JP2015221867A - Prepreg, manufacturing method therefor and carbon fiber reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg having quick curing property, less in single yarn fuzz of a carbon fiber on a molded body surface after molding, excellent in designability and good in appearance quality even during clear coating.SOLUTION: There is a prepreg manufactured by impregnating a matrix resin having a minimum viscosity at 90 to 115°C of 1.0 to 5.0 Pa s and curing time when heating the prepreg at 150°C of 1 to 5 minutes into a carbon fiber having knot bundle strength of 100 to 600 MPa and ratio of a major axis and a minor axis of a cross section of a single yarn of 1.10 to 1.30, and having the number of single yarn fuzz with a width of 5 μm or more and a length of 5 mm or more of 50/mor less on a surface of the prepreg, a flow rate of the matrix resin of 10 to 20 mass% and a maximum cross section height Rt of the prepreg of 80 μm or less.

Description

  The present invention relates to a carbon fiber prepreg used for production of a carbon fiber reinforced composite material, and in particular, can provide a carbon fiber reinforced composite material having a good appearance quality, and the carbon fibers are uniformly and uniformly arranged. The present invention relates to a carbon fiber prepreg.

  Carbon fiber prepreg is widely used in sports and leisure applications as an intermediate material for molded products such as golf shafts, fishing rods, badminton shafts and tennis racket frames, as well as aircraft structural members and industrial equipment members. It's being used. In recent years, not only excellent mechanical properties, but also carbon fibers have electrical conductivity, and the composite material has excellent electromagnetic wave shielding properties, so it can also be used in the case of electronic and electrical equipment such as laptop computers and video cameras. In particular, by applying a press molding method or the like, thinning of the casing, weight reduction of equipment, and the like have been achieved. Further, not only high performance and light weight of the molded product to be obtained, but in recent years, there has been a focus on applications in which carbon fibers are made to appear for the purpose of design while satisfying them.

  The properties required for prepregs used in such applications are of course excellent physical properties of molded products such as heat resistance and impact resistance, but at the same time, they are suitable for press molding and are stored at room temperature. It is excellent in stability and has a fast curing speed at the curing temperature. In particular, when a mold is used for forming a prepreg, the curing speed is important. In such a molding method, if the curing time of the prepreg is halved for the prepreg user, the production amount can be doubled without increasing the mold, and the productivity is improved. In general, the viscosity of the thermosetting resin decreases at a high temperature. There is a press molding method as a typical molding using the above-mentioned mold, but if the curing time is long, the time for low viscosity becomes long, and when molding a large and thick molded product, There may be a problem that the thermosetting resin flows unnecessarily too much and the carbon fiber is disturbed and the dimensional accuracy is deteriorated.

  In addition, in order to show the appearance of carbon fiber, which is the purpose of design, transparent coating (clear coating) is necessary, and carbon fiber single yarn fluff (hereinafter referred to as `` single yarn fluff '') in the carbon fiber bundle. ), Partial fluctuation of the position of the carbon fiber bundle, partial twist of the carbon fiber single yarn in the carbon fiber bundle, etc. are present on the surface of the prepreg and appear on the surface of the molded body after molding, so that the appearance quality is impaired. There was a problem. When such poor appearance quality occurs, painting is required to cover up the poor appearance quality, so the design of carbon fiber cannot be demonstrated and the weight increases. Few examples have been used for applications where clear coating is applied to prepregs, and further improvements in designability have been desired.

  Regarding the prior art, Patent Document 1 describes a method of using an acid catalyst and accelerating the ring-opening reaction of a benzoxazine resin to increase the curing speed. However, the flame retardancy and the resin composition are limited. It only satisfies fast curability, and nothing is mentioned about the design of the surface of the molded product.

  Further, Patent Documents 2 to 4 describe improvement of moldability that regulates the resin flow at the time of molding and suppresses the occurrence of defects that greatly impair the appearance by the method of suppressing resin flow. It is not aimed at improving the design properties of the fiber reinforced composite material, but is limited to the improvement of molding defects.

  Moreover, in the process of manufacturing a prepreg, as a method for minimizing the occurrence of fluff due to scratches on the carbon fiber yarn that occurs when passing through the alignment portion, Patent Document 5 discloses a suppression method by vibrating the zigzag comb up and down. Have been described. However, since the fluff described here is a method for suppressing caterpillar-like fluff, there is no effect of suppressing single yarn fluff, and the design properties are not sufficiently satisfied.

  Patent Document 6 describes a method of providing a carbon fiber prepreg having a uniform appearance by uniformly aligning carbon fiber bundles and uniform surface brightness and optical reflection. In addition, there is no mention of a method for improving the single yarn fluff seen on the surface of the molded body, and the design property cannot be sufficiently satisfied when a higher appearance quality is required.

JP 2008-056795 A JP 2009-292977 A JP 2009-292976 A JP 2004-099814 A JP-A-7-227840 International Publication No. 2012/051407

  The present invention is for solving such problems, while having fast curability, at the same time, there are few carbon fiber single yarn fluffs on the surface of the molded article after molding, excellent design, However, the object is to provide a prepreg with good appearance quality.

  The present invention for achieving the above object is characterized by the following (A) to (D).

(A) Carbon fiber having a knot bundle strength of 100 to 600 MPa and a ratio of the major axis to the minor axis of the single yarn of 1.10 to 1.30, the minimum viscosity at 90 to 115 ° C. is 1.0 to A prepreg impregnated with a matrix resin that is 5.0 Pa · s and has a curing time of 1 to 5 minutes when heated at 150 ° C., having a width of 5 μm or more on the prepreg surface and a length of 5 mm The prepreg in which the number of single yarn fluffs is 50 / m ² or less, the flow rate of the matrix resin is 10 to 20% by mass, and the maximum cross-sectional height Rt of the surface of the prepreg is 80 μm or less.

(B) The prepreg according to (A), wherein the knot bundle strength is 150 to 300 MPa, the fiber basis weight is 50 to 200 g / m ² , and the resin mass content is 20 to 40%.

(C) Carbon fiber having a knot bundle strength of 100 to 600 MPa and a ratio of the major axis to the minor axis of the single yarn of 1.10 to 1.30, the minimum viscosity at 90 to 115 ° C. is 1.0 to A method for producing a prepreg that impregnates a matrix resin that is 5.0 Pa · s and has a curing time of 1 to 5 minutes when heated at 150 ° C. The following steps (1) and (2) are performed: A method for producing a prepreg, comprising:
(1) A step of guiding carbon fibers to a fiber opening portion through a free-rotating pass roll subjected to a satin finish after the carbon fibers are drawn from the creel with a tension of 80 to 250 g per bundle of carbon fibers.
(2) A step of opening the carbon fiber by bringing the carbon fiber into contact with a plurality of ladder-shaped rolls that vibrate laterally while applying heat to the carbon fibers that are aligned so as to be parallel to each other in one direction.

  (D) A carbon fiber reinforced composite material obtained by curing the prepreg according to (A) or (B) or the prepreg obtained by the prepreg production method according to (C).

  The properties described herein are measured by the following methods.

<Long and short diameter ratio of single yarn cross section>
A cross section of 25 carbon fiber single yarns is observed with a scanning microscope, and the distance between the two points that are the farthest away from each other on the outer circumference and the intersection between the straight line group that is almost perpendicular to the straight line connecting the two points and the outer circumference The ratio of the distance between two short points is measured, and the long / short diameter ratio is obtained as an average value.

<Strength and elastic modulus of carbon fiber>
According to JIS R 7601: 1986, the tensile strength and elastic modulus of the strand characteristics are measured.

<Nodule bundle strength>
According to JIS L 1013: 1981, a nodule is formed at the center between the grips of the sample, and the tensile strength is measured. Insert and fix both ends of the sample to be measured in the chuck. Here, the sample length between the chucks is 250 mm, and the tension is measured so that the knot of the sample is located at the center between the chucks, and the maximum load value is measured. The value obtained by dividing this maximum load value by the cross-sectional area (of the nodule portion) of the sample is taken as the nodule bundle strength. Here, an average value of n = 6 (each n = 3 for right knot and left knot) is used for arbitrarily selected samples.

<Tack>
The tack in the prepreg of the present invention is measured as follows.

  After exposure for 15 to 30 minutes in a measurement environment of a temperature of 24 ± 2 ° C. and a humidity of 50 ± 5% RH, a cover glass of 18 mm × 18 mm is used with a PICMA Tack Tester II manufactured by Toyo Seiki Seisakusho Co., Ltd. It is obtained by pressure-bonding to a prepreg with a load of 92 N for 5 seconds, peeling off at a speed of 30 mm / min, and measuring the maximum value of the resistance force at the time of peeling. What is used for a microscope measurement can be used for a cover glass, for example, micro cover glass 18mmx18mm and thickness: 0.12-0.17mm (made by MATSUNAMI) can use it conveniently.

<Maximum section height Rt>
The maximum cross-sectional height Rt representing the surface smoothness of the prepreg is defined as the maximum cross-sectional height of the roughness curve in JIS B 0601: 2001, and is measured as follows. A prepreg cut to a width of 100 mm is used as a test piece, and the surface smoothness of each test piece is measured with a contact-type surface roughness measuring instrument. As the contact-type surface roughness measuring instrument, for example, a surface roughness measuring instrument SE-3500 manufactured by Kosaka Laboratory Ltd. is used, and a detector is provided with a diamond needle having a stylus tip radius of 2 μm and a measuring force of 0. What can be measured at 7 mN is used, and the measurement is performed at a measurement speed of 2 mm / sec and a width of 90 mm so as to be orthogonal to the unidirectional prepreg fiber direction (n = 3).

<Resin flow rate>
A laminated base material obtained by cutting a prepreg into 10 cm squares and laminating four sheets at 0 ° / 90 ° / 90 ° / 0 ° is taken as one sample (W1). Thereafter, the upper and lower surfaces are sandwiched between a perforated film and a glass cloth, and then heated in a press machine at 160 ° C. and a pressure of 3.0 MPa for 10 minutes (W2). The resin flow rate (W) can be obtained by the following equation. As the resin flow measuring instrument, for example, a 9 ton lever operation type compression molding machine manufactured by Toho Machinery Co., Ltd. can be suitably used.

For the glass cloth, it is necessary to use WE181D100BS6E (181 mesh) manufactured by Nittobo Co., Ltd. in terms of the amount of resin absorption. As the perforated film, for example, model A400P manufactured by AIRTECH can be preferably used.
W = (W1-W2) / W1 × 100.

<Curing time>
The prepreg is cut into 6 mm squares, sandwiched from above and below by 18 mm square glass covers, and then placed on a curing measuring device and cured at a temperature of 150 ° C. The glass surface is pushed in with a rod, and the time when the fluidity of the protruding resin is lost is measured (n = 3). In addition, as a hardening measuring device, the gelation tester by Eucalyptus Giken Co., Ltd. can be used conveniently, for example.

<Number of fuzz>
Width of about 5μm or more occurring in the prepreg surface visually, the single yarn fluff or 5mm long of to 1 m ² measured, expressed in the fluff number (pieces / m ^2).

<Resin viscosity>
The resin viscosity described in the text is measured by using a dynamic viscoelasticity method. As a measuring device, for example, an RDA-II type device manufactured by Rheometrics, Inc. can be used. The minimum viscosity in the present invention means that when the temperature is raised from room temperature, the resin viscosity is once lowered and then the viscosity is increased, but this means the minimum viscosity value in this profile. Moreover, the temperature which shows this minimum viscosity is defined as minimum viscosity temperature. These characteristics were measured using such an apparatus under the conditions of vibration: 3.14 radians / second, heating rate: 1.5 ° C./min, parallel plate with a radius of 25 mm, and gap: 1.0 mm. The

  The carbon fiber prepreg according to the present invention has a good uniformity, a carbon fiber single yarn on the molding surface is extremely small, and a carbon fiber reinforced composite material having an excellent appearance design can be obtained. In applications where the appearance of the carbon fiber reinforced composite material after molding can be seen directly, the product value of the product can be greatly increased, and there is no need to coat the surface over multiple layers, so the weight of the product can be reduced. Useful.

FIG. 1 is a cross-sectional view showing an example of a poor appearance quality state of a carbon fiber reinforced composite material. FIG. 2 is a model front view showing an example of a surface single yarn fluff of a carbon fiber reinforced composite material. FIG. 3 is a schematic view showing an embodiment of a prepreg manufacturing apparatus used for manufacturing the prepreg of the present invention. FIG. 4 is a schematic view showing an embodiment of a fiber-spreading device used for manufacturing the prepreg of the present invention.

The present invention relates to a prepreg comprising carbon fibers and a thermosetting resin. As the carbon fiber used in the present invention, any of polyacrylonitrile (hereinafter referred to as PAN) system, pitch system, etc. may be used, or a mixture thereof may be used. The carbon fiber used in the present invention preferably has a number of filaments per bundle of 1000 to 12000 / yarn. By setting the number of filaments to 1000 yarns / yarn or more, productivity when producing a prepreg of 50 to 200 g / m ² that is the basis weight of the present invention can be kept high, and 12000 yarns / yarn or less. By doing so, the spread spots at the time of opening the fibers after arranging the carbon fibers can be suppressed, so that the unevenness of the surface due to the spread spots after molding can be suppressed. Moreover, if it is 3000-6000 piece / yarn, the effect will be acquired notably, but it is more preferable.

By setting the fiber weight of the prepreg of the present invention to 50 g / m ² or more, it is possible to obtain a prepreg with excellent cracking and surface smoothness on the prepreg, and by setting it to 200 g / m ² or less, The laminate is lightweight. A more preferable range is 100 to 150 g / m ² .

  Although the sizing adhesion amount of the carbon fiber used in the present invention is not specified, it is preferably 0.8% to 2.2%. By adjusting the sizing adhesion amount to 0.8% or more, the convergence property of the carbon fiber bundle is improved and the fluff is less likely to fluff, so that no single yarn fluff remains on the prepreg surface. Moreover, by setting it as 2.2% or less, the expansibility of a carbon fiber bundle becomes favorable and the surface smoothness of a prepreg becomes favorable.

  In order to suppress the amount of single yarn fluff of the carbon fiber bundle, the carbon fiber preferably has a tensile strength of 3.0 GPa to 4.8 GPa and a knot bundle strength of 100 to 600 MPa. Further, the carbon fiber strength is more preferably 3.5 to 4.3 GPa, and the knot bundle strength is more preferably 150 to 300 MPa. By setting the knot bundle strength to 100 MPa or more, when the carbon fiber bundle is drawn, the abrasion resistance of the carbon fiber on the pass roll to be threaded is improved, and the quality of the prepreg is improved. Further, by setting the pressure to 600 MPa or less, when the yarn is excessively scraped on the pass roll, the carbon fiber single yarn does not remain on the prepreg surface. It is preferable to set the tensile strength to 3.0 GPa or more because dynamic characteristics can be set high. Moreover, by setting it as 4.8 GPa or less, when a carbon fiber passes a yarn path in the process of manufacturing a prepreg, the development of fluff on a single yarn can be prevented.

  Further, the carbon fiber used in the present invention is characterized in that the ratio of the major axis to the minor axis diameter of the single yarn cross section measured by the above method is 1.10 to 1.30. Within this range, when the carbon fiber bundles are arranged in a sheet form, the carbon fiber bundles after forming can be made uniform without appearing unevenness without causing the spread spots of the carbon fiber bundles. Further, the major axis / minor axis ratio of the single yarn cross section is more preferably in the range of 1.15 to 1.20.

  The carbon fiber having a ratio of the major axis to the minor axis of the single yarn cross-section of the present invention of 1.10 to 1.30 and a knot bundle strength of 100 to 600 MPa includes, for example, a component of 5% by mass or less in polyacrylonitrile. The copolymerized polymer is wet-spun using an organic solvent, preferably dimethyl sulfoxide as a solvent, and the temperature, solvent concentration of the coagulation bath, take-up speed, etc. are set to desired values. Preferably, after applying an oil containing a silicone component, it is dried and preferably subjected to steam drawing to obtain a polyacrylonitrile-based carbon fiber precursor fiber, which is flame-resistant, carbonized, and subjected to a surface treatment. It can be manufactured by applying sizing.

  The matrix resin used in the prepreg of the present invention is not particularly limited in type, but a thermosetting resin having a fast curing property is preferably used. Examples of the thermosetting resin include polyester resin, vinyl ester resin, and epoxy resin. Curing agents, thickeners, anti-shrinking agents and the like used for the thermosetting resin are appropriately used and are not particularly limited. As the thermosetting resin, an epoxy resin is preferable.

  Specific examples of the epoxy resin include a glycidyl ether obtained from a polyol, a glycidyl amine obtained from an amine having a plurality of active hydrogens, a glycidyl ester obtained from a polycarboxylic acid, and a compound having a plurality of double bonds in the molecule. Examples include polyepoxide obtained by oxidation. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as tetrabromobisphenol A type epoxy resin, novolac type epoxy such as phenol novolac type epoxy resin, cresol novolac type epoxy resin Resins, glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, tetraglycidylxylenediamine, and the like, or combinations thereof are preferably used.

  As a hardening | curing agent used for this epoxy resin composition, if it is a compound which has an active group which can react with an epoxy group, it can be used. For example, as amine-based curing agents, aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiethyldiphenylmethane, diaminodiethyldiphenylsulfone, etc. Aromatic amines, tertiary amines such as benzyldimethylamine, tetramethylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, basic active hydrogen compounds such as dicyandiamide, adipic acid dihydrazide, etc. Organic acid dihydrazide, 2-methylimidazole, 2-ethyl-4-methylimidazole, and other imidazoles. In addition, as acid anhydride-based curing agents, aliphatic acid anhydrides such as polyazibic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, polysebacic acid anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene Arocyclic acid anhydrides such as dicarboxylic acid anhydrides, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, aromatic acid anhydrides such as glycerol tristrimellitate, het anhydride, tetrabromophthalic anhydride, etc. Halogen type acid anhydride is mentioned. In the present invention, an amine curing agent, particularly a basic active hydrogen compound can be preferably used as the curing agent because it is cured at a relatively low temperature and has good storage stability.

  In the present invention, in order to increase the curing activity of the thermosetting resin, an appropriate curing accelerator can be used in combination with these curing agents. Preferable examples include a combination of an amine curing agent such as dicyandiamide as a curing agent with a urea derivative or an imidazole derivative as a curing accelerator, a carboxylic acid anhydride or a polyphenol compound as a curing agent, and a tertiary as a curing accelerator. Examples include combining amines and imidazole derivatives. In the present invention, since it cures at a relatively low temperature and has good storage stability, an amine curing agent as a curing agent, especially dicyandiamide, and a urea curing accelerator composed of a urea derivative as a curing accelerator are used in combination. It is preferable. Among these, urea-based curing accelerators include 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 1,1 ′-(4-methyl-m- Phenylene) bis (3,3′-dimethylurea) and the like are preferably used. Among them, a compound having two urea groups in the molecule, such as 1,1 ′-(4-methyl-m-phenylene) bis (3 , 3′-dimethylurea) is preferably used.

  The minimum viscosity of the thermosetting resin of the present invention is 1.0 to 5.0 Pa · s in a temperature range of 90 to 115 ° C. By setting the minimum viscosity to 1.0 Pa · s or more, the thermosetting resin can be impregnated without protruding from the carbon fiber bundle at the time of impregnation. By setting the minimum viscosity to 5.0 Pa · s or less, more than at the time of impregnation. The carbon fiber bundle can be satisfactorily impregnated with the resin. 1.5 to 3.5 Pa · s is more preferable.

  The thermosetting resin of the present invention is characterized by being cured in 1 to 5 minutes when heated at 150 ° C. It is preferable to set it to 1 minute or longer because work efficiency such as setting of a laminated plate in a mold is maintained. In addition, curing within 5 minutes is preferable because production efficiency during molding is improved.

  The matrix resin having a minimum viscosity of 1.0 to 5.0 Pa · s of the present invention and cured in 1 to 5 minutes when heated at 150 ° C. is, for example, a liquid bisphenol A type epoxy resin as a base resin. Solid bisphenol A type epoxy resin and phenol novolak type epoxy resin are heated and stirred under a constant temperature atmosphere, and then amine type curing agent and urea type curing accelerator, preferably having two urea groups in the molecule. Add a urea curing accelerator, mix by heating and stirring under a constant temperature condition, cool, and then extract the resin to make a prepared resin, but this characteristic can be adjusted by adjusting the blending ratio. Can be produced.

  The resin mass content is preferably 20 to 40%. By setting the resin mass content to 20% or more, it is possible to maintain the tackiness necessary for maintaining the shape of the continuous fibers and handling during molding, and to “scratch” due to insufficient surface resin amount during molding. Can be suppressed. As used herein, “scratch” refers to a resin on the surface of a molded product when a sheet-like prepreg is laminated and cured so that the direction of the carbon fiber bundle is 0 ° direction a and 90 ° direction b as shown in FIG. Refers to a phenomenon in which the resin deficient portion c occurs due to the fluidization of. Further, it is preferable to set the mass content of the resin to 40% or less because “fiber crack” d caused by the flow of the resin and the flow of the carbon fiber during press molding can be suppressed.

  Moreover, the resin flow rate of the prepreg obtained by this invention is 10-20 mass%, and 12-14 mass% is preferable. The amount of 10% by mass or more is preferable because the fluidity of the resin is improved and the resin penetrates into the unimpregnated portion in the prepreg layer. By setting the resin flow rate to 20% by mass or less, it is possible to suppress “fiber cracking” caused by the flow of the resin and the flow of carbon fibers during press molding.

  Moreover, the curing time when the prepreg obtained by the present invention is heated in a temperature atmosphere of 150 ° C. is 1 to 5 minutes. By setting it as 1 minute or more, the fluidity | liquidity of the resin into a carbon fiber layer is made favorable, a void generation | occurrence | production can be suppressed, and the "fiber crack" by a resin flow can be suppressed by setting it as less than 5 minutes.

  The prepreg of the present invention is characterized in that the maximum cross-sectional height Rt of the obtained roughness curve is 80 μm or less. When the maximum cross-sectional height Rt is 80 μm or less, molding can be performed without leaving irregularities on the appearance of the resulting molded body.

  Furthermore, the prepreg of the present invention preferably has a tack value on both surfaces of 10 to 30 N, more preferably 15 to 20 N. By setting it to 10N or more, it is possible to suppress local lifting that leads to poor quality such as generation of voids in the molded product during the pasting work between prepregs, and it can be sufficiently adhered to the release paper that holds the prepreg and stored. Further, peeling of the prepreg and the release paper is suppressed during transportation, and good handleability can be obtained during molding. Moreover, by setting it as 30 N or less, even when sticking is bad at the time of lamination | stacking, it can peel without tearing a prepreg, and it can stick again.

Further, as shown in FIG. 2, in the obtained prepreg 3, the number of carbon fiber bundle single yarn fluff 4 having a width of about 5 μm or more and a length of 5 mm or more is 50 pieces / m ² or less, preferably 30 pieces / m ² . It is characterized by that. When the single yarn fluff of the carbon fiber bundle appears on the surface of the molded product, the appearance quality of the part deteriorates, so it is necessary to apply the coating. However, the appearance quality after molding is reduced to 50 pieces / m ² or less. Is improved, and a shaped article having a design property can be obtained.

The maximum cross-sectional height Rt of the prepreg surface of the present invention is 80 μm or less, the resin flow amount is 10 to 20% by mass, and the curing time is 1 to 5 minutes when heated at 150 ° C., and the prepreg A method for producing a prepreg having a number of carbon fiber yarns of 50 μm / m ² or less having a width of 5 μm or more and a length of 5 mm or more on the surface is as follows.

  In order to manufacture the unidirectional prepreg, as shown in FIG. 3, after pulling out the carbon fiber bundle 6 from the creel 5, the carbon fiber is uniformly opened in advance by a fiber opening means to produce the carbon fiber sheet 10, and the matrix The resin film sheets 12 and 15 coated with the resin are sandwiched between the top and bottom of the sheet-like carbon fiber, and impregnated with impregnation rolls 20 and 21 to impregnate the resin into the carbon fiber, and then the release paper 24 on the upper surface. Then, the unidirectional prepreg 27 is wound up in a state 26 where it is combined with the release paper on the lower surface. The carbon fiber bundle is drawn from the creel by drawing the carbon fiber with a tension of 80 to 250 g per bundle of carbon fiber, and is guided to the opening portion through a satin-processed free-rotating pass roll and carbon fiber. Open the sheet. By making the pass roll satin-finished and freely rotating, the carbon fibers can be prevented from being scratched. Further, the tension per bundle of carbon fibers is more preferably 90 to 150 g. By making it 80 g or more, there is no slackness of carbon fibers, and it can be evenly aligned, and by making it 250 g or less, when passing a satin-finished pass roll, excessive contact is suppressed, Scratching of the carbon fiber is suppressed.

  As a method of opening the carbon fiber sheet, as shown in FIG. 4, the carbon fibers 28 drawn out so as to be parallel to each other in one direction are aligned by passing through a comb 31 under a certain tension, and heated by a heating device 34. Further, this can be achieved by opening the fibers while making contact with a plurality of ladder-shaped rolls 33 that vibrate laterally. The opening device for carbon fiber sheets has opening members arranged in multiple stages along the running direction of a plurality of carbon fiber bundles aligned so as to be parallel to each other in a continuously supplied direction. This spread member has a spread roll that vibrates in the axial direction of at least six or more rolls. Each spread roll is alternately arranged in the vertical direction with respect to the traveling direction, and only the lower spread vibration rolls 33a and 33b vibrate, and the upper free roll 33c grips the carbon fiber bundle. The position can be adjusted as appropriate for the purpose. Moreover, it is preferable that the roll surface has a ladder shape in order to minimize scratching with the carbon fiber bundle.

  Moreover, it is preferable that the opening member heats the opening member of a required step as needed. In particular, in the case of a carbon fiber bundle to which a sizing agent is adhered, when the opening roll is vibrated in a heated state, the sizing agent is softened by the heated roll and the opening action is improved. For example, when the opening means includes an opening member that vibrates in the axial direction, the carbon fiber bundle can be uniformly widened, and the surface smoothness can be improved by flattening the carbon fiber bundle.

  The carbon fiber, thermosetting resin composition, carbon fiber prepreg and carbon fiber reinforced composite material of the present invention will be described below with reference to examples. The properties of the carbon fiber, resin composition, prepreg, and carbon fiber reinforced composite material of each example are summarized in Table 1.

Example 1
<Production of carbon fiber>
An acrylonitrile polymer consisting of 99.5 mol% of acrylonitrile and 0.5 mol% of itaconic acid and having an intrinsic viscosity [η] of 1.80 was introduced into a coagulation bath comprising a dimethyl sulfoxide aqueous solution using a 3000-hole die. A coagulated yarn was obtained. At this time, the coagulation temperature, the take-up speed, and the concentration of the coagulation solvent were adjusted so that the ratio of the major axis to the minor axis of the single yarn cross section when the carbon fiber was made was 1.18. The coagulated yarn was washed and drawn with water, and a surfactant was added, followed by drying and densification, and steam drawing to obtain a 3000 filament precursor.

  The precursor was subjected to a carbonization step, unwound while twisting when unwinding from the creel, made flame resistant, and carbonized at a maximum temperature of 1400 ° C. Then, after anodizing continuously with the same tension to impart conformity with the matrix, 1.4% by mass of a sizing agent containing an epoxy compound is adhered and dried to obtain a fineness of 200 tex, a filament number of 3000, a strand. A carbon fiber having a strength of 3500 MPa and an elastic modulus of 230 GPa was obtained. Untwisted carbon fibers were obtained by untwisting the carbon fibers in the opposite direction than the number given during firing. The carbon fiber had a surface smoothness Ra of 30.0 nm. The major-minor diameter ratio of the single yarn cross section was 1.18.

<Preparation of resin composition>
Resin consisting of a mixture of bisphenol A type liquid epoxy resin, bisphenol A type solid epoxy resin, phenol novolac type epoxy resin, polyvinyl formal as thermoplastic resin, dicyandiamide as curing agent, and 2,4-toluenebis (dimethylurea) mixture A composition was prepared. Under the present circumstances, the 150 degreeC hardening time was adjusted to 1 to 5 minutes mainly by adjusting the compounding quantity and ratio of a hardening | curing agent among these. Moreover, the solid and liquid compounding ratio of the epoxy resin and the amount of polyvinyl formal were adjusted to obtain a resin composition having a minimum viscosity of 2.2 Pa · s at 90 to 115 ° C.

<Preparation of prepreg>
The prepared resin composition was applied onto release paper using a reverse roll coater to prepare a resin sheet. The resin basis weight of the resin sheet was 36.5 g / m ² . Next, the produced carbon fibers are aligned in one direction in a sheet shape so that the basis weight of the carbon fibers is 148 g / m ^2, and opened on six ladder-shaped rolls at the opening portion, The resin sheet was piled up from both sides of the carbon fiber, heated and pressed to impregnate the resin composition, and a unidirectional prepreg was produced. A prepreg was produced by the above method, and the number of single yarn fluffs on the prepreg surface was measured. As a result, the result was 20 / m ² .

<Production of carbon fiber reinforced composite material plate>
The produced prepreg was cut into a size of 300 mm × 200 mm, and a total of four layers were laminated so that the fiber axis direction of the carbon fibers was 0 ° / 0 ° / 90 ° / 90 ° / 0 °. The laminate sandwiched between release films was evacuated for 5 minutes in order to remove air from the laminate, and then press molded at a mold temperature of 160 ° C., a pressure of 3.0 MPa, and a curing time of 3 minutes. Then, the carbon fiber reinforced composite material board was obtained by leaving still at 130 degreeC temperature atmosphere for 2 hours.

<Appearance inspection of carbon fiber reinforced composite material plate>
As a result of producing 30 carbon fiber reinforced composite plates by the above method, and two inspectors on the surface of the composite plate for the presence or absence of appearance defects such as fiber cracks and scrapes, there is no appearance failure. It was a good result.

(Example 2)
From Example 1, the spinning / drawing conditions and the imparting oil agent were adjusted to obtain a carbon fiber having a long / short diameter ratio of 1.28, a strength of 4400 MPa, and an elastic modulus of 240 GPa. As a result of molding as in Example 1, the number of single yarn fluffs was 40 pieces / m ² , and there were no appearance defects such as fiber cracks and scrapes, and the results were good.

(Comparative Example 1)
The polymer from Example 1 was once extruded into the air, immediately introduced into the coagulation liquid, and the carbon fiber having a major axis ratio of 1.04, a strength of 4900 MPa, and an elastic modulus of 230 GPa was obtained by adjusting the spinning / drawing conditions and the imparting oil agent. Obtained. As a result of molding as in Example 1, the number of single yarn fluffs was 280 / m ^2, and there were many carbon fiber single yarn fluffs on the molding surface, resulting in poor appearance quality.

(Comparative Example 2)
A carbon fiber was prepared in the same manner as in Example 1, and a resin composition was prepared in the same manner as in Example 1 except that the amount of polyvinyl formal was changed from Example 1. A resin composition having a minimum viscosity of 0.85 Pa · s. I got a thing. As a result of molding as in Example 1, there was no problem with the number of single yarn fluffs of 20 / m ² , but the result was inferior in appearance quality due to scumming on the molding surface.

(Comparative Example 3)
A carbon fiber was prepared by the same method as in Example 1, and a resin composition was prepared in the same manner as in Example 1 except that the blending amount of polyvinyl formal was changed from Example 1. A resin composition having a minimum viscosity of 6.5 Pa · s. I got a thing. As a result of molding as in Example 1, there was no problem with the number of single yarn fluffs of 20 / m ² , but the molded product was inferior in appearance quality due to occurrence of fiber cracking due to the surface resin flow.

(Comparative Example 4)
As a result of producing carbon fiber and resin by the same method as in Example 1 and not opening the carbon fiber in the process of producing the prepreg, the number of single yarn fluffs was 15 / m ² , but there was no problem. As a result, the molded product had irregularities in the molded appearance.

  The present invention can be applied to a personal computer casing that uses a clear-coated carbon fiber reinforced composite material for the purpose of weight reduction, high rigidity, and appearance design. Moreover, the application range is not limited to these.

1: Carbon fiber single yarn (0 °)
2: Carbon fiber single yarn (90 °)
a: Carbon fiber reinforced composite material (outermost layer)
b: Carbon fiber reinforced composite material (second layer)
c: Resin waste d: Fiber crack 3: Unidirectional carbon fiber prepreg sheet 4: Carbon fiber single yarn fluff 5: Carbon fiber bobbin 6: Carbon fiber bundle 7: Pass roll 8: Guide roll 9: Comb 10: Carbon fiber sheet 11: Resin film roll (upper side)
12: Resin film sheet 13: Introduction roll 14: Resin film roll (lower side)
15: resin film sheet 16: introduction roll 17: nip roll 18: nip roll 19: heating device 20: impregnation roll 21: impregnation roll 22: nip roll 23: nip roll 24: recovered release paper roll 25: recovered release paper 26: unidirectional carbon Fiber prepreg 27: Unidirectional carbon fiber prepreg roll 28: Carbon fiber bundle 29: Pass roll 30: Guide roll 31: Comb 32: Guide roll 33a: Opening vibration roll 33b: Opening vibration roll 33c: Free roll 34: Heating device 35: Carbon fiber bundle

Claims (4)

Carbon fiber having a knot bundle strength of 100 to 600 MPa and a ratio of the major axis to the minor axis of the single yarn of 1.10 to 1.30, the minimum viscosity at 90 to 115 ° C. is 1.0 to 5.0 Pa. A prepreg impregnated with a matrix resin that is s and has a curing time of 1 to 5 minutes when heated at 150 ° C., having a width of 5 μm or more on the prepreg surface and a length of 5 mm or more. A prepreg having a number of yarn fluffs of 50 pieces / m ² or less, a flow rate of the matrix resin of 10 to 20% by mass, and a maximum cross-sectional height Rt of the surface of the prepreg of 80 μm or less. The prepreg according to claim 1, wherein the knot bundle strength is 150 to 300 MPa, the fiber basis weight is 50 to 200 g / m ² , and the resin mass content is 20 to 40%. Carbon fiber having a knot bundle strength of 100 to 600 MPa and a ratio of the major axis to the minor axis of the single yarn of 1.10 to 1.30, the minimum viscosity at 90 to 115 ° C. is 1.0 to 5.0 Pa. S, a method for producing a prepreg impregnated with a matrix resin having a curing time of 1 to 5 minutes when heated at 150 ° C., which comprises the following steps (1) and (2) A manufacturing method of a prepreg characterized.
(1) A step of guiding carbon fibers to a fiber opening portion through a free-rotating pass roll subjected to a satin finish after the carbon fibers are drawn from the creel with a tension of 80 to 250 g per bundle of carbon fibers.
(2) A step of opening the carbon fiber by bringing the carbon fiber into contact with a plurality of ladder-shaped rolls that vibrate laterally while applying heat to the carbon fibers that are aligned so as to be parallel to each other in one direction. A carbon fiber reinforced composite material obtained by curing the prepreg according to claim 1 or 2 or the prepreg obtained by the method for producing a prepreg according to claim 3.

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