JP2016124887A - Carbon filament/polycarbonate resin composite material, and production process for carbon filament/polycarbonate resin composite pellet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce a high quality carbon filament/polycarbonate resin composite pellet with good yield by a pull-trusion process.SOLUTION: In producing a carbon filament/polycarbonate resin composite pellet by a pull-trusion process, the following (1) to (4) conditions are met: (1) the carbon fiber content in the carbon filament/polycarbonate resin composite is 5 to 40 mass%; (2) the melt resin temperature is 290 to 340°C; (3) setting the diameter of impregnation roll as a (mm), the width of the filament bundle as b (mm), the contact area between the impregnation roll and the filament bundle is 0.6πab to 1.4πab; and (4) the pull speed of the resin impregnated filament bundle is 1 to 12 kg/hr.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a carbon long fiber / polycarbonate resin composite material and a carbon long fiber / polycarbonate resin composite pellet, and in particular, a high-quality carbon long fiber / polycarbonate resin composite material and carbon long fiber by a pull-trusion method. / Relates to a method for efficiently producing polycarbonate resin composite pellets with a high yield.

Polycarbonate resins are widely used in many fields as resins having excellent mechanical strength, heat resistance, transparency, dimensional stability, and the like. Among them, with the recent development of the information industry, the number of cases used as a housing for electrical and electronic equipment has increased greatly.
In such applications, electromagnetic wave shielding is important in order to prevent electromagnetic waves generated in equipment from leaking to the outside and to prevent malfunctions due to the invasion of electromagnetic waves from the outside. The resin material itself is generally insulative and has no electromagnetic shielding properties. For this reason, in order to provide electromagnetic shielding properties, it is necessary to mix a conductive substance. There are various conductive materials such as carbon black, carbon fiber, and metal fiber. In particular, it is known that carbon long fibers provide high electromagnetic shielding properties and are excellent in reinforcing effect.

  Conventionally, as a method for continuously producing a long fiber / resin composite pellet, an electric wire coating method, a pultrusion method (for example, Patent Documents 1 and 2), and a direct roving method are known.

Hereinafter, these methods will be described with reference to FIGS.
9A to 9C, 1 is an extruder, 2 is a hopper, 3 is a screw, 4 is a crosshead die, 4A is a die, 5 is a water tank, 6 is a take-up roll, 7 is a cutter, and 8 is a mesh. A conveyor 9 is a vent port of the extruder 1.
In any method, the resin pellets 11 are charged from the hopper 2 of the extruder 1, melted and kneaded by the screw 3, and then extruded from the crosshead die 4 or the die 4 </ b> A together with the long fiber bundle (roving) 12.

  In the wire coating method, as shown in FIG. 9 (a), a long fiber bundle (roving) 12 is fed to the crosshead die 4, and the long fiber bundle 12 is coated with a molten resin from the screw 3 to form a resin-coated long fiber bundle. 13 is cooled in the water tank 5 and then cut with a cutter 7 to obtain a long fiber / resin composite pellet 13A.

  In the pultrusion method, as shown in FIG. 9 (b), the long fiber bundle (roving) 12 is sent out from above the crosshead die 4, and the long fiber bundle is formed by an impregnation roll (not shown) provided in the crosshead die 4. The molten resin is impregnated between the fibers in the long fiber bundle by widening and loosening in a band shape to obtain a resin-impregnated long fiber bundle 14, which is cooled in the water tank 5 and then cut with a cutter 7 to cut the long fiber / Resin composite pellets 14A are obtained.

  In the direct roving method, as shown in FIG. 9 (c), a long fiber bundle (roving) 12 is directly introduced from the vent port 9 of the extruder 1 to obtain a resin composite long fiber 15, which is water-cooled on a mesh conveyor 8. After that, it is cut with a cutter 7 to obtain a long fiber / resin composite pellet 15A.

JP-A-1-16612 JP-A-5-169445

Among the conventional methods for producing long fiber / resin composite pellets, in the direct roving method, a long fiber bundle is supplied directly from the vent port to the extruder, so the fibers break in the extruder and the fiber length is fully utilized. Long fiber / resin composite pellets cannot be produced.
In a composite pellet with a short fiber length, the electromagnetic wave shielding property and the reinforcing effect are insufficient, so it is important to leave the fiber length in the pellet long.

  The wire coating method and the pultrusion method are preferable in that the fiber length in the pellet can be left long, but in the wire coating method, only the periphery of the long fiber bundle is coated with a resin, so the obtained pellet The fiber is easy to come off.

Pultrusion method in which resin is impregnated between the fibers of the long fiber bundle is preferable in that it is difficult for fibers to come off from the pellet. However, if carbon long fiber / polycarbonate resin composite pellets are produced by the pull trusion method, resin impregnation There is a problem that fiber breakage easily occurs.
This is because the polycarbonate resin has a high viscosity, and thus a large tension is applied to the long fiber bundle in the molten resin impregnation bath. Increasing the melting temperature of the polycarbonate resin can lower the viscosity and prevent fiber breakage, but in this case, the good physical properties of the polycarbonate resin are impaired due to thermal degradation of the polycarbonate resin.
In addition, since amorphous resin such as polycarbonate resin has poor adhesion to carbon fiber compared to crystalline resin such as nylon, the obtained pellets may be obtained by the pultrusion method in which the resin is impregnated. There was also a problem that the fibers were likely to fall off.
The fiber breakage is a factor that greatly impairs the productivity, and the dropping of the fiber from the pellet is a problem in terms of product yield and quality. For these reasons, the pultrusion method has not been put to practical use in the production of carbon long fiber / polycarbonate resin composite pellets.

  An object of the present invention is to provide a method for efficiently producing a high-quality carbon long fiber / polycarbonate resin composite material and a carbon long fiber / polycarbonate resin composite pellet with a high yield by a pultrusion method.

As a result of intensive studies to solve the above-mentioned problems, the present inventor appropriately controls the molten resin temperature and other manufacturing conditions in the pultrusion method, thereby preventing fiber breakage and fiber falling off from the pellets. Found that you can.
That is, the gist of the present invention is as follows.

[1] A continuous long fiber bundle of carbon fibers is run in a molten resin bath of polycarbonate resin, and the long fiber bundle is widened in a band shape with an impregnation roll in the molten resin bath. In manufacturing a carbon long fiber / polycarbonate resin composite material by impregnating a resin into a long fiber bundle and taking out the resin-impregnated long fiber bundle from the molten resin bath, the following conditions (1) to (4) must be satisfied: A method for producing a carbon long fiber / polycarbonate resin composite material.
(1) The carbon fiber content of the carbon long fiber / polycarbonate resin composite material is 5 to 40% by mass.
(2) The molten resin temperature is 290 to 340 ° C.
(3) When the diameter of the impregnation roll is a (mm) and the width of the long fiber bundle is b (mm), the contact area between the impregnation roll and the long fiber bundle is 0.6πab to 1.4πab. is there.
(4) The take-up speed of the resin-impregnated long fiber bundle is 1 to 12 kg / hr.

[2] In [1], two or more of the impregnating rolls are provided in parallel such that the roll axial direction is a direction intersecting with the traveling direction of the long fiber bundle, and the adjacent impregnating rolls A method for producing a carbon long fiber / polycarbonate resin composite material, characterized in that the distance between them is equal to or less than the diameter a (mm) of the impregnating roll.

[3] The carbon long fiber / polycarbonate resin according to [1] or [2], wherein the carbon fiber long fiber bundle is preheated to 100 to 300 ° C. and then introduced into the molten resin bath. A method for producing a composite material.

[4] The carbon long fiber / polycarbonate resin composite material produced by the method for producing a carbon long fiber / polycarbonate resin composite material according to any one of [1] to [3] is cut into carbon long fiber / polycarbonate resin composite pellets. A method for producing a carbon long fiber / polycarbonate resin composite pellet.

[5] The method for producing a carbon long fiber / polycarbonate resin composite pellet according to [4], wherein the carbon long fiber / polycarbonate resin composite material has a cut length of 4 to 10 mm.

  According to the present invention, high-quality carbon long fiber / polycarbonate resin composite materials and carbon long fiber / polycarbonate resin composite pellets can be efficiently produced with high yield by the pultrusion method.

It is a typical top view which shows an example of the manufacturing apparatus of CF / PC pellet suitable for implementation of this invention. (A) is a schematic cross-sectional view of a resin impregnation cell and a preheating cell portion of the CF / PC pellet manufacturing apparatus of FIG. 1, and (b) is a schematic diagram showing the arrangement of impregnation rolls and guide rolls. is there. It is a figure which shows another example of the manufacturing apparatus of CF / PC pellet suitable for implementation of this invention, Comprising: (a) A figure is typical sectional drawing of a resin impregnation cell and a preheating cell part, (b) The figure is a schematic view showing the arrangement of the impregnation roll and the guide roll. It is a figure which shows the example of arrangement | positioning of an impregnation roll, (a) A figure is a front view, (b) A figure and (c) figure are side views. It is a figure which shows the example of arrangement | positioning of an impregnation roll, (a) A figure is a front view, (b) A figure and (c) figure are side views. It is a figure which shows arrangement | positioning of the impregnation roll employ | adopted by the comparative example 3, (a) A figure is a front view, (b) A figure is a side view. It is a figure which shows arrangement | positioning of the impregnation roll employ | adopted in Examples 1-5 and Comparative Examples 1, 2, and 5, (a) A figure is a front view, (b) A figure is a side view. It is a figure which shows arrangement | positioning of the impregnation roll employ | adopted by the comparative example 4, (a) A figure is a front view, (b) A figure is a side view. It is a schematic diagram which shows the manufacturing method of the conventional long fiber / resin composite pellet, (a) figure shows an electric wire coating method, (b) figure shows a pultrusion method, (c) figure shows a direct roving method, respectively. .

  Hereinafter, embodiments of the present invention will be described in detail.

The carbon long fiber / polycarbonate resin composite material of the present invention (hereinafter referred to as “CF / PC material”), and the CF / PC material produced by the method of the present invention may be referred to as “CF / PC material of the present invention”. ) According to the pultrusion method, the carbon fiber long fiber bundle is continuously run in the polycarbonate resin molten resin bath, and the long fiber bundle is impregnated in the molten resin bath. When the CF / PC material is manufactured by impregnating the long fiber bundle with a resin by widening it in a belt shape and taking out the resin-impregnated long fiber bundle from the molten resin bath, the following (1) to (4) The condition is set so as to satisfy the conditions, and the carbon long fiber / polycarbonate resin composite pellet (hereinafter referred to as “CF / PC pellet”) of the present invention is used. The manufactured CF / PC pellets are sometimes referred to as “CF / PC pellets of the present invention.”) The production method of the above is characterized by cutting and pelletizing the CF / PC material thus obtained. And
(1) The carbon fiber content of the carbon long fiber / polycarbonate resin composite material is 5 to 40% by mass.
(2) The molten resin temperature is 290 to 340 ° C.
(3) When the diameter of the impregnation roll is a (mm) and the width of the long fiber bundle is b (mm), the contact area between the impregnation roll and the long fiber bundle is 0.6πab to 1.4πab. is there.
(4) The take-up speed of the resin-impregnated long fiber bundle is 1 to 12 kg / hr.
In the present invention, the molten resin of the polycarbonate resin may be composed of only the polycarbonate resin, or may be composed of a polycarbonate resin composition containing the polycarbonate resin and other components. This molten resin will be described later as “impregnated resin of the present invention”.

[Pultrusion method]
First, with reference to FIGS. 1-3, the manufacturing method of the CF / PC material and the CF / PC pellet by the pultrusion method in this invention is demonstrated.
FIG. 1 is a schematic plan view showing an example of an apparatus for producing CF / PC pellets suitable for carrying out the present invention, and FIG. 2 (a) is a schematic cross-sectional view showing the main part of the apparatus of FIG. (A longitudinal sectional view of the resin impregnation cell and the preheating cell portion as viewed from the direction of arrow II in FIG. 1), FIG. 2 (b) is a schematic diagram showing the arrangement of the impregnation roll and the guide roll, and FIG. It corresponds to the figure seen from the direction of arrow B. FIGS. 3A and 3B show different modes corresponding to FIGS. 2A and 2B, respectively.

  In FIGS. 1 and 2, reference numeral 20 denotes an extruder (usually a twin-screw extruder is used), which has a resin hopper 21 on the base end side, and the tip 20 </ b> A side is a lower part of the resin impregnation cell 22. The molten resin 10 from the extruder 20 is extruded into the resin impregnation cell 22. A preheating cell 23 for preheating a long fiber bundle of carbon fibers (hereinafter sometimes referred to as “CF roving”) 31 is provided on the upstream side of the resin impregnation cell 22. Reference numeral 24 denotes a shaping die. In the process of passing through the shaping die 24, the CF roving 31 impregnated with the molten resin 10 is formed into a predetermined cross-sectional shape. 25 is a water tank, 26 is a pelletizer, and a take-up roll and a cutter are provided inside.

The CF roving 31 continuously drawn out from the CF roving wound body 30 is preheated to a predetermined temperature by a heater (not shown) in the preheating cell 23 and then passes through the resin impregnation cell 22 while being impregnated rolls 41 to 44. The molten resin penetrates between the carbon fibers and is impregnated.
The resin-impregnated CF roving 32 drawn out by the take-up roll in the pelletizer 26 through the shaping die 24 is cooled in the water tank 25, and the CF / PC material 33 from the water tank 25 is made into a predetermined length by the cutter in the pelletizer 26. The CF / PC pellet 34 is cut.

  As shown in FIG. 2, in the resin impregnated cell 22, an inlet side guide roll 40 </ b> A that changes the traveling direction of the CF roving 31 from the horizontal direction to the vertically downward direction, and an outlet side guide that changes from the vertically downward direction to the horizontal direction. A roll 40B is provided, and four impregnating rolls 41, 42, 43, and 44 are provided between the guide rolls 40A and 40B. The guide rolls 40 </ b> A and 40 </ b> B and the impregnation rolls 41 to 44 are arranged side by side so that the roll axis direction is orthogonal to the traveling direction of the CF roving 31.

  The guide roll 40A is provided above the liquid level L of the molten resin 10 in the resin impregnation cell 22, and the guide roll 40B is, for example, the outlet of the resin impregnated CF roving 32 of the shaping die 24 in the molten resin 10. It is provided at the height position.

  In FIG. 2, the diameters a of the impregnating rolls 41 to 44 are all equal, and the diameters of the guide rolls 40A and 40B are slightly smaller than the diameters of the impregnating rolls 41 to 44, but may be equal to the diameters of the impregnating rolls 41 to 44. It can be large.

  In FIG. 2, the impregnating rolls 41 to 44 are provided at equal intervals in the molten resin 10, and the interval c between adjacent impregnating rolls is 4 times or less of the diameter a of the impregnating roll, that is, 4 a or less. is there. Further, the guide roll 40A is provided at a position that is separated from the uppermost impregnation roll 41 by more than four times the diameter a of the impregnation roll, and the guide roll 40B has a diameter of the impregnation roll that is lower than the lowermost impregnation roll 44. It is provided at a position separated by a distance larger than 4 times a.

  As described above, in this CF / PC pellet manufacturing apparatus, the CF roving 31 fed from the CF roving winding body 30 is preheated to about 100 to 300 ° C. in the preheating cell 23, and then enters the resin impregnation cell 22. The guide roll 40A heads vertically downward, contacts the impregnation rolls 41 to 44 in the molten resin 10, and is widened in a band shape. The molten resin 10 is impregnated between the carbon fibers of the CF roving 31 that has been widened and loosened, and the resin-impregnated CF roving 32 is shaped by the shaping die 24 through the guide roll 40B, and taken up in the pelletizer 26. Taken by the roll. A CF / PC pellet 34 is obtained by cutting the CF / PC material 33 obtained by cooling the resin-impregnated CF roving 32 in the water tank 25 with a cutter in the pelletizer 26.

1 and 2 show an example of a CF / PC pellet manufacturing apparatus suitable for carrying out the present invention. The CF / PC pellet manufacturing apparatus used in the present invention is shown in FIGS. It is not limited to what is shown.
For example, in FIGS. 1 and 2, in the preheating cell 23 and the resin impregnation cell 22, the traveling direction of the CF roving 31 in the preheating cell 23 is the horizontal direction, and the traveling direction of the CF roving 31 in the resin impregnation cell 22 is the vertical direction. As shown in FIG. 3, the preheating cell 23A and the resin-impregnated cell 22 both have an I-shaped cross section so that the running direction of the CF roving is a vertical direction. May be provided continuously. In this case, the inlet side guide roll 40A shown in FIG. 2 can be omitted.

  The CF / PC pellet manufacturing apparatus shown in FIG. 3 is the same as that shown in FIG. 2 except that the preheating cell 23A and the resin-impregnated cell 22 are provided in a continuous cylindrical shape, and the inlet side guide roll 40A is not provided. The configuration of the water tank 25, pelletizer 26, etc. after the shaping die 24 is the same as that shown in FIG. 1, and the production of CF / PC pellets is performed in the same manner as described above.

  In the present invention, in the production of such CF / PC materials and CF / PC pellets, conditions are set so as to satisfy the conditions (1) to (4) described above.

<Carbon fiber content of CF / PC material>
In the present invention, the carbon fiber content of the CF / PC material is 5 to 40% by mass, preferably 10 to 30% by mass, and more preferably 15 to 25% by mass.
When the carbon fiber content of the CF / PC material is higher than the above upper limit, the moldability of the CF / PC material and the CF / PC pellets, and further, a molded product obtained by molding them becomes inferior. In addition, the amount of resin is relatively small, and there is a possibility that the falling off of the fiber becomes a problem.
When the carbon fiber content of the CF / PC material is less than the above lower limit, sufficient electromagnetic shielding properties cannot be obtained.

<Molten resin temperature>
In the present invention, the molten resin temperature (the temperature of the molten resin 10 in the resin impregnated cell 22 in FIGS. 1, 2 and 3) is 290 to 340 ° C., preferably 300 to 330 ° C., more preferably 310 to 330 ° C. And
When the molten resin temperature is lower than the above lower limit, the melted polycarbonate resin has a high viscosity, so that fiber breakage easily occurs. When the molten resin temperature is higher than the above upper limit, there is no problem of fiber breakage, but the original physical properties of the polycarbonate resin are impaired due to thermal degradation of the polycarbonate resin. The thermal deterioration of the polycarbonate resin can be grasped by the degree of decrease in the molecular weight of the polycarbonate resin.

<Contact area between impregnation roll and CF roving>
In the present invention, the contact area between the impregnation roll and the CF roving is set to 0.6πab to 1.4πab with respect to the diameter a (mm) of the impregnation roll and the width b (mm) of the CF roving. Here, π is a circumferential ratio of 3.14.

This contact area will be described with reference to FIGS.
The CF roving 31 is in contact with the impregnating rolls 41 to 44 with a width b (mm) with respect to the impregnating rolls 41 to 44 having a diameter a (mm). In the present invention, the contact area between the impregnation roll and the CF roving is the total area in which the CF roving 31 is in contact with all of the impregnation rolls 41 to 44.
The contact area between the guide rolls 40A and 40B and the CF roving 31 is not included.

  Here, the impregnation roll is provided in the molten resin 10 in order to impregnate the CF roving 31 with the molten resin 10, and usually two or more rolls are adjacently impregnated in the molten resin 10. The distance c between the rolls is set to be not more than 4 times the diameter a of the impregnating roll (that is, not more than 4a), preferably not more than 3 times the diameter a (that is, not more than 3a), and not less than the thickness of the CF roving 31. . Therefore, even if it is provided in the molten resin 10, the gap between the adjacent rolls is provided more than 4 times the diameter a of the impregnating roll as in the guide roll 40B of FIGS. The roll is not included in the impregnation roll.

  The contact area between the impregnation roll and the CF roving should be changed by appropriately designing the diameter of the impregnation roll, the number of impregnation rolls, the distance between the impregnation rolls, the position of the impregnation roll, the distance between the impregnation roll and the guide roll, etc. Can do.

  For example, as shown in FIGS. 4A and 4B, when the impregnating rolls 51 to 53 are arranged side by side at a relatively small interval, a relatively large interval as shown in FIGS. 5A and 5B. The contact area with the CF roving per impregnating roll is larger than in the case where they are arranged side by side, and the total contact area is therefore larger. As shown in FIGS. 4 (c) and 5 (c), when the positions of the impregnating rolls 51 to 53 in the plane projection direction are different even if the interval is the same, FIGS. 4 (b) and 5 (b). As shown in (), the contact area is larger than when the positions are the same. The same applies to the positions of the guide rolls provided above and below the impregnation roll.

Further, the contact area can be changed by changing the diameter of the impregnation roll.
In addition, about the number of impregnation rolls, what is necessary is just two or more, and there is no restriction | limiting in particular, Usually, 2-6, Preferably it is 2-4.
Further, the diameter a (mm) of the impregnation roll is appropriately determined according to the CF roving width b (mm), the size of the resin impregnation cell, etc., but for CF roving having a width b of 3 to 20 mm. The diameter a of the impregnating roll is preferably 8 to 16 mm, particularly 10 to 14 mm, and the diameter a of the impregnating roll is preferably designed to be about 0.5 to 4 times the width b of the CF roving.
The diameters a of the plurality of impregnating rolls do not have to be the same and may be different. Further, the intervals c between adjacent impregnating rolls do not have to be the same and may be different.

In the present invention, the contact area between the impregnating roll and the CF roving designed as described above is in the range of 0.6πab to 1.4πab with respect to the diameter a of the impregnating roll and the width b of the CF roving.
If this contact area is larger than the above upper limit, the tension applied to the CF roving becomes large and fiber breakage becomes a problem. If the contact area is smaller than the lower limit, the molten resin is not sufficiently impregnated between the carbon fibers of the CF roving. Then, fiber removal from the obtained pellet becomes a problem. This contact area is preferably 0.8πab to 1.2πab, more preferably 0.9πab to 1.1πab.

<Retraction speed of resin-impregnated CF roving>
In the present invention, the take-up speed of the resin-impregnated CF roving, that is, the take-up speed of the resin-impregnated CF roving 32 taken from the shaping die 24 by the take-up roll in the pelletizer 26 in FIG. 1 is 1 to 12 kg / hr, preferably 3 to 11 kg / hr, more preferably 5 to 10 kg / hr.

If the take-up speed is higher than the upper limit, the tension applied to the CF roving is too high, so that fiber breakage easily occurs. Even if the take-off speed is low, there is no problem in terms of fiber breakage or fiber removal, but it is not preferable in terms of productivity.
The take-up speed is more preferably adjusted within the above range in the correlation with the molten resin temperature, slightly faster when the molten resin temperature is high, and slightly slower when the molten resin temperature is low, and can be adjusted as appropriate. It is preferable from the viewpoint of preventing fiber breakage and productivity.

[Manufacture of CF / PC pellets]
The CF / PC material obtained by the above pultrusion method is cut with a pelletizer 26 to obtain CF / PC pellets.
In the present invention, the cutting length of the CF / PC pellet, that is, the length of the obtained CF / PC pellet is not particularly limited, but is preferably 4 to 10 mm, particularly preferably 5 to 8 mm. The pellets thus obtained include CF roving having a fiber length substantially the same as the cut length. When the cutting length is too short, the CF roving length in the pellet is also short, and the electromagnetic shielding property of the molded product obtained using the pellet tends to be lowered, and the fiber may fall off. Conversely, if the cutting length is too long, the moldability is impaired.
The diameter of the CF / PC pellet is determined by the width of the CF / PC pellet used, the resin impregnation amount, etc., but is usually about 2.5 to 3.5 mm.

[CF roving]
Next, CF roving used in the present invention, that is, a long fiber bundle of carbon fibers will be described.

The carbon fiber constituting the CF roving may be any carbon fiber such as polyacrylonitrile (PAN), petroleum / petroleum pitch, rayon, and lignin, and in particular, PAN-based carbon using PAN as a raw material. A fiber is preferable in that it has excellent mechanical properties and is easily available.
The fiber diameter (diameter per filament) of the carbon fiber is preferably 5 to 10 μm on average. The CF roving is preferably a fiber bundle in which about 1000 to 50000 (1 to 50 k) of such carbon fibers are converged with a sizing agent such as a polyurethane sizing agent.
The width b of such CF roving is usually about 3 to 20 mm and the thickness is about 0.1 to 1 mm.

  1 to 3, CF roving is sent out using only one CF roving winding body. However, when producing a CF / PC material having a high carbon fiber content, two or more CF roving windings are used. Two or more CF rovings may be run in parallel in the resin-impregnated cell using a rotating body.

[Impregnating resin]
Next, the CF / PC material of the present invention and the impregnating resin for producing the CF / PC pellet (hereinafter sometimes referred to as “impregnating resin of the present invention”) will be described. This impregnating resin contains a polycarbonate resin, and may be composed only of the polycarbonate resin. Other thermoplastic resins other than the polycarbonate resin and the polycarbonate resin, elastomers, and electromagnetic shielding properties are further improved. It may be a polycarbonate resin composition containing an inorganic conductive material such as carbon black, carbon nanotube, and SUS powder for improvement, and various additives for improving characteristics.

<Polycarbonate resin>
As the polycarbonate resin used in the impregnation resin of the present invention, any conventionally known polycarbonate resin can be used. Examples of the polycarbonate resin include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, and aromatic polycarbonate resins are preferable.

  The aromatic polycarbonate resin is an optionally branched aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method). Further, it may be a polycarbonate resin produced by a melting method and produced by adjusting the amount of OH groups of terminal groups.

Typical examples of the aromatic dihydroxy compound that is one of the raw materials of the aromatic polycarbonate resin used in the present invention include, for example, bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl). Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Further, polyhydric phenols having 3 or more hydroxy groups in the molecule such as 1,1,1-tris (4-hydroxylphenyl) ethane, 1,3,5-tris (4-hydroxyphenyl) benzene, etc. are branched. A small amount can be used in combination as an agent.
Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. These aromatic dihydroxy compounds can be used alone or in admixture of two or more.

  In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 -Polyhydroxy compounds such as tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. May be used as a part of the aromatic dihydroxy compound, and the amount used thereof may be And from 0.01 to 10 mol% against, and preferably 0.1 to 2 mol%.

  In the polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Representative examples of the carbonic acid diester include substituted diaryl carbonates typified by diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with the dicarboxylic acid or dicarboxylic acid ester preferably. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  When an aromatic polycarbonate resin is produced by a transesterification method, a catalyst is usually used. Although there is no limitation on the catalyst species, generally basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more. In the transesterification method, the polymerization catalyst is generally deactivated with p-toluenesulfonic acid ester or the like.

  Preferred polycarbonate resins are aromatic polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane or derived from 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. Aromatic polycarbonate copolymer. Further, for the purpose of imparting flame retardancy and the like, a polymer or oligomer having a siloxane structure can be copolymerized. The polycarbonate resin may be a mixture of two or more kinds of polymers and / or copolymers having different raw materials, and may have a branched structure up to 0.5 mol%.

  The terminal hydroxyl group content of a polycarbonate resin such as an aromatic polycarbonate resin greatly affects the thermal stability, hydrolysis stability, color tone, and the like. In order to have practical physical properties, the terminal hydroxyl group content of the polycarbonate resin is usually 30 to 2000 ppm, preferably 100 to 1500 ppm, and more preferably 200 to 1000 ppm. As the terminator, p-tert-butylphenol, phenol, cumylphenol, p-long chain alkyl-substituted phenol and the like can be used.

  The amount of the residual monomer in the polycarbonate resin such as aromatic polycarbonate resin is 150 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less in the aromatic dihydroxy compound. When synthesized by the transesterification method, the residual amount of carbonic acid diester is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less.

  The molecular weight of the polycarbonate resin such as aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent, and preferably in the range of 13,000 to 50,000. More preferably, more than 13,000 and not more than 40,000, particularly preferably in the range of 18,000 to 30,000. By setting the viscosity average molecular weight to 13,000 or more, mechanical properties are more effectively exhibited in the obtained CF / PC material and CF / PC pellets, and further, a molded product obtained using the CF / PC material. By making it below, the moldability of the obtained CF / PC material and CF / PC pellet becomes better. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed, or a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed to be within the above molecular weight range.

  Furthermore, the polycarbonate resin used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material-recycled polycarbonate resin. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. Further, the form of the recycled polycarbonate resin is not particularly limited, and any non-conforming product, pulverized product such as sprue or runner, and pellets obtained by melting them can be used.

<Elastomer>
The impregnating resin of the present invention may contain an elastomer. By containing an elastomer, it is possible to improve the impact resistance of the obtained CF / PC material and CF / PC pellets, and also the molded product obtained by using this.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. The method for producing the graft copolymer may be any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft. From the viewpoint of easy control of productivity and particle size, an emulsion polymerization method is preferred, and a multistage emulsion polymerization method is more preferred. Examples of the multistage emulsion polymerization method include polymerization methods described in JP-A No. 2003-261629.

The rubbery polymer generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, (partial) hydrogenated polybutadiene rubber, butadiene-styrene copolymer, (partial) hydrogenated polybutadiene-styrene copolymer, butadiene-styrene block copolymer, (partial) water. One or more vinyl monomers that can be copolymerized with butadiene and butadiene, such as a polybutadiene-styrene block copolymer, a butadiene-acrylonitrile copolymer, and an acrylic rubber copolymer based on butadiene-isobutyl acrylate Butadiene rubber such as a copolymer with polyisobutylene, polyisobutylene, polyisobutylene-styrene copolymer, isobutylene rubber such as polyisobutylene-styrene block copolymer, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl) Acrylate), butyla Polyalkyl acrylate rubber such as relate / 2-ethylhexyl acrylate copolymer, silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene -Ethylene-alpha olefin rubbers such as propylene rubber, ethylene-butene rubber, ethylene-octene rubber, ethylene-acrylic rubber, fluorine rubber, and the like. These may be used alone or in admixture of two or more.
Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, butadiene-styrene copolymer, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN (Interpenetrating Polymer composed of polyorganosiloxane rubber and polyalkyl acrylate rubber). Network) type composite rubber is preferred.

Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more.
Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth) acrylic acid ester compounds are preferable, and (meth) acrylic acid ester compounds are more preferable from the viewpoint of mechanical properties and surface appearance. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. These may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same applies hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kane Ace (registered trademark, the same applies hereinafter) M-511 "," Kane Ace M-711 "," Kane Ace M-731 ", manufactured by Kaneka Corporation Kane Ace M-600 " "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01", and the like.

  When the impregnating resin of the present invention contains an elastomer, the content thereof is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 4 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. Moreover, it is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. When the elastomer content is less than the above lower limit, the impact resistance improvement effect by the elastomer is insufficient, and when the elastomer content exceeds the above upper limit, the flame retardancy and heat resistance are reduced, and the obtained CF / Appearance defects of molded products formed by molding PC materials and CF / PC pellets may occur.

<Inorganic conductive material>
The impregnating resin of the present invention may contain an inorganic conductive material.
As the inorganic conductive material, a known inorganic conductive material that is usually blended in a thermoplastic resin can be used. By using the inorganic conductive material, it is formed of carbon long fibers in the obtained molded product. A further excellent electromagnetic wave shielding property can be obtained by continuing the network to be further continued through the intervention of an inorganic conductive material. Examples of such inorganic conductive materials include carbon-based conductive materials such as carbon black, carbon fiber, graphite, carbon whisker, and carbon nanotube, metal powders such as SUS powder, and metal-based inorganic conductive materials such as metal oxides. Examples include materials, carbon fibers, whiskers, and composite conductive materials in which the surface of glass fibers is coated with metal. Among these, metal powder such as conductive carbon black, carbon nanotube, and SUS powder is preferable. These inorganic conductive materials may be used alone or in combination of two or more.

The electrically conductive carbon black, generally large specific surface area, is preferably one having a developed secondary aggregate (structure), the specific surface area (BET equation nitrogen adsorption method) 30~1500m ² / g, inter alia 50～1300M ² / g, more preferably 70 to 900 m ² / g, and particularly preferably 100 to 850 m ² / g. When the specific surface area exceeds 1500 m ² / g, the fluidity and appearance of the obtained CF / PC material and CF / PC pellets, and further the molded product obtained by using the CF / PC material tend to deteriorate, and less than 30 m ² / g. Then, there exists a possibility that electroconductivity may become difficult to express.

As the conductive carbon black having a dibutylphthalate (DBP) absorption of preferably has a 100~500cm ³ / 100g, among others 120~450cm ³ / 100g, those which are particularly 150~400cm ³ / 100g, conductive Is more preferable in terms of the balance between the property and impact resistance.

In the present invention, BET equation nitrogen adsorption method specific surface area ^(unit: m 2 / g), DBP absorption ^(unit: cm 3 / 100g) are those measured according to JIS K6217.

  Examples of such preferable conductive carbon black include a furnace method conductive carbon black in which raw material hydrocarbons are thermally decomposed by the combustion heat of crude oil or gas to generate carbon black, and a ketjen obtained by a heavy oil gasification process. Examples thereof include black and acetylene black obtained by pyrolyzing acetylene gas. For example, “Vulcan XC-72” manufactured by Cabot Corporation, “Ketjen Black EC” manufactured by Mitsubishi Chemical Corporation, “Denka” manufactured by Denki Kagaku Kogyo Co., Ltd. Black "etc. are marketed.

  As the conductive carbon black, one kind may be used alone, or two or more kinds having different physical properties, raw materials or manufacturing processes may be mixed and used.

  The carbon nanotube is a carbon fibril having a hollow structure, preferably having an outer diameter of 3.5 to 70 nm and an aspect ratio of 5 or more, and particularly preferably an outer diameter of 4 to 60 nm and an aspect ratio of 10 or more. When the fibril outer diameter is less than 3.5 nm, the dispersibility in the resin is inferior, and when it exceeds 70 nm, the conductivity tends to be inferior. Moreover, when the aspect ratio is less than 5, the conductivity tends to be inferior.

  Carbon nanotubes have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms and an inner hollow region, each layer and hollow region being substantially around the cylindrical axis of the fibril. Columnar fibrils arranged concentrically. Furthermore, the regularly arranged carbon atoms in the outer region are preferably graphite-like, and the diameter of the hollow region is preferably 2 to 20 nm. Such carbon nanotubes are described in detail in Japanese Patent Publication No. 62-5000943 and US Pat. No. 4,663,230. About the manufacturing method, as described in the above-mentioned patent publications and US patent specifications, transition metal-containing particles (for example, iron, cobalt, nickel-containing particles using alumina as a support) contain carbon such as CO and hydrocarbons. Examples include a method in which a gas is brought into contact with a gas at a high temperature of 850 to 1200 ° C., and carbon generated by thermal decomposition is grown in a fiber form starting from a transition metal. Such carbon nanotubes are commercially available from Hyperion Catalysis under the trade name “Graphite Fibril” and are readily available.

Examples of the metal powder include gold, silver, copper, nickel, magnesium, zinc, aluminum, iron and the like, or an alloy containing two or more of these metals. Among these, SUS powder is particularly an electromagnetic wave shield. It is preferable in terms of imparting properties and cost.
Metal powder such as SUS powder is difficult to impart electromagnetic wave shielding properties by itself, but can provide high electromagnetic wave shielding properties in combination with carbon long fibers.

  The shape of the metal powder is not particularly limited, such as a rod shape such as a fiber, a spherical shape, a flake shape (scale shape), etc., but if the particle size is too large, the moldability and mechanical strength of the pellet may be impaired. If it is too small, the electromagnetic shielding effect tends to be inferior, so that the average particle size is preferably about 1 to 1000 μm, particularly about 10 to 500 μm. Here, the particle diameter of the metal powder is the length of the long side if it is a rod-shaped metal powder, the diameter if it is a spherical metal powder, and the largest diameter if it is a granular metal powder. Corresponds to the diameter of the part.

  Only one type of metal powder may be used, or two or more types having different materials, sizes, and shapes may be used in combination.

  When the inorganic conductive material as described above, in particular, an inorganic conductive material such as a carbon-based conductive material is used for the impregnating resin of the present invention, the inorganic conductive material is preferably used with respect to 100 parts by mass of the polycarbonate resin. Is 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 12 parts by mass or less. It is preferable to use for. If the blending amount of the inorganic conductive material is less than the above lower limit value, the effect of improving the electromagnetic wave shielding property by using the inorganic conductive material cannot be sufficiently obtained, and the CF / PC material obtained when the above upper limit value is exceeded, and There is a risk that the formability of the CF / PC pellet may be impaired.

  Further, among the inorganic conductive materials, particularly when metal powder such as SUS powder is used for the impregnating resin of the present invention, the metal powder is preferably 5 parts by mass or more, more preferably 7 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is preferably used in an amount of at least 10 parts by mass, more preferably at least 10 parts by mass, preferably at most 100 parts by mass, more preferably at most 90 parts by mass, even more preferably at most 80 parts by mass. If the blending amount of the metal powder is less than the above lower limit value, the effect of improving the electromagnetic wave shielding property by using the metal powder cannot be sufficiently obtained, and if it exceeds the above upper limit value, the CF / PC material and CF / PC pellet obtained. There is a risk that the moldability of the resin may be impaired.

Inorganic conductive materials such as carbon black, carbon nanotubes, and metal powder are preferably blended as a masterbatch containing these in a high concentration because the inorganic conductive material can be uniformly dispersed in the resin. In this case, the resin used for the masterbatch may be the same polycarbonate resin as the polycarbonate resin used in the impregnation resin of the present invention, or may be a different polycarbonate resin, such as a resin other than the polycarbonate resin, such as a polystyrene resin. Etc. Although there is no restriction | limiting in particular in content of inorganic electroconductive substances, such as carbon black, a carbon nanotube, a metal powder, in a masterbatch, Usually, it is about 20-50 mass%.
When a polycarbonate resin is contained in these master batches, the polycarbonate resin is also used as the polycarbonate resin in the impregnating resin of the present invention, and the numerical value standard of the blending amount of the above-mentioned elastomer and inorganic conductive material and various additives described below Contained in the polycarbonate resin.

<Other thermoplastic resins>
When the impregnating resin of the present invention contains a thermoplastic resin other than the polycarbonate resin, the type and blending amount can be appropriately selected for the purpose of improving the performance such as moldability and chemical resistance. Examples of the thermoplastic resin other than the polycarbonate resin include polyester resin, polyamide resin, polyolefin resin, polyphenylene ether resin, styrene resin, polysulfone, polyethersulfone, polyphenylene sulfide, polyacrylate, polyamideimide, polyetherimide, and the like. .

  Examples of the polyester resin include polybutylene terephthalate, polyethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene and polypropylene. Examples of the polyphenylene ether resins include polyphenylene ether resins and mixed resins of polyphenylene ether and polystyrene and / or HIPS (impact polystyrene). Examples of the styrene resin include polystyrene, HIPS, AS resin, ABS resin, and the like. As the thermoplastic resin other than the polycarbonate resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether resin, HIPS, AS resin, ABS resin and the like are preferably used.

  When the impregnating resin of the present invention contains a thermoplastic resin other than the polycarbonate resin, the blending amount thereof is preferably less than 50% by mass of the total amount of the polycarbonate resin and the thermoplastic resin other than the polycarbonate resin, more preferably. It is 40 mass% or less, Most preferably, it is 30 mass% or less.

<Additives>
In the impregnating resin of the present invention, in order to obtain desired physical properties, various additives as necessary, for example, stabilizers such as ultraviolet absorbers, antioxidants, heat stabilizers, pigments, dyes, lubricants, flame retardants, An anti-dripping agent, a release agent, a slidability improving agent, and the like can be blended.

(Antioxidant)
Examples of the antioxidant include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(me Citylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, etc. These may be used in combination of two or more.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  When using antioxidant, the compounding quantity is 0.001-1 mass part normally with respect to 100 mass parts of polycarbonate resins in the impregnation resin of this invention, Preferably it is 0.01-0.5 mass part. When the blending amount of the antioxidant is less than 0.001 part by mass, the effect as an antioxidant is insufficient, and when it exceeds 1 part by mass, the effect reaches a peak and is not economical.

(Heat stabilizer)
As the heat stabilizer, at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms, phosphorous acid ester compound, phosphorous acid, and tetrakis ( And at least one selected from the group of 2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite.

  Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4-di-). tert-butylphenyl) phosphite, tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, Distearyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Sphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Examples thereof include phosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in admixture of two or more. Among the above, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

  When using a heat stabilizer, the compounding quantity is 0.001-1 mass part normally with respect to 100 mass parts of polycarbonate resins in the impregnation resin of this invention, Preferably it is 0.01-0.5 mass part. When the blending amount of the heat stabilizer is less than 0.001 part by mass, the effect as the heat stabilizer is insufficient, and when it exceeds 1 part by mass, the hydrolysis resistance may deteriorate.

(Release agent)
The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight of the aliphatic hydrocarbon is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  When using a mold release agent, the compounding quantity is 0.001-2 mass part normally with respect to 100 mass parts of polycarbonate resin in the impregnation resin of this invention, Preferably it is 0.01-1 mass part. When the blending amount of the release agent is less than 0.001 part by mass, the effect of releasability may not be sufficient, and when it exceeds 2 parts by mass, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

(UV absorber)
Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  When using an ultraviolet absorber, the compounding quantity is 0.01-3 mass parts normally with respect to 100 mass parts of polycarbonate resin in the impregnation resin of this invention, Preferably it is 0.1-1 mass part. When the blending amount of the ultraviolet absorber is less than 0.01 parts by mass, the effect of improving weather resistance may be insufficient, and when it exceeds 3 parts by mass, problems such as mold deposit may occur.

(Dye and pigment)
Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments. Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  When using a dye and pigment, the compounding quantity is 20 mass parts or less normally with respect to 100 mass parts of polycarbonate resin in the impregnation resin of this invention, Preferably it is 15 mass parts or less, More preferably, it is 12 mass parts or less. When the amount of the dye / pigment exceeds 20 parts by mass, the impact resistance may not be sufficient.

  Carbon black also functions as an inorganic conductive material. When carbon black is used as the inorganic conductive material, the blending amount can be set larger than the blending amount as the dye / pigment as described above.

(Flame retardants)
Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  When using a flame retardant, the compounding quantity is 1-30 mass parts normally with respect to 100 mass parts of polycarbonate resin in the impregnation resin of this invention, Preferably it is 3-25 mass parts, More preferably, it is 5-20 mass parts. is there. When the blending amount of the flame retardant is less than 1 part by mass, the flame retardancy may not be sufficient, and when it exceeds 30 parts by mass, the heat resistance may decrease.

(Anti-dripping agent)
Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  When using a dripping inhibitor, the compounding quantity is 0.02-4 mass parts normally with respect to 100 mass parts of polycarbonate resin in the impregnation resin of this invention, Preferably it is 0.03-3 mass parts. When the blending amount of the anti-dripping agent exceeds 5 parts by mass, the appearance of a molded product formed by molding the obtained CF / PC material or CF / PC pellet may be deteriorated.

<Method for producing impregnated resin of the present invention>
In the present invention, when the impregnating resin of the present invention comprises only a polycarbonate resin, the polycarbonate resin is used, that is, the polycarbonate resin is introduced from the hopper 21 of the extruder 20 shown in FIG. CF / PC materials and CF / PC pellets can be produced by the method.

  When a polycarbonate resin composition comprising an elastomer, an inorganic conductive material, and other additives is used as the impregnation resin of the present invention, a polycarbonate resin and an elastomer, an inorganic conductive material, other additives, and the like are used. Using them at a predetermined ratio, that is, supplying them at a predetermined ratio from the hopper 21 of the extruder 20 of FIG. 1 to produce CF / PC material and CF / PC pellets by the above-described pultrusion method. Can do.

In this case, the polycarbonate resin and various components blended as necessary may be mixed in advance using various mixers such as a tumbler or a Henschel mixer, and then charged into the hopper 21 of the extruder 20 and melt kneaded. Alternatively, the components may not be mixed in advance, or only a part of the components may be mixed in advance and supplied to an extruder using a feeder to be melt-kneaded.
Further, for example, a resin composition obtained by mixing some components in advance, supplying them to an extruder and melt-kneading is used as a master batch, and this master batch is mixed with the remaining components again and melt-kneaded. Good.

[Electromagnetic wave shielding molding]
By molding the CF / PC material or CF / PC pellet of the present invention, a molded product having excellent electromagnetic shielding properties can be obtained. The molding method of the CF / PC material or CF / PC pellet of the present invention is not particularly limited, and a molding method generally used for a thermoplastic resin composition, for example, injection molding, hollow molding, extrusion molding, A molding method such as sheet molding, thermoforming, rotational molding, and lamination molding can be applied. Among these, injection molding is common for the production of electromagnetic wave shielding molded articles.

The CF / PC material or CF / PC pellet of the present invention can be used alone to form a molded product, but if necessary, it can be mixed with other components such as other resin pellets. It can also be used for molding.
Further, the CF / PC pellet of the present invention can be formed into a composite molded product by multicolor composite molding with other resin pellets.

  Although there is no restriction | limiting in particular about the application field of the molded article obtained from the CF / PC material or CF / PC pellet of this invention, For example, an OA apparatus, AV apparatus, a measuring apparatus, a transport apparatus by which electromagnetic wave shielding property is requested | required In addition, examples include housing applications such as communication equipment and radar devices, connectors, and packaging materials.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Materials used]
The raw material components used in the following examples and comparative examples are as shown in Table 1 below.

[Evaluation method]
In the examples and comparative examples, productivity, pellet quality, and the like were evaluated by the following methods.

<Presence of fiber breakage>
The presence or absence of fiber breakage during the production of pellets for 1 hour was evaluated.

<Pellet fibers falling off>
The obtained pellets were visually observed and examined for the presence or absence of fibers, and evaluated according to the following criteria.
A: There is no omission. O: There is omission of less than 20% of the whole.
Δ: Omission of 20% or more and less than 40% of the whole.
X: There is omission of 40% or more of the whole.

<Molecular weight retention>
The viscosity average molecular weight (Mv) of the polycarbonate resin was determined by using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity ([η]) at a temperature of 20 ° C. (unit: dl / g). From the formula: [η] = 1.23 × 10 ⁻⁴ M ^0.83 , the viscosity average molecular weight of the aromatic polycarbonate resin in the obtained pellet was calculated. Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity (ηsp) at each solution concentration (C) (g / dl).
Viscosity average molecular weight of raw material aromatic polycarbonate resin: The percentage of the ratio of the measured viscosity average molecular weight to 21,000 was defined as the molecular weight retention rate. A larger value indicates that the polycarbonate resin is less deteriorated and its physical properties are maintained.

<Fiber length / pellet length ratio>
About 100 obtained pellets, the pellet length and the fiber length of the carbon fiber in a pellet were measured, and fiber length / pellet length ratio was calculated | required, respectively. The closer this value is to 1, the more carbon fiber length is maintained.

[Examples 1-5, Comparative Examples 1-5]
CF / PC pellets were produced by the pultrusion method shown in FIGS.
Each component described in Table 1 above is blended in the proportion of the resin composition blend shown in Table 2 below, and this is put into a hopper 21 of a 40 mm single screw extruder (VS40-32V manufactured by Tanabe Plastics Machinery) 20. Then, it was melt-kneaded at a cylinder temperature of 280 ° C. and a screw rotation speed of 80 rpm and extruded as an impregnating resin into the resin impregnation cell 22.
With respect to this impregnating resin, CF roving 31 was used so that the carbon fiber content in the obtained CF / PC pellets had a ratio shown in Table 2. The CF roving 31 was preheated to 150 ° C. in the preheating cell 23.
The impregnation resin temperature, the contact area between the impregnation roll and the CF roving, and the take-up speed of the resin impregnation CF roving were as shown in Table 2, and the cut length of the pellet was 9 mm. The diameter of this pellet was about 2.8 mm.
As the impregnation rolls, those having a diameter a = 12 mm were used. The CF roving contacts the impregnating roll with a width b = 8 mm. The thickness of the CF roving is 0.3 mm. The contact area between the impregnation roll and the CF roving was changed by changing the number of impregnation rolls as follows.

In Examples 1 to 5 and Comparative Examples 1, 2, and 5, as shown in FIG. 7, three impregnating rolls 51 to 53 are used, and the gap between adjacent impregnating rolls is substantially equal to the thickness of the CF roving 31. Placed in close proximity to each other.
In this case, in the impregnating roll 51 and the impregnating roll 53, the CF roving 31 contacts in a quarter region of the outer periphery of the impregnating roll, and the impregnating roll 52 and the CF roving 31 contact in half a region of the outer periphery of the impregnating roll. Therefore, the contact area is calculated as follows.
Contact area = b × aπ × 1/4 + b × aπ × 1/2 + b × aπ × 1/4
= Πab

In Comparative Example 3, as shown in FIG. 6, two impregnation rolls 51 to 52 were used, and the adjacent impregnation rolls were arranged close to each other so as to be almost equal to the thickness of the CF roving 31.
In this case, in the impregnating roll 51 and the impregnating roll 52, the CF roving 31 contacts in a quarter region of the outer periphery of the impregnating roll, so the contact area is calculated as follows.
Contact area = b × aπ × 1/4 + b × aπ × 1/4
= 0.5πab

In Comparative Example 4, as shown in FIG. 8, four impregnating rolls 51 to 54 were used, and the adjacent impregnating rolls were arranged close to each other so as to be approximately equal to the thickness of the CF roving 31.
In this case, in the impregnating roll 15 and the impregnating roll 54, the CF roving 31 contacts in a quarter region of the outer periphery of the impregnating roll, and in the impregnating roll 52 and the impregnating roll 53, the CF roving 31 is 1 / out of the outer periphery of the impregnating roll. Since contact is made in the area of 2, the contact area is calculated as follows.
Contact area = b × aπ × 1/4 + b × aπ × 1/2 + b × aπ × 1/2 + b × aπ × 1/4
= 1.5πab

  The above-mentioned evaluation was performed on the CF / PC pellets and the obtained CF / PC pellets, and the results are shown in Table 2.

[Comparative Example 6]
Using molten resin kneaded and kneaded at the same ratio as in Example 1 and CF roving, pellets were manufactured by the wire coating method shown in FIG.
The molten resin temperature and the take-up speed of the resin-coated CF roving were as shown in Table 2.
The above-mentioned evaluation was performed at the time of pellet manufacture and the obtained pellet, and the results are shown in Table 2.

[Comparative Example 7]
Pellets were produced by the direct roving method shown in FIG. 9 (c) using a molten resin kneaded and kneaded at the same ratio as in Example 1 and CF roving.
The melt resin temperature and the take-up speed of the resin composite CF roving were as shown in Table 2.
The above-mentioned evaluation was performed at the time of pellet manufacture and the obtained pellet, and the results are shown in Table 2.

Table 2 shows the following.
In Comparative Example 6 using the wire coating method, there is no problem of fiber breakage, but there is a problem of fiber dropout. Further, in Comparative Example 7 by the direct roving method, there is no problem of fiber breakage and fiber falling off from the pellet, but the fiber length cannot be left long, and the fiber length / pellet length ratio is very small.

  On the other hand, according to the present invention, in Examples 1 to 5 in which the CF / PC pellets were produced by the pultrusion method satisfying the above conditions (1) to (4), the fiber was cut and the fibers from the pellets And a good CF / PC pellet having a fiber length / pellet length ratio close to 1 can be obtained while leaving the fiber length long.

Even in the pultrusion method, in Comparative Example 1 where the molten resin temperature is lower than the specified range of the present invention, there is a problem of fiber breakage and falling off of fibers from the pellets. In Comparative Example 2, which is higher than the range, there is a problem of thermal deterioration of the polycarbonate resin.
Further, in Comparative Example 3 where the contact area between the impregnation roll and the CF roving is smaller than the specified range of the present invention, the resin is not sufficiently uniformly impregnated, so that the fibers fall off from the pellets. In Comparative Example 4, which is larger than the specified range of the present invention, fiber breakage occurs.
Further, in Comparative Example 5 in which the take-up speed of the resin-impregnated CF roving is too fast, fiber breakage becomes a problem, and some fibers fall off from the pellet.

  From the above, according to the present invention, according to the pultrusion method that satisfies the conditions (1) to (4) described above, high-quality CF free from the problems of thermal degradation of the polycarbonate resin and dropout of fibers from the pellets. / PC pellets can be produced with high yield and high productivity.

20 Extruder 21 Hopper 22 Resin impregnation cell 23, 23A Preheating cell 24 Shaping die 25 Water tank 26 Pelletizer 30 CF roving wound body 31 CF roving 32 Resin impregnation CF roving 33 CF / PC material 34 CF / PC pellets 40A, 40B Guide Roll 41, 42, 43, 44, 51, 52, 53, 54 Impregnation roll

Claims (5)

A long fiber bundle of carbon fibers is continuously run in a molten resin bath of polycarbonate resin, and the long fiber bundle is widened in a band shape with an impregnation roll in the molten resin bath. When the carbon long fiber / polycarbonate resin composite material is produced by impregnating the resin with the resin and taking out the resin-impregnated long fiber bundle from the molten resin bath, the following conditions (1) to (4) are satisfied. A process for producing a carbon long fiber / polycarbonate resin composite material.
(1) The carbon fiber content of the carbon long fiber / polycarbonate resin composite material is 5 to 40% by mass.
(2) The molten resin temperature is 290 to 340 ° C.
(3) When the diameter of the impregnation roll is a (mm) and the width of the long fiber bundle is b (mm), the contact area between the impregnation roll and the long fiber bundle is 0.6πab to 1.4πab. is there.
(4) The take-up speed of the resin-impregnated long fiber bundle is 1 to 12 kg / hr.   In Claim 1, two or more said impregnation rolls are provided in parallel so that the roll axial direction is a direction intersecting with the traveling direction of the long fiber bundle, and the interval between the adjacent impregnation rolls Is a diameter a (mm) or less of the impregnating roll, and a method for producing a carbon long fiber / polycarbonate resin composite material.   3. The method of producing a carbon long fiber / polycarbonate resin composite material according to claim 1, wherein the carbon fiber long fiber bundle is preheated to 100 to 300 ° C. and then introduced into the molten resin bath. .   A carbon length obtained by cutting the carbon long fiber / polycarbonate resin composite material produced by the method for producing a carbon long fiber / polycarbonate resin composite material according to any one of claims 1 to 3 to obtain a carbon long fiber / polycarbonate resin composite pellet. Manufacturing method of fiber / polycarbonate resin composite pellet.   The method for producing a carbon long fiber / polycarbonate resin composite pellet according to claim 4, wherein the carbon long fiber / polycarbonate resin composite material has a cut length of 4 to 10 mm.

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