JP2015081262A - Regenerated carbon fiber-reinforced plastic molding and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a regenerated carbon fiber-reinforced plastic molding which uses regenerated carbon fiber and is excellent in strength, a regenerated carbon fiber-reinforced plastic molding which can prevent scattering of regenerated carbon fiber and has high safety and their production method.SOLUTION: A method of producing a regenerated carbon fiber-reinforced plastic molding comprises wetting a lump of regenerated carbon fiber 1 with a binder aqueous solution 2 to adhere a water-soluble binder resin to the surface of the regenerated carbon fiber and defibrating the lump of the regenerated carbon fiber in the state of being adhered with the water-soluble binder resin to obtain treated regenerated carbon fiber 12, supplying base-material resin pellets 4 and 5 to a kneading extruder 7 through a main feeder 71 while supplying the treated regenerated carbon fiber 12, together with a nonwoven tape 3 composed of a resin fiber of a melting point higher than that of the base-material resin, to the kneading extruder 7 through a side feeder 72 and injection-molding a granulated product P obtained by the kneading extrusion.

Description

  The present invention relates to a recycled carbon fiber reinforced plastic molded body and a method for producing the same.

Carbon fiber reinforced plastic (hereinafter referred to as “CFRP”) is carbon fiber (CF) dispersed in a base resin, is lightweight, and has high specific strength and specific rigidity. Widely used for golf shafts, tennis rackets, fishing rods, etc. Recently, it is also used for main structural members such as wings and fuselage of large aircraft.
Moreover, it is predicted that the market scale of CFRP will continue to expand (Non-Patent Document 1).

On the other hand, it is considered that the amount of CFRP to be discarded (hereinafter referred to as “waste CFRP”) increases with the expansion of the market scale.
Incidentally, in the case of aircraft, since safety is very important, quality is considered first, and the yield of CFRP is said to be 50%. That is, many parts are discarded for trimming. In addition, cured prepregs cut according to the mold or expired are discarded.

Since the waste CFRP is incombustible in a normal state, the final disposal process is extremely troublesome. Therefore, conventionally, it was crushed and disposed of in landfills.
However, since carbon fiber consumes a lot of energy during its production, it is very wasteful to dispose of carbon fiber as described above, and reuse is desired.

  Therefore, as a method for recycling waste CFRP, various methods have been proposed in which waste CFRP is treated by incineration or superheated steam to decompose the base resin and extract non-combustible carbon fibers. (See Patent Literature 1 to Patent Literature 4, Non-Patent Literature 2 to Non-Patent Literature 4).

JP 2005-307121 A JP 2008-285600 A JP 2008-285601 A JP 2013-147545 JP

M.H. Akonda, C.A. Lawrence, B.M. Weager, Composites: Part A 43, pp. 79-86, (2012) Ruriko MONOBE, Kazuya OKUBO, Toru FUJII, 33rd SAMPE Europe International Technical Conference & Forum 2012 (SEICO 12): Strong Features to Support the Lift-off, pp.315-320, (2012) Carbon Fiber Association, Reinforced Plastics, Vol. 52, No. 10, pp.485-491, (2006) Mohamad Anas Nahil, Paul T. Williams, Journal of Analytical and Applied Pyrolysis, Vol.91, pp. 67-75, (2011)

By the way, in general, virgin carbon fibers are sizing treated continuously in a spinning process using rubber-modified epoxy resin or the like as a sizing agent, and more than 1000 fibers are bundled, so that they are easy to handle. .
That is, the carbon fibers do not stick to each other to form a strand. Therefore, scattering of carbon fibers can be suppressed even in the dispersion step of dispersing in the base material resin.

On the other hand, the sizing agent adhering to the virgin carbon fiber is burned down in the regenerated carbon charcoal fiber, not only the one treated by incineration or superheated steam, but also the one treated by the chemical treatment method.
Therefore, the regenerated carbon fiber has an inactive carbon surface exposed, and for example, it cannot be said that the tensile strength and bending strength of a molded article obtained by combining with polypropylene as an injection molding compound are sufficient.
Moreover, since there is no sizing agent, it is easy to scatter during defibration, and the scattered recycled carbon fiber floats in the air, and as a result, there is a risk of causing unexpected accidents such as deterioration of working environment and electric leakage in the factory.

  In view of the above circumstances, the present invention has as its first object to provide a regenerated carbon fiber reinforced plastic molded article excellent in strength using a regenerated carbon fiber and a method for producing the same, and in addition, scattering of the regenerated carbon fiber. The second object of the present invention is to provide a recycled carbon fiber reinforced plastic molded body that can prevent the above-described problem and has high safety, and a method for producing the same.

  In order to achieve the above object, a recycled carbon fiber reinforced plastic molded body (hereinafter referred to as “the molded body of the present invention”) according to the present invention is a natural paste or chemical along at least a part of the surface of the recycled carbon fiber. A recycled carbon fiber reinforced plastic molded body in which a recycled carbon fiber is dispersed in a matrix resin in the presence of a water-soluble binder resin layer constituting the paste, and the recycled carbon fiber is incorporated into the matrix resin. In addition, resin fibers made of a resin having a melting point higher than that of the base material resin are dispersed.

  On the other hand, the method for producing a regenerated carbon fiber reinforced plastic molded body according to the present invention (hereinafter referred to as “the production method of the present invention 1”) is a method for treating a regenerated carbon fiber mass obtained by heat treating waste CFRP with Wet with an aqueous solution of binder resin (hereinafter referred to as “binder aqueous solution”), disassemble the regenerated carbon fiber lump with the water-soluble binder resin attached to the surface of the regenerated carbon fiber, and then dry and rehydrate the water-soluble binder resin. After wetting the regenerated carbon fiber with a binder aqueous solution during the process of defibrating the regenerated carbon fiber mass obtained by heat treatment of the waste CFRP with a defibrating machine, From a process-regenerated carbon fiber manufacturing process to obtain a process-regenerated carbon fiber to which a water-soluble binder resin is attached after drying and a resin fiber having a melting point higher than that of the base resin A non-woven fabric or woven fabric having a belt shape is fed from the feeder of the kneading extruder to the kneading extruder, and the treated regenerated carbon fiber is fed into the kneading extruder from the same feeder of the kneading extruder, and the base resin is fed into the kneading extruder. It is characterized by comprising a step of extruding from a kneading extruder after kneading together.

  In addition, a method for producing a recycled carbon fiber reinforced plastic molded body according to the present invention (hereinafter referred to as “production method of the present invention 2”) is a method of treating a recycled carbon fiber mass obtained by heat-treating waste CFRP with a binder aqueous solution. Wet the product with a water-soluble binder resin on the surface of the regenerated carbon fiber, and then dry the regenerated carbon fiber lump, and then dry it to obtain a treated regenerated carbon fiber with a water-soluble binder resin attached, or waste CFRP. A treated regenerated carbon fiber in which the regenerated carbon fiber mass obtained by heat treatment is wetted with a binder aqueous solution during the process of defibrating with a defibrating machine, and then dried after defibrating and attached with a water-soluble binder resin A process for producing a regenerated carbon fiber, and the process regenerated carbon fiber obtained in this process is wrapped in a non-woven fabric made of resin fibers having a melting point higher than that of the base resin. It the packaging body was charged from the feeder of the kneading extruder were kneaded in both the matrix resin in the kneading extruder, is characterized in that it comprises a step of extruding the kneading extruder.

  In the production method of the present invention 1 and the production method of the present invention 2, resin fibers having a melting point higher than that of the base resin are put into a kneading extruder in the form of a nonwoven fabric or a woven fabric, but the nonwoven fabric is preferred. That is, the nonwoven fabric tends to be uniformly decomposed and dispersed when kneaded by a kneading extruder.

The kneading extruder is not particularly limited, but a biaxial or multiaxial kneading extruder is preferable.
The defibrating machine is not particularly limited, but it is preferable that the defibrating part is covered with a cover or the like so that the fine powder of recycled carbon fiber is not scattered as much as possible at the time of defibrating. What can supply the aqueous solution of water-soluble binder resin (For example, the brand name planting machine made from Shinko Engineering Co., Ltd.) is preferable.
The regenerated carbon fiber lump may be preliminarily defibrated to a small regenerated carbon fiber lump that is not so scattered, and then the small regenerated carbon fiber lump may be wetted with a binder aqueous solution.

The production method of the present invention 1 and the production method of the present invention 2 are not particularly limited. For example, the base material resin pellets are put into the kneading extruder from the main feeder of the kneading extruder, and the treated recycled carbon fiber and the nonwoven fabric are used. A tape, a woven fabric tape, or a package obtained by wrapping the treated regenerated carbon fiber with a non-woven fabric or a woven fabric may be put into the kneading extruder from the side feeder.
Further, the production method of the present invention 1 and the production method of the present invention 2 are not particularly limited. For example, the kneaded extrudate is extruded from a kneading extruder and granulated, and the granulated material is put into an injection molding machine. Then, a regenerated carbon fiber reinforced plastic molding can be produced by injection molding.

In the present invention, the water-soluble binder resin is not particularly limited. For example, polyvinyl alcohol, old rice, or starch derived from old used rice is preferable, and polyvinyl alcohol is more preferable because it is obtained at a relatively low cost.
In the present invention, the matrix resin is not particularly limited, and examples thereof include polyolefin resins and unsaturated polyester resins.

Although it does not specifically limit as said polyolefin resin, The thing containing at least any one polypropylene resin of a homopolymer, a random copolymer, and a block copolymer as a main component is preferable.
In addition, when the polyolefin resin contains a polypropylene resin as a main component, it is preferable to include maleic acid-modified polypropylene in addition to the polypropylene resin.

  The resin fiber having a melting point higher than that of the base resin is not particularly limited. For example, when the base resin is polypropylene, polyethylene terephthalate fiber, polyamide fiber, and aramid fiber can be used. These may be used alone or in combination.

  The concentration of the binder resin in the aqueous binder solution is not particularly limited. For example, when polyvinyl alcohol is used, 1 wt% to 5 wt% is preferable. That is, if the concentration is too high, the viscosity is too high and it is difficult to uniformly adhere to the entire surface of the regenerated carbon fiber, and if the concentration is too low, the regenerated carbon fiber strands are not sufficiently focused and scattered during defibration. There is a risk that the effect of preventing the ink will not be sufficiently exhibited, and sufficient strength expression of the obtained molded article cannot be expected.

In the granulated product, the total polypropylene and the treated recycled carbon fiber in the granulated product are preferably in a weight ratio of total polypropylene: treated recycled carbon fiber = 50: 50 to 95: 5.
That is, if the amount of the treated regenerated carbon fiber is too small or too large, there is a possibility that sufficient strength expression of the obtained molded article cannot be expected.

The adhesion amount of the water-soluble binder resin of the treated regenerated carbon fiber is not particularly limited, but is preferably an adhesion amount that covers 50% or more of the surface area of the regenerated carbon fiber. Moreover, when the adhesion thickness of water-soluble binder resin is too thick, there exists a possibility of impairing the interface strength between base material resin and regenerated carbon fiber, and it is preferable that the adhesion thickness of aqueous binder resin is 0.1 micrometer-1 micrometer. .
The blending amount of the resin fiber having a melting point higher than that of the base resin is not particularly limited, but is preferably 2 to 15 parts by weight with respect to 100 parts by weight of the base resin.
If the blending amount of resin fibers having a melting point higher than that of the base resin is too large, the toughness may be lowered, and if it is too small, the effect of improving the toughness may be lost.

  In the molded body of the present invention, the regenerated carbon fiber is dispersed in the base material resin in a state where there is a layer of a water-soluble binder resin constituting natural glue or chemical glue along at least a part of the surface of the regenerated carbon fiber. Recycled carbon fiber reinforced plastic molded body, in which resin fibers made of a resin having a melting point higher than that of the matrix resin are dispersed in the matrix resin, so that the recycled carbon fiber is effectively used. In addition, it is excellent in strength.

That is, since the layer of the water-soluble binder resin exists along at least a part of the surface of the regenerated carbon fiber, the regenerated carbon fiber and the base material resin are firmly bonded via the water-soluble binder resin.
For example, when polyvinyl alcohol is used as the water-soluble binder resin, the adhesiveness with the base resin is more than doubled compared to untreated regenerated carbon fibers, and the characteristics as a reinforcing agent are remarkable even with regenerated carbon fibers. You will be able to demonstrate it. Further, the critical fiber length of the regenerated carbon fiber can be shortened by 10% or more.
In addition to the regenerated carbon fiber, resin fibers made of a resin having a melting point higher than that of the base resin are dispersed, so that the toughness is higher than that of the base resin alone, and cracking occurs even when force is applied in the bending direction. Can be prevented.

  As described above, the production method of the present invention 1 regenerates a regenerated carbon fiber lump obtained by heat treating waste CFRP with a binder aqueous solution so that a water-soluble binder resin is adhered to the regenerated carbon fiber surface. After defibrating the carbon fiber mass, obtain a treated regenerated carbon fiber with a water-soluble binder resin adhering to it, or heat the waste CFRP to heat the regenerated carbon fiber mass with a defibrator. Wet the regenerated carbon fiber with a binder aqueous solution during the process, and then dry it after defibration to obtain a treated regenerated carbon fiber to which a water-soluble binder resin is adhered, and a melting point is obtained from the strip-shaped base resin. A non-woven fabric or woven fabric made of high resin fibers is fed from the feeder of the kneading extruder to the kneading extruder, and before the same feeder of the kneading extruder. Since the process-regenerated carbon fiber is supplied into the kneading extruder and kneaded together with the base material resin in the kneading extruder, and is provided with a step of extruding from the kneading extruder, the molded article of the present invention can be stably produced with high productivity. Can be manufactured.

In other words, the water-soluble binder resin adheres when the regenerated carbon fiber mass is defibrated. Can be prevented.
Further, since the treated regenerated carbon fiber is wound from the feeder into the kneading extruder by the nonwoven fabric or the woven fabric, the treated regenerated carbon fiber is supplied into the kneading extruder in a stable amount, and the treated regenerated carbon fiber is extruded into the composition. Can be dispersed almost uniformly.
Further, the nonwoven fabric or woven fabric is finely cut by a kneading screw in a kneading extruder, and resin fibers having a melting point higher than that of the base resin are uniformly dispersed as reinforcing fibers in the molded body.

  In the production method of the present invention 2, as described above, the recycled carbon fiber mass obtained by heat treating the waste CFRP is wetted with an aqueous binder solution, and the water-soluble binder resin is adhered to the surface of the recycled carbon fiber. After defibrating the carbon fiber mass, obtain a treated regenerated carbon fiber with a water-soluble binder resin adhering to it, or heat the waste CFRP to heat the regenerated carbon fiber mass with a defibrator. Processed regenerated carbon fiber manufacturing process obtained by wetting the regenerated carbon fiber with a binder aqueous solution during the process and then drying it after defibration to obtain a treated regenerated carbon fiber with a water-soluble binder resin attached, and the treated regenerated carbon obtained in this process A package in which fibers are wrapped in a nonwoven fabric made of resin fibers having a melting point higher than that of the base resin is introduced from the feeder of the kneading extruder, and the base resin is also used in the kneading extruder. After kneading. Thus it comprises the step of extruding the kneading extruder can be produced with high productivity stably molded body of the present invention.

In other words, the water-soluble binder resin adheres when the regenerated carbon fiber mass is defibrated. Can be prevented.
In addition, since the treated regenerated carbon fiber is supplied into the kneading extruder from the feeder in a state of being wrapped with a nonwoven fabric or a woven fabric, the treated regenerated carbon fiber can be fed into the kneading extruder in a stable amount. The regenerated carbon fiber can be dispersed almost uniformly in the extruded composition.
Further, the nonwoven fabric or woven fabric is finely cut by a kneading screw in a kneading extruder, and resin fibers having a melting point higher than that of the base resin are uniformly dispersed as reinforcing fibers in the molded body.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure showing one embodiment of the manufacturing method of this invention 1, Comprising: It is explanatory drawing explaining the manufacturing process of the process regenerated carbon fiber in order of a process. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure showing one embodiment of the manufacturing method of this invention 1, Comprising: It is a schematic sectional drawing of the kneading extruder explaining the granulation method of the pellet containing the reproduction | regeneration carbon fiber. It is a schematic perspective view of the processed carbon fiber containing envelope used in one embodiment of the production method of the present invention 2. It is a schematic sectional drawing of the kneading extruder explaining the granulation method of the pellet containing a regenerated carbon fiber using the package of FIG. It is a figure explaining the process of producing the process reproduction | regeneration carbon fiber of the reference example 1. FIG. It is a figure showing the fiber length distribution in the test piece of the reference example 1 and the comparative example 1 by contrast. It is a figure showing the tensile strengths of the test pieces of Reference Example 1 and Comparative Example 1 in comparison. It is a copy of the SEM photograph which shows the fracture surface of the tensile test piece of the test piece of the reference example 1 and the comparative example 1, Comprising: The figure (a) is the reference example 1, and the figure (b) is the comparative example 1. Each fracture surface is shown. It is a figure showing the bending strength of the test piece of the reference example 1 and the comparative example 1 by contrast.

Hereinafter, the present invention will be described in detail with reference to the drawings showing embodiments thereof.
FIG. 1 and FIG. 2 show one embodiment of the manufacturing method of the present invention 1.

  As shown in FIG. 1, in this production method, a regenerated carbon fiber lump 1 obtained by heat treating waste CFRP is immersed in a polyvinyl alcohol aqueous solution 2 as a binder aqueous solution, and stirred as necessary to regenerate carbon. After sufficiently impregnating the polyvinyl alcohol aqueous solution 2 between the fiber and the regenerated carbon fiber, the polyvinyl alcohol as the water-soluble binder resin is taken out from the polyvinyl alcohol aqueous solution 2 and oven-dried or naturally dried. A treated regenerated carbon fiber mass 11 attached to the surface is obtained.

Then, the treated regenerated carbon fiber mass 11 is defibrated using the defibrating machine M to obtain a treated regenerated carbon fiber 12.
The obtained treated regenerated carbon fiber 12 is in a state where short (generally 0.5 to 25 mm) strands of regenerated carbon fiber are bundled through polyvinyl alcohol.

Next, the polypropylene pellet 4 serving as a base material resin and the maleic acid-modified polypropylene pellet 5 are supplied into the twin-screw kneading extruder 7 through the main feeder 71 of the twin-screw kneading extruder 7, and the side feeder 72 is In addition to the nonwoven fabric tape 3 made of polyethylene terephthalate resin fibers having a melting point higher than that of the base resin, the obtained treated and regenerated carbon fibers 12 are fed into the biaxial kneading extruder 7.
Then, the polypropylene pellets (hereinafter referred to as “PP pellets”) 4 and the maleic acid-modified polypropylene pellets (hereinafter referred to as “maleic-modified PP pellets”) 5 are melted, and the treated recycled carbon fibers 12 are contained in the base resin. To disperse. At the same time, the nonwoven fabric 3 is finely sheared between the screws 73 (only one side appears in FIG. 2) and dispersed in the base resin.

The extruded kneaded product is cut to obtain a granulated body P containing regenerated carbon fibers. The granulated body P containing regenerated carbon fiber may contain a pigment or other filler.
Next, although not shown, a molded body is obtained by injection molding using the obtained granulated body P.

According to the said manufacturing method, since the regenerated carbon fiber lump 1 is made into the treated regenerated carbon fiber lump 11 and then defibrated, it is possible to prevent the regenerated carbon fibers from being scattered during defibrating.
Further, since the treated regenerated carbon fiber 12 is supplied together with the nonwoven fabric 3 from the side feeder 72, the treated regenerated carbon fiber 12 is drawn in by the nonwoven fabric tape 3 and smoothly and stably continuously into the kneading extruder 7. To be supplied.
Furthermore, since the nonwoven fabric tape 3 is supplied, the nonwoven fabric tape 3 is efficiently dispersed and uniformly dispersed in the kneading extruder 7 by kneading by the kneading extruder 7.

And since the obtained carbon fiber is disperse | distributed in the state which polyvinyl alcohol adhered to the surface, the obtained molded object becomes a thing excellent in adhesiveness with base material resin, and excellent in intensity | strength.
Further, since resin fibers having a melting point higher than that of the base resin are dispersed in the base resin in addition to the regenerated carbon fiber, the toughness of the molded body is increased and the strength is further increased.

3 and 4 show one embodiment of the production method of the second aspect of the present invention.
As shown in FIG. 3, this manufacturing method forms a package 6 in which a treated regenerated carbon fiber 12 obtained in the same manner as in the above embodiment is wrapped with a nonwoven fabric sheet 30 made of polyethylene terephthalate fiber, and FIG. As shown, it is the same as the above embodiment except that the package 6 is supplied from the side feeder 72 of the kneading extruder 7.
According to this manufacturing method, although there is a possibility that the dispersibility may be slightly lowered as compared with the case where the nonwoven fabric tape 3 is used, it is not necessary to provide a supply device for the nonwoven fabric tape 3 and the conventional kneading extruder is used as it is. Can do.

In the above embodiment, the regenerated carbon fiber is immersed in the polyvinyl alcohol aqueous solution. However, a binder aqueous solution such as polyvinyl alcohol is sprayed on the surface of the regenerated carbon fiber lump by spraying, and the binder aqueous solution is regenerated. You may make it impregnate between the regenerated carbon fiber of the fiber lump and the regenerated carbon fiber.
In the above embodiment, the molded body is obtained by injection molding, but other molding methods such as extrusion molding and press molding can also be used.

  Examples of the present invention will be described in detail below.

(Reference Example 1)
(1) Polyvinyl alcohol treatment of regenerated carbon fiber Mass regenerated carbon fiber extracted by thermally decomposing a base resin (epoxy resin) of waste CFRP at a temperature of 600 ° C. is compressed into a screw-type compression kneading and grinding device (planting machine SM 05 0.75, manufactured by Shinko Machine Co., Ltd.) to obtain recycled carbon fiber.
As shown in FIG. 5, granular polyvinyl alcohol (28311-25, Nacalai Tesque Co., Ltd.) was poured into water so that the polyvinyl alcohol concentration would be 3.0% by weight, and 30 times using a stirrer with a heater. Dispersed for minutes. Thereafter, the temperature of the aqueous solution was raised and maintained at 90 ° C. for 60 minutes, and then the heater was turned off to naturally cool the aqueous solution. Into the prepared aqueous polyvinyl alcohol solution, the regenerated carbon fiber obtained as described above is put, and the regenerated carbon fiber is impregnated with the aqueous polyvinyl alcohol solution, and then dried in an electric furnace at 50 ° C. for 24 hours. To obtain a treated regenerated carbon fiber.
(2) Granulation of granulated body P and preparation of test piece As shown in Fig. 3, the nonwoven fabric sheet obtained by cutting a polypropylene nonwoven fabric tape (6640-1A, Shinwa Co., Ltd.). A strap-shaped package (length 1000 mm × diameter 10 mm, content of treated recycled carbon fiber 70% by weight) 6 wrapped in 30 was produced.
As shown in FIG. 4, PP pellets (J708UG, Prime Polymer Co., Ltd.) 4 and maleic acid-modified PP pellets (Yumex 1001, Sanyo Chemical Industries) from the main feeder 71 of a twin-screw kneading extruder (ZSK 18, Coperion Corporation) 7 Co., Ltd.) 5 and the strap-like package 6 produced as described above from the side feeder 72 is introduced every predetermined time, and the ratio of the treated recycled carbon fiber to the total PP is 30:70 by weight. A granulated body 6 was produced. Here, the content ratio of PP pellets, maleic acid PP pellets and PP nonwoven fabric in the total PP was PP pellet: maleic acid PP pellets: PP nonwoven fabric = 55: 5: 10 by weight ratio.
The RCF / PP pellets obtained as described above are put into a hopper of an injection molding machine (PLASTER ET40V, Toyo Machine Metal Co., Ltd.), and the 1A type multipurpose stipulated in JIS K7162 as a recycled carbon fiber reinforced plastic injection molded body A test piece (hereinafter referred to as “RCF / PP injection molding test piece”) was injection molded.

(Comparative Example 1)
An RCF / PP injection-molded test piece was injection-molded in the same manner as in Example 1 except that a regenerated carbon fiber that was not surface-treated was used instead of the treated regenerated carbon fiber.

[Measurement of remaining fiber length in injection molded specimen]
Samples cut out from the test pieces obtained in Example 1 and Comparative Example 1 were placed in a 500 ° C. desktop muffle furnace (KDF-S70, Denken Co., Ltd.) and heat-treated for 60 minutes to form PP as a base material. Evaporate to separate the matrix and fiber.
The fibers obtained by the separation were dispersed in water in a beaker, and the collected ones were placed on a slide glass to prepare a preparation.
The fibers in each preparation were observed using a digital microscope (VH-8000, Keyence Co., Ltd.), a total fiber length of 600 or more was measured, and the fiber length distribution was shown in comparison with FIG.
Moreover, the weight average value Lv of the fiber length which considered the fiber volume was calculated _| required using the following formulas, and it showed in contrast with the following Table 1.

Here, L _i is the remaining fiber length, the N _i is the number of fibers remaining fiber length L _i.

  From FIG. 6 and Table 1, with respect to the treated regenerated carbon fiber subjected to the surface treatment for attaching polyvinyl alcohol and the regenerated carbon fiber not subjected to the surface treatment, the residual fiber length distribution and the average fiber length of the regenerated carbon fiber due to the polyvinyl alcohol treatment It can be seen that there is no change.

[Tension test of injection molded specimen]
The tensile strength of the RCF / PP injection molded test pieces prepared in Reference Example 1 and Comparative Example 1 was measured by n number, and the average value was shown in comparison with FIG.
The tensile strength was measured using a precision universal testing machine (AG-1 100 kN, Shimadzu Corporation) at a test speed of 1 mm / min.
From FIG. 7, it can be seen that the tensile strength of the RCF / PP injection-molded test piece is improved by 8.0% on average by applying the polyvinyl alcohol treatment to the surface of the regenerated carbon fiber.
Moreover, the fracture surface of the test piece after a tensile test was observed with SEM (scanning electron microscope), respectively, and a copy of the SEM photograph is shown in FIG.
As shown to Fig.8 (a), although the polypropylene resin which remain | survived on the fiber surface was able to be confirmed in the fracture surface of the test piece of the reference example 1, as shown in FIG.8 (b), it has not surface-treated. The polypropylene resin remaining on the surface of the regenerated carbon fiber could not be confirmed on the fracture surface of the test piece of Comparative Example 1 using the regenerated carbon fiber.
That is, it is considered that the tensile strength of the RCF / PP injection molded specimen is improved by improving the interfacial shear strength between RCF / PP by polyvinyl alcohol treatment from the result of the tensile test and the SEM photograph.

[Three-point bending test of injection molded specimen]
The RCF / PP injection molded test pieces prepared in Reference Example 1 and Comparative Example 1 were cut into the shape of a class I test piece (length 80 mm, thickness 4 mm, width 10 mm) specified in JIS K7017. . The bending strength of the obtained test piece was measured by n number, and the average value was shown in comparison with FIG.
The bending strength was measured using a precision universal testing machine (AG-1 100 kN, Shimadzu Corporation) at a test speed of 2 mm / min specified in JIS K 7017.
From FIG. 9, it can be seen that by applying polyvinyl alcohol treatment to the surface of the regenerated carbon fiber, the bending strength of the polypropylene injection molded test piece containing the regenerated carbon fiber is improved by 3.6% on average.
The improvement in bending strength is also thought to be due to the improvement in interfacial shear strength between the regenerated carbon fiber and polypropylene, as in the previous section.

(Example 1)
A test piece was prepared in the same manner as in Reference Example 1 except that a non-woven sheet 30 obtained by cutting a polyethylene phthalate resin non-woven tape (polyester spunbond non-woven marix: Unitika Ltd.) was used instead of the polypropylene non-woven fabric, and its tensile strength. And the bending strength was measured.

(Example 2)
As shown in FIG. 2, a polyethylene phthalate resin nonwoven fabric tape (polyester spunbond nonwoven fabric Marix: Unitika Ltd.) 3 was used to create a granulated product, and a test piece was produced using this granulated product. Test pieces were prepared in the same manner as in Reference Example 1, and the tensile strength and bending strength were measured.

  The tensile strength and bending strength of the test pieces of Examples 1 and 2 are shown in Table 2 in comparison with the tensile strength and bending strength of the test piece of Reference Example 1.

  As shown in Table 2 above, it can be seen that the molded article of the present invention is superior in strength.

DESCRIPTION OF SYMBOLS 1 Regenerated carbon fiber lump 11 Processed regenerated carbon fiber lump 12 Processed regenerated carbon fiber 2 Polyvinyl alcohol aqueous solution (binder aqueous solution)
3 Non-woven tape 30 Non-woven sheet 4 Polypropylene pellet (base resin)
5 Maleic acid-modified polypropylene pellets (matrix resin)
6 Package 7 Twin-screw kneading extruder 71 Main feeder 72 Side feeder 73 Screw M Defibrator P Granulated body

Claims (15)

  Recycled carbon fiber reinforced plastic molding in which the regenerated carbon fiber is dispersed in the matrix resin in the presence of a water-soluble binder resin layer that forms natural glue or chemical glue along at least part of the surface of the regenerated carbon fiber A recycled carbon fiber reinforced plastic molded body in which resin fibers made of a resin having a melting point higher than that of the matrix resin are dispersed in the matrix resin in addition to the recycled carbon fiber.   The regenerated carbon fiber reinforced plastic molded article according to claim 1, wherein the water-soluble binder resin is polyvinyl alcohol or old starch derived starch.   The recycled carbon fiber reinforced plastic molded body according to claim 1 or 2, wherein the base material resin is a polyolefin resin or an unsaturated polyester resin.   The regenerated carbon fiber reinforced plastic molded article according to claim 3, wherein the polyolefin resin contains a polypropylene resin as a main component of at least one of a homopolymer, a random copolymer, and a block copolymer.   The recycled carbon fiber reinforced plastic molded article according to claim 4, wherein the polyolefin resin contains maleic acid-modified polypropylene.   The recycled carbon fiber reinforced plastic molding according to any one of claims 1 to 4, wherein the resin fiber having a melting point higher than that of the base resin is at least one selected from the group consisting of polyethylene terephthalate fiber, polyamide fiber, and aramid fiber. body. A method for producing a recycled carbon fiber reinforced plastic molded body according to claim 1,
Regenerated carbon fiber lump obtained by heat treatment of waste carbon fiber reinforced plastic is wetted with an aqueous solution of water-soluble binder resin, and the regenerated carbon fiber lump is defibrated with the water-soluble binder resin adhered to the surface of the regenerated carbon fiber. After that, it is dried to obtain a treated regenerated carbon fiber to which a water-soluble binder resin is adhered, or a regenerated carbon fiber mass obtained by heat treatment of waste carbon fiber reinforced plastic is defibrated by a defibrating machine. A process for producing a regenerated carbon fiber obtained by wetting a regenerated carbon fiber with an aqueous solution of a water-soluble binder resin and then drying it after defibration to obtain a treated regenerated carbon fiber having a water-soluble binder resin attached thereto;
A belt-like nonwoven fabric or woven fabric made of resin fibers having a melting point higher than that of the base resin is supplied from the feeder of the kneading extruder to the kneading extruder, and the treated carbon fiber is fed into the kneading extruder from the same feeder of the kneading extruder. A method for producing a recycled carbon fiber reinforced plastic molded article comprising a step of supplying and extruding from a kneading extruder after kneading together with a base material resin in a kneading extruder. A method for producing a recycled carbon fiber reinforced plastic molded body according to claim 1,
Regenerated carbon fiber lump obtained by heat treating waste carbon fiber reinforced plastic is wetted with an aqueous solution of water-soluble binder resin, and the regenerated carbon fiber lump is defibrated with the water-soluble binder resin attached to the surface of the regenerated carbon fiber. After that, it is dried to obtain a treated regenerated carbon fiber to which a water-soluble binder resin is adhered, or a regenerated carbon fiber mass obtained by heat treatment of waste carbon fiber reinforced plastic is defibrated by a defibrating machine. A process for producing a regenerated carbon fiber obtained by wetting a regenerated carbon fiber with an aqueous solution of a water-soluble binder resin and then drying it after defibration to obtain a treated regenerated carbon fiber having a water-soluble binder resin attached thereto;
The treated regenerated carbon fiber obtained in this step is charged from a feeder of a kneading extruder while wrapped in a nonwoven fabric made of resin fibers having a melting point higher than that of the base resin, and kneaded together with the base resin in the kneading extruder. A method for producing a recycled carbon fiber reinforced plastic molded body comprising a step of extruding from an extruder.   The method for producing a recycled carbon fiber reinforced plastic molded article according to claim 7 or 8, wherein the extruded extruded product is granulated by being extruded from a kneading extruder, and the granulated product is put into an injection molding machine and injection molded. .   The base material resin pellet is charged into the kneading extruder from the main feeder of the kneading extruder, and the treated and regenerated carbon fiber and the nonwoven fabric tape or the woven fabric tape are charged into the kneading extruder from the side feeder. A method for producing a recycled carbon fiber reinforced plastic molded product according to claim 1.   The method for producing a recycled carbon fiber reinforced plastic molded article according to any one of claims 7 to 10, wherein the water-soluble binder resin is polyvinyl alcohol or starch derived from old and old rice.   The method for producing a recycled carbon fiber reinforced plastic molded body according to any one of claims 7 to 11, wherein the base material resin is a polyolefin resin or an unsaturated polyester resin.   The method for producing a recycled carbon fiber reinforced plastic molded article according to claim 12, wherein the polyolefin resin contains, as a main component, at least one of a homopolymer, a random copolymer, and a block copolymer.   The method for producing a recycled carbon fiber reinforced plastic molded article according to claim 13, wherein the polyolefin resin contains maleic acid-modified polypropylene.   The recycled carbon fiber reinforced plastic molding according to any one of claims 7 to 14, wherein the resin fiber having a melting point higher than that of the base resin is at least one selected from the group consisting of polyethylene terephthalate fiber, polyamide fiber, and aramid fiber. Body manufacturing method.