0001]The present invention is a carbon fiber bundle comprising impregnating aid molding the thermoplastic resin is coated, the aggregate of the molding composition, a method of manufacturing a molding material, and a method of manufacturing an assembly of molding material it is intended.
BACKGROUND
[0002]As high strength, and means for obtaining a resin material brittle fracture is suppressed, and the resin is known that a composite material reinforced with carbon fibers. In particular, a composite material reinforced thermoplastic resin as the matrix resin in the carbon fiber is easy processability and has excellent recyclability, application to various fields is expected as a molding material.
　For example, Patent Document 1, a polycarbonate resin was coated on the carbon fiber bundle was attached impregnation aids, by cutting into pellets, molding the carbon fibers during the melt-kneading of the injection molding is easily dispersed proposed It is. Patent Document 2, the molding material obtained by coating the polycarbonate resin in the carbon fiber bundles adhered with the phenolic resin have been proposed.
CITATION
Patent Document
[0003]
Patent Document 1: WO 2013/137246 Patent
Patent Document 2: Japanese Patent 2014-159560 JP
Summary of the Invention
Problems that the Invention is to Solve
[0004]
　However, in the molding material described in Patent Documents 1 and 2, it falls off the carbon fibers when cutting the carbon fiber bundle coated with the resin (drop off), causes a decrease in productivity. Therefore, more high productivity, molding materials having excellent handling property is demanded.
　An object of the present invention is to solve the above problems of the conventional molding materials, to suppress the dropping of the carbon fibers from the molding material, the molding material having improved productivity and handling, assembly of the molding material, and to provide a manufacturing method of assembly of the molding material and the molding material.
Means for Solving the Problems
[0005]
　In order to solve the above problems, the present invention provides the following means.
[0006]
<1>
　to the carbon fiber bundle comprising impregnating aid is an aggregate of the molding material a thermoplastic resin is coated,
　the molding material length in the axial direction of the carbon fiber bundle L, to the molding material of the carbon fiber bundle when the gripping force F, the molding material satisfying 100 ≦ F / L (N / m) is present more than 30% of the total aggregates,
aggregates of the molding material.
<2>
　The molding material, a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, and the axial length of the carbon fiber bundle, the length of the molding material is substantially identical to < assembly of the molding material according to 1>.
<3>
　When the molding material was observed by cutting in the axial direction, the molding material satisfying the following formula (1), collection of the molding material according to <2>.
　0.4 ≦ carbon fiber single yarn area × carbon fiber bundle of the single number of yarns / thermoplastic resin of the inner circumferential enclosed by the area ≦ 0.9 ··· (1)
　where, surrounded by the inner periphery of the thermoplastic resin and area is the average value of the aggregate of the molding material.
<4>
　impregnating aid is one or more selected from the group consisting of phosphoric acid ester and an aliphatic hydroxycarboxylic acid based polyester <1> to <3> assembly of the molding material according to any one.
<5>
　impregnating aid is a solid at 20 ° C., <1> ~ <4> assembly of the molding material according to any one.
<6>
　linear expansion coefficient of the thermoplastic resin K 1(10 -4 / ° C.), the coefficient of linear expansion of the impregnating aid K 2 (10 -4 when a / ° C.), the aggregate of the molding material satisfies the following formula (2), <1> to <5> either assembly of the molding material according to any one of claims.
　0.1 <| K 1 -K 2 | · · ·
(2) <7>
　The solubility parameter (SP) value of the thermoplastic resin S 1 ((cal / cm 3 ) 1/2 ), impregnation aids the SP value S 2 ((cal / cm 3 ) 1/2 when a) the aggregate of the molding material satisfies the following formula (3), the molding material according to one of claims <1> to <6> or collection of.
　| S 1 -S 2 | <1.5 · · ·
(3) <8>
　the axial length of the carbon fiber bundle is 1 ~ 30mm, <1> ~ <7> according to any one the aggregate of the molding material.
<9>
　thermoplastic resin comprises an amorphous resin, <2> to <8> assembly of the molding material according to any one.
<10>
　thermal comprising thermoplastic resin and polycarbonate, <2> to <9> assembly of the molding material according to any one.
<11>
　The thermoplastic resin is not impregnated within a carbon fiber bundle, <1> to <10> assembly of the molding material according to any one.
<12>
　F / L (N / m) to <11> assembly of the molding material according to any one .
<13>
　<1> to <12> an aggregate of the molding material according to any one,
　when the water content W of the carbon fiber bundle comprising impregnating aid (wt%), 0.001 ≦ W (wt%) <0.4, aggregation of the molding material.
<14>
　diameter D of the cross-sectional shape when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material 1 and minor axis D 2 D is the ratio of the 1 / D 2 is 1.1 or more 1. 8 or less, <1> to <13> assembly of the molding material according to any one.
<15>
　A method of manufacturing a molding material sheath structure coated with a thermoplastic resin around the carbon fiber bundle comprising impregnating aid the carbon fiber bundle, when impregnating aid is crystalline resin has a melting point or more, the non while in the case of-crystalline resin heated above the glass transition temperature, is integrated by coating a thermoplastic resin, the manufacturing method of the molding material.
<16>
　<15> using the method of manufacturing a molding material according to a method of producing an assembly of molding material,
　the molding material in the axial direction of the carbon fiber bundle length L, a molding material of the carbon fiber bundle when the gripping force F to the molding material satisfying 100 ≦ F / L (N / m) <100,000 is present more than 30% of the total aggregate, the production method of assembly of the molding material.
<17>
　to produce a covering body which is integrally coated with a thermoplastic resin in the carbon fiber bundle, which after cooling below the glass transition temperature of the thermoplastic resin to produce a molding material by cutting, <15> method of manufacturing a molding material according to.
<18>
　<15> or method of manufacturing a molding material according to <17>,
　when the water content W of the carbon fiber bundle comprising impregnating aid (wt%), 0.001 ≦ W (wt% ) <0.4, the manufacturing method of the molding material.
<19>
　the carbon fiber bundle comprising impregnating aid, a molding material a thermoplastic resin is coated,
　the gripping force of the molding material length in the axial direction of the carbon fiber bundle L, the molding material of the carbon fiber bundle F when a molding material satisfying 80 ≦ F / L (N / m).
<20>
　The molding material, a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, and the axial length of the carbon fiber bundle, the length of the molding material, which is the substantially same <19> molding material described.
<21>
　When the molding material was observed by cutting in the axial direction, the molding material satisfying the following formula (1), molding material according to <20>.
　0.4 ≦ carbon fiber single yarn area × carbon fiber bundle of the single number of yarns / thermoplastic resin of the inner circumferential enclosed by the area 0.9 · · · ≦ (1)
<22>
　impregnating aid is phosphoric acid esters and molding material according to 1 is more than <19> - <21> any one selected from the group consisting of aliphatic hydroxycarboxylic acid based polyester.
<23>
　impregnating aid is a solid at 20 ℃, <19> ~ < 22> molding material according to any one.
<24>
　coefficient of linear expansion of the thermoplastic resin K 1 (10 -4 / ° C.), the coefficient of linear expansion of the impregnating aid K 2 (10 -4 / ° C.) and the time, the molding material satisfying the following formula (2) the molding material according to item 1 or <19> - <23>.
　0.1 <| K 1 -K 2 | · · · (2)
<25>
　Thermoplastic solubility parameter (SP) value of the resin S 1 ((cal / cm 3 ) 1/2 ), the SP value of the impregnation aid S 2 ((cal / cm 3 ) 1/2 and) when, the molding material satisfying the following formula (3), the molding material according to item 1 or <19> - <24>.
　| S 1 -S 2 | <1.5 · · ·
(3) <26>
　axial length of the carbon fiber bundle is 1 ~ 30mm, <19> ~ <25> according to any one molding material.
<27>
　thermoplastic resin comprises an amorphous resin, <19> - <26> molding material according to any one.
<28>
　thermoplastic resin comprises a polycarbonate, <19> - <27> molding material according to any one.
<29>
　The thermoplastic resin is not impregnated within a carbon fiber bundle, the molding material according to item 1 or <19> - <28>.
<30>
　F / L (N / m) < molding material according to item 1 or satisfying 100,000 <19> - <29>.
<31>
　<19> - <30> A molding material according to any one,
　when the water content W of the carbon fiber bundle comprising impregnating aid (wt%), 0.001 ≦ W (wt %) <0.4, the molding material.
<32>
　diameter D of the cross-sectional shape when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material 1 and minor axis D 2 D is the ratio of the 2 / D 1 is 1.1 or more 1. 8 or less, the molding material according to item 1 or <19> - <31>.
Effect of the invention
[0007]
　With the assembly of the molding material in the present invention, at the time of injection molding, it is possible to prevent the falling off of carbon fiber from the molding material, it can be produced a molded body with high production efficiency. Further, by using the assembly of the molding material in the present invention, clogging in the hopper dryer of a molding machine at the time of injection molding, problems on molding is reduced, excellent handling property.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008]
An example of the molding material in [1] the present invention.
[2] An example in which carbon fibers are dropped from the molding material.
[Figure 3] a cross-sectional view of the molding material in the present invention (YZ cross section in FIG. 1).
[4] Carbon fibers from a molding material falls off, an example of a cross section of the molding material (in FIG. 2 YZ cross section).
DESCRIPTION OF THE INVENTION
[0009]
[Carbon Fiber]
　carbon fibers contained in the molding material of the present invention, polyacrylonitrile (PAN) based, oil and petroleum pitch-based, rayon-based, lignin etc., may be any carbon fibers. In particular, PAN-based carbon fibers of PAN as a raw material, preferable is excellent in productivity and mechanical properties in a factory scale.
　As the carbon fibers, an average diameter of the single yarn of carbon fibers contained is 5 ~ 10 [mu] m is preferably used. Incidentally, general carbon fibers, monofilament (single yarn) of 1,000 to 50,000 present are carbon fiber filaments became fiber bundle. The carbon fiber bundle in the present invention, such common but also include carbon fiber filaments, the carbon fiber filaments, further and those doubling superimposed, such that the twisting applying twists to doubling It is also included. The carbon fibers contained in the molding material of the present invention, to enhance adhesion between the carbon fibers and polycarbonate, by surface treatment, was introduced an oxygen-containing functional groups on the surface is also preferable.
[0010]
　Further, as described above, when making the easily impregnated carbon fiber bundle by including impregnating aid carbon fiber bundle, in order to stabilize the step of uniformly attached to the carbon fiber bundle impregnated aid, the carbon fiber bundle as it is preferably those treated with sizing agent for imparting convergence. The sizing agent may be a known for carbon fiber filament production. As the carbon fiber bundle, even if the oil used to increase the sliding property during production remained, it can be used without problems in the present invention. Incidentally, hereinafter, the impregnation aid in the sense of the preamble including the other processing agents such as the above sizing agent, sometimes a representation of the surface treatment agent.
[0011]
[Impregnating aid]
　is not particularly limited to the impregnation aids for use in the present invention may be a single kind or may be one containing a plurality of kinds of impregnation aids.
　As the impregnation aids for use in the present invention, preferably to be of one or more selected from the group consisting of phosphoric acid ester and an aliphatic hydroxycarboxylic acid based polyester, of course, phosphoric acid ester and an aliphatic hydroxycarboxylic acid it may include both the system polyester.
[0012]
　In the present invention, phosphoric acid esters in the case of using the phosphoric acid ester as impregnating aid is not particularly limited, such as a blend of phosphate ester monomer or oligomeric phosphoric acid ester can be mentioned, specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, aromatic phosphate esters represented by triphenyl phosphate, and the like. Preferably trimethyl phosphate or triphenyl phosphate.
[0013]
　In the present invention, when using an aliphatic hydroxycarboxylic acid based polyester as impregnating aid, which is a polyester composed of an aliphatic hydroxycarboxylic acid residue, it may be a homopolymer polyester consisting solely of aliphatic hydroxy acid residue it may be a copolyester containing a plurality of kinds of aliphatic hydroxycarboxylic acid residue. Further, examples of the aliphatic hydroxycarboxylic acid based polyester, of the residues constituting the polymer, in an amount of less than 50 mole%, residues of other aliphatic hydroxycarboxylic acid residue, for example, diol residues or dicarboxylic it may be a copolyester including acid residue but homopolymer not added intentionally copolymerization component is preferred in terms easily available. Note that the aliphatic hydroxycarboxylic acid based polyester, a hydroxyl group and a carboxyl group in the same molecule also includes polymers of lactones are compounds produced by dehydration condensation.
[0014]
　In the present invention, the aliphatic hydroxycarboxylic acid based polyester that can be used as impregnating aid is not particularly limited, .epsilon.-caprolactone, .delta.-caprolactone, beta-propiolactone, .gamma.-butyrolactone, .delta.-valerolactone, .gamma.-valerolactone lactones, each homopolymer of enantholactone, and preferably as a copolymer of two or more monomers, .epsilon.-caprolactone, .delta.-caprolactone, beta-propiolactone, .gamma.-butyrolactone, .delta.-valerolactone, gamma - valerolactone, and a weight average molecular weight from 3,000 to 50,000 in the homopolymer of enantholactone, and one or more selected from the group consisting of a weight-average molecular weight from 3,000 to 50,000 a copolymer of two or more monomers more preferable to be of.
Particularly preferably, a weight average molecular weight of 3000 to 50,000 in the homopolymer of ε- caprolactone or δ- caprolactone. Incidentally, the term polymers of lactones in the present invention, in fact, lactones not a polymer only obtained by ring-opening polymerization, the aliphatic hydroxycarboxylic acid or its derivative is an equivalent of the lactone and the raw material polymers of similar structure to be included.
　Is not particularly limited to the amount of the impregnation additive included in the carbon fiber bundle is preferably 3 to 15 parts by mass with respect to 100 parts by weight of the carbon fibers, and more preferably 5 to 12 parts by weight.
[0015]
[Thermoplastic Resin]
　The thermoplastic resin used in the present invention, for example, a polyolefin resin, a polystyrene resin, a thermoplastic polyamide resin, a polyester resin, a polyacetal resin (polyoxymethylene resin), a polycarbonate resin, (meth) acrylic resins, polyarylate resins, polyphenylene ether resins, polyimide resins, polyether nitrile resins, phenoxy resins, polyphenylene sulfide resins, polysulfone resins, polyketone resins, polyether ketone resins, thermoplastic urethane resins, fluorine-based resins, thermoplastic polybenzimidazole resin, and vinyl resins.
[0016]
　As the polyolefin resin, for example, it is possible to increase the polyethylene resin, polypropylene resin, polybutadiene resin, polymethylpentene resin. As the vinyl resins, vinyl chloride resins, vinylidene chloride resins, vinyl acetate resins, polyvinyl alcohol resins. As the polystyrene resin, e.g., polystyrene resins, acrylonitrile - styrene resin (AS resin), acrylonitrile - butadiene - styrene resin (ABS resin) and the like. As the polyamide resin, for example, polyamide 6 resin (nylon 6), polyamide 11 resin (nylon 11), polyamide 12 resin (nylon 12), polyamide 46 (nylon 46), polyamide 66 resin (nylon 66), polyamide 610 it can be mentioned resins (nylon 610), and the like. As the polyester resin, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene butylene terephthalate resin, polytrimethylene terephthalate resin, a liquid crystal polyester. As the (meth) acrylic resin, for example, a polymethyl methacrylate. As the polyphenylene ether resin, for example, a modified polyphenylene ether. As the polyimide resins include, for example, thermoplastic polyimide, polyamideimide resin, a polyetherimide resin. As the polysulfone resin, for example, modified polysulfone resins, polyether sulfone resins. As the polyether ketone resin, for example, can be cited polyether ketone resins, polyether ether ketone resins, polyether ketone ketone resin. The fluorine-based resin, for example, a polytetrafluoroethylene.
[0017]
　The thermoplastic resin used in the present invention may be only one kind, or may be two or more types. As a mode of using two or more kinds of thermoplastic resin in the present invention, for example, and embodiments mutually softening point or melting point in combination with different thermoplastic resins, aspects average molecular weight from each other are used together different thermoplastic resin it can be mentioned, but not limited thereto.
[0018]
[Non-crystalline resin]
　The thermoplastic resin in the present invention is preferably a resin containing a non-crystalline resin. As described later, the molding material, when a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, is coated with the molten state of the thermoplastic resin in the carbon fiber bundle, then coated body is cooled to produce a molding material Te. Upon cooling, the outer peripheral side and inner peripheral side of the thermoplastic resin cooling difference occurs, the thermoplastic resin shrinkage occurs. Coated body is cooled from the outside of the thermoplastic resin, a thermoplastic resin towards the outside shrinks. As a result, if the molding material of the core-sheath structure, easy to be a gap in the core portion of the center (portion of the carbon fiber bundle). With the resin containing a non-crystalline resin as a thermoplastic resin, the crystalline resin in comparison shrinkage is low and because the shrinkage of the thermoplastic resin is a sheath component is small, to suppress the gap generation core portion of the molding material can.
[0019]
Thermal linear expansion coefficient of the thermoplastic resin and the linear expansion coefficient of the impregnating aid]
　assembly of the molding material of the invention, the linear expansion of the thermoplastic resin K 1 (10 -4 / ° C.), the linear expansion of the impregnating aid rate K 2 (10 -4 when a / ° C.), preferably satisfies the following formula (2).
　0.1 <| K 1 -K 2 | · · · (2)
　for molding material satisfying formula (2) is, where there is a difference in the linear expansion coefficient of the thermoplastic resin present and its surroundings impregnation aids, carbon Although the fiber is likely to fall off tendency, the molding material of the present invention satisfies the formula (2), and less likely to fall out of carbon fibers.
[0020]
[Thermal solubility parameter (SP) value of thermoplastic resin]
　assembly of the molding material in the present invention, the solubility parameter (SP) value of the thermoplastic resin S 1 ((cal / cm 3 ) 1/2 ), impregnated the SP value of the aid S 2 ((cal / cm 3 ) 1/2 when a), it is preferable that the aggregate of the molding material satisfies the following formula (3).
　| S 1 -S 2 | <1.5 · · · (3)
　By satisfying equation (3), partially impregnated aid and heat in coating the thermoplastic resin in the carbon fiber bundle comprising impregnating aid carbon fiber bundle is not easily fall out in a molding material for the thermoplastic resin tends to mix.
[0021]
[Polycarbonate]
　As the thermoplastic resin in the present invention, it is preferable to use a resin containing a polycarbonate. In this case, the kind of the polycarbonate is not particularly limited, those obtained by the reaction of various dihydroxyaryl compounds and phosgene, or those obtained by transesterification of a dihydroxy aryl compound and diphenyl carbonate. Typical examples include 2,2'-bis (4-hydroxyphenyl) propane, a polycarbonate obtained by the reaction of so-called bisphenol A and phosgene or diphenyl carbonate.
[0022]
　The dihydroxyaryl compound as a raw material of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxyphenyl) propane, 2, 2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 2,2'-bis (4-hydroxy -3-t-butylphenyl) propane, 2,2'-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3-cyclohexyl-phenyl) propane, 2,2'-bis (4-hydroxy-3-methoxyphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopent Emissions, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1,1'-bis (4-hydroxyphenyl) cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3 '- dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, bis and the like (4-hydroxyphenyl) ketone. These dihydroxyaryl compounds may be used alone or in combination.
[0023]
　Preferred dihydroxyaryl compounds, bisphenol to form a highly aromatic polycarbonate in heat resistance, 2,2'-bis (4-hydroxyphenyl) bis propane (hydroxyphenyl) alkanes, bis (4-hydroxyphenyl) cyclohexane bis (such as hydroxyphenyl) cycloalkanes, dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone, and the like dihydroxydiphenyl ketone. Particularly preferred dihydroxyaryl compounds include 2,2'-bis (4-hydroxyphenyl) propane which forms a bisphenol A type aromatic polycarbonate.
[0024]
　Incidentally, heat resistance, within a range not to impair the mechanical strength, making the bisphenol A type aromatic polycarbonate, a part of bisphenol A, may be substituted by other dihydroxyaryl compound. The compounding fluidity, appearance gloss, flame retardant properties, thermal stability, weather resistance, in order to increase the impact resistance within a range that does not impair the mechanical strength, various polymers, fillers, stabilizers, pigments, etc. it may be. For the purpose of improving the flame retardancy, it is also possible to blend a phosphate to polycarbonate as a flame retardant.
[0025]
Molding material]
　The molding material of the present invention, the carbon fiber bundle comprising impregnating aid, which thermoplastic resin is coated, usually a particulate. Molding material is a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, and the axial length of the carbon fiber bundle, the length of the molding material is preferably a substantially identical. At this time, the carbon fiber bundle core, a thermoplastic resin is a sheath. Molding material is a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, and the axial length of the carbon fiber bundle, it is preferable that the length of the molding material are the same, the coating material the is to permit the degree of error may occur normally when cut with a cutter or the like. More specifically, the length of the molding material, may the axial length of the carbon fiber bundle is less than 5%.
　That is, the molding material is obtained by, for example to cut the coating material around the carbon fiber bundle is coated with a thermoplastic resin by a cutter, core-sheath to core component carbon fiber bundle, a thermoplastic resin as a sheath component more preferably pellet structure (hereinafter sometimes referred to as core-sheath type pellet).
[0026]
　Further, the molding material of the particulate is preferably the axial length of the carbon fiber bundle is 1 ~ 30 mm, more preferably 2 ~ 10 mm, more preferred if 2 ~ 5 mm. There is no particular limitation on the diameter of the core-sheath pellets (e.g. been sheath-core pellets according to FIG. 3), preferably is not more than 2 times 1/10 or more pellets length, 1/4 of the pellet length more preferably a equal to or less than the above and the pellet length. The axial carbon fiber bundle in the longitudinal direction of the single yarn of carbon fibers contained in the carbon fiber bundle.
[0027]
[Impregnation state of the core-sheath structure and impregnating aid]
　In the present invention, the thermoplastic resin is preferably not impregnated within a carbon fiber bundle. Here, the thermoplastic resin is not impregnated within a carbon fiber bundle, and a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, and cutting the molding material in the axial direction observation when the infiltration thickness of the carbon fiber bundle inside direction of the thermoplastic resin refers to is 50μm or less. Note that the axial direction is a direction toward the center axis (direction perpendicular to the axial direction of the carbon fiber bundle contained in the molding material), Z-axis direction in FIG. 1 is a axial direction.
　Although thermoplastic resin molding material is hardly fall out of the carbon fiber when being impregnated within a carbon fiber bundle, the manufacturing cost of the molding material is increased. Molding material of the present invention is a molding material a thermoplastic resin excellent in terms of production cost since it is difficult falling off even though the carbon fiber not impregnated within a carbon fiber bundle.
[0028]
[Aggregate of the molding material]
　and assembly of the molding material in the present invention has the above (granular) molding material are assembled, molding length in the axial direction of the carbon fiber bundle L, the carbon fiber bundle when the gripping force F for molding material, the molding material satisfying 100 ≦ F / L (N / m) is present more than 30% of the total aggregate.
　100 ≦ F / L (N / m) means a shed difficulty carbon fibers from the molding material. Forming an assembly of the molding material in the present invention, when the molding material of the particulate is, for example, has a cylindrical shape as shown in FIG. 1, the carbon fibers of the carbon fiber bundle from the molding material falls off, for example, FIG. 2, the molding material only thermoplastic resin component as in FIG.
[0029]
　Is less than the value of F / L is 80 (N / m), the carbon fibers become easily fall off from the molding material. At below F / L value 80 (N / m), as well as the manufacturing process of the molding material, even in the molding site using a molding material, or dry-blending a molding material, when or air transport the carbon fibers fall off from the molding material, hopper dryer of an injection molding machine is equal to the clogging troubles in the molding occurs.
　Preferably, the molding material satisfying 100 ≦ F / L (N / m) is, is 40% or more of the total aggregate, more preferably at least 50%, even more preferably 60% or more. In less than 30%, when dry blending the aggregate of the molding material and, during air transportation, the amount of carbon fiber from a molding material falls off much, the productivity of the molded article is lowered.
　Further, from the viewpoint of poor dispersion of the carbon fibers in the injection molding, it is preferable that F / L is less than 100,000 (N / m), more preferably 10,000 (N / m) or less.
　Assembly of the molding material of the present invention, the molding material satisfying the F / L (N / m) <100,000 is preferably those which occur more than 30% of the total aggregate.
[0030]
　When a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, the gripping force F to the forming material of the carbon fiber bundle can be measured as follows. That is, the molding material from the collection of the molding material extraction 100 randomly using Imada Co. force gauge fitted with a pin of φ0.8mm to the tip, pushing the pins into the carbon fiber bundle of the core portion of the molding material, the maximum load was measured when the carbon fiber was eliminated. Here, since not be measured if the carbon fiber bundle of the molding material taken out has already dropped off, the gripping force of the molding material was 0 (N).
　As is apparent from the above measurement method, the gripping force to the molding material of the carbon fiber bundle indicates a force carbon fiber bundle is gripped in the molding material.
[0031]
　Molding material of the present invention, the carbon fiber bundle comprising impregnating aid, a molding material a thermoplastic resin is coated, the molding material length in the axial direction of the carbon fiber bundle L, the molding material of the carbon fiber bundle when the gripping force F, is preferably a molding material satisfying 80 ≦ F / L (N / m). Here, the F / L of the molding material, the average value of F / L of the 100 of the molding material. Of the molding material of the present invention F / L (N / m) is preferably 80 or more, more preferably 90 or more, more preferably 150 or more, particularly preferably 200 or more , and most preferably 250 or more. Further, the molding material of the present invention F / L (N / m) is preferably less than 100,000 (N / m), more preferably 10,000 (N / m) or less.
　If a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, the gripping force F to the forming material of the carbon fiber bundle, measured by the measuring method described above for 100 of the molding material randomly picked It was obtained as an average value.
[0032]
[Axial direction of the cross-sectional observation]
　assembly of the molding material in the present invention is a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle was observed by cutting the molding material in the axial direction time, it is preferable that the molding material satisfying the following formula (1).
　0.4 ≦ carbon fiber single yarn area × carbon fiber bundle of the single number of yarns / thermoplastic resin of the inner circumferential enclosed by the area ≦ 0.9 ··· (1)
　where, surrounded by the inner periphery of the thermoplastic resin and area is the average value of the aggregate of the molding material.
　Single yarn number of the carbon fiber single yarn area × carbon fiber bundle indicates when observed by cutting the molding material in the axial direction, the area of only carbon fibers of the core portion of the carbon fibers.
[0033]
　The area surrounded by the inner periphery of the thermoplastic resin, for example, 202 shown in FIG. If the carbon fiber bundle (201) is missing from the molding material, since 301 of FIG. 4 is a cavity may be measuring the area surrounded by the inner periphery of the thermoplastic resin shown in 302 of FIG. 4.
　Since the area bounded by the inner periphery of the single number of yarns / thermoplastic resin of the carbon fiber single yarn area × carbon fiber bundle is less than 0.4, the carbon fibers from the molding material will be easily fall off, 0.4 or higher It is preferred. A more preferred range is 0.5 or more. Further, from the viewpoint of poor dispersion of the carbon fibers in the injection molding, it is preferable area surrounded by the inner periphery of the single number of yarns / thermoplastic resin of the carbon fiber single yarn area × carbon fiber bundle is 0.9 or less.
[0034]
[Phase state of impregnation aids]
　impregnation aids of the present invention is preferably a solid at 20 ° C.. Before producing the molding material of the present invention, it may to be prepared in advance of carbon fiber bundles comprising impregnating aid. Carbon fiber bundle comprising impregnating aid is, for example, is stored in a state wound on a paper tube or the like, the impregnating aid is solid at room temperature, because the solution of the fiber bundle unwinding is easy.
[0035]
　Molding material of the invention, the major axis of the cross-sectional shape when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material (D 1 ) and minor axis (D 2 ratio D of) 1 / D 2 is 1 it is preferably .1 to 1.8. D 1 / D 2 limit is more preferably 1.6 or less, more preferably 1.5 or less, still more preferably, 1.4 or less. D 1 / D 2 lower limit is more preferably 1.2 or more. Sectional shape when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material is preferably an oval or circle.
　D 1 / D 2 is the carbon fiber bundle from the molding material and is small is likely to easily fall off. D 1 / D 2 in the case of the molding material is large flat shape, because the carbon fiber bundle can be crushed by a thermoplastic resin, in order to not easily fall off. On the other hand, in the present invention, D 1 / D 2 is also a molded material in the above range, can grip the bundle of carbon fibers on the molding material.
　Incidentally, the major axis of the cross section of the molding material (D 1 and) is the maximum diameter of the shape of the cross section of the molding material, the short diameter means the largest diameter of the perpendicular diameter to the major diameter.
　Molding material in the present invention is D 1 / D 2 and the carbon fiber content (carbon fiber mass ratio, Wf unit: mass%) 100 × is the relationship between (D 1 / D 2 ) / Wf is 2.0 above is preferably 40.0 or less.
　× 100 (D 1 / D 2 ) / Wf limit is more preferably 20.0 or less, more preferably 9.0 or less, still more preferably, 8.0 or less. × 100 (D 1 / D 2 ) / Wf is the lower limit of more preferably 3.0 or more, 4.0 or more is more preferable.
　× 100 (D 1 / D 2 when) / Wf is at 40.0 or less, there is a tendency that the carbon fiber bundle is likely to fall off from the molding material. This carbon fiber content (carbon fiber mass ratio, Wf unit: mass%) molding material is large, naturally many percent of carbon fiber bundles, carbon fiber bundles from the molding material is for easily fall off. In the present invention, 100 × (D 1/ D 2 ) / Wf is also a molded material of the preferred range, it can be gripped to the forming material of the carbon fiber bundle.
　Incidentally, the carbon fiber content (carbon fiber mass ratio, Wf unit: mass%) and is the ratio of the mass of the carbon fiber to the total mass, including without impregnation aids such as only the carbon fibers and the thermoplastic resin .
[0036]
[Method of molding
　material] 1. Coating
　method for producing a molding material in the present invention is a method of manufacturing a molding material sheath structure coated with a thermoplastic resin around the carbon fiber bundle comprising impregnating aids, carbon Moto繊維束is impregnated aid There above the melting point in case of crystalline resin, while in the case of amorphous resin heated above the glass transition temperature, it is preferable to integrally coat the thermoplastic resin.
　This was included in the carbon fiber bundle impregnated aid (solidified in some cases), liquefied or softened impregnating aid is heated above the melting point or glass transition temperature of the impregnation aids, focuses the carbon fiber bundle by coating the thermoplastic resin tends to state, and possible to reduce the gap of the carbon fiber bundle of the molding material, it is because the can be prevented from falling off the carbon fibers from the molding material.
　Further, the carbon fiber bundle, by heating above the melting point or glass transition temperature of the thermoplastic resin to be coated, immediately after coating of a thermoplastic resin, the thermoplastic resin near the interface of the carbon fiber bundle and a thermoplastic resin It prevents sudden solidification, by suppressing interfacial peeling, it is possible to improve the familiarity of the interface of the carbon fiber bundle and a thermoplastic resin.
　In this specification, previously heated to keep the step impregnation aids, sometimes referred to as "preheat".
[0037]
　2. Cooling
　the molding material in the present invention is to produce a covering body which is integrally coated with a thermoplastic resin in the carbon fiber bundle, it is preferable to produce by cutting it. The covering body in the present specification, after coating the thermoplastic resin in the carbon fiber bundle, refers to a state before being cut.
　Covering body is preferably cut after cooling below the glass transition temperature of the coated thermoplastic resin. By cutting the covering body is cooled, the coated thermoplastic resin has become somewhat hardened from the soft state, the shear stress is concentrated during cutting, shearing stress in order to cut the carbon fiber bundles as core becomes sufficiently and the carbon fiber bundle to be pulled out from the cover body is reduced to be falling off is disconnected, the present inventors consider.
[0038]
[Moisture content of the carbon fiber]
　aggregates of the molding material in the present invention, when the moisture content of the carbon fiber bundle comprising impregnating aid was W (wt%), 0.001 ≦ W (w%) <0. it is preferable that the 4. The moisture content of the carbon fiber bundle (wt%) is a percentage of carbon fiber bundles 100 wt%, represented by the following formula (4).
　Moisture content W water content of the (wt%) = carbon fibers of the carbon fiber bundle (wt) ÷ weight of the carbon fiber bundle that contains moisture (wt) × 100 ··· (4 )
　the moisture content of the carbon fiber bundle when W is small, when the thermoplastic resin was coated carbon fiber bundle, the water is vaporized and expanded inside of the jacket, less the gap of the carbon fiber bundle of the molding material increases, the carbon from the molding material falling off of the fibers can be prevented. Carbon fiber bundle Included moisture content W (wt%) is more preferably less than 0.4 (w%), more preferred is less than 0.2 (w%).
[0039]
[Use of the assembly of the molding material]
　assembly of the molding material in the present invention is used as a material for injection molding. Molding material in the present invention, it is possible to manufacture at a simple process, there is an effect capable of producing an injection molded product with high production efficiency.
Example
[0040]
[Evaluation and Analysis Method]
　shows an embodiment given below, but the invention is not limited thereto. Incidentally, the values in this example, was determined according to the following method.
[0041]
(Content of the surface treatment agent, content)
　the amount of the surface treating agent such as impregnation aids contained in the carbon fiber bundle, a carbon fiber bundle cut by the length of 1 m, was placed in a crucible, the furnace temperature It was placed in a muffle furnace set at 550 ° C. 15 minutes, and burning and removing a surface treatment agent components, was determined from the mass of the remaining carbon fiber.
[0042]
(Percentage of the molding material in which the carbon fibers are dropped out (number proportion))
　taken out 1000 from a set of molded material obtained molding material randomly counted the number of the molding material in which the inner carbon fiber is missing, the following was calculated ratio of the number of molding material to fall off the carbon fibers by equation (5).
　The number of molding material carbon fiber is missing (number) / 1000 (number) × 100 · · · (5)
[0043]
(In shaking tests, dropout rate (weight ratio) of the carbon fiber)
　each embodiment, for about 250g weighed assembly of the molding materials prepared in Comparative Example, shaken for 1 minute was introduced into Sieve the mesh opening 2mm It was. Then removed aggregates of the molding material of fiber shedding by shaking the sieve device, from the weight before and after the shaking, and measuring the carbon fiber shedding amount, carbon fiber dropout rate by the following equation (6) (weight ratio ) was calculated.
　Carbon fiber falling weight (g) collection of / weighed molded material (g) × 100 ··· (6 )
[0044]
(Molded gripping force of the material of the carbon fiber bundle)
　is taken out 100 of an aggregate of the resulting molding material molding material randomly, with Imada Co. force gauge fitted with a pin of φ0.8mm to the tip, forming push pins carbon fiber bundle of the core material, the maximum load was measured when the carbon fibers are dropped. Here, since not be measured if the carbon fiber bundle of the molding material taken out has already dropped off, the gripping force of the molding material was 0 (N).
　Further, the average value of the molding material 100 of the gripping force is taken out as F (N), by dividing the pellet length L of the molding material obtained this F, it was F / L (N / m) .
　Next, the ratio for the 100 resulting molded material, F / L is counted 100 (N / m) or more of the number, by the following equation (7), to meet the 100 ≦ F / L of the assembly of the molding material ( %) and the.
　The number of molding material satisfying 100 ≦ F / L ÷ 100 (number) × 100 ··· (7)
[0045]
(Thermoplastic area surrounded by the inner periphery of the resin)
　was taken out 100 of an aggregate of the resulting molded material molded material (core-sheath structure) randomly. The axial direction to cut the cross section of the molding material was observed by Keyence Corp. digital microscope (VHX-1000), to calculate the area enclosed by the inner periphery of the thermoplastic resin, 100 molding material taken out the average value was the area surrounded by the inner periphery of the thermoplastic resin (thermoplastic resin is a sheath of sheath-core structure). Next, using a single yarn number of single yarns area and carbon fiber bundles of carbon fibers used in Examples and Comparative Examples of the present invention, value was calculated by the following formula (1).
　Area surrounded by the inner periphery of the single number of yarns / thermoplastic resin of the carbon fiber single yarn area × carbon fiber bundle (1)
[0046]
[Raw materials Preparation]
　raw materials used in the present invention are as follows.
(Carbon fiber
　bundle) PAN-based carbon fibers Toho Tenax Co. STS40-24K,
　24000 This carbon fiber single fiber diameter 7.0μm filament number, tensile strength 4000 MPa.
(Impregnation
　aid) 1. Polycaprolactone (manufactured by Daicel Chemical Industries, PLACCEL (R) H1P molecular weight
　10000) 2. Triphenyl phosphate (Daihachi Chemical Co., Ltd.
　TPP) 3. Bisphenol A bis (diphenyl phosphate) (Daihachi Chemical Co., Ltd.; CR-741)
(thermoplastic resin)
　Polycarbonate: manufactured by Teijin Ltd.: L-1225Y
　glass transition temperature: 0.99 ° C.,
　the linear expansion coefficient (10 -4 / ° C. ): 0.7
　solubility parameter ((cal / cm 3 ) 1/2 ): 9.7
[0047]
[Example 1]
　as impregnating aid with polycaprolactone (manufactured by Daicel Chemical Industries, PLACCEL (R) H1P molecular weight 10000) was passed through the carbon fiber bundle in which emulsification was in solution in the non-volatile content of 20 wt% after removed the solution excessively adhered by nip rolls, then by drying by passing over a hot air drying furnace heated to 180 ° C. 2 minutes to obtain a carbon fiber bundle comprising impregnating aid. Thereafter, along a two metal rolls heated 60mm diameter to 200 ° C., subjected to heat treatment again, and the water content contained in the carbon fiber bundle with 0.1 wt%. The content of the impregnation additive included in the carbon fiber bundle was 10 parts by weight per 100 parts by weight of the carbon fibers.
[0048]
　Then, a carbon fiber bundle comprising impregnating aid obtained above, along a two metal rolls heated 60mm diameter to 100 ° C. and while heating the carbon fiber bundle to 60 ° C. (heating . may be referred to as preheat Further, the phase state of impregnation aids after preheating was a liquid), leaving with cross-head die for electric wire coating of diameter 3 mm, polycarbonate (Teijin Ltd.:. L coated with -1225Y), with producing coated body, which was cooled through a water bath it was circulated 20 ° C. cooling water. At this time, by using a radiation thermometer, was measured the temperature of the cover was 120 ° C.. Then cut to a length of 3mm by a pelletizer, a carbon fiber content (Wf (carbon fiber mass ratio)) is 20 mass% (carbon fibers per 100 parts by weight of polycarbonate is 394.7 parts by weight), diameter 3.2 mm, length 3 mm, to obtain a molding material is a sheath-core pellets suitable for injection molding.
　Molding material prepared continuously, to produce 10,000 molding material (aggregate of the molding material). The results are shown in Table 1.
[0049]
　Incidentally, the coefficient of linear expansion of the thermoplastic resin K 1 (10 -4 / ° C.) is 0.7, the linear expansion coefficient K of the impregnation aid 2 (10 -4 for / ° C.) is 1.2, | K 1 -K 2 | is 0.5, the solubility parameter of the thermoplastic resin (SP) value S 1 ((cal / cm 3 ) 1/2 ) is 9.7, the SP value of the impregnation aid S 2 ( (cal / cm 3 ) 1/2 for) is 10.2, | S 1 -S 2 | is 0.5.
　The molding material, using a Japan Steel Works 110ton electric injection molding machine (J110AD), cylinder temperature C1 / C2 / C3 / C4 / N = 280 ℃ / 290 ℃ / 300 ℃ / 300 ℃ / 300 ℃ (C1 ~ C4 cavity, N is the injection molded at a molding cycle of 35 seconds at the nozzle), to obtain a tensile test dumbbell thick 4 mm. During molding, not the carbon fibers fall off from the core-sheath pellets, trouble on the forming did not occur.
[0050]
　Molding material from the collection of the resulting molding material randomly 100 to take out the, the shape of the cross section when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material, the major axis (D 1 and) minor axis ( D 2 after obtaining an average value by measuring), D 1 / D 2 result of calculating the, was 1.25. Since the carbon fiber content of the molding material of Example 1 is 20 wt%, 100 × (D 1 / D 2 When calculating the) / Wf, 100 × 1.25 / 20 = 1.25 / 0.2 ≒ 6.3 to become.
[0051]
Example 2
　The temperature of the carbon fiber bundle when the preheating, except for changing from 60 ° C. to 170 ° C., was prepared aggregates of the molding material in the same manner as in Example 1. The results are shown in Table 1.
[0052]
[Example 3]
　The carbon fiber weight ratio (wf), except for changing the 20 wt% to 40 wt% to prepare a collection of the molding material in the same manner as in Example 1. The results are shown in Table 1.
　Molding material from the collection of the resulting molding material randomly 100 to take out the, the shape of the cross section when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material, the major axis (D 1 and) minor axis ( D 2 after obtaining an average value by measuring), D 1 / D 2 result of calculating the, was 1.46. Since the carbon fiber content of the molding material of Example 3 is 40 wt%, 100 × (D 1 / D 2 ) / the Wf to calculate the, 100 × 1.46 / 40% = 1.46 / 0.4 ≒ a 3.7.
[0053]
Example 4
　except that the length of the molding material (the length of sheath-core pellets) was 1 mm, was prepared aggregates of the molding material in the same manner as in Example 1. The results are shown in Table 1.
[0054]
[Example 5]
　Except that the length of the molding material (the length of sheath-core pellets) was 10 mm, was prepared aggregates of the molding material in the same manner as in Example 1. The results are shown in Table 1.
[0055]
Example 6
　except that the set temperature of the cooling water to 80 ° C. was coated carbon fibers in the thermoplastic resin in the same manner as in Example 1. Temperature of the coating material were elevated to 160 ° C. from 120 ° C.. The results are shown in Table 1.
[0056]
Example 7
　in the first embodiment, by creating a carbon fiber bundle without (along to the two metal rolls of 60mm diameter heated to 200 ° C.) heat treatment again, the carbon fibers used the water content contained in the bundle, except for changing from 0.1 wt% to 0.4 wt%, was created in the same manner as in example 1 molded material aggregate. The results are shown in Table 1.
[0057]
Example 8
　instead of the impregnating aid polycaprolactone, using triphenyl phosphate, when preheating, creating except that the temperature of the carbon fiber bundle 170 ° C., Example 1 Similarly molding assembly did. The results are shown in Table 1.
　Incidentally, the solubility parameter of the thermoplastic resin (SP) value S 1 ((cal / cm 3 ) 1/2 ) is 9.7, the SP value of the impregnation aid S 2 ((cal / cm 3 ) 1/2 ) it is because it is 10.5, | S 1 -S 2 | is 0.8.
[0058]
Example 9
　instead of the impregnating aid polycaprolactone, with bisphenol A bis (diphenyl phosphate), except that the temperature of the carbon fiber bundle when preheating to 170 ° C., the molding material set in the same manner as in Example 1 It created the body. The results are shown in Table 1.
　Incidentally, the solubility parameter of the thermoplastic resin (SP) value S 1 ((cal / cm 3 ) 1/2 ) is 9.7, the SP value of the impregnation aid S 2 ((cal / cm 3 ) 1/2 ) it is because it is 10.3, | S 1 -S 2 | is 0.6.
[0059]
[Comparative Example 1]
　When coating the thermoplastic resin, without preheating the carbon fiber bundle, by which the temperature at the time of coating the thermoplastic resin to 30 ° C., the impregnating aid at the time of coating the thermoplastic resin while the phase state to a solid, except that the production of the molding material to prepare a collection of the molding material in the same manner as in example 1. The results are shown in Table 1.
[0060]
[Comparative Example 2]
　When coating the thermoplastic resin, after the temperature of the carbon fiber bundle 170 ° C. by preheating the carbon fiber bundle, once cooled, the temperature at the time of coating the thermoplastic resin in the 30 ° C. , except that the production of the molding material to prepare a collection of the molding material in the same manner as in example 1. The results are shown in Table 1.
[0061]
　The molding material of all embodiments, the length of the axial length and the molding material of the carbon fiber bundle was identical. Further, the molding material of all embodiments, when the thermoplastic resin is observed by cutting those not impregnated within a carbon fiber bundle (molding material in the axial direction, of the thermoplastic resin to the carbon fiber bundle inside direction the thickness of penetration was 50μm or less). Further, assembly of the molding material in all embodiments, the molding material satisfying the F / L (N / m) <100,000 were present more than 30% of the total aggregate.
[0062]
[Table 1]

Industrial Applicability
[0063]
　With the assembly of the molding material in the present invention, at the time of injection molding, it is possible to prevent the falling off of carbon fiber from the molding material, it can be produced a molded body with high production efficiency. Further, by using the assembly of the molding material in the present invention, clogging in the hopper dryer of a molding machine at the time of injection molding, problems on molding is reduced, excellent handling property.
[0064]
　Has been described with reference to the details to the specific embodiments of the present invention, it is possible that various changes and modifications without departing from the spirit and scope of the invention will be apparent to those skilled in the art.
　This application is based on Japanese Patent Application filed on November 1, 2016 (Japanese Patent Application No. 2016-214221), the contents of which are incorporated herein by reference.
DESCRIPTION OF SYMBOLS
[0065]
201 carbon fiber bundle
202 thermoplastic inner circumference of the resin
cavity 301 carbon fiber bundle is no longer fall off
the inner periphery of 302 thermoplastic resin

WE CLAIM

A carbon fiber bundle comprising impregnating aid is an aggregate of the molding material a thermoplastic resin is coated,
　the molding material length in the axial direction of the carbon fiber bundle L, the gripping force F to the forming material of the carbon fiber bundle when a molding material satisfying 100 ≦ F / L (N / m) is present more than 30% of the total aggregates,
aggregates of the molding material.
[Requested item 2]
　The molding material, a core-sheath structure in which the thermoplastic resin is coated on the periphery of the carbon fiber bundle, and the axial length of the carbon fiber bundle, the length of the molding material, to claim 1 which is substantially identical the aggregate of the molding material described.
[Requested item 3]
　When the molding material was observed by cutting in the axial direction, the molding material satisfying the following formula (1), collection of the molding material according to claim 2.
　0.4 ≦ carbon fiber single yarn area × carbon fiber bundle of the single number of yarns / thermoplastic resin of the inner circumferential enclosed by the area ≦ 0.9 ··· (1)
　where, surrounded by the inner periphery of the thermoplastic resin and area is the average value of the aggregate of the molding material.
[Requested item 4]
　Impregnating aid is an aggregate of the molding material according to any one of claims 1 to 3 is one or more selected from the group consisting of phosphoric acid ester and an aliphatic hydroxycarboxylic acid based polyester.
[Requested item 5]
　Impregnating aid is a solid at 20 ° C., a set of molding material according to any one of claims 1-4.
[Requested item 6]
　Linear expansion coefficient of the thermoplastic resin K 1 (10 -4 / ° C.), the coefficient of linear expansion of the impregnating aid K 2 (10 -4 when a / ° C.), the aggregate of the molding material satisfies the following formula (2) , collection of the molding material according to any one of claims 1-5.
　0.1 <| K 1 -K 2 | · · · (2)
[Requested item 7]
　The solubility parameter (SP) value of the thermoplastic resin S 1 ((cal / cm 3 ) 1/2 ), the SP value of the impregnation aid S 2 ((cal / cm 3 ) 1/2 when a), assembly of the molding material satisfies the following formula (3), assembly of the molding material according to any one of claims 1-6.
　| S 1 -S 2 | <1.5 · · · (3)
[Requested item 8]
　The axial length of the carbon fiber bundle is 1 ~ 30 mm, the aggregate of the molding material according to any one of claims 1 to 7.
[Requested item 9]
　Thermoplastic resin comprises an amorphous resin, the aggregate of the molding material according to any one of claims 2-8.
[Requested item 10]
　Thermoplastic resin comprises a polycarbonate, aggregates of the molding material according to any one of claims 2-9.
[Requested item 11]
　The thermoplastic resin is not impregnated within a carbon fiber bundle, the aggregate of the molding material according to any one of claims 1 to 10.
[Requested item 12]
　Molding material which satisfies F / L (N / m) <100,000 is present more than 30% of the total aggregates, aggregates of the molding material according to any one of claims 1 to 11.
[Requested item 13]
　An aggregate of the molding material according to claim 1 to 12 any one,
　when the water content W of the carbon fiber bundle comprising impregnating aid (wt%), 0.001 ≦ W (wt%) <0.4, aggregation of the molding material.
[Requested item 14]
　Long diameter D of the cross-sectional shape when cut in a direction perpendicular to the axial direction of the carbon fiber bundle of the molding material 1 and minor axis D 2 is the ratio of the D 1 / D 2 at 1.1 to 1.8 there, the aggregate of the molding material according to any one of claims 1-13.
[Requested item 15]
　A method of manufacturing a molding material sheath structure coated with a thermoplastic resin around the carbon fiber bundle comprising impregnating aid the carbon fiber bundle, when impregnating aid is crystalline resin has a melting point or more, the non while in the case of-crystalline resin heated above the glass transition temperature, is integrated by coating a thermoplastic resin, the manufacturing method of the molding material.
[Requested item 16]
　Using the method of manufacturing the molding material according to claim 15, a method for producing the aggregate of the molding material,
　the molding material length in the axial direction of the carbon fiber bundle L, gripping into the molding material of the carbon fiber bundle when a force F, the molding material satisfying 100 ≦ F / L (N / m) <100,000 is present more than 30% of the total aggregate, the production method of assembly of the molding material.
[Requested item 17]
　To produce a covering body which is integrally coated with a thermoplastic resin in the carbon fiber bundle, which after cooling below the glass transition temperature of the thermoplastic resin to produce a molding material by cutting, according to claim 15 method of manufacturing a molding material.
[Requested item 18]
　A method of manufacturing a molding material according to claim 15 or 17,
　when the water content W of the carbon fiber bundle comprising impregnating aid (wt%), 0.001 ≦ W (wt%) <0.4 in a method of manufacturing a molding material.
[Requested item 19]
　A carbon fiber bundle comprising impregnating aid, a molding material a thermoplastic resin is coated,
　the molding material length in the axial direction of the carbon fiber bundle L, when the gripping force F to the forming material of the carbon fiber bundle , the molding material satisfying 80 ≦ F / L (N / m).
[Requested item 20]
　The molding material, a core-sheath structure in which the thermoplastic resin around is covered carbon fiber bundle, and the axial length of the carbon fiber bundle, the length of the molding material, to claim 19 which is substantially identical molding material described.
[Requested item 21]
　When the molding material was observed by cutting in the axial direction, the molding material satisfying the following formula (1), the molding material of claim 20.
　0.4 ≦ carbon fiber single yarn area × carbon fiber bundle of the single number of yarns / thermoplastic resin of the inner circumferential enclosed by the area ≦ 0.9 ··· (1)
[Requested item 22]
　Impregnating aid is molding material according to any one of claims 19-21 is one or more selected from the group consisting of phosphoric acid ester and an aliphatic hydroxycarboxylic acid based polyester.
[Requested item 23]
　Impregnating aid is a solid at 20 ° C., the molding material according to any one of claims 19-22.
[Requested item 24]
　Linear expansion coefficient of the thermoplastic resin K 1 (10 -4 / ° C.), the coefficient of linear expansion of the impregnating aid K 2 (10 -4 when a / ° C.), the molding material satisfying the following formula (2), claim molding material according to 19-23 any one.
　0.1 <| K 1 -K 2 | · · · (2)
[Requested item 25]
　The solubility parameter (SP) value of the thermoplastic resin S 1 ((cal / cm 3 ) 1/2 ), the SP value of the impregnation aid S 2 ((cal / cm 3 ) 1/2 when a), molding material satisfies the following formula (3), the molding material according to any one of claims 19-24.
　| S 1 -S 2 | <1.5 · · · (3)
[Requested item 26]
　The axial length of the carbon fiber bundle is 1 ~ 30 mm, the molding material according to any one of claims 19-25.
[Requested item 27]
　Thermoplastic resin comprises an amorphous resin, molding material according to any one of claims 19-26.
[Requested item 28]
　Thermoplastic resin comprises a polycarbonate molding material as claimed in any one of claims 19-27.
[Requested item 29]
　The thermoplastic resin is not impregnated within a carbon fiber bundle, the molding material according to any one of claims 19-28.
[Requested item 30]
　F / L (N / m)