Entitled reinforcing fiber bundle and a carbon fiber-reinforced thermoplastic resin molded article using the same, and manufacturing method of the reinforcing fiber bundle

Technical field

[0001]

　The present invention relates to a thermoplastic reinforcing fiber bundle is used as a reinforcing material for resins and carbon fiber-reinforced thermoplastic resin molded article using the same, and a method for producing a reinforcing fiber bundle.

Background technique

[0002]

　Reinforcing fibers carbon fiber composite material obtained by combining a plastic (CFRP) is specific strength, it has been put into practical use in various fields as a lightweight structural material since the inelastic modulus superior remarkably, or in practical attempts progressed . For example CFRP using a thermosetting resin is earnest employed as aircraft materials for aircraft. However, a special molding method (autoclave molding method or RTM method) is not very high productivity because it is necessary. Thus, for example, the application of CFRP using thermosetting resin for automotive is limited to luxury cars. Therefore, in recent years, in order promote the application to production vehicles, is capable of high-speed molding of stamping molding, easily thermoplastic resin performed also material recycling, CFRP is particularly used with a matrix resin of polypropylene is beginning to be noted.

[0003]

　Generally, polyolefins represented by polypropylene (PP) has poor adhesion to the carbon fibers. Thus, for example, in the CFRP using the polypropylene matrix resin, using an emulsion acid-modified PP grafted modified with maleic anhydride is dispersed in water, a method of improving the adhesion has been disclosed (Patent Documents 1 and Patent Document 2). However, in this method, the conditions such as the amount of surfactant is small in the emulsion, the foreign matter that may be causing aggregation of modified PP in the process of preparing the reinforcing fiber bundle occurs in the emulsion, the fiber surface defect acid-modified PP aqueous dispersion (sizing agent) to the step of continuously applying may occur. Further, due to this foreign material may not be able to impart sufficient adhesiveness to the fiber surface and the matrix resin.

[0004]

　On the other hand, in order to improve the strength of the interface between the carbon fiber surface and the matrix resin, for example, a method of water-dispersible polymer particles such as acid-modified PP is adding a specific alcohol and polyvinyl alcohol in an emulsion dispersed (Patent Document 3), a method of adding a polyimine resin (Patent Document 4) have been proposed. However, from the industrial further improvement of the properties are required.

CITATION

Patent Document

[0005]

Patent Document 1: Laid-Open Publication No. 6-107442
Patent Document 2: International Publication No. 2006/101269
Patent Document 3: Laid-Open Patent Publication No. 2013-177705
Patent Document 4: Laid-Open Patent Publication No. 2012-184377

Summary of the Invention

Problems that the Invention is to Solve

[0006]

　The present invention has been made in order to solve the problems of the above prior art. That object of the present invention, the reinforcing fibers to improve the adhesion of the fiber bundle in the carbon fiber-reinforced thermoplastic resin molded body (reinforcement) and the matrix resin, even less amount of fibers which exhibit a sufficient reinforcing effect bundle and carbon fiber-reinforced thermoplastic resin molded article using the same, and to provide a method for producing a reinforcing fiber bundle.

Means for Solving the Problems

[0007]

　The present inventors have made intensive studies in order to solve the above problems, the modified polyolefin (A1) containing emulsion for use in the process for preparing a reinforcing fiber bundle (sizing, etc.), the particular amine compound (B It found that) the coexistence of a very effective, and have completed the present invention. Specifically, the subject matter of the present invention is as follows.

[0008]

　[1] comprising at least a modified polyolefin carboxylic acid metal salt to bind to the polymer chain (A1), and an amine represented by the following general formula (1) relative to carboxylate groups 1 mol in the modified polyolefin (A1) compound (B) reinforcing fiber bundle comprising a bundle of carbon fibers treated with an emulsion containing 0.1 to 5,000 moles. 　　-NH
　R 2 · · · (1) (In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

[0009]

　[2] The emulsion was immersed carbon fiber bundle, then dried to obtained [1] reinforcing fiber bundle according.
　[3] The mass proportion of the modified polyolefin (A1) is from 0.001 to 10 mass% in the emulsion [1] reinforcing fiber bundle according.
　[4] emulsion, in addition to the modified polyolefin (A1), further comprising [1] reinforcing fiber bundle according unmodified polyolefin (A2).
　[5] deposition amount of the modified polyolefin occupying the reinforcing fiber bundle (A1), also the total adhesion amount of unmodified polyolefin modified polyolefin occupying the reinforcing fiber bundle may include a (A2) (A1) and the unmodified polyolefin (A2) is 0.1 to 5.0 mass% [1] reinforcing fiber bundle according.

[0010]

　[6] [1] The reinforcing fiber bundle according to a molded article obtained by combining the matrix resin (C), carbon fiber reinforced heat volume ratio of the reinforcing fiber bundle accounted for molded product is 10% to 70% thermoplastic resin molded article.
　[7] the matrix resin (C) is a modified polyolefin (C1) and / or unmodified polyolefin (C2) [6] Carbon fiber-reinforced thermoplastic resin molded article according.
　[8] unmodified polyolefin (C2) is the polypropylene melting point Tm as measured by differential scanning calorimetry (DSC) is 120 ~ 165 ℃ (C2-1) and density 890 ~ 960 kg / m 3 polyethylene (C2 is at least one selected from -2) [7] the carbon-fiber-reinforced thermoplastic resin molded article according.
　[9] The content of the matrix resin modified polyolefin occupying the (C) (C1) is 0 to 50 mass% [7] the carbon-fiber-reinforced thermoplastic resin molded article according.
　[10] unidirectional material, unidirectional laminate, or in the form of random stampable sheet [6] Carbon fiber-reinforced thermoplastic resin molded article according.

[0011]

　[11] containing at least a modified polyolefin carboxylic acid metal salt to bind to the polymer chain (A1), and an amine represented by the following general formula (1) relative to carboxylate groups 1 mol in the modified polyolefin (A1) method for producing a reinforcing fiber bundle compound (B) carbon fiber bundle was immersed in an emulsion containing 0.1 to 5,000 mol, characterized in that subsequent drying. 　　-NH
　R 2 · · · (1) (In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

Effect of the Invention

[0012]

　According to the present invention, since the modified polyolefin as the sizing agent (A1) is uniformly attached to the fiber surface, thereby improving the adhesion between the fiber and the matrix resin in the carbon fiber-reinforced thermoplastic resin molded article. As a result, a sufficient reinforcing effect is exhibited even with a smaller amount of fiber. Carbon fiber-reinforced thermoplastic resin molded article using the reinforcing fiber bundle of the present invention, for example, automobile parts, very useful for applications particularly structural composites parts rigidity and durability are required for aircraft components such as is there.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013]

FIG. 1 is a SEM photograph of unidirectional material obtained in Example 6.
FIG. 2 is a SEM photograph of a random stampable sheet obtained in Example 6.
3 is a SEM photograph of unidirectional material obtained in Comparative Example 4.
It is a SEM photograph of unidirectional material obtained in [4] Comparative Example 5.
[5] Example 8 was 5 hours of continuous immersion in a SEM photograph of the surface portion of the subsequent dry reinforcing fiber bundle.
[6] to 18 hours of continuous immersion in Example 9 is an SEM photograph of the surface portion of the subsequent dry reinforcing fiber bundle.
[7] Example 10 48 hours continuously immersed in a SEM photograph of the surface portion of the subsequent dry reinforcing fiber bundle.
In [8] Comparative Example 7, 1 hour continuously immersed, a SEM photograph of the surface portion of the subsequent dry reinforcing fiber bundle.
[9] Examples 8-10 are schematic views showing the sizing bath used in Comparative Example 7.
FIG. 10 is a SEM photograph of unidirectional material obtained in Example 11.

DESCRIPTION OF THE INVENTION

[0014]

　[Carbon fiber bundles]
　reinforcing fiber bundle of the present invention consists of the treated carbon fiber bundle with the emulsion comprising the specified ingredients. The carbon fiber bundle before treatment, for example, polyacrylonitrile (PAN) based, oil, coal pitch-based, rayon-based, carbon fiber bundles of lignin. Among these, from the viewpoint of productivity and mechanical properties on an industrial scale, PAN-based carbon fibers are particularly preferred. But the average diameter of the single yarn of the carbon fiber bundle is not particularly limited, from the viewpoint of mechanical properties and surface appearance, preferably 1 ~ 20 [mu] m, more preferably 4 ~ 10 [mu] m. Is not particularly limited also single yarn number of carbon fiber bundles, from the viewpoint of productivity and properties, preferably 100 to 100,000, more preferably present from 1,000 to 50,000.

[0015]

　Carbon fiber bundle of the pretreatment, in order to enhance the adhesion between the fiber and the matrix resin, it is preferred that oxygen-containing functional group is introduced into the fiber surface. Introduction amount of oxygen-containing functional groups, for example, identified by surface oxygen concentration ratio of oxygen on the fiber surface as measured by X-ray photoelectron spectroscopy and (O) is an atomic ratio of the number of carbon (C) [O / C] it can. The surface oxygen concentration ratio is preferably from 0.05 to 0.5, more preferably 0.08 to 0.4, particularly preferably from 0.1 to 0.3. If the surface oxygen concentration ratio is 0.05 or more, can be secured functional group of the carbon fiber surfaces, it can be firmly bonded by the matrix resin. On the other hand, if more than 0.5 the surface oxygen concentration ratio, take the handling property and productivity of the balance of the carbon fiber.

[0016]

　[Modified polyolefin (A1)]
　modified polyolefin used in the present invention (A1) is at least containing modified polyolefin carboxylic acid metal salt to bind to the polymer chain. The modified polyolefin (A1), specifically, having a carboxylate group represented by the following formula constituting the metal carboxylate (2). The total amount of the carboxylate groups, the resin per gram, preferably 0.05 to 5 mmol equivalents, more preferably 0.1 to 4 mmoles equivalents, particularly preferably 0.3 to 3 mmol equivalents. Incidentally, Q in formula (2) + represents an alkali metal ion or an ammonium ion or an analogue thereof. Examples of the alkali metal ions, specifically can be exemplified lithium ion, sodium ion, potassium ion and rubidium ions. Potassium ions are preferred among these. As the aminoalcohol ion or analogs thereof, can be exemplified ammonium ion itself, primary aminoalcohol ion, secondary aminoalcohol ion, a tertiary ammonium ion and quaternary ammonium ion. Of these, ammonium ions (NH 4 + ), a quaternary ammonium ion (NR 1 R 2 R 3 R 4+ ; R 1 ~ R 4 carbonization of different having 1 carbon atoms which may be 10 in mutually identical hydrogen group).

[0017]

[Formula 1]

[0018]

　As the raw material of the modified polyolefin (A1) (raw material polyolefin (A0)), for example, propylene polymer backbone content of the ethylene-based polymer and a propylene caused skeletal content of ethylene due exceeds 50 mol% is more than 50 mol% it can be used without limitation. The ethylene polymer, for example, mention may be made of ethylene homopolymer, a copolymer of ethylene and α- olefin having 3 to 10 carbon atoms. Examples of the propylene-based polymer, for example, a propylene homopolymer, propylene and ethylene and / or copolymers of α- olefin having 4 to 10 carbon atoms. Specific examples of suitable raw material polyolefin (A0), homopolypropylene, homo polyethylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer.

[0019]

　Modified polyolefin (A1) may, for example, the polymer chains to a carboxylic acid group of the starting polyolefin (A0) as described above, a carboxylic acid anhydride group or carboxylic acid ester groups grafted introduced, and salts with cations that group is the modified resin converted to the state. In the following description, the carboxylic acid groups introduced into the polymer chain, may be referred to as graft carboxylic acid group are collectively a carboxylic acid anhydride group or carboxylic acid ester group. For the preparation of the modified polyolefin (A1), for example, it can be used a carboxylic acid group, a monomer having a carboxylic acid anhydride group or carboxylic acid ester group as a modifier. Each of these functional groups of the monomers may be neutralized or saponified, it may not be. Examples of such monomers include ethylenically unsaturated carboxylic acids and anhydrides thereof as well as their esters preferred. However, the carboxylic acid monomer having an unsaturated vinyl groups other than ethylenically unsaturated carboxylic acids can also be used.

[0020]

　Specific examples of ethylenically unsaturated carboxylic acids used in the production of the modified polyolefin (A1), include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid It is. Specific examples of anhydrides, nadic (Endoshisu - bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride. Specific examples of esters include methyl ethylenically unsaturated carboxylic acids, monoesters or diesters of ethyl or propyl and the like. These monomers may be used in combination of two or more. Of these, ethylenically unsaturated carboxylic acid anhydrides are preferred, maleic anhydride is particularly preferred.

[0021]

　The monomers as described above, for example, by grafting to the polymer chains of the starting polyolefin such as ethylene-based resin and a propylene resin (A0), can be introduced the desired graft carboxylic acid groups on the polymer chain. As a specific method, for example, the raw material polyolefin (A0) in an organic solvent by graft reaction in the presence of a monomer and a polymerization initiator, then the method to remove the solvent; heating and melting the raw material polyolefin (A0) , the melt and the monomer and a polymerization method initiator and mixed and stirred to a graft reaction; supplying a mixture of raw material polyolefin (A0) and the monomer and a polymerization initiator into an extruder, heated and kneaded and the like; a method of grafting reaction while.

[0022]

　The polymerization initiator used in these methods are not particularly limited, and known polymerization initiators can be used without limitation. Specific examples thereof include benzoyl peroxide, di-chlorobenzoyl peroxide, dicumyl peroxide, di -tert- butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1, 4- bis (tert- butylperoxy-isopropyl), and benzene. The polymerization initiators may be used in combination of two or more. The organic solvent is not particularly limited, and specific examples thereof include xylene, aromatic hydrocarbons such as toluene; hexane, aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; ethyl ketone, and methyl isobutyl ketone ketone solvents; and the like. The organic solvents may be used as a mixture of two or more. Among them, aromatic hydrocarbons, aliphatic hydrocarbons, preferably alicyclic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and more preferably.

[0023]

　Carboxylic acid group as described above, by neutralizing or saponifying desired raw material polyolefin carboxylic acid anhydride or carboxylic acid ester group is introduced (A0), a carboxylic acid metal salt to bind to the polymer chain comprising at least a modified polyolefin (A1) is obtained a. Specifically, for example, in preparing an emulsion containing the polyolefin may be performed neutralization or saponification, if needed. The modified polyolefin (A1), although depending on denaturing conditions may include a polyolefin that is not modified, the present invention defines a modified product including polyolefins such unmodified as modified polyolefin.

[0024]

　In the present invention, in addition to the modified polyolefin (A1), optionally may be used in combination unmodified polyolefin free both graft carboxylic acid group and its carboxylic acid metal salt (A2). When used in combination unmodified polyolefin (A2), the content of the modified polyolefin (A2) is from 1 to 50% by weight, based on the total weight of the modified polyolefin (A1) and the unmodified polyolefin (A2), preferably 3 to 40 wt%, more preferably 5 to 30 mass%. By fall in this range, it is linked to the improvement of the mechanical strength of the carbon fiber-reinforced thermoplastic resin molded article of the present invention. The unmodified polyolefin (A2), already mentioned, can be used without limitation raw polyolefin (A0) for the preparation of a modified polyolefin (A1). Unmodified polyolefin (A2) is the raw material polyolefin (A0) for the preparation of a modified polyolefin (A1) may be in itself, the raw material polyolefin (A0) may be a different polyolefin, preferably non the modified polyolefin (A1) and a raw material polyolefin (A0) having different properties from each other.

[0025]

　In a preferred embodiment of the present invention, the unmodified polyolefin (A2), for example, homopolypropylene, propylene-ethylene copolymer (ethylene caused skeletal content; and 3 to 95 mol%), propylene-1-butene copolymer (1-butene due skeletal content: 5 to 95 mol%), propylene-ethylene-1-butene copolymer (ethylene caused skeletal content: 10 to 25 mol%, 1-butene due skeletal content; 1-30 mol%), ethylene-vinyl acetate copolymer (vinyl acetate caused skeletal content: 25 to 50 mass%) and different two or more blend selected from these polymers.

[0026]

　[Amine compound (B)]
　The amine compound (B) used in the present invention, a primary amine compound represented by the following general formula (1).

[0027]

　　-NH　R 2 · · · (1) (In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

[0028]

　R is undesirable, when the number of carbon atoms is 11 or more hydrocarbon groups, the amine compound in the drying process of the carbon fibers after immersion in an emulsion as described below may not be sufficiently removed. The hydrocarbon group may be an aromatic hydrocarbon, may be an aliphatic hydrocarbon group may be an alicyclic hydrocarbon group, but the operator during the sizing process aliphatic from the viewpoint of working environment and health hydrocarbon group or alicyclic hydrocarbon group is preferred.

[0029]

　Specific examples of preferred amine compounds (B), ammonia (aqueous ammonia), methylamine, ethylamine, n- butylamine, isobutylamine, sec- butylamine, n- pentylamine, isoamylamine, n- hexylamine, cyclohexylamine, to heptylamine, octylamine, include decylamine. Above all, the ease of removal of the drying process and the availability of the point, ammonia (aqueous ammonia) is preferred.

[0030]

　[Emulsion]
　The emulsion for use in the present invention, above-described modified polyolefin (A1) and amine compound (B) comprises at least, the dispersoid (mainly modified polyolefin (A1)) is dispersed in a dispersion medium (water) consisting of Te is a liquid. Typically, the amine compound particulate modified polyolefin in an aqueous solution containing (B) (A1) is an emulsion of dispersed form.

[0031]

　Weight ratio of modified polyolefin (A1) in the emulsion is from 0.001 to 10 mass%, preferably from 0.01 to 5 mass%. The amount of the amine compound in the emulsion (B) is from 0.1 to 5,000 mol per carboxylate group 1 mol of the modified polyolefin (A1) in, preferably 0.5 to 3,000 moles , more preferably from 1 to 1,000 moles. By using such a specific amount of amine compound (B), aggregation of modified polyolefin in the emulsion (A1) is effectively suppressed.

[0032]

　The emulsion may be added a surfactant (D) within a range that does not impair the present invention. By the use of surfactant (D), it can be more effectively prevent aggregation of polymer particles in the emulsion. However, the amount of the surfactant (D) in the emulsion is preferably not more than 5 parts by mass of the modified polyolefin (A1) 100 parts by weight. 5 parts by mass exceeding the adhesive property may deteriorate.

[0033]

　Type of surfactant (D) is not particularly limited. For example, surfactants of the hydrophilic moiety is ionic (cationic, anionic, zwitterionic), either can be used non-ionic surfactant (nonionic surfactant). Among them, nonionic surface active agent which does not contain a counter ion of a metal or a halogen such as to promote the decomposition of the thermoplastic resin is preferred. Nonionic surfactants, modified polyolefin (A1) is the time of adhering to the carbon fibers, the surfactant also adheres simultaneously to improve the openability of carbon fiber bundle in the spreading step. In particular, nonionic surfactants liquid at least 20 ° C. is effective in improving the spreadability of the carbon fiber bundle.

[0034]

　Surfactant with (D), it is also preferable from the viewpoint of preventing aggregation in combination with compounds having a function of lowering the surface tension of the emulsion. Specific examples of such compounds include lower aliphatic alcohols, alicyclic alcohols, glycols, polyvinyl alcohol. The amount of the compound may be the same extent as the surfactant.

[0035]

　Processing of the carbon fiber bundle]
　In the present invention, performs the processing of the carbon fiber bundle with the emulsion described above. This process (the and preferably the inside of the fiber) of at least the modified polyolefin (A1) fiber surface is treated to be attached to, typically a sizing process. Since a certain amount of the amine compound to a modified polyolefin (A1) is in the emulsion (B) coexist, the aggregation of the modified polyolefin (A1) is effectively suppressed, modified polyolefin the fiber surface (A1) is uniformly adhered, resulting adhesion is improved. The total adhesion amount of the reinforcing fiber bundle accounted modified polyolefin (A1) and if necessary with unmodified polyolefin used (A2) is preferably from 0.1 to 5.0 mass%, more preferably from 0.5 to 2. 0 wt%.

[0036]

　In particular this process, emulsion immersing the carbon fiber bundle, it is preferably carried out by subsequent drying.

[0037]

　As a specific method, such as spraying, roller dipping method, a roller transfer method. It may be used in combination method. Among them, a roller dipping method is preferred from the viewpoint of productivity and uniformity. In particular, repeated squeezing and opening via an immersion roller provided in the emulsion bath, it is preferable to immerse the emulsion to the inside of the carbon fiber bundle. The total deposition amount of the adjustment of the modified polyolefin (A1) and optionally unmodified polyolefin used (A2) to carbon fiber bundle, for example, the mass ratio of the Ya-modified polyolefin in the emulsion (A1) and an unmodified polyolefin (A2) it can be done by adjusting the squeezing rollers.

[0038]

　Thereafter, the drying step of the carbon fiber bundle, to remove low boiling components such as moisture and the amine compound (B) as required. Thus, at least a modified polyolefin (A1) is fiber surface (and preferably the inside of the fiber) obtained reinforcing fiber bundle attached to. Low-boiling components such as moisture and an amine compound (B) is preferably completely removed, in some cases may be left part. The drying method is not particularly limited, heat treatment, air-drying, a method such as centrifugation can be used. Among them, preferable heat treatment in terms of cost. The heating means, for example hot air, hot plate, roller, infrared heaters can be used. Temperature of drying treatment is in the range of the surface temperature 50 ~ 200 ° C. of the carbon fiber bundle, it is preferable to remove moisture and alcohol components.

[0039]

　[Carbon fiber-reinforced thermoplastic resin molded article]
　reinforcing fiber bundle of the present invention described above is very useful as a reinforcing material for a thermoplastic resin molded article. That is, the carbon fiber-reinforced thermoplastic resin molded article of the present invention, the reinforcing fiber bundle of the present invention is a molded article obtained by combining the matrix resin (C). The volume ratio of the reinforcing fiber bundle accounts for the molded body is 10 to 70%, preferably 25 to 55%. Since the reinforcing fiber bundle of the present invention has good adhesion to the matrix resin, sufficient reinforcing effect is exhibited even with a smaller amount of fiber.

[0040]

　The matrix resin (C) is not particularly limited, a known resin can be used. Specific examples of the matrix resin (C) is a polyolefin resin, polyamide resin, polyester resin, polycarbonate resin, polyacetal resin, polyether ketone resin, polyether ether ketone resins, and thermoplastic resins such as a polysulfone resin. Among them, high-speed moldability, light weight, mechanical properties of the molded article, from the viewpoint of material recycling property, it is preferable polyolefin resins, particularly modified polyolefin (C1) and / or unmodified polyolefin (C2) is preferred. When used in combination unmodified polyolefin (C2), the amount of the modified polyolefin (C1) is unmodified polyolefin (C2) 100 parts by weight per modified polyolefin maleic anhydride graft modification rate anhydride is from 0.1 to 7 mass% the (C1), preferably 0.1 to 30 parts by weight, and more preferably is blended 1-20 parts by weight, the adhesive strength of the fibers and the resin is further improved. Incidentally, process for preparing the modified polyolefin (C1) can be carried out according to a method for the preparation of the above-mentioned modified polyolefin (A1).

[0041]

　In the present invention, as the matrix resin (C), a propylene homopolymer or a propylene · alpha-olefin random copolymer such as unmodified polypropylene (C2) and / or modified polypropylene (C1) that is a preferred embodiment to use it is one. In particular, the unmodified polyolefin (C2) is the polypropylene melting point Tm as measured by differential scanning calorimetry (DSC) is 120 ~ 165 ℃ (C2-1) and density 890 ~ 960 kg / m 3 polyethylene (C2- a is preferably one or more selected from 2). It is preferable that the content of the modified polyolefin (C1) occupying the matrix resin (C) is 0 to 50 mass%.

[0042]

　Reinforcing fiber bundle, it is preferable to spread as required prior to composite the matrix resin (C). This opening, the matrix resin (C) is sufficiently impregnated into the reinforcing fiber bundle, little unevenness of properties such as strength high-quality molded article can be obtained.

[0043]

　The form of the carbon fiber-reinforced thermoplastic resin molded article, for example, unidirectional material, unidirectional laminate, random stampable sheet (quasi-isotropic material) and the like. Also, cross-ply laminate may be in the form of a long fiber-containing pellets or textile material.

[0044]

　(Unidirectional material (UD material))
　The unidirectional material (UD material) is typically a shaped body comprising a fiber in a state of aligning pull the opened fibers bundles in one. For example, after aligning pull the opened fibers bundles, by contacting the molten matrix resin (C), the unidirectional carbon fiber reinforced thermoplastic resin molded article is obtained. It is also a laminate formed by integrally laminating a plurality of unidirectional material (unidirectional carbon fiber reinforced thermoplastic resin molded article).

[0045]

　(Unidirectional laminates)
　The unidirectional laminates, typically a plurality of unidirectional material in the same direction (0 °) unidirectional laminates or the like by laminating any number (n) to the n it is a laminate of.

[0046]

　(Random stampable sheet)
　A random stampable sheet (quasi-isotropic material), shows the isotropic properties when viewed at a certain size (e.g., fiber length 5 or more times the size of), in stamping molding or press molding a sheet which can be molded into complex shapes. Typically, a material obtained by cutting the unidirectional material into small pieces (e.g., 10 × 10mm ~ 100 × 100mm) was placed in an arbitrary direction, laminating a sheet-like molded body obtained by compressing. The random stampable sheet, for example, those as small as possible anisotropy of mechanical properties due to the orientation of the fibers, and impregnated with the matrix resin to that cut the fiber bundle to a length of 5 ~ 50 mm, Matrix those in a sheet-like sandwich into a film molded from resin.

[0047]

　(Cross-ply laminate)
　Cross-ply laminate is a laminate formed by integrally laminating a plurality of unidirectional carbon fiber reinforced thermoplastic resin molded article in two different directions, e.g., 0 ° / 90 ° / 0 ° / 90 ° / 90 ° / 0 ° / 90 ° / 0 was laminated so that the front and back target structure called ° ((0 ° / 90 ° ) n) s laminate, 0 ° / 45 ° in four different directions / 90 ° / 135 ° / 135 ° / 90 ° / 45 ° / 0 was laminated so that the front and back target structure called ° ((0 ° / 45 ° / 90 ° / 135 °) n) s laminate, two different One direction in 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 0 non-target of the stack, such as °, further laminated by laminating the fabric to the surface of the laminate body, and the like.

[0048]

　Specific methods of producing a unidirectional carbon fiber-containing thermoplastic resin molded article is not particularly limited. For example, melt extrusion laminating method, according to the pultrusion method, molded article matrix resin (C) is sufficiently impregnated in the fiber is obtained. While those with less impregnation of the matrix resin (C), that is, when producing a molded article having a layer of semi-impregnation aligned pull the reinforcing fiber bundle for example on a sheet made of a matrix resin (C) in one direction Te, it may be heated press, if necessary.

[0049]

　(Long fiber-containing pellets)
　long fiber-containing pellets are molded body of the form of pellets as a molding material for use in various molding methods. For example, to obtain a strand impregnated with the modified polyolefin (A1) the reinforcing fiber bundle by extrusion in the molding machine or in the impregnation die, by cutting the strands into a desired length, made of carbon fiber and a thermoplastic resin core it is possible to obtain long fiber-containing pellets sheath.

[0050]

　The length of the long fiber-containing pellets, preferably 3 ~ 100 mm, more preferably 5 ~ 50 mm. Using this pellet, the desired molded article is obtained by performing, for example, injection molding or press molding. The method called recent direct molding method, that supplies the continuous fiber and matrix resin to a molding machine, inside the molding machine was dispersed into the cutting and the matrix resin of the long fibers at the same time, as it is injection molded or press molding this the method can also be used.

[0051]

　Furthermore, unidirectional material, unidirectional laminate, random stampable sheet (quasi-isotropic material), the molded article obtained by cross-ply laminate or fabric material by press molding or cutting also useful.
Example

[0052]

　Hereinafter will be described in more detail the present invention through examples. However, the present invention is not limited thereto. The materials used in the examples are as follows.

[0053]

　[Carbon fiber bundle]
　Examples 1-4, Comparative Example 1: Commercially available carbon fibers (Formosa Plastics Corporation, trade name TC-36S (12K), [ O / C] = 0.22)
　Example 5 and 7, Comparative examples 2, 3 and 6: commercially available carbon fibers (Formosa plastics Corporation, trade name TC-35 (12K), [ O / C] = 0.25)
　examples 8-10 and Comparative example 7: commercially available carbon fiber (Formosa plastics Corporation, trade name TC-35R (12K), [ O / C] = 0.30)

[0054]

　[Raw material resins for emulsion]
　(maleic anhydride-modified polypropylene)
　were used maleic anhydride-modified polypropylene prepared in Preparation Example 1 to be described later.
　(Maleic acid-modified polyethylene resin anhydride)
　with maleic acid modified polyethylene prepared in Preparation Example 2 to be described later.
　(Unmodified polypropylene resin)
　was used propylene-1-butene-ethylene copolymer prepared in Preparation Example 3 to be described later.
　(Unmodified polyethylene resin)
　density 0.87 g / cm 3 , MFR (230 ° C.) 5.4 g / 10 min ethylene-propylene random copolymer (EPR abbreviated: manufactured by Mitsui Chemicals, Inc. TAFMER P, ethylene due backbone content = 82 mol%) was used.

[0055]

　[Amine compound (B)]
　of aqueous ammonia (Junsei Chemical Co., ammonia concentration of 28 wt%)

[0056]

　[Matrix resin (C)]
　Examples 1-4, Comparative Examples 1-3: Commercially available unmodified polypropylene resin (Prime Polymer Co., Ltd., trade name Prime Polypro J105G, MFR (230 ℃, 2.16kg load) = 9. 0 g / 10 min, melting point = 162 ° C.), and a commercially available acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., registered trademark Admer QE800, MFR (230 ℃, 2.16kg load) = 9.0 g / 10 min) mixture of (weight ratio; J105 / QE800 = 95/5 or 90/10, either or both of)
　example 5: commercially available unmodified polypropylene resin (Prime polymer Co., Ltd., trade name Prime Polypro J106MG, MFR (230 ℃, 2.16kg load) = 15.0 g / 10 min, melting point = 162 ° C.)], and a commercially available acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., registered trademark Admer E800, MFR (230 ℃, 2.16kg load) = 9.0 g / 10 min) mixture of (mass ratio; J106MG / QE800 = 90/10 )

[0057]

　Production Example 1]
　(Preparation of maleic anhydride-modified polypropylene)
　Polypropylene (Prime Polymer Co., Ltd., trade name J106G, MFR (230 ℃, 2.16kg ) = 15g / 10 min) with respect to 100 parts by weight of a dialkyl peroxide (manufactured by NOF Corporation, Perhexa (R) 25B) 1 part by weight, powdered maleic anhydride (manufactured by NOF Corporation, CRYSTAL MAN (registered trademark)) 3 parts by weight were premixed. The mixture was fed to a twin-screw extruder of 30mmφ thermostated at 190 ° C., the strands obtained by melt-kneaded to obtain maleic anhydride-modified polypropylene was cooled in a water bath at 200 rpm. To remove residual unreacted maleic anhydride-modified and the maleic anhydride-modified polypropylene was vacuum dried for two hours at 40 ° C.. Maleic acid content of the resulting maleic acid-modified polypropylene was 4.5 wt%.

[0058]

　The measurement method of the graft ratio is as follows: dissolved polymer to 200mg and chloroform 4800mg heated 30 minutes put 50 ° C. into a sample bottle of 10ml completely. Material NaCl, put chloroform liquid cell having an optical path length of 0.5 mm, and a background. Then dissolved polymer solution put in the liquid cell, photometer (manufactured by JASCO Corporation, apparatus name FT-IR460plus) was used to measure the infrared absorption spectrum at integration number 32 times. Regard graft ratio of maleic acid, maleic anhydride and measuring the absorption of the carbonyl group of a solution in chloroform to prepare a calibration curve. The absorption peak (1780 cm in the carbonyl group of the sample -1 near the maximum peak, 1750 ~ 1813Cm -1 ) from the area of, on the basis of a calibration curve prepared previously, to calculate the acid component content in the polymer, this and the graft ratio (wt%).

[0059]

　Production Example 2]
　(maleic anhydride Preparation of modified polyethylene resin)
　ethylene-propylene copolymer (ethylene caused skeletal content = 95 mol%, density = 920 kg / m 3 was charged) a 500g glass reactor, nitrogen It was melted at under 160 ℃. Then, maleic anhydride 15g, and di -t- butyl peroxide 1.5g was continuously fed over 5 hours to the reaction system (temperature 160 ° C.). Then, after further heating for 1 hour the reaction was removed 0.5 hours deaerated volatiles in 10mmHg vacuum a molten state. After cooling, to obtain a maleic anhydride grafted modified polyethylene resin. A result of measuring the maleic acid graft amount in the polymer, grafted amount was 2.7 wt%.

[0060]

　Production Example 3]
　(unprepared modified polypropylene-based
　resin) by the method described in Polymerization Example 4 of WO2006 / 098 452 specification, to obtain a propylene-1-butene-ethylene copolymer. Propylene caused skeletal content = 66 mol%, ethylene due skeletal content = 11 mol%, 1-butene due skeletal content = 23 mol%, melt flow rate (230 ° C., 2.16 kg load) was = 6.5 g / 10 min It was.

[0061]

　[Example 1]
　(Preparation of emulsion)
　propylene-1-butene-ethylene copolymer 100 parts by mass of the obtained anhydrous 10 parts by weight maleic acid-modified polypropylene obtained in Production Example 1 and Production Example 3, the surfactant It was mixed potassium oleate 3 parts by weight of a (D). The mixture twin screw extruder (Ikegai Tekko Co., device name PCM-30, L / D = 40) using, in accordance with the method described in Example of JP-A-10-131048 discloses emulsion It was prepared. The resulting emulsion solids and 45% by weight of (water dispersion), the acid value was 11.5MgKOH / solids 1g converted value).

[0062]

　Then, the emulsion 2.3 parts by weight, ammonia water (ammonia concentration 28 mass%) 5 parts by weight, by mixing distilled water 92.7 parts by mass, to obtain an emulsion comprising components (A) and (B) . This in the emulsion, 0.09% by mass concentration of modified polypropylene containing induced carboxylic acid potassium salt from maleic anhydride-modified polypropylene, the concentration of the propylene-1-butene-ethylene copolymer 0.91% by weight , ammonia (NH 3 concentration) was 1.4 wt%.

[0063]

　(Carbon fiber treatment bundle)
　The emulsion, a commercially available carbon fiber using a roller impregnation method was attached to a carbon fiber bundle consisting of (Formosa Plastics Corporation, trade name TC-36S (12K)). Then, 130 ° C. online, and dried for 2 minutes to remove the low-boiling components, to obtain a reinforcing fiber bundle of the present invention. Then, the the reinforcing fiber bundle, as the matrix resin (C), commercially available unmodified polypropylene resin (Prime Polymer Co., Ltd., trade name Prime Polypro J105G) and commercially available acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., registered trademark Admer QE800 ) using a mixture (mass ratio 95/5 or 90/10), to produce a carbon fiber reinforced thermoplastic resin molded article of the present invention.

[0064]

　[Examples 2-4 and Comparative Example 1]
　ammonia in the emulsion (NH 3 except that the concentration of)

[0065]

　[Example 5]
　Ammonia (NH in the emulsion 3 was prepared blending composition so that the concentration of) Then, 130 ° C. online, and dried for 2 minutes to remove the low-boiling components, to produce a reinforcing fiber bundle. Then, the the reinforcing fiber bundle, as the matrix resin (C), commercially available unmodified polypropylene resin (Prime Polymer Co., Ltd., trade name Prime Polypro J106MG) and commercially available acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., registered trademark Admer QE800 ) using a mixture (mass ratio 90/10) was prepared carbon fiber reinforced thermoplastic resin molded article of the present invention.

[0066]

　[Comparative Example 2]
　Commercially available carbon fiber bundle and (Formosa Plastics Corporation, trade name TC-35 (standard grade epoxy-based sizing agent is attached to 12K)), commercially available unmodified polypropylene resin as the matrix resin (C) ( Prime polymer Co., Ltd., trade name Prime Polypro J105G) and commercially available acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., using a mixture of R Admer QE800) (mass ratio 90/10), carbon fiber reinforced thermoplastic resin molded article It was produced.

[0067]

　[Comparative Example 3]
　Polyvinyl alcohol (PVA) (Chang Chun Plastics Co., Ltd., trade name BP-05G) with an aqueous solution concentration of 0.7 wt% of a commercially available carbon fiber using a roller impregnation method (Formosa Plastics Corp. , it was attached to the trade name TC-35 (12K)). Then, online 140 ° C., and dried for 1 minute to remove water to obtain a reinforcing fiber bundle PVA is adhered 0.4 wt%. And the reinforcing fiber bundle, as the matrix resin (C), commercially available unmodified polypropylene resin (Prime Polymer Co., Ltd., trade name Prime Polypro J105G) and commercially available acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., registered trademark Admer QE800) of mixture (weight ratio 90/10) was used to prepare a carbon fiber reinforced thermoplastic resin molded article.

[0068]

　The evaluation results of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1. Each measurement was conducted in the following manner.

[0069]

　
　The reinforcing fiber bundle of about 5g was dried 3 hours at 120 ° C., its mass W 1 was measured (g). Then, the reinforcing fiber bundle was heated for 15 minutes at 450 ° C. in a nitrogen atmosphere, then cooled to room temperature, the mass W 2 was measured (g). Adhesion amount was calculated by the following equation.
　Adhesion amount (%) = [(W 1 -W 2 ) / W 2 ] × 100

[0070]

　
　Evaluation of interfacial shear shear strength of the reinforcing fiber bundle and a matrix resin of the present invention (fragmentation method) were measured by the following methods. 100μm thickness of the resin film made of a matrix resin (C) to (20 cm × 20 cm square) were prepared. And on one of the resin film, placing a single monofilament 20cm length taken from the reinforcing fiber bundle in a straight line, and the other resin film was placed on top to sandwich the single fiber. This 200 ° C. for 3 minutes, was pressure-pressed at a pressure of 4 MPa, to prepare a sample monofilaments embedded in the resin. The sample is further cut, single fiber was obtained thickness 0.2mm was buried in the center, width 5 mm, a test piece of length 30 mm. Further to prepare a total of five test pieces in the same way.

[0071]

　These for the 5 test pieces, the test length 14mm using conventional tensile test jig, subjected to tensile test under the conditions of strain rate 0.3 mm / min, the average breaking fiber when fiber breakage no longer takes place the length of (l) was measured using a transmission optical microscope. Interfacial shear strength by fragmentation method (τ) (MPa) was calculated from the following equation.

[0072]

　τ＝（σf・ｄ）／２Ｌc、　　　Ｌc＝（４／３）・Ｌ

[0073]

　Here, Lc is the critical fiber length, L is the average value of the final fiber breakage length of (μm), σf is the tensile strength of the fibers (MPa), d is the fiber diameter ([mu] m). (Reference: Osawa et al., Fiber Journal Vol.33, No.1 (1977))

[0074]

　σf is the tensile strength distribution of the fibers was determined by the following method as a Weibull distribution. That is, using a single fiber, a sample length of 5 mm, 25 mm, by the method of least squares from the mean tensile strength obtained by 50 mm, determine the relation between the average tensile strength and sample length, the average tensile strength at the sample length Lc It was calculated.

[0075]

[Table 1]

[0076]

　[Example 6]
　(unidirectional material)
　using a reinforcing fiber bundle obtained in Example 5, the apparatus combining an extruder to melt the resin in the apparatus described in JP 2013-227695, unidirectional a sheet of wood was prepared by the following procedure. The matrix resin (C) at that time, using the same resin as that used in Example 5. Specifically, JP by opening device described in 2013-227695 JP by opening the reinforcing fiber bundle, film shape by the matrix resin (C) was melted T-die by heating the reinforcing fiber bundle and the extruder and then, sandwiched between release paper, heated at pressure roller, the matrix resin (C) impregnating the reinforcing fiber bundle by pressurizing, then cooled to obtain a sheet of unidirectional material solidifies. Extruder and the temperature of the T die 250 ° C., the temperature of the pressure roll was 275 ° C..

[0077]

　The thickness of the sheet obtained unidirectional material 130 .mu.m, fiber volume fraction Vf was 0.4. To confirm the impregnation situation, SEM (scanning electron microscope) was conducted (JEOL Ltd., device name JSM7001F, accelerating voltage 10 kV, the reflected electron image) of the observation using. Specifically embedded unidirectional material epoxy resin, and polishing the surface to produce a smooth cross-section by polishing machine and subjected to SEM observation. 1, the SEM is a photograph (500 times), the filaments of the white portion reinforcing fiber bundle, a black portion is the matrix resin (C). The SEM photograph as apparent from, and the matrix resin (C) is impregnated very well to the reinforcing fiber bundle, non-impregnated portions or voids were observed.

[0078]

　Note relates fiber volume fraction of the above, the method of testing fiber content of carbon fiber reinforced plastics has been described in JIS K7075, where determined by the following method. A sample was cut out of the sheet into a square of 50 mm × 50 mm, the mass was measured Wc (g). The cut samples were heated for 1 hour at 480 ° C., the resin was removed by thermal degradation, and measuring the mass Wf of only carbon fibers (g), was determined fiber deposition fraction Vf the following equation.

[0079]

　Xian-dimensional volume fraction Vf = (Wf / Wc) × ρc / ρf

[0080]

　Here, rho] c is the density of the sample (g / cm 3 ), .rho.f the density of the carbon fiber used in the sample (g / cm 3 is).

[0081]

　(Unidirectional laminates)
　Further, the sheet of unidirectional material with 8 layers laminated in 0 ° direction, which press apparatus equipped with a mold for flat plate (Co. Shinto Metal Industries, Ltd., device name NSF -37HHC) it was placed in. Then, 200 ° C., then 3 minutes under pressure compressed by 5 MPa, then immediately cooled while under pressure, to obtain a unidirectional laminate of 1.0mm thickness.

[0082]

　Cut out the obtained unidirectional laminate produced four test pieces (250 mm × 15 mm), perform tensile testing machine (Zwick Co., device name Z100) a tensile test at 2 mm / min using a (according to ASTM D3039) the elastic modulus and rupture strength were measured and averaged value of the four specimens. As a result, the elastic modulus 96.6GPa, breaking strength was 935MPa. Moreover, short-span bending test apparatus (manufactured by Shimadzu Corporation, apparatus name Shimadzu Autograph AG-5KNX) was used to measure the interlaminar shear stress (ILSS) (conforming to ASTM D2344). As a result, ILSS was 28.9MPa.

[0083]

　(Random stampable sheet)
　Moreover, to cut the sheet of the unidirectional material into pieces of 30 ~ 50mm × 30 ~ 50mm, placing these pieces to be overlapped 8-9 layers in and any point in random directions the laminate (random oriented body), 200 ° C. using the same equipment and apparatus used during the production unidirectional laminate, pressurizing and pressure compressed 3 minutes at 10 MPa, and cooled immediately leave then pressurized state, 1. to obtain a random stampable sheet of 0mm thickness of the sheet.

[0084]

　Against random stampable sheet obtained were subjected to the same tensile test and tensile test performed on unidirectional laminates. As a result, the elastic modulus 22.6GPa, breaking strength was 138 MPa. Further, SEM observation was performed in the same way as for the seat of the unidirectional material. And FIG. 2 is a SEM photograph (150 times). The SEM photograph as is apparent from, the layer aligned fibers in the same direction, were eight layers laminated in arbitrary fiber orientation.

[0085]

　[Comparative Example 4]
　(unidirectional material)
　Comparative Example 2 Commercially available carbon fiber bundle used in using (Formosa Plastics Corporation, epoxy-based sizing agent standard stocks attached to the product name TC-35 (12K)) except, to prepare a sheet of unidirectional material in the same manner as in example 6, was subjected to SEM observation. Figure 3 is its SEM photograph (500 times). As is apparent from this SEM photograph, the portion being peeled at the interface between the reinforcing fiber bundles of filaments and the matrix resin (C) was present.

[0086]

　(Unidirectional laminates)
　Further, using a sheet of the unidirectional material, to produce a unidirectional laminate in the same manner as in Example 6 was measured interlaminar shear stress (ILSS). The ILSS was 17.3MPa.

[0087]

　[Comparative Example 5]
　(unidirectional material)
　except for the use of reinforcing fiber bundle obtained in Comparative Example 3, to prepare a sheet of unidirectional material in the same manner as in Example 6, was subjected to SEM observation. Figure 4 is its SEM photograph (500 times). As is apparent from this SEM photograph, non-impregnated portion (white portion) of the matrix resin (C) with respect to the reinforcing fiber bundle was present.

[0088]

　(Unidirectional laminates)
　Further, using a sheet of the unidirectional material, to produce a unidirectional laminate in the same manner as in Example 6 was measured interlaminar shear stress (ILSS). The ILSS was 19.5MPa.

[0089]

　Evaluation results of Example 6 and Comparative Examples 4-5 are shown in Table 2.

[0090]

[Table 2]

[0091]

　[Example 7]
　(Preparation of emulsion)
　maleic anhydride-modified polyethylene 10 parts obtained in Production Example 2 and ethylene-propylene random copolymer (manufactured by Mitsui Chemicals, Inc. TAFMER P) 100 parts by weight of a surfactant ( were mixed 1.5 parts by weight of potassium oleate as D), by the same method as in example 1 to obtain an emulsion comprising components (a) and component (B). The resulting emulsion solids and 45% by weight of (water dispersion), the acid value was 5.0 mgKOH / solids 1g converted value).

[0092]

　Then, the emulsion 2.3 parts by weight, ammonia water (ammonia concentration 28 wt%) 10 parts by weight, by mixing distilled water 88 part by weight an emulsion comprising components (A) and (B). This emulsion, 0.09% by mass concentration of modified polyethylene containing induced carboxylic acid potassium salt from the maleic anhydride-modified polyethylene, concentration of EPR is 0.91 wt%, ammonia (NH 3 concentration) is was 2.8 wt%.

[0093]

　(Carbon fiber treatment bundle)
　The emulsion, a commercially available carbon fiber using a roller impregnation method (Formosa Plastics Corporation, trade name TC-35 (12K)) was attached to the carbon fiber bundle consisting of. Then, 130 ° C. online, and dried for 2 minutes to remove the low-boiling components, to obtain a reinforcing fiber bundle of the present invention. Then, the the reinforcing fiber bundle, as the matrix resin (C), commercially available unmodified polyethylene (Prime Polymer Co., Ltd., trade name Prime Polypro 1300J), and maleic acid 2.0 wt% grafted modified polyethylene anhydrous (ASTM D1238 the melt flow rate measured at 190 ° C. according to the used mixture of 1.8 g / 10 min) (mass ratio 98.75 / 1.25), to produce a carbon fiber reinforced thermoplastic resin molded article of the present invention . The evaluation results are shown in Table 3.

[0094]

　[Comparative Example 6]
　ammonia in the emulsion (NH 3 except that the concentration of) The evaluation results are shown in Table 3.

[0095]

[table 3]

[0096]

　Example 8
　Formosa Plastics Corp. carbon fiber bundle (trade name TC35R-12K) 4 present and in the sizing bath 9 potassium carboxylate used in Example 1 containing modified polypropylene / propylene-1 - butene-ethylene copolymer (weight ratio; 1/9) in ammonia are each 1.5 mass% and 1.0 mass% and becomes thus prepared sizing liquid (emulsion), does not contact the fiber bundles with each other as such, the linear velocity is continuously immersed in 7m / min speed (immersion time: 5 seconds) to nip rolls (linear pressure: 205N / m) made of a rubber roller 1 and the steel roller 2 is passed through, followed 130 ° C. in by drying for 2 minutes, to obtain a continuous dry carbon fiber bundle. Incidentally, the present continuous immersion and drying equipment, with a mechanism to be supplied into the supply pump 7 thus continuously immersion tank 5 sizing agent is installed separately prepared sizing agents auxiliary tank be reduced by immersion there.

[0097]

　The continuous immersion test, after the start of the carbon fiber bundle supply was carried out for 48 hours at the longest. And selecting any nine locations of the four dry carbon fiber bundle every predetermined time was measured and adhesion amount of the components (A), the coefficient of variation, the SEM photograph of the fiber bundle surface. As component (A) adhesion measuring said method. Moreover, SEM photographs were measured at an acceleration voltage of 20kV using a JEOL Ltd. (JEOL JSM-5600) (1,000-fold magnification). Measurement sample was used gold-deposited by vacuum sputtering before SEM measurement.

[0098]

　In the carbon fiber bundle 3 hours after the supply of the immersion bath, the variation coefficient of adhesion amount of component (A) was increased in 3 hours. According to the fifth hour of the SEM photograph (FIG. 5), projecting foreign matter carbon fiber surface was large amount observed. As for the sizing solution used in Example 8, the surface tension was measured separately (KRUSS Co. using a surface tension meter K100. Measurements by ring method) was 44.2mN / m.

[0099]

　Example 9
　In Example 8, except for changing the ammonia concentration to the value shown in Table 4 was subjected to the same continuous immersion test as in Example 8. Up to 12 hours after the carbon fiber bundle supply to the immersion tank, deposition amount and its variation coefficient of the component (A) is stabilized remained doubled variation coefficient 18 hours. According to 18 hours SEM photograph (FIG. 6), it was found that the projecting foreign matter is slightly observed carbon fiber surface. As for the sizing solution used in Example 9, the surface tension was measured separately (using the surface tension meter K100 KRUSS Co.. Measurement by ring method) was 43.4mN / m.

[0100]

　[Example 10]
　In Example 8, except for changing the ammonia concentration to the value shown in Table 4 was subjected to the same continuous immersion test as in Example 8. Until the carbon fiber bundle supply 24 hours after the immersion tank is deposited amount and its variation coefficient of the component (A) was confirmed to be stable transition. In 48 hours of the SEM photograph (FIG. 7), it was found that is not observed at all projecting foreign matter on the surface of the carbon fibers. As for the sizing solution used in Example 10, the surface tension was measured separately (KRUSS Co. using a surface tension meter K100. Measurements by ring method) was 43.2mN / m.

[0101]

　[Comparative Example 7]
　In Example 8, except for using no ammonia was subjected to the same continuous immersion test as in Example 8. Carbon fiber bundle aggregate with 1 hour after supply to the immersion tank is produced, it was confirmed that the coefficient of variation of the component (A) coating weight is rapidly increased. According to the first hour of the SEM photograph (FIG. 6), it was found that the whisker foreign matter is a large amount observed carbon fiber surface. As for the sizing solution used in Comparative Example 7, the surface tension was measured separately (KRUSS Co. using a surface tension meter K100. Measurements by ring method) was 50.0mN / m.

[0102]

[Table 4]

[0103]

　As apparent from the results of Examples 8-10 and Comparative Example 7, the modified polyolefin resin containing potassium carboxylate salt known polymer chain in the sizing solution by the addition of ammonia, sizing carbon fibers agent is found to be stably attached. The reason is considered that makes it easy penetration of the sizing agent molecules to the carbon fiber surface of the microstructure by surface tension of the sizing solution is reduced. It is also conceivable contribute to exhibit the effect of the present invention to increase particle stability of the dispersion containing a sizing agent by ammonia addition.

[0104]

　[Example 11]
　(unidirectional material)
　using a reinforcing fiber bundle obtained in Example 10, the apparatus combining an extruder to melt the resin in the apparatus described in JP 2013-227695, unidirectional a sheet of wood was prepared by the following procedure. The matrix resin (C) at that time, using the same resin as that used in Example 5. Specifically, JP by opening device described in 2013-227695 JP by opening the reinforcing fiber bundle, film shape by the matrix resin (C) was melted T-die by heating the reinforcing fiber bundle and the extruder and then, sandwiched between release paper, heated at pressure roller, the matrix resin (C) impregnating the reinforcing fiber bundle by pressurizing, then cooled to obtain a sheet of unidirectional material solidifies. Extruder and the temperature of the T die 260 ° C., the temperature of the pressure roll was 270 ° C..

[0105]

　The thickness of the sheet obtained unidirectional material 150 [mu] m, fiber volume fraction Vf was 0.356. To confirm the impregnation situation, SEM (scanning electron microscope) was conducted (JEOL Ltd., device name JSM7001F, accelerating voltage 10 kV, the reflected electron image) of the observation using. Specifically embedded unidirectional material epoxy resin, and polishing the surface to produce a smooth cross-section by polishing machine and subjected to SEM observation. 10, the SEM is a photograph (500 times), the filaments of the white portion reinforcing fiber bundle, a black portion is the matrix resin (C). The SEM photograph as apparent from, and the matrix resin (C) is impregnated very well to the reinforcing fiber bundle, non-impregnated portions or voids were observed.

[0106]

　(Unidirectional laminates)
　Further, the sheet of unidirectional material with 7-layer laminate in the 0 ° direction, which press apparatus equipped with a mold for flat plate (Co. Shinto Metal Industries, Ltd., device name NSF -37HHC) it was placed in. Then, 230 ° C., and 5MPa for 5 minutes under pressure compressor, then immediately cooled while under pressure, to obtain a unidirectional laminate of 1.0mm thickness.

[0107]

　Cut out the obtained unidirectional laminate produced four test pieces (250 mm × 15 mm), perform tensile testing machine (Zwick Co., device name Z100) a tensile test at 2 mm / min using a (according to ASTM D3039) the elastic modulus and rupture strength were measured and averaged value of the four specimens. As a result, the elastic modulus 83.0GPa, breaking strength was 1180 MPa. Moreover, short-span bending test apparatus (manufactured by Shimadzu Corporation, apparatus name Shimadzu Autograph AG-5KNX) was used to measure the interlaminar shear stress (ILSS) (conforming to ASTM D2344). As a result, ILSS was 27.2MPa.

DESCRIPTION OF SYMBOLS

[0108]

　1 rubber roller
　2 steel rollers
　3 solution sagging collecting plate
　4 liquid sagging recovery tank
　5 emulsion of containing immersion tank
　6 carbon fiber running direction of
　7 emulsion supply pump

The scope of the claims

[Claim 1]

　Comprising at least a modified polyolefin carboxylic acid metal salt to bind to the polymer chain (A1), and the modified polyolefin (A1) a carboxylate group 1 mol per the following general formula (1) represented by the amine compound in (B ) reinforcing fiber bundle comprising a bundle of carbon fibers treated with an emulsion containing 0.1 to 5,000 moles. 　　-NH
　R 2 · · · (1) (In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

[Claim 2]

　Emulsion was immersed carbon fiber bundle, the reinforcing fiber bundle of claim 1, wherein obtained by subsequent drying.

[Claim 3]

　Weight ratio of modified polyolefin (A1) is, the reinforcing fiber bundle of claim 1, wherein from 0.001 to 10 mass% in the emulsion.

[Claim 4]

　Emulsion, in addition to the modified polyolefin (A1), the reinforcing fiber bundle of claim 1, further comprising an unmodified polyolefin (A2).

[Claim 5]

　Strengthening adhesion amount of the fiber bundle accounted modified polyolefin (A1), also the total adhesion amount of unmodified polyolefin modified polyolefin occupying the reinforcing fiber bundle may include a (A2) (A1) and the unmodified polyolefin (A2), 0. reinforcing fiber bundle of claim 1, wherein from 1 to 5.0 mass%.

[Claim 6]

　The reinforcing fiber bundle of claim 1 wherein, a molded article obtained by combining the matrix resin (C), carbon fiber reinforced thermoplastic resin molded volume ratio of the reinforcing fiber bundle accounted for molded product is 10% to 70% body.

[Claim 7]

　The matrix resin (C) is a modified polyolefin (C1) and / or unmodified polyolefin (C2) in a claim 6 carbon fiber-reinforced thermoplastic resin molded article according.

[8.]

　Unmodified polyolefin (C2) is, polypropylene (C2-1) and density 890 ~ 960 kg / m is the melting point Tm is 120 ~ 165 ° C. as measured by differential scanning calorimetry (DSC) 3 Polyethylene is a (C2-2) carbon fiber-reinforced thermoplastic resin molded article according to claim 7, wherein at least one selected from the.

[Claim 9]

　The content of the modified polyolefin (C1) occupying the matrix resin (C) is 0 to 50 wt% claim 7 carbon fiber-reinforced thermoplastic resin molded article according.

[Claim 10]

　Unidirectional material, unidirectional laminate, or carbon fiber-reinforced thermoplastic resin molded article according to claim 6, wherein in the form of a random stampable sheet.

[Claim 11]

　Comprising at least a modified polyolefin carboxylic acid metal salt to bind to the polymer chain (A1), and the modified polyolefin (A1) a carboxylate group 1 mol per the following general formula (1) represented by the amine compound in (B ) 0.1 to carbon fiber bundles were immersed in the emulsion containing 5,000 mol, method for producing a reinforcing fiber bundle subsequently characterized by drying. 　　-NH
　R 2 · · · (1) (In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)