or -CO-O-, or R ₈ and R ₁₀ may combine to form an alkylene group having 2 to 11 carbon atoms), Formula (IV)

(Wherein R _{11 to} R ₁₄ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- O-, -O-CO- or -CO-O- may be substituted), or the following general formula (V)

(Wherein R _{15 to} R ₂₀ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- May be substituted by O-, -O-CO- or -CO-O-, R ₂₁ represents a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group has a hydroxyl group; And the CH ₂ group in the hydrocarbon group may be substituted by —O—, —O—CO— or —CO—O—), the general formula (VI)

（式中、Ｒ_２２〜Ｒ_２４は、それぞれ炭素数１〜８の炭化水素基を表し、該炭化水素基は水酸基を有していてもよい）、一般式（ＶＩＩ）

(Wherein R _{22 to} R ₂₄ each represent a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may have a hydroxyl group), general formula (VII)

（式中、Ｒ_２５は、炭素数１〜８の炭化水素基を表し、該炭化水素基は水酸基を有していてもよい）、一般式（ＶＩＩＩ）

(Wherein R ₂₅ represents a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may have a hydroxyl group), general formula (VIII)

（式中、Ｒ_２６〜Ｒ_２８は、それぞれ炭素数１〜２２の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。さらに、Ｒ_２６〜Ｒ_２８のいずれかに、次の一般式（ＩＸ）または（Ｘ）で示される１以上の分岐構造を有し、かつ少なくとも１以上の水酸基を含む）であることを特徴とする。

(In the formula, each of R _{26 to} R ₂₈ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O—, —O—CO— or —CO—O—, and any one of R _{26 to} R _{28 represented} by the following general formula (IX) or (X) And having at least one hydroxyl group).

（式中、Ｒ_２９、Ｒ_３０は、それぞれ炭素数１〜２０の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。但し、Ｒ_２９とＲ_３０の炭素数の合算値が２１以下である。）

(Wherein R ₂₉ and R ₃₀ each represent a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O-, -O-CO- or -CO-O-, provided that the total number of carbon atoms of R ₂₉ and R ₃₀ is 21 or less.)

（式中、Ｒ_３１〜Ｒ_３３は、それぞれ水酸基または炭素数１〜１９の炭化水素基を表し、該炭化水素基は水酸基を有していてもよく、該炭化水素基中のＣＨ_２基は、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−により置換されていてもよい。但し、Ｒ_３１とＲ_３２とＲ_３３の炭素数の合算値が２１以下である。）

(Wherein R _{31 to} R ₃₃ each represent a hydroxyl group or a hydrocarbon group having 1 to 19 carbon atoms, the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is , -O-, -O-CO- or -CO-O-, provided that the total number of carbon atoms of R ₃₁ , R ₃₂ and R ₃₃ is 21 or less.)

In the general formulas (III) to (V) and (VIII) of the present invention, R ₈ , R _{11 to} R ₂₀ , and R _{26 to} R ₂₈ each represent a hydrocarbon group having 1 to 22 carbon atoms, The hydrogen group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group may be substituted with —O—, —O—CO— or —CO—O—. By setting the number of carbon atoms to be between 1 and 22, the steric hindrance of the molecular structure is moderately small, the reaction promoting effect is increased, and the adhesion is improved. More preferably, it exists in the range of 1-14, More preferably, it exists in the range of 1-8. On the other hand, when the number of carbon atoms exceeds 22, the steric hindrance of the molecular structure may be somewhat large and the reaction promoting effect may be reduced.

R _{21 in the} general formula (V) of the present invention is a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and CH in the hydrocarbon group _Two groups may be substituted by -O-, -O-CO- or -CO-O-. By setting the number of carbon atoms to be between 1 and 22, the steric hindrance of the molecular structure is moderately small, the reaction promoting effect is increased, and the adhesion is improved. More preferably, it exists in the range of 1-14, More preferably, it exists in the range of 1-8. On the other hand, when the number of carbon atoms exceeds 22, the steric hindrance of the molecular structure may be somewhat large and the reaction promoting effect may be reduced.

R _{9 in the} general formula (III) of the present invention represents any of an alkylene group having 2 to 22 carbon atoms, an alkenylene group having 2 to 22 carbon atoms, or an alkynylene group having 2 to 22 carbon atoms. By setting the number of carbon atoms to between 2 and 22, the steric hindrance of the molecular structure is moderately small, the reaction promoting effect is increased, and the adhesion is improved. Preferably it exists in the range of 3-22, More preferably, it exists in the range of 3-14, More preferably, it exists in the range of 3-8. On the other hand, when the number of carbon atoms exceeds 22, the steric hindrance of the molecular structure may be somewhat large and the reaction promoting effect may be reduced.

R _{10 in} the above general formula (III) of the present invention is hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and CH ₂ in the hydrocarbon group. The group may be substituted by -O-, -O-CO- or -CO-O-. By setting the number of carbon atoms to be between 1 and 22, the steric hindrance of the molecular structure is moderately small, the reaction promoting effect is increased, and the adhesion is improved. More preferably, it exists in the range of 1-14, More preferably, it exists in the range of 1-8. On the other hand, when the number of carbon atoms exceeds 22, the steric hindrance of the molecular structure may be somewhat large and the reaction promoting effect may be reduced.

  Here, a C1-C22 hydrocarbon group is a group which consists only of a carbon atom and a hydrogen atom, and any of a saturated hydrocarbon group and an unsaturated hydrocarbon group may be included, even if it contains a ring structure. Also good. As the hydrocarbon group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, oleyl group, A docosyl group, a benzyl group, a phenyl group, etc. are mentioned.

Further, the hydrocarbon group having 1 to 22 carbon atoms may be one in which a CH ₂ group in the hydrocarbon group is substituted with —O—. Examples of the case where the CH ₂ group in the hydrocarbon group having 1 to 22 carbon atoms is substituted by —O— include, for example, a straight chain, such as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxy Polyether groups such as methyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxyethoxymethyl group, methoxyethoxyethyl group, polyethylene glycol group and polypropylene glycol group Can be mentioned. Examples of cyclic compounds include ethylene oxide, tetrahydrofuran, oxepane, and 1,3-dioxolane.

Further, the hydrocarbon group having 1 to 22 carbon atoms may be one in which a CH ₂ group in the hydrocarbon group is substituted by —O—CO— or —CO—O—. Examples of the case where the CH ₂ group in the hydrocarbon group having 1 to 22 carbon atoms is substituted by —O—CO— or —CO—O— include, for example, an acetoxymethyl group, an acetoxyethyl group, an acetoxypropyl group, Examples include an acetoxybutyl group, a methacryloyloxyethyl group, a benzoyloxyethyl group, a methoxycarbonyl group, and an ethoxycarbonyl group.

  The hydrocarbon group having 1 to 22 carbon atoms may have a hydroxyl group, and examples of the case where the hydrocarbon group having 1 to 22 carbon atoms has a hydroxyl group include, for example, a hydroxymethyl group and a hydroxyethyl group. , Hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxycyclohexyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyoctadecyl group, hydroxyoleyl group And a hydroxydocosyl group and the like.

  In the present invention, the tertiary amine compound (B1) preferably has an acid dissociation constant pKa of the conjugate acid of 9 or more, more preferably 11 or more. When the acid dissociation constant pKa is 9 or more, the component (B1) can easily extract hydrogen ions from oxygen-containing functional groups such as a carboxyl group and a hydroxyl group of the carbon fiber, so the functional group on the surface of the carbon fiber and the epoxy of the component (A) The reaction with the group is promoted, and the effect of improving adhesion is increased. Specific examples of such tertiary amine compounds include DBU (pKa12.5), DBN (pKa12.7), 1,8-bis (dimethylamino) naphthalene (pKa12.3), and the like.

  In the present invention, the tertiary amine compound and / or tertiary amine salt (B1) preferably has a boiling point of 160 ° C. or higher, more preferably in the range of 160 to 350 ° C., and still more preferably 160 to 260. Within the range of ° C. When the boiling point is less than 160 ° C., the volatilization becomes intense in the step of heat treatment for 30 to 600 seconds in the temperature range of 160 to 260 ° C., and the reaction promoting effect may be reduced.

  The tertiary amine compound (B1) and / or tertiary amine salt used in the present invention includes aliphatic tertiary amines, aromatic-containing aliphatic tertiary amines, aromatic tertiary amines and heterocyclic rings. Formula tertiary amines and their salts. Next, a specific example is given.

  Specific examples of the aliphatic tertiary amines include, for example, triethylamine, tripropylamine, triisopropylamine, tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, dimethylpropylamine, dimethylbutylamine, Dimethylpentylamine, dimethylhexylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine, dimethyloleylamine, dimethyldocosylamine, diethylpropylamine, Diethylbutylamine, diethylpentylamine, diethylhexylamine, diethylcyclohexylamine, diethyl Octylamine, diethyldecylamine, diethyldodecylamine, diethyltetradecylamine, diethylhexadecylamine, diethyloctadecylamine, diethyloleylamine, diethyldocosylamine, dipropylmethylamine, diisopropylethylamine, dipropylethylamine, dipropylbutylamine, dibutyl Methylamine, dibutylethylamine, dibutylpropylamine, dihexylmethylamine, dihexylmethylamine, dihexylpropylamine, dihexylbutylamine, dicyclohexylmethylamine, dicyclohexylethylamine, dicyclohexylpropylamine, dicyclohexylbutylamine, dioctylmethylamine, dioctylethylamine, dioctylpropylamine, Didecyl Tylamine, didecylethylamine, didecylpropylamine, didecylbutylamine, didodecylmethylamine, didodecylethylamine, didodecylpropylamine, didodecylbutylamine, ditetradecylmethylamine, ditetradecylethylamine, ditetradecylpropylamine, Ditetradecylbutylamine, dihexadecylmethylamine, dihexadecylethylamine, dihexadecylpropylamine, dihexadecylbutylamine, trimethanolamine, triethanolamine, triisopropanolamine, tributanolamine, trihexanolamine, diethylmethanolamine , Dipropylmethanolamine, diisopropylmethanolamine, dibutylmethanolamine, diisobutylmethanolamine, Ditertiarybutylmethanolamine, di (2-ethylhexyl) methanolamine, dimethylethanolamine, diethylethanolamine, dipropylethanolamine, diisopropylethanolamine, dibutylethanolamine, diisobutylethanolamine, ditertiarybutylethanolamine, di (2- Ethylhexyl) ethanolamine, dimethylpropanolamine, diethylpropanolamine, dipropylpropanolamine, diisopropylpropanolamine, dibutylpropanolamine, diisobutylpropanolamine, ditertiarybutylpropanolamine, di (2-ethylhexyl) propanolamine, methyldimethanolamine, Ethyldimethanolamine, propyldimethanolamine, Sopropyldimethanolamine, butyldimethanolamine, isobutyldimethanolamine, tertiarybutyldimethanolamine, (2-ethylhexyl) dimethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, isopropyldiethanolamine, butyldiethanolamine, isobutyldiethanolamine, Tertiary butyl diethanolamine, (2-ethylhexyl) diethanolamine, dimethylaminoethoxyethanol, etc. are mentioned.

  Aliphatic tertiary amines may be compounds having two or more tertiary amino groups in the molecule, and compounds having two or more tertiary amino groups in the molecule include N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetraethyl-1,3-propanediamine, N, N-diethyl-N ′, N′-dimethyl-1,3- Examples include propanediamine, tetramethyl-1,6-hexamethylenediamine, pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, and trimethylaminoethylethanolamine.

  Specific examples of aromatic-containing aliphatic tertiary amines include, for example, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dipropylbenzylamine, N, N′-dibutylbenzylamine N, N-dihexylbenzylamine, N, N-dicyclohexylbenzylamine, N, N-dioctylbenzylamine, N, N-didodecylbenzylamine, N, N-dioleylbenzylamine, N, N-dibenzylmethyl Amine, N, N-dibenzylethylamine, N, N-dibenzylpropylamine, N, N-dibenzylbutylamine, N, N-dibenzylhexylamine, N, N-dibenzylcyclohexylamine, N, N-di Benzyloctylamine, N, N-dibenzyldodecylamine, N, N-dibenzyloleylamine Tribenzylamine, N, N-methylethylbenzylamine, N, N-methylpropylbenzylamine, N, N-methylbutylbenzylamine, N, N-methylhexylbenzylamine, N, N-methylcyclohexylbenzylamine, N , N-methyloctylbenzylamine, N, N-methyldodecylbenzylamine, N, N-methyloleylbenzylamine, N, N-methylhexadecylbenzylamine, N, N-methyloctadecylbenzylamine, 2- (dimethylamino) Methyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (diethylaminomethyl) phenol, 2,4,6-tris (dipropylaminomethyl) phenol, 2,4, 6-Tris (dibutylaminomethyl) pheno , 2,4,6-tris (dipentylamino methyl) phenol, and 2,4,6-tris (dihexyl aminomethyl) phenol and the like.

  Specific examples of aromatic tertiary amines include, for example, triphenylamine, tri (methylphenyl) amine, tri (ethylphenyl) amine, tri (propylphenyl) amine, tri (butylphenyl) amine, tri (phenoxyphenyl) ) Amine, tri (benzylphenyl) amine, diphenylmethylamine, diphenylethylamine, diphenylpropylamine, diphenylbutylamine, diphenylhexylamine, diphenylcyclohexylamine, N, N-dimethylaniline, N, N-diethylaniline, N, N- Dipropylaniline, N, N-dibutylaniline, N, N-dihexylaniline, N, N-dicyclohexylaniline, (methylphenyl) dimethylamine, (ethylphenyl) dimethylamine, (propylphenyl) dimethylamine, (butylphenyl) Nyl) dimethylamine, bis (methylphenyl) methylamine, bis (ethylphenyl) methylamine, bis (propylphenyl) methylamine, bis (butylphenyl) methylamine, N, N-di (hydroxyethyl) aniline, N, Examples include N-di (hydroxypropyl) aniline, N, N-di (hydroxybutyl) aniline, and diisopropanol-p-toluidine.

  Specific examples of the heterocyclic tertiary amines include, for example, pyridine compounds such as picoline, isoquinoline and quinoline, imidazole compounds, pyrazole compounds, morpholine compounds, piperazine compounds, piperidine compounds, pyrrolidine compounds, Examples include cycloamidine compounds, proton sponge derivatives, and hindered amine compounds.

  Examples of the pyridine compound include N, N-dimethyl-4-aminopyridine, bipyridine, and 2,6-lutidine. Examples of imidazole compounds include 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 1-cyanoethyl-2. -Undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-phenylimidazole, 1- (2-hydroxyethyl) imidazole 1-benzyl-2-formylimidazole, 1-benzyl-imidazole, 1-allylimidazole and the like.

  Examples of pyrazole compounds include pyrazole and 1,4-dimethylpyrazole. Examples of the morpholine compound include 4- (2-hydroxyethyl) morpholine, N-ethylmorpholine, N-methylmorpholine, and 2,2'-dimorpholine diethyl ether. Examples of piperazine compounds include 1- (2-hydroxyethyl) piperazine and N, N-dimethylpiperazine. Examples of piperidine compounds include N- (2-hydroxyethyl) piperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-hexylpiperidine, N-cyclohexylpiperidine and N-octylpiperidine. Examples of the pyrrolidine compound include N-butylpyrrolidine and N-octylpyrrolidine. Examples of the cycloamidine compounds include 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5-diazabicyclo [4,3,0] -5-nonene (DBN), 1,4. -Diazabicyclo [2.2.2] octane and 5,6-dibutylamino-1,8-diaza-bicyclo [5,4,0] undecene-7 (DBA). Examples of other heterocyclic amines include hexamethylenetetramine, hexaethylenetetramine, and hexapropyltetramine.

  Specific examples of the DBU salt include DBU phenol salt (U-CAT SA1, manufactured by San Apro Corporation), DBU octylate (U-CAT SA102, manufactured by San Apro Corporation), DBU p-toluene. Sulfonate (U-CAT SA506, manufactured by San Apro Co., Ltd.), DBU formate (U-CAT SA603, manufactured by San Apro Co., Ltd.), DBU orthophthalate (U-CAT SA810), and DBU phenol novolac resin salt (U-CAT SA810, SA831, SA841, SA851, 881, manufactured by San Apro Corporation) and the like.

  Specific examples of the proton sponge derivative include 1,8-bis (dimethylamino) naphthalene, 1,8-bis (diethylamino) naphthalene, 1,8-bis (dipropylamino) naphthalene, 1,8- Bis (dibutylamino) naphthalene, 1,8-bis (dipentylamino) naphthalene, 1,8-bis (dihexylamino) naphthalene, 1-dimethylamino-8-methylamino-quinolidine, 1-dimethylamino-7-methyl- 8-methylamino-quinolidine, 1-dimethylamino-7-methyl-8-methylamino-isoquinoline, 7-methyl-1,8-methylamino-2,7-naphthyridine, and 2,7-dimethyl-1,8 -Methylamino-2,7-naphthyridine and the like.

  Examples of the hindered amine compound include tetrakis butane-1,2,3,4-tetracarboxylate (1,2,2,6,6-pentamethyl-4-piperidinyl) (for example, LA-52 (manufactured by ADEKA)). ), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (for example, LA-72 (manufactured by ADEKA), TINUVIN765 (manufactured by BASF)), carbonic acid = bis (2,2, 6,6-tetramethyl-1-undecyloxypiperidin-4-yl) (for example, LA-81 (manufactured by ADEKA)), methacrylic acid-1,2,2,6,6-pentamethyl-4-piperidyl ( For example, LA-82 (manufactured by ADEKA)), malonic acid-2-((4-methoxyphenyl) methylene), 1,3-bis (1,2,2,6,6-pentamethyl-4- Peridinyl) ester, Chimassorb 119, 2-dodecyl-N- (1,2,2,6,6-pentamethyl-4-piperidinyl) succin-imide, 1,2,3,4-butanetetracarboxylic acid-1-hexadecyl- 2,3,4-tris (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid-1,2,3-tris (1,2, 2,6,6-pentamethyl-4-piperidinyl) -4-tridecyl, decanedioic acid-1-methyl-10- (1,2,2,6,6-pentamethyl-4-piperidinyl), 4- (ethenyloxy) -1,2,2,6,6-pentamethylpiperidine, 2-((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) -2-butylpropanedioic acid bis 1,2,2,6,6-pentamethyl-4-piperidinyl), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, LA -63P (made by ADEKA), LA-68 (made by ADEKA), TINUVIN622LD (made by BASF), TINUVIN144 (made by BASF), etc. are mentioned.

  These tertiary amine compounds and tertiary amine salts may be used alone or in combination of two or more.

The number of carbon atoms of at least one of R _{26 to} R _{28 in} the general formula (VIII) of the present invention is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. When at least one carbon number of R _{11 to} R ₁₃ is 2 or more, a side reaction in which a tertiary amine compound and / or a tertiary amine salt works as an initiator, for example, homopolymerization of an epoxy resin is suppressed, Adhesion is further improved. Moreover, it is preferable that the compound shown by the said general formula (VIII) of this invention has at least 1 or more hydroxyl group. By having one or more hydroxyl groups, the interaction with the functional group on the surface of the carbon fiber is enhanced, and the proton of the functional group on the surface of the carbon fiber can be efficiently extracted to increase the reactivity with the epoxy group.

  In the present invention, the compound represented by the general formula (III) is N-benzylimidazole, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) and a salt thereof, or 1,5 -Diazabicyclo [4,3,0] -5-nonene (DBN) and salts thereof are preferred, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) and salts thereof, or 1,5 -Diazabicyclo [4,3,0] -5-nonene (DBN) and its salts are preferred.

  In the present invention, the compound represented by the general formula (IV) is preferably 1,8-bis (dimethylamino) naphthalene.

  In the present invention, the compound represented by the general formula (V) is preferably 2,4,6-tris (dimethylaminomethyl) phenol.

In the present invention, the compound represented by the general formula (VI) is preferably 2,6-lutidine or 4-pyridinemethanol.
In the present invention, the compound represented by the general formula (VII) is preferably N-ethylmorpholine.

  In the present invention, the compound represented by the general formula (VIII) is tributylamine or N, N-dimethylbenzylamine, diisopropylethylamine, triisopropylamine, dibutylethanolamine, diethylethanolamine, triisopropanolamine, triethanolamine. N, N-diisopropylethylamine is preferred.

Moreover, it is preferable that the compound shown by the said general formula (VIII) of this invention has at least 1 or more hydroxyl group. By having one or more hydroxyl groups, the interaction with the functional group on the surface of the carbon fiber is enhanced, and the proton of the functional group on the surface of the carbon fiber can be efficiently extracted to increase the reactivity with the epoxy group. In addition, at least two, preferably three of R _{26 to} R _{28 in} the general formula (VIII) of the present invention include a branched structure represented by the general formula (IX) or the general formula (X). preferable. By having a branched structure, steric hindrance is enhanced, the reaction between epoxy rings can be suppressed, and the effect of promoting the reaction between the carbon fiber surface functional group and the epoxy can be enhanced. Furthermore, it is preferable that at least two, preferably three, of R _{26 to} R _{28 in} the general formula (VIII) of the present invention have a hydroxyl group. By having a hydroxyl group, the interaction with the functional group on the surface of the carbon fiber is enhanced, the proton of the functional group on the surface of the carbon fiber can be efficiently extracted, and the reactivity with the epoxy can be enhanced.

  Among these tertiary amine compounds and tertiary amine salts, triisopropylamine and dibutylethanol are preferred because they have a high effect of promoting the reaction between the functional group on the surface of the carbon fiber and the epoxy resin and can suppress the reaction between the epoxy rings. Amine, diethylethanolamine, triisopropanolamine, diisopropylethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2,6-lutidine, DBU, DBU salt, DBN, DBN salt and 1,8-bis (dimethyl) Amino) naphthalene is preferably used.

  Next, (B2) will be described.

  (B2) The quaternary ammonium salt having a cation moiety represented by any one of the above general formulas (I) and (II) used in the present invention has a ratio of 0. It is necessary to mix 1 to 25 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass. When the blending amount is less than 0.1 part by mass, the formation of a covalent bond between (A) the epoxy compound and the oxygen-containing functional group on the surface of the carbon fiber is not promoted, and the adhesion between the carbon fiber and the matrix resin is poor. It will be enough. On the other hand, if the blending amount exceeds 25 parts by mass, (B2) covers the carbon fiber surface and the covalent bond formation is inhibited, and the adhesion between the carbon fiber and the matrix resin becomes insufficient.

(B2) used in the present invention The mechanism by which the covalent bond formation is promoted by the incorporation of the quaternary ammonium salt having a cation moiety represented by either the above general formula (I) or (II) is not clear. Such an effect can be obtained only with a quaternary ammonium salt having a specific structure. Therefore, R _{1 to} R ₅ in the above general formula (I) or (II) must each be a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group. In addition, the CH ₂ group in the hydrocarbon group may be substituted by —O—, —O—CO— or —CO—O—. When the carbon number is 23 or more, the reason is not clear, but the adhesiveness is insufficient. Here, a C1-C22 hydrocarbon group is a group which consists only of a carbon atom and a hydrogen atom, and any of a saturated hydrocarbon group and an unsaturated hydrocarbon group may be included, even if it contains a ring structure. Also good. Examples of the hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, oleyl group, A docosyl group, a benzyl group, a phenyl group, etc. are mentioned.

Examples of the case where the CH ₂ group in the hydrocarbon group having 1 to 22 carbon atoms is substituted by —O— include, for example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl And polyether groups such as methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxyethoxymethyl group, methoxyethoxyethyl group, polyethylene glycol group and polypropylene glycol group.

Examples of the case where the CH ₂ group in the hydrocarbon group having 1 to 22 carbon atoms is substituted by —O—CO— or —CO—O— include hydrocarbons having 1 to 22 carbon atoms and ester structures. Examples of the group to be included include an acetoxymethyl group, an acetoxyethyl group, an acetoxypropyl group, an acetoxybutyl group, a methacryloyloxyethyl group, a benzoyloxyethyl group, a methoxycarbonyl group, and an ethoxycarbonyl group.

  Examples of the case where the hydrocarbon group having 1 to 22 carbon atoms has a hydroxyl group include, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, and a hydroxycyclohexyl group. , Hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyoctadecyl group, hydroxyoleyl group, hydroxydocosyl group and the like.

Especially, it is preferable that the carbon number of R < ₁ > -R < ₅ > of (B2) quaternary ammonium salt which has a cation part exists in the range of 1-14, More preferably, it exists in the range of 1-8. When the carbon number is less than 14, when the quaternary ammonium salt acts as a reaction accelerator, the steric hindrance is moderately small and the reaction promoting effect is enhanced, and the adhesion is further improved.

In the present invention, the number of carbon atoms of R ₃ and R _{4 in} the quaternary ammonium salt having a cation moiety (B2) represented by the general formula (I) is preferably 2 or more, more preferably 3 or more. More preferably, it is 4 or more. When the carbon number is 2 or more, homopolymerization of the epoxy resin due to the quaternary ammonium salt acting as an initiator is suppressed, and the adhesiveness is further improved.

In the present invention, R ₆ and R ₇ of the quaternary ammonium salt having a cation moiety (B2) represented by the general formula (II) are each hydrogen or a hydrocarbon group having 1 to 8 carbon atoms. And the CH ₂ group in the hydrocarbon group may be substituted by —O—, —O—CO— or —CO—O—. When hydrogen or the number of carbon atoms is less than 8, the ratio of active sites in the molecule is high, and a large adhesion improvement effect can be obtained even with a small amount.

  In the present invention, (B2) the molecular weight of the cation moiety of the quaternary ammonium salt having a cation moiety is preferably in the range of 100 to 400 g / mol, more preferably in the range of 100 to 300 g / mol. More preferably, it is in the range of 100 to 200 g / mol. When the molecular weight of the cation moiety is 100 g / mol or more, volatilization is suppressed even during the heat treatment, and a large adhesive improvement effect can be obtained even with a small amount. On the other hand, when the molecular weight of the cation moiety is 400 g / mol or less, the ratio of the active moiety in the molecule is high, and a large adhesion improvement effect can be obtained even with a small amount.

  In the present invention, examples of the cation moiety of the quaternary ammonium salt represented by the general formula (I) include tetramethylammonium, ethyltrimethylammonium, trimethylpropylammonium, butyltrimethylammonium, trimethylpentylammonium, hexyltrimethylammonium, Cyclohexyltrimethylammonium, trimethyloctylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, trimethyloctadecylammonium, trimethyloleylammonium, docosyltrimethylammonium, benzyltrimethylammonium, trimethylphenylammonium, diethyldimethylammonium Dimethyl, dimethyldipropylammonium, dibutyldimethylammonium, dimethyldipentylammonium, dihexyldimethylammonium, dicyclohexyldimethylammonium, dimethyldioctylammonium, didecyldimethylammonium, ethyldecyldimethylammonium, didodecyldimethylammonium, ethyldodecyldimethylammonium, ditetradecyl Dimethyl ammonium, ethyl tetradecyl dimethyl ammonium, dihexadecyl dimethyl ammonium, ethyl hexadecyl dimethyl ammonium, dimethyl dioctadecyl ammonium, ethyl octadecyl dimethyl ammonium, dimethyl dioleyl ammonium, ethyl dimethyl oleyl ammonium, didocosyl dimethyl ammonium, Silethyldimethylammonium, dibenzyldimethylammonium, benzylethyldimethylammonium, benzyldimethylpropylammonium, benzylbutyldimethylammonium, benzyldecyldimethylammonium, benzyldodecyldimethylammonium, benzyltetradecyldimethylammonium, benzylhexadecyldimethylammonium, benzyloctadecyldimethyl Ammonium, benzyldimethyloleylammonium, dimethyldiphenylammonium, ethyldimethylphenylammonium, dimethylpropylphenylammonium, butyldimethylphenylammonium, decyldimethylphenylammonium, dodecyldimethylphenylammonium, tetradecyldimethylphenylammonium , Hexadecyldimethylphenylammonium, dimethyloctadecylphenylammonium, dimethyloleylphenylammonium, tetraethylammonium, triethylmethylammonium, triethylpropylammonium, butyltriethylammonium, triethylpentylammonium, triethylhexylammonium, triethylcyclohexylammonium, triethyloctylammonium, decyl Triethylammonium, dodecyltriethylammonium, tetradecyltriethylammonium, hexadecyltriethylammonium, triethyloctadecylammonium, triethyloleylammonium, benzyltriethylammonium, triethylphenylammonium, diethyldipropylan Ni, dibutyl diethyl ammonium, diethyl dipentyl ammonium, diethyl dihexyl ammonium, diethyl dicyclohexyl ammonium, diethyl dioctyl ammonium, didecyl diethyl ammonium, didodecyl diethyl ammonium, ditetradecyl diethyl ammonium, diethyl dihexadecyl ammonium, diethyl dioctadecyl ammonium, diethyl Dioleylammonium, dibenzyldiethylammonium, diethyldiphenylammonium, tetrapropylammonium, methyltripropylammonium, ethyltripropylammonium, butyltripropylammonium, benzyltripropylammonium, phenyltripropylammonium, tetrabutylammonium, tributy Methylammonium, tributylethylammonium, tributylpropylammonium, benzyltributylammonium, tributylphenylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, methyltrioctylammonium, ethyltrioctylammonium, trioctylpropylammonium, Butyl trioctyl ammonium, dimethyl dioctyl ammonium, diethyl dioctyl ammonium, dioctyl dipropyl ammonium, dibutyl dioctyl ammonium, tetradecyl ammonium, tetradodecyl ammonium, 2-hydroxyethyl trimethyl ammonium, 2-hydroxyethyl triethyl ammonium, 2-hy Droxyethyltripropylammonium, 2-hydroxyethyltributylammonium, polyoxyethylenetrimethylammonium, polyoxyethylenetriethylammonium, polyoxyethylenetripropylammonium, polyoxyethylenetributylammonium, bis (2-hydroxyethyl) dimethylammonium, bis (2-hydroxyethyl) diethylammonium, bis (2-hydroxyethyl) dipropylammonium, bis (2-hydroxyethyl) dibutylammonium, bis (polyoxyethylene) dimethylammonium, bis (polyoxyethylene) diethylammonium, bis ( Polyoxyethylene) dipropylammonium, bis (polyoxyethylene) dibutylammonium, tris (2-hydride) Xylethyl) methylammonium, tris (2-hydroxyethyl) ethylammonium, tris (2-hydroxyethyl) propylammonium, tris (2-hydroxyethyl) butylammonium, tris (polyoxyethylene) methylammonium, tris (polyoxyethylene) Examples include ethylammonium, tris (polyoxyethylene) propylammonium, and tris (polyoxyethylene) butylammonium.

  Examples of the cation moiety of the quaternary ammonium salt represented by the general formula (II) include 1-methylpyridinium, 1-ethylpyridinium, 1-ethyl-2-methylpyridinium, and 1-ethyl-4-methylpyridinium. 1-ethyl-2,4-dimethylpyridinium, 1-ethyl-2,4,6-trimethylpyridinium, 1-propylpyridinium, 1-butylpyridinium, 1-butyl-2-methylpyridinium, 1-butyl-4- Methylpyridinium, 1-butyl-2,4-dimethylpyridinium, 1-butyl-2,4,6-trimethylpyridinium, 1-pentylpyridinium, 1-hexylpyridinium, 1-cyclohexylpyridinium, 1-octylpyridinium, 1-decyl Pyridinium, 1-dodecylpyridinium, - tetradecyl pyridinium, 1-hexadecyl pyridinium, 1-octadecyl pyridinium, 1-oleyl pyridinium, and 1-docosyl pyridinium, and 1-benzyl pyridinium and the like.

  In the present invention, examples of the anion moiety of the quaternary ammonium salt (B2) having a cation moiety include halogen ions of fluoride anion, chloride anion, bromide anion and iodide anion. Moreover, for example, a hydroxide anion, an acetate anion, an oxalate anion, a sulfate anion, a benzoate anion, an iodate anion, a methylsulfonate anion, a benzenesulfonate anion, and a toluenesulfonate anion are exemplified.

  Especially, as a counter ion, it is preferable that it is a halogen ion from a viewpoint that the size is small and it does not inhibit the reaction promotion effect of a quaternary ammonium salt.

  In the present invention, these quaternary ammonium salts may be used alone or in combination.

  In the present invention, (B2) the quaternary ammonium salt having a cation moiety includes, for example, trimethyloctadecylammonium chloride, trimethyloctadecylammonium bromide, trimethyloctadecylammonium hydroxide, trimethyloctadecylammonium acetate, trimethyloctadecylammonium benzoate, trimethyl Octadecylammonium-p-toluenesulfonate, trimethyloctadecylammonium hydrochloride, trimethyloctadecylammonium tetrachloroiodate, trimethyloctadecylammonium hydrogensulfate, trimethyloctadecylammonium methylsulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltri Mechi Ammonium hydroxide, benzyltrimethylammonium acetate, benzyltrimethylammonium benzoate, benzyltrimethylammonium-p-toluenesulfonate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium acetate, tetra Butylammonium benzoate, tetrabutylammonium-p-toluenesulfonate, (2-methoxyethoxymethyl) triethylammonium chloride, (2-methoxyethoxymethyl) triethylammonium bromide, (2-methoxyethoxymethyl) triethylammonium hydroxide, (2-Methoxyethoxymethyl) triethylammonium-p-toluenesulfonater (2-acetoxyethyl) trimethylammonium chloride, (2-acetoxyethyl) trimethylammonium bromide, (2-acetoxyethyl) trimethylammonium hydroxide, (2-acetoxyethyl) trimethylammonium-p-toluenesulfonate, (2- Hydroxyethyl) trimethylammonium chloride, (2-hydroxyethyl) trimethylammonium bromide, (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium-p-toluenesulfonate, bis (polyoxyethylene) dimethyl Ammonium chloride, bis (polyoxyethylene) dimethylammonium bromide, bis (polyoxyethylene) dimethylammonium hydroxide, Bis (polyoxyethylene) dimethylammonium-p-toluenesulfonate, 1-hexadecylpyridinium chloride, 1-hexadecylpyridinium bromide, 1-hexadecylpyridinium hydroxide, 1-hexadecylpyridinium-p-toluenesulfonate, etc. Is mentioned.

  In the present invention, the compound represented by the general formula (I) includes benzyltrimethylammonium bromide, tetrabutylammonium bromide, trimethyloctadecylammonium bromide, (2-methoxyethoxymethyl) triethylammonium chloride, (2-acetoxyethyl) trimethyl. Ammonium chloride and (2-hydroxyethyl) trimethylammonium bromide are preferred, and tetrabutylammonium bromide and (2-methoxyethoxymethyl) triethylammonium chloride are preferred.

  In the present invention, the compound represented by the general formula (II) is preferably 1-hexadecylpyridinium chloride.

  Next, (B3) will be described.

  The (B3) quaternary phosphonium salt and / or phosphine compound used in the present invention needs to be blended in an amount of 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) epoxy compound. It is preferable to mix | blend 10 mass parts, and it is more preferable to mix | blend 0.1-8 mass parts. When the blending amount is less than 0.1 part by mass, (A) the covalent bond formation between the epoxy compound and the oxygen-containing functional group on the carbon fiber surface is not promoted, and the adhesion between the carbon fiber and the thermosetting resin Is insufficient. On the other hand, when the blending amount exceeds 25 parts by mass, (B3) covers the carbon fiber surface, the covalent bond formation is inhibited, and the adhesion between the carbon fiber and the thermosetting resin becomes insufficient.

  The (B3) quaternary phosphonium salt or phosphine compound used in the present invention is preferably the following general formula (XI) or (XII)

(In the above chemical formula, R _{34 to} R ₄₀ each represent a hydrocarbon group having 1 to 22 carbon atoms, the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is A quaternary ammonium salt or a phosphine compound having a cation moiety represented by any one of -O-, -O-CO- and -CO-O-.

  The inventors of the present invention have (B3) a quaternary phosphonium salt and / or a phosphine compound, preferably any one of the above general formulas (XI) or (XII) with respect to 100 parts by mass of the component (A) (B3 ) Bifunctional or higher only when a sizing agent containing 0.1 to 25 parts by mass of a quaternary phosphonium salt and / or a phosphine compound is applied to a carbon fiber and heat-treated under specific conditions. As a result of the promotion of covalent bond formation between the epoxy resin and the oxygen fiber-containing functional groups such as carboxyl groups and hydroxyl groups that are originally contained on the carbon fiber surface or introduced by oxidation treatment, It has been found that the adhesion of the resin is greatly improved.

In the present invention, the mechanism by which the covalent bond formation is promoted by the incorporation of the quaternary phosphonium salt or phosphine compound is not clear, but by using a quaternary phosphonium salt or phosphine compound having a specific structure, the present invention is preferably used. An effect is obtained. That is, as the (B3) quaternary phosphonium salt and / or phosphine compound used in the present invention, R _{34 to} R _{40 in the} general formula (XI) or (XII) are each a hydrocarbon group having 1 to 22 carbon atoms. Preferably, the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is substituted by —O—, —O—CO— or —CO—O—. Also good. When the carbon number is 23 or more, the reason is not clear, but the adhesion may be insufficient. Here, a C1-C22 hydrocarbon group is a group which consists only of a carbon atom and a hydrogen atom, and any of a saturated hydrocarbon group and an unsaturated hydrocarbon group may be included, even if it contains a ring structure. Also good. As the hydrocarbon group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, oleyl group, Examples include docosyl group, vinyl group, 2-propynyl group, benzyl group, phenyl group, cinnamyl group, and naphthylmethyl group.

Further, examples of the case where a CH ₂ group in the hydrocarbon group having 1 to 22 carbon atoms is substituted by -O-, as linear, e.g., a methoxymethyl group, ethoxymethyl group, propoxymethyl group , Butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxyethoxymethyl group, methoxyethoxyethyl group, polyethylene glycol group, and polypropylene glycol group An ether group is mentioned. Moreover, as a cyclic thing, ethylene oxide, tetrahydrofuran, oxepane, 1, 3- dioxolane etc. are mentioned, for example.

Examples of the case where the CH ₂ group in the hydrocarbon group having 1 to 22 carbon atoms is substituted by —O—CO— or —CO—O— include, for example, an acetoxymethyl group, an acetoxyethyl group, an acetoxypropyl group Group, acetoxybutyl group, methacryloyloxyethyl group, benzoyloxyethyl group, methoxycarbonyl group, ethoxycarbonyl group and the like.

  Examples of the case where the hydrocarbon group having 1 to 22 carbon atoms has a hydroxyl group include, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, and a hydroxycyclohexyl group. , A hydroxyoctyl group, a hydroxydecyl group, a hydroxydodecyl group, a hydroxytetradecyl group, a hydroxyhexadecyl group, a hydroxyoctadecyl group, a hydroxyoleyl group, and a hydroxydocosyl group.

Among them, (B3) the number of carbon atoms of _R 34 _{to R 40} of the quaternary phosphonium salt or phosphine compound is preferably in the range of 1-14. When the carbon number is less than 14, when the quaternary ammonium salt acts as a reaction accelerator, the steric hindrance is moderately small and the reaction promoting effect is enhanced, and the adhesion is further improved.

In the present invention, the carbon number of R _{34 to} R _{37 in} the (B3) quaternary phosphonium salt represented by the general formula (XI) is preferably 2 or more, more preferably 3 or more, Preferably it is 4 or more. When the carbon number is 2 or more, homopolymerization of the epoxy resin due to the quaternary phosphonium salt acting as an initiator is suppressed, and the adhesiveness is further improved.

In the present invention, R ₃₉ and R ₄₀ of the (B3) phosphine compound represented by the general formula (XII) are each preferably a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group is It may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group may be substituted with —O—, —O—CO— or —CO—O—. When the number of carbon atoms is less than 8, the ratio of active sites in the molecule is high, and a large effect of improving adhesion can be obtained even with a small amount.

  In the present invention, the molecular weight of the cation moiety of (B3) quaternary phosphonium salt is preferably within the range of 100 to 400 g / mol, more preferably within the range of 100 to 300 g / mol, and even more preferably 100. Within the range of ~ 200 g / mol. When the molecular weight of the cation moiety is 100 g / mol or more, volatilization is suppressed even during the heat treatment, and a large adhesive improvement effect can be obtained even with a small amount. On the other hand, when the molecular weight of the cation moiety is 400 g / mol or less, the ratio of the active moiety in the molecule is high, and a large adhesion improvement effect can be obtained even with a small amount.

  In the present invention, examples of the cation moiety of the aliphatic quaternary phosphonium salt represented by the general formula (VII) include tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyltrimethyl. Propylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldipropylphosphonium, dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, (2-methoxyethoxymethyl) triethylphosphonium, (2-acetoxyethyl) trimethylphosphonium Chloride, (2-acetoxyethyl) trimethylphosphonium, (2-hydroxyethyl) ) Trimethylphosphonium, tributyl-n-octylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, tributyl (1,3-dioxolan-2-ylmethyl) phosphonium, di-t-butyldimethylphosphonium, and trihexyltetradecylphosphonium and bis (Polyoxyethylene) dimethylphosphonium and the like.

  Examples of the cation moiety of the aromatic quaternary phosphonium salt represented by the general formula (VII) include tetraphenylphosphonium, triphenylmethylphosphonium, diphenyldimethylphosphonium, ethyltriphenylphosphonium, n-butyltriphenylphosphonium, Benzyltriphenylphosphonium, isopropyltriphenylphosphonium, vinyltriphenylphosphonium, allyltriphenylphosphonium, triphenylpropargylphosphonium, t-butyltriphenylphosphonium, heptyltriphenylphosphonium, triphenyltetradecylphosphonium, hexyltriphenylphosphonium, ( Methoxymethyl) triphenylphosphonium, 2-hydroxybenzyltriphenylphosphonium, (4-carbo (Cibutyl) triphenylphosphonium, (3-carboxypropyl) triphenylphosphonium, cinnamyltriphenylphosphonium, cyclopropyltriphenylphosphonium, 2- (1,3-dioxan-2-yl) ethyltriphenylphosphonium, 1- (1 , 3-dioxolan-2-yl) ethyltriphenylphosphonium, (1,3-dioxolan-2-yl) methyltriphenylphosphonium, 4-ethoxybenzyltriphenylphosphonium, ethoxycarbonylmethyl (triphenyl) phosphonium, etc. It is done.

  In the present invention, examples of the anion moiety of the (B3) quaternary phosphonium salt include halogen ions of fluoride anion, chloride anion, bromide anion and iodide anion. Also, for example, hydroxide anion, acetate anion, oxalate anion, hydrogen sulfate anion, benzoate anion, iodate anion, methylsulfonate anion, benzenesulfonate anion, tetraphenylborate ion, tetrafluoroborate ion, hexafluoro Examples include phosphate ions, bis (trifluoromethylsulfonyl) imide ions, and toluenesulfonate anions.

  In the present invention, these quaternary phosphonium salts may be used alone or in combination.

  In the present invention, (B3) quaternary phosphonium salts include, for example, trimethyloctadecylphosphonium chloride, trimethyloctadecylphosphonium bromide, trimethyloctadecylphosphonium hydroxide, trimethyloctadecylphosphonium acetate, trimethyloctadecylphosphonium benzoate, trimethyloctadecylphosphonium-p -Toluenesulfonate, trimethyloctadecylphosphonium hydrochloride, trimethyloctadecylphosphonium tetrachloroiodate, trimethyloctadecylphosphonium hydrogensulfate, trimethyloctadecylphosphonium methylsulfate, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium hydro Sid, benzyltrimethylphosphonium acetate, benzyltrimethylphosphonium benzoate, benzyltrimethylphosphonium-p-toluenesulfonate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium Benzoate, tetrabutylphosphonium-p-toluenesulfonate, (2-methoxyethoxymethyl) triethylphosphonium chloride, (2-methoxyethoxymethyl) triethylphosphonium bromide, (2-methoxyethoxymethyl) triethylphosphonium hydroxide, (2 -Methoxyethoxymethyl) triethylphosphonium-p-toluenesulfonate, (2-acetoxy Til) trimethylphosphonium chloride, (2-acetoxyethyl) trimethylphosphonium bromide, (2-acetoxyethyl) trimethylphosphonium hydroxide, (2-acetoxyethyl) trimethylphosphonium-p-toluenesulfonate, (2-hydroxyethyl) trimethylphosphonium Chloride, (2-hydroxyethyl) trimethylphosphonium bromide, (2-hydroxyethyl) trimethylphosphonium hydroxide, (2-hydroxyethyl) trimethylphosphonium-p-toluenesulfonate, bis (polyoxyethylene) dimethylphosphonium chloride, bis ( Polyoxyethylene) dimethylphosphonium bromide, bis (polyoxyethylene) dimethylphosphonium hydroxide, bis (polyoxyethylene) Len) dimethylphosphonium-p-toluenesulfonate, tetraphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate.

  Further, (B3) quaternary phosphonium salts other than the above general formula (XI) include acetonitrile triphenylphosphonium chloride, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazole-1- Iroxytris (dimethylamino) phosphonium hexafluorophosphate, trans-2-butene-1,4-bis (triphenylphosphonium chloride), (4-carboxybutyl) triphenylphosphonium bromide, (3-carboxypropyl) triphenyl Phosphonium bromide, (2,4-dichlorobenzyl) triphenylphosphonium chloride, 2-dimethylaminoethyltriphenylphosphonium bromide, ethoxycarbonylmethyl (triphenyl) phospho Umbromide, (formylmethyl) triphenylphosphonium chloride, N-methylanilinotriphenylphosphonium iodide, phenacyltriphenylphosphonium bromide, etc. are exemplified, and these quaternary phosphonium salts are also (B3) quaternary phosphonium salts of the present invention. Can be used as

  Examples of the phosphine compound represented by the general formula (XII) include triethylphosphine, tripropylphosphine, tributylphosphine, tri-t-butylphosphine, tripentylphosphine, trihexylphosphine, tricyclopentylphosphine, and tricyclohexylphosphine. , Trioctylphosphine, triphenylphosphine, tri (2-furyl) phosphine, dimethylpropylphosphine, dimethylbutylphosphine, dimethylpentylphosphine, dimethylhexylphosphine, dimethylcyclohexylphosphine, dimethyloctylphosphine, dimethyldecylphosphine, dimethyldodecylphosphine, dimethyl Tetradecylphosphine, dimethylhexadecylphosphine, dimethyloctadecylphos , Dimethyloleylphosphine, dimethyldocosylphosphine, diethylpropylphosphine, diethylbutylphosphine, diethylpentylphosphine, diethylhexylphosphine, diethylcyclohexylphosphine, diethyloctylphosphine, diethyldecylphosphine, diethyldodecylphosphine, diethyltetradecylphosphine, diethyl Hexadecylphosphine, diethyloctadecylphosphine, diethyloleylphosphine, diethyldocosylphosphine, diethylphenylphosphine, ethyldiphenylphosphine, dipropylmethylphosphine, dipropylethylphosphine, dipropylbutylphosphine, dibutylmethylphosphine, dibutylethylphosphine, dibutylpropyl Phosphine, Jihe Silmethylphosphine, dihexylethylphosphine, dihexylpropylphosphine, dihexylbutylphosphine, dicyclohexylmethylphosphine, dicyclohexylethylphosphine, dicyclohexylpropylphosphine, dicyclohexylbutylphosphine, dicyclohexylphenylphosphine, dioctylmethylphosphine, dioctylethylphosphine, dioctylpropylphosphine, didecyl Methylphosphine, didecylethylphosphine, didecylpropylphosphine, didecylbutylphosphine, didodecylmethylphosphine, didodecylethylphosphine, didodecylpropylphosphine, didodecylbutylphosphine, ditetradecylmethylphosphine, ditetradecylethylphosphine, Ditetradecyl Propylphosphine, Ditetradecylbutylphosphine, Dihexadecylmethylphosphine, Dihexadecylethylphosphine, Dihexadecylpropylphosphine, Dihexadecylbutylphosphine, Trimethanolphosphine, Triethanolphosphine, Tripropanolphosphine, Tributanolphosphine, Tri Hexanol phosphine, diethyl methanol phosphine, dipropyl methanol phosphine, diisopropyl methanol phosphine, dibutyl methanol phosphine, diisobutyl methanol phosphine, di-t-butyl methanol phosphine, di (2-ethylhexyl) methanol phosphine, dimethyl ethanol phosphine, diethyl ethanol phosphine, di Propylethanolphosphine, diisopropyl Tanolphosphine, dibutylethanolphosphine, diisobutylethanolphosphine, di-t-butylethanolphosphine, di-t-butylphenylphosphine, di (2-ethylhexyl) ethanolphosphine, dimethylpropanolphosphine, diethylpropanolphosphine, dipropylpropanolphosphine, diisopropyl Propanolphosphine, dibutylpropanolphosphine, diisobutylpropanolphosphine, di-t-butylpropanolphosphine, di (2-ethylhexyl) propanolphosphine, methyldimethanolphosphine, ethyldimethanolphosphine, propyldimethanolphosphine, isopropyldimethanolphosphine, butyldi Methanol phosphine, isobutyl dimeta Phosphine, t-butyldimethanolphosphine, (2-ethylhexyl) dimethanolphosphine, methyldiethanolphosphine, ethyldiethanolphosphine, propyldiethanolphosphine, isopropyldiethanolphosphine, butyldiethanolphosphine, isobutyldiethanolphosphine, t-butyldiethanolphosphine, (2 -Ethylhexyl) diethanolphosphine, isopropylphenylphosphine, methoxydiphenylphosphine, ethoxydiphenylphosphine, triphenylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylcyclohexylphosphine, diphenylpropylphosphine, diphenylbutylphosphine, diphenyl-t-butylphosphine Diphenylpentylphosphine, diphenylhexylphosphine, diphenyloctylphosphine, diphenylbenzylphosphine, phenoxydiphenylphosphine, diphenyl-1-pyrenylphosphine, phenyldimethylphosphine, trimethylphosphine, tri-n-octylphosphine, tri-o-tolylphosphine, Examples include tri-m-tolylphosphine and tris-2,6-dimethoxyphenylphosphine.

  Further, as (B3) phosphine other than the above general formula (XII), phenyl-2-pyridylphosphine, triphenylphosphine oxide, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) Examples include propane and 1,4-bis (diphenylphosphino) butane.

  In the present invention, the compound represented by the general formula (XI) is preferably tetrabutylphosphonium bromide or tetraphenylphosphonium bromide.

  In the present invention, the compound represented by the general formula (XII) is preferably tributylphosphine or triphenylphosphine.

  In the present invention, the sizing agent may contain one or more components other than the component (A) and the component (B). For example, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, compounds obtained by adding polyalkylene oxides such as polyethylene oxide and polypropylene oxide to higher alcohols, polyhydric alcohols, alkylphenols, and styrenated phenols, and ethylene oxide and propylene oxide. Nonionic surfactants such as block copolymers are preferably used. Moreover, you may add a polyester resin, an unsaturated polyester compound, etc. suitably in the range which does not affect the effect of this invention.

  In the present invention, the sizing agent can be diluted with a solvent. Examples of such a solvent include water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, dimethylformamide, and dimethylacetamide. Among them, handling is easy and advantageous from the viewpoint of safety. Therefore, water is preferably used.

  In this invention, it is preferable that the adhesion amount of a sizing agent is the range of 0.1-10 mass parts with respect to 100 mass parts of carbon fibers, More preferably, it is the range of 0.2-3 mass parts. When the carbon fiber is woven, if the amount of the sizing agent is 0.1 parts by mass or more, it can withstand friction caused by a metal guide that passes through, the generation of fuzz is suppressed, the smoothness of the carbon fiber sheet, etc. Excellent quality. On the other hand, if the amount of sizing agent attached is 10 parts by mass or less, a matrix resin such as an epoxy resin is impregnated inside the carbon fiber bundle without being obstructed by the sizing agent film around the carbon fiber bundle, and in the resulting composite material The generation of voids is suppressed, the quality of the composite material is excellent, and at the same time the mechanical properties are excellent.

  In the present invention, the thickness of the sizing agent layer applied to the carbon fiber and dried is preferably in the range of 2 to 20 nm, and the maximum value of the thickness does not exceed twice the minimum value. By such a uniform sizing agent layer, a large effect of improving adhesiveness can be obtained stably, and further, high-order processability is stable.

  In the present invention, examples of the carbon fiber to which the sizing agent is applied include polyacrylonitrile (PAN) -based, rayon-based, and pitch-based carbon fibers. Of these, PAN-based carbon fibers having an excellent balance between strength and elastic modulus are preferably used.

  Next, a method for producing a PAN-based carbon fiber will be described.

  As a spinning method for obtaining a carbon fiber precursor fiber, spinning methods such as wet, dry, and dry-wet can be used. Among these, it is preferable to use a wet or dry wet spinning method from the viewpoint that a high-strength carbon fiber is easily obtained. As the spinning dope, a polyacrylonitrile homopolymer or copolymer solution or suspension can be used.

  The spinning solution is spun, coagulated, washed with water, and drawn into a precursor fiber by passing it through a die, and the resulting precursor fiber is subjected to a flameproofing treatment and carbonization treatment. Get fiber. As conditions for carbonization treatment and graphitization treatment, the maximum heat treatment temperature is preferably 1100 ° C. or higher, more preferably 1400 to 3000 ° C.

  In the present invention, carbon fibers having fineness are preferably used from the viewpoint of obtaining carbon fibers having high strength and elastic modulus. Specifically, the single fiber diameter of the carbon fiber is preferably 7.5 μm or less, more preferably 6 μm or less, and further preferably 5.5 μm or less. There is no particular lower limit for the single fiber diameter, but if it is 4.5 μm or less, single fiber cutting is likely to occur in the process, and the productivity may decrease.

  The obtained carbon fiber is usually subjected to an oxidation treatment to introduce an oxygen-containing functional group in order to improve adhesion with the matrix resin. As the oxidation treatment method, vapor phase oxidation, liquid phase oxidation, and liquid phase electrolytic oxidation are used. From the viewpoint of high productivity and uniform treatment, liquid phase electrolytic oxidation is preferably used.

  In the present invention, examples of the electrolytic solution used in the liquid phase electrolytic oxidation include an acidic electrolytic solution and an alkaline electrolytic solution.

  Examples of the acidic electrolyte include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, and carbonic acid, organic acids such as acetic acid, butyric acid, oxalic acid, acrylic acid, and maleic acid, or ammonium sulfate and ammonium hydrogen sulfate. And the like. Of these, sulfuric acid and nitric acid exhibiting strong acidity are preferably used.

  Specific examples of the alkaline electrolyte include aqueous solutions of hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, Aqueous solutions of carbonates such as barium carbonate and ammonium carbonate, aqueous solutions of bicarbonates such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate and ammonium bicarbonate, ammonia, tetraalkylammonium hydroxide And an aqueous solution of hydrazine. Among these, from the viewpoint of not containing an alkali metal that causes curing inhibition of the matrix resin, an aqueous solution of ammonium carbonate and ammonium hydrogen carbonate or an aqueous solution of tetraalkylammonium hydroxide exhibiting strong alkalinity is preferably used.

  In the present invention, (A) from the viewpoint that the covalent bond formation between the epoxy compound and the oxygen-containing functional group on the surface of the carbon fiber is promoted, and the adhesiveness is further improved, after the carbon fiber is electrolytically treated with an alkaline electrolyte, Alternatively, it is preferable to apply a sizing agent after electrolytic treatment in an acidic aqueous solution followed by washing with an alkaline aqueous solution. When electrolytic treatment is performed, the excessively oxidized portion on the carbon fiber surface becomes a fragile layer and exists at the interface, which may be the starting point of destruction when made into a composite material. It is considered that formation of a covalent bond is promoted by dissolution and removal with an aqueous solution. In addition, when there is a residue of the acidic electrolyte on the surface of the carbon fiber, protons in the residue are captured by the component (B), and the hydrogen ion of the oxygen-containing functional group on the surface of the carbon fiber by the component (B), which is the role to be originally played. The effect of pulling out may decrease. For this reason, it is preferable to perform electrolytic treatment in an acidic aqueous solution, and then neutralize and wash the acidic electrolytic solution with an alkaline aqueous solution. For the above reasons, a further improvement in adhesion can be obtained by a combination of carbon fibers subjected to a specific treatment and a sizing agent.

  The concentration of the electrolytic solution used in the present invention is preferably in the range of 0.01 to 5 mol / liter, more preferably in the range of 0.1 to 1 mol / liter. When the concentration of the electrolytic solution is 0.01 mol / liter or more, the electrolytic treatment voltage is lowered, which is advantageous in terms of operating cost. On the other hand, when the concentration of the electrolytic solution is 5 mol / liter or less, it is advantageous from the viewpoint of safety.

  The temperature of the electrolytic solution used in the present invention is preferably in the range of 10 to 100 ° C, more preferably in the range of 10 to 40 ° C. When the temperature of the electrolytic solution is 10 ° C. or higher, the efficiency of the electrolytic treatment is improved, which is advantageous in terms of operating cost. On the other hand, when the temperature of the electrolytic solution is 100 ° C. or lower, it is advantageous from the viewpoint of safety.

  In the present invention, the amount of electricity in the liquid phase electrolytic oxidation is preferably optimized in accordance with the carbonization degree of the carbon fiber, and a larger amount of electricity is required when processing the carbon fiber having a high elastic modulus.

In the present invention, the current density in the liquid phase electrolytic oxidation is preferably in the range of 1.5 to 1000 amperes / m ² per 1 m ² of the surface area of the carbon fiber in the electrolytic treatment solution, more preferably 3 to 500 amperes. / M ² within the range. When the current density is 1.5 amperes / m ² or more, the efficiency of the electrolytic treatment is improved, which is advantageous in terms of operating cost. On the other hand, when the current density is 1000 amperes / m ² or less, it is advantageous from the viewpoint of safety.

  In the present invention, from the viewpoint that (A) the covalent bond formation between the epoxy compound and the oxygen-containing functional group on the carbon fiber surface is promoted, and the adhesion is further improved, the carbon fiber is made alkaline water-soluble after the oxidation treatment. It is preferable to wash. Among these, it is preferable to perform a liquid phase electrolysis treatment with an acidic electrolyte and then wash with an alkaline aqueous solution.

  In the present invention, the pH of the alkaline aqueous solution used for washing is preferably in the range of 7 to 14, more preferably in the range of 10 to 14. Specific examples of alkaline aqueous solutions include aqueous solutions of hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. And aqueous solutions of carbonates such as ammonium carbonate, aqueous solutions of bicarbonates such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate and ammonium bicarbonate, ammonia, tetraalkylammonium hydroxide and hydrazine An aqueous solution of Among these, from the viewpoint of not containing an alkali metal that causes curing inhibition of the matrix resin, an aqueous solution of ammonium carbonate or ammonium hydrogen carbonate, or an aqueous solution of tetraalkylammonium hydroxide exhibiting strong alkalinity is preferably used.

  In the present invention, as a method for washing carbon fibers with an alkaline aqueous solution, for example, a dipping method and a spray method can be used. Especially, it is preferable to use a dip method from a viewpoint that washing | cleaning is easy, Furthermore, it is a preferable aspect to use a dip method, vibrating a carbon fiber with an ultrasonic wave.

  In the present invention, it is preferable that the carbon fiber is washed with an electrolytic treatment or an alkaline aqueous solution, then washed with water and dried. In this case, if the drying temperature is too high, the functional groups present on the outermost surface of the carbon fiber are likely to disappear due to thermal decomposition. Therefore, it is desirable to dry at the lowest possible temperature. Specifically, the drying temperature is preferably 250 ° C. Hereinafter, drying at 210 ° C. or lower is more preferable.

  Examples of the means for applying (coating) the sizing agent to the carbon fiber include a method of immersing the carbon fiber in a sizing liquid through a roller, a method of contacting the carbon fiber with a roller to which the sizing liquid is attached, and a sizing liquid being atomized. There is a method of spraying on carbon fiber. Further, the sizing agent applying means may be either a batch type or a continuous type, but a continuous type capable of improving productivity and reducing variation is preferably used. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the carbon fiber is uniformly attached within an appropriate range. Moreover, it is also a preferable aspect that the carbon fiber is vibrated with ultrasonic waves when the sizing agent is applied.

  In this invention, after apply | coating a sizing agent to carbon fiber, it is required to heat-process for 30 to 600 second in the temperature range of 160-260 degreeC. The heat treatment conditions are preferably in a temperature range of 170 to 250 ° C. for 30 to 500 seconds, and more preferably in a temperature range of 180 to 240 ° C. for 30 to 300 seconds. If the heat treatment condition is less than 160 ° C. and / or less than 30 seconds, the covalent bond formation between the epoxy resin of the sizing agent and the oxygen-containing functional group on the surface of the carbon fiber is not promoted, and the carbon fiber and the matrix resin Adhesiveness is insufficient. On the other hand, when the heat treatment condition exceeds 260 ° C. and / or exceeds 600 seconds, volatilization of the tertiary amine compound and / or tertiary amine salt occurs, and the covalent bond formation is not promoted, and the carbon fiber and the matrix resin The adhesiveness of the is insufficient.

  The heat treatment can also be performed by microwave irradiation and / or infrared irradiation. When carbon fiber is heat-treated by microwave irradiation and / or infrared irradiation, the microwave penetrates into the carbon fiber and is absorbed, so that the carbon fiber as the object to be heated can be heated to a desired temperature in a short time. . In addition, since the inside of the carbon fiber can be quickly heated by microwave irradiation and / or infrared irradiation, the temperature difference between the inside and outside of the carbon fiber bundle can be reduced, and the adhesion unevenness of the sizing agent can be reduced. It becomes possible to do.

  In the present invention, the strand strength of the obtained carbon fiber bundle is preferably 3.5 GPa or more, more preferably 4 GPa or more, and further preferably 5 GPa. Moreover, it is preferable that the strand elastic modulus of the obtained carbon fiber bundle is 220 GPa or more, More preferably, it is 240 GPa or more, More preferably, it is 280 GPa or more.

  In the present invention, the strand tensile strength and elastic modulus of the carbon fiber bundle can be determined according to the following procedure in accordance with the resin impregnated strand test method of JIS-R-7608 (2004). As the resin formulation, “Celoxide (registered trademark)” 2021P (manufactured by Daicel Chemical Industries) / 3 boron trifluoride monoethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) / Acetone = 100/3/4 (part by mass) is used. As curing conditions, normal pressure, 130 ° C., and 30 minutes are used. Ten strands of the carbon fiber bundle were measured, and the average value was defined as the strand tensile strength and the strand elastic modulus.

  In the present invention, the carbon fiber has a surface oxygen concentration (O / C), which is a ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy. The thing within the range of 05-0.50 is preferable, More preferably, it is a thing within the range of 0.06-0.30, More preferably, it is a thing within the range of 0.07-0.20. When the surface oxygen concentration (O / C) is 0.05 or more, an oxygen-containing functional group on the surface of the carbon fiber can be secured and strong adhesion with the matrix resin can be obtained. Moreover, when the surface oxygen concentration (O / C) is 0.5 or less, a decrease in strength of the carbon fiber itself due to oxidation can be suppressed.

The surface oxygen concentration of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, carbon fibers from which dirt and the like adhering to the carbon fiber surface were removed with a solvent were cut into 20 mm, spread and arranged on a copper sample support base, and then AlKα ₁ and ₂ were used as X-ray sources. The chamber is kept at 1 × 10 ⁻⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is set to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area, _K.P. E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area, E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

Here, the surface oxygen concentration is calculated as an atomic ratio by using a sensitivity correction value unique to the apparatus from the ratio of the O _1s peak area to the C _1s peak area. As the X-ray photoelectron spectroscopy apparatus, ESCA-1600 manufactured by ULVAC-PHI Co., Ltd. was used, and the sensitivity correction value unique to the apparatus was 2.33.

  The molding substrate of the present invention preferably has a woven fabric or braided form. In the present invention, a carbon fiber bundle coated with a sizing agent is used as a molding base material in the form of a woven fabric or braid, and the molding base material in the form is laminated and set on a molding die, and the inside of the die is heated. A curable resin is injected and cured to form a carbon fiber reinforced composite material. Alternatively, a molding base material in the form of a woven fabric or braid is filmed with a thermosetting resin to form a molding material, the molding material is laminated, bagged, and autoclaved to form a carbon fiber reinforced composite material. Alternatively, a base material for molding in the form of a woven fabric or braid is used as a molding material with a film-like thermoplastic resin as a matrix resin or a thermoplastic resin stretched on a nonwoven fabric, and the molding material is laminated and pressed to form carbon. Mold fiber reinforced composite material.

  Fabrics with carbon fiber bundles as woven yarns include plain fabrics, twill weaves, satin weaves and other bi-directional fabrics that use carbon fiber bundles in both longitudinal and lateral directions, as well as unidirectional and unidirectional fabrics in which warp yarns are stopped with thin wefts. Examples include multiaxial weaving with stacked materials. A braid using a carbon fiber bundle is a base material in which a plurality of carbon fiber bundles are assembled in a cylindrical shape, and is preferable in that an integral preform can be created with a continuous carbon fiber bundle. .

  The plain weave has the effect that the number of crossing points is large and the form is easy to stabilize because one warp and one weft are alternately raised and lowered. Furthermore, due to the large number of crossing points between warp and weft, the two surfaces of warp and weft may peel off even when any stress such as impact force perpendicular to the surface or compressive stress in the fiber axis direction is applied. This is preferable in that it can exhibit high mechanical properties.

  Unidirectional weave and multiaxial weave are preferable in that a carbon fiber reinforced composite material having high mechanical properties and a high carbon fiber deposition content can be obtained. Unidirectional weaving is a woven fabric (with a crimp structure) in which carbon fiber bundles are arranged parallel to each other in one direction as warp yarns, and weft yarns made of glass fibers or chemical fibers perpendicular to each other cross each other to form a woven structure, It consists of a warp consisting of a carbon fiber bundle, an auxiliary warp of glass fiber or chemical fiber arranged parallel to this, and a weft of glass fiber or chemical fiber arranged so as to be perpendicular thereto, and the auxiliary warp and the weft are mutually By crossing, a woven fabric having a so-called non-crimp structure in which the woven fabric is formed by holding the carbon fiber bundle in an almost unbent state can be used. The unidirectional crimp structure can improve the resin impregnation property because the bending becomes a flow path of the matrix resin, but the mechanical strength of the carbon fiber may be reduced by the bending. The non-crimp fabric has an effect that the compressive strength is kept high and the auxiliary yarn becomes a flow path of the matrix resin, and the impregnation property of the resin can be improved.

  Next, the molding material and the carbon fiber reinforced composite material according to the present invention will be described. A molding material according to the present invention is a composite of a sizing agent-coated carbon fiber as a molding substrate in the form of a woven fabric or braid described above and a thermosetting resin or thermoplastic resin as a matrix resin. It is.

  Examples of the thermosetting resin used in the molding material of the present invention include unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, melamine resins, urea resins, cyanate ester resins, and bismaleimide resins. Among them, it is preferable to use an epoxy resin because it has an advantage of excellent balance of mechanical properties and small curing shrinkage. For the purpose of improving toughness and the like, the thermosetting resin can contain a thermoplastic resin described later or an oligomer thereof.

  Examples of the thermoplastic resin used in the molding material of the present invention include “polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), liquid crystal polyester, and the like. Polyester resins: Polyethylene resins such as polyethylene (PE), polypropylene (PP), polybutylene, acid-modified polyethylene (m-PE), acid-modified polypropylene (m-PP), acid-modified polybutylene; polyoxymethylene (POM) Polyarylene sulfide resins such as polyamide (PA) and polyphenylene sulfide (PPS); polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PE) K), polyether nitrile (PEN); fluororesin such as polytetrafluoroethylene; crystalline resin such as liquid crystal polymer (LCP), “polystyrene (PS), acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS) Styrenic resins such as polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), unmodified or modified polyphenylene ether (PPE), polyimide (PI), polyamideimide (PAI), polyether Amorphous resins such as “imide (PEI), polysulfone (PSU), polyethersulfone, polyarylate (PAR)”; phenol resins, phenoxy resins, polystyrene elastomers, polyolefin elastomers, polyurethanes -Based elastomer, polyester-based elastomer, polyamide-based elastomer, polybutadiene-based elastomer, polyisoprene-based elastomer, various thermoplastic elastomers such as fluororesin and acrylonitrile-based elastomer, and at least one selected from these copolymers and modified products The thermoplastic resin is preferably used.

  When a thermosetting resin is used as the matrix resin, the molding material is reduced in viscosity by dissolving the matrix resin in a solvent such as methyl ethyl ketone or methanol, and the viscosity is reduced by heating with a wet method in which the base material for molding is impregnated, It can be produced by a hot melt method (dry method) for impregnating a molding substrate.

  The wet method is a method in which a molding base material in the form of a woven fabric or braided carbon fiber bundle is immersed in a matrix resin solution, and then the solvent is evaporated using a pull-up oven or the like. , A method of directly impregnating a base material for molding with a matrix resin whose viscosity has been reduced by heating, or a coating film prepared from the matrix resin is once placed on a release paper or the like, and then either side of the base material for molding or It is a method of impregnating a matrix resin into a molding substrate by stacking the film from one side and heating and pressing. The hot melt method is preferable because substantially no solvent remains in the molding material.

  After laminating the obtained molding material, a carbon fiber reinforced composite material is produced by a method of heating and curing the matrix resin while applying pressure to the laminate. As a method for applying heat and pressure, a press molding method, an autoclave molding method, a packing molding method, a wrapping tape method, an internal pressure molding method, a vacuum pressure molding, and the like are employed. Carbon fiber reinforced composite materials are obtained by impregnating a matrix resin directly into a molding substrate without using a molding material, followed by heat curing, such as a hand lay-up method, a resin injection molding method, and a resin transfer. -It can also be produced by a molding method such as a molding method. In these methods, it is preferable to prepare a resin by mixing two liquids of a matrix resin main component and a curing agent immediately before use.

  Further, the molding substrate of the present invention is preferably used in which a carbon fiber bundle is formed into a woven or braided shape, and a spacer resin different from the matrix resin is unevenly distributed on the molding substrate surface in the form. Is done. The spacer resin is bonded within a range of 1 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the woven or braided base material. The spacer resin may be adhered to the inside of the substrate, or may be unevenly distributed on the surface thereof.

  In the present specification, “unevenly distributed” means a state in which the spacer resin is present on the surface of 70% by volume or more, preferably 80% by volume or more, and more preferably 90% by volume or more of the spacer resin used. When the spacer resin is adhered to the base material within the above range, tackiness (adhesiveness) between the base materials when the base material for molding is laminated to obtain a preform can be imparted. Furthermore, it not only causes moderate stiffness in the base material, but also exhibits a form stabilizing effect of the base material such as preventing misalignment when the base material is a woven fabric, etc., and has excellent handling properties. A material is obtained.

  Further, in the carbon fiber reinforced composite material obtained by laminating a molding base material using a spacer resin, the spacer resin was particularly shocked by becoming a crack stopper, relieving residual stress during molding, etc. Sometimes damage between layers of the molding substrate can be suppressed, and an effect (high toughening effect) that excellent mechanical properties (especially CAI, tensile strength, compressive strength) can be achieved.

  Furthermore, when the spacer resin is unevenly distributed and bonded to the surface of the base material, when the base material is laminated, it becomes a spacer and a space can be secured between the fabrics (spacer effect). When it is subjected to injection molding, it becomes a flow path for the matrix resin, which not only facilitates impregnation, but also increases the speed and improves the productivity of the composite material. In addition, since the toughening effect is concentrated and manifested between the base layers of the composite material, an unexpected effect that the effect is manifested even higher (interlayer reinforcing effect) may be exhibited.

  It is preferable that the spacer resin is substantially unevenly distributed and adhered to the substrate surface. In this case, in the single-layer base material, it may be unevenly distributed on one side of the base material or may be unevenly distributed on both sides of the base material, but the spacer resin is bonded at a lower cost. In the case, the former is preferable, and the latter is preferable when it is not desired to use the front and back of the substrate properly. In the multilayer base material, the spacer resin may be bonded only to the surface layer, but it is preferable to bond the spacer resin to the surface of each layer because a higher effect is exhibited. The spacer resin is applied to the molding substrate in a molten state, and the spacer resin is frozen and pulverized, and is naturally dispersed as particles having an average particle diameter of about 1 to 500 μm while being lightweight on the substrate surface. You can do it. After the dispersion, by applying pressure while heating with a far infrared heater or the like, it is possible to produce a molding base material in which the spacer resin is unevenly distributed on the base material surface.

When the substrate is a unidirectional woven fabric or a bi-directional woven fabric, the basis weight is 50 to 500 g / m ² , more preferably 100 to 350 g from the viewpoint of impregnation of the matrix resin into the substrate and mechanical properties. / M ² , more preferably in the range of 150 to 250 g / m ² . The thickness is preferably in the range of 0.1 to 0.8 mm, more preferably 0.15 to 0.7 mm, and still more preferably 0.2 to 0.6 mm.

If the substrate is woven multi-axis, the basis weight 150~1500g / m ^2, more preferably 300~1000g / m ^2, more preferably in the range of 400 to 800 / m ^2. The reason why the basis weight may be larger than the unidirectional woven fabric is that, particularly when there is a stitch thread or the like in the thickness direction, the resin flow path in the thickness direction is secured, so that the impregnation becomes easier, This is because if the basis weight is small, the meaning of making a multilayer becomes dilute.

Since the spacer resin is applied to the base material, it is preferable that the base material has a cover factor of 90% or more in order to minimize the dropout and to maximize the characteristics of the carbon fiber itself. More preferably 97% or more, still more preferably 99% or more. With such a cover factor, there is no carbon fiber (in some cases, auxiliary yarn, stitch yarn, knot yarn, etc.) in the substrate in a unit area of 100 mm × 100 mm when the planar substrate is viewed from the perpendicular direction. It refers to the percentage of the opening (not covered), and is calculated by the cover factor (%) = total area of the opening (mm ² ) / 10000. For such an opening, image processing is performed based on an image optically captured by a CCD camera, a scanner, or the like, and a total area may be calculated.

  The melting point or flow start temperature of the spacer resin is preferably in the range of 50 to 150 ° C. from the viewpoint of the processing temperature for developing the tack when the molding base material is laminated. More preferably, it is 70-140 degreeC, More preferably, it exists in the range of 90-120 degreeC. Here, the melting point refers to the melting temperature of the resin measured by a differential scanning calorimeter (DSC), and the resin showing the melting point by DSC is based on the melting point. The resin that does not show a melting point is based on the flow start temperature measured from viscoelasticity measurement (Shimadzu flow tester CFT500D, heating rate 1.5 ° C./min).

  The spacer resin is not particularly limited as long as it is a resin that improves the handleability of the molding substrate and improves the mechanical properties of the carbon fiber reinforced composite material obtained by using the same, and is not limited to thermosetting resin and / or thermoplasticity. A resin can be appropriately selected and used.

  Examples of the thermosetting resin used as the spacer resin include epoxy, phenol, polybenzimidazole, benzoxazine, cyanate ester, unsaturated polyester, vinyl ester, urea, melamine, bismaleimide, polyimide, polyamideimide, and the like. It is possible to use a copolymer, a modified body, a resin blended with two or more kinds, a resin to which an elastomer, a rubber component, a curing agent, a curing accelerator, a catalyst, and the like are added.

  Examples of the thermoplastic resin used as the spacer resin include polyester, polyolefin, styrene resin, polyoxymethylene, polyamide, polyurethane, polyurea, polydicyclopentadiene, polycarbonate, polymethylene methacrylate, polyvinyl chloride, polyphenylene sulfide, polyphenylene ether, Polyetherimide, polysulfone, polyarylate, polyethersulfone, polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyarylate, polyethernitrile, polyimide, polyamideimide, phenol, phenoxy, polytetrafluoroethylene, etc. Fluorine-based resins and elastomers (preferably butadiene / acrylonitrile and its carboxylic acids). Is a modified amine, fluoroelastomer, polysiloxane elastomer), rubber (butadiene, styrene / butadiene, styrene / butadiene / styrene, styrene / isoprene / styrene, natural rubber, etc.), resin for RIM (eg polyamide 6, polyamide 12, Polyurethane, polyurea, including a catalyst that forms polydicyclopentadiene), cyclic oligomer (including a catalyst that forms a polycarbonate resin, polybutylene terephthalate resin, etc.) and the like, copolymers thereof, modified products, and the like Two or more kinds of blended resins can be used.

  When a thermosetting resin is used as the main component of the spacer resin, it is preferably at least one selected from epoxy, unsaturated polyester, and phenol, and of these, epoxy is particularly preferable. Use of an epoxy is preferable because not only the handling property of the substrate is excellent because of high adhesiveness but also high mechanical properties can be exhibited particularly when an epoxy resin is used as a matrix resin. When epoxy is the main component of the spacer resin, a curing agent, a curing catalyst, or the like may or may not be included, but the latter is preferable from the viewpoint of the life of the spacer resin. Even in the former case, if the curing agent or the curing catalyst has a high potential, it is not a big problem.

  When a thermoplastic resin is used as the main component of the spacer resin, it is preferably at least one selected from polyamide, polysulfone, polyethersulfone, polyetherimide, polyphenylene ether, polyimide, polyamideimide, and phenoxy. Of these, polyamide, polyetherimide, polyphenylene ether, polyether sulfone, and phenoxy are particularly preferable.

  Such a thermoplastic resin is a main component of the spacer resin, and the blending amount thereof is preferably in the range of 70 to 100% by mass. More preferably, it is 75-97 mass%, More preferably, it exists in the range of 80-95 mass%. If the blending amount is less than 70% by mass, it is not preferable because it is difficult to obtain a composite material having excellent mechanical properties, which is an object of the present invention. Here, when a thermoplastic resin is a main component, since the adhesiveness to the fabric and the adhesive processability may be inferior, it is preferable to add a small amount of a tackifier, a plasticizer and the like.

As a method of molding a carbon fiber reinforced composite material from a molding base material in which the spacer resin is unevenly distributed on the surface, for example, various molding methods such as injection molding (RTM, RFI, RIM, vacuum pressure molding, etc.) and press molding, A molding method combining them is exemplified. More preferable molding methods include injection molding with high productivity. Among them, RTM (for example, a molding method in which a resin is pressurized and injected into a cavity formed by a male mold and a female mold. Preferably, the cavity is decompressed. And vacuum injection (for example, either a male mold or a female mold and a bag formed of a bag material such as a film (for example, nylon film, silicon rubber)) A molding method in which a resin is injected with a differential pressure (preferably, a resin diffusion medium (media) is placed in a preform in a cavity to promote resin impregnation, and the media is separated from the composite material after molding). It is preferably used from the aspect of.
The resin used in the above RTM molding may be any resin that can react with the spacer resin. However, an epoxy resin that is relatively inexpensive, has a high degree of freedom in composition design, and can react with various functional groups is most suitable. It can be used suitably.

  Such an epoxy resin is a compound containing a plurality of epoxy groups in the molecule. For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2,2 ′ , 6,6'-tetramethyl-4,4'-biphenoldiglycidyl ether, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N , O-triglycidyl-4-amino-3-methylphenol, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N, N, N ′, N′-tetraglycidyl-4,4 ′ -Methylenedianiline, N, N, N ', N'-tetraglycidyl-2,2'-di Tyl-4,4′-methylenedianiline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (diglycidylaminomethyl) cyclohexane, ethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, vinylcyclohexene di Epoxide, 3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl, bis-3,4-epoxycyclohexylmethyl adipate 1,6-dihydroxynaphthalene diglycidyl ether, 9,9-bis (4-hydroxyphenyl) fluorene diglycidyl ether, tris (p-hydroxyphenyl) methane triglycidyl ether, tetrakis (p-hydroxyphenyl) ethane Tetraglycidyl ether, phenol novolak glycidyl ether, cresol novolac glycidyl ether, glycidyl ether of a condensation product of phenol and dicyclopentadiene, glycidyl ether of phenol aralkyl resin, triglycidyl isocyanurate, N-glycidyl phthalimide, 5-ethyl-1, 3-Diglycidyl-5-methylhydantoin, 1,3-diglycidyl-5,5-dimethylhydantoin, bisphenol A diglycidyl ether and tolylene Examples thereof include oxazolidone type epoxy resins obtained by addition of isocyanate.

  Such an epoxy resin is used in combination with a curing agent. Examples of such a curing agent include aliphatic polyamines, aromatic polyamines, dicyandiamides, polycarboxylic acids, polycarboxylic acid hydrazides, acid anhydrides, polymercaptans, polyphenols, and the like, and imidazoles and Lewis acid complexes. And catalytically acting curing agents such as onium salts.

  When a curing agent that performs such stoichiometric reaction is used, a curing accelerator that catalyzes the reaction, for example, imidazole, Lewis acid complex, onium salt, phosphine, and the like may be blended. The curing agent for the liquid thermosetting resin used in the RTM molding is preferably an aliphatic polyamine, an aromatic polyamine, an acid anhydride, or imidazole, and is particularly aromatic for the purpose of producing a structural material having excellent heat resistance. Amines are most preferably used as curing agents.

  Applications of the carbon fiber reinforced composite material of the present invention include, for example, personal information such as personal computers, displays, office automation equipment, mobile phones, personal digital assistants, facsimile machines, compact discs, portable MDs, portable radio cassettes, PDAs (electronic notebooks, etc.) Terminal), video camera, digital still camera, optical equipment, audio, air conditioner, lighting equipment, entertainment equipment, toy goods, other electrical appliances such as home appliances and internal members such as trays and chassis and their cases, Mechanical parts, building materials such as panels, motor parts, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, suspension parts, exhaust gas valves and other valves, fuel-related, exhaust and intake pipes, air Intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil Temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioning thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine base In, wiper motor related parts, distributor, starter switch, starter relay, transmission Wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, fuse connector, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest, horn Terminal, Step motor rotor, Lamp socket, Lamp reflector, Lamp housing, Brake piston, Noise shield, Radiator support, Spare tire cover, Seat shell, Solenoid bobbin, Engine oil filter, Ignition case, Under cover, Scuff plate, Pillar trim, Propeller Shaft, wheel, fender, fascia, bumper, bumper beam, bonnet, aero parts , Platforms, cowl louvers, roofs, instrument panels, spoilers and various modules, parts related to motorcycles, parts and skins, landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs, etc. Aircraft related parts, members and skins, windmill blades and the like. In particular, it is preferably used for aircraft members, windmill blades, automobile outer plates, casings of electronic devices, trays, chassis, and the like.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited by these Examples.
<Strand tensile strength and elastic modulus of carbon fiber bundle>
The strand tensile strength and strand elastic modulus of the carbon fiber bundle were determined according to the following procedure in accordance with the resin impregnated strand test method of JIS-R-7608 (2004). As the resin formulation, “Celoxide (registered trademark)” 2021P (manufactured by Daicel Chemical Industries) / 3 boron trifluoride monoethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) / Acetone = 100/3/4 (part by mass) is used. As curing conditions, normal pressure, temperature of 125 ° C., and time of 30 minutes were used. Ten strands of the carbon fiber bundle were measured, and the average value was defined as the strand tensile strength and the strand elastic modulus.

<Surface oxygen concentration of carbon fiber (O / C)>
The surface oxygen concentration (O / C) of the carbon fiber was determined by X-ray photoelectron spectroscopy according to the following procedure. First, the carbon fiber from which the dirt adhering to the surface with a solvent is removed is cut to about 20 mm and spread on a copper sample support. Next, the sample support is set in the sample chamber, and the inside of the sample chamber is kept at 1 × 10 ⁻⁸ Torr. Subsequently, AlKα ₁ and ₂ were used as an X-ray source, and measurement was performed with a photoelectron escape angle of 90 °. In addition, the kinetic energy value (KE) of the main peak of C _1s was adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area, _K.P. E. As a linear base line in the range of 1191 to 1205 eV. In addition, the O _1s peak area is _{expressed as K.I.} E. As a linear base line in the range of 947 to 959 eV. Here, the surface oxygen concentration is calculated as an atomic ratio by using a sensitivity correction value unique to the apparatus from the ratio of the O _1s peak area to the C _1s peak area. As the X-ray photoelectron spectroscopy apparatus, ESCA-1600 manufactured by ULVAC-PHI Co., Ltd. was used, and the sensitivity correction value unique to the apparatus was 2.33.

<Measurement method of sizing adhesion amount>
About 2 g of sizing-attached carbon fiber bundle was weighed (W1) (reading up to the fourth decimal place) and then placed in an electric furnace (capacity 120 cm ³ ) set at a temperature of 450 ° C. in a nitrogen stream of 50 ml / min for 15 minutes. Leave to allow the sizing agent to completely pyrolyze. Then, the carbon fiber bundle is transferred to a container in a dry nitrogen stream of 20 liters / minute and cooled for 15 minutes, and the carbon fiber bundle is weighed (W2) (reads up to the fourth decimal place), and the sizing adhesion amount is obtained by W1-W2. . A value obtained by converting this sizing adhesion amount into an amount with respect to 100 parts by mass of the carbon fiber bundle (rounded off to the third decimal place) was defined as a mass part of the adhering sizing agent. The measurement was performed twice, and the average value was defined as the mass part of the sizing agent.

(Reference Example 1) Fabrication of woven fabric using sizing agent-coated carbon fibers A sizing agent-coated carbon fiber bundle (density 1.8 g / cm ³ , 24,000 pieces) is used as warp yarn, and glass fiber ECE225 1/0 1Z (Nitto) A plain weave fabric in which sizing agent-coated carbon fiber bundles were substantially arranged in one direction was produced using weft yarn (manufactured by Bobo Co., Ltd.). The warp yarn density was 7.2 yarns / 25 mm, and the weft yarn density was 7.5 yarns / 25 mm. The carbon fiber basis weight of the woven fabric was 190 g / m ² .

Reference Example 2 Production of Liquid Thermosetting Resin The main agent and the curing agent were individually adjusted according to the following formulation, and these were mixed immediately before use to obtain a liquid thermosetting resin composition.
(Main ingredient)
"JER (registered trademark)" 630, manufactured by Mitsubishi Chemical Corporation: 10 parts by mass "jER (registered trademark)" 825, manufactured by Mitsubishi Chemical Corporation: 35 parts by mass-"Araldite (registered trademark)" MY721 ( Huntsman Advanced Materials): 40 parts by mass. GAN (Nippon Kayaku Co., Ltd. epoxy resin): 15 parts by mass (hardener component)
"Epicure (registered trademark)" W (aromatic polyamine manufactured by Mitsubishi Chemical Corporation): 27 parts by mass 3,3'-DAS (aromatic polyamine manufactured by Mitsui Chemicals): 7 parts by mass '-DDS (aromatic polyamine manufactured by Wakayama Seika Co., Ltd.): 4 parts by mass · TBC (t-butylcatechol manufactured by Ube Industries, Ltd.): 1 part by mass

Reference Example 3 Preparation of Preform Spacer Resin A resin or the like is mixed into a slurry according to the following formulation to make a slurry, and kneaded and cut at 200 ° C. by a twin screw extruder S-1 KRC kneader (manufactured by Kurimoto Steel Works). Thus, the preform spacer pellets of the present invention were obtained.
"Sumika Excel (registered trademark) (R)" PES5003P (a powder obtained by freeze-pulverizing polyethersulfone manufactured by Sumitomo Chemical Co., Ltd. Amorphous thermoplastic resin having a glass transition temperature of 230 ° C): 60 parts by mass “Epicoat (registered trademark)” 806 (epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.): 20 parts by mass. NC-3000 (epoxy resin manufactured by Nippon Kayaku Co., Ltd.): 10 parts. “Epicoat (registered trademark)” 630 (Epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.): 10 parts by mass The shear viscosity of the obtained spacer resin for preform was 350 Pa · s. The glass transition temperature was 75 ° C.
Next, the pellets are freeze-ground in a liquid nitrogen using a hammer mill (PULVERIZER, manufactured by Horikawa Micron Co., Ltd.), and then classified with a sieve having an opening size of 210 μm to obtain a binder composition for particulate preform. It was. The average particle size of the obtained particles was measured and found to be about 100 μm.

(Reference Example 4) Production of Reinforcing Fiber Substrate After the particulate spacer resin obtained in Reference Example 3 was sprayed on one side of the woven fabric made of the sizing agent-coated carbon fiber at a spraying amount of 30 g / m ² , the surface temperature was It heated using the far-red heater so that it might become 160 degreeC, and the reinforced fiber base material which adhered the binder composition for preforms was obtained. Even when the particle-adhering surface of the reinforcing fiber substrate was rubbed with a finger, the particles did not fall off.

Reference Example 5 Preparation of Preform The reinforcing fiber substrate obtained in Reference Example 4 was cut out, and the direction in which the orientation angle of the carbon fiber was 0 ° was used as a reference [+ 45 ° / 0 ° / −45 ° / 90 °. ], And this was repeated three times, and the substrates were bonded to each other at 0.1 MPa for 1 hour with a press bagged and heated to 80 ° C. A reform was formed.

Reference Example 6 Production of Carbon Fiber Reinforced Composite Material A preform obtained on a stainless steel plate provided with a release agent (“Daifree (registered trademark)”, manufactured by Daikin Industries, Ltd.) was placed on a peel ply ( Peel ply B-4444 (manufactured by Richmond Co., Ltd.) and a resin diffusion medium (TSX-400P, manufactured by Nippon Netron Co., Ltd.) are overlaid thereon, and a nylon film (VACPAK HS8171 6 / 66SHEETING, AIR CRAFTO PRODUCTS. INC) Is heated to 70 ° C. in a hot air oven, the inside of the preform is sucked with a vacuum pump so that the vacuum pressure is −0.1 MPa or less, and held for 60 minutes. The liquid thermosetting resin of Reference Example 2 maintained at 70 ° C. through the diffusion medium was injected.
After completion of the injection, the temperature was raised to 130 ° C. at 1.5 ° C. per minute, and then heated at 130 ° C. for 2 hours to be cured. Thereafter, the mold was removed and the carbon fiber reinforced composite material plate was taken out, heated in a hot air oven from 30 ° C. to 180 ° C. at 1.5 ° C. per minute, and heated at 180 ° C. for 2 hours to cure.

<Volume content Vf of reinforcing fiber>
The thickness of arbitrary three points of the carbon fiber reinforced composite material plate was measured to 0.01 mm using a micrometer, and the average value was used to calculate the thickness by the following method. The three points are points 30 mm inside from the edge of the carbon fiber reinforced composite material plate and sufficiently separated from each other.
Vf (%) = [FAW × PLY / (ρ × t)] / 10
FAW: basis weight of carbon fiber constituting the carbon fiber reinforced base material (g / m ² )
PLY: number of laminated carbon fiber reinforced substrates ρ: density of carbon fibers (g / cm ³ )
t: Thickness (cm) of carbon fiber reinforced composite material after curing

<Measurement of post-impact compressive strength of carbon fiber reinforced composites>
From the carbon fiber reinforced composite material plate, a rectangular test piece having a length of 152.4 mm and a width of 101.6 mm was cut out with the orientation direction of the carbon fiber being 0 ° as the longitudinal direction of the test piece, and JIS K 7089 ( 1996), a drop weight impact of 6.76 J per 1 mm thickness of the test piece was applied, and then the post-impact compressive strength was measured according to JIS K 7089 (1996). The n number was set to 5 for the same level.

  The materials and components used in each example and each comparative example are as follows.

-(A1) component: A-1 to A-7
A-1: “jER (registered trademark)” 152 (manufactured by Mitsubishi Chemical Corporation)
Phenol novolac glycidyl ether epoxy equivalent: 175 g / mol, epoxy group number: 3
A-2: “EPICLON (registered trademark)” N660 (manufactured by DIC Corporation)
Cresol novolak glycidyl ether Epoxy equivalent: 206 g / mol, Epoxy group number: 3
A-3: “Araldite (registered trademark)” MY721 (manufactured by Huntsman Advanced Materials)
N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane Epoxy equivalent: 113 g / mol, number of epoxy groups: 4
A-4: “jER (registered trademark)” 828 (manufactured by Mitsubishi Chemical Corporation)
Diglycidyl ether of bisphenol A Epoxy equivalent: 189 g / mol, Number of epoxy groups: 2
A-5: “jER (registered trademark)” 1001 (manufactured by Mitsubishi Chemical Corporation)
Diglycidyl ether of bisphenol A Epoxy equivalent: 475 g / mol, Number of epoxy groups: 2
A-6: “Denacol (registered trademark)” EX-810 (manufactured by Nagase ChemteX Corporation)
Diglycidyl ether of ethylene glycol Epoxy equivalent: 113 g / mol, Number of epoxy groups: 2
A-7: TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.)
Tetraglycidyl metaxylenediamine Epoxy equivalent: 100 g / mol, Number of epoxy groups: 4

・ Applicable to both (A1) component and (A2) component: A-8
A-8: “Denacol (registered trademark)” EX-611 (manufactured by Nagase ChemteX Corporation)
Sorbitol polyglycidyl ether epoxy equivalent: 167 g / mol, number of epoxy groups: 4
Number of hydroxyl groups: 2

-(A2) component: A-9, A-10
A-9: “Denacol (registered trademark)” EX-731 (manufactured by Nagase ChemteX Corporation)
N-glycidyl phthalimide epoxy equivalent: 216 g / mol, number of epoxy groups: 1
Number of imide groups: 1
A-10: “Adeka Resin (registered trademark)” EPU-6 (manufactured by ADEKA Corporation)
Urethane modified epoxy Epoxy equivalent: 250 g / mol, Epoxy group number: 1 or more Urethane group: 1 or more

-(B1) component: B-1 to B-13, B-25 to B-27
B-1: “DBU (registered trademark)” (manufactured by Sun Apro Co., Ltd.)
1,8-diazabicyclo [5,4,0] -7-undecene, molecular weight: 152, corresponding to formula (III) B-2: tributylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 185.4, formula Applicable to (VIII) B-3: N, N-dimethylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 135.21, applicable to formula (VIII) B-4: 1,8-bis (dimethylamino) ) Naphthalene (Aldrich)
Another name: proton sponge, molecular weight: 214.31, corresponding to formula (IV) B-5: 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Alias: DMP-30, molecular weight: 265.39, corresponding to formula (V) B-6: DBN (manufactured by San Apro Co., Ltd.), molecular weight: 124, corresponding to formula (III) 1,5-diazabicyclo [4,3 , 0] -5-nonene B-7: imidazole compound 1-benzyl-imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 158.2, corresponding to formula (III) B-8: U-CAT SA1 ( (San Apro Co., Ltd.)
DBU-phenol salt, molecular weight: 246.11, corresponding to formula (III) B-9: U-CAT SA102 (manufactured by San Apro Co., Ltd.)
DBU-octylate: molecular weight: 296.45, corresponding to formula (III) B-10: U-CAT SA506 (manufactured by San Apro Co., Ltd.)
DBU-p-toluenesulfonate, molecular weight: 324.44, corresponding to formula (III) B-11: N-ethylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 115.17, formula (VII) Applicable B-12: 2,6-lutidine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 107.15, applicable to formula (VI) B-13: 4-pyridinemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), Molecular weight: 109.13, applicable to formula (VI) B-25: Triisopropanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 191.27, applicable to formula (VIII) B-26: Triethanolamine (Tokyo) Kasei Kogyo Co., Ltd.), molecular weight: 149.19, corresponding to formula (VIII) B-27: N, N-diisopropylethylamine (Tokyo Kasei Kogyo Co., Ltd.), molecular weight: 129.24, formula (VIII) In This

-(B2) component: B-14 to B-20
B-14: Benzyltrimethylammonium bromide (R ₁ has 7 carbon atoms, R _{2 to} R ₄ each have 1 carbon atom, anion site is bromide anion, manufactured by Tokyo Chemical Industry Co., Ltd., corresponds to formula (I))
B-15: Tetrabutylammonium bromide (R _{1 to} R ₄ each have 4 carbon atoms, the anion portion is a bromide anion, manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to formula (I))
B-16: Trimethyloctadecyl ammonium bromide (R ₁ has 18 carbon atoms, R _{2 to} R ₄ each have 1 carbon atom, anion sites are bromide anions, manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to formula (I))
B-17: (2-methoxyethoxymethyl) triethylammonium chloride (R ₁ has 4 carbon atoms, R _{2 to} R ₄ have 2 carbon atoms, anion sites are chloride anions, manufactured by Tokyo Chemical Industry Co., Ltd., Corresponds to formula (I)
B-18: (2-acetoxyethyl) trimethylammonium chloride (R ₁ has 4 carbon atoms, R _{2 to} R ₄ each have 1 carbon atom, anion sites are chloride anions, manufactured by Tokyo Chemical Industry Co., Ltd., formula (Applicable to (I))
B-19: (2-hydroxyethyl) trimethylammonium bromide (R ₁ has 2 carbon atoms, R _{2 to} R ₄ each have 1 carbon atom, anion sites are bromide anion, manufactured by Tokyo Chemical Industry Co., Ltd., formula ( Corresponds to I)
B-20: 1-hexadecylpyridinium chloride (R ₅ has 16 carbon atoms, R ₆ and R ₇ are each a hydrogen atom, anion sites are chloride anions, manufactured by Tokyo Chemical Industry Co., Ltd., formula (II) )

-(B3) component: B-21 to B-24
B-21: Tetrabutylphosphonium bromide (R _{25 to} R ₂₈ each have 4 carbon atoms, the anion portion is bromide anion, manufactured by Tokyo Chemical Industry Co., Ltd.) Molecular weight: 339, corresponding to formula (XI) B-22: Tetra Phenylphosphonium bromide (R _{25 to} R ₂₈ each have 6 carbon atoms, anion site is bromide anion, manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 419, corresponding to formula (XI) B-23: tributylphosphine (R ₂₉ -R ₃₁ each having 4 carbon atoms, manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 202, corresponding to formula (XII) B-24: triphenylphosphine (R ₂₉ -R ₃₁ having 6 carbon atoms each, Tokyo Kasei Kogyo Co., Ltd.), Molecular weight: 262

-(C) component (other components): C-1 to C-2
C-1: “Denacol (registered trademark)” EX-141 (manufactured by Nagase ChemteX Corporation)
Phenyl glycidyl ether epoxy equivalent: 151 g / mol, number of epoxy groups: 1
C-2: Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 116

Example 1
The present embodiment includes the following steps I to III.
-Step I: Process for producing carbon fiber as raw material A copolymer composed of 99 mol% of allylonitrile and 1 mol% of itaconic acid is spun and fired, the total number of filaments is 24,000, and the total fineness is 1. Carbon fiber having 1,000 tex, specific gravity of 1.8, strand tensile strength of 6.2 GPa and strand tensile modulus of 300 GPa was obtained. Subsequently, the carbon fiber was subjected to an electrolytic surface treatment using an aqueous solution of ammonium hydrogen carbonate having a concentration of 0.1 mol / l as an electrolytic solution at an electric charge of 100 coulomb per 1 g of the carbon fiber. The carbon fiber subjected to the electrolytic surface treatment was subsequently washed with water and dried in heated air at a temperature of 150 ° C. to obtain a carbon fiber as a raw material. At this time, the surface oxygen concentration O / C was 0.20. This was designated as carbon fiber A.

Step II: A step of attaching a sizing agent to carbon fibers The above (A-1) and (B-1) are mixed at a mass ratio of 100: 1, and acetone is further mixed, so that the sizing agent is uniform. An acetone solution of about 1% by mass dissolved in was obtained. Using an acetone solution of this sizing agent, the sizing agent was applied to the surface-treated carbon fiber by an immersion method, and then heat treated at a temperature of 210 ° C. for 90 seconds to obtain a sizing agent-coated carbon fiber bundle. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.

Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, it was a high value of 285 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Table 1.

(Examples 2 to 5)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of attaching sizing agent to carbon fiber As shown in Table 1, the mass ratio of (A-1) and (B-1) was changed in the range of 100: 3 to 100: 20. Except for the above, a sizing agent-coated carbon fiber was obtained in the same manner as in Example 1. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, it was a high value of 270 to 296 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Table 1.

(Comparative Example 1)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
Step II: Step of attaching sizing agent to carbon fiber Sizing agent-coated carbon in the same manner as in Example 1 except that only (A-1) was used in Step II of Example 1. Fiber was obtained. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength after impact (CAI), it was a low value of 232 MPa. This indicates that the adhesion between the carbon fiber and the matrix resin is poor. The results are shown in Table 1.

(Comparative Example 2)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of attaching sizing agent to carbon fiber In Step II of Example 1, except that the mass ratio of (A-1) and (B-1) was changed to 100: 30, Sizing agent-coated carbon fibers were obtained in the same manner as in Example 1. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength after impact (CAI), it was a low value of 237 MPa. This indicates that the adhesion between the carbon fiber and the matrix resin is poor. The results are shown in Table 1.

(Example 6) to (Example 15)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of attaching sizing agent to carbon fiber As shown in Table 2, (A-1) to (A-10) as components (A) and (B-10) as components (B) The mixture was mixed at a mass ratio of 100: 3 and further mixed with acetone to obtain an acetone solution of about 1% by mass in which the sizing agent was uniformly dissolved. Using this acetone solution of the sizing agent, the sizing agent was applied to the surface-treated carbon fiber by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 180 seconds to obtain a sizing agent-coated carbon fiber. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, it was a high value of 255 to 293 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Table 2.

(Comparative Example 3) to (Comparative Example 7)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
Step II: Step of attaching sizing agent to carbon fiber As shown in Table 2, a sizing agent-coated carbon fiber was obtained in the same manner as in Example 1 except that the sizing agent component was changed. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the post-impact compressive strength (CAI), it was a low value of 225 to 235 MPa. This indicates that the adhesion between the carbon fiber and the matrix resin is poor. The results are shown in Table 2.

(Example 16) to (Example 41)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
Step II: Step of attaching sizing agent to carbon fiber As shown in Tables 3-1 and 3-2, (A) as component (A-2), (B) as component (B-1) -(B-9) and (B-11)-(B-27) are mixed at a mass ratio of 100: 3, and further acetone is mixed to obtain an acetone solution of about 1% by mass in which the sizing agent is uniformly dissolved. It was. Using this acetone solution of the sizing agent, the sizing agent was applied to the surface-treated carbon fiber by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 180 seconds to obtain a sizing agent-coated carbon fiber. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, it was a high value of 251 to 298 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Tables 3-1 and 3-2.

(Comparative Example 8)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
Step II: Step of attaching sizing agent to carbon fiber As shown in Table 3-2, the sizing agent-coated carbon fiber was prepared in the same manner as in Example 1 except that only (A-2) was used. Obtained. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, the value was as low as 230 MPa. This indicates that the adhesion between the carbon fiber and the matrix resin is poor. The results are shown in Table 3-2.

(Example 42) to (Example 44)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of attaching sizing agent to carbon fiber As shown in Table 4, (A-1) as component (A), (B-1) as component (B-1), (B-17), (B-22) was mixed at a mass ratio of 100: 3, and acetone was further mixed to obtain an acetone solution of about 1% by mass in which the sizing agent was uniformly dissolved. Using this acetone solution of the sizing agent, the sizing agent was applied to the surface-treated carbon fiber by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 180 seconds to obtain a sizing agent-coated carbon fiber. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the post-impact compressive strength (CAI), it was as high as 267 to 299 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Table 4.

(Example 45) to (Example 47)
-Step I: Step of producing carbon fiber as raw material Implemented except that sulfuric acid aqueous solution having a concentration of 0.05 mol / l was used as the electrolytic solution, and the amount of electricity was subjected to electrolytic surface treatment at 20 coulomb per gram of carbon fiber. Same as Example 1. At this time, the surface oxygen concentration O / C was 0.20. This was designated as carbon fiber B.
-Step II: Step of attaching sizing agent to carbon fiber As shown in Table 4, (A-1) as component (A), (B-1) as component (B-1), (B-17), (B-22) was mixed at a mass ratio of 100: 3, and acetone was further mixed to obtain an acetone solution of about 1% by mass in which the sizing agent was uniformly dissolved. Using this acetone solution of the sizing agent, the sizing agent was applied to the surface-treated carbon fiber by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 180 seconds to obtain a sizing agent-coated carbon fiber. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, it was a high value of 255 to 279 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Table 4.

(Example 48) to (Example 50)
-Step I: Step of producing carbon fiber as a raw material The carbon fiber B obtained in Example 45 was immersed in an aqueous solution of tetraethylammonium hydroxide (pH = 14) and pulled up while being vibrated with ultrasonic waves. At this time, the surface oxygen concentration O / C was 0.17. This was designated as carbon fiber C.
-Step II: Step of attaching sizing agent to carbon fiber As shown in Table 4, (A-1) as component (A), (B-1) as component (B-1), (B-17), (B-22) was mixed at a mass ratio of 100: 3, and acetone was further mixed to obtain an acetone solution of about 1% by mass in which the sizing agent was uniformly dissolved. Using this acetone solution of the sizing agent, the sizing agent was applied to the surface-treated carbon fiber by a dipping method, followed by heat treatment at a temperature of 210 ° C. for 180 seconds to obtain a sizing agent-coated carbon fiber. The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength (CAI) after impact, it was a high value of 266 to 295 MPa. This has shown that the adhesiveness of carbon fiber and matrix resin is favorable. The results are shown in Table 4.
As described above, it can be seen that the mechanical properties when carbon fiber A is used are superior to those when carbon fiber B is used. Further, it is understood that the carbon fiber B is immersed in a tetraethylammonium hydroxide aqueous solution (pH = 14) and the carbon fiber C pulled up while being vibrated with ultrasonic waves has the same mechanical characteristics as the carbon fiber A. .

(Comparative Example 9)
-Step I: Step of producing carbon fiber as raw material The same procedure as in Example 45 was performed.
-Step II: Step of attaching sizing agent to carbon fiber As shown in Table 4, a sizing agent-coated carbon fiber was obtained in the same manner as in Example 45 except that only (A-1) was used. . The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength after impact (CAI), it was a low value of 222 MPa. This indicates that the adhesion between the carbon fiber and the matrix resin is poor. The results are shown in Table 4.

(Comparative Example 10)
-Step I: Step of producing carbon fiber as raw material The same procedure as in Example 48 was performed.
Step II: Step of attaching sizing agent to carbon fiber As shown in Table 4, a sizing agent-coated carbon fiber was obtained in the same manner as in Example 48 except that only (A-1) was used. . The adhesion amount of the sizing agent was adjusted to 1 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Production to Carbon Fiber Reinforced Composite Material to Evaluation Carbon fiber reinforced composite materials were produced according to Reference Examples 1 to 6. Vf of the obtained carbon fiber reinforced composite material was 58%. As a result of evaluating the compressive strength after impact (CAI), it was a low value of 233 MPa. This indicates that the adhesion between the carbon fiber and the matrix resin is poor. The results are shown in Table 4.

  As described above, the molding substrate, molding material, and carbon fiber reinforced composite material of the present invention are lightweight, yet have excellent strength and elastic modulus. Therefore, aircraft members, spacecraft members, automobile members, ship members, and civil engineering buildings. It can be suitably used in many fields such as materials and sports equipment.

Claims (16)

A molding base material using a carbon fiber to which a sizing agent containing the following components (A) and (B) is applied, the form of which is a woven fabric or braided string.
Component (A): Epoxy compound (A1) having two or more epoxy groups, and / or one or more epoxy groups, a hydroxyl group, an amide group, an imide group, a urethane group, a urea group, a sulfonyl group, and a sulfo group Epoxy compound (A2) having at least one functional group selected from
Component (B): 0.1 to 25 parts by mass of at least one reaction accelerator selected from the group consisting of the following [a], [b] and [c] with respect to 100 parts by mass of component (A)
[A] A tertiary amine compound and / or a tertiary amine salt (B1) having a molecular weight of 100 g / mol or more, which is used as at least the component (B)
[B] At least the following general formula (I) used as component (B)

(Wherein R _{1 to} R ₄ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- Optionally substituted by O-, -O-CO- or -CO-O-), or general formula (II)

(In the formula, R ₅ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group represents —O—, — R ₆ and R ₇ each independently represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and CH ₂ group in the hydrocarbon group may be substituted by O—CO— or —CO—O—. May be substituted by —O—, —O—CO— or —CO—O—.) A quaternary ammonium salt (B2) having a cation moiety
[C] Quaternary phosphonium salt and / or phosphine compound (B3) used as at least component (B) The tertiary amine compound and / or tertiary amine salt having a molecular weight of 100 g / mol or more in the above [a] is represented by the following general formula (III)

(In the formula, R ₈ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group represents —O—, —O, R ₉ may be any one of an alkylene group having 2 to 22 carbon atoms, an alkenylene group having 2 to 22 carbon atoms, or an alkynylene group having 2 to 22 carbon atoms, which may be substituted with —CO— or —CO—O—. R ₁₀ represents hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is —O— , -O-CO- or -CO-O-, or R ₈ and R ₁₀ may combine to form an alkylene group having 2 to 11 carbon atoms), a general formula ( IV)

(In the formula, each of R _{11 to} R ₁₄ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- Optionally substituted by O-, -O-CO- or -CO-O-), general formula (V)

(Wherein R _{15 to} R ₂₀ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O-, -O-CO- or -CO-O- R ₂₁ represents a hydroxyl group or a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group has a hydroxyl group. And the CH ₂ group in the hydrocarbon group may be substituted by —O—, —O—CO— or —CO—O—), the general formula (VI)

(Wherein R _{22 to} R ₂₄ each represent a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may have a hydroxyl group), general formula (VII)

(Wherein R ₂₅ represents a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may have a hydroxyl group), or general formula (VIII)

(In the formula, each of R _{26 to} R ₂₈ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O—, —O—CO— or —CO—O—, and any one of R _{26 to} R _{28 represented} by the following general formula (IX) or (X) The base material for molding according to claim 1, wherein the base material has a branched structure of (1) and contains at least one hydroxyl group.

(Wherein R ₂₉ and R ₃₀ each represent a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- It may be substituted by O-, -O-CO- or -CO-O-, provided that the total number of carbon atoms of R ₂₉ and R ₃₀ is 21 or less.)

(Wherein R _{31 to} R ₃₃ each represent a hydroxyl group or a hydrocarbon group having 1 to 19 carbon atoms, the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is , -O-, -O-CO- or -CO-O-, provided that the total number of carbon atoms of R ₃₁ , R ₃₂ and R ₃₃ is 21 or less.)   The compound represented by the general formula (III) is 1,5-diazabicyclo [4,3,0] -5-nonene or a salt thereof, or 1,8-diazabicyclo [5,4,0] -7-undecene or The base material for molding according to claim 2, wherein the base material is a salt thereof.   The molding substrate according to claim 2, wherein the compound represented by the general formula (VIII) has at least two or more branched structures.   The molding substrate according to claim 2 or 4, wherein the compound represented by the general formula (VIII) is triisopropanolamine or a salt thereof. In the general formula (I) of [b], R ₃ and R ₄ each represent a hydrocarbon group having 2 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the hydrocarbon group The molding substrate according to claim 1, wherein the CH ₂ group therein may be substituted by —O—, —O—CO— or —CO—O—.   The base material for molding according to claim 1 or 6, wherein an anion portion of the quaternary ammonium salt having a cation portion (B2) of [b] is a halogen ion. The (B3) quaternary phosphonium salt and / or phosphine compound of the above [c] is represented by the following general formula (XI)

(In the formula, each of R _{34 to} R ₃₇ represents a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- A quaternary phosphonium salt having a cation moiety represented by the formula (XII), which may be substituted by O—, —O—CO— or —CO—O—

(Wherein R _{38 to} R ₄₀ each represent a hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a hydroxyl group, and the CH ₂ group in the hydrocarbon group is- The molding material according to claim 1, wherein the molding material is one or more selected from phosphine compounds represented by O-, -O-CO- or -CO-O-). Base material.   (A) The epoxy equivalent of a component is less than 360 g / mol, The base material for shaping | molding in any one of Claims 1-8 characterized by the above-mentioned.   (A) The base material for shaping | molding in any one of Claims 1-9 whose (A) component is an epoxy compound which has a 3 or more epoxy group.   (A) Component contains an aromatic ring in a molecule | numerator, The base material for shaping | molding in any one of Claims 1-10 characterized by the above-mentioned.   The molding substrate according to any one of claims 1 to 11, wherein the component (A1) is any one of a phenol novolac epoxy resin, a cresol novolac epoxy resin, and tetraglycidyldiaminodiphenylmethane.   The substrate for molding according to any one of claims 1 to 12, wherein the surface oxygen concentration O / C measured by X-ray photoelectron spectroscopy of the carbon fiber is 0.05 to 0.5. .   The carbon fiber is one that has been subjected to liquid phase electrolytic oxidation in an alkaline electrolytic solution or liquid phase electrolytic oxidation in an acidic electrolytic solution, and subsequently washed with an alkaline aqueous solution. The base material for shaping | molding in any one of 1-13.   A molding material comprising a molding substrate according to any one of claims 1 to 14 and a thermosetting resin or a thermoplastic resin. A carbon fiber reinforced composite material obtained by molding the molding material according to claim 15.