Patent Application
20150292146
This disclosure relates to a stampable sheet comprising a carbon fiber composite material of carbon fibers and a thermoplastic resin and, specifically, to a stampable sheet which can achieve compatibility between high flowability and mechanical properties when a molded article is made using the same.
A carbon fiber composite material comprising carbon fibers and a thermoplastic resin is used to manufacture various molded articles because high mechanical properties can be obtained. Specifically, when a stampable sheet comprising a carbon fiber composite material of carbon fibers and a thermoplastic resin is used for molding, because a rapid molding is possible by heat press molding, such a use is considered to be suitable for molding of mass-production articles.
With respect to conventional stampable sheets, in a stampable sheet wherein a paper or nonwoven fabric comprising carbon fibers is impregnated with a resin (for example, JP 2002-212311 A), although the mechanical properties of the stampable sheet are excellent, the flowability at the time of molding is low and moldability is poor. This is because the carbon fibers, which are reinforcing fibers, are dispersed and therefore stress is hard to be concentrated and, while the reinforcing effect due to the carbon fibers is sufficiently exhibited, the carbon fibers are crossed to each other to restrict their movements and therefore the carbon fibers become hard to be moved. In general, when carbon fibers are placed in a resin, the viscosity increases sharply and it becomes difficult to flow. Further, when the fiber length of carbon fibers in a resin is too long, the viscosity also tends to increase.
On the other hand, in an SMC (Sheet Molding Compound) in which a resin is impregnated into cut carbon fiber bundles, although the flowability is high and moldability is excellent, the mechanical properties are poor. This is because a stress is liable to be concentrated at end portions of the carbon fibers because the carbon fibers are formed in a bundle and, therefore, it is difficult to exhibit high mechanical properties, but the carbon fibers can move easily because they do not form networks, and therefore a good flowability can be obtained at the time of molding (for example, JP 2010-163536 A).
Further, separately from the above-described JP 2002-212311 A and JP 2010-163536 A, various technologies have been proposed with the aim of achieving high mechanical properties of a manufactured molded article and a good flowability at the time of molding. For example, in JP 2011-178890 A, a composite material is proposed wherein the proportion of specified carbon fiber bundles relative to the total amount of fibers in a carbon fiber composite material is suppressed, and the average number of fibers in the respective specified carbon fiber bundles is controlled in a specified range. However, in such a carbon fiber composite material as described in JP 2011-178890 A wherein the carbon fiber bundles in the carbon fiber composite material are thin, the proportion of the bundles is small and the carbon fibers are refined, although the mechanical properties of a molded article manufactured using the same are excellent, the flowability at the time of molding is low and the moldability is poor. This is because the carbon fibers, which are reinforcing fibers, are sufficiently dispersed and therefore stress is hard to be concentrated, and while the reinforcing effect due to the carbon fibers is sufficiently exhibited, the carbon fibers are crossed to each other to restrict their movements and therefore the carbon fibers become hard to be moved.
On the other hand, in JP 2011-178891 A, a composite material is proposed wherein the proportion of specified carbon fiber bundles in a carbon fiber composite material relative to the total amount of fibers, similar to that described above, is set higher, and the average number of fibers in the respective specified carbon fiber bundles is controlled in another specified range. However, in such a carbon fiber composite material as described in JP 2011-178891 A wherein the carbon fiber bundles are thick and the proportion of the bundles is great, although the flowability at the time of manufacturing a molded article using the same is high and moldability is excellent, the followability in molding of carbon fibers to a small-shape part is poor, the mechanical properties are low and variation in the mechanical properties is great. Namely, whereas the carbon fibers can move easily since they do not form networks, because the carbon fiber bundles are thick, the followability of carbon fibers is poor when a component having small member parts is molded, stress is liable to be concentrated at end portions of the carbon fibers and, therefore, it is difficult to obtain high mechanical properties.
Accordingly, it could be helpful to provide a stampable sheet having a controlled range of conditions which can satisfy both a high flowability at the time of molding and high mechanical properties after molding, that have not been achieved by the conventional stampable sheet comprising a carbon fiber paper or nonwoven sheet or by the conventional SMC.
We thus provide a stampable sheet comprising discontinuous carbon fibers and a thermoplastic resin as a matrix resin, characterized in that a viscosity η of the stampable sheet in a state where the matrix resin in the stampable sheet is molten is η0≦η<η0 exp(0.20Vf) (Pa·s), and a proportion Z of refined carbon fiber bundles (A), in which Mn/(Ln×D) is less than 8.5×10−1 (mg/mm2), to the total weight of carbon fibers in the stampable sheet is 10≦Z<90 (wt %) where, η: apparent viscosity of the stampable sheet at a time when the matrix resin is molten (a viscosity at a temperature of a solidification start temperature of the matrix resin+50° C.), Vf: carbon fiber content (%) per unit volume of the stampable sheet, η0: hypothetical resin viscosity of the matrix resin obtained by extending a characteristic line up to a position of Vf=0% in a characteristic chart which is obtained by changing the Vf and represents a relationship between the Vf and the viscosity of the stampable sheet, Mn: weight of carbon fiber bundles, Ln: fiber length of carbon fibers, D: fiber diameter of carbon fibers.
In such a stampable sheet, the configuration of the stampable sheet is controlled particularly to satisfy both a good flowability and high mechanical properties at a good balance by comprehensive consideration of the following factors: a factor that the melt viscosity of a composite material (namely, the viscosity η of a stampable sheet in a state where its matrix resin is molten) increases sharply when carbon fibers are placed in its matrix resin of a thermoplastic resin; a factor that, although the flowability at the time of molding decreases when the viscosity increases, reduction of the flowability can be suppressed by increasing the rate of the amount of carbon fiber bundles in which carbon fibers are in a bundle form, and thus it is possible to realize a good flowability; a factor that, if the rate of carbon fiber bundles becomes too high, although a good flowability can be obtained, it becomes difficult to obtain high mechanical properties of a molded article; and a factor that the controlled range of form of carbon fiber bundles in view of good flowability does not always equal to the controlled range of form of carbon fiber bundles in view of high mechanical properties.
More concretely, when the viscosity η of the stampable sheet is η0≦η<η0 exp(0.20Vf)(Pa·s), although it is higher than the viscosity of the resin alone as a natural result, the viscosity η is suppressed to become too high and thus a good flowability at the time of molding can be secured. The viscosity η is preferably η0≦η<η0 exp(0.13Vf)(Pa·s), and more preferably η0≦η<η0 exp(0.10Vf)(Pa·s). Further, refined carbon fiber bundles (A) in which Mn/(Ln×D) is less than 8.5×10−1 (mg/mm2) are carbon fiber bundles which have a relatively high degree of refinement and are likely to exhibit high mechanical properties. When a proportion Z of such refined carbon fiber bundles (A) to the total weight of carbon fibers is 10≦Z<90 (wt %), it becomes possible to exhibit high mechanical properties at a good balance while securing a good flowability as described above.
Further, in the above-described stampable sheet, it is further possible to employ a configuration wherein the proportion Z of refined carbon fiber bundles (A), in which Mn/(Ln×D) is less than 8.5×10−1 (mg/mm2), to the total weight of carbon fibers is 10≦Z<70 (wt %), that a proportion Y of refined carbon fiber bundles (B), in which Mn/(Ln×D) is 8.5×10−1 (mg/mm2) or more, to the total weight of carbon fibers is 30≦Z<90 (wt %), an average value X of Mn/Ln of the carbon fiber bundles (B) is 1.1×10−2≦X≦8.1×10−2 (mg/mm), and the Y satisfies Y≧100X+30.
In particular, flowability of the stampable sheet can be further improved by controlling the proportion Y of carbon fiber bundles (B) in which Mn/(Ln×D) is 8.5×10−1 (mg/mm2) or more, namely, carbon fiber bundles (B) which have a relatively low degree of refinement and are likely to exhibit high flowability, to the total weight of carbon fibers; the average value X of Mn/Ln of the carbon fiber bundles (B); and the range of the relationship between Y and X. To realize the compatibility between high flowability and mechanical properties more securely, a more preferred range of the average value X of Mn/Ln of the carbon fiber bundles (B) is 1.5×10−2≦X≦5.5×10−2 (mg/mm).
Further, to realize the compatibility between high flowability and mechanical properties, it is preferred that a standard deviation σ of a number of fibers xn=Mn/(Ln×F) forming a bundle of the above-described carbon fiber bundles (B) is 50≦σ≦400, where, F is a fineness of carbon fibers, and the calculation methods of the number of fibers xn and the standard deviation σ will be described later. If the above-described standard deviation σ is lower than 50, the flowability is deteriorated, and if the above-described standard deviation σ is more than 400, the mechanical properties are deteriorated, and the dispersion of the mechanical properties becomes great.
The above-described standard deviation σ is more preferably 100≦σ≦380, and further preferably 150≦σ≦360.
Further, as aforementioned, since the viscosity is likely to become high and the flowability is likely to be lowered if the fiber length of carbon fibers becomes too long, in the stampable sheet, it is preferred that the fiber length of carbon fibers Ln in a stampable sheet is 5 to 25 mm.
In the stampable sheet, although the kind of the matrix resin comprising thermoplastic resin is not particularly restricted, it is preferred to be any of polyamide, polypropylene and polyphenylene sulfide from the viewpoint of moldability.
Further, in the stampable sheet, to realize a good flowability more securely while realizing high mechanical properties, it is preferred that a single fiber flexural stiffness of carbon fibers forming the above-described carbon fiber bundles (A) is 1.0×10−11 to 2.8×10−11 (Pa·m4).
To realize a further high flowability, the above-described η0 is preferably 2.0×102≦η0≦5.0×104 (Pa·s). If η0 becomes lower than 2.0×102, there is a fear that the resin may become brittle and the properties may be lowered, and if η0 becomes greater than 5.0×104, there is a fear that the viscosity may become high even when the gradient of the characteristic line is small and therefore the flowability may deteriorate.
To realize the compatibility between high flowability and mechanical properties more securely, the viscosity η of a stampable sheet is preferably η0 exp(0.07Vf)≦η<η0 exp(0.20Vf)(Pa·s), and the Vf is preferably 5≦Vf≦70(%).
Further, when the viscosity η of a stampable sheet is η0 exp(0.07Vf)≦η<η0 exp(0.20Vf)(Pa·s), it is preferred that carbon fiber aggregates in the stampable sheet comprise a carbon fiber nonwoven fabric made by carding method.
Alternatively, to realize a higher flowability, the viscosity η of the above-described stampable sheet is preferably η0≦η<η0 exp(0.07Vf) (Pa·s), and the Vf is preferably 5≦Vf<70(%).
Furthermore, when the viscosity η of the above-described stampable sheet is η0≦η<η0 exp(0.07Vf)(Pa·s), it is preferred that carbon fiber aggregates in the stampable sheet comprise a carbon fiber nonwoven fabric made by air laid method.
Thus, in the stampable sheet, it becomes possible to provide an excellent stampable sheet wherein both an excellent flowability at the time of molding and high mechanical properties of a molded article can be achieved, and wherein the mechanical properties are in a narrow range of variation.
Hereinafter, our stampable sheets will be explained in detail together with Examples and Comparative Examples.
First, the viscosity η of the stampable sheet in a state where the matrix resin in the stampable sheet is molten is η0≦η<η0 exp(0.20Vf)(Pa·s). As shown in
Next, although the carbon fibers are not particularly restricted, high-strength and high-elastic modulus carbon fibers can be used, and one kind of carbon fibers may be used or two or more kinds of carbon fibers may be used together. In particular, carbon fibers such as PAN-based, pitch-based and rayon-based ones can be exemplified. From the viewpoint of the balance between the strength and the elastic modulus of a molded article to be obtained, PAN-based carbon fibers are more preferable. The density of carbon fibers is preferably 1.65 to 1.95 g/cm3, and more preferably 1.70 to 1.85 g/cm3. If the density is too high, the lightness in weight of a carbon fiber-reinforced plastic obtained is poor and, if too low, there is a possibility where the mechanical properties of a carbon fiber-reinforced plastic obtained become low.
Further, the carbon fibers are preferably formed as a bundle from the viewpoint of productivity, and it is preferred that the number of single fibers in the bundle is many. The number of single fibers for the carbon fiber bundle can be 1,000 to 350,000, and in particular, it is preferably 10,000 to 100,000. However, the carbon fiber bundle is required to satisfy our conditions.
The single fiber flexural stiffness of carbon fibers is, as aforementioned, preferably 1.0×10−11 to 2.8×10−11 Pa·m4, and more preferably 1.0×10−11 to 1.5×10−11 Pa·m4. Such a single fiber flexural stiffness in the above-described range makes it possible, in the process of manufacturing carbon fiber aggregates described later, to stabilize the quality of carbon fiber aggregates obtained.
Further, for the purpose of improving the adhesive property between carbon fibers and a matrix resin and the like, it is preferred that the carbon fibers are surface treated. As a method of the surface treatment, there are electrolytic treatment, ozone treatment, ultraviolet treatment and the like. Further, for the purpose of preventing the fuzz generation of carbon fibers, improving the convergence of carbon fibers, improving the adhesive property between carbon fibers and a matrix resin, and the like, a sizing agent may be provided to the carbon fibers. As a sizing agent, a compound having a functional group such as an epoxy group, a urethane group, an amino group, and a carboxyl group can be used, and one kind or two or more kinds of these compounds may be used.
Further, as a sizing treatment, a treatment method is employed wherein a liquid containing a sizing agent (a sizing liquid) is provided after drying wet carbon fiber bundles which are wetted by water and have a moisture content of about 20 to about 80 wt % by generally known surface treatment process and washing process.
Although the method of providing a sizing agent is not particularly restricted, for example, typical examples of the method include a method of dipping the fibers into a sizing liquid via rollers, a method of bringing the fibers into contact with a roller adhered with a sizing agent, and a method of spraying an atomized sizing agent. Further, although any of a batch type and a continuous type may be employed, a continuous type is preferred because it provides a good productivity and helps to minimize the degree of variation. At that time, so that the adhesion amount of the effective components of the sizing agent relative to the carbon fibers can become uniform within an adequate range, it is preferred to control the concentration and the temperature of the sizing agent, the tension of the yarns and the like. Further, it is more preferred to vibrate the carbon fibers by a ultrasonic wave at the time of providing the sizing agent.
Although the temperature and the time for drying should be adjusted depending upon the adhesion amount of the compound, from the viewpoints of completely removing the solvent used for providing the sizing agent, shortening the time required for the drying, on the other hand, preventing the heat deterioration of the sizing agent and preventing the carbon fiber bundles from being grown stiff and being deteriorated with the bundle spreading property, the temperature for drying is preferably 150° C. or higher and 350° C. or lower, and more preferably 180° C. or higher and 250° C. or lower.
The adhesion amount of a sizing agent relative to the mass of only the carbon fibers is preferably 0.01 mass % or more and 10 mass % or less, more preferably 0.05 mass % or more and 5 mass % or less, and further preferably 0.1 mass % or more and 5 mass % or less. If less than 0.01 mass %, the effect for improving the adhesive property is hardly exhibited. If more than 10 mass %, there is a possibility where the properties of a molded article may be reduced.
A thermoplastic resin is used as a matrix resin. The material of the thermoplastic matrix resin is not particularly restricted, and it can be appropriately selected within a range that does not greatly reduce the mechanical properties of the carbon fiber-reinforced plastic as a molded article. For example, a polyolefin-based resin such as polyethylene or polypropylene, a polyamide-based resin such as nylon 6 or nylon 6,6, a polyester-based resin such as polyethylene terephthalate or polybutylene terephthalate, or a resin such as a polyphenylene sulfide, a polyetherketone, a polyethersulfone, or an aromatic polyamide, can be used. Among them, the thermoplastic resin preferably comprises any of polyamide, polypropylene and polyphenylene sulfide.
Typical examples of the process of obtaining carbon fiber aggregates include carding and air laid. The carding means an operation of arranging the direction of discontinuous fibers or unraveling fibers by applying a shear force in an approximately same direction to the aggregates of discontinuous carbon fibers with a comb-like member. Generally, it is performed using a carding machine equipped with a roll having many needle-like projections on the surface and/or a roll wound with a metallic wire having saw blade-like projections.
When such a carding is carried out, it is preferred to shorten the time (residence time) during which carbon fibers are present in the carding machine, for the purpose of preventing the carbon fibers from being folded. More specifically, it is preferred to transfer the carbon fibers existing on the wires wound onto a cylinder roll of a carding machine to a doffer roll in minimal time. Therefore, to accelerate such a transfer, it is preferred to rotate the cylinder roll at a high rotational speed, for example, 250 rpm or higher. Further, for the same reason, it is preferred that the surface speed of the doffer roll is set at a high speed, for example, 10 m/min. or higher.
The process of carding the carbon fiber bundles is not particularly restricted, and a general one can be used. For example, as shown in
Discontinuous carbon fiber bundles 9 are supplied to belt conveyer 8, and the carbon fiber bundles 9 are introduced onto the outer circumferential surface of cylinder roll 2 through the outer circumferential surface of feed roll 7 and then through the outer circumferential surface of take-in roll 3. Up to this stage, the carbon fiber bundles 9 are refined and become floc-like aggregates of carbon fiber bundles. Although a part of the floc-like aggregates of carbon fiber bundles introduced onto the outer circumferential surface of cylinder roll wind around the outer circumferential surface of worker rolls 5, these carbon fibers are stripped off by stripper rolls 6 and returned again onto the outer circumferential surface of the cylinder roll 2. Many needles, projections exist at standing conditions on the outer circumferential surfaces of the respective rolls of feed roll 7, take-in roll 3, cylinder roll 2, worker rolls 5 and stripper rolls 6, and in the above-described steps, by the operation of the needles, the carbon fiber bundles are refined into predetermined-condition bundles, and oriented to some extent. The carbon fiber bundles, refined into predetermined-condition bundles through such steps, move onto the outer circumferential surface of doffer roll 4 as a sheet-like web 10 which is one form of the carbon aggregates.
As for air laid, it is not particularly restricted too, and a general method can be used. Examples of general air laid processes include Honshu Paper process, Kroyer process, Danweb process, J&J process, KC process, Scott process and the like (refer to “Base and application of non-woven fabric” (Non-woven fabric seminar in Japan Fibrous Machine Society, published in 1993)). More specifically, the examples include a process having a step of introducing cut carbon fiber bundle single materials or cut carbon fiber bundles and thermoplastic resin fibers into a tube, a step of blowing compressed air to refine fibers, and a step of obtaining carbon fiber aggregates which are dispersed and fixed; and a process having a step of refining cut carbon fiber bundle single materials or cut carbon fiber bundles and thermoplastic resin fibers by a refining means (for example, a pin cylinder) to form a carbon fiber nonwoven fabric as carbon fiber aggregates.
The carbon fiber aggregates, as referred to herein, mean aggregates in a state where discontinuous carbon fiber bundles are refined and oriented by the above-described carding or air laid, and in which their configuration is maintained by entanglement or friction between fibers. Examples of such carbon fiber aggregates include a thin sheet-like web and a nonwoven fabric made of laminated webs that are, when necessary, entangled or adhered together.
The carbon fiber aggregates may comprise only carbon fiber bundle single materials, or may include carbon fiber bundles and thermoplastic resin fibers. It is preferred to add thermoplastic resin fibers because it makes it possible to prevent carbon fibers from fracturing in the carding or air laid process. Carbon fibers are difficult to twine around and liable to break, because they are rigid and brittle. Therefore, carbon fiber aggregates consisting of only carbon fibers have potential problems that they are liable to be cut off and the carbon fibers are liable to fall out. Carbon fiber aggregates containing thermoplastic resin fibers, which are flexible, resistant to breakage and liable to twine, make it possible to form carbon fiber aggregates having a high uniformity. When carbon fiber aggregates include thermoplastic resin fibers, the ratio of carbon fiber content in the carbon fiber aggregates is preferably 20-95 wt %, more preferably 50-95 wt %, and further preferably 70-95 wt %. If the ratio of carbon fiber content is too low, it becomes difficult to obtain high mechanical properties when manufacturing carbon fiber composite material. On the other hand, if the ratio of carbon fiber content is too high, the above-described effect to promote the uniformity of carbon fiber aggregates cannot be obtained.
When carbon fiber aggregates contain thermoplastic resin fibers, the fiber length of thermoplastic resin fibers are not particularly limited as long as it is in a desired range such as configuration preservation of carbon fiber aggregates and prevention of fallout of carbon fibers. In general, thermoplastic resin fibers having a fiber length of approximately 10-100 mm can be used. The fiber length of thermoplastic resin fibers can be determined in relation to the fiber length of carbon fibers. For example, a greater tension is applied to a fiber having a longer fiber length at the time of elongating carbon fiber aggregates. Therefore, when aligning carbon fibers in the longitudinal direction of carbon fiber aggregates by applying tension to carbon fibers, it is possible to configure the fiber length of the carbon fibers to be longer than the fiber length of thermoplastic resin fibers. In the opposite case, it is possible to configure the fiber length of the carbon fibers to be shorter than the fiber length of thermoplastic resin fibers.
Further, it is preferred to provide a crimp to the above-described thermoplastic resin fibers for the objective of enhancing the effect of tangle due to the thermoplastic resin fibers. The degree of the crimp is not particularly limited as long as it is in a desired range and, generally, thermoplastic resin fibers having a number of crimps of approximately 5 to 25 crests per 25 mm and a rate of crimp of approximately 3 to 30% can be used.
The material for such thermoplastic resin fibers is not particularly restricted, and it can be selected suitably within a range that does not greatly reduce the mechanical properties of the carbon fiber composite material. For example, it is possible to use fibers which are prepared by spinning a resin such as a polyolefin-group resin such as polyethylene or polypropylene, a polyamide-group resin such as nylon 6 or nylon 6,6, a polyester-group resin such as polyethylene terephthalate or polybutylene terephthalate, a polyetherketone, a polyethersulfone or an aromatic polyamide. It is preferred that such a material for thermoplastic resin fibers is appropriately selected in accordance with the combination with a matrix resin. In particular, thermoplastic resin fibers prepared using the same resin as a matrix resin, a resin having a compatibility with a matrix resin or a resin having a high adhesive property with a matrix resin is preferred, because the mechanical properties of a carbon fiber-reinforced plastic are not lowered. For example, the thermoplastic resin fibers are preferred to be composed of at least one kind of fibers selected from the group consisting of polyamide fibers, polyphenylene sulfide fibers, polypropylene fibers, polyetheretherketone fibers and phenoxy resin fibers.
When a matrix resin is impregnated into the carbon fiber aggregates, a method may be employed wherein carbon fiber aggregates containing thermoplastic resin fibers are prepared and the thermoplastic resin fibers contained in the carbon fiber aggregates are used as the matrix resin as they are, or a method may also be employed wherein carbon fiber aggregates not containing thermoplastic resin fibers are used as a raw material, and a matrix resin is impregnated at an arbitrary stage for producing a carbon fiber composite material. Further, even when carbon fiber aggregates containing thermoplastic resin fibers are used as the raw material, a matrix resin can be impregnated at an arbitrary stage of producing a carbon fiber composite material. In such a case, a resin forming thermoplastic resin fibers and a matrix resin may be an identical resin, and may be resins different from each other. When the resin forming thermoplastic resin fibers and the matrix resin are different from each other, it is preferred that both resins have a compatibility or a high affinity.
When the stampable sheet comprising the carbon fiber composite material is produced, a thermoplastic resin as a matrix resin is impregnated into the above-described carbon fiber aggregates, and the impregnation step for manufacturing the carbon fiber composite material can be carried out using a press machine having a heating function. The press machine is not particularly restricted as long as it can realize temperature and pressure required for impregnation of the matrix resin, a usual press machine having a plane-like platen moved vertically, or a so-called double belt press machine having a mechanism to run a pair of endless steel belts can be used. In such an impregnation step, after the matrix resin is prepared in a sheet-like form such as a film, a nonwoven fabric or a woven fabric, it is laminated with the carbon fiber aggregates and, at that condition, the matrix resin can be melted and impregnated using the above-described press machine. Further, a method can also be employed wherein discontinuous fibers are prepared using a matrix resin, by mixing them and inorganic fibers at a step for making carbon fiber aggregates, carbon fiber aggregates containing the matrix resin and the inorganic fibers are prepared, and the carbon fiber aggregates are heated and pressed using the press machine and the like.
The carbon fiber content Vf (%) per unit volume of a stampable sheet comprising carbon fiber composite material is preferably 5≦Vf<80(%), more preferably 5≦Vf≦70(%), and further preferably 10≦Vf≦50(%). If the value of Vf becomes less than 5%, there is a fear that the reinforcing effect by the carbon fibers may become small. Further, if the value of Vf becomes 80% or more, it becomes difficult to secure high flowability and there is a fear that it may become difficult to mold the stampable sheet.
Next, Examples and Comparative Examples will be explained.
First, the properties and determination methods used in the Examples and Comparative Examples will be explained.
A sample with a size of 100 mm×100 mm was cut out from a carbon fiber composite material and, thereafter, the sample was heated in an electric furnace heated at 500° C. for about 1 hour to burn off organic substances such as the matrix resin. After cooling to room temperature, the mass of the residual carbon fiber aggregates was determined and, thereafter, carbon fiber bundles were all extracted from the carbon fiber aggregates by a pincette. With respect to all the extracted carbon fiber bundles, using a balance capable of measuring up to a degree of 1/10,000 g, the weigh Mn and the length Ln of each carbon fiber bundle are determined. After the determination, for each bundle, Mn/Ln, Mn/(Ln×D) and xn=Mn/(Ln×F) are calculated, where D is a diameter of carbon fibers, F is a fineness of carbon fibers, and xn is a number of fibers forming a carbon fiber bundle. The determination is carried out at a condition where fiber bundles in which the value of Mn/(Ln×D) is less than 8.5×10−1 mg/mm2 are referred to as carbon fiber bundles (A) and the total weight of the carbon fiber bundles (A) is referred to as MA. Further, the determination is carried out at a condition where carbon fiber bundles in which Mn/(Ln×D) is 8.5×10−1 mg/mm2 or more are referred to as carbon fiber bundles (B), the total weight of the carbon fiber bundles (B) is referred to as MB and the total number of the bundles is referred to as NB. For fiber bundles refined to a degree at which the bundles cannot be extracted by a pincette, the weight thereof was determined in the lump at the last. Further, when the fiber length is so small that determination of weight becomes difficult, the fiber length may be classified at an interval of about 0.2 mm and the weights of a plurality of classified bundles may be determined in the lump, and an average value thereof may be used. After classifying and determining all bundles, for the carbon fiber bundles (A), Z=MA/(MA+MB)×100 (wt %) is calculated to obtain the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers. Next, for the carbon fiber bundles (B), Y=MB/(MA+MB)×100 (wt %), X=Σ(Mn/Ln)/NB, x=Σ{Mn/(Ln×F)}/NB and σ={1/NB×Σ(xn−x)2}1/2 are calculated to obtain the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers, the average value X of Mn/Ln in carbon fiber bundles (B), the average value x of number of fibers forming a fiber bundle, and the standard variation σ of number of fibers forming a fiber bundle.
The viscosity is determined using APA2000 (supplied by ALPHA TECHNOLOGIES, Inc.) as follows: a sample having a size of 4.3 cm3 is interposed between parallel plates, the temperature is raised to a temperature of the melting point +60° C., the viscosity is measured under conditions where the frequency is 1 Hz and the strain is 5% while cooling down the temperature at a speed of 10° C./min. and, thereafter, the viscosity of the sample is determined as a value of viscosity (Pa·s) at the solidification start temperature at which the viscosity begins to increase sharply.
A sample of about 2 g was cut off from a molded article of a stampable sheet and the mass thereof was determined. Thereafter, the sample was heated in an electric furnace heated at 500° C. for one hour to burn off organic substances such as matrix resin. After cooling to room temperature, the mass of the residual carbon fibers was determined. The rate of the mass of the carbon fibers to the mass of the sample before being burned off with organic substances such as matrix resin was determined, and it was defined as the percentage content of carbon fibers.
A flexural strength was determined on the basis of JIS-K7171. For the flexural strength, the CV value (coefficient of variation [%]) was also calculated. When the CV value was less than 5%, the variance of the flexural strength was small and judged as ‘good (∘)’ and, when the CV value was 5% or more, the variance of the flexural strength was large and judged as ‘bad (x)’
(5) Single Fiber Flexural Stiffness (Pa·m4)
It was calculated by Single fiber flexural stiffness=E×I.
Here, E: single fiber elastic modulus, I: geometrical moment of inertia.
The cross section of a fiber was supposed as a true circle, the geometrical moment of inertia I was determined from the fiber diameter D, and the flexural stiffness was determined from the single fiber tensile elastic modulus E and the geometrical moment of inertia I.
After two sheets of carbon fiber composite materials each having a size of 100 mm×100 mm×2 mm were preheated at 240° C., the two sheets were stacked and placed on a press table heated at 80° C., and pressed at 10 MPa for 30 seconds. The area of the sheet after this pressing A2 and the area before the pressing A1 were measured, and A2/A1 was determined as a flowability (%).
First, carbon fibers and carbon fiber bundles (before cutting) used in Examples and Comparative Examples will be explained.
A continuous carbon fiber bundle having a fiber diameter of 7 μm, a tensile elastic modulus of 230 GPa, a single fiber flexural stiffness of 2.71×10−11 Pa·m4 and a number of filaments of 12,000.
A continuous carbon fiber bundle having a fiber diameter of 5.5 μm, a tensile elastic modulus of 294 GPa, a single fiber flexural stiffness of 1.32×10−11 Pa·m4 and a number of filaments of 12,000.
The carbon fiber bundle (1) was cut at a fiber length of 25 mm, the cut carbon fiber bundles and nylon 6 short fibers (fineness of short fiber: 1.7 dtex, cut length: 51 mm, number of crimps: 12 crests per 25 mm, rate of crimp: 15%) were mixed at a mass ratio of 90:10, and the mixture was introduced into a carding machine. The web having come out was cross wrapped to form sheet-like carbon fiber aggregates comprising carbon fibers and nylon 6 fibers and having an areal weight of 100 g/cm2. In the obtained carbon fiber aggregates, the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 85 wt %, the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers was 15 wt %, the average value X of Mn/Ln was 0.01 mg/mm, the average value x of number of fibers forming a fiber bundle was 144 and the standard variation σ of number of fibers forming a fiber bundle was 88.
The winding direction of the sheet-like carbon fiber aggregates was referred to as 0°, sheets of the carbon fiber aggregates were stacked and, further, after a nonwoven fabric comprising nylon resin (“CM1001”, ηr=2.3, supplied by Toray Industries, Inc.) was stacked so that the volume ratio of the carbon fibers to the thermoplastic resin fibers became 20:80 as the whole of the stacked carbon fiber aggregates, the whole was nipped by stainless plates, and after preheating at 250° C. for 90 seconds, it was hot pressed at 250° C. for 180 seconds while being applied with a pressure of 1.0 MPa. Then, it was cooled to 50° C. at the pressed condition to obtain a flat plate of carbon fiber composite material having a thickness of 2 mm. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 365 MPa, and the CV value was less than 5%.
When a sample having a size of 100 mm×100 mm was cut out from the obtained flat plate and the flow test and the viscosity determination test were performed, flowability was 150%, viscosity η was 5.0×105 Pa·s and η0 was 1.5×104 Pa·s. The conditions and the results of the determinations and the evaluations are shown in Table 1.
A flat plate of carbon fiber composite material was obtained in a manner similar to that of Example 1 except that the carbon fiber bundle (1) was cut at a fiber length of 15 mm, carbon fiber aggregates in which the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 65 wt %, the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers was 35 wt %, the average value X of Mn/Ln was 0.017 mg/mm, the average value x of number of fibers forming a fiber bundle was 246 and the standard variation σ of number of carbon fibers forming a fiber bundle was 110 were stacked to obtain a flat plate of carbon fiber composite material having a thickness of 2 mm. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 360 MPa, and the CV value of the flexural strength was less than 5%.
When a sample having a size of 100 mm×100 mm was cut out from the obtained flat plate and the flow test and the viscosity determination test were performed, flowability was 170%, viscosity η was 3.0×105 Pa·s and η0 was 1.5×104 Pa·s.
They were carried out under conditions similar to Example 2 except that the average value X of Mn/Ln, the average value x of number of fibers forming a fiber bundle, the standard variation σ of number of fibers forming a fiber bundle, the Vf and the like were changed from Example 2. The results were shown in Table 1.
It was carried out in a manner similar to Example 6 except that a melt flow nonwoven fabric comprising nylon resin (“CM1041”, ηr=4.3, supplied by Toray Industries, Inc.) was used, carbon fiber aggregates in which the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 55 wt %, the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers was 45 wt %, the average value X of Mn/Ln was 0.027 mg/mm, the average value x of number of fibers forming a fiber bundle was 390 and the standard variation σ of number of fibers forming a fiber bundle was 250 were stacked, and a flat plate of carbon fiber composite material having a thickness of 2 mm was obtained. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 350 MPa, and the CV value of the flexural strength was less than 5%.
When a sample having a size of 100 mm×100 mm was cut out from the obtained flat plate and the flow test and the viscosity determination test were performed, flowability was 230%, viscosity η was 5.5×104 Pa·s and η0 was 1.8×104 Pa·s.
It was carried out in a manner similar to Example 6 except that the fiber length L of carbon fibers was changed. The results were shown in Table 1.
It was carried out in a manner similar to Example 1 except that the carbon fiber bundle (2) was cut at a fiber length of 15 mm, carbon fiber aggregates in which the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 50 wt %, the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers was 50 wt %, the average value X of Mn/Ln was 0.025 mg/mm, the average value x of number of fibers forming a fiber bundle was 585 and the standard variation σ of number of carbon fibers forming a fiber bundle was 350 were stacked, and a flat plate of carbon fiber composite material having a thickness of 2 mm was obtained. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 400 MPa, and the CV value of the flexural strength was less than 5%.
When a sample having a size of 100 mm×100 mm was cut out from the obtained flat plate and the flow test and the viscosity determination test were performed, flowability was 300%, viscosity η was 2.0×104 Pa·s and no was 1.5×104 Pa·s.
It was carried out in a manner similar to Example 9 except that the fiber length L, the ratio of carbon fiber bundles (B), the average value X of Mn/Ln, the average value x of number of fibers forming a fiber bundle and the standard variation σ of number of fibers forming a fiber bundle were changed. The results were shown in Table 1.
The carbon fiber bundle (1) was cut at a fiber length of 15 mm, the cut carbon fiber bundles and nylon 6 short fibers (fineness of short fiber: 1.7 dtex, cut length: 10 mm) were mixed at a mass ratio of 80:20, and the mixture was introduced into an air laid machine. The nonwoven fabric having come out was heat treated to form sheet-like carbon fiber aggregates comprising carbon fibers and nylon 6 fibers and having an areal weight of 200 g/cm2. In the obtained carbon fiber aggregates, the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 30 wt %, the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers was 70 wt %, the average value X of Mn/Ln was 0.028 mg/mm, the average value x of number of fibers forming a fiber bundle was 400 and the standard variation σ of number of fibers forming a fiber bundle was 315.
The winding direction of the sheet-like carbon fiber aggregates was referred to as 0°, sheets of the carbon fiber aggregates were stacked, and further, after a nonwoven fabric comprising co-polymerized nylon resin (“E3500”, supplied by Toray Industries, Inc.) was stacked so that the volume ratio of the carbon fibers to the thermoplastic resin fibers became 20:80 as the whole of the stacked carbon fiber aggregates, the whole was nipped by stainless plates, and after preheating at 250° C. for 90 seconds, it was hot pressed at 250° C. for 180 seconds while being applied with a pressure of 1.0 MPa. Then, it was cooled to 50° C. at the pressed condition to obtain a flat plate (stampable sheet) of carbon fiber composite material having a thickness of 2 mm. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 330 MPa, and the CV value was less than 5%.
When a sample having a size of 100 mm×100 mm was cut out from the obtained flat plate and the flow test and the viscosity determination test were performed, flowability was 370%, viscosity η was 1.1×104 Pa·s and η0 was 3.0×103 Pa·s. The conditions and the results of the determinations and the evaluations are shown in Table 2.
They were carried out in a manner similar to Example 11 except that the Vf was changed. The results were shown in Table 2.
They were carried out in a manner similar to Example 1 except that the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers, the ratio Y of carbon fiber bundles (B), the average value X of Mn/Ln, the average value x of number of fibers forming a fiber bundle, the standard variation σ of number of fibers forming a fiber bundle, the Vf, the resin and the like were changed from Example 1. The results were shown in Table 2.
The carbon fiber bundle (1) was cut at a fiber length of 15 mm, the cut carbon fiber bundles were uniformly dispersed on a matched die mold having a size of 300 mm×300 mm, a nylon resin melt blow nonwoven fabric (“CM1001”, ηr=2.3, supplied by Toray Industries, Inc.) was stacked so that the volume ratio of the carbon fibers to the thermoplastic resin fibers became 20:80, and carbon fiber aggregates in which the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 1 wt %, the ratio Y of carbon fiber bundles (B) to the total weight of carbon fibers was 99 wt %, the average value X of Mn/Ln was 0.55 mg/mm, the average value x of number of fibers forming a fiber bundle was 7944 and the standard variation σ of number of fibers forming a fiber bundle was 955 were stacked to obtain a flat plate of carbon fiber composite material having a thickness of 2 mm. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 200 MPa, and the CV value was more than 5%. The result was shown in Table 3.
It was carried out in a manner similar to Example 1 except that the carbon fiber bundle (1) was cut at a fiber length of 15 mm, carbon fiber aggregates in which the ratio Z of carbon fiber bundles (A) to the total weight of carbon fibers was 95 wt %, the average value X of Mn/Ln was 0.01 mg/mm, the average value x of number of fibers forming a fiber bundle was 140 and the standard variation σ of number of carbon fibers forming a fiber bundle was 40 were stacked to obtain a flat plate of carbon fiber composite material having a thickness of 2 mm. When the flexural strengths in 0° and 90° directions were determined relative to the 0° direction of the surface layer of the obtained flat plate, the average value of the flexural strengths in 0° and 90° directions was 365 MPa, and the CV value of the flexural strength was less than 5%.
When a sample having a size of 100 mm×100 mm was cut out from the obtained flat plate and the flow test and the viscosity determination test were performed, flowability was only 120%, viscosity η was 5.0×105 Pa·s and no was 1.5×104 Pa·s.
2.71 × 10−11
2.71 × 10−11
The stampable sheet can be applied for manufacturing any carbon fiber reinforced molded article required with combination of high flowability and mechanical properties and few variations in mechanical properties, that have not been achieved by the conventional technologies.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-235635 | Oct 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2013/077973 | 10/15/2013 | WO | 00 |
