JP5533849B2 - Molding materials and carbon fiber reinforced composite materials - Google Patents

Description

  The present invention relates to a molding material and a 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 the carbon fiber has been performed for the purpose of improving the impregnation property of the matrix resin into the carbon fiber.

  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. Although there is no detailed description of the adhesion improvement mechanism in this proposal, 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

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

  The inventors have (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 at a specific ratio. When the sizing agent containing is applied to carbon fiber and heat-treated at a specific temperature, the adhesion between the carbon fiber and the thermoplastic resin can be improved, which can improve the mechanical properties of the molding material and carbon fiber reinforced composite material. The present invention has been conceived.

  That is, the present invention is a molding material having a columnar shape composed of at least the following components (A) and (B), carbon fibers and a thermoplastic resin, and the carbon fibers are arranged substantially parallel to the axial direction, The length of the carbon fiber is substantially the same as the length of the molding material.

  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)

  Moreover, according to the preferable aspect of the molding material of this invention, 0.001-0.3 mass part is contained in the said invention with respect to 100 mass parts of carbon fiber in (B) component, It is characterized by the above-mentioned.

  According to a preferred embodiment of the molding material 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. 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）

(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- 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 embodiment of the molding material 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 salt thereof, or 1,8-diazabicyclo [5,4,0] -7-undecene or a salt thereof.

  According to a preferred aspect of the molding material of the present invention, in the above invention, the compound represented by the general formula (VIII) has at least two or more branched structures.

  According to a preferred aspect of the molding material 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 aspect of the molding material of the present invention, in the above invention, in the general formula (I) of [b], R ₃ and R ₄ each represent 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—. And

  Moreover, according to a preferred aspect of the molding material 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 material 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 molding material 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 molding material 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.

  In addition, according to a preferred aspect of the molding material of the present invention, in the above-described invention, the component (A) contains an aromatic ring in the molecule.

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

  According to a preferred aspect of the molding material of the present invention, in the above invention, the thermoplastic resin is a polyarylene sulfide resin, a polyether ether ketone resin, a polyphenylene ether resin, a polyoxymethylene resin, a polyamide resin, a polyester resin, It is at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a styrene resin, and a polyolefin resin.

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

  Moreover, according to the preferable aspect of the molding material of this invention, in the said invention, the sizing agent which contains (A) component and (B) component is 0.1-10 mass parts with respect to 100 mass parts of carbon fibers. It comprises 1 to 80% by mass of sizing agent-coated carbon fibers and 20 to 99% by mass of a thermoplastic resin to be adhered.

  Further, according to a preferred aspect of the molding material of the present invention, in the above invention, after the carbon fiber is subjected to liquid phase electrolytic oxidation in an alkaline electrolytic solution or liquid phase electrolytic oxidized in an acidic electrolytic solution, Subsequently, it is washed with an alkaline aqueous solution.

  According to a preferred aspect of the molding material of the present invention, in the above invention, the structure B mainly composed of the carbon fibers is a core structure, and the structure A mainly composed of the thermoplastic resin is a sheath structure. The structure B has a core-sheath structure in which the periphery of the structure B is covered with the structure A.

  According to a preferred aspect of the molding material of the present invention, in the above invention, the length of the columnar molding material is 1 to 50 mm.

  Moreover, according to a preferred aspect of the molding material of the present invention, in the above invention, the molding material is a long fiber pellet.

  Further, according to a preferred aspect of the molding material of the present invention, in the above invention, the thermoplastic resin is a polyarylene sulfide resin, and the component (C) has a [d] mass average molecular weight of 10,000 or more. And 0.1 to 100 parts by mass of polyarylene sulfide having a dispersity represented by mass average molecular weight / number average molecular weight of 2.5 or less with respect to 100 parts by mass of carbon fiber.

  Further, according to a preferred aspect of the molding material of the present invention, in the above invention, the thermoplastic resin is a polyamide resin, and (e) a phenol-based polymer is used as the component (C), and 100 masses of carbon fiber. 0.1-100 mass parts is contained with respect to a part.

  Further, according to a preferred aspect of the molding material of the present invention, in the above invention, the thermoplastic resin is a polyolefin resin, and as the component (C), [f] terpene resin is 100 parts by mass of carbon fiber. It is characterized by including 0.1-100 mass parts with respect to this.

  Further, according to a preferred aspect of the molding material of the present invention, in the above invention, the thermoplastic resin is a polyolefin resin, and as the component (C), [g] a first propylene resin and [ h] 0.1 to 100 parts by mass of a mixture of the second propylene resin having an acyl group in the side chain with respect to 100 parts by mass of the carbon fiber.

  Further, according to a preferred aspect of the molding material of the present invention, in the above invention, a part or all of the component (C) is impregnated in carbon fiber.

  Moreover, according to the preferable aspect of the carbon fiber reinforced composite material of this invention, it shape | molds the molding material in any one of said, 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 material and a carbon fiber reinforced composite material having excellent adhesion to a thermoplastic resin can be obtained.

FIG. 1 is a perspective view showing an example of a molding material according to an embodiment of the present invention. FIG. 2 is a perspective view showing another example of the molding material according to the embodiment of the present invention.

  Hereinafter, in more detail, the molding material concerning this invention and the form for implementing the carbon fiber reinforced composite material formed by shape | molding this molding material are demonstrated. The present invention is a columnar molding material composed of a carbon fiber and a thermoplastic resin to which a sizing agent containing the following components (A) and (B) is applied, and the carbon fiber is substantially in the axial direction. The carbon fibers are arranged in parallel, and the length of the carbon fibers is substantially the same as the length of the molding material. 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, regarding the relationship with the thermoplastic resin, (A1) and (A2) will be described as follows.

  In the case of (A1), the remaining epoxy group not participating in the covalent bond with the carbon fiber used in the present invention reacts with the thermoplastic resin-containing functional group to form a covalent bond, or forms a hydrogen bond. Conceivable. Moreover, it is preferable that the structure of (A1) contains one or more unsaturated groups. When the thermoplastic resin is a radical polymerization resin such as polyethylene or polypropylene, the unsaturated group and the thermoplastic of (A1). It is possible for the unsaturated group of the resin to undergo a radical reaction to form a strong interface.

  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 thermoplastic resin. If the thermoplastic resin is polyamide, polyester and acid-modified polyolefin, the hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group of (A2), and these thermoplastic resins It is considered that a strong interface can be formed by the interaction with the contained amide group, ester group, acid anhydride group, carboxyl group such as terminal, hydroxyl group and amino group.

  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 component (B) is preferably 0.001 to 0.3 parts by mass, more preferably 0.005 to 0.2 parts by mass, and still more preferably 0 to 100 parts by mass of the carbon fiber. It is preferable to contain 0.01-0.1 mass part. When component (B) is 0.001 to 0.3 parts by mass with respect to 100 parts by mass of carbon fiber, the reaction between oxygen-containing functional groups such as carboxyl groups and hydroxyl groups of carbon fiber and (A) epoxy compound is accelerated. As a result, the adhesion improvement effect is increased.

  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 high density, and the adhesion between the carbon fiber and the thermoplastic 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 thermoplastic 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 thermoplastic 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 carbon fiber reinforced composite material composed of carbon fibers and a thermoplastic 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 characteristics different from those of the thermoplastic 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 thermoplastic resin is improved, and the 0 ° tensile strength of the carbon fiber reinforced composite material And other 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 thermoplastic resin, the fiber reinforced composite Improve mechanical properties such as 0 ° tensile strength of the material. 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. Specific examples include “Denacol (registered trademark)” EX-731 (manufactured by Nagase ChemteX Corporation).

  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 can be mentioned. 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 covalent bond formation between the (A) 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 thermoplastic resin is improved. It becomes insufficient. 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 thermoplastic 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)

(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- 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 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. 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 covalent bond formation between the (A) 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 thermoplastic resin is improved. It becomes insufficient. 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 thermoplastic 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. 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.

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, the covalent bond formation between the (A) 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 thermoplastic resin is improved. It becomes insufficient. On the other hand, if 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 thermoplastic 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 an oxygen-containing functional group such as a carboxyl group or a hydroxyl group originally contained in the carbon fiber surface or introduced by oxidation treatment, It has been found that the adhesion 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 sizing agent is attached in an amount of 0.1 part by mass or more, when carbon fiber is used as a molding material, it can withstand friction caused by a metal guide that passes therethrough, fuzz generation is suppressed, and the carbon fiber sheet is smooth. Excellent quality and quality. On the other hand, if the sizing agent adhesion amount is 10 parts by mass or less, the composite material obtained by impregnating the inside of the carbon fiber bundle with a thermoplastic resin such as an epoxy resin without being hindered by the sizing agent film around the carbon fiber bundle Generation of voids is suppressed, and 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 the adhesion to the thermoplastic 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 thermoplastic 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, the carbon fiber is subjected to electrolytic treatment 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 in} 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 thermoplastic 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. When the heat treatment condition is less than 160 ° C. and / or less than 30 seconds, the formation of a covalent bond 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 thermoplastic resin The adhesiveness of the 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 thermoplastic resin Adhesiveness with 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 thermoplastic 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 an X-ray source. The chamber is kept at 1 × 10 ⁻⁸ Torr. The kinetic energy value (KE) of the C _1s main peak is adjusted 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.

  Next, the molding material and the carbon fiber reinforced composite material according to the present invention will be described. The molding material concerning this invention is comprised from the above-mentioned sizing agent application | coating carbon fiber and a thermoplastic resin. As shown in FIG. 1, the molding material 1 of the present invention has a cylindrical shape, and a plurality of carbon fibers 2 are arranged substantially parallel to the axial direction of the cylinder, and the periphery of the carbon fibers is covered with a thermoplastic resin 3. It has been broken. That is, the carbon fiber 2 forms a cylindrical core structure, and the thermoplastic resin 3 forms a sheath structure that covers the core structure made of the carbon fiber 2. If the molding material 1 of this invention comprises a core-sheath structure with the carbon fiber 2 and the thermoplastic resin 3, it does not ask | require the shape, such as columnar shape, prismatic column shape, elliptical column shape. In the present specification, “arranged substantially in parallel” means a state in which the long axis of the carbon fiber and the long axis of the molding material 1 are oriented in the same direction. The angle deviation is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less.

  Moreover, in the molding material 1 of this invention, it is preferable that it is a long fiber pellet in which the length of carbon fiber and the length L of a molding material are substantially the same. In the present specification, “substantially the same length” means that in the pellet-shaped molding material 1, the carbon fibers 2 are cut in the middle of the pellet, or significantly longer than the total length of the molding material 1. It means that the short carbon fiber 2 is not substantially contained. In particular, it is not necessary to limit the amount of carbon fibers shorter than the length L of the molding material 1, but the content of carbon fibers having a length of 50% or less of the length L of the molding material 1 is 30% by mass or less. In some cases, it is evaluated that a carbon fiber bundle significantly shorter than the entire length of the molding material 1 is not substantially contained. Furthermore, the content of carbon fibers having a length of 50% or less of the total length of the molding material 1 is preferably 20% by mass or less. The total length of the molding material 1 is the length L in the carbon fiber orientation direction in the molding material 1. Since the carbon fiber 2 has a length equivalent to that of the molding material 1, the carbon fiber length in the molded product can be increased, so that excellent mechanical properties can be obtained.

  The molding material of the present invention is preferably used after being cut to a length in the range of 1 to 50 mm. By adjusting to the above length, the fluidity and handleability during molding can be sufficiently enhanced. Further, the molding material of the present invention can be used depending on the molding method even if it is continuous or long. For example, as a thermoplastic yarn prepreg, it can be wound around a mandrel while heating to obtain a roll-shaped molded product.

  Examples of the thermoplastic resin 3 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 (PEKK) , Polyether nitrile (PEN); fluororesin such as polytetrafluoroethylene; crystalline resin such as liquid crystal polymer (LCP); polystyrene (PS), acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS), etc. Styrenic resin, polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), unmodified or modified polyphenylene ether (PPE), polyimide (PI), polyamideimide (PAI), polyetherimide ( Amorphous resins such as PEI), polysulfone (PSU), polyethersulfone, polyarylate (PAR); phenol resins, phenoxy resins, polystyrene elastomers, polyolefin elastomers, polyurethane resins At least one selected from a copolymer, a modified body, and the like of various elastomers such as a lastmer, a polyester-based elastomer, a polyamide-based elastomer, a polybutadiene-based elastomer, a polyisoprene-based elastomer, a fluororesin, and an acrylonitrile-based elastomer A thermoplastic resin is preferably used. In addition, as a thermoplastic resin, the thermoplastic resin composition containing multiple types of these thermoplastic resins may be used in the range which does not impair the objective of this invention.

  Moreover, what provided the impregnation adjuvant between the carbon fiber 2 and the thermoplastic resin 3 as a molding material of this invention can be used conveniently. FIG. 2 is a perspective view of a molding material 1A according to the present invention. In the molding material 1A, a plurality of carbon fibers 2 are arranged substantially parallel to the axial direction of the cylinder, the periphery of the carbon fibers 2 is covered with the impregnation aid 4, and the periphery of the impregnation aid 4 is covered with the thermoplastic resin 3. The structure to cover is made. In order to improve the mechanical properties of a molded product obtained by molding a molding material, it is generally preferable to use a high molecular weight thermoplastic resin. However, a high molecular weight thermoplastic resin has a high melt viscosity and is a carbon fiber. There is a problem that it is difficult to impregnate the bundle. On the other hand, in order to improve the impregnation property of the thermoplastic resin into the carbon fiber bundle, it is preferable to use a low molecular weight thermoplastic resin having a low melt viscosity, but a molded article using the low molecular weight thermoplastic resin. Will greatly reduce the mechanical properties.

  Therefore, after impregnating a bundle of carbon fibers with a relatively low molecular weight resin (prepolymer) as an impregnation aid 4, a mechanical property is obtained by using a relatively high molecular weight thermoplastic resin 3 as a matrix resin. It is possible to produce an excellent molding material with high productivity.

  Hereinafter, the suitable form about the molding material which uses an impregnation adjuvant is demonstrated.

  When the polyarylene sulfide resin is used as the thermoplastic resin, the impregnation aid, that is, the component (C) has a mass average molecular weight of 10,000 or more and a dispersity represented by mass average molecular weight / number average molecular weight. It is preferable to use 2.5 or less polyarylene sulfide [d] (hereinafter abbreviated as PAS), and the impregnation aid PAS is 0.1 to 100 parts by mass with respect to 100 parts by mass of carbon fiber. It is suitable to use so that it may become a part.

  The molecular weight of PAS, which is an impregnation aid, is 10,000 or more, preferably 15,000 or more, more preferably 18,000 or more in terms of mass average molecular weight. When the mass average molecular weight is less than 10,000, a low molecular weight component may cause a thermal decomposition reaction during molding at a higher temperature (for example, 360 ° C.), generating decomposition gas and causing environmental pollution around the molding equipment. . Although there is no restriction | limiting in particular in the upper limit of a mass mean molecular weight, 1,000,000 or less can be illustrated as a preferable range, More preferably, it is 500,000 or less, More preferably, it is 200,000 or less, High impregnation property in this range As well as moldability can be obtained.

  The degree of dispersion of the molecular weight distribution of PAS, that is, the dispersity represented by the ratio of the weight average molecular weight to the number average molecular weight (mass average molecular weight / number average molecular weight) is 2.5 or less, preferably 2.3 or less, and 2.1 The following is more preferable, and 2.0 or less is more preferable. As the degree of dispersion increases, the amount of low-molecular components contained in PAS tends to increase, which may cause environmental pollution around the molding equipment as described above. In addition, the said mass average molecular weight and number average molecular weight can be calculated | required, for example using SEC (size exclusion chromatography) equipped with the differential refractive index detector.

  PAS is preferably 0.1 to 100 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 15 to 30 parts by mass with respect to 100 parts by mass of carbon fiber. By setting PAS to 0.1 to 100 parts by mass with respect to 100 parts by mass of carbon fiber, a molded product having high mechanical properties can be produced with high productivity.

  When a polyamide resin is used as the thermoplastic resin, it is preferable to use an [e] phenolic polymer as the impregnation aid, that is, the component (C), and the [e] phenolic polymer is added to 100 parts by mass of carbon fiber. It is suitable to use so that it may become 0.1-100 mass parts with respect to.

  Examples of the phenolic polymer used as the impregnation aid include phenol obtained by a condensation reaction of phenol or a phenol substituent derivative (precursor a) and a hydrocarbon having two double bonds (precursor b). System polymers.

  As said precursor a, what has 1-3 substituents chosen from an alkyl group, a halogen atom, and a hydroxyl group on the benzene ring of phenol is used preferably. Specific examples include cresol, xylenol, ethylphenol, butylphenol, t-butylphenol, nonylphenol, 3,4,5-trimethylphenol, chlorophenol, bromophenol, chlorocresol, hydroquinone, resorcinol, orcinol, These may be used alone or in combination of two or more. In particular, phenol and cresol are preferably used.

  Examples of the precursor b include aliphatic hydrocarbons such as butadiene, isoprene, pentadiene and hexadiene, cyclohexadiene, vinylcyclohexene, cycloheptadiene, cyclooctadiene, 2,5-norbornadiene, tetrahydroindene, dicyclopentadiene, monocyclic ring Alicyclic hydrocarbons such as monoterpenes (dipentene, limonene, terpinolene, terpinene, ferrandylene), bicyclic sesquiterpenes (kadinene, serinene, caryophyllene), etc., which are used alone or in combination of two or more May be. In particular, monocyclic monoterpenes and dicyclopentadiene are preferably used.

  The phenolic polymer is preferably 0.1 to 100 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 15 to 30 parts by mass with respect to 100 parts by mass of the carbon fiber. By setting the phenolic polymer to 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbon fiber, a molded product having high mechanical properties can be produced with high productivity.

  When a polyolefin resin is used as the thermoplastic resin, it is preferable to use [f] terpene resin as impregnation aid, that is, component (C), and [f] terpene resin is used with respect to 100 parts by mass of carbon fiber. Thus, it is preferable to use it at 0.1 to 100 parts by mass.

  As a terpene resin used as an impregnation aid, a terpene monomer alone or a copolymer obtained with a terpene monomer and an aromatic monomer or the like in the presence of a Friedel-Crafts type catalyst in an organic solvent. Resins composed of coalesced are listed.

  Terpene resin is a thermoplastic polymer that has a lower melt viscosity than polyolefin resin, and lowers the viscosity of the resin composition and improves moldability in the final molding process such as injection molding and press molding. Is possible. At this time, since the terpene resin has good compatibility with the polyolefin resin, the moldability can be effectively improved.

  As the terpene monomer, α-pinene, β-pinene, dipentene, d-limonene, myrcene, alloocimene, ocimene, α-ferrandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1, Examples include monocyclic monoterpenes such as 4-cineole, α-terpineol, β-terpineol, γ-terpineol, sabinene, paramentadienes, and carenes. Examples of the aromatic monomer include styrene and α-methylstyrene.

  Of these, α-pinene, β-pinene, dipentene, and d-limonene are preferable because of their good compatibility with polyolefin resins, and a homopolymer of the compound is more preferable. A hydrogenated terpene resin obtained by hydrogenation treatment of the terpene resin is preferable because the compatibility with the polyolefin resin is improved.

  Moreover, it is preferable that the glass transition temperature of a terpene-type resin is 30-100 degreeC. This is for improving the handleability of the resin composition of the present invention. When the glass transition temperature is 30 ° C. or lower, the terpene resin becomes semi-solid or liquid at the time of molding and the material may not be quantitatively input. On the other hand, if the glass transition temperature is 100 ° C. or higher, the terpene-based resin is rapidly solidified during the molding process, and the moldability may not be improved.

  Moreover, it is preferable that the number average molecular weights of terpene-type resin are 500-5000. When the number average molecular weight is 500 or less, the mechanical properties of the molded product may be impaired because the mechanical strength of the terpene resin is low. In addition, when the viscosity is more than 5000, the viscosity of the terpene-based resin is increased, and the moldability may not be improved. This is because the impregnation aid flows most easily in the mixture of the carbon fiber, the impregnation aid, and the polyolefin resin, and facilitates movement.

  Furthermore, the terpene resin needs to be compatible with the polyolefin resin in order to effectively improve the moldability of the polyolefin resin composition. Here, the SP value of the polyolefin resin depends on the type, but since this value is usually about 8 to 9, the SP value of the terpene resin needs to be 6.5 to 9.5. More preferably, it is 7.5-9. When the SP value is outside the range of 6.5 to 9.5, it tends to be hardly compatible with the polyolefin-based resin, and it is difficult to improve moldability.

  Here, the SP value is a solubility parameter, and it has been empirically obtained that the closer the SP value of the two components is, the higher the solubility is. Several methods for determining the SP value are known, but the same determination method may be used in the comparison. Specifically, it is desirable to use the method of Fedors (reference SP value basics / application and calculation, March 31, 2005, first edition, issuer Toshiguchi Taniguchi, published by Information Technology Corporation, pages 66-67).

  The terpene resin is preferably 0.1 to 100 parts by mass, more preferably 10 to 70 parts by mass, and further preferably 15 to 30 parts by mass with respect to 100 parts by mass of the carbon fiber. By setting the terpene resin to 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbon fiber, a molded product having high mechanical properties can be produced with high productivity.

  Further, when the thermoplastic resin is a polyolefin resin, as the impregnation aid, that is, the component (C), [g] the first propylene resin and [h] the second propylene resin having an acyl group in the side chain It is preferable to use a mixture of resins, and [g] a mixture of the first propylene-based resin and [h] the second propylene-based resin having an acyl group in the side chain, with respect to 100 parts by mass of the carbon fiber, It is suitable to set it as 0.1-100 mass parts.

  Examples of the [g] first propylene-based resin used as the impregnation aid include a propylene homopolymer or a copolymer of propylene and at least one α-olefin, conjugated diene, non-conjugated diene or the like.

  Examples of the monomer repeating unit constituting the α-olefin include ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 2-12 carbon atoms excluding propylene such as 1-hexene, 4,4 dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene and 1-dodecene Examples of the monomer repeating unit constituting the α-olefin, conjugated diene, and non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the like. One type or two or more types can be selected.

  [g] The skeleton structure of the first propylene-based resin includes propylene homopolymer, one or two or more random or block copolymers of propylene and the other monomers, or other heat. Examples thereof include a copolymer with a plastic monomer. For example, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, and the like are preferable.

  In particular, in order to increase the affinity with the polyolefin resin, it is preferable that [g] the first propylene resin has 50 mol% or more of a structural unit derived from propylene. [G] In order to reduce the crystallinity of the first propylene-based resin and [h] increase the affinity with the second propylene-based resin and increase the strength of the resulting molded product, The propylene-based resin preferably has 50 to 99 mol% of structural units derived from propylene, more preferably 55 to 98 mol%, and still more preferably 60 to 97 mol%. Identification of the monomer repeating unit in the propylene-based resin can be performed using a general polymer compound analysis technique such as IR, NMR, mass spectrometry, and elemental analysis.

  [h] As a raw material for the second propylene-based resin, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, and ethylene / propylene / 1-butene copolymer represented by propylene and α -Monomers of olefins alone or in copolymers with two or more, neutralized or non-neutralized monomers with acyl groups, and / or saponified or unsaponified carboxylic acids A monomer having an ester can be obtained by graft polymerization. The monomer repeating unit and the skeleton structure of the copolymer of propylene and α-olefin alone or in combination of two or more types can be selected based on the same idea as [g] the first propylene resin.

  Here, as a monomer having an acyl group which is neutralized or not neutralized, and a monomer having a carboxylic acid ester group which is saponified or not saponified, for example, ethylene Examples thereof include unsaturated carboxylic acids and anhydrides thereof, and esters thereof, and compounds having unsaturated vinyl groups other than olefins.

  Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and the like, and its anhydride includes nadic acid ( Registered trademark) (endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, and the like.

  From the viewpoint of enhancing the interaction with the reinforcing fiber, [h] the content of the carboxylate bonded to the polymer chain of the second propylene-based resin is [C] per 1 g of the second propylene-based resin. The total amount is preferably 0.05 to 5 mmol equivalent in terms of acyl group represented by = O) -O-. More preferably, it is 0.1-4 mmol equivalent, More preferably, it is 0.3-3 mmol equivalent. As a method for analyzing the content of the carboxylate as described above, a method of quantitatively detecting a metal species forming a salt by ICP emission analysis, or a method using IR, NMR, elemental analysis, etc. A method for quantifying the carbonyl carbon of the acid salt is mentioned.

  In the molding material of the present invention, when the molding material of the present invention is injection molded by impregnating a carbon fiber bundle with a mixture of [g] the first propylene resin and [h] the second propylene resin, The mixture of [g] the first propylene resin and [h] the second propylene resin melt-kneaded in the cylinder of the molding machine diffuses into the polyolefin resin, and the carbon fiber bundle becomes the polyolefin resin. It helps to disperse, and at the same time, helps the polyolefin resin replace and impregnate the carbon fiber bundle. In achieving this role, [g] the first propylene resin, [h] the second propylene resin, the order of the mass average molecular weight of the polyolefin resin is polyolefin resin> [g] first propylene resin If resin> [h] second propylene resin, [g] first propylene resin and [h] second propylene resin component can easily diffuse into the polyolefin resin.

  From the viewpoint of exhibiting the above impregnation and dispersibility and from the viewpoint of [g] entanglement of molecular chains with the first propylene resin, and [g] enhancing the interaction with the first propylene resin. [h] The mass average molecular weight Mw of the second propylene-based resin is preferably 1,000 to 50,000. More preferably, it is 2,000-40,000, More preferably, it is 5,000-30,000. The mass average molecular weight is measured using gel permeation chromatography (GPC).

  [G] The first propylene-based resin has a mass average molecular weight Mw of 30,000 or more and less than 150,000 from the viewpoint of achieving the above-mentioned impregnation and dispersibility and affinity with the polyolefin resin. Propylene resin (g-1) is 30 to 100% by mass, and mass average molecular weight Mw is 150,000 or more and 500,000 or less, and propylene resin (g-2) is 0 to 70% by mass. It is preferable to become. If the mass average molecular weight Mw of the propylene-based resin (g-2) becomes too large, it may be difficult to achieve impregnation and dispersibility, and is preferably within the above-described range.

  [g] The mixture of the first propylene resin and the second propylene resin having [h] acyl group in the side chain is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbon fiber. Preferably it is 10-70 mass parts, More preferably, you may be 15-30 mass parts. [g] The mixture of the first propylene resin and the second propylene resin having [h] acyl group in the side chain is 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbon fiber. A molded article having mechanical characteristics can be manufactured with high productivity.

  Hereinafter, the interaction with (A) when the preferred thermoplastic resin is used will be described.

In the case of a polyarylene sulfide resin, a covalent bond between a terminal thiol group or carboxyl group and an epoxy group contained in (A1), a sulfide group in the main chain and an epoxy group contained in (A1) or (A2) It is considered that a strong interface can be formed by a hydrogen bond with a contained hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group.
In the case of polyether ether ketone resin, polyphenylene ether resin or polyoxymethylene resin, a covalent bond between a terminal hydroxyl group and an epoxy group contained in (A1), an ether group in the main chain, and (A1) It is considered that a strong interface can be formed by a hydrogen bond with the contained epoxy group or the hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group contained in (A2).
In the case of a polyamide resin, a covalent bond between a carboxyl group or amino group at the terminal and an epoxy group contained in (A1), an amide group in the main chain, and an epoxy group contained in (A1) or (A2) It is considered that a strong interface can be formed by a hydrogen bond with a contained hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group.

In the case of a polyester resin or polycarbonate resin, a covalent bond between a carboxyl group or hydroxyl group at the terminal and an epoxy group contained in (A1), an ester group in the main chain, an epoxy group contained in (A1), It is considered that a strong interface can be formed by hydrogen bonding with the hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group contained in (A2).
In the case of a styrenic resin such as ABS resin, a cyano group in the side chain, an epoxy group contained in (A1), a hydroxyl group, an amide group, an imide group, a urethane group, a urea group contained in (A2), It is considered that a strong interface can be formed by hydrogen bonding with a sulfonyl group or a sulfo group.

Among polyolefin resins, particularly in the case of polyolefin resins modified with acid, a covalent bond between an acid anhydride group or carboxyl group in the side chain and an epoxy group contained in (A1), It is considered that a strong interface can be formed by a hydrogen bond with a contained hydroxyl group, amide group, imide group, urethane group, urea group, sulfonyl group, or sulfo group.
In addition, the thermoplastic resin used in the present invention is preferably a polyarylene sulfide resin or a polyether ether ketone resin from the viewpoint of heat resistance. From the viewpoint of dimensional stability, polyphenylene ether resin is preferable. From the viewpoint of friction and wear characteristics, polyoxymethylene resin is preferred. From the viewpoint of strength, a polyamide resin is preferable. From the viewpoint of surface appearance, an amorphous resin such as polycarbonate or styrene resin is preferred. From the viewpoint of lightness, polyolefin resin is preferable.

  Next, the preferable aspect for manufacturing the molding material of this invention is demonstrated.

  As a method for producing the molding material of the present invention, for example, a pultrusion method (pultrusion method) in which a carbon fiber impregnated with a thermoplastic resin is drawn while pulling a carbon fiber coated with a sizing agent. In the pultrusion method, a resin additive is added to the thermoplastic resin as necessary, and the continuous carbon fiber is drawn through the crosshead die while the thermoplastic resin is supplied from the extruder to the crosshead die in a molten state. The fiber is impregnated with a thermoplastic resin, the continuous carbon fiber impregnated with the molten resin is heated, cooled, and then cut perpendicularly to the drawing direction to obtain the molding material 1. In the molding material 1, carbon fibers are arranged in parallel in the length direction with the same length. In pultrusion, basically, a continuous carbon fiber bundle is drawn and the thermoplastic resin is impregnated. While the carbon fiber bundle is passed through the cross head, the thermoplastic resin is supplied to the cross head from an extruder or the like. In addition to the impregnation method, the carbon fiber bundle is impregnated through an impregnation bath containing a thermoplastic resin emulsion, suspension or solution, and the thermoplastic resin powder is sprayed or put into the carbon fiber bundle. It is also possible to use a method in which a carbon fiber bundle is passed through the tank, a thermoplastic resin powder is adhered to the carbon fiber, and then the thermoplastic resin is melted and impregnated. Particularly preferred is the crosshead method. Further, the resin impregnation operation in these pultrusion moldings is generally performed in one stage, but this may be divided into two or more stages, and the impregnation method may be different.

  Further, the molding material having the impregnation aid, that is, the component (C) is impregnated with the impregnation aid, that is, the carbon fiber coated with the component (C) after impregnating the carbon fiber coated with the sizing agent. It is manufactured by coating with a thermoplastic resin by the pultrusion method.

  Applications of the carbon fiber reinforced composite material formed by molding the molding material of the present invention include, for example, personal computers, displays, OA equipment, mobile phones, personal digital assistants, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (Personal digital assistants such as electronic notebooks), video cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment equipment, toy products, other electrical appliances such as housings, trays, chassis, etc. Interior materials and cases, mechanical parts, panels and other building materials applications, motor parts, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, suspension parts, exhaust gas valves and other valves, fuel-related, exhaust systems Or suck Various 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, cooling Water 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 vane, wiper motor related parts, distributor, starter switch, starter , Wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, 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 device case, under cover, scuff plate, Pillar trim, propeller shaft, wheel, fender, fascia, bumper, bumper beam, Bonnets, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules, automobile-related parts, parts and skins, landing gear pods, winglets, spoilers, edges, ladders, elevators, and failings And aircraft related parts such as ribs, members and outer plates, 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, measurement was performed using AlKα ₁ , ₂ as the X-ray source and 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 at 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.

<Bending characteristic evaluation method for injection molded products>
A bending strength test piece having a length of 130 ± 1 mm and a width of 25 ± 0.2 mm was cut out from the obtained injection molded product. According to the test method specified in ASTM D-790 (2004), using a three-point bending test jig (indenter 10 mm, fulcrum 10 mm), the support span is set to 100 mm, and the bending strength is measured at a crosshead speed of 5.3 mm / min. did. In this example, “Instron (registered trademark)” universal testing machine 4201 type (manufactured by Instron) was used as a testing machine. The number of measurements was n = 5, and the average value was the bending strength.

(Reference Example 1)
<Preparation of polyphenylene sulfide prepolymer>
In a 1000 liter autoclave equipped with a stirrer, 47.5% sodium hydrosulfide 118 kg (1000 mol), 96% sodium hydroxide 42.3 kg (1014 mol), N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) 163 kg (1646 mol), sodium acetate 24.6 kg (300 mol), and 150 kg of ion-exchanged water are gradually heated to 240 ° C. over 3 hours while passing nitrogen at normal pressure, and passed through a rectifying column. After distilling 211 kg of water and 4 kg of NMP, the reaction vessel was cooled to 160 ° C. In addition, 0.02 mol of hydrogen sulfide per 1 mol of the sulfur component charged during this liquid removal operation was scattered out of the system.
Next, 147 kg (1004 mol) of p-dichlorobenzene and 129 kg (1300 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. While stirring at 240 rpm, the temperature was raised to 270 ° C. at a rate of 0.6 ° C./min and held at this temperature for 140 minutes. Water was cooled to 250 ° C. at a rate of 1.3 ° C./min while 18 kg (1000 mol) of water was injected over 15 minutes. Thereafter, it was cooled to 220 ° C. at a rate of 0.4 ° C./min, and then rapidly cooled to near room temperature to obtain slurry (E). This slurry (E) was diluted with 376 kg of NMP to obtain a slurry (F).
14.3 kg of slurry (F) heated to 80 ° C. was filtered off with a sieve (80 mesh, opening 0.175 mm) to obtain 10 kg of crude PPS resin and slurry (G). The slurry (G) was charged into a rotary evaporator, replaced with nitrogen, treated at 100 to 160 ° C. under reduced pressure for 1.5 hours, and then treated at 160 ° C. for 1 hour in a vacuum dryer. The amount of NMP in the obtained solid was 3% by mass.

After adding 12 kg of ion-exchanged water (1.2 times the amount of slurry (G)) to this solid, it was stirred at 70 ° C. for 30 minutes to make a slurry again. This slurry was subjected to suction filtration with a glass filter having an opening of 10 to 16 μm. 12 kg of ion-exchanged water was added to the obtained white cake, and the mixture was stirred again at 70 ° C. for 30 minutes to form a slurry again. The above operation was repeated until the polyphenylene sulfide prepolymer reached a predetermined amount.
4 g of the obtained polyphenylene sulfide oligomer was collected and subjected to Soxhlet extraction with 120 g of chloroform for 3 hours. Chloroform was distilled off from the obtained extract, and 20 g of chloroform was again added to the resulting solid, which was dissolved at room temperature to obtain a slurry-like mixture. This was slowly added dropwise to 250 g of methanol while stirring, and the precipitate was suction filtered through a glass filter having an opening of 10 to 16 μm, and the resulting white cake was vacuum dried at 70 ° C. for 3 hours to obtain a white powder.
The white powder had a weight average molecular weight of 900. The absorption spectrum in the infrared spectroscopic analysis of this white powder revealed that the white powder was polyphenylene sulfide (PAS). Moreover, as a result of analyzing the thermal characteristics of this white powder using a differential scanning calorimeter (temperature increase rate 40 ° C./min), it shows a broad endotherm at about 200 to 260 ° C., and the peak temperature is 215 ° C. I understood it.
Moreover, this white powder was obtained from cyclic polyphenylene sulfide having 4 to 11 repeating units and cyclic polyphenylene sulfide having 2 to 11 repeating units based on mass spectral analysis of components separated by high performance liquid chromatography and molecular weight information by MALDI-TOF-MS. It was a mixture of chain polyphenylene sulfide, and the mass ratio of cyclic polyphenylene sulfide to linear polyphenylene sulfide was found to be 9: 1.

(Reference Example 2)
<Preparation of propylene-based resin mixture PP>
As the first propylene-based resin (g), propylene / butene / ethylene copolymer (g-1) (constituent unit derived from propylene (hereinafter also referred to as “C3”) = 66 mol%, Mw = 90,000. ) 91 parts by mass, as a raw material for the second propylene resin (h), maleic anhydride-modified propylene / ethylene copolymer (C3 = 98 mol%, Mw = 25,000, acid content = 0.81 mmol equivalent) ) 9 parts by mass, 3 parts by mass of potassium oleate were mixed as a surfactant. This mixture was supplied at a rate of 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40), and from the supply port provided in the vent portion of the extruder, A 20% aqueous potassium hydroxide solution was continuously supplied at a rate of 90 g / hour and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder mouth, and further poured into warm water at 80 ° C. to obtain an emulsion. The obtained emulsion had a solid content concentration of 45%.
The maleic anhydride-modified propylene / ethylene copolymer (C3 = 98 mol%, Mw = 25,000, acid content = 0.81 mmol equivalent) is 96 parts by mass of propylene / ethylene copolymer, maleic anhydride. It was obtained by mixing 4 parts by mass and 0.4 parts by mass of perhexi 25B (manufactured by NOF Corporation) as a polymerization initiator and performing modification at a heating temperature of 160 ° C. for 2 hours.

  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-7
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: N, N-dimethylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 135.21, corresponding to formula (VIII) B-3: 1,8-bis (dimethylamino) naphthalene (manufactured by Aldrich)
Another name: proton sponge, molecular weight: 214.31, corresponding to formula (IV) B-4: 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Alias: DMP-30, molecular weight: 265.39, applicable to formula (V) B-5: DBN (manufactured by San Apro Co., Ltd.), molecular weight: 124, applicable to formula (III) 1,5-diazabicyclo [4,3 , 0] -5-Nonene B-6: triisopropanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight: 191.27, corresponding to formula (VIII) B-7: U-CAT SA506 (manufactured by San Apro Co., Ltd.) ), Corresponding to formula (III) DBU-p-toluenesulfonate, molecular weight: 324.44

-(B2) component: B-8 to B-14
B-8: 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., corresponding to formula (I))
B-9: 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-10: 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-11: (2-methoxyethoxymethyl) triethylammonium chloride (R ₁ has 4 carbon atoms, R _{2 to} R ₄ each have 2 carbon atoms, anion sites are chloride anions, manufactured by Tokyo Chemical Industry Co., Ltd., Corresponds to formula (I)
B-12: (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-13: (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-14: 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-15 to B-17
B-15: 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., corresponding to formula (XI)) Molecular weight: 339
B-16: Tetraphenylphosphonium bromide (R _{25 to} R ₂₈ each have 6 carbon atoms, the anion portion is a bromide anion, manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to formula (XI)), molecular weight: 419
B-17: Triphenylphosphine (R _{29 to} R ₃₁ each have 6 carbon atoms, manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to formula (XII)), molecular weight: 262

-Component (C): C-1 to C-4
C-1: polyphenylene sulfide prepolymer prepared in Reference Example C-2: terpene phenol polymer (monocyclic monoterpene phenol and phenol adduct, YP902 manufactured by Yasuhara Chemical Co., Ltd.)
C-3: Terpene resin (resin composed of polymer polymerized using α-pinene and β-pinene as main components, YS resin PX1250 resin manufactured by Yasuhara Chemical Co., Ltd.)
C-4: Propylene-based resin mixture prepared in Reference Example 4

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

Thermoplastic resin polyarylene sulfide (PPS) resin pellets: “Torelina (registered trademark)” A900 (manufactured by Toray Industries, Inc.)
Polyamide 6 (PA6) resin pellet: “Amilan (registered trademark)” CM1001 (manufactured by Toray Industries, Inc.)
Polypropylene (PP) resin pellets (polyolefin resin): a mixture of unmodified PP resin pellets and acid-modified PP resin pellets, unmodified PP resin pellets: “Prime Polypro (registered trademark)” J830HV (manufactured by Prime Polymer Co., Ltd.) 50 Mass parts, acid-modified PP resin pellets: “Admer (registered trademark)” QE800 (manufactured by Mitsui Chemicals) 50 mass parts Polycarbonate (PC) resin pellets: “Lexan (registered trademark)” 141R (SABIC)
ABS resin pellet (styrene resin): “Toyolac (registered trademark)” T-100A (manufactured by Toray Industries, Inc.).

Example 1
The present embodiment includes the following steps I to IV.
-Step I: Process for producing carbon fiber as raw material A copolymer composed of 99 mol% acrylonitrile and 1 mol% itaconic acid is spun and fired, the total number of filaments is 24,000, and the total fineness is 1,000. A carbon fiber having a tex, a specific gravity of 1.8, a strand tensile strength of 6.2 GPa, and a 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 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: Step of adhering sizing agent to carbon fiber (A-4) and (B-1) were mixed at a mass ratio of 100: 1, and acetone was further mixed so that the sizing agent was uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.

Step III: Step of producing long fiber pellets A cross-head die processed into a wave shape that allows continuous sizing agent-coated carbon fibers to pass through was attached to the tip of a single screw extruder. Next, while drawing continuous sizing agent-coated carbon fibers through a crosshead die at a speed of 5 m / min, PPS resin pellets are fed from the extruder to the crosshead die in a molten state, and continuous sizing agent-coated carbon fibers Impregnated with PPS resin, heated melt impregnated material, cooled, cut to 7 mm perpendicular to the drawing direction, carbon fibers were arranged almost parallel to the axial direction, and the length of the carbon fibers was the molding material A long fiber pellet (form A) was obtained which was substantially the same as the length of. The extruder was sufficiently kneaded at a barrel temperature of 320 ° C. and a rotation speed of 150 rpm, and further deaerated from a downstream vacuum vent. The supply of PPS resin pellets was adjusted so that the sizing agent-coated carbon fiber was 80 parts by mass with respect to 20 parts by mass.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 330 ° C. and a mold temperature of 100 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 1. As a result, it was found that the bending strength was 280 MPa and the mechanical properties were sufficiently high.

(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 In Step II of Example 1, as shown in Table 1, the mass ratio of (A-4) and (B-1) is 100: 3 A sizing agent-coated carbon fiber was obtained in the same manner as in Example 1 except that it was changed within the range of ˜100: 20. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 1. As a result, it was found that the bending strength was 279 to 285 MPa, and the mechanical properties were sufficiently high.

(Comparative Examples 1-5)
-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 In Step II of Example 1, the mass ratio of component (A), component (B), component (D) (other components) is shown in Table 1. A sizing agent-coated carbon fiber was obtained in the same manner as in Example 1 except that it was changed as shown. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 1. As a result, it was found that the bending strength was 250 to 268 MPa, and the mechanical properties were insufficient.

(Examples 6 to 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 Except for changing the mass ratio of component (A) and component (B) as shown in Table 2 in step II of Example 1, Sizing agent-coated carbon fibers were obtained in the same manner as in Example 1. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 2. As a result, it was found that the bending strength was 272 to 303 MPa, and the mechanical properties were sufficiently high.

(Example 16)
-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 (A-4) and (B-7) are mixed at a mass ratio of 100: 3, and acetone is further mixed, so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 2. As a result, it was found that the bending strength was 271 MPa and the mechanical properties were sufficiently high.

(Example 17)
-Step I: Step of producing carbon fiber as a raw material The carbon fiber B obtained in Example 16 was immersed in a tetraethylammonium hydroxide aqueous solution (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 (A-4) and (B-7) are mixed at a mass ratio of 100: 3, and acetone is further mixed, so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 2. As a result, it was found that the bending strength was 279 MPa and the mechanical properties were sufficiently high.

(Comparative Example 6)
Step I: Step of producing carbon fiber as a raw material The same as in Example 16.
Step II: Step of attaching sizing agent to carbon fiber Only (A-4) was 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 2. As a result, it was found that the bending strength was 251 MPa and the mechanical properties were insufficient.

(Comparative Example 7)
-Step I: Step of producing carbon fiber as raw material The same as in Example 17.
Step II: Step of attaching sizing agent to carbon fiber Only (A-4) was 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 2. As a result, it was found that the bending strength was 255 MPa and the mechanical properties were insufficient.

(Examples 18 to 24)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of adhering sizing agent to carbon fiber In step II of Example 1, except that (A) component and (B) component were changed as shown in Table 3-1. Sizing agent-coated carbon fibers were obtained in the same manner as in Example 1. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 3-1. As a result, it was found that the bending strength was 286 to 300 MPa, and the mechanical properties were sufficiently high.

(Example 25)
-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 (A-1) and (B-8) are mixed at a mass ratio of 100: 3, and acetone is further mixed so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 3-1. As a result, it was found that the bending strength was 285 MPa and the mechanical properties were sufficiently high.

(Example 26)
-Step I: Step of producing carbon fiber as a raw material The carbon fiber B obtained in Example 25 was immersed in a tetraethylammonium hydroxide aqueous solution (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 (A-1) and (B-8) are mixed at a mass ratio of 100: 3, and acetone is further mixed so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 3-1. As a result, it was found that the bending strength was 292 MPa and the mechanical properties were sufficiently high.

(Examples 27 to 35)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of attaching a sizing agent to carbon fiber In the step II of Example 1, except that the components (A) and (B) were changed as shown in Table 3-2. Sizing agent-coated carbon fibers were obtained in the same manner as in Example 1. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 3-2. As a result, it was found that the bending strength was 280 to 296 MPa, and the mechanical properties were sufficiently high.

(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 Only (A-1) was 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 1. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 3-2. As a result, it was found that the bending strength was 270 MPa and the mechanical properties were insufficient.

(Example 36)
The present embodiment includes the following steps I to IV.
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
Step II: Step of adhering sizing agent to carbon fiber (A-4) and (B-3) were mixed at a mass ratio of 100: 3, and acetone was further mixed to dissolve the sizing agent uniformly. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.

-Step III: Step of producing long fiber pellets (C-1) prepared in Reference Example 1 is melted in a melting bath at 240 ° C and supplied to a kiss coater with a gear pump. (C-1) was apply | coated from the kiss coater on the roll heated at 230 degreeC, and the film was formed.
A sizing agent-coated carbon fiber was passed through the roll while being in contact therewith, and a certain amount of (C-1) was adhered per unit length of the sizing agent-coated carbon fiber.
The sizing agent-coated carbon fibers to which (C-1) is attached are supplied into a furnace heated to 350 ° C., and are freely rotated by bearings. ) And passed through 10 roll bars (φ200mm) installed in the furnace in a twisted manner, and highly polymerized to PAS while sufficiently impregnating (C-1) with carbon fiber coated with sizing agent It was converted into a body. Next, air was blown onto the carbon fiber strand drawn from the furnace to cool it, and then wound with a drum winder.
In addition, from the wound carbon fiber strand, 10 strands having a length of 10 mm were cut, and in order to separate the carbon fiber and the polyarylene sulfide, a Soxhlet extractor was used and 1-chloronaphthalene was used at 210 ° C. for 6 hours. Refluxing was performed for a time, and the extracted polyarylene sulfide was subjected to molecular weight measurement. The obtained PPS had a mass average molecular weight (Mw) of 26,800, a number average molecular weight (Mn) of 14,100, and a dispersity (Mw / Mn) of 1.90. Next, the mass reduction rate ΔWr of the extracted polyarylene sulfide was measured and found to be 0.09%. Moreover, the adhesion amount of (C-1) was 20 mass parts with respect to 100 mass parts of carbon fibers.

Subsequently, the PPS resin was melted at 360 ° C. by a single screw extruder and extruded into a crosshead die attached to the tip of the extruder, and at the same time, the sizing agent-coated carbon fiber impregnated with (C-1) was also used above. The molten PPS resin was coated on the sizing agent-coated carbon fibers impregnated with (C-1) by continuously feeding into the crosshead die (speed: 30 m / min). Next, after cooling, the core-sheath structure is cut into 7 mm perpendicular to the drawing direction, the carbon fibers are arranged substantially parallel to the axial direction, and the length of the carbon fibers is substantially the same as the length of the molding material Long fiber pellets (form B) were obtained. The supply of the PPS resin pellets was adjusted so that the sizing agent-coated carbon fiber was 20% by mass with respect to the whole.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 330 ° C. and a mold temperature of 100 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 4. As a result, it was found that the bending strength was 285 MPa and the mechanical properties were sufficiently high.

(Examples 37 to 42)
-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 Example 36, except that component (A) and component (B) were changed as shown in Table 4 in step II of Example 36. A sizing agent-coated carbon fiber was obtained in the same manner as described above. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 36. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 4. As a result, it was found that the bending strength was 284 to 290 MPa, and the mechanical properties were sufficiently high.

(Comparative Example 9)
-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 Only (A-4) was 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 36. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 4. As a result, it was found that the bending strength was 266 MPa and the mechanical properties were insufficient.

(Example 43)
The present embodiment includes the following steps I to IV.
-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 (A-8) and (B-1) are mixed at a mass ratio of 100: 3, and acetone is further mixed so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Step III: Step (C-2) for producing long fiber pellets is melted in a 190 ° C melting bath and supplied to the kiss coater with a gear pump. (C-2) was apply | coated from the kiss coater on the roll heated at 180 degreeC, and the film was formed.
A sizing agent-coated carbon fiber was passed through the roll while being in contact therewith, and a certain amount of (C-2) was adhered per unit length of the sizing agent-coated carbon fiber.
The sizing agent-coated carbon fibers to which (C-2) is attached are supplied into a furnace heated to 180 ° C., and are freely rotated by bearings. Ten rolls (φ50 mm) arranged alternately on the upper and lower sides in a straight line ) And 10 roll bars (φ200 mm) installed in the furnace in a twisted manner, and (C-2) was sufficiently impregnated with the carbon fiber coated with sizing agent. The adhesion amount of (C-2) was 20 parts by mass with respect to 100 parts by mass of the carbon fiber.

Subsequently, the PA6 resin is melted at 300 ° C. in a single screw extruder and extruded into a crosshead die attached to the tip of the extruder, and at the same time, the sizing agent-coated carbon fiber impregnated with (C-2) is also described above. By continuously feeding into the crosshead die (speed: 30 m / min), the melted PA6 resin was coated on the sizing agent-coated carbon fibers impregnated with (C-2). Next, after cooling, the core-sheath structure is cut into 7 mm perpendicular to the drawing direction, the carbon fibers are arranged substantially parallel to the axial direction, and the length of the carbon fibers is substantially the same as the length of the molding material Long fiber pellets (form B) were obtained. The supply of PA6 resin pellets was adjusted so that the sizing agent-coated carbon fiber was 30% by mass with respect to the whole.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 5. As a result, it was found that the bending strength was 381 MPa and the mechanical properties were sufficiently high.

(Examples 44 to 48)
-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 Example 43, except that component (A) and component (B) were changed as shown in Table 5 in step II of Example 43. A sizing agent-coated carbon fiber was obtained in the same manner as described above. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 43. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 5. As a result, it was found that the bending strength was 372 to 379 MPa, and the mechanical properties were sufficiently high.

(Comparative Example 10)
-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 Only (A-8) was mixed with acetone to obtain an about 1% by mass acetone solution 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 43. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 5. As a result, it was found that the bending strength was 362 MPa and the mechanical properties were insufficient.

(Example 49)
The present embodiment includes the following steps I to V.
-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 (A-8) and (B-6) are mixed at a mass ratio of 100: 3, and acetone is further mixed, so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Step (C-3) for producing long fiber pellets is melted in a 190 ° C. melting bath and supplied to the kiss coater with a gear pump. (C-3) was applied from a kiss coater on a roll heated to 180 ° C. to form a film.
A sizing agent-coated carbon fiber was passed through the roll while being in contact therewith, and a certain amount of (C-3) was adhered per unit length of the sizing agent-coated carbon fiber.
The sizing agent-coated carbon fibers with (C-3) attached are supplied into a furnace heated to 180 ° C., and are freely rotated by bearings. ) And 10 roll bars (φ200 mm) installed in the furnace in a twisted manner, and (C-3) was sufficiently impregnated with the sizing agent-coated carbon fiber. The adhesion amount of (C-3) was 20 parts by mass with respect to 100 parts by mass of the carbon fiber.

Subsequently, the sizing agent-coated carbon fiber impregnated with (C-3) at the same time as the PP resin was melted at 240 ° C. by a single screw extruder and extruded into a crosshead die attached to the tip of the extruder. The molten PP resin was coated on the sizing agent-coated carbon fibers impregnated with (C-3) by continuously feeding into the crosshead die (speed: 30 m / min). Next, after cooling, the core-sheath structure is cut into 7 mm perpendicular to the drawing direction, the carbon fibers are arranged substantially parallel to the axial direction, and the length of the carbon fibers is substantially the same as the length of the molding material Long fiber pellets (form B) were obtained. The supply of the PP resin pellets was adjusted so that the sizing agent-coated carbon fibers were 20% by mass with respect to the whole.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 6-1. As a result, it was found that the bending strength was 155 MPa and the mechanical properties were sufficiently high.

(Examples 50 to 54)
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
-Step II: Step of attaching a sizing agent to carbon fibers In Step II of Example 49, except that (A) component and (B) component were changed as shown in Table 6-1 Sizing agent-coated carbon fibers were obtained in the same manner as in Example 49. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 49. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 6-1. As a result, it was found that the bending strength was 145 to 159 MPa, and the mechanical properties were sufficiently high.

(Comparative Example 11)
-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 Only (A-8) was mixed with acetone to obtain an about 1% by mass acetone solution 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 49. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 6-1. As a result, it was found that the bending strength was 135 MPa and the mechanical properties were insufficient.

(Example 55)
The present embodiment includes the following steps I to V.
-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 (A-8) and (B-6) are mixed at a mass ratio of 100: 3, and acetone is further mixed, so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Step III: Step for producing long fiber pellets (C-4) The emulsion of (C-4) was adjusted to a solid content concentration of 27% by mass and adhered by a roller impregnation method, and then dried at 210 ° C for 2 minutes to obtain moisture. Was removed to obtain a composite of sizing agent-coated carbon fibers and first and second propylene resins. The adhesion amount of (C-4) was 20 parts by mass with respect to 100 parts by mass of the carbon fiber.
Subsequently, the PP resin was melted at 300 ° C. with a single screw extruder and extruded into a crosshead die attached to the tip of the extruder, and at the same time, the sizing agent-coated carbon fiber to which (C-4) was adhered was also described above. By continuously feeding into the crosshead die (speed: 30 m / min), the melted PP resin was coated on the sizing agent-coated carbon fiber to which (C-4) was adhered. Next, after cooling, the core-sheath structure is cut into 7 mm perpendicular to the drawing direction, the carbon fibers are arranged substantially parallel to the axial direction, and the length of the carbon fibers is substantially the same as the length of the molding material Long fiber pellets (form B) were obtained. The supply of the PP resin pellets was adjusted so that the sizing agent-coated carbon fibers were 20% by mass with respect to the whole.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 6-2. As a result, it was found that the bending strength was 158 MPa and the mechanical properties were sufficiently high.

(Examples 56 to 60)
-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 55, except that (A) component and (B) component were changed as shown in Table 6-2. Sizing agent-coated carbon fibers were obtained in the same manner as in Example 55. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 55. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 6-2. As a result, it was found that the bending strength was 145 to 162 MPa, and the mechanical properties were sufficiently high.

(Comparative Example 12)
-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 Only (A-8) was mixed with acetone to obtain an about 1% by mass acetone solution 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 55. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 6-2. As a result, it was found that the bending strength was 135 MPa and the mechanical properties were insufficient.

(Example 61)
The present embodiment includes the following steps I to IV.
-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 (A-10) and (B-6) are mixed at a mass ratio of 100: 3, and acetone is further mixed so that the sizing agent is uniformly dissolved. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.

Step III: Step of producing long fiber pellets A cross-head die processed into a wave shape that allows continuous sizing agent-coated carbon fibers to pass through was attached to the tip of a single screw extruder. Next, while drawing the continuous sizing agent-coated carbon fiber through the crosshead die at a speed of 5 m / min, the PC resin pellets are supplied from the extruder to the crosshead die in a molten state, and the continuous sizing agent-coated carbon fiber is supplied. PC resin is impregnated, the molten impregnated material is heated, cooled, cut to 7 mm perpendicular to the drawing direction, carbon fibers are arranged almost parallel to the axial direction, and the length of the carbon fibers is the molding material A long fiber pellet (form A) was obtained which was substantially the same as the length of. The extruder was sufficiently kneaded at a barrel temperature of 300 ° C. and a rotation speed of 150 rpm, and further deaerated from a downstream vacuum vent. The supply of the PC resin pellets was adjusted so that the sizing agent-coated carbon fiber was 20 parts by mass and the PC resin was 80 parts by mass.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 320 ° C. and a mold temperature of 70 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 7. As a result, it was found that the bending strength was 210 MPa and the mechanical properties were sufficiently high.

(Examples 62 to 66)
-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 Example 61, except that (A) component and (B) component were changed as shown in Table 7 in Step II of Example 61. A sizing agent-coated carbon fiber was obtained in the same manner as described above. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 61. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 7. As a result, it was found that the bending strength was 200 to 209 MPa, and the mechanical properties were sufficiently high.

(Comparative Example 13)
-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 Only (A-10) was mixed with acetone to obtain an about 1% by mass acetone solution 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 61. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 7. As a result, it was found that the bending strength was 190 MPa and the mechanical properties were insufficient.

(Example 67)
The present embodiment includes the following steps I to IV.
-Step I: Step of producing carbon fiber as a raw material The same as in Example 1.
Step II: Step of adhering sizing agent to carbon fiber (A-1) and (B-1) were mixed at a mass ratio of 100: 3, and acetone was further mixed to dissolve the sizing agent uniformly. A 1% by weight acetone solution was obtained. 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
Step III: Step of producing long fiber pellets A cross-head die processed into a wave shape that allows continuous sizing agent-coated carbon fibers to pass through was attached to the tip of a single screw extruder. Next, while drawing continuous sizing agent-coated carbon fibers through the crosshead die at a speed of 5 m / min, the ABS resin pellets are supplied from the extruder to the crosshead die in a molten state, and continuous sizing agent-coated carbon fibers are obtained. Impregnated with ABS resin, heated melt impregnated material, cooled, cut to 7 mm perpendicular to the drawing direction, carbon fibers are arranged almost parallel to the axial direction, and the length of the carbon fibers is the molding material A long fiber pellet (form A) was obtained which was substantially the same as the length of. The extruder was sufficiently kneaded at a barrel temperature of 250 ° C. and a rotation speed of 150 rpm, and further deaerated from a downstream vacuum vent. The supply of the ABS resin pellets was adjusted so that the PC resin was 80 parts by mass with respect to 20 parts by mass of the sizing agent-coated carbon fibers.
-Step IV: injection molding process:
Using the J350EIII type injection molding machine manufactured by Nippon Steel Works, the long fiber pellets obtained in the previous step were molded into test pieces for characteristic evaluation at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 8. As a result, it was found that the bending strength was 180 MPa and the mechanical properties were sufficiently high.

(Examples 68 to 72)
-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 Example 67, except that component (A) and component (B) were changed as shown in Table 8 in step II of Example 67. A sizing agent-coated carbon fiber was obtained in the same manner as described above. The adhesion amount of the sizing agent was 0.5 part by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 67. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 8. As a result, it was found that the bending strength was 165 to 180 MPa, and the mechanical properties were sufficiently high.

(Comparative Example 14)
-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 Only (A-1) was 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 0.5 parts by mass with respect to 100 parts by mass of the surface-treated carbon fiber.
-Steps III and IV:
A test piece for property evaluation was molded in the same manner as in Example 67. Next, the obtained test piece for property evaluation was evaluated according to the above-described injection molded product evaluation method. The results are summarized in Table 8. As a result, it was found that the bending strength was 155 MPa and the mechanical properties were insufficient.

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

Claims (26)

A molding material having a columnar shape composed of at least the following components (A) and (B), carbon fibers and a thermoplastic resin, wherein the carbon fibers are arranged substantially parallel to the axial direction, and the length of the carbon fibers Is substantially the same as the length of the molding material.
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 molding material according to claim 1, wherein the component (B) contains 0.001 to 0.3 parts by mass with respect to 100 parts by mass of the carbon fiber. 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. 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)

(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- 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 molding material according to claim 1, wherein the molding material has a branched structure of at least one 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 molding material according to claim 3, which is a salt thereof.   The molding material according to claim 3, wherein the compound represented by the general formula (VIII) has at least two or more branched structures.   6. The molding material according to claim 3, 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 material according to claim 1, wherein the CH ₂ group therein may be substituted by —O—, —O—CO— or —CO—O—.   The molding material according to claim 1 or 7, wherein the anion portion of the quaternary ammonium salt having a cation portion (B2) in [b] is a halogen ion. The (B3) quaternary phosphonium salt and / or phosphine compound of [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-). .   The epoxy equivalent of (A) component is less than 360 g / mol, The molding material in any one of Claims 1-9 characterized by the above-mentioned.   The molding material according to claim 1, wherein the component (A) is an epoxy compound having three or more epoxy groups.   (A) Component contains an aromatic ring in a molecule | numerator, The molding material in any one of Claims 1-11 characterized by the above-mentioned.   The molding material according to claim 1, wherein the component (A1) is a phenol novolac epoxy resin, a cresol novolac epoxy resin, or tetraglycidyldiaminodiphenylmethane.   The thermoplastic resin is at least selected from the group consisting of polyarylene sulfide resins, polyether ether ketone resins, polyphenylene ether resins, polyoxymethylene resins, polyamide resins, polyester resins, polycarbonate resins, styrene resins, and polyolefin resins. The molding material according to claim 1, wherein the molding material is one kind of thermoplastic resin.   The molding material according to claim 1, wherein the surface oxygen concentration O / C measured by X-ray photoelectron spectroscopy of the carbon fiber is 0.05 to 0.5.   The sizing agent comprising component (A) and component (B) is attached to 0.1 to 10 parts by mass of sizing agent-coated carbon fiber with respect to 100 parts by mass of carbon fiber, and thermoplastic. The molding material according to claim 1, comprising 20 to 99% by mass of a resin.   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 molding material in any one of 1-16.   The structure B mainly composed of carbon fibers is a core structure, the structure A mainly composed of a thermoplastic resin is a sheath structure, and the structure B has a core-sheath structure in which the structure A is covered. The molding material according to any one of claims 1 to 17.   The molding material according to claim 1, wherein a length of the columnar molding material is 1 to 50 mm.   The molding material according to claim 1, wherein the molding material is in the form of long fiber pellets.   The thermoplastic resin is a polyarylene sulfide resin, and as component (C), [d] has a mass average molecular weight of 10,000 or more and a dispersity expressed by mass average molecular weight / number average molecular weight is 2.5. The molding material according to any one of claims 1 to 20, wherein the polyarylene sulfide is 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbon fiber.   The thermoplastic resin is a polyamide resin, and further contains 0.1 to 100 parts by mass of [e] phenolic polymer as a component (C) with respect to 100 parts by mass of carbon fiber. Item 21. The molding material according to any one of Items 1 to 20.   The thermoplastic resin is a polyolefin-based resin, and further includes 0.1 to 100 parts by mass of [f] terpene-based resin with respect to 100 parts by mass of carbon fiber as component (C). Item 21. The molding material according to any one of Items 1 to 20.   The thermoplastic resin is a polyolefin resin, and as a component (C), a mixture of [g] the first propylene resin and [h] the second propylene resin having an acyl group in the side chain is carbon. The molding material according to any one of claims 1 to 20, comprising 0.1 to 100 parts by mass with respect to 100 parts by mass of the fiber.   The molding material according to any one of claims 21 to 24, wherein a part or all of the component (C) is impregnated in carbon fiber.   A carbon fiber reinforced composite material obtained by molding the molding material according to any one of claims 1 to 25.

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