Patent Application
20130337253
The present invention relates to an injection molded body comprising a fiber reinforced thermoplastic resin composition formed by combining a thermoplastic resin and fibrous filler and a method for producing the same, and relates to an injection molded body wherein the weight average fiber length of the fibrous filler in the injection molded body is 300 μm or more, and which is little in variation of strength and low in warping, and a method for producing the same.
In more detail, the present invention relates to an injection molded body formed with three layers of a skin layer, a core layer and a skin layer in the thickness direction by injection molding, which comprises a skin layer randomly oriented with fibrous filler and a core layer oriented with fibrous filler in a direction perpendicular to a flow direction at the time of injection molding and which is strengthened as the whole of the injection molded body and lowered in warping by making the thickness of the core layer small, and a method for producing the same.
A thermoplastic resin is molded, from its excellent moldability and processability, by various processing methods, for example, injection molding, blow molding, sheet molding, film molding, extrusion molding, press molding, etc., and is used for producing products for uses in a wide range such as electric/electronic equipment, OA (office automation) equipment, equipment for vehicles, miscellaneous goods, etc. In particular, injection molding becomes a main processing method for a thermoplastic resin in terms of a high productivity and a high shape freedom.
Further, in case where particularly high strength, stiffness and thermal resistance are required for a thermoplastic resin, a method for modifying the raw material by adding fibrous filler is generally employed. As a typical example of such a raw material, exemplified are fiber reinforced thermoplastic resin pellets obtained by melt kneading a thermoplastic resin and glass fibers or carbon fibers together by an extruder when the thermoplastic resin is pelletized. However, if injection molding is carried out using the fiber reinforced thermoplastic resin pellets thus obtained, because the fibrous filler is oriented in a core layer in a direction perpendicular to a resin flow direction at the time of injection molding and oriented in a skin layer in the resin flow direction, anisotropy is generated in strength and shrinkage. As a result, with respect to a molded body obtained, there has been a defect that its warping becomes great.
As means for solving such a defect, long fiber pellets for the purpose of strengthening and reducing the warping by lengthening fibers remaining in the molded body has been developed. However, even if the long fiber pellets are used, when a usual injection molding is carried out, because the orientation directions of fibrous filler are different between in the skin layer and in the core layer, it is still in a situation where a satisfactory advantage cannot be obtained.
As a molding method for preventing warping, Patent documents 1 and 2 describe an injection press molding method, but there is no description therein as to a method for controlling orientation of fibers in a molded product. Further, with respect to a method for reducing warping in a molded body, Patent document 3 describes an effect for reducing warping by giving a characteristic to a resin to be combined, but it does not intend to control warping from anisotropy of fiber orientation. Further, as means for disturbing orientation of fibers in a molded body, Patent document 4 describes a structure of a mold having a movable insert die. In this mold, orientation of fibers is disturbed by rotating the cavity surface to give a shear to a material to be molded into a molded body, but the quantity for disturbing the orientation is small, and there is a limitation in shape of the molded body. Furthermore, Patent document 5 describes a molding device with a mold for injection press molding which has a structure of a waste cavity (dummy cavity), but it does not describe as to molding of a fiber reinforced resin at all.
An object of the present invention is to solve the above-described problems in the conventional technologies and to provide an injection molded body which is excellent in strength and stiffness, small in anisotropy of strength in the molded body and extremely low in warping, and a method for producing the same.
To achieve the above-described object, an injection molded body according to the present invention comprises a fiber reinforced thermoplastic resin composition formed by combining fibrous filler (b) with a thermoplastic resin (a) so that a weight average fiber length in the injection molded body is 300 μm or more, and has a skin layer, a core layer and a skin layer in this order in a thickness direction, and it is characterized in that a thickness of the core layer, in which a primary orientation direction of the fibrous filler (b) is 40° or less when a direction perpendicular to a flow direction of the fiber reinforced thermoplastic resin composition at the time of injection molding is set at 0°, is 20% or less relatively to a thickness of the injection molded body (a thickness of the whole of the injection molded body having the skin layer, the core layer and the skin layer in this order).
In such an injection molded body according to the present invention, since the thickness of the core layer in the injection molded body having the skin layer, the core layer and the skin layer in this order is suppressed small to be 20% or less relatively to the thickness of the whole of the injection molded body as compared with a conventional molded body, influence due to the anisotropy in strength and shrinkage, originating from a condition where the orientation directions of fibrous filler in the core layer and the skin layer are different from each other, can be suppressed small, and it becomes possible to suppress the warping of the molded body generated by the anisotropy extremely low.
In the above-described injection molded body according to the present invention, it is preferred that the fibrous filler (b) is combined so that the weight average fiber length in the injection molded body is 600 μm or more.
Further, as the above-described thermoplastic resin (a), for example, at least one selected from the group consisting of a polypropylene, a polyamide, a polysulfene sulfide, a polyimide, a polyetherketone and a polyetheretherketone can be used.
Further, as the above-described fibrous filler (b), for example, at least one selected from the group consisting of carbon fibers, glass fibers and aramide fibers can be used.
Further, although the thickness of the whole of the injection molded body is not particularly limited, if the thickness of the injection molded body is in a range of 0.5 mm to 10 mm, the effect for reducing the warping due to the present invention is exhibited remarkably.
Further, it is preferred that the orientation direction of the fibrous filler (b) in the above-described skin layer is random as much as possible.
Such an injection molded body according to the present invention can be produced by the following first or second method. First, the first method according to the present invention is a method for producing an injection molded body by injection molding a fiber reinforced thermoplastic resin composition formed by combining fibrous filler (b) with a thermoplastic resin (a) so that a weight average fiber length in the injection molded body is 300 μm or more, by injection press molding, characterized in that pressing is carried out after 80 vol. % or more of a main cavity volume of a mold is filled with said fiber reinforced thermoplastic resin composition. Here, the “main cavity” means a cavity formed in a shape equal to a shape of a product to be molded.
In this first method, a manner can be employed wherein in a pressing step, the fiber reinforced thermoplastic resin composition of 10 vol. % or more of the main cavity volume of the mold is pushed out from a flow end part of the fiber reinforced thermoplastic resin composition outside the main cavity of the mold (for example, into a waste cavity which is different from the main cavity formed in a shape equal to a shape of a product to be molded).
Further, as the above-described fiber reinforced thermoplastic resin composition, long fiber pellets with a same length as a length of the fibrous filler (b) can be used, and using them, the injection press molding can be carried out.
The second method according to the present invention is a method for producing an injection molded body by injection molding a fiber reinforced thermoplastic resin composition formed by combining fibrous filler (b) with a thermoplastic resin (a) so that a weight average fiber length in the injection molded body is 300 μm or more, by injection press molding in which a mold is started to be closed after injection is started, characterized in that injection molding is carried out at a condition where a ratio (t2/t1) of a difference (t2) between a time for finishing injection (tif) and a time for finishing to close the mold (tpf) to a difference (t1) between a time for starting to close the mold (tps) and the time for finishing injection (tif) becomes 1.1 or more.
Also in this second method, as the above-described fiber reinforced thermoplastic resin composition, long fiber pellets with a same length as a length of the fibrous filler (b) can be used, and using them, the injection press molding can be carried out.
In the injection molded body and the method for producing the same according to the present invention, since the thickness of the core layer relative to the thickness of the injection molded body can be made small, and in the obtained injection molded body, the core layer in which the fibrous filler is strongly oriented in the direction perpendicular to the resin flow direction becomes small, the influence due to anisotropy between the core layer and the skin layer can be suppressed small, and warping originating from the anisotropy can be suppressed extremely low. Therefore, the injection molded body according to the present invention can be suitably used, in particular, for a molded body required with a low warping property, for example, for a housing, a chassis or a gear of electric/electronic equipment, a hood, a door panel, a roof, a back door, a door inner, a radiator core support of vehicle parts, etc. In particular, it can be suitably used for large-sized parts with large areas.
Hereinafter, as to the present invention, embodiments will be explained in detail.
In the present invention, a fiber reinforced thermoplastic resin composition combining a thermoplastic resin (a) and fibrous filler (b) is injection molded, and in a molded body formed by injection molding, the weight average fiber length in the injection molded body is 300 μm or more. In such an injection molded body comprising the fiber reinforced thermoplastic resin composition, when the molded body is produced, a core layer in which the fibrous filler is oriented in a direction perpendicular to a flow direction of the thermoplastic resin composition (hereinafter, also referred to as “TD direction”) and a skin layer in which the fibrous filler is oriented mainly in the flow direction of the thermoplastic resin composition (hereinafter, also referred to as “MD direction”) are formed.
The weight average fiber length in the injection molded body in the present invention is a value determined by burning the injection molded body to ashes at 500° C. for 2 hours, taking out the fibrous filler in the molded body, putting the fibrous filler taken out into water, dispersing it uniformly using a ultrasonic washer, sampling 1 cc thereof into a Petri dish having a depression of 10×10 mm and thereafter drying it, taking a photograph of the fibrous filler in the Petri dish, and measuring the lengths of about 1000 fibers and calculating the value by the following equation.
Weight average fiber length=Σ(Mi2×Ni)/Σ(Mi×Ni)
Mi: fiber length (mm)
Ni: number of fibers
In case where a resin composition called generally as short fiber pellets, in which fibrous filler in an injection molded body is less than 300 μm, is used, for example, as shown in
If the fibrous filler in an injection molded body becomes longer (that is, becomes long fibers), for example, as shown in
As a method for making the weight average fiber length of the fibrous filler in the injection molded body large, it is preferred to carry out injection molding using long fiber pellets with a same length as a length of the fibrous filler. However, even if long fiber pellets are used, if the injection molding is carried out by a usual method, because the thickness of a core layer in which the fibrous filler is oriented in a direction perpendicular to a flow direction of the thermoplastic resin composition becomes about 30-50% relatively to a thickness of a molded body, the influence of the core layer becomes strong, and because the strength of the molded body is different between at the skin layer and at the core layer, warping is generated in the injection molded body. In the injection molded body according to the present invention, since the thickness of the core layer can be suppressed to be 20% or less relatively to the thickness of the molded body by using the first method or the second method as described later, the influence of the core layer can be suppressed and the anisotropy of the properties can be suppressed, and an injection molded body with low warping can be obtained.
In the present invention, the thickness of the core layer is controlled at 20% or less relatively to the thickness of the injection molded body. Where, the thickness of the core layer is determined as follow. The image data of the fibrous filler in the injection molded body are obtained using a 3D X-ray computed tomography scanner (type: TDM1000IS) supplied by Yamato Material Co., Ltd., after the obtained image data are binarized with respect to fibrous filler and thermoplastic resin using a 3D image processing software “TRI” series supplied by RATOC SYSTEM ENGINEERING CO., LTD., a primary orientation direction is calculated from the orientation directions of the respective fibers, and when the flow direction of the resin composition at the time of producing the molded body is set at 90° and a direction perpendicular to the flow direction of the resin composition is set at 0°, a part exhibiting 40° or less as its primary orientation direction is determined to be a core layer, and the thickness thereof is decided. Moreover, the orientation directions of the fibrous filler in the skin layer are determined as follow. The image data of the fibrous filler in the injection molded body are obtained using a 3D X-ray computed tomography scanner (type: TDM1000IS) supplied by Yamato Material Co., Ltd., after the obtained image data are binarized with respect to fibrous filler and thermoplastic resin using a 3D image processing software “TRI” series supplied by RATOC SYSTEM ENGINEERING CO., LTD., a primary orientation direction is calculated from the orientation directions of the respective fibers, and a condition where 40% or less of the whole of fibers are distributed within ±10% of the primary orientation direction is determined to be a random orientation condition.
Next, methods of the injection press molding (the first method and the second method) for producing the above-described injection molded body according to the present invention will be explained.
First, the first method of the injection press molding according to the present invention is a method for filling the fiber reinforced thermoplastic resin composition into the cavity at a predetermined mold opening state to form a skin layer, and thereafter, controlling the thickness of a core layer by flowing out the resin of the core layer by pressing (mold closing). As the molding machine used for the injection press molding, any type of known machines capable of injection pressing can be used, and a horizontal type and a vertical type can be both used.
The timing for starting pressing when the injection press molding is performed is important on account of controlling the thickness of the core layer, and from the viewpoint of controlling the thickness of the core layer relatively to the thickness of the whole of the injection molded body, it is important to start pressing after filling of the resin at 80 vol. % or more of a main cavity volume of a mold before pressing is finished. Furthermore, it is preferred to use a mold for injection molding with a structure having a waste cavity into which the resin in the core layer, in which the fibrous filler is oriented in a direction perpendicular to the resin flow, is discharged outside the main cavity in the pressing step. This waste cavity preferably has a volume of 10 vol. % or more of the main cavity volume so as to be able to discharge (so as to be able to push out) the resin of the core layer sufficiently in the pressing step.
Such a preferable mold structure used for the first method of injection molding according to the present invention and injection molding steps will be explained using
Next, the steps for molding will be explained. As shown in
In the injection molded body obtained by such a first method according to the present invention, because the anisotropy of properties is small, a part peculiarly low in strength does not exist, and a stable product strength and an extremely low warping property are exhibited.
Next, the second method of the injection press molding according to the present invention will be explained.
Similarly to the above-described first method, the second method of the injection press molding according to the present invention is a method for filling (injecting) the fiber reinforced thermoplastic resin composition into the cavity at a predetermined mold opening state to form a skin layer, and thereafter, controlling the thickness of a core layer by flowing out the resin of the core layer by pressing (mold closing). As the molding machine used for the injection press molding, any type of known machines capable of injection pressing can be used, and a horizontal type and a vertical type can be both used.
The timing for starting pressing when the injection press molding is performed is important on account of controlling the thickness of the core layer, and in the second method according to the present invention, the injection molding is carried out by injection press molding in which a mold is started to be closed after injection is started. At that time, from the viewpoint of controlling the thickness of the core layer relatively to the thickness of the whole of the injection molded body, injection molding and mold closing (pressing) are carried out at timings such that, when a difference between a time for starting injection (tis) and a time for starting pressing (a time for starting to close a mold) (tps) is referred to as t0, a difference between the time for starting pressing (tps) and a time for finishing injection (tif) is referred to as t1, and a difference between the time for finishing injection (tif) and a time for finishing pressing (tpf) is referred to as t2, a ration (t2/t1) of t2 to t1 becomes 1.1 or more. It is further preferred to make t0/t1 greater than 1.1. Further, a method for starting pressing (mold closing) after finishing injection (
A preferable mold structure used for the second method of injection molding according to the present invention and injection molding steps will be explained using
Next, the steps for molding in the above-described second method will be explained. As shown in
Thus, also in the injection molded body obtained by the second method according to the present invention, because the anisotropy of properties is small, a part peculiarly low in strength does not exist, and a stable product strength and an extremely low warping property are exhibited.
The timings for injection and start and finish of mold closing in the above-described second method can be expressed as shown in
As the thermoplastic resin (a) used in the present invention, although it is not particularly restricted, for example, can be usefully used a polyethylene or polypropylene resin, a polystyrene resin, an ABS resin, a polyacetal resin, a polycarbonate resin, a Nylon resin, a PBT (polybutylene terephthalate) resin, a PET (polyethylene terephthalate) resin, a PPS (polyphenylene sulfide) resin, an LCP (liquid crystal polyester) resin, a PEEK (polyetheretherketone) resin, etc., and further, a blend of two kinds or more thereof may be used.
Further, as the fibrous filler (b) used in the present invention, in the first method, one having a diameter (fiber diameter) of 1 to 20 μm is preferable. If the fiber diameter is less than 1 μm, the dispersion becomes poor, and if more than 20 μm, the foreign matter effect becomes strong and the strength is reduced, and therefore, such conditions are not preferred. More preferably, the fiber diameter in a range of 5 to 15 μm is desirable from the viewpoint of balance between dispersion and reinforcement effect. Further, in the second method, fibrous filler having a diameter (fiber diameter) of 1 to 30 μm is preferable. If the fiber diameter is less than 1 μm, the dispersion becomes poor, and if more than 30 μm, the foreign matter effect becomes strong and the strength is reduced, and therefore, such conditions are not preferred. More preferably, the fiber diameter in a range of 3 to 15 μm is desirable from the viewpoint of balance between dispersion and reinforcement effect.
Further, in the present invention, usually, molding is carried out by forming the fiber reinforced thermoplastic resin composition into pellets. The pellets comprising the fiber reinforced thermoplastic resin composition can be produced the following methods and the like.
(1) method for blending thermoplastic resin (a) and fibrous filler (b) and melt extruding the blend
(2) method for drawing after dipping continuous fibrous filler (b) in molten thermoplastic resin (a) and impregnating the resin
(3) method for coating thermoplastic resin (a) around continuous fibrous filler (b) and cutting
(4) method for coating thermoplastic resin (a) around continuous fibrous filler (b) and impregnating the resin by twisting the continuous fibers
In particular, in order to control the weight average fiber length of the fibrous filler in the injection molded body at 300 μm or more, it is preferred to use pellets obtained by a method for drawing after dipping continuous fibrous filler (b) in thermoplastic resin (a) and impregnating the resin, a method for coating thermoplastic resin (a) around continuous fibrous filler (b) and cutting, a method for coating thermoplastic resin (a) around continuous fibrous filler (b) and impregnating the resin by twisting the continuous fibers, or a method for coating thermoplastic resin (a) around continuous fibrous filler (b) after pre-impregnating a low-viscosity resin or the like thereinto and cutting.
As the fibrous filler (b) used in the present invention, although carbon fibers, glass fibers, aramide fibers, wholly aromatic polyamide fibers, metal fibers, etc. can be exemplified, carbon fibers, glass fibers and aramide fibers are preferred.
As the carbon fibers used in the present invention, for example, polyacrylonitrile (PAN) based, pitch based, cellulose based and the like can be exemplified. Among these, PAN based carbon fibers excellent in strength and elastic modulus are preferable.
As the PAN based carbon fibers used in the present invention, carbon fibers having a tensile elongation at breakage of 1.0% or more are preferred. In case where the tensile elongation at breakage is less than 1.0%, breakage of carbon fibers is liable to occur in the process for producing the resin composition or in the injection molding process in the present invention, it is difficult to make the fiber length of carbon fibers left in the molded body long, and the mechanical properties of the molded body become poor.
Further, particularly in order to solve the aforementioned problems in the conventional technologies more securely, the above-described tensile elongation at breakage of carbon fibers is preferably 1.5% or more, more preferably 1.7% or more, and further preferably 1.9% or more. Although there is no upper limit for the tensile elongation at breakage of PAN based carbon fibers used in the present invention, generally it is less than 5%.
As a method for spinning such PAN based carbon fibers, wet spinning, dry-wet spinning or the like can be exemplified, and arbitrary spinning method can be selected depending upon required properties.
As the glass fibers used in the present invention, although any glass fibers generally sold on the market can be used, for example, E-glass fibers are preferred from the viewpoints of cost and performance.
It is possible to give an affinity with the thermoplastic resin (a) to the fibrous filler (b) by surface treatment. For example, silane based coupling agent, borane based coupling agent, titanate based coupling agent, etc. can be used, and as the silane based coupling agent, amino-silane based coupling agent, epoxy-silane based coupling agent, or acryl-silane based coupling agent can be used.
In the present invention, although preferably the fiber reinforced thermoplastic resin composition prepared as pellets is injection molded, the shape of the pellets is not particularly restricted, and in the first method, as the length of the pellets, for example, usually a range of 3 to 15 mm can be employed. If the length of the pellets is too small, the length of fibers left in an injection molded body becomes small, the orientation of fibers in the skin layer in a resin flow direction becomes strong, there is a fear that an isotropy is generated and the strength and the impact resistance are reduced. Further, if the length of the pellets is too great, because there is a case where they are not properly fed into a molding machine, the length of the pellets is preferably in a range of 3 to 12 mm, and more preferably in a range of 6 to 10 mm. Further, in the second method, for example, long fiber pellets with a length in a range of 3 to 30 mm can be used. Similarly to the above description, if the length of the pellets is too small, the length of fibers left in an injection molded body becomes small, the orientation of fibers in the skin layer in a resin flow direction becomes strong, there is a fear that an isotropy is generated and the strength and the impact resistance are reduced. Further, if the length of the pellets is too great, because there is a case where they are not properly fed into a molding machine, the length of the pellets is preferably in a range of 3 to 20 mm, and more preferably in a range of 4 to 20 mm.
Further, to the fiber reinforced thermoplastic resin composition, in accordance with use, various additives, for example, a known additive such as a dispersant, a lubricant, a plasticizer, an antioxidant, an antistatic agent, an optical stabilizer, a ultraviolet absorbent, a metal deactivator, a crystallization accelerator, a foaming agent, a colorant, a cross linking agent or an antibacterial agent can be added.
Although the content of the fibrous filler (b) used in the present invention is not particularly restricted, in the first method, for example, a range of 5 parts by weight to 50 parts by weight relatively to 100 parts by weight of the thermoplastic resin (a) is suitable. If it is less than 5 parts by weight, even if the core layer is controlled, the control does not greatly affect the strength, and if more than 50 parts by weight, reduction of moldability ascribed to increase in viscosity is great, and it becomes difficult to make the core layer thin in the injection press molding. A range of 10 parts by weight to 40 parts by weight is more preferable from the viewpoints of electric conductivity, mechanical strength and economy of an obtained injection molded body. Further, in the second method, a range of 3 parts by weight to 50 parts by weight relatively to 100 parts by weight of the thermoplastic resin (a) is suitable. Similarly to the above description, if it is less than 3 parts by weight, even if the core layer is controlled, the control does not greatly affect the strength, and if more than 50 parts by weight, reduction of moldability ascribed to increase in viscosity is great, and it becomes difficult to make the core layer thin in the injection press molding. A range of 5 parts by weight to 40 parts by weight is more preferable from the viewpoints of mechanical strength, economy and electric conductivity of an injection molded body.
Hereinafter, the present invention will be explained more concretely raising Examples. The estimations of material properties were carried out based on the following methods.
[Flexural Elastic Modulus]
A test piece was cut out at a strip form with a width of 15 mm and a length of 80 mm from a central part of a test piece 31 with a size of 80 mm×80 mm×2 mm thickness shown in
[Determination of Thickness of Core Layer]
A test piece was cut out at a form of 5 mm square from a central part of the test piece with a size of 80 mm×80 mm×2 mm thickness prepared by the above-described method, and using a 3D X-ray computed tomography scanner (type: TDM1000IS) supplied by Yamato Material Co., Ltd., the image data of the fibrous filler in the injection molded body were obtained.
After the obtained image data are binarized with respect to fibrous filler and thermoplastic resin using a 3D image processing software “TRI” series supplied by RATOC SYSTEM ENGINEERING CO., LTD., a primary orientation direction is calculated from the orientation directions of the respective fibers.
When the resin flow direction was set at 90° and a direction perpendicular to the resin flow direction was set at 0°, a part exhibiting 40° or less as its primary orientation direction was determined to be a core layer.
[Distribution of Fiber Length]
A test piece was cut out at a size of 20 mm×20 mm from a central part of the test piece with a size of 80 mm×80 mm×2 mm thickness prepared by the above-described method, and by burning it to ashes at 500° C. for 2 hours, the carbon fibers in the molded product were taken out. The carbon fibers taken out were put into a beaker with 3 liters of water, and the carbon fibers were uniformly dispersed in water using a ultrasonic washer. 1 cc of the aqueous solution dispersed uniformly with carbon fibers was sucked up by a pipette having a tip diameter of 8 mm, and after it was sampled into a Petri dish having a depression of 10×10 mm, it was dried. A photograph of the carbon fibers in the Petri dish was taken, and measuring the lengths of about 1000 fibers, an average fiber length was calculated. The equation for the calculation is as follows.
Weight average fiber length=Σ(Mi2×Ni)/Σ(Mi×Ni)
Mi: fiber length (mm)
Ni: number of fibers
[Amount of Warping]
Using an L-shaped mold having a movable side mold 32, a fixed side mold 33, a main cavity 34 and a waste cavity 35 shown in
Amount of warping (mm)=70.7×X
First, Examples of the first method of the present invention will be explained below.
First, PAN based continuous carbon fiber bundles as the fibrous filler (b) were heated, and a molten resin was measured and applied thereto by a gear pump. Then, the resin was impregnated into the carbon fiber bundles in an atmosphere heated at a temperature higher than the temperature for melting, and a composite of the continuous carbon fiber bundles and the resin was obtained (impregnation step).
Next, the thermoplastic resin (a) was deposited into a hopper of an extruder, and by extruding it to a coating die at a melt-kneaded condition and at the same time supplying the above-described composite continuously into the coating die, the resin composition comprising the thermoplastic resin (a) was coated to the composite, and by controlling the discharge amount of the extruder and the supply amount of the composite, continuous fiber reinforced resin strands with a carbon fiber content of 20 wt. % were obtained (coating step).
Thereafter, the above-described continuous fiber reinforced resin strands were cooled and solidified, and they were cut at a length of 6.0 mm using a cutter to obtain sheath-core type long fiber pellets.
The result of estimation of the molded body injection press molded using these pellets was excellent in mechanical properties and amount of warping as shown in Table 1. Further, the result of measuring the orientation of fibers of the injection molded body of this Example 1 is shown in
Moldings were carried out using the long fiber pellets obtained in Example 1 at the same condition as that in Example 1 other than changing molding conditions to those shown in Table 1. The results of estimations of these molded bodies are shown in Table 1. These Examples were excellent in mechanical properties and amount of warping as compared with Comparative Examples 1-3. Further, the result of measuring the orientation of fibers of the injection molded body of Comparative Example 1 is shown in
The same condition as that in Example 2 was employed other than changing the content of carbon fibers of the continuous fiber reinforced resin strands to 30 wt. %. The result of estimation of this molded body was excellent in mechanical properties and amount of warping as shown in Table 1.
The thermoplastic resin (a) was deposited into a main hopper of a twin-screw extruder (“TEX30α” supplied by JSW Corporation (The Japan Steel Works, LTD.)), chopped strands of the fibrous filler (b) were supplied from the side of the extruder at an amount of 20 wt. % relatively to 100 of the thermoplastic resin (a), they were extruded in a gut-like form after being melt kneaded at 260° C., the extruded materials were cooled and solidified, and they were cut at a length of 3.0 mm using a cutter to obtain short fiber pellets. The result of estimation of the injection molded body using these pellets is shown in Table 1, and the mechanical properties were low and the anisotropy was high. Further, the amount of warping was great. Furthermore, the result of measuring the orientation of fibers of the injection molded body of this Comparative Example 4 is shown in
Long fiber pellets were obtained at the same condition as that in Example 1 other than changing the thermoplastic resin (a) to polypropylene. Using these long fiber pellets, molded bodies were obtained by molding at the conditions shown in Table 2. The results of these molded bodies are shown in Table 2, and these Examples were excellent in mechanical properties and amount of warping as compared with Comparative Examples 5 and 6.
Long fiber pellets were obtained at the same condition as that in Example 1 other than changing the thermoplastic resin (a) to PPS resin. Using these long fiber pellets, molded bodies were obtained by molding at the conditions shown in Table 2. The results of these molded bodies are shown in Table 2, and these Examples were excellent in mechanical properties and amount of warping as compared with Comparative Examples 7 and 8.
Long fiber pellets were obtained at the same condition as that in Example 1 other than changing the fibrous filler (b) to glass fibers and setting the content of the glass fibers at 30 wt. %. Using these long fiber pellets, molded bodies were obtained by molding at the conditions shown in Table 3. The results of these molded bodies are shown in Table 3, and these Examples were excellent in mechanical properties and amount of warping as compared with Comparative Examples 9 and 10.
The thermoplastic resins (a) used in the above-described Examples and Comparative Examples are as follows.
Nylon 6 resin: “AMILAN” CM1001 supplied by Toray Industries, Inc.
Polypropylene resin: “Prime Polypro” J137 supplied by Prime Polymer Co., Ltd.
PPS resin: “TORELINA” M2888 supplied by Toray Industries, Inc.
Similarly, the fibrous fillers (b) are as follows.
Carbon fibers: “TORAYCA” T700S supplied by Toray Industries, Inc. (diameter: 7 μm, PAN based carbon fibers)
Glass fibers: RS240QR483 supplied by Nitto Boseki Co., Ltd. (diameter: 17 μm, E-glass)
Next, Examples of the second method of the present invention will be explained below.
First, PAN based continuous carbon fiber bundles as the fibrous filler (b) were heated, and a molten resin was measured and applied thereto by a gear pump. Then, the resin was impregnated into the carbon fiber bundles in an atmosphere heated at a temperature higher than the temperature for melting, and a composite of the continuous carbon fiber bundles and the resin was obtained (impregnation step).
Next, the thermoplastic resin (a) was deposited into a hopper of an extruder, and by extruding it to a coating die at a melt-kneaded condition and at the same time supplying the above-described composite continuously into the coating die, the resin composition comprising the thermoplastic resin (a) was coated to the composite, and by controlling the discharge amount of the extruder and the supply amount of the composite, continuous fiber reinforced resin strands with a carbon fiber content of 20 wt. % relatively to the sum with the thermoplastic resin (a) were obtained (coating step).
Thereafter, the above-described continuous fiber reinforced resin strands were cooled and solidified, and they were cut at a length of 6.0 mm using a cutter to obtain sheath-core type long fiber pellets.
The molding condition at the time of being injection press molded using these pellets and the result of estimation of the obtained molded body are shown in Table 4. As understood from Table 4, the molded body obtained by the molding condition according to the present invention was excellent in mechanical properties and amount of warping. The result of measuring the orientation of fibers of the injection molded body of this Example 16 is shown in
Moldings were carried out using the long fiber pellets obtained in Example 16 at the same condition as that in Example 1 other than changing molding conditions to those shown in Table 4. The results of estimations of the obtained injection molded bodies are shown in Table 4. These Examples were excellent in mechanical properties and amount of warping as compared with Comparative Examples 11-13. Where, as the result of measuring the orientation of fibers of the injection molded body of Comparative Example 11, a result approximately equal to the aforementioned one shown in
The same condition as that in Example 2 was employed other than changing the content of carbon fibers of the above-described continuous fiber reinforced resin strands to 30 wt. % relatively to the sum with the thermoplastic resin (a). The result of estimation of the obtained injection molded body was excellent in mechanical properties and amount of warping as shown in Table 4.
The thermoplastic resin (a) was deposited into a main hopper of a twin-screw extruder (“TEX30α” supplied by JSW Corporation (The Japan Steel Works, LTD.)), chopped strands of the fibrous filler (b) were supplied from the side of the extruder at an amount of 20 wt. % relatively to the sum with the thermoplastic resin (a), they were extruded in a gut-like form after being melt kneaded at 260° C., the extruded materials were cooled and solidified, and they were cut at a length of 3.0 mm using a cutter to obtain short fiber pellets. The result of estimation of the injection molded body using the obtained short fiber pellets is shown in Table 4, and the mechanical properties were low and the anisotropy was high. Further, the amount of warping was great. Where, as the result of measuring the orientation of fibers of the injection molded body of this Comparative Example 14, a result approximately equal to the aforementioned one shown in
Long fiber pellets were obtained at the same condition as that in Example 16 other than changing the thermoplastic resin (a) to polypropylene. Using the obtained long fiber pellets, injection molded bodies were obtained by injection press molding at the molding conditions shown in Table 5. The results of the obtained injection molded bodies are shown in Table 5, and Examples 22-24 were excellent in mechanical properties and amount of warping as compared with Comparative Examples 15 and 16.
Long fiber pellets were obtained at the same condition as that in Example 1 other than changing the thermoplastic resin (a) to PPS resin. Using the obtained long fiber pellets, injection molded bodies were obtained by injection press molding at the molding conditions shown in Table 5. The results of the obtained injection molded bodies are shown in Table 5, and Examples 25-27 were excellent in mechanical properties and amount of warping as compared with Comparative Examples 17 and 18.
Long fiber pellets were obtained at the same condition as that in Example 1 other than changing the fibrous filler (b) to glass fibers and setting the content of the glass fibers at 30 wt. %. Using the obtained long fiber pellets, injection molded bodies were obtained by injection press molding at the molding conditions shown in Table 6. The results of the obtained injection molded bodies are shown in Table 6, and Examples 28-30 were excellent in mechanical properties and amount of warping as compared with Comparative Examples 19 and 20.
The thermoplastic resins (a) used in the above-described Examples and Comparative Examples in the second method are as follows.
Nylon 6 resin: “AMILAN” CM1001 supplied by Toray Industries, Inc.
Polypropylene resin: “Prime Polypro” J137 supplied by Prime Polymer Co., Ltd.
PPS resin: “TORELINA” M2888 supplied by Toray Industries, Inc.
Similarly, the fibrous fillers (b) are as follows.
Carbon fibers: “TORAYCA” T700S supplied by Toray Industries, Inc. (diameter: 7 μm, PAN based carbon fibers)
Glass fibers: RS240QR483 supplied by Nitto Boseki Co., Ltd. (diameter: 17 μm, E-glass)
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-041545 | Feb 2011 | JP | national |
| 2011-078006 | Mar 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/054629 | 2/24/2012 | WO | 00 | 8/28/2013 |
