WO2019146486A1 - Reinforcing fiber bundle and method for manufacturing same, and chopped fiber bundle and fiber-reinforced resin molding material using same - Google Patents
Reinforcing fiber bundle and method for manufacturing same, and chopped fiber bundle and fiber-reinforced resin molding material using same Download PDFInfo
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- WO2019146486A1 WO2019146486A1 PCT/JP2019/001221 JP2019001221W WO2019146486A1 WO 2019146486 A1 WO2019146486 A1 WO 2019146486A1 JP 2019001221 W JP2019001221 W JP 2019001221W WO 2019146486 A1 WO2019146486 A1 WO 2019146486A1
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- reinforcing fiber
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
Definitions
- the present invention relates to a reinforced fiber bundle and a chopped fiber bundle which are excellent in productivity, flowability at the time of molding, and mechanical properties of a molded article, a method of producing the same, and a method of producing a fiber reinforced resin molding material using the same.
- a molding material comprising a bundle of discontinuous reinforcing fibers (for example, carbon fibers) (hereinafter also referred to as fiber bundle) and a matrix resin
- fiber bundle a molding material comprising a fiber bundle having a large number of single yarns is excellent in flowability during molding, but the mechanical properties of the molded article tend to be inferior.
- a fiber bundle adjusted to an arbitrary number of single yarns is used as a fiber bundle in a molding material for the purpose of coexistence of flowability at the time of molding and mechanical characteristics of a molded product.
- Patent Literatures 1 and 2 disclose a method of performing separation treatment using a multi-fiber bundle winding body in which a plurality of fiber bundles are previously wound. There is. However, since these methods are limited by the number of single yarns of the pre-processed fiber bundle, the adjustment range is limited and it is difficult to adjust to the desired number of single yarns.
- Patent Documents 3 to 6 disclose methods of longitudinally slitting a fiber bundle into a desired number of single yarns using a disk-shaped rotary blade. Although these methods can adjust the number of single yarns by changing the pitch of the rotary blade, the longitudinally slit fiber bundle has no convergence, so the yarn after the longitudinal slit is wound on a bobbin. And handling such as unrolling the fiber bundle from the wound bobbin tends to be difficult.
- the branched fiber bundle generated by the longitudinal slit may be wound around a guide roll, a feed roll, or the like, and the transport may not be easy.
- it is set as a molding material, since many single yarns are contained, there existed a problem of being inferior to fluidity.
- Patent Documents 7 and 8 propose reinforcing fibers coated with a polyamide-based sizing agent for the purpose of improving process stability and composite physical properties. Although the process stability and the physical properties of the composite are improved, there is a problem that the productivity is inferior because drying or modification takes time in the sizing agent application process.
- the present invention provides a reinforced fiber bundle and a chopped fiber bundle excellent in productivity and flowability in molding and mechanical characteristics of a molded product, a method for producing the same, and fiber reinforced resin molding using the same.
- the task is to provide materials.
- the present invention has the following composition.
- the fiber number per unit width is not less than 600 / mm and less than 1,600 / mm, and the drape value of the reinforcing fiber bundle is not less than 120 mm and not more than 240 mm, described in (1) Reinforcement fiber bundle.
- the reinforcing fiber bundle according to (1) or (2) which has a hardness of 39 g or more and 200 g or less.
- the reinforcing fiber bundle according to any one of (1) to (3) wherein the adhesion amount of the polyamide resin is 0.1% by weight or more and 5% by weight or less.
- the width after taking out from water is W2, and the width change ratio W2 / W1 is 0.5 or more and 1.1 when the width before immersion is W1.
- the reinforcing fiber bundle according to any one of (1) to (4) which is characterized by the following.
- the reinforced fiber bundle is immersed in water at 25 ° C.
- the reinforcing fiber bundle according to any one of the above is 110 mm or more and 240 mm or less (1) to (5)
- the reinforcing fiber bundle according to any one of the above is (7)
- a chopped fiber bundle characterized in that a width change ratio W4 / W3 when the width is W4 and the width before immersion is W3 is 0.6 or more and 1.1 or less.
- a fiber-reinforced resin molding material comprising the chopped fiber bundle according to (9) or (10) and a matrix resin.
- the water-soluble polyamide is imparted to the reinforcing fiber to which the first sizing agent including any of compounds having functional groups such as epoxy group, urethane group, amino group and carboxyl group or a mixture thereof is attached
- the manufacturing method of the reinforced fiber bundle characterized by doing.
- a sizing agent for the widening reinforcing fiber bundle The method for producing a reinforced fiber bundle according to (14), further comprising a sizing agent application step (II) of producing a reinforced fiber bundle by reacting with a crosslinking agent after applying.
- any of (14) to (18) The manufacturing method of the reinforced fiber bundle as described in. (20) The method for producing a reinforcing fiber bundle according to any one of (13) to (19), including the step of heat treating the reinforcing fiber to which a water-soluble polyamide is imparted. (21) The method for producing a reinforced fiber bundle according to (20), wherein the temperature of the heat treatment is 130 to 350 ° C. (22) The method for producing a reinforcing fiber bundle according to (20) or (21), wherein the heat treatment time is 0.33 to 15 minutes.
- the water-soluble polyamide is obtained by polymerizing a diamine having a tertiary amino group and / or an oxyethylene group in the main chain and a dicarboxylic acid, (13) The manufacturing method of the reinforced fiber bundle in any one of (23).
- a separation step (III) in which a separation means having a plurality of protrusions is pushed into the reinforcement fiber bundle to generate a separation treatment part while traveling the reinforcement fiber bundle along the longitudinal direction ,
- Re-piercing step (V) in which the separating means is extracted from the reinforcing fiber bundle, passed through the entanglement storage part including the entangled part, and then the separating means is reinserted into the reinforcing fiber bundle;
- Any one of (13) to (25) further including a fiber separation treatment step (VI) of alternately forming a fiber separation treated section divided into a plurality of bundles and an unsorted fiber treatment processed section.
- the manufacturing method of the reinforced fiber bundle as described in.
- (27) The reinforcement according to (26), wherein in the separation
- the method of manufacturing a reinforcing fiber bundle of the present invention it is possible to enhance the productivity of the divided fiber / shape-stabilized reinforcing fiber bundle.
- the obtained reinforcing fiber bundle is cut / dispersed to form a discontinuous fiber intermediate substrate, the flowability during molding and the mechanical properties of the molded article can be well-balancedly expressed.
- FIG. 1 It is a schematic plan view which shows an example of the separation fiber bundle which performed the separation process in the manufacturing method of the reinforced fiber bundle which concerns on this invention to the fiber bundle.
- An example which inserts a separating means in the fiber bundle to run is shown, (A) is a schematic plan view, (B) is a schematic side view.
- An example of the movement cycle which inserts the separating means which moves to a fiber bundle is shown, (A) is a schematic plan view, (B) is a schematic side view.
- a carbon fiber, glass fiber, an aramid fiber, and a metal fiber are preferable.
- carbon fiber is preferable.
- the carbon fiber is not particularly limited, but for example, carbon fibers of polyacrylonitrile (PAN), pitch, rayon and the like can be preferably used from the viewpoint of the improvement of the mechanical properties and the weight reduction effect of the fiber reinforced thermoplastic resin, These may be used alone or in combination of two or more.
- PAN-based carbon fibers are more preferable from the viewpoint of the balance between the strength and elastic modulus of the fiber-reinforced thermoplastic resin to be obtained.
- the single fiber diameter of the reinforcing fiber is preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more, and still more preferably 4 ⁇ m or more. Moreover, 20 micrometers or less are preferable, as for the single fiber diameter of a reinforced fiber, 15 micrometers or less are more preferable, and 10 micrometers or less are more preferable.
- the strand strength of the reinforcing fiber is preferably 3.0 GPa or more, more preferably 4.0 GPa or more, and still more preferably 4.5 GPa or more. 200 GPa or more is preferable, as for the strand elasticity modulus of a reinforced fiber, 220 GPa or more is more preferable, and 240 GPa or more is more preferable. If the strand strength or elastic modulus of the reinforcing fiber is in this range, respectively, the mechanical properties of the molded article can be enhanced.
- the number of single yarns per unit width of the expanded reinforcing fiber bundle is preferably 600 yarns / mm or more, more preferably 700 yarns / mm or more, and still more preferably 800 yarns / mm or more. If it is less than 600 / mm, there is a concern that the flowability of the molding material may be poor.
- the number of single yarns per unit width of the reinforcing fiber bundle is preferably 1,600 / mm or less, more preferably 1,400 / mm or less, and even more preferably 1,200 / mm or less. If it exceeds 1,600 / mm, there is a concern that the mechanical properties of the molded article may be inferior.
- the method of deriving the number of single yarns per unit width of the reinforcing fiber bundle constituting the fiber reinforced resin molding material will be described later.
- the thickness of the widened reinforcing fiber bundle is preferably 0.01 mm or more, more preferably 0.03 mm or more, and still more preferably 0.05 mm or more. If it is less than 0.01 mm, there is a concern that the flowability of the molding material may be poor.
- the thickness of the reinforcing fiber bundle is preferably 0.2 mm or less, more preferably 0.18 mm or less, and still more preferably 0.16 mm or less. If it exceeds 0.2 mm, there is a concern that the mechanical properties of the molded article may be inferior.
- the sizing agent used in the present invention comprises a primary sizing agent and a secondary sizing agent.
- the primary sizing agent is first applied to the reinforcing fiber bundle, and then the secondary sizing agent is applied to the reinforcing fiber bundle.
- a water-soluble polyamide is preferably contained as a main component, and the water-soluble polyamide is polycondensed from a diamine having a tertiary amino group and / or an oxyethylene group in the main chain and a carboxylic acid.
- the polyamide resin is obtained by the following method: N, N'-bis (.gamma.-aminopropyl) piperazine having a piperazine ring, N-(.
- Alkyl diamines containing oxyethylene groups in the main chain of monomers, oxyethylene alkylamines and the like are useful.
- dicarboxylic acids include adipic acid and sebacic acid.
- the primary sizing agent any of compounds having functional groups such as epoxy group, urethane group, amino group, carboxyl group or the like in order to lower the heat treatment temperature or shorten the heat treatment time. What mixed is good.
- crosslinking agent it does not specifically limit as a kind of crosslinking agent, It is preferable that it is at least 1 sort (s) of resin chosen from a melamine resin, a urea resin, a phenol resin, and an epoxy resin.
- the lower limit of the weight ratio of the crosslinking agent to the sizing agent is preferably 0.02 or more, more preferably 0.03 or more, and still more preferably 0.04 or more.
- the upper limit of the weight ratio of the crosslinking agent to the sizing agent is preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.6 or less. Within this range, it is possible to lower the heat treatment temperature or shorten the heat treatment time.
- the water-soluble polyamide of the present invention may be a copolymer.
- the copolymerization component include lactams such as ⁇ -pyrrolidone, ⁇ -piperidone, ⁇ -caprolactam, ⁇ -methyl- ⁇ -caprolactam, ⁇ -methyl- ⁇ -caprolactam, ⁇ -laurolactam, etc.
- lactams such as ⁇ -pyrrolidone, ⁇ -piperidone, ⁇ -caprolactam, ⁇ -methyl- ⁇ -caprolactam, ⁇ -methyl- ⁇ -caprolactam, ⁇ -laurolactam, etc.
- the copolymerization ratio is determined within a range that does not interfere with the physical property of water solubility.
- the polymer does not completely dissolve in water unless the proportion of copolymerization components having a lactam ring is within 30% by weight.
- the solubility is increased when the solution is made acidic using an organic and inorganic acid, and it becomes water soluble and can be used.
- organic acid include acetic acid, chloracetic acid, propionic acid, maleic acid, oxalic acid and fluoroacetic acid
- inorganic acid include common mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
- This water-soluble polyamide may be used as a primary sizing agent for reinforcing fiber bundles to which a sizing agent has not been applied, or as a secondary sizing agent to reinforcing fiber bundles to which a sizing agent has been applied beforehand.
- 5 weight% or less is preferable, as for the adhesion amount of all the sizing agents provided to the reinforcement fiber bundle, 4 weight% or less is more preferable, and 3 weight% or less is more preferable. If the adhesion amount of the sizing agent exceeds 5% by weight, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in failure to obtain an ideal chopped fiber bundle form. 0.1 weight% or more is preferable, as for the adhesion amount of a sizing agent, 0.3 weight% or more is more preferable, and 0.5 weight% or more is more preferable.
- the adhesion amount of the sizing agent is less than 0.1% by weight, the adhesion between the matrix and the reinforcing fibers tends to be reduced, and the mechanical properties of the molded article may be lowered, when trying to produce the molded article .
- the filament is broken and fluff is generated, the unwinding property from the bobbin may be reduced, and winding on the nip roller and the cutter blade may occur. The method for deriving the adhesion amount of the sizing agent will be described later.
- the sizing agent is preferably uniformly attached to the surface of the reinforcing fiber.
- these sizing agents are dissolved in water or alcohol, an aqueous acidic solution of 0.1% by weight or more, preferably in a concentration of 1% by weight to 20% by weight.
- the sizing agent processing solution concentration, temperature, yarn tension and the like so that the adhesion amount of the sizing agent active component to the fibers uniformly adheres within an appropriate range. Moreover, it is more preferable to vibrate the fiber bundle with ultrasonic waves at the time of applying the sizing agent.
- any method such as heat treatment, air drying, centrifugation and the like may be used, and among them, heat treatment is preferable from the viewpoint of cost.
- heat treatment for example, hot air, a hot plate, a roller, an infrared heater or the like can be used.
- the heat treatment conditions are also important, and are related to the handling and the adhesion to the matrix material. That is, the heat treatment temperature and time after applying the sizing agent to the fiber bundle should be adjusted according to the components of the sizing agent and the adhesion amount.
- the water-soluble polyamide it is preferable to carry out heat treatment after drying at room temperature to 180 ° C. to remove moisture, from the viewpoint of preventing heat deterioration.
- 130 degreeC or more is preferable and, as for the minimum of heat processing temperature, 200 degreeC or more is more preferable.
- 350 degrees C or less is preferable and, as for the upper limit of heat processing temperature, 280 degrees C or less is more preferable.
- the heat treatment temperature is a temperature at which the water-soluble polyamide self-crosslinks or loses water solubility by oxygen in air.
- the polyamide after this treatment may have an ester bond and / or a carbon-carbon double bond.
- the heat treatment makes the water-soluble polymer insoluble and loses the hygroscopicity, so that the filament-concentrated strand is not sticky, the post-processing workability is improved, and the adhesion to the matrix material is improved and the fiber is easy to handle.
- the heat treatment time is preferably 0.3 minutes or more. Moreover, 10 minutes or less are preferable, 6 minutes or less are more preferable, and 2 minutes or less are more preferable. Within this range, the line speed can be increased to improve productivity.
- the hardness of the fiber bundle can be further increased by performing the aging treatment in an atmosphere of 23 ⁇ 5 ° C. after the heat treatment.
- Sizing agents using this water-soluble polyamide resin are excellent in affinity with various matrix materials and can significantly improve the composite physical properties, but in particular, polyamide resins, polyimide resins, polyamideimide resins, and polyetheramideimide resins It has the effect of improving adhesion in resin.
- the water-soluble polyamide When used as a secondary sizing agent, it may be applied to the reinforcing fiber bundle to which the primary sizing agent is applied in the same manner as the above method, or may be applied in the process of producing the reinforcing fiber bundle.
- the sizing agent In the production of a specific reinforcing fiber bundle, to illustrate the application of the sizing agent at any time during the manufacturing process of the reinforcing fiber bundle, for example, the sizing agent is contained in a solvent (including a dispersion medium in the case of dispersion).
- a sizing agent is applied to a fiber bundle by preparing a dissolved (including dispersed) sizing agent treatment liquid and applying the sizing agent treatment liquid to a fiber bundle, followed by drying, evaporation and removal of a solvent. Generally done.
- 200 degreeC or more is preferable, as for the thermal decomposition start temperature of the sizing agent in this invention, 250 degreeC or more is more preferable, and 300 degreeC or more is more preferable.
- the method of deriving the thermal decomposition start temperature will be described later.
- the drape value D1 of the reinforcing fiber bundle after application of the sizing agent used in the present invention is preferably 120 mm or more, preferably 145 mm or more, and more preferably 170 mm or more.
- the drape value D1 is smaller than 120 mm, the filament is broken and fluff is generated, so that the unwinding property from the bobbin may be reduced and winding on the nip roller and the cutter blade may occur.
- the drape value D1 of the reinforcing fiber bundle after the sizing agent application is preferably 240 mm or less, preferably 230 mm or less, and more preferably 220 mm or less.
- the drape value measured by the same method as the above method is taken as the drape value D2.
- 110 mm or more is preferable, as for the minimum of drape value D2 (bundle hardness), 145 mm or more is more preferable, and 170 mm or more is more preferable.
- the upper limit of the drape value D1 (bundle hardness) is preferably 240 mm or less, more preferably 230 mm or less, and still more preferably 220 mm or less.
- the drape value D2 When the drape value D2 is smaller than 110 mm, the filament is broken and fluff is generated, which may cause the lowering of the unwinding property from the bobbin and the winding on the nip roller and the cutter blade.
- the drape value D2 exceeds 240 mm, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound.
- single yarn breakage may occur at the time of cutting, which may result in the failure to obtain an ideal chopped fiber form.
- the bundle hardness of the reinforcing fiber bundle after application of the sizing agent used in the present invention is preferably 39 g or more, more preferably 70 g or more, and still more preferably 120 g or more. If the hardness is less than 39 g, the filament may be broken and fuzz may be generated to reduce the unwinding property from the bobbin and to cause winding on the nip roller and the cutter blade.
- the bundle hardness of the reinforcing fiber bundle constituting the fiber-reinforced thermoplastic resin molding material is preferably 200 g or less, more preferably 190 g or less, and still more preferably 180 g or less.
- the width before immersing the reinforcing fiber bundle after application of the sizing agent used in the present invention in water is W1
- the reinforcing fiber bundle is immersed in water at 25 ° C. for 5 minutes, then taken out and drained for 1 minute.
- the width change ratio W2 / W1 of the reinforcing fiber bundle is preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.7 or more.
- the width change ratio W2 / W1 of the reinforcing fiber bundle is smaller than 0.5, the water-soluble physical property of the sizing agent attached to the reinforcing fiber bundle remains, so that the fiber is divided after being subjected to fiber separation treatment
- the fiber bundle may re-aggregate, which makes it difficult to maintain the form of the fiber bundle adjusted to the optimum number of single yarns. If the fiber bundle can not be maintained in the form of a fiber bundle adjusted to the optimum number of single yarns, the split fiber bundle is cut / dispersed to make the intermediate substrate of the optimum form in making the discontinuous fiber bundle an intermediate substrate And it becomes difficult to achieve well-balanced flowability during molding and mechanical properties of the molded article.
- the width change rate W2 / W1 is preferably 1.1 or less. If the width change ratio W2 / W1 exceeds 1.1, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in failure to obtain an ideal chopped fiber bundle form.
- the method of deriving the width change ratio W2 / W1 of the reinforcing fiber bundle will be described later.
- the separation fiber bundle is a reinforcing fiber in which a separation treatment section divided into a plurality of bundles and a non-division treatment section are alternately formed along a longitudinal direction of a fiber bundle consisting of a plurality of single yarns. It is a bundle, and a sizing agent is applied to the reinforcing fiber bundle.
- the unsplitted section may be continuous or discontinuous in the width direction of the split fiber bundle.
- the length of the division process area which adjoins one undivided process area may be the same, and may differ.
- FIG. 1 shows an example of a divided fiber bundle in which the fiber bundle in the present invention is subjected to separation treatment
- FIG. 2 shows an example of the divided treatment.
- the manufacturing method of the separation fiber bundle in the present invention will be described with reference to FIG.
- FIG. 2 is (A) a schematic plan view and (B) a schematic side view showing an example in which a separating means is pushed into a traveling fiber bundle.
- the fiber bundle traveling direction a (arrow) in the figure is the longitudinal direction of the fiber bundle 100, which indicates that the fiber bundle 100 is continuously supplied from a fiber bundle supply device (not shown).
- the separating means 200 has a projecting portion 210 having a projecting shape that easily penetrates into the fiber bundle 100, and inserts into the traveling fiber bundle 100, and the separating part 150 substantially parallel to the longitudinal direction of the fiber bundle 100. Generate Here, it is preferable that the separating means 200 pierce in the direction along the side surface of the fiber bundle 100.
- the side surface of the fiber bundle means a vertical surface at the end of the cross section (for example, the fiber bundle 100 shown in FIG. Corresponding to the side surface).
- the number of the provided protrusions 210 may be one or more than one per fiber dividing means 200.
- the frequency of wear of the protrusions 210 is reduced, which also makes it possible to reduce the frequency of replacement. Furthermore, it is also possible to use a plurality of separating means 200 simultaneously depending on the number of fiber bundles to be separated.
- the plurality of separating units 200 can be arranged in parallel, alternately, in a phase-shifted manner, or the like to arbitrarily arrange the plurality of protrusions 210.
- the fiber bundle 100 consisting of a plurality of single yarns is divided into a smaller number of divided fiber bundles by the separation means 200, the plurality of single yarns are not substantially aligned in the fiber bundle 100. Since there are many entangled parts at the single yarn level, there may be a case where the intertwining part 160 where the single yarn is entangled is formed in the vicinity of the contact part 211 during the separation processing.
- forming the entangled portion 160 means, for example, forming (moving) the intermingling of single yarns existing in advance in the separation processing section into the contact part 211 by the separation means 200, or separation
- forming (manufacturing) an assembly in which single yarns are newly entangled by means 200 may be mentioned.
- the sizing agent is applied to the surface of the reinforcing fibers, the reinforcing fibers are restrained from each other, and the generation of single yarn due to rubbing or the like at the time of the split treatment is significantly reduced. And the occurrence of the entangled portion 160 described above can be significantly reduced.
- the separation means 200 is removed from the fiber bundle 100.
- the separation processing section 110 subjected to the separation processing is generated, and at the same time, the entangled portion 160 generated as described above is accumulated in the end portion of the separation processing section 110, and the entangled portion 160 Is generated by the entanglement storage unit 120 that has accumulated.
- the fluff generated from the fiber bundle during the separation processing is generated as the fluff pool 140 in the vicinity of the entanglement accumulation unit 120 during the separation processing.
- the separation means 200 is pushed into the fiber bundle 100 again to generate the undivided treatment section 130, and the separation treatment section 110 and the undivided treatment section 130 are formed along the longitudinal direction of the fiber bundle 100.
- Split fiber bundles 180 alternately arranged are formed.
- the content of the unsplit processing section 130 is preferably 3% or more and 50% or less.
- the content rate of the undivided fiber treatment zone 130 is defined as the ratio of the total generation length of the undivided fiber treated zone 130 to the total length of the fiber bundle 100.
- the content rate of the undivided fiber processing section 130 is less than 3%, the divided fiber bundle 180 is cut / dispersed, and the fluidity when used for forming as an intermediate base of the discontinuous fiber bundle becomes poor, 50% If it exceeds, the mechanical properties of a molded article molded using it will be degraded.
- the length of the said division processing area 110 is 30 mm or more and 1500 mm or less, and the length of the said undivision processing area 130 is 1 mm or more and 150 mm or less Is preferred.
- the traveling speed of the fiber bundle 100 is preferably a stable speed with less fluctuation, and more preferably a constant speed.
- the separating means 200 is not particularly limited as long as the object of the present invention can be achieved, and it is preferable that the separating means 200 has a shape such as a metallic needle or a thin plate. It is preferable that the separating means 200 be provided with a plurality of separating means 200 in the width direction of the fiber bundle 100 to be subjected to the separating treatment, and the number of the separating means 200 is different from that of the fiber bundle 100 to be subjected to the separating treatment. It can select arbitrarily by composition single yarn number F (piece).
- the number of separating means 200 is preferably (F / 10,000-1) or more and (F / 50-1) or less in the width direction of the fiber bundle 100.
- the separating means 200 is pushed into the stationary fiber bundle 100 (arrow (1)) and then the separating means
- the separation processing unit 150 may be generated while traveling 200 along the fiber bundle 100 (arrow (2)), and then the separation means 200 may be removed (arrow (3)).
- FIG. 4 (A) the fiber bundle 100 which has been at rest is moved by a predetermined distance at the timings indicated by the arrows (3) and (4), and then the separating means 200 is moved to the original position. (The arrow (4)) may be returned, or, as shown in FIG. 4 (B), the fiber bundle 100 is not moved, and the movement is continued until the separating means 200 passes through the entanglement storage section 120 (arrow (4 )).
- the separation processing time during which the separation means 200 is inserted (arrow The time of the operation shown in (2) and the time (the time of the operation shown in arrows (3), (4), (1)) until extraction of the separating means 200 and pushing into the fiber bundle again are controlled.
- the moving direction of the separating means 200 is the repetition of (1) to (4) in the figure.
- the separation processing time during which the separation means is inserted (the time of operation shown by the arrow (2) or the arrow (6)) and the time until extraction of the separation means 200 and insertion into the fiber bundle again (arrow ( Preferably, 3), (4), (5) or the time of operation shown by arrows (3), (4), (1)) is controlled. Also in this case, the moving direction of the separating means 200 is the repetition of (1) to (4) in the figure.
- the separation processing section and the undivision processing section are alternately formed by the separation means 200, and the division processing section is divided into a ratio within a predetermined range with respect to the total length of the fiber bundle. Fiber bundles are produced.
- an undivided treated section of an arbitrary length is secured (for example, in FIG. It is also possible to resume separation processing from near the end of the separation processing section without processing the next separation processing unit 150 after securing the processing section 130.
- FIG. 4A in the case of performing separation processing while moving the fiber bundle 100 intermittently, after the separation means 200 performs separation processing (arrow (2)), the fibers By making the moving length of the bundle 100 shorter than the length of the separation processing immediately before, the position (arrow (1)) at which the separation means 200 is pushed in again overlaps the separation treatment section where the separation treatment was performed immediately before. be able to.
- FIG. 4 (B) in the case of performing separation processing while moving the separation means 200 itself, once the separation means 200 is removed (arrow (3)), the predetermined length is moved The separating means 200 can be pushed into the fiber bundle again (arrow (5)) without causing (arrow (4)).
- the width of the fiber bundle 100 is not because the single yarns are not substantially aligned in the fiber bundle. Even if the separating means 200 is pushed in again at the same position as the position where the separating process has already been performed or the position where the separating means 200 has been pulled out, the pushing-in position at the single yarn level tends to shift easily.
- the formed separation processing section can be present as a separate separation processing section without the divided state (void) being continuous.
- the length of the fiber separation treatment section (fiber separation distance 170) which performs fiber separation processing once depends on the single yarn entangled state of the fiber bundle to be subjected to the fiber separation processing, it is preferably 30 mm or more and less than 1,500 mm. If it is less than 30 mm, the effect of the fiber separation treatment is insufficient, and if it is 1,500 mm or more, there is a fear of yarn breakage or fuzzing depending on the reinforcing fiber bundle.
- separating means 200 when a plurality of separating means 200 are provided, it is possible to provide a plurality of divided treatment sections and undivided processing sections alternately formed substantially in parallel with the width direction of the fiber bundle. At this time, as described above, it is possible to arbitrarily arrange the plurality of projecting portions 210 by arranging the plurality of separating means 200 in parallel, alternately, shifting the phase, or the like.
- the plurality of protrusions 210 can also be controlled independently. Although the details will be described later, it is also preferable that the individual protrusions 210 be subjected to separation processing independently depending on the time required for the separation processing and the pressing force detected by the protrusions 210.
- the fiber bundle is unwound from a unwinding device (not shown) or the like, which unrolls the fiber bundle, disposed on the upstream side in the fiber bundle traveling direction.
- a unwinding direction of the fiber bundle it is conceivable to use a side-by-side method in which the fiber bundle is drawn out perpendicularly to the rotational axis of the bobbin or a longitudinal-out method in which it is drawn out in the same direction as the rotational axis of the bobbin Sideways method is preferable in consideration of
- the installation posture of the bobbin at the time of unwinding can be installed in any direction.
- the end face of the bobbin on the side other than the fixed surface of the creel rotary shaft is installed in a state where the end face of the creel is not pierced with the fixed direction.
- the fiber bundle slips off from the package (the bobbin in which the fiber bundle is wound on the bobbin) and is separated from the package, or the fiber bundle separated from the package is wound around the creel rotating shaft It is thought that it becomes difficult to unroll.
- the package is placed parallel to the rollers on two rollers arranged in parallel, and the package is rolled on the rollers arranged.
- the surface unrolling method of unrolling the fiber bundle is also applicable.
- adjustment of the number of single yarns after separation is possible by the method of widening the fiber bundle and the pitch of the plurality of separation means arranged in the width direction of the fiber bundle.
- the pitch of the separating means By reducing the pitch of the separating means and providing more separating means in the fiber bundle width direction, it is possible to separate into so-called fine bundles with a smaller number of single yarns.
- the term “widening” refers to a process of widening the width of the fiber bundle 100.
- the widening method is not particularly limited, and a vibration widening method of passing a vibrating roll, an air widening method of blowing compressed air, and the like are preferable.
- the punching and drawing of the separating means 200 is repeated to form the separating unit 150.
- the ratio of the fiber treatment section 130 can also be determined arbitrarily.
- the predetermined time interval may always be the same, but may be increased or shortened depending on the distance of progress of the separation processing, or according to the state of the fiber bundle at that time, for example, fiber bundle
- the predetermined time interval may be shortened, or the like, depending on the situation.
- the separating means 200 When the separating means 200 is pushed into the fiber bundle 100, the forming unit 200 continues to push the protrusion 210 as the separating process proceeds, so the separating means 200 receives a pressing force from the forming unit 160. .
- the plurality of single yarns are not substantially aligned in the fiber bundle 100, but there are many parts entangled at the single yarn level, and in the longitudinal direction of the fiber bundle 100, there are many entanglements. There may be few places. In the place where there is much single yarn interlacing, the rise in pressing force at the time of separation processing becomes faster, and conversely, in the place where there is little single yarn intermingling, the rise in pressing force becomes late. Therefore, the separating means 200 of the present invention is preferably provided with pressing force detecting means for detecting pressing force from the fiber bundle 100.
- the tension of the fiber bundle 100 may change before and after the separating means 200
- at least one tension detecting means for detecting the tension of the fiber bundle 100 may be provided in the vicinity of the separating means 200.
- a plurality of tension differences may be calculated.
- the means for detecting the pressing force, the tension, and the tension difference may be provided individually, or may be provided in combination.
- the tension detecting means for detecting the tension be disposed in the range separated from the separating means 200 by at least one of 10 to 1,000 mm at the front and the rear along the longitudinal direction of the fiber bundle 100.
- the upper limit value is preferably set in the range of 0.01 to 5 N / mm in the case of pressing force and tension, and the tension difference is set in the range of 0.01 to 0.8 N / mm.
- the upper limit may be varied within a range of ⁇ 10% depending on the state of the fiber bundle.
- the unit of pressing force, tension, and tension difference indicates the force acting on the width of the fiber bundle 100.
- the separating means 200 If it falls below the upper limit range of pressing force, tension and tension difference, the separating means 200 is pushed immediately to reach the pressing force, tension and tension difference to be taken out of the separating means 200, so the separating distance is sufficient As a result, the fiber separation processing section 110 becomes too short, and the fiber bundle subjected to the fiber separation processing to be obtained in the present invention can not be obtained.
- the cutting of the single yarn in the fiber bundle 100 increases before reaching the pressing force, tension, or tension difference which pulls out the separating means 200, It becomes easy to generate problems such as jumping out of the fiber bundle subjected to the separation treatment in the form of split ends, increase of fluffs to be generated, and the like.
- the splitted hair that has jumped out is wound around the roll being transported, and the fluff is deposited on the drive roll to cause slippage in the fiber bundle, which makes it easy to cause a transport failure.
- the separation is performed before applying a force enough to cut the fiber bundle 100 at the time of separation processing. Since the means 200 is removed, the fiber bundle 100 is not subjected to an excessive force, and continuous separation processing becomes possible.
- the fiber bundle processing section 110 is long, and the shape of the entanglement accumulation part 120 is stable in the longitudinal direction, while suppressing the occurrence of branch breakage and fuzz such as the fiber bundle 100 being partially cut.
- the pressing force is 0.04 to 2.0 N / mm
- the tension is 0.02 to 0.2 N / mm
- the tension difference is 0.05 to 0.5 N / mm. Is preferred.
- An imaging means for detecting the presence or absence of twisting of the fiber bundle 100 is provided in a range separated from the separating means 200 inserted into the fiber bundle 100 by at least one of 10 to 1,000 mm before and after the fiber bundle 100 in the longitudinal direction. Is also preferred.
- this imaging by predetermining the position of the twist and controlling so as not to push the separating means 200 into the twist, it is possible to prevent the piercing error.
- the twist approaches the inserted separating means 200 the narrowing of the fiber bundle 100 can be prevented by extracting the separating means 200, that is, not performing the separation process of the twist.
- the pushing error means that the separating means 200 is pushed into the twist and only the fiber bundle 100 is pushed in the pushing direction of the separating means 200, and the separating process is not performed.
- the width of the fiber bundle 100 changes, the number of separated single yarns also changes. In some cases, the separation process can not be performed for the number of single yarns.
- the fiber bundle 100 is cut at the single yarn level to generate many fluffs, so the shape of the entanglement storage portion 120 where the entangled portions 160 are accumulated becomes large. If a large entanglement accumulation portion 120 is left, it becomes easy to be caught by the fiber bundle 100 unwound from the roll.
- the traveling speed of the fiber bundle 100 may be changed in addition to the control so as not to push the dividing means 200 into the above-mentioned twist. Specifically, after the twisting is detected, the traveling speed of the fiber bundle 100 is increased until the twisting passes through the separating means 200 at the timing when the separating means 200 is removing from the fiber bundle 100. Can efficiently avoid twisting.
- the image processing unit may further include an image processing unit configured to calculate an image obtained by the imaging unit, and a pressing control unit configured to control the pressing force of the separating unit 200 based on the calculation result of the image processing unit.
- the image operation processing means detects twist
- the passability of the twist when the separating means passes the twist can be improved.
- FIG. 5 is an explanatory view showing an example of a movement cycle in which the rotary separating means is pushed.
- the rotating and separating means 220 has a rotating mechanism provided with a rotating shaft 240 orthogonal to the longitudinal direction of the fiber bundle 100, and a protrusion 210 is provided on the surface of the rotating shaft 240.
- the projecting portion 210 provided on the rotary separating means 220 is pushed into the fiber bundle 100, and the separating process starts .
- the rotary separation means 220 have a pressing force detection mechanism and a rotation stop position holding mechanism. By both mechanisms, the rotation stop position is held at the position of FIG. 5 (A) and separation is continued until a predetermined pressing force acts on the rotation separation means 220.
- a predetermined pressing force is exceeded, such as the entangled portion 160 being formed in the projecting portion 210, as shown in FIG. 5 (B)
- the rotating and separating means 220 starts to rotate.
- the protrusion 210 black circle mark
- the next protrusion 210 (white circle mark) penetrates the fiber bundle 100.
- FIG. 5 (A) to FIG. 5 (C) is shorter, the unsorted section becomes shorter, so if it is desired to increase the ratio of the section subjected to fiber bundle split, FIG. It is preferable to shorten the operation of FIG.
- a fiber bundle with a high proportion of fiber division means a fiber bundle with a long fiber division length in the fiber bundle, or a fiber with an increased frequency of generation between a part subjected to fiber division treatment and a part without fiber division treatment It is a bunch.
- the number of the projections 210 is preferably 3 to 12 and more preferably 4 to 8 at equal intervals on the outer edge of the disk.
- the rotational separation unit 220 is an imaging unit that detects twist. It is preferable to have. Specifically, when the imaging means normally detects a twist, the rotation separating means 220 intermittently repeats rotation and stop to perform the separation process, and when the twist is detected, the rotation amount is detected.
- the fiber bundle width can be stabilized by increasing the rotation speed of the fiber means 220 from normal and / or shortening the stop time. It is also possible to keep the stop time at zero, i.e. continuously rotating without stopping.
- the rotational separation means 220 may always be kept rotating. At that time, it is preferable to make either one of the traveling speed of the fiber bundle 100 and the rotational speed of the rotational separation means 220 relatively faster or slower. In the case of the same speed, the operation of piercing / extracting the protruding portion 210 into / from the fiber bundle 100 is performed, and although the separation processing section can be formed, the separation effect on the fiber bundle 100 is weak. It may not be done enough. Also, if either one of the speeds is relatively too fast or too slow, the number of contact between the fiber bundle 100 and the projecting portion 210 increases, which may cause breakage due to abrasion, resulting in poor continuous productivity. Sometimes.
- a reciprocation mechanism may be further provided, in which the separating means 200 and the rotary separating means 220 are pushed in and out by reciprocating movement of the separating means 200 and the rotary separating means 220.
- a reciprocating mechanism for reciprocating the separating means 200 and the rotational separating means 220 along the delivery direction of the fiber bundle 100.
- linear actuators such as pneumatic and electric cylinders and sliders can be used.
- the number of separation processing sections is at least the number of (F / 10,000-1) or more and (F / 50-1) or less in the area in the width direction. It is preferable to have Here, F is the total number of single yarns (pieces) constituting the fiber bundle to be subjected to the separation treatment.
- the number of splitting treatment sections cuts the split fiber bundle into a predetermined length and discontinuous fibers In forming the reinforced composite material, since the reinforcing fiber bundle end in the discontinuous fiber reinforced composite material is finely divided, the discontinuous fiber reinforced composite material having excellent mechanical properties can be obtained.
- the separation processing section is provided with periodicity or regularity in the longitudinal direction of the fiber bundle 100, a predetermined amount can be obtained if the separation fiber bundle is cut into a predetermined length in a later step.
- the number of fiber bundles can be easily controlled.
- FIG. 6 shows an example of the timing of the sizing agent application process in the process of manufacturing a reinforcing fiber bundle in the method of manufacturing a reinforcing fiber bundle according to the present invention.
- the sizing agent application process 400 is performed with the pattern A performed before the split treatment process 300.
- a pattern B to be performed after the fiber separation treatment process 300 is shown. Both timings of pattern A and pattern B are possible.
- FIG. 7 shows a timing example of the sizing agent application process 400 during the process of manufacturing the reinforcing fiber bundle in the method of manufacturing a reinforcing fiber bundle including the fiber bundle widening process 301 according to the present invention.
- the sizing agent applying step 400 is the fiber bundle widening step 301.
- a pattern C which is performed before the above, a pattern D which is performed between the fiber bundle widening step 301 and the separation processing step 300, and a pattern E which is performed after the separation processing step 300 are shown.
- the timing of the pattern D is most preferable from the viewpoint of achieving the optimum separation processing.
- FIG. 8 is the timing of the sizing agent application process including the sizing agent application process and the drying process in the manufacturing process of the reinforcing fiber bundle in the manufacturing method of the reinforcing fiber bundle which constitutes the fiber reinforced thermoplastic resin molding material according to the present invention.
- the sizing agent applying process 400 includes a sizing agent applying process 401 and a drying process 402.
- the sizing agent applying process 400 including the sizing agent applying process 401 and the drying process 402 is performed.
- a pattern F performed prior to the separation processing step 300 and a pattern G performed after the separation processing step 300 are shown in the process of forming the separation fiber bundle 180 through the processing step 300. There is. Either timing of pattern F or pattern G is possible.
- the pattern F is substantially the same as the pattern A in FIG. 6 and the pattern G is substantially the same as the pattern B in FIG.
- FIG. 9 is another manufacturing method of the reinforced fiber bundle which comprises the fiber reinforced thermoplastic resin molding material based on this invention WHEREIN:
- another sizing agent provision process including a sizing agent application process and a drying process
- the timing example of is shown.
- the sizing agent application process 401 and the drying process 402 in the sizing agent application process 400 are separated and performed at different timings.
- the sizing agent application step 401 is performed before the fiber separation treatment step 300, and the drying step 402 is performed after the fiber separation treatment step 300.
- FIG. 10 shows a timing example of a sizing agent application process including a sizing agent application process and a drying process in the method for producing a reinforced fiber bundle including the fiber bundle widening process according to the present invention, and the fiber bundle 100 is fiber bundle widening.
- the sizing agent applying step 401 of the sizing agent applying step is performed prior to the fiber bundle widening step 301,
- the drying step 402 a pattern I performed between the fiber bundle widening step 301 and the separation processing step 300 and a pattern J performed after the separation processing step 300 are shown.
- FIG. 11 shows another timing example of the sizing agent application process including the sizing agent application process and the drying process in the method for producing a reinforced fiber bundle including the fiber bundle widening process according to the present invention
- the fiber bundle 100 is a fiber
- the sizing agent application step 401 of the sizing agent application step comprises the fiber bundle widening step 301 and the splitting treatment step A pattern K is shown which is performed between 300 and 300, and the drying step 402 is performed after the separation processing step 300.
- the average bundle width of the chopped reinforcing fiber bundle constituting the fiber-reinforced thermoplastic resin molding material of the present invention is preferably 0.03 mm or more, more preferably 0.05 mm or more, and still more preferably 0.07 mm or more. If it is less than 0.03 mm, there is a concern that the flowability of the molding material may be poor. 3 mm or less is preferable, as for the average bundle
- the upper limit of the average number of fibers in the chopped reinforcing fiber bundle used in the present invention is preferably 4,000 or less, more preferably 3,000 or less, and still more preferably 2,000 or less. Within this range, the mechanical properties of the molded article can be enhanced.
- the lower limit of the number of fibers in the bundle is preferably 50 or more, more preferably 100 or more, and still more preferably 200 or more. Within this range, the flowability of the molding material can be enhanced. The method of deriving the average number of fibers will be described later.
- the width before immersing the chopped reinforcing fiber bundle after applying a sizing agent to water according to the present invention is W3 and the reinforcing fiber bundle is immersed in water at 25 ° C. for 5 minutes, then taken out and drained for 1 minute
- the width change ratio W4 / W3 of the reinforcing fiber bundle is preferably 0.6 or more, more preferably 0.7 or more, and still more preferably 0.8 or more.
- width change ratio W4 / W3 of the reinforcing fiber bundle is smaller than 0.6, the water-soluble physical properties of the sizing agent attached to the reinforcing fiber bundle remain, and the fiber bundle may reaggregate, Reaggregation makes it difficult to maintain the form of the fiber bundle adjusted to the optimum number of single yarns. If it can not be maintained in the form of a fiber bundle adjusted to the optimum number of single yarns, it can not be made an intermediate substrate of the optimum form, and it is possible to balance the flowability during molding and the mechanical properties of the molded article in a balanced manner. It will be difficult.
- the width change ratio W4 / W3 is preferably 1.1 or less.
- width change ratio W4 / W3 exceeds 1.1, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in failure to obtain an ideal chopped fiber bundle form.
- the method of deriving the width change ratio W4 / W3 of the reinforcing fiber bundle will be described later.
- the matrix thermoplastic resin to be impregnated into the bundle of chopped fiber bundles is not particularly limited.
- PBT polybutylene terephthalate
- PET polyethylene terephthalate
- PPS polypropylene
- PPS polyphenylene sulfide
- PEEK polyetheretherketone
- liquid crystal polymer polyvinyl chloride
- fluorine resin such as polytetrafluoroethylene, silicone, and the like.
- it is preferable to use a polyamide-based resin as the above-mentioned thermoplastic resin and it
- the thermoplastic polyamide resin used in the present invention can be obtained, for example, by polycondensation of nylon 6, nylon 11, nylon 12 or diamine and diamine with dicarboxylic acid obtained by ring-opening polymerization of cyclic lactam or polycondensation of ⁇ -aminocarboxylic acid.
- Copolymerized nylon such as 12 can be suitably used.
- nylon 6, 66, 610 is preferred in view of mechanical properties and cost.
- copper halide or derivatives thereof used in the present invention copper iodide, copper bromide, copper chloride, a complex salt of mercaptobenzimidazole and copper iodide, and the like can be mentioned. Among them, copper iodide and a complex salt of mercaptobenzimidazole and copper iodide can be suitably used.
- the addition amount of the copper halide or its derivative is preferably in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyamide resin.
- the addition amount is less than 0.001 part, it is not possible to suppress resin decomposition, smoke and odor during preheating, and if it is 5 parts by weight or more, improvement of the improvement effect can not be observed. Furthermore, 0.002 to 1 part by weight is preferable because of the balance between the heat stabilization effect and the cost.
- the method for impregnating the bundle of chopped fiber bundles with the matrix resin is not particularly limited, and the method for impregnating the thermoplastic resin may be exemplified by a bundle of thermoplastic resin fibers.
- the thermoplastic resin fibers contained in the bundle-like aggregate may be used as it is as a matrix resin, or a bundle-like aggregate containing no thermoplastic resin fiber as a raw material, a fiber-reinforced thermoplastic resin molding material
- the matrix resin may be impregnated at any stage of production of.
- the matrix resin can be impregnated at any stage of producing a fiber-reinforced thermoplastic resin molding material.
- the resin constituting the thermoplastic resin fiber and the matrix resin may be the same resin or different resins.
- the resin constituting the thermoplastic resin fiber is different from the matrix resin, it is preferable that the two have compatibility or high affinity.
- impregnation of the bundle-like aggregate with the thermoplastic resin which is a matrix resin can be carried out using an impregnation press.
- the press is not particularly limited as long as it can realize the temperature and pressure necessary for the impregnation of the matrix resin, and a normal press having a flat platen which moves up and down, and a mechanism on which a pair of endless steel belts travel So-called double belt presses can be used.
- the matrix resin is formed into a sheet form such as a film, nonwoven fabric or woven fabric and then laminated with a discontinuous fiber mat, and the matrix resin can be melted and impregnated using the above-mentioned press or the like in that state.
- the particulate matrix resin may be dispersed on the bundle assembly to form a laminate, or the chopped fiber bundle may be dispersed at the same time as the dispersion and may be mixed inside the bundle assembly.
- the volume content of reinforcing fibers in the fiber-reinforced resin molding material is preferably 20% by volume or more of the total volume, more preferably 25% by volume or more, and still more preferably 30% by volume or more. If the volume content of reinforcing fibers is less than 20% by volume, the mechanical properties of the fiber-reinforced resin molding material also tend to decrease. On the other hand, the volume content of reinforcing fibers in the fiber-reinforced resin molding material is preferably 70% by volume or less, more preferably 65% by volume or less, and still more preferably 60% by volume or less. If the volume content of reinforcing fibers exceeds 70% by volume, the mechanical properties of the fiber-reinforced resin molding material are likely to be improved, but the moldability tends to be reduced.
- Reinforcing fiber bundle (1) Carbon fiber bundle ("PX35” manufactured by ZOLTEK, 50,000 single yarns, "13" (epoxy) sizing agent, sizing agent adhesion amount 1.5% by weight) was used.
- Reinforcing fiber bundle (2) A carbon fiber bundle ("PX35” manufactured by ZOLTEK, 50,000 single yarns, no sizing agent) was used.
- Reinforcing fiber bundle (3) A glass fiber bundle (240 TEX manufactured by Nitto Boshoku, 1,600 single yarns) was used.
- Resin Sheet (1) A sheet having a basis weight of 150 g / m 2 was produced using a polyamide masterbatch consisting of polyamide 6 resin ("Amilan” (registered trademark) CM 1001, manufactured by Toray Industries, Inc.).
- Resin sheet (2) 90% by mass of unmodified polypropylene resin (Prime Polymer Co., Ltd., “Prime PolyPro” (registered trademark) J106MG) and acid-modified polypropylene resin (Mitsui Chemical Co., Ltd., “Admar” Sheets were made using a polypropylene masterbatch consisting of 10% by weight (registered trademark) QE 800).
- Sizing agent (1) A water-soluble polyamide ("T-70" manufactured by Toray Industries, Inc.) was used.
- Sizing agent (2) A water-soluble polyamide ("A-90” manufactured by Toray Industries, Inc.) was used.
- Sizing agent (3) A water-soluble polyamide ("P-70” manufactured by Toray Industries, Inc.) was used.
- Sizing agent (4) A water-soluble polyamide ("P-95” manufactured by Toray Industries, Inc.) was used.
- the shortest distance between the tip of the reinforcing fiber bundle not fixed to the table and the side surface of the table was measured, and this was taken as the drape value D1.
- the measured reinforcing fiber bundle was immersed in water at 25 ° C. for 5 minutes, then taken out, and the water was removed.
- the reinforcing fiber bundle is dried at 80 ° C. under vacuum conditions for 24 hours, is absolutely dried, and is taken as a post-immersion treatment drape value D2 in the same manner as the above method.
- the hardness of the reinforcing fiber bundle was measured using HANDLE-O-Meter ("CAN-1 MCB" manufactured by Daiei Kagaku Seiki, Ltd.) according to JIS L-1096 E method (handle ohm method). .
- the reinforcing fiber bundle was opened and adjusted so that the length of the test piece used for hardness measurement was 10 cm, and the width was 1 mm with 1,700 to 550 filaments.
- the slit width was set to 20 mm.
- One reinforcing fiber bundle as a test piece was placed on the test table provided with the slit groove, and the resistance (g) generated when the test piece was pushed into the groove to a predetermined depth (8 mm) with a blade was measured. .
- the hardness of the reinforcing fiber bundle was obtained from the average value of three measurements.
- Wf weight content of reinforcing fibers in fiber-reinforced resin molding material
- the fiber-reinforced resin molding material was molded by a method described later to obtain a flat molded article of 500 ⁇ 400 mm.
- the flat plate longitudinal direction set to 0 °
- 16 pieces (total 32 pieces) of 100 ⁇ 25 ⁇ 2 mm test pieces are cut out from the obtained flat plate from 0 ° and 90 ° directions, respectively, according to JIS K 7074 (1988) .
- Bending strength was determined.
- the bending strength was determined to be A at 350 MPa or more and B at less than 350 MPa.
- resin sheet 2 in a state where two fiber reinforced resin molding materials of dimensions 150 mm ⁇ 150 mm ⁇ 2 mm are stacked, the temperature is raised to 120 ° C. after preheating so that the substrate center temperature (temperature between two sheets stacked) becomes 220 ° C. It was placed on a heated press platen and pressurized at 10 MPa for 30 seconds. The area A2 (mm 2 ) after this compression and the area A1 (mm 2 ) of the substrate before pressing were measured, and A2 / A1 ⁇ 100 was taken as the flow rate (%). The fluidity was determined to be less than 200% C, 200% or more and less than 300% B, and 300% or more A.
- the step of separating the reinforcing fiber bundle and the step passing property of continuously cutting and dispersing the divided reinforcing fiber bundle were determined as follows.
- C The reinforcing fiber bundle can not be separated. Alternatively, separation fibers can be used, but the separated reinforcing fiber bundle is wound eight times or more in ten times at the bobbin or cutter portion.
- Example 1 Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll oscillating in the axial direction at 10 Hz, apply a widening treatment, and then pass a 50 mm wide width regulating roll To obtain a reinforced fiber bundle expanded to 50 mm.
- the expanded reinforcing fiber bundle is continuously immersed in a resin treatment solution in which a secondary sizing agent (sizing agent (1)) is diluted with purified water, and then a 250 ° C. hot roller and a 250 ° C. drying oven (air) Under the atmosphere) and heat treatment for 1.5 minutes.
- a secondary sizing agent sizing agent (1)
- the sizing agent adhesion amount of the reinforcing fiber bundle was 0.1% by weight. In addition, this is the total adhesion amount which does not contain a primary sizing agent.
- An iron plate for separation processing equipped with a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained reinforcing fiber bundle is parallel to the reinforcing fiber bundle width direction at 1 mm intervals.
- the set separation processing means was prepared. This separation processing means was intermittently pulled out and inserted into the reinforcing fiber bundle. At this time, the reinforcing fiber bundle traveling at a constant speed of 10 m / min was pierced with the separating treatment means for 3 seconds, the separating treatment means was removed in 0.2 seconds, and the process of piercing again was repeated. As shown in Table 1, the obtained fiber bundle width W3 was about 1 mm.
- the obtained reinforcing fiber bundle is continuously charged into a rotary cutter, cut at a fiber length of 25 mm, a cutting angle of 20 °, and dispersed so as to disperse uniformly, so that the fiber orientation is isotropic.
- a fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 250 g / m 2 .
- Example 2 The evaluation was performed in the same manner as Example 1 except that the adhesion amount of the sizing agent (1) was 2% by weight. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 3 Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a 30 mm wide width regulating roll To obtain a widened fiber bundle widened to 30 mm.
- Example 2 The evaluation was performed in the same manner as in Example 2 except that the widening width was set to 30 mm.
- Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 4 Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a 90 mm width regulating roll To obtain an expanded fiber bundle expanded to 85 mm.
- Example 2 The evaluation was performed in the same manner as in Example 2 except that the widening width was 85 mm.
- Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 5 Evaluation was performed in the same manner as in Example 2 except that the heat treatment temperature and time of the secondary sizing agent were set to 350 ° C. and 16 minutes. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 6 Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (2).
- Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 7 Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (3).
- Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 8 Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (4).
- Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 1 The evaluation was performed in the same manner as in Example 1 except that the secondary sizing agent was not applied. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 9 The evaluation was performed in the same manner as in Example 2 except that the heat treatment temperature and time of the secondary sizing agent were set to 100 ° C. and 0.3 minutes. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- Example 2 Evaluation was performed in the same manner as in Example 2 except that the reinforcing fiber bundle (1) was changed to the reinforcing fiber bundle (2).
- Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
- the reinforcing fiber bundle (1) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 39 mm width A wide fiber bundle was obtained.
- a mother liquor in which the sizing agent (1) is dissolved in water is prepared and applied to a reinforcing fiber bundle (1) containing an epoxy sizing agent which is a crosslinking agent by a dipping method so as to obtain a coverage of 4.1% by weight. Drying was carried out with a hot roller at 250 ° C. for 0.5 minutes. As shown in Table 1, the fiber number per unit width of the reinforcing fiber bundle (1) was 1,290 fibers / mm, the bundle thickness was 0.07 mm, the drape value was 135 mm, and the bundle hardness was 78 g.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to obtain a reinforced fiber bundle (1) having an average number of fibers in the bundle of 1,120 and an average bundle width of 0.6 mm.
- the fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (1) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to a width of 32 mm. A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated again to divide the expanded reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 990 and an average bundle width of 0.6 mm.
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 210 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,030 and an average bundle width of 0.7 mm .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll of 41 mm width A wide fiber bundle was obtained.
- the fiber number per unit width of the reinforcing fiber bundle (4) was 1,220 fibers / mm, the bundle thickness was 0.07 mm, the drape value was 233 mm, and the bundle hardness was 195 g.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,880 and an average bundle width of 0.4 mm .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 37 mm width A wide fiber bundle was obtained.
- the reinforcing fiber bundle (4) Adjusts the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (2) is 0.04, and so that the adhesion amount is 2.8% by weight, the reinforcing fiber bundle 4) and dried for 0.5 minutes with a hot roller at 250 ° C.
- the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,350 fibers / mm
- the bundle thickness was 0.07 mm
- the drape value was 133 mm
- the bundle hardness was 78 g.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 5,230 and an average bundle width of 3.4 mm. .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- Example 15 Unwind the reinforcing fiber bundle (3) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening treatment, and then pass a width regulating roll to 3 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (3) to obtain a reinforcing fiber bundle (3) having an average number of fibers in the bundle of 410 and an average bundle width of 0.7 mm.
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (3) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 210 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 930 and an average bundle width of 0.6 mm.
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- Example 17 The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 28 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to divide the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 1,540 and an average bundle width of 0.6 mm .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- Example 18 The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 13 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,120 and an average bundle width of 0.3 mm .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 210 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to a width of 11 mm. A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 930 and an average bundle width of 0.6 mm.
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- Example 20 The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll. A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 2,330 and an average bundle width of 0.7 mm. .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- Example 21 The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 33 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 2,110 and an average bundle width of 0.6 mm .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 33 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to divide the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,140 and an average bundle width of 0.7 mm. .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 15 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to divide the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 1,280 and an average bundle width of 0.7 mm. .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- Example 24 The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,180 and an average bundle width of 0.6 mm .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,320 and an average bundle width of 0.02 mm. .
- fiber orientation isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed.
- a discontinuous fiber non-woven fabric was obtained.
- the basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 .
- the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C.
- the reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 39 mm width A wide fiber bundle was obtained.
- a mother liquor in which the additional sizing agent (4) is dissolved in water is prepared, applied to the reinforcing fiber bundle (4) by the immersion method so as to obtain an adhesion amount of 2.7% by weight, 0. 2 by a hot roller at 250 ° C. Drying was performed for 5 minutes.
- the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,270
- the bundle thickness was 0.07 mm
- the drape value was 112 mm
- the bundle hardness was 38 g.
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 970 and an average bundle width of 0.6 mm.
- the fiber number per unit width of the reinforcing fiber bundle (1) was 1,230 fibers / mm
- the bundle thickness was 0.07 mm
- the drape value was 54 mm
- the bundle hardness was 27 g.
- a separation iron plate having a projecting shape with a thickness of 0.07 mm, a width of 3 mm and a height of 20 mm is provided in the width direction of the reinforcing fiber bundle
- separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The operation of piercing again was repeated, and the widened reinforcing fiber bundle (1) was separated to obtain a reinforcing fiber bundle (1) having an average number of fibers in the bundle of 930 and an average bundle width of 0.6 mm.
- the present invention can provide a reinforced fiber bundle and a chopped fiber bundle thereof which are excellent in productivity, flowability in molding, and mechanical characteristics of a molded article, a method of producing the same, and a fiber-reinforced resin molding material using the same.
- the reinforcing fiber bundle obtained by the manufacturing method of the present invention is a material of the discontinuous reinforcing fiber composite, and is mainly suitable for automobile interior and exterior, electric / electronic equipment housing, bicycle, aircraft interior material, transport box etc. Used.
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Abstract
A reinforcing fiber bundle characterized in that a first sizing agent including any compound having an epoxy group, a urethane group, an amino group, a carboxyl group, or another functional group, or a mixture of such compounds, and a second sizing agent including a polyamide-based resin are adhered to the surfaces of reinforcing fibers. A method for manufacturing the reinforcing fiber bundle, and a chopped fiber bundle and a fiber-reinforced resin molding material in which the reinforcing fiber bundle is used. Provided are: a reinforcing fiber bundle having excellent production yield or fluidity during molding, and excellent optical characteristics in a molded article, and a chopped fiber bundle obtained from the reinforcing fiber bundle; a method for manufacturing the reinforcing fiber bundle; and a fiber-reinforced resin molding material in which the reinforcing fiber bundle is used.
Description
本発明は、生産性や成形の際の流動性、成形品の力学特性に優れる強化繊維束とそのチョップド繊維束、およびその製造方法、ならびにそれを用いた繊維強化樹脂成形材料その製造方法に関する。
The present invention relates to a reinforced fiber bundle and a chopped fiber bundle which are excellent in productivity, flowability at the time of molding, and mechanical properties of a molded article, a method of producing the same, and a method of producing a fiber reinforced resin molding material using the same.
不連続の強化繊維(例えば、炭素繊維)の束状集合体(以下、繊維束ということもある。)とマトリックス樹脂からなる成形材料を用いて、加熱、加圧成形により、所望形状の成形品を製造する技術は広く知られている。このような成形材料において、単糸数が多い繊維束からなる成形材料では成形の際の流動性には優れるが、成形品の力学特性は劣る傾向がある。これに対し、成形時の流動性と成形品の力学特性の両立を狙い、成形材料内の繊維束として、任意の単糸数に調整した繊維束が使用されている。繊維束の単糸数を調整する方法として、例えば特許文献1、2には、複数の繊維束を事前に巻き取った複数繊維束巻取体を用いて、分繊処理を行う方法が開示されている。しかし、これらの方法は、事前処理の繊維束の単糸数の制約を受けるため、調整範囲が限定され、所望の単糸数へ調整しづらいものであった。
A molded article of a desired shape by heating and pressure molding using a molding material comprising a bundle of discontinuous reinforcing fibers (for example, carbon fibers) (hereinafter also referred to as fiber bundle) and a matrix resin The technology to manufacture is widely known. In such a molding material, a molding material comprising a fiber bundle having a large number of single yarns is excellent in flowability during molding, but the mechanical properties of the molded article tend to be inferior. On the other hand, a fiber bundle adjusted to an arbitrary number of single yarns is used as a fiber bundle in a molding material for the purpose of coexistence of flowability at the time of molding and mechanical characteristics of a molded product. As a method of adjusting the number of single yarns of a fiber bundle, for example, Patent Literatures 1 and 2 disclose a method of performing separation treatment using a multi-fiber bundle winding body in which a plurality of fiber bundles are previously wound. There is. However, since these methods are limited by the number of single yarns of the pre-processed fiber bundle, the adjustment range is limited and it is difficult to adjust to the desired number of single yarns.
また、特許文献3~6には、円盤状の回転刃を用いて繊維束を所望の単糸数に縦スリットする方法が開示されている。これらの方法は、回転刃のピッチを変更することで単糸数の調整が可能ではあるものの、長手方向にわたって縦スリットされた繊維束は集束性がないため、縦スリット後の糸をボビンに巻き取ったり、巻き取ったボビンから繊維束を巻き出すことといった取扱いが困難になりやすい。また、縦スリット後の繊維束を搬送する際には、縦スリットによって発生した枝毛状の繊維束が、ガイドロールや送りロールなどに巻きつき、搬送が容易でなくなる恐れがある。また成形材料とした際に、単糸が多く含まれるため流動性に劣るという問題があった。
Further, Patent Documents 3 to 6 disclose methods of longitudinally slitting a fiber bundle into a desired number of single yarns using a disk-shaped rotary blade. Although these methods can adjust the number of single yarns by changing the pitch of the rotary blade, the longitudinally slit fiber bundle has no convergence, so the yarn after the longitudinal slit is wound on a bobbin. And handling such as unrolling the fiber bundle from the wound bobbin tends to be difficult. In addition, when transporting the fiber bundle after the longitudinal slit, the branched fiber bundle generated by the longitudinal slit may be wound around a guide roll, a feed roll, or the like, and the transport may not be easy. Moreover, when it is set as a molding material, since many single yarns are contained, there existed a problem of being inferior to fluidity.
特許文献7、8には、工程安定性やコンポジット物性向上を狙った、ポリアミド系のサイジング剤が塗布された強化繊維が提案されている。工程安定性やコンポジット物性は向上したものの、サイジング剤塗布工程において乾燥あるいは変性に時間がかかるため生産性に劣るという問題があった。
Patent Documents 7 and 8 propose reinforcing fibers coated with a polyamide-based sizing agent for the purpose of improving process stability and composite physical properties. Although the process stability and the physical properties of the composite are improved, there is a problem that the productivity is inferior because drying or modification takes time in the sizing agent application process.
そこで本発明は、上記要求に鑑み、生産性や成形の際の流動性、成形品の力学特性に優れる強化繊維束とそのチョップド繊維束、およびその製造方法、ならびにそれを用いた繊維強化樹脂成形材料を提供することを課題とする。
Therefore, in view of the above requirements, the present invention provides a reinforced fiber bundle and a chopped fiber bundle excellent in productivity and flowability in molding and mechanical characteristics of a molded product, a method for producing the same, and fiber reinforced resin molding using the same. The task is to provide materials.
上記課題を解決するために、本発明は以下の構成を有する。
(1)強化繊維表面に、エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、または、それらを混合したものを含む第1のサイジング剤と、ポリアミド系樹脂を含む第2のサイジング剤とが付着していることを特徴とする強化繊維束。
(2)単位幅当りの繊維本数が600本/mm以上1,600本/mm未満であり、強化繊維束のドレープ値が120mm以上240mm以下であることを特徴とする、(1)に記載の強化繊維束。
(3)硬度が39g以上200g以下であることを特徴とする(1)または(2)に記載の強化繊維束。
(4)ポリアミド系樹脂の付着量が0.1重量%以上5重量%以下であることを特徴とする(1)~(3)のいずれかに記載の強化繊維束。
(5)前記強化繊維束を5分間水に浸漬後、水から取り出した後における幅をW2とし、浸漬前における幅をW1とした場合の幅変化率W2/W1が0.5以上1.1以下であることを特徴とする(1)~(4)のいずれかに記載の強化繊維束。
(6)前記強化繊維束を25℃、5分間水に浸漬し、絶乾した後の空気中でのドレープ値D2が、110mm以上240mm以下であることを特徴とする(1)~(5)のいずれかに記載の強化繊維束。
(7)複数の束に分繊された分繊処理区間と、未分繊処理区間とが交互に形成されている(1)~(6)のいずれかに記載の強化繊維束。
(8)1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さが異なる長さを含むことを特徴とする、(1)~(7)のいずれかに記載の強化繊維束。
(9)(1)~(8)のいずれかに記載の強化繊維束を切断してなるチョップド繊維束であって、前記チョップド繊維束を25℃、5分間水に浸漬後、取り出した後における幅をW4とし、浸漬前における幅をW3とした場合の幅変化率W4/W3が0.6以上1.1以下であることを特徴とするチョップド繊維束。
(10)前記強化繊繊維束を長手方向に対して所定角度θ(0°<θ<90°)で切断してなる(9)に記載のチョップド繊維束。
(11)(9)または(10)に記載のチョップド繊維束とマトリックス樹脂とを含む繊維強化樹脂成形材料。
(12)前記マトリックス樹脂がポリアミドであることを特徴とする、(11)に記載の繊維強化樹脂成形材料。
(13)エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、または、それらを混合したものを含む第1のサイジング剤が付着した強化繊維に水溶性ポリアミドを付与することを特徴とする強化繊維束の製造方法。
(14)前記強化繊維束を開繊、拡幅する拡幅工程(I)を含むことを特徴とする、(13)に記載の強化繊維束の製造方法
(15)拡幅した前記強化繊維束にサイジング剤を塗布した後に架橋剤と反応させて強化繊維束を作製するサイジング剤付与工程(II)をさらに含むことを特徴とする(14)に記載の強化繊維束の製造方法。
(16)前記架橋剤がメラミン樹脂、ユリア樹脂、フェノール樹脂、エポキシ樹脂から選ばれる少なくとも1種の樹脂からなることを特徴とする、(15)に記載の強化繊維束の製造方法。
(17)前記架橋剤と前記サイジング剤の重量比が0.02以上1以下であることを特徴とする、(14)~(16)のいずれかに記載の強化繊維束の製造方法。
(18)前記サイジング剤付与工程(II)において、強化繊維束の全サイジング剤付着量が0.5重量%以上5重量%以下となるように前記サイジング剤を塗布することを特徴とする、(14)~(17)のいずれかに記載の強化繊維束の製造方法。
(19)前記拡幅工程(I)において、強化繊維束の単位幅あたりの単糸数が1,600本/mm以下になるように拡幅することを特徴とする、(14)~(18)のいずれかに記載の強化繊維束の製造方法。
(20)水溶性ポリアミドが付与された前記強化繊維を熱処理する工程を含むことを特徴とする、(13)~(19)のいずれかに記載の強化繊維束の製造方法。
(21)前記熱処理の温度が130~350℃であることを特徴とする、(20)に記載の強化繊維束の製造方法。
(22)前記熱処理の時間が0.33~15分であることを特徴とする、(20)または(21)に記載の強化繊維束の製造方法。
(23)前記熱処理後の水溶性ポリアミドがエステル結合、および/または、炭素-炭素の二重結合を有することを特徴とする、(20)~(22)のいずれかに記載の強化繊維束の製造方法。
(24)前記水溶性ポリアミドが、主鎖中に三級アミノ基および/またはオキシエチレン基を有するジアミンとジカルボン酸とを重合して得られたものからなることを特徴とする、(13)~(23)のいずれかに記載の強化繊維束の製造方法。
(25)前記強化繊維を分繊処理する工程を含むことを特徴とする、(13)~(24)のいずれかに記載の強化繊維束の製造方法。
(26)前記強化繊維束を長手方向に沿って走行させながら、複数の突出部を具備する分繊手段を前記強化繊維束に突き入れて分繊処理部を生成する分繊工程(III)と、
少なくとも1つの前記分繊処理部における前記突出部と前記強化繊維束との接触部に単糸が交絡する絡合部を形成する絡合工程(IV)と、
前記分繊手段を前記強化繊維束から抜き取り、前記絡合部を含む絡合蓄積部を通過させた後、前記分繊手段を前記強化繊維束に再度突き入れる再突き入れ工程(V)と、
複数の束に分割された分繊処理区間と未分繊処理区間とを交互に形成する分繊処理工程(VI)とをさらに含むことを特徴とする、(13)~(25)のいずれかに記載の強化繊維束の製造方法。
(27)前記分繊処理工程(VI)において、1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さが異なる長さを含むことを特徴とする(26)に記載の強化繊維束の製造方法。 In order to solve the above-mentioned subject, the present invention has the following composition.
(1) A first sizing agent containing a compound having a functional group such as an epoxy group, a urethane group, an amino group and a carboxyl group on the surface of a reinforcing fiber, or a mixture thereof, and a polyamide resin A reinforcing fiber bundle characterized in that it contains a second sizing agent.
(2) The fiber number per unit width is not less than 600 / mm and less than 1,600 / mm, and the drape value of the reinforcing fiber bundle is not less than 120 mm and not more than 240 mm, described in (1) Reinforcement fiber bundle.
(3) The reinforcing fiber bundle according to (1) or (2), which has a hardness of 39 g or more and 200 g or less.
(4) The reinforcing fiber bundle according to any one of (1) to (3), wherein the adhesion amount of the polyamide resin is 0.1% by weight or more and 5% by weight or less.
(5) After immersing the reinforcing fiber bundle in water for 5 minutes, the width after taking out from water is W2, and the width change ratio W2 / W1 is 0.5 or more and 1.1 when the width before immersion is W1. The reinforcing fiber bundle according to any one of (1) to (4), which is characterized by the following.
(6) The reinforced fiber bundle is immersed in water at 25 ° C. for 5 minutes, and after drying, the drape value D2 in air is 110 mm or more and 240 mm or less (1) to (5) The reinforcing fiber bundle according to any one of the above.
(7) The reinforced fiber bundle according to any one of (1) to (6), in which a separation treatment section divided into a plurality of bundles and an undivision treatment section are alternately formed.
(8) The reinforced fiber bundle according to any one of (1) to (7), characterized in that the lengths of adjacent division processing sections including one undivided processing section include different lengths. .
(9) A chopped fiber bundle obtained by cutting the reinforcing fiber bundle according to any one of (1) to (8), wherein the chopped fiber bundle is immersed in water at 25 ° C. for 5 minutes and then taken out. A chopped fiber bundle characterized in that a width change ratio W4 / W3 when the width is W4 and the width before immersion is W3 is 0.6 or more and 1.1 or less.
(10) The chopped fiber bundle according to (9), which is obtained by cutting the reinforcing fiber bundle at a predetermined angle θ (0 ° <θ <90 °) with respect to the longitudinal direction.
(11) A fiber-reinforced resin molding material comprising the chopped fiber bundle according to (9) or (10) and a matrix resin.
(12) The fiber-reinforced resin molding material according to (11), wherein the matrix resin is a polyamide.
(13) The water-soluble polyamide is imparted to the reinforcing fiber to which the first sizing agent including any of compounds having functional groups such as epoxy group, urethane group, amino group and carboxyl group or a mixture thereof is attached The manufacturing method of the reinforced fiber bundle characterized by doing.
(14) The method for producing a reinforcing fiber bundle according to (13), including a widening step (I) for opening and widening the reinforcing fiber bundle (15) A sizing agent for the widening reinforcing fiber bundle The method for producing a reinforced fiber bundle according to (14), further comprising a sizing agent application step (II) of producing a reinforced fiber bundle by reacting with a crosslinking agent after applying.
(16) The method for producing a reinforced fiber bundle according to (15), wherein the crosslinking agent comprises at least one resin selected from melamine resin, urea resin, phenol resin and epoxy resin.
(17) The method for producing a reinforcing fiber bundle according to any one of (14) to (16), wherein the weight ratio of the crosslinking agent to the sizing agent is 0.02 or more and 1 or less.
(18) In the sizing agent applying step (II), the sizing agent is applied such that the total sizing agent adhesion amount of the reinforcing fiber bundle is 0.5% by weight or more and 5% by weight or less ( 14) The method for producing a reinforcing fiber bundle according to any one of (17) to (17).
(19) In the widening step (I), widening is performed so that the number of single yarns per unit width of the reinforcing fiber bundle is not more than 1,600 / mm, any of (14) to (18) The manufacturing method of the reinforced fiber bundle as described in.
(20) The method for producing a reinforcing fiber bundle according to any one of (13) to (19), including the step of heat treating the reinforcing fiber to which a water-soluble polyamide is imparted.
(21) The method for producing a reinforced fiber bundle according to (20), wherein the temperature of the heat treatment is 130 to 350 ° C.
(22) The method for producing a reinforcing fiber bundle according to (20) or (21), wherein the heat treatment time is 0.33 to 15 minutes.
(23) The reinforcing fiber bundle according to any one of (20) to (22), wherein the water-soluble polyamide after the heat treatment has an ester bond and / or a carbon-carbon double bond. Production method.
(24) The water-soluble polyamide is obtained by polymerizing a diamine having a tertiary amino group and / or an oxyethylene group in the main chain and a dicarboxylic acid, (13) The manufacturing method of the reinforced fiber bundle in any one of (23).
(25) The method for producing a reinforcing fiber bundle according to any one of (13) to (24), including the step of separating the reinforcing fibers.
(26) A separation step (III) in which a separation means having a plurality of protrusions is pushed into the reinforcement fiber bundle to generate a separation treatment part while traveling the reinforcement fiber bundle along the longitudinal direction ,
An intertwining step (IV) of forming an intertwining portion in which a single yarn is intertwined in a contact portion between the protruding portion and the reinforcing fiber bundle in at least one of the separation processing portions;
Re-piercing step (V) in which the separating means is extracted from the reinforcing fiber bundle, passed through the entanglement storage part including the entangled part, and then the separating means is reinserted into the reinforcing fiber bundle;
(13) Any one of (13) to (25), further including a fiber separation treatment step (VI) of alternately forming a fiber separation treated section divided into a plurality of bundles and an unsorted fiber treatment processed section. The manufacturing method of the reinforced fiber bundle as described in.
(27) The reinforcement according to (26), wherein in the separation treatment step (VI), the lengths of the separation treatment sections adjacent to each other across one undivided treatment section include different lengths. Method of manufacturing fiber bundle.
(1)強化繊維表面に、エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、または、それらを混合したものを含む第1のサイジング剤と、ポリアミド系樹脂を含む第2のサイジング剤とが付着していることを特徴とする強化繊維束。
(2)単位幅当りの繊維本数が600本/mm以上1,600本/mm未満であり、強化繊維束のドレープ値が120mm以上240mm以下であることを特徴とする、(1)に記載の強化繊維束。
(3)硬度が39g以上200g以下であることを特徴とする(1)または(2)に記載の強化繊維束。
(4)ポリアミド系樹脂の付着量が0.1重量%以上5重量%以下であることを特徴とする(1)~(3)のいずれかに記載の強化繊維束。
(5)前記強化繊維束を5分間水に浸漬後、水から取り出した後における幅をW2とし、浸漬前における幅をW1とした場合の幅変化率W2/W1が0.5以上1.1以下であることを特徴とする(1)~(4)のいずれかに記載の強化繊維束。
(6)前記強化繊維束を25℃、5分間水に浸漬し、絶乾した後の空気中でのドレープ値D2が、110mm以上240mm以下であることを特徴とする(1)~(5)のいずれかに記載の強化繊維束。
(7)複数の束に分繊された分繊処理区間と、未分繊処理区間とが交互に形成されている(1)~(6)のいずれかに記載の強化繊維束。
(8)1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さが異なる長さを含むことを特徴とする、(1)~(7)のいずれかに記載の強化繊維束。
(9)(1)~(8)のいずれかに記載の強化繊維束を切断してなるチョップド繊維束であって、前記チョップド繊維束を25℃、5分間水に浸漬後、取り出した後における幅をW4とし、浸漬前における幅をW3とした場合の幅変化率W4/W3が0.6以上1.1以下であることを特徴とするチョップド繊維束。
(10)前記強化繊繊維束を長手方向に対して所定角度θ(0°<θ<90°)で切断してなる(9)に記載のチョップド繊維束。
(11)(9)または(10)に記載のチョップド繊維束とマトリックス樹脂とを含む繊維強化樹脂成形材料。
(12)前記マトリックス樹脂がポリアミドであることを特徴とする、(11)に記載の繊維強化樹脂成形材料。
(13)エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、または、それらを混合したものを含む第1のサイジング剤が付着した強化繊維に水溶性ポリアミドを付与することを特徴とする強化繊維束の製造方法。
(14)前記強化繊維束を開繊、拡幅する拡幅工程(I)を含むことを特徴とする、(13)に記載の強化繊維束の製造方法
(15)拡幅した前記強化繊維束にサイジング剤を塗布した後に架橋剤と反応させて強化繊維束を作製するサイジング剤付与工程(II)をさらに含むことを特徴とする(14)に記載の強化繊維束の製造方法。
(16)前記架橋剤がメラミン樹脂、ユリア樹脂、フェノール樹脂、エポキシ樹脂から選ばれる少なくとも1種の樹脂からなることを特徴とする、(15)に記載の強化繊維束の製造方法。
(17)前記架橋剤と前記サイジング剤の重量比が0.02以上1以下であることを特徴とする、(14)~(16)のいずれかに記載の強化繊維束の製造方法。
(18)前記サイジング剤付与工程(II)において、強化繊維束の全サイジング剤付着量が0.5重量%以上5重量%以下となるように前記サイジング剤を塗布することを特徴とする、(14)~(17)のいずれかに記載の強化繊維束の製造方法。
(19)前記拡幅工程(I)において、強化繊維束の単位幅あたりの単糸数が1,600本/mm以下になるように拡幅することを特徴とする、(14)~(18)のいずれかに記載の強化繊維束の製造方法。
(20)水溶性ポリアミドが付与された前記強化繊維を熱処理する工程を含むことを特徴とする、(13)~(19)のいずれかに記載の強化繊維束の製造方法。
(21)前記熱処理の温度が130~350℃であることを特徴とする、(20)に記載の強化繊維束の製造方法。
(22)前記熱処理の時間が0.33~15分であることを特徴とする、(20)または(21)に記載の強化繊維束の製造方法。
(23)前記熱処理後の水溶性ポリアミドがエステル結合、および/または、炭素-炭素の二重結合を有することを特徴とする、(20)~(22)のいずれかに記載の強化繊維束の製造方法。
(24)前記水溶性ポリアミドが、主鎖中に三級アミノ基および/またはオキシエチレン基を有するジアミンとジカルボン酸とを重合して得られたものからなることを特徴とする、(13)~(23)のいずれかに記載の強化繊維束の製造方法。
(25)前記強化繊維を分繊処理する工程を含むことを特徴とする、(13)~(24)のいずれかに記載の強化繊維束の製造方法。
(26)前記強化繊維束を長手方向に沿って走行させながら、複数の突出部を具備する分繊手段を前記強化繊維束に突き入れて分繊処理部を生成する分繊工程(III)と、
少なくとも1つの前記分繊処理部における前記突出部と前記強化繊維束との接触部に単糸が交絡する絡合部を形成する絡合工程(IV)と、
前記分繊手段を前記強化繊維束から抜き取り、前記絡合部を含む絡合蓄積部を通過させた後、前記分繊手段を前記強化繊維束に再度突き入れる再突き入れ工程(V)と、
複数の束に分割された分繊処理区間と未分繊処理区間とを交互に形成する分繊処理工程(VI)とをさらに含むことを特徴とする、(13)~(25)のいずれかに記載の強化繊維束の製造方法。
(27)前記分繊処理工程(VI)において、1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さが異なる長さを含むことを特徴とする(26)に記載の強化繊維束の製造方法。 In order to solve the above-mentioned subject, the present invention has the following composition.
(1) A first sizing agent containing a compound having a functional group such as an epoxy group, a urethane group, an amino group and a carboxyl group on the surface of a reinforcing fiber, or a mixture thereof, and a polyamide resin A reinforcing fiber bundle characterized in that it contains a second sizing agent.
(2) The fiber number per unit width is not less than 600 / mm and less than 1,600 / mm, and the drape value of the reinforcing fiber bundle is not less than 120 mm and not more than 240 mm, described in (1) Reinforcement fiber bundle.
(3) The reinforcing fiber bundle according to (1) or (2), which has a hardness of 39 g or more and 200 g or less.
(4) The reinforcing fiber bundle according to any one of (1) to (3), wherein the adhesion amount of the polyamide resin is 0.1% by weight or more and 5% by weight or less.
(5) After immersing the reinforcing fiber bundle in water for 5 minutes, the width after taking out from water is W2, and the width change ratio W2 / W1 is 0.5 or more and 1.1 when the width before immersion is W1. The reinforcing fiber bundle according to any one of (1) to (4), which is characterized by the following.
(6) The reinforced fiber bundle is immersed in water at 25 ° C. for 5 minutes, and after drying, the drape value D2 in air is 110 mm or more and 240 mm or less (1) to (5) The reinforcing fiber bundle according to any one of the above.
(7) The reinforced fiber bundle according to any one of (1) to (6), in which a separation treatment section divided into a plurality of bundles and an undivision treatment section are alternately formed.
(8) The reinforced fiber bundle according to any one of (1) to (7), characterized in that the lengths of adjacent division processing sections including one undivided processing section include different lengths. .
(9) A chopped fiber bundle obtained by cutting the reinforcing fiber bundle according to any one of (1) to (8), wherein the chopped fiber bundle is immersed in water at 25 ° C. for 5 minutes and then taken out. A chopped fiber bundle characterized in that a width change ratio W4 / W3 when the width is W4 and the width before immersion is W3 is 0.6 or more and 1.1 or less.
(10) The chopped fiber bundle according to (9), which is obtained by cutting the reinforcing fiber bundle at a predetermined angle θ (0 ° <θ <90 °) with respect to the longitudinal direction.
(11) A fiber-reinforced resin molding material comprising the chopped fiber bundle according to (9) or (10) and a matrix resin.
(12) The fiber-reinforced resin molding material according to (11), wherein the matrix resin is a polyamide.
(13) The water-soluble polyamide is imparted to the reinforcing fiber to which the first sizing agent including any of compounds having functional groups such as epoxy group, urethane group, amino group and carboxyl group or a mixture thereof is attached The manufacturing method of the reinforced fiber bundle characterized by doing.
(14) The method for producing a reinforcing fiber bundle according to (13), including a widening step (I) for opening and widening the reinforcing fiber bundle (15) A sizing agent for the widening reinforcing fiber bundle The method for producing a reinforced fiber bundle according to (14), further comprising a sizing agent application step (II) of producing a reinforced fiber bundle by reacting with a crosslinking agent after applying.
(16) The method for producing a reinforced fiber bundle according to (15), wherein the crosslinking agent comprises at least one resin selected from melamine resin, urea resin, phenol resin and epoxy resin.
(17) The method for producing a reinforcing fiber bundle according to any one of (14) to (16), wherein the weight ratio of the crosslinking agent to the sizing agent is 0.02 or more and 1 or less.
(18) In the sizing agent applying step (II), the sizing agent is applied such that the total sizing agent adhesion amount of the reinforcing fiber bundle is 0.5% by weight or more and 5% by weight or less ( 14) The method for producing a reinforcing fiber bundle according to any one of (17) to (17).
(19) In the widening step (I), widening is performed so that the number of single yarns per unit width of the reinforcing fiber bundle is not more than 1,600 / mm, any of (14) to (18) The manufacturing method of the reinforced fiber bundle as described in.
(20) The method for producing a reinforcing fiber bundle according to any one of (13) to (19), including the step of heat treating the reinforcing fiber to which a water-soluble polyamide is imparted.
(21) The method for producing a reinforced fiber bundle according to (20), wherein the temperature of the heat treatment is 130 to 350 ° C.
(22) The method for producing a reinforcing fiber bundle according to (20) or (21), wherein the heat treatment time is 0.33 to 15 minutes.
(23) The reinforcing fiber bundle according to any one of (20) to (22), wherein the water-soluble polyamide after the heat treatment has an ester bond and / or a carbon-carbon double bond. Production method.
(24) The water-soluble polyamide is obtained by polymerizing a diamine having a tertiary amino group and / or an oxyethylene group in the main chain and a dicarboxylic acid, (13) The manufacturing method of the reinforced fiber bundle in any one of (23).
(25) The method for producing a reinforcing fiber bundle according to any one of (13) to (24), including the step of separating the reinforcing fibers.
(26) A separation step (III) in which a separation means having a plurality of protrusions is pushed into the reinforcement fiber bundle to generate a separation treatment part while traveling the reinforcement fiber bundle along the longitudinal direction ,
An intertwining step (IV) of forming an intertwining portion in which a single yarn is intertwined in a contact portion between the protruding portion and the reinforcing fiber bundle in at least one of the separation processing portions;
Re-piercing step (V) in which the separating means is extracted from the reinforcing fiber bundle, passed through the entanglement storage part including the entangled part, and then the separating means is reinserted into the reinforcing fiber bundle;
(13) Any one of (13) to (25), further including a fiber separation treatment step (VI) of alternately forming a fiber separation treated section divided into a plurality of bundles and an unsorted fiber treatment processed section. The manufacturing method of the reinforced fiber bundle as described in.
(27) The reinforcement according to (26), wherein in the separation treatment step (VI), the lengths of the separation treatment sections adjacent to each other across one undivided treatment section include different lengths. Method of manufacturing fiber bundle.
本発明に係る強化繊維束の製造方法によれば、分繊・形態安定化された強化繊維束の生産性を高めることが可能になる。得られた強化繊維束を切断/散布し、不連続繊維中間基材とした際に、成形の際の流動性と成形品の力学特性をバランスよく発現させることができる。
According to the method of manufacturing a reinforcing fiber bundle of the present invention, it is possible to enhance the productivity of the divided fiber / shape-stabilized reinforcing fiber bundle. When the obtained reinforcing fiber bundle is cut / dispersed to form a discontinuous fiber intermediate substrate, the flowability during molding and the mechanical properties of the molded article can be well-balancedly expressed.
本発明で使用される強化繊維の種類としては制限がないが、炭素繊維、ガラス繊維、アラミド繊維、金属繊維が好ましい。なかでも炭素繊維が好ましい。炭素繊維としては、特に限定されないが、例えば、ポリアクリロニトリル(PAN)系、ピッチ系、レーヨン系などの炭素繊維が力学特性の向上、繊維強化熱可塑性樹脂の軽量化効果の観点から好ましく使用でき、これらは1種または2種以上を併用してもよい。中でも、得られる繊維強化熱可塑性樹脂の強度と弾性率とのバランスの観点から、PAN系炭素繊維がさらに好ましい。
Although there is no restriction | limiting as a kind of reinforcing fiber used by this invention, A carbon fiber, glass fiber, an aramid fiber, and a metal fiber are preferable. Among them, carbon fiber is preferable. The carbon fiber is not particularly limited, but for example, carbon fibers of polyacrylonitrile (PAN), pitch, rayon and the like can be preferably used from the viewpoint of the improvement of the mechanical properties and the weight reduction effect of the fiber reinforced thermoplastic resin, These may be used alone or in combination of two or more. Among them, PAN-based carbon fibers are more preferable from the viewpoint of the balance between the strength and elastic modulus of the fiber-reinforced thermoplastic resin to be obtained.
強化繊維の単繊維径は0.5μm以上が好ましく、2μm以上がより好ましく、4μm以上がさらに好ましい。また、強化繊維の単繊維径は20μm以下が好ましく、15μm以下がより好ましく、10μm以下がさらに好ましい。強化繊維のストランド強度は3.0GPa以上が好ましく、4.0GPa以上がより好ましく、4.5GPa以上がさらに好ましい。強化繊維のストランド弾性率は200GPa以上が好ましく、220GPa以上がより好ましく、240GPa以上がさらに好ましい。強化繊維のストランド強度または弾性率がそれぞれ、この範囲であれば、成形品の力学特性を高めることができる。
The single fiber diameter of the reinforcing fiber is preferably 0.5 μm or more, more preferably 2 μm or more, and still more preferably 4 μm or more. Moreover, 20 micrometers or less are preferable, as for the single fiber diameter of a reinforced fiber, 15 micrometers or less are more preferable, and 10 micrometers or less are more preferable. The strand strength of the reinforcing fiber is preferably 3.0 GPa or more, more preferably 4.0 GPa or more, and still more preferably 4.5 GPa or more. 200 GPa or more is preferable, as for the strand elasticity modulus of a reinforced fiber, 220 GPa or more is more preferable, and 240 GPa or more is more preferable. If the strand strength or elastic modulus of the reinforcing fiber is in this range, respectively, the mechanical properties of the molded article can be enhanced.
強化繊維束を拡幅する工程において、拡幅された強化繊維束の単位幅あたり単糸数は600本/mm以上が好ましく、700本/mm以上がより好ましく、800本/mm以上がさらに好ましい。600本/mm未満の場合、成形材料の流動性に劣る懸念がある。強化繊維束の単位幅あたり単糸数は1,600本/mm以下が好ましく、1,400本/mm以下がより好ましく、1,200本/mm以下がさらに好ましい。1,600本/mmを超える場合、成形品の力学特性が劣る懸念がある。繊維強化樹脂成形材料を構成する強化繊維束の単位幅あたり単糸数の導出方法は後述する。
In the step of expanding the reinforcing fiber bundle, the number of single yarns per unit width of the expanded reinforcing fiber bundle is preferably 600 yarns / mm or more, more preferably 700 yarns / mm or more, and still more preferably 800 yarns / mm or more. If it is less than 600 / mm, there is a concern that the flowability of the molding material may be poor. The number of single yarns per unit width of the reinforcing fiber bundle is preferably 1,600 / mm or less, more preferably 1,400 / mm or less, and even more preferably 1,200 / mm or less. If it exceeds 1,600 / mm, there is a concern that the mechanical properties of the molded article may be inferior. The method of deriving the number of single yarns per unit width of the reinforcing fiber bundle constituting the fiber reinforced resin molding material will be described later.
強化繊維を拡幅する工程において、拡幅された強化繊維束の厚みは0.01mm以上が好ましく、0.03mm以上がより好ましく、0.05mm以上がさらに好ましい。0.01mm未満の場合、成形材料の流動性に劣る懸念がある。また、強化繊維束の厚みは0.2mm以下が好ましく、0.18mm以下がより好ましく、0.16mm以下がさらに好ましい。0.2mmを超える場合、成形品の力学特性が劣る懸念がある。
In the step of widening the reinforcing fibers, the thickness of the widened reinforcing fiber bundle is preferably 0.01 mm or more, more preferably 0.03 mm or more, and still more preferably 0.05 mm or more. If it is less than 0.01 mm, there is a concern that the flowability of the molding material may be poor. The thickness of the reinforcing fiber bundle is preferably 0.2 mm or less, more preferably 0.18 mm or less, and still more preferably 0.16 mm or less. If it exceeds 0.2 mm, there is a concern that the mechanical properties of the molded article may be inferior.
本発明で使用されるサイジング剤は1次サイジング剤と2次サイジング剤からなる。1次サイジング剤がまず強化繊維束に付与され、その後、2次サイジング剤が強化繊維束に付与される。2次サイジング剤の種類としては、水溶性ポリアミドを主成分として含有することがよく、水溶性ポリアミドは主鎖中に三級アミノ基および/またはオキシエチレン基を有するジアミンとカルボン酸より重縮合して得られるポリアミド樹脂であり、前記ジアミンとして、ピペラジン環を有するN、N′-ビス(γ―アミノプロピル)ピペラジン、N-(β―アミノエチル)ピペラジン等主鎖中に三級アミノ基を含むモノマ、オキシエチレンアルキルアミン等の主鎖中にオキシエチレン基を含むアルキルジアミンが有用である。又、ジカルボン酸としてはアジピン酸、セバシン酸等がある。また、1次サイジング剤には、熱処理温度を低くしたり、熱処理時間を短縮したりするため、エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、あるいは、それらを混合したものがよい。また、あらかじめ溶剤あるいは強化繊維表層に架橋剤を添加することがよい。架橋剤の種類としては特に限定されないが、メラミン樹脂、ユリア樹脂、フェノール樹脂、エポキシ樹脂から選ばれる少なくとも1種の樹脂であることが好ましい。サイジング剤に対する架橋剤の重量比の下限は0.02以上が好ましく、0.03以上がより好ましく、0.04以上がさらに好ましい。一方、サイジング剤に対する架橋剤の重量比の上限は1以下が好ましく、0.8以下がより好ましく、0.6以下がさらに好ましい。この範囲であれば熱処理温度を低くしたり、熱処理時間を短縮することが可能である。
The sizing agent used in the present invention comprises a primary sizing agent and a secondary sizing agent. The primary sizing agent is first applied to the reinforcing fiber bundle, and then the secondary sizing agent is applied to the reinforcing fiber bundle. As a type of secondary sizing agent, a water-soluble polyamide is preferably contained as a main component, and the water-soluble polyamide is polycondensed from a diamine having a tertiary amino group and / or an oxyethylene group in the main chain and a carboxylic acid. The polyamide resin is obtained by the following method: N, N'-bis (.gamma.-aminopropyl) piperazine having a piperazine ring, N-(. Beta.-aminoethyl) piperazine or the like containing a tertiary amino group in the main chain as the diamine Alkyl diamines containing oxyethylene groups in the main chain of monomers, oxyethylene alkylamines and the like are useful. Examples of dicarboxylic acids include adipic acid and sebacic acid. In addition, as the primary sizing agent, any of compounds having functional groups such as epoxy group, urethane group, amino group, carboxyl group or the like in order to lower the heat treatment temperature or shorten the heat treatment time. What mixed is good. In addition, it is preferable to add a crosslinking agent to the solvent or the surface layer of the reinforcing fiber in advance. Although it does not specifically limit as a kind of crosslinking agent, It is preferable that it is at least 1 sort (s) of resin chosen from a melamine resin, a urea resin, a phenol resin, and an epoxy resin. The lower limit of the weight ratio of the crosslinking agent to the sizing agent is preferably 0.02 or more, more preferably 0.03 or more, and still more preferably 0.04 or more. On the other hand, the upper limit of the weight ratio of the crosslinking agent to the sizing agent is preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.6 or less. Within this range, it is possible to lower the heat treatment temperature or shorten the heat treatment time.
本発明の水溶性のポリアミドは共重合体であってもよい。共重合成分としては、例えばα-ピロリドン、α-ピペリドン、ε-カプロラクタム、α-メチル-ε-カプロラクタム、ε-メチル-ε-カプロラクタム、ε-ラウロラクタムなどのラクタムをあげることができ、二元共重合もしくは多元共重合も可能であるが、共重合比率は水溶性という物性を妨げない範囲において決定される。好ましくはラクタム環を持つ共重合成分比率を30重量%以内にしないとポリマーが水に完溶しなくなる。
The water-soluble polyamide of the present invention may be a copolymer. Examples of the copolymerization component include lactams such as α-pyrrolidone, α-piperidone, ε-caprolactam, α-methyl-ε-caprolactam, ε-methyl-ε-caprolactam, ε-laurolactam, etc. Although copolymerization or multi-component copolymerization is also possible, the copolymerization ratio is determined within a range that does not interfere with the physical property of water solubility. Preferably, the polymer does not completely dissolve in water unless the proportion of copolymerization components having a lactam ring is within 30% by weight.
しかしながら、前記範囲外の共重合成分比率に難水溶性のポリマーであっても、有機及び無機酸を用いて溶液を酸性にした場合溶解性が増大し、水可溶性になり使用が可能になる。有機酸としては、酢酸、クロル酢酸、プロピオン酸、マレイン酸、しゅう酸、フルオロ酢酸等があり、無機酸としては、一般的な鉱酸類である塩酸、硫酸、リン酸等を挙げることができる。
However, even if the polymer is a poorly water-soluble polymer having a copolymerization component ratio outside the above range, the solubility is increased when the solution is made acidic using an organic and inorganic acid, and it becomes water soluble and can be used. Examples of the organic acid include acetic acid, chloracetic acid, propionic acid, maleic acid, oxalic acid and fluoroacetic acid, and examples of the inorganic acid include common mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
この水溶性ポリアミドはサイジング剤が付与されていない強化繊維束に1次サイジング剤として用いてもよいし、サイジング剤が前もって付与されている強化繊維束に2次サイジング剤として用いてもよい。
This water-soluble polyamide may be used as a primary sizing agent for reinforcing fiber bundles to which a sizing agent has not been applied, or as a secondary sizing agent to reinforcing fiber bundles to which a sizing agent has been applied beforehand.
強化繊維束に付与された全サイジング剤の付着量は5重量%以下が好ましく、4重量%以下がより好ましく、3重量%以下がさらに好ましい。サイジング剤の付着量が5重量%を超えると、繊維束の柔軟性が欠けてきて硬くなりすぎ、ボビンの巻き取り、巻き出しがスムーズにいかなくなる可能性がある。また、カット時に単糸割れを引き起こし、理想のチョップド繊維束形態が得られない可能性が生じる。サイジング剤の付着量は0.1重量%以上が好ましく、0.3重量%以上がより好ましく、0.5重量%以上がさらに好ましい。
5 weight% or less is preferable, as for the adhesion amount of all the sizing agents provided to the reinforcement fiber bundle, 4 weight% or less is more preferable, and 3 weight% or less is more preferable. If the adhesion amount of the sizing agent exceeds 5% by weight, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in failure to obtain an ideal chopped fiber bundle form. 0.1 weight% or more is preferable, as for the adhesion amount of a sizing agent, 0.3 weight% or more is more preferable, and 0.5 weight% or more is more preferable.
サイジング剤の付着量が0.1重量%未満の場合、成形品を作製しようとすると、マトリックスと強化繊維との接着性が低下する傾向にあり、成形品の力学特性が低くなる可能性がある。また、フィラメントがばらけ、毛羽が発生することにより、ボビンからの巻き出し性が低下したり、ニップローラー、カッター刃への巻きつきが発生しうる。サイジング剤の付着量の導出方法は後述する。
If the adhesion amount of the sizing agent is less than 0.1% by weight, the adhesion between the matrix and the reinforcing fibers tends to be reduced, and the mechanical properties of the molded article may be lowered, when trying to produce the molded article . In addition, since the filament is broken and fluff is generated, the unwinding property from the bobbin may be reduced, and winding on the nip roller and the cutter blade may occur. The method for deriving the adhesion amount of the sizing agent will be described later.
サイジング剤は、強化繊維表面に均質に付着したものであることが好ましい。均質に付着させる方法としては特に限定されるものではないが、例えば、これらサイジング剤を水またはアルコール、酸性水溶液0.1重量%以上、好ましくは1重量%~20重量%の濃度に溶解して、その高分子溶液にローラーを介して繊維束をサイジング剤処理液に浸漬する方法、サイジング剤処理液の付着したローラーに繊維束を接する方法、サイジング剤処理液を霧状にして繊維束に吹き付ける方法などがある。この際、繊維に対するサイジング剤有効成分の付着量が適正範囲内で均一に付着するように、サイジング剤処理液濃度、温度、糸条張力などをコントロールすることが好ましい。また、サイジング剤付与時に繊維束を超音波で加振させることはより好ましい。
The sizing agent is preferably uniformly attached to the surface of the reinforcing fiber. There is no particular limitation on the method of depositing uniformly, for example, these sizing agents are dissolved in water or alcohol, an aqueous acidic solution of 0.1% by weight or more, preferably in a concentration of 1% by weight to 20% by weight. The method of immersing the fiber bundle in the sizing agent treatment liquid through the roller in the polymer solution, the method of contacting the fiber bundle with the roller to which the sizing agent treatment liquid is attached, spraying the sizing agent treatment liquid in the form of mist There is a method. At this time, it is preferable to control the sizing agent processing solution concentration, temperature, yarn tension and the like so that the adhesion amount of the sizing agent active component to the fibers uniformly adheres within an appropriate range. Moreover, it is more preferable to vibrate the fiber bundle with ultrasonic waves at the time of applying the sizing agent.
強化繊維束に付着したサイジング剤中の水やアルコールなどの溶剤を除去するには、熱処理や風乾、遠心分離などのいずれの方法を用いてもよいが、中でもコストの観点から熱処理が好ましい。熱処理の加熱手段としては、例えば、熱風、熱板、ローラー、赤外線ヒーターなどを使用することができる。この加熱処理条件も重要であり、取り扱い性、マトリックス材との接着性の良否に関わってくる。すなわち、サイジング剤を繊維束に付与した後の加熱処理温度と時間はサイジング剤の成分と付着量によって調整すべきである。前記水溶性ポリアミドの場合、熱劣化を防止する観点から、室温~180℃で乾燥し、水分を除去した後、熱処理するのが好ましい。熱処理温度の下限は130℃以上が好ましく、200℃以上がより好ましい。熱処理温度の上限は350℃以下が好ましく、280℃以下がより好ましい。この熱処理温度は、前記水溶性ポリアミドが空気中の酸素によって自己架橋したり、水溶性を失う温度である。この処理後のポリアミドはエステル結合、および/または、炭素-炭素の二重結合を有してもよい。熱処理により、水溶性ポリマーが不溶になり吸湿性も失うため、フィラメントを集束したストランドのべたつきがなくなり、後加工の作業性が向上するだけでなく、マトリックス材への密着性がよくなり取り扱いやすい繊維束を提供できる。熱処理時間としては0.3分以上が好ましい。また10分以下が好ましく、6分以下がより好ましく、2分以下がさらに好ましい。この範囲であれば、ライン速度を上げ生産性を高めることができる。なお、熱処理後、23±5℃の雰囲気下でエイジング処理を行うことで、繊維束の硬度をさらに高めることができる。
In order to remove the solvent such as water or alcohol in the sizing agent attached to the reinforcing fiber bundle, any method such as heat treatment, air drying, centrifugation and the like may be used, and among them, heat treatment is preferable from the viewpoint of cost. As a heating means of the heat treatment, for example, hot air, a hot plate, a roller, an infrared heater or the like can be used. The heat treatment conditions are also important, and are related to the handling and the adhesion to the matrix material. That is, the heat treatment temperature and time after applying the sizing agent to the fiber bundle should be adjusted according to the components of the sizing agent and the adhesion amount. In the case of the water-soluble polyamide, it is preferable to carry out heat treatment after drying at room temperature to 180 ° C. to remove moisture, from the viewpoint of preventing heat deterioration. 130 degreeC or more is preferable and, as for the minimum of heat processing temperature, 200 degreeC or more is more preferable. 350 degrees C or less is preferable and, as for the upper limit of heat processing temperature, 280 degrees C or less is more preferable. The heat treatment temperature is a temperature at which the water-soluble polyamide self-crosslinks or loses water solubility by oxygen in air. The polyamide after this treatment may have an ester bond and / or a carbon-carbon double bond. The heat treatment makes the water-soluble polymer insoluble and loses the hygroscopicity, so that the filament-concentrated strand is not sticky, the post-processing workability is improved, and the adhesion to the matrix material is improved and the fiber is easy to handle. Can provide a bundle. The heat treatment time is preferably 0.3 minutes or more. Moreover, 10 minutes or less are preferable, 6 minutes or less are more preferable, and 2 minutes or less are more preferable. Within this range, the line speed can be increased to improve productivity. The hardness of the fiber bundle can be further increased by performing the aging treatment in an atmosphere of 23 ± 5 ° C. after the heat treatment.
この水溶性ポリアミド樹脂を用いたサイジング剤は各種マトリックス材との親和性に優れておりコンポジット物性を著しく向上せしめるが、特にポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、及びポリエーテルアミドイミド系樹脂において優れた密着性の改善効果がある。
Sizing agents using this water-soluble polyamide resin are excellent in affinity with various matrix materials and can significantly improve the composite physical properties, but in particular, polyamide resins, polyimide resins, polyamideimide resins, and polyetheramideimide resins It has the effect of improving adhesion in resin.
前記水溶性ポリアミドを2次サイジング剤として用いる場合は、1次サイジング剤が付与された強化繊維束に前記方法と同様のつけ方でもよいし、強化繊維束の製造工程において付与してもよい。特定の強化繊維束の製造において、該強化繊維束の製造工程中のいずれかのタイミングで行われるサイジング剤の付与について例示すると、例えば、サイジング剤を溶媒(分散させる場合の分散媒含む)中に溶解(分散も含む)したサイジング剤処理液を調製し、該サイジング剤処理液を繊維束に塗布した後に、溶媒を乾燥・気化させ、除去することにより、サイジング剤を繊維束に付与することが一般的に行われる。
When the water-soluble polyamide is used as a secondary sizing agent, it may be applied to the reinforcing fiber bundle to which the primary sizing agent is applied in the same manner as the above method, or may be applied in the process of producing the reinforcing fiber bundle. In the production of a specific reinforcing fiber bundle, to illustrate the application of the sizing agent at any time during the manufacturing process of the reinforcing fiber bundle, for example, the sizing agent is contained in a solvent (including a dispersion medium in the case of dispersion). A sizing agent is applied to a fiber bundle by preparing a dissolved (including dispersed) sizing agent treatment liquid and applying the sizing agent treatment liquid to a fiber bundle, followed by drying, evaporation and removal of a solvent. Generally done.
本発明におけるサイジング剤の熱分解開始温度は200℃以上が好ましく、250℃以上がより好ましく、300℃以上がさらに好ましい。熱分解開始温度の導出方法は後述する。
200 degreeC or more is preferable, as for the thermal decomposition start temperature of the sizing agent in this invention, 250 degreeC or more is more preferable, and 300 degreeC or more is more preferable. The method of deriving the thermal decomposition start temperature will be described later.
本発明で使用されるサイジング剤塗布後の強化繊維束のドレープ値D1は120mm以上がよく、145mm以上が好ましく、170mm以上がより好ましい。ドレープ値D1が120mmより小さくなるとフィラメントがばらけ、毛羽が発生することにより、ボビンからの巻き出し性の低下、ニップローラー、カッター刃への巻きつきが発生しうる。また、サイジング剤塗布後の強化繊維束のドレープ値D1は240mm以下であることがよく、230mm以下が好ましく、220mm以下がより好ましい。ドレープ値D1が240mmを超えると、繊維束の柔軟性が欠けてきて硬くなりすぎ、ボビンの巻き取り、巻き出しがスムーズにいかなくなる可能性がある。また、カット時に単糸割れを引き起こし、理想のチョップド繊維束形態が得られない可能性がある。強化繊維束のドレープ値の導出方法は後述する。
The drape value D1 of the reinforcing fiber bundle after application of the sizing agent used in the present invention is preferably 120 mm or more, preferably 145 mm or more, and more preferably 170 mm or more. When the drape value D1 is smaller than 120 mm, the filament is broken and fluff is generated, so that the unwinding property from the bobbin may be reduced and winding on the nip roller and the cutter blade may occur. Moreover, the drape value D1 of the reinforcing fiber bundle after the sizing agent application is preferably 240 mm or less, preferably 230 mm or less, and more preferably 220 mm or less. When the drape value D1 exceeds 240 mm, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, and an ideal chopped fiber bundle form may not be obtained. The method of deriving the drape value of the reinforcing fiber bundle will be described later.
次にドレープ値D1を測定した強化繊維束を25℃の水に、5分間浸漬処理後、取り出し、絶乾した後、前記方法と同様の方法で測定したドレープ値をドレープ値D2とする。ドレープ値D2(束硬さ)の下限は110mm以上が好ましく、145mm以上がより好ましく、170mm以上がさらに好ましい。またドレープ値D1(束硬さ)の上限は240mm以下が好ましく、230mm以下がより好ましく、220mm以下がさらに好ましい。ドレープ値D2が110mmより小さくなるとフィラメントがばらけ、毛羽が発生することにより、ボビンからの巻き出し性の低下、ニップローラー、カッター刃への巻きつきが発生しうる。一方、ドレープ値D2が240mmを超えると、繊維束の柔軟性が欠けてきて硬くなりすぎ、ボビンの巻き取り、巻き出しがスムーズにいかなくなる可能性がある。また、カット時に単糸割れを引き起こし、理想のチョップド繊維形態が得られない可能性が生じる。
Next, after immersing the reinforced fiber bundle whose drape value D1 has been measured in water at 25 ° C. for 5 minutes, it is taken out and completely dried, and the drape value measured by the same method as the above method is taken as the drape value D2. 110 mm or more is preferable, as for the minimum of drape value D2 (bundle hardness), 145 mm or more is more preferable, and 170 mm or more is more preferable. The upper limit of the drape value D1 (bundle hardness) is preferably 240 mm or less, more preferably 230 mm or less, and still more preferably 220 mm or less. When the drape value D2 is smaller than 110 mm, the filament is broken and fluff is generated, which may cause the lowering of the unwinding property from the bobbin and the winding on the nip roller and the cutter blade. On the other hand, when the drape value D2 exceeds 240 mm, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in the failure to obtain an ideal chopped fiber form.
本発明で使用されるサイジング剤塗布後の強化繊維束の束硬度は39g以上が好ましく、70g以上がより好ましく、120g以上がさらに好ましい。硬度が39g未満の場合、フィラメントがばらけ、毛羽が発生することにより、ボビンからの巻き出し性の低下、ニップローラー、カッター刃への巻きつきが発生しうる。繊維強化熱可塑性樹脂成形材料を構成する強化繊維束の束硬度は200g以下であることが好ましく、190g以下がより好ましく、180g以下がさらに好ましい。強化繊維束の硬度が200gを超えると、強化繊維束のワインダーでの巻き取り性が低下し、本発明の効果を発揮しない。強化繊維束の束硬度の導出方法は後述する。
The bundle hardness of the reinforcing fiber bundle after application of the sizing agent used in the present invention is preferably 39 g or more, more preferably 70 g or more, and still more preferably 120 g or more. If the hardness is less than 39 g, the filament may be broken and fuzz may be generated to reduce the unwinding property from the bobbin and to cause winding on the nip roller and the cutter blade. The bundle hardness of the reinforcing fiber bundle constituting the fiber-reinforced thermoplastic resin molding material is preferably 200 g or less, more preferably 190 g or less, and still more preferably 180 g or less. When the hardness of the reinforcing fiber bundle exceeds 200 g, the winding property of the reinforcing fiber bundle in the winder decreases, and the effect of the present invention is not exerted. The method for deriving the bundle hardness of the reinforcing fiber bundle will be described later.
本発明で使用されるサイジング剤塗布後の強化繊維束を水へ浸漬する前の幅をW1、強化繊維束を25℃の水に、5分間浸漬した後、取り出し、1分間水を切った後における幅をW2とすると、強化繊維束の幅変化率W2/W1は0.5以上が好ましく、0.6以上がより好ましく、0.7以上がさらに好ましい。強化繊維束の幅変化率W2/W1が0.5より小さいと強化繊維束に付着されているサイジング剤の水可溶の物性が残っていることにより、分繊処理をした後、分繊された繊維束が再凝集することがあり、再凝集すると、最適な単糸数に調整された繊維束の形態を保持することが困難になる。最適な単糸数に調整された繊維束の形態に保持できないと、分繊繊維束を切断/散布し、不連続繊維束の中間基材とする際に、最適な形態の中間基材にすることが困難となり、成形の際の流動性と成形品の力学特性をバランスよく発現させることが困難となる。また幅変化率W2/W1は1.1以下であることが好ましい。幅変化率W2/W1が1.1を超えると繊維束の柔軟性が欠けてきて硬くなりすぎ、ボビンの巻き取り、巻き出しがスムーズにいかなくなる可能性がある。また、カット時に単糸割れを引き起こし、理想のチョップド繊維束形態が得られない可能性が生じる。強化繊維束の幅変化率W2/W1の導出方法は後述する。
The width before immersing the reinforcing fiber bundle after application of the sizing agent used in the present invention in water is W1, and the reinforcing fiber bundle is immersed in water at 25 ° C. for 5 minutes, then taken out and drained for 1 minute. Assuming that the width of the reinforcing fiber bundle is W2, the width change ratio W2 / W1 of the reinforcing fiber bundle is preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.7 or more. When the width change ratio W2 / W1 of the reinforcing fiber bundle is smaller than 0.5, the water-soluble physical property of the sizing agent attached to the reinforcing fiber bundle remains, so that the fiber is divided after being subjected to fiber separation treatment The fiber bundle may re-aggregate, which makes it difficult to maintain the form of the fiber bundle adjusted to the optimum number of single yarns. If the fiber bundle can not be maintained in the form of a fiber bundle adjusted to the optimum number of single yarns, the split fiber bundle is cut / dispersed to make the intermediate substrate of the optimum form in making the discontinuous fiber bundle an intermediate substrate And it becomes difficult to achieve well-balanced flowability during molding and mechanical properties of the molded article. The width change rate W2 / W1 is preferably 1.1 or less. If the width change ratio W2 / W1 exceeds 1.1, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in failure to obtain an ideal chopped fiber bundle form. The method of deriving the width change ratio W2 / W1 of the reinforcing fiber bundle will be described later.
次に、本発明における分繊繊維束について説明する。分繊繊維束とは、複数の単糸からなる繊維束の長手方向に沿って、複数の束に分繊された分繊処理区間と、未分繊処理区間とが交互に形成された強化繊維束であり、前記強化繊維束にサイジング剤が塗布されているものである。未分繊処理区間は分繊繊維束の幅方向で連続であってもよいし、不連続であってもよい。また、1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さは同一であってもよいし、異なっていてもよい。
Next, the split fiber bundle in the present invention will be described. The separation fiber bundle is a reinforcing fiber in which a separation treatment section divided into a plurality of bundles and a non-division treatment section are alternately formed along a longitudinal direction of a fiber bundle consisting of a plurality of single yarns. It is a bundle, and a sizing agent is applied to the reinforcing fiber bundle. The unsplitted section may be continuous or discontinuous in the width direction of the split fiber bundle. Moreover, the length of the division process area which adjoins one undivided process area may be the same, and may differ.
本発明における分繊繊維束の製造方法について説明する。図1は、本発明における繊維束に分繊処理を施した分繊繊維束の一例を示しており、図2は、その分繊処理の一例を示している。本発明における分繊繊維束の製造方法について、図2を用いて説明する。図2は、走行する繊維束に分繊手段を突き入れた一例を示す(A)概略平面図、(B)概略側面図である。図中の繊維束走行方向a(矢印)が繊維束100の長手方向であり、図示されない繊維束供給装置から連続的に繊維束100が供給されていることを表す。
The manufacturing method of the separation fiber bundle in the present invention will be described. FIG. 1 shows an example of a divided fiber bundle in which the fiber bundle in the present invention is subjected to separation treatment, and FIG. 2 shows an example of the divided treatment. The manufacturing method of the separation fiber bundle in the present invention will be described with reference to FIG. FIG. 2 is (A) a schematic plan view and (B) a schematic side view showing an example in which a separating means is pushed into a traveling fiber bundle. The fiber bundle traveling direction a (arrow) in the figure is the longitudinal direction of the fiber bundle 100, which indicates that the fiber bundle 100 is continuously supplied from a fiber bundle supply device (not shown).
分繊手段200は、繊維束100に突き入れ易い突出形状を有する突出部210を具備しており、走行する繊維束100に突き入れ、繊維束100の長手方向に略平行な分繊処理部150を生成する。ここで、分繊手段200は、繊維束100の側面に沿う方向に突き入れることが好ましい。繊維束の側面とは、繊維束の断面が、横長の楕円もしくは横長の長方形のような扁平形状であるとした場合の断面端部における垂直方向の面(例えば、図2に示す繊維束100の側表面に相当する)である。また、具備する突出部210は、1つの分繊手段200につき1つでもよく、また複数であってもよい。1つの分繊手段200で突出部210が複数ある場合、突出部210の磨耗頻度が減ることから、交換頻度を減らすことも可能となる。さらに、分繊する繊維束数に応じて、複数の分繊手段200を同時に用いることも可能である。複数の分繊手段200を、並列、互い違い、位相をずらす等して、複数の突出部210を任意に配置することができる。
The separating means 200 has a projecting portion 210 having a projecting shape that easily penetrates into the fiber bundle 100, and inserts into the traveling fiber bundle 100, and the separating part 150 substantially parallel to the longitudinal direction of the fiber bundle 100. Generate Here, it is preferable that the separating means 200 pierce in the direction along the side surface of the fiber bundle 100. When the cross section of the fiber bundle is a flat shape such as a horizontally long oval or a horizontally long rectangle, the side surface of the fiber bundle means a vertical surface at the end of the cross section (for example, the fiber bundle 100 shown in FIG. Corresponding to the side surface). In addition, the number of the provided protrusions 210 may be one or more than one per fiber dividing means 200. When there are a plurality of protrusions 210 in one separating means 200, the frequency of wear of the protrusions 210 is reduced, which also makes it possible to reduce the frequency of replacement. Furthermore, it is also possible to use a plurality of separating means 200 simultaneously depending on the number of fiber bundles to be separated. The plurality of separating units 200 can be arranged in parallel, alternately, in a phase-shifted manner, or the like to arbitrarily arrange the plurality of protrusions 210.
複数の単糸からなる繊維束100を、分繊手段200により本数のより少ない分繊束に分けていく場合、複数の単糸は、実質的に繊維束100内で、引き揃った状態ではなく、単糸レベルでは交絡している部分が多いため、分繊処理中に接触部211付近に単糸が交絡する絡合部160を形成する場合がある。
When the fiber bundle 100 consisting of a plurality of single yarns is divided into a smaller number of divided fiber bundles by the separation means 200, the plurality of single yarns are not substantially aligned in the fiber bundle 100. Since there are many entangled parts at the single yarn level, there may be a case where the intertwining part 160 where the single yarn is entangled is formed in the vicinity of the contact part 211 during the separation processing.
ここで、絡合部160を形成するとは、例えば、分繊処理区間内に予め存在していた単糸同士の交絡を分繊手段200により接触部211に形成(移動)させる場合や、分繊手段200によって新たに単糸が交絡した集合体を形成(製造)させる場合等が挙げられる。
Here, forming the entangled portion 160 means, for example, forming (moving) the intermingling of single yarns existing in advance in the separation processing section into the contact part 211 by the separation means 200, or separation The case of forming (manufacturing) an assembly in which single yarns are newly entangled by means 200 may be mentioned.
本発明における分繊繊維束においては強化繊維表面にサイジング剤を塗布しているため、強化繊維同士が拘束されており、上記分繊処理時における擦過等による単糸の発生を大幅に削減することができ、上記記載の絡合部160の発生を大幅に削減することができる。
In the split fiber bundle of the present invention, since the sizing agent is applied to the surface of the reinforcing fibers, the reinforcing fibers are restrained from each other, and the generation of single yarn due to rubbing or the like at the time of the split treatment is significantly reduced. And the occurrence of the entangled portion 160 described above can be significantly reduced.
任意の範囲に分繊処理部150を生成した後、分繊手段200を繊維束100から抜き取る。この抜き取りによって分繊処理が施された分繊処理区間110が生成し、それと同時に上記のように生成された絡合部160が分繊処理区間110の端部部位に蓄積され、絡合部160が蓄積した絡合蓄積部120が生成する。また、分繊処理中に繊維束から発生した毛羽は毛羽溜まり140として分繊処理時に絡合蓄積部120付近に生成する。
After the separation processing unit 150 is generated in an arbitrary range, the separation means 200 is removed from the fiber bundle 100. By this extraction, the separation processing section 110 subjected to the separation processing is generated, and at the same time, the entangled portion 160 generated as described above is accumulated in the end portion of the separation processing section 110, and the entangled portion 160 Is generated by the entanglement storage unit 120 that has accumulated. In addition, the fluff generated from the fiber bundle during the separation processing is generated as the fluff pool 140 in the vicinity of the entanglement accumulation unit 120 during the separation processing.
その後再度分繊手段200を繊維束100に突き入れることで、未分繊処理区間130が生成し、繊維束100の長手方向に沿って、分繊処理区間110と未分繊処理区間130とが交互に配置されてなる分繊繊維束180が形成される。本発明における分繊繊維束180では、未分繊処理区間130の含有率が3%以上50%以下であることが好ましい。ここで、未分繊処理区間130の含有率とは、繊維束100の全長に対し未分繊処理区間130の合計生成長の割合として定義する。未分繊処理区間130の含有率が3%未満だと、分繊繊維束180を切断/散布し、不連続繊維束の中間基材として成形に用いる際の流動性が乏しくなり、50%を超えるとそれを用いて成形した成形品の力学特性が低下する。
Thereafter, the separation means 200 is pushed into the fiber bundle 100 again to generate the undivided treatment section 130, and the separation treatment section 110 and the undivided treatment section 130 are formed along the longitudinal direction of the fiber bundle 100. Split fiber bundles 180 alternately arranged are formed. In the split fiber bundle 180 in the present invention, the content of the unsplit processing section 130 is preferably 3% or more and 50% or less. Here, the content rate of the undivided fiber treatment zone 130 is defined as the ratio of the total generation length of the undivided fiber treated zone 130 to the total length of the fiber bundle 100. If the content rate of the undivided fiber processing section 130 is less than 3%, the divided fiber bundle 180 is cut / dispersed, and the fluidity when used for forming as an intermediate base of the discontinuous fiber bundle becomes poor, 50% If it exceeds, the mechanical properties of a molded article molded using it will be degraded.
また、個々の区間の長さとしては、上記分繊処理区間110の長さが、30mm以上1500mm以下であることが好ましく、上記未分繊処理区間130の長さが、1mm以上150mm以下であることが好ましい。
Moreover, as length of each section, it is preferable that the length of the said division processing area 110 is 30 mm or more and 1500 mm or less, and the length of the said undivision processing area 130 is 1 mm or more and 150 mm or less Is preferred.
繊維束100の走行速度は変動の少ない安定した速度が好ましく、一定の速度がより好ましい。
The traveling speed of the fiber bundle 100 is preferably a stable speed with less fluctuation, and more preferably a constant speed.
分繊手段200は、本発明の目的が達成できる範囲であれば特に制限がなく、金属製の針や薄いプレート等の鋭利な形状のような形状を備えたものが好ましい。分繊手段200は、分繊処理を行う繊維束100の幅方向に対して、複数の分繊手段200を設けることが好ましく、分繊手段200の数は、分繊処理を行う繊維束100の構成単糸本数F(本)によって任意に選択できる。分繊手段200の数は、繊維束100の幅方向に対して、(F/10,000-1)個以上(F/50-1)個未満とすることが好ましい。(F/10,000-1)個未満であると、後工程で強化繊維複合材料にした際に力学特性の向上が発現しにくく、(F/50-1)個以上であると分繊処理時に糸切れや毛羽立ちの恐れがある。
The separating means 200 is not particularly limited as long as the object of the present invention can be achieved, and it is preferable that the separating means 200 has a shape such as a metallic needle or a thin plate. It is preferable that the separating means 200 be provided with a plurality of separating means 200 in the width direction of the fiber bundle 100 to be subjected to the separating treatment, and the number of the separating means 200 is different from that of the fiber bundle 100 to be subjected to the separating treatment. It can select arbitrarily by composition single yarn number F (piece). The number of separating means 200 is preferably (F / 10,000-1) or more and (F / 50-1) or less in the width direction of the fiber bundle 100. When it is less than (F / 10,000-1), improvement of mechanical properties is hardly expressed when it is made into a reinforcing fiber composite material in a later step, and separation treatment is carried out when it is (F / 50-1) or more Sometimes there is a risk of thread breakage or fuzz.
本発明では、繊維束が走行する場合に限らず、図3に示すように、静止状態の繊維束100に対して、分繊手段200を突き入れ(矢印(1))、その後、分繊手段200を繊維束100に沿って走行(矢印(2))させながら分繊処理部150を生成し、その後、分繊手段200を抜き取る(矢印(3))方法でもよい。その後は、図4(A)に示すように、静止していた繊維束100を矢印(3)、(4)で示すタイミングにて所定距離だけ移動させた後に、分繊手段200を元の位置(矢印(4))に戻してもよいし、図4(B)に示すように、繊維束100は移動させず、分繊手段200が絡合蓄積部120を経過するまで移動(矢印(4))させてもよい。
In the present invention, not only when the fiber bundle travels, but as shown in FIG. 3, the separating means 200 is pushed into the stationary fiber bundle 100 (arrow (1)) and then the separating means The separation processing unit 150 may be generated while traveling 200 along the fiber bundle 100 (arrow (2)), and then the separation means 200 may be removed (arrow (3)). Thereafter, as shown in FIG. 4 (A), the fiber bundle 100 which has been at rest is moved by a predetermined distance at the timings indicated by the arrows (3) and (4), and then the separating means 200 is moved to the original position. (The arrow (4)) may be returned, or, as shown in FIG. 4 (B), the fiber bundle 100 is not moved, and the movement is continued until the separating means 200 passes through the entanglement storage section 120 (arrow (4 )).
繊維束100を所定距離だけ移動させつつ分繊処理を行う場合には、図3(B)または図4(A)に示すように、分繊手段200を突き入れている分繊処理時間(矢印(2)で示す動作の時間)と、分繊手段200を抜き取り、再度繊維束に突き入れるまでの時間(矢印(3)、(4)、(1)で示す動作の時間)が、制御されることが好ましい。この場合、分繊手段200の移動方向は図の(1)~(4)の繰り返しとなる。
In the case of performing separation processing while moving the fiber bundle 100 by a predetermined distance, as shown in FIG. 3 (B) or FIG. 4 (A), the separation processing time during which the separation means 200 is inserted (arrow The time of the operation shown in (2) and the time (the time of the operation shown in arrows (3), (4), (1)) until extraction of the separating means 200 and pushing into the fiber bundle again are controlled. Is preferred. In this case, the moving direction of the separating means 200 is the repetition of (1) to (4) in the figure.
また、繊維束100は移動させず、分繊手段200が絡合蓄積部120を通過するまで分繊手段200を移動させつつ分繊処理を行う場合には、図4(B)に示すように、分繊手段を突き入れている分繊処理時間(矢印(2)または矢印(6)で示す動作の時間)と、分繊手段200を抜き取り、再度繊維束に突き入れるまでの時間(矢印(3)、(4)、(5)または矢印(3)、(4)、(1)で示す動作の時間)が、制御されることが好ましい。この場合にも、分繊手段200の移動方向は図の(1)~(4)の繰り返しとなる。
Further, as shown in FIG. 4B, when the fiber separation process is performed while moving the separation means 200 until the separation means 200 passes through the entanglement storage unit 120 without moving the fiber bundle 100. The separation processing time during which the separation means is inserted (the time of operation shown by the arrow (2) or the arrow (6)) and the time until extraction of the separation means 200 and insertion into the fiber bundle again (arrow ( Preferably, 3), (4), (5) or the time of operation shown by arrows (3), (4), (1)) is controlled. Also in this case, the moving direction of the separating means 200 is the repetition of (1) to (4) in the figure.
このように、分繊手段200によって、分繊処理区間と未分繊処理区間とが交互に形成され、未分繊処理区間が繊維束の全長に対して所定範囲内の比率になるように分繊繊維束が製造される。
In this manner, the separation processing section and the undivision processing section are alternately formed by the separation means 200, and the division processing section is divided into a ratio within a predetermined range with respect to the total length of the fiber bundle. Fiber bundles are produced.
なお、繊維束100を構成する単糸の交絡状態によっては、任意長さの未分繊処理区間を確保する(例えば図2において、分繊処理区間110を処理後、所定長さの未分繊処理区間130を確保した上で次の分繊処理部150を処理する)ことなく、分繊処理区間の終端部近傍から、引き続き分繊処理を再開することもできる。例えば、図4(A)に示すように、繊維束100を間欠的に移動させながら分繊処理を行う場合は、分繊手段200が分繊処理を行った(矢印(2))後、繊維束100の移動長さを、直前で分繊処理した長さより短くすることで、再度分繊手段200を突き入れる位置(矢印(1))が、直前に分繊処理した分繊処理区間に重ねることができる。一方、図4(B)に示すように分繊手段200自身を移動させながら分繊処理を行う場合は、一旦、分繊手段200を抜き取った後(矢印(3))、所定長さを移動させる(矢印(4))ことなく、再び分繊手段200を繊維束に突き入れる(矢印(5))ことができる。
In addition, depending on the interlacing state of single yarns constituting the fiber bundle 100, an undivided treated section of an arbitrary length is secured (for example, in FIG. It is also possible to resume separation processing from near the end of the separation processing section without processing the next separation processing unit 150 after securing the processing section 130. For example, as shown in FIG. 4A, in the case of performing separation processing while moving the fiber bundle 100 intermittently, after the separation means 200 performs separation processing (arrow (2)), the fibers By making the moving length of the bundle 100 shorter than the length of the separation processing immediately before, the position (arrow (1)) at which the separation means 200 is pushed in again overlaps the separation treatment section where the separation treatment was performed immediately before. be able to. On the other hand, as shown in FIG. 4 (B), in the case of performing separation processing while moving the separation means 200 itself, once the separation means 200 is removed (arrow (3)), the predetermined length is moved The separating means 200 can be pushed into the fiber bundle again (arrow (5)) without causing (arrow (4)).
このような分繊処理は、繊維束100を構成する複数の単糸同士が交絡している場合、繊維束内で単糸が実質的に引き揃った状態にはないため、繊維束100の幅方向に対して、既に分繊処理された位置や、分繊手段200を抜き取った箇所と同じ位置に再度分繊手段200を突き入れても、単糸レベルで突き入れる位置がずれやすく、直前に形成された分繊処理区間とは、分繊された状態(空隙)が連続することなく、別々の分繊処理区間として存在させることができる。
In such separation processing, when a plurality of single yarns constituting the fiber bundle 100 are entangled, the width of the fiber bundle 100 is not because the single yarns are not substantially aligned in the fiber bundle. Even if the separating means 200 is pushed in again at the same position as the position where the separating process has already been performed or the position where the separating means 200 has been pulled out, the pushing-in position at the single yarn level tends to shift easily. The formed separation processing section can be present as a separate separation processing section without the divided state (void) being continuous.
分繊処理1回あたり分繊する分繊処理区間の長さ(分繊距離170)は、分繊処理を行う繊維束の単糸交絡状態にもよるが、30mm以上1,500mm未満が好ましい。30mm未満であると分繊処理の効果が不十分であり、1,500mm以上になると強化繊維束によっては糸切れや毛羽立ちの恐れがある。
Although the length of the fiber separation treatment section (fiber separation distance 170) which performs fiber separation processing once depends on the single yarn entangled state of the fiber bundle to be subjected to the fiber separation processing, it is preferably 30 mm or more and less than 1,500 mm. If it is less than 30 mm, the effect of the fiber separation treatment is insufficient, and if it is 1,500 mm or more, there is a fear of yarn breakage or fuzzing depending on the reinforcing fiber bundle.
さらに、分繊手段200が複数設けられる場合には、交互に形成される分繊処理区間と未分繊処理区間とを、繊維束の幅方向に対して、略平行に複数設けることもできる。この際、前述したように、複数の分繊手段200を、並列、互い違い、位相をずらす等して、複数の突出部210を任意に配置することができる。
Furthermore, when a plurality of separating means 200 are provided, it is possible to provide a plurality of divided treatment sections and undivided processing sections alternately formed substantially in parallel with the width direction of the fiber bundle. At this time, as described above, it is possible to arbitrarily arrange the plurality of projecting portions 210 by arranging the plurality of separating means 200 in parallel, alternately, shifting the phase, or the like.
また更に、複数の突出部210を、独立して制御することもできる。詳細は後述するが、分繊処理に要する時間や、突出部210が検知する押圧力により、個々の突出部210が独立して分繊処理することも好ましい。
Furthermore, the plurality of protrusions 210 can also be controlled independently. Although the details will be described later, it is also preferable that the individual protrusions 210 be subjected to separation processing independently depending on the time required for the separation processing and the pressing force detected by the protrusions 210.
いずれの場合であっても、繊維束走行方向の上流側に配置した、繊維束を巻き出す巻き出し装置(図示せず)などから繊維束を巻き出す。繊維束の巻き出し方向は、ボビンの回転軸と垂直に交わる方向に引き出す横出し方式や、ボビン(紙管)の回転軸と同一方向に引き出す縦出し方式が考えられるが、解除撚りが少ないことを勘案すると横出し方式が好ましい。
In any case, the fiber bundle is unwound from a unwinding device (not shown) or the like, which unrolls the fiber bundle, disposed on the upstream side in the fiber bundle traveling direction. As the unwinding direction of the fiber bundle, it is conceivable to use a side-by-side method in which the fiber bundle is drawn out perpendicularly to the rotational axis of the bobbin or a longitudinal-out method in which it is drawn out in the same direction as the rotational axis of the bobbin Sideways method is preferable in consideration of
また、巻き出し時のボビンの設置姿勢については、任意の方向に設置することができる。中でも、クリールにボビンを突き刺した状態において、クリール回転軸固定面でない側のボビンの端面が水平方向以外の方向を向いた状態で設置する場合は、繊維束に一定の張力がかかった状態で保持されることが好ましい。繊維束に一定の張力が無い場合は、繊維束がパッケージ(ボビンに繊維束が巻き取られた巻体)からズレ落ちパッケージから離れる、もしくは、パッケージから離れた繊維束がクリール回転軸に巻きつくことで、巻き出しが困難になることが考えられる。
Further, the installation posture of the bobbin at the time of unwinding can be installed in any direction. Above all, in the case where the end face of the bobbin on the side other than the fixed surface of the creel rotary shaft is installed in a state where the end face of the creel is not pierced with the fixed direction, Preferably. When the fiber bundle does not have a constant tension, the fiber bundle slips off from the package (the bobbin in which the fiber bundle is wound on the bobbin) and is separated from the package, or the fiber bundle separated from the package is wound around the creel rotating shaft It is thought that it becomes difficult to unroll.
また、巻き出しパッケージの回転軸固定方法としては、クリールを使う方法の他に、平行に並べた2本のローラーの上に、ローラーと平行にパッケージを載せ、並べたローラーの上でパッケージを転がすようにして、繊維束を巻き出す、サーフェス巻き出し方式も適用可能である。
Also, as a method for fixing the rotating shaft of the unwinding package, in addition to the method using a creel, the package is placed parallel to the rollers on two rollers arranged in parallel, and the package is rolled on the rollers arranged. Thus, the surface unrolling method of unrolling the fiber bundle is also applicable.
また、クリールを使った巻き出しの場合、クリールにベルトをかけ、その一方を固定し、もう一方に錘を吊るす、バネで引っ張るなどして、クリールにブレーキをかけることで、巻き出し繊維束に張力を付与する方法が考えられる。この場合、巻き径に応じて、ブレーキ力を可変することが、張力を安定させる手段として有効である。
In addition, in the case of unwinding using a creel, apply a belt to the creel, fix one of them, suspend the weight to the other, pull it with a spring, etc. and apply a brake to the creel to unroll the fiber bundle. It is conceivable to apply tension. In this case, varying the braking force according to the winding diameter is effective as a means for stabilizing tension.
また、分繊後の単糸本数の調整には、繊維束を拡幅する方法と、繊維束の幅方向に並べて配置した複数の分繊手段のピッチによって調整が可能である。分繊手段のピッチを小さくし、繊維束幅方向により多くの分繊手段を設けることで、より単糸本数の少ない、いわゆる細束に分繊処理が可能となる。また、分繊手段のピッチを狭めずとも、分繊処理を行う前に繊維束を拡幅し、拡幅した繊維束をより多くの分繊手段で分繊することでも、単糸本数の調整が可能である。
Moreover, adjustment of the number of single yarns after separation is possible by the method of widening the fiber bundle and the pitch of the plurality of separation means arranged in the width direction of the fiber bundle. By reducing the pitch of the separating means and providing more separating means in the fiber bundle width direction, it is possible to separate into so-called fine bundles with a smaller number of single yarns. In addition, it is possible to adjust the number of single yarns by widening the fiber bundle before the separation treatment and separating the widened fiber bundle by more separation means without narrowing the separation means pitch. It is.
ここで拡幅とは、繊維束100の幅を拡げる処理を意味する。拡幅処理方法としては特に制限がなく、振動ロールを通過させる振動拡幅法、圧縮した空気を吹き付けるエア拡幅法などが好ましい。
Here, the term “widening” refers to a process of widening the width of the fiber bundle 100. The widening method is not particularly limited, and a vibration widening method of passing a vibrating roll, an air widening method of blowing compressed air, and the like are preferable.
本発明では分繊手段200の突き入れと抜き取りを繰り返して分繊処理部150を形成する。その際、再度突き入れるタイミングは、分繊手段200を抜き取った後の経過時間で設定することが好ましい。また、再度抜き取るタイミングも、分繊手段200を突き入れた後の経過時間で設定することが好ましい。突き入れ、および/または抜き取りのタイミングを時間で設定することで、所定距離間隔の分繊処理区間110および、未分繊処理区間130を生成することが可能となり、分繊処理区間110と未分繊処理区間130の比率も任意に決定することが可能となる。また、所定時間間隔は、常時同じでもよいが、分繊処理を進めた距離に応じて長くしていく、もしくは短くしていくことや、その時々の繊維束の状態に応じて、例えば繊維束が元々もっている毛羽や単糸の交絡が少ない場合には、所定時間間隔を短くするなど、状況に応じて変化させてもよい。
In the present invention, the punching and drawing of the separating means 200 is repeated to form the separating unit 150. At that time, it is preferable to set the timing for pushing in again by the elapsed time after the separating means 200 is removed. In addition, it is preferable to set the timing of extraction again by the elapsed time after the separating means 200 is pushed. By setting the timing of penetration and / or extraction with time, it becomes possible to generate the separation processing section 110 and the undivision processing section 130 of a predetermined distance interval, The ratio of the fiber treatment section 130 can also be determined arbitrarily. Also, the predetermined time interval may always be the same, but may be increased or shortened depending on the distance of progress of the separation processing, or according to the state of the fiber bundle at that time, for example, fiber bundle When there is little entanglement of fluff or single yarn originally possessed, the predetermined time interval may be shortened, or the like, depending on the situation.
繊維束100に分繊手段200を突き入れると、分繊処理の経過にしたがって、生成する絡合部160が突出部210を押し続けるため、分繊手段200は絡合部160から押圧力を受ける。
When the separating means 200 is pushed into the fiber bundle 100, the forming unit 200 continues to push the protrusion 210 as the separating process proceeds, so the separating means 200 receives a pressing force from the forming unit 160. .
前述の通り、複数の単糸は実質的に繊維束100内で引き揃った状態ではなく、単糸レベルで交絡している部分が多く、さらに繊維束100の長手方向においては、交絡が多い箇所と少ない箇所が存在する場合がある。単糸交絡の多い箇所は分繊処理時の押圧力の上昇が早くなり、逆に、単糸交絡の少ない箇所は押圧力の上昇が遅くなる。したがって、本発明の分繊手段200には、繊維束100からの押圧力を検知する押圧力検知手段を備えることが好ましい。
As described above, the plurality of single yarns are not substantially aligned in the fiber bundle 100, but there are many parts entangled at the single yarn level, and in the longitudinal direction of the fiber bundle 100, there are many entanglements. There may be few places. In the place where there is much single yarn interlacing, the rise in pressing force at the time of separation processing becomes faster, and conversely, in the place where there is little single yarn intermingling, the rise in pressing force becomes late. Therefore, the separating means 200 of the present invention is preferably provided with pressing force detecting means for detecting pressing force from the fiber bundle 100.
また、分繊手段200の前後で繊維束100の張力が変化することがあるため、分繊手段200の近辺には繊維束100の張力を検知する張力検知手段を少なくとも1つ備えてもよく、複数備えて張力差を演算してもよい。これら押圧力、張力、張力差の検知手段は、個別に備えることもでき、いずれかを組み合わせて設けることもできる。ここで、張力を検知する張力検知手段は、分繊手段200から繊維束100の長手方向に沿って前後の少なくとも一方10~1,000mm離れた範囲に配置することが好ましい。
Further, since the tension of the fiber bundle 100 may change before and after the separating means 200, at least one tension detecting means for detecting the tension of the fiber bundle 100 may be provided in the vicinity of the separating means 200. A plurality of tension differences may be calculated. The means for detecting the pressing force, the tension, and the tension difference may be provided individually, or may be provided in combination. Here, it is preferable that the tension detecting means for detecting the tension be disposed in the range separated from the separating means 200 by at least one of 10 to 1,000 mm at the front and the rear along the longitudinal direction of the fiber bundle 100.
これら押圧力、張力、張力差は、検出した値に応じて分繊手段200の抜き出しを制御することが好ましい。検出した値の上昇に伴って、任意に設定した上限値を超えた場合に分繊手段200を抜き出すよう制御することが更に好ましい。上限値は、押圧力、張力の場合は0.01~5N/mmの範囲、張力差は0.01~0.8N/mmの範囲で上限値を設定することが好ましい。なお、上限値は、繊維束の状態に応じて、±10%の幅で変動させてもよい。ここで、押圧力、張力、張力差の単位(N/mm)は、繊維束100の幅あたりに作用する力を示す。
It is preferable to control the extraction of the separating means 200 in accordance with the detected values of these pressing force, tension, and tension difference. It is more preferable to control so as to withdraw the separating means 200 when the arbitrarily set upper limit is exceeded with the increase of the detected value. The upper limit value is preferably set in the range of 0.01 to 5 N / mm in the case of pressing force and tension, and the tension difference is set in the range of 0.01 to 0.8 N / mm. The upper limit may be varied within a range of ± 10% depending on the state of the fiber bundle. Here, the unit of pressing force, tension, and tension difference (N / mm) indicates the force acting on the width of the fiber bundle 100.
押圧力、張力、張力差の上限値の範囲を下回ると、分繊手段200を突き入れてすぐに、分繊手段200を抜き取る押圧力や張力、張力差に到達するため、十分な分繊距離が取れず、分繊処理区間110が短くなりすぎ、本発明で得ようとする分繊処理が施された繊維束が得られなくなる。一方、上限値の範囲を上回ると、分繊手段200を突き入れた後、分繊手段200を抜き取る押圧力や張力、張力差に到達する前に繊維束100に単糸の切断が増えるため、分繊処理が施された繊維束が枝毛状に飛び出すことや、発生する毛羽が増えるなどの不具合が発生しやすくなる。飛び出した枝毛は、搬送中のロールに巻きついたり、毛羽は駆動ロールに堆積し繊維束に滑りを発生させたりする等、搬送不良を発生させやすくする。
If it falls below the upper limit range of pressing force, tension and tension difference, the separating means 200 is pushed immediately to reach the pressing force, tension and tension difference to be taken out of the separating means 200, so the separating distance is sufficient As a result, the fiber separation processing section 110 becomes too short, and the fiber bundle subjected to the fiber separation processing to be obtained in the present invention can not be obtained. On the other hand, beyond the upper limit range, after pushing the separating means 200, the cutting of the single yarn in the fiber bundle 100 increases before reaching the pressing force, tension, or tension difference which pulls out the separating means 200, It becomes easy to generate problems such as jumping out of the fiber bundle subjected to the separation treatment in the form of split ends, increase of fluffs to be generated, and the like. The splitted hair that has jumped out is wound around the roll being transported, and the fluff is deposited on the drive roll to cause slippage in the fiber bundle, which makes it easy to cause a transport failure.
分繊手段200の抜き取りタイミングを時間で制御する場合とは異なり、押圧力、張力、張力差を検知する場合には、分繊処理時に繊維束100を切断するほどの力がかかる前に分繊手段200を抜き取るため、繊維束100に無理な力がかからなくなり、連続した分繊処理が可能になる。
Unlike in the case where the extraction timing of the separating means 200 is controlled by time, when the pressing force, tension, and tension difference are detected, the separation is performed before applying a force enough to cut the fiber bundle 100 at the time of separation processing. Since the means 200 is removed, the fiber bundle 100 is not subjected to an excessive force, and continuous separation processing becomes possible.
更に、繊維束100が部分的に切断されたような枝切れや毛羽立ちの発生を抑えつつ、分繊処理区間110が長く、かつ、絡合蓄積部120の形状が長手方向に安定的な繊維束100を得るためには、押圧力は、0.04~2.0N/mm、張力は0.02~0.2N/mm範囲、張力差は0.05~0.5N/mmの範囲とすることが好ましい。
Furthermore, the fiber bundle processing section 110 is long, and the shape of the entanglement accumulation part 120 is stable in the longitudinal direction, while suppressing the occurrence of branch breakage and fuzz such as the fiber bundle 100 being partially cut. In order to obtain 100, the pressing force is 0.04 to 2.0 N / mm, the tension is 0.02 to 0.2 N / mm, and the tension difference is 0.05 to 0.5 N / mm. Is preferred.
繊維束100に突き入れた分繊手段200から繊維束100の長手方向に沿った前後の少なくとも一方10~1,000mm離れた範囲において、繊維束100の撚りの有無を検知する撮像手段を具備することも好ましい。この撮像により、撚りの位置をあらかじめ特定し、撚りに分繊手段200を突き入れないように制御することで、突き入れミスを防止することができる。また、突き入れた分繊手段200に撚りが接近した際に、分繊手段200を抜き出すこと、つまり撚りを分繊処理しないことで、繊維束100の狭幅化を防ぐことが出来る。ここで、突き入れミスとは、撚りに分繊手段200を突き入れてしまい、繊維束100を分繊手段200の突き入れ方向に押し動かすのみで、分繊処理されないことをいう。
An imaging means for detecting the presence or absence of twisting of the fiber bundle 100 is provided in a range separated from the separating means 200 inserted into the fiber bundle 100 by at least one of 10 to 1,000 mm before and after the fiber bundle 100 in the longitudinal direction. Is also preferred. By this imaging, by predetermining the position of the twist and controlling so as not to push the separating means 200 into the twist, it is possible to prevent the piercing error. In addition, when the twist approaches the inserted separating means 200, the narrowing of the fiber bundle 100 can be prevented by extracting the separating means 200, that is, not performing the separation process of the twist. Here, the pushing error means that the separating means 200 is pushed into the twist and only the fiber bundle 100 is pushed in the pushing direction of the separating means 200, and the separating process is not performed.
分繊手段200が繊維束100の幅方向に複数存在し、かつ、等間隔に配置される構成では、繊維束100の幅が変化すると、分繊された単糸本数も変化するため、安定した単糸本数の分繊処理が行えなくなることがある。また、撚りを無理やり分繊処理すると、繊維束100を単糸レベルで切断し毛羽を多く発生させるため、絡合部160が集積されてなる絡合蓄積部120の形状が大きくなる。大きな絡合蓄積部120を残しておくと、巻体から解舒される繊維束100に引っかかりやすくなる。
In the configuration in which a plurality of separating means 200 exist in the width direction of the fiber bundle 100 and are arranged at equal intervals, when the width of the fiber bundle 100 changes, the number of separated single yarns also changes. In some cases, the separation process can not be performed for the number of single yarns. In addition, when the twist is forcibly split, the fiber bundle 100 is cut at the single yarn level to generate many fluffs, so the shape of the entanglement storage portion 120 where the entangled portions 160 are accumulated becomes large. If a large entanglement accumulation portion 120 is left, it becomes easy to be caught by the fiber bundle 100 unwound from the roll.
繊維束100の撚りを検知した場合、前述の撚りに分繊手段200を突き入れないように制御する以外にも、繊維束100の走行速度を変化させてもよい。具体的には、撚りを検知した後、分繊手段200が繊維束100から抜き出ているタイミングで、撚りが分繊手段200を経過するまでの間、繊維束100の走行速度を早くすることで、効率よく撚りを回避することができる。
When the twist of the fiber bundle 100 is detected, the traveling speed of the fiber bundle 100 may be changed in addition to the control so as not to push the dividing means 200 into the above-mentioned twist. Specifically, after the twisting is detected, the traveling speed of the fiber bundle 100 is increased until the twisting passes through the separating means 200 at the timing when the separating means 200 is removing from the fiber bundle 100. Can efficiently avoid twisting.
また、撮像手段で得られた画像を演算する画像演算処理手段を更に備え、画像演算処理手段の演算結果に基づき、分繊手段200の押圧力を制御する押圧力制御手段を更に備えてもよい。例えば、画像演算処理手段が撚りを検知した場合、分繊手段が撚りを経過する際の撚りの通過性をよくすることが出来る。具体的には、撮像手段により撚りを検知し、突出部210が検知した撚りに接触する直前から通過するまで、押圧力が低減するように分繊手段200を制御することが好ましい。撚りを検知した際、押圧力の上限値の0.01~0.8倍の範囲に低減させることが好ましい。この範囲を下回る場合、実質的に押圧力を検知できなくなり、押圧力の制御が困難になったり、制御機器自体の検出精度を高める必要が生じる。また、この範囲を上回る場合には、撚りを分繊処理する頻度が多くなり、繊維束が細くなる。
The image processing unit may further include an image processing unit configured to calculate an image obtained by the imaging unit, and a pressing control unit configured to control the pressing force of the separating unit 200 based on the calculation result of the image processing unit. . For example, when the image operation processing means detects twist, the passability of the twist when the separating means passes the twist can be improved. Specifically, it is preferable to detect the twist by the imaging unit and control the separating unit 200 so that the pressing force is reduced until immediately before the protrusion 210 contacts the detected twist. When twisting is detected, it is preferable to reduce it to the range of 0.01 to 0.8 times the upper limit value of the pressing force. Below this range, the pressing force can not be substantially detected, which makes it difficult to control the pressing force and needs to increase the detection accuracy of the control device itself. Moreover, when it exceeds this range, the frequency which carries out the division | segmentation process of twist increases, and a fiber bundle becomes thin.
突出部210を備えた分繊手段200を単純に繊維束100に突き入れる以外にも、分繊手段として回転可能な回転分繊手段220を用いることも好ましい態様である。図5は、回転分繊手段を突き入れる移動サイクルの一例を示す説明図である。回転分繊手段220は繊維束100の長手方向に直交する回転軸240を備えた回転機構を有しており、回転軸240の表面には突出部210が設けられている。図中の繊維束走行方向b(矢印)に沿って繊維束100が走行するのに合わせ、回転分繊手段220に設けられた突出部210が繊維束100に突き入れられ、分繊処理が始まる。ここで、図示は省略するが、回転分繊手段220は、押圧力検知機構と回転停止位置保持機構を有していることが好ましい。双方機構によって、所定の押圧力が回転分繊手段220に作用するまでは、図5(A)の位置で回転停止位置を保持し分繊を続ける。突出部210に絡合部160が生じる等、所定の押圧力を超えると、図5(B)のように、回転分繊手段220が回転を始める。その後、図5(C)のように、突出部210(黒丸印)が繊維束100から抜け、次の突出部210(白丸印)が繊維束100に突き入る動作を行う。図5(A)~図5(C)の動作が短ければ短いほど、未分繊処理区間は短くなるため、繊維束の分繊処理区間の割合を多くしたい場合には図5(A)~図5(C)の動作を短くすることが好ましい。
In addition to simply inserting the separating means 200 having the projecting portion 210 into the fiber bundle 100, it is also a preferable embodiment to use a rotatable separating means 220 as a separating means. FIG. 5 is an explanatory view showing an example of a movement cycle in which the rotary separating means is pushed. The rotating and separating means 220 has a rotating mechanism provided with a rotating shaft 240 orthogonal to the longitudinal direction of the fiber bundle 100, and a protrusion 210 is provided on the surface of the rotating shaft 240. As the fiber bundle 100 travels along the fiber bundle traveling direction b (arrow) in the figure, the projecting portion 210 provided on the rotary separating means 220 is pushed into the fiber bundle 100, and the separating process starts . Here, although not shown in the drawings, it is preferable that the rotary separation means 220 have a pressing force detection mechanism and a rotation stop position holding mechanism. By both mechanisms, the rotation stop position is held at the position of FIG. 5 (A) and separation is continued until a predetermined pressing force acts on the rotation separation means 220. When a predetermined pressing force is exceeded, such as the entangled portion 160 being formed in the projecting portion 210, as shown in FIG. 5 (B), the rotating and separating means 220 starts to rotate. Thereafter, as shown in FIG. 5C, the protrusion 210 (black circle mark) is removed from the fiber bundle 100, and the next protrusion 210 (white circle mark) penetrates the fiber bundle 100. As the operation in FIG. 5 (A) to FIG. 5 (C) is shorter, the unsorted section becomes shorter, so if it is desired to increase the ratio of the section subjected to fiber bundle split, FIG. It is preferable to shorten the operation of FIG.
回転分繊手段220に突出部210を多く配置することで、分繊処理割合の多い繊維束100を得られたり、回転分繊手段220の寿命を長くしたりすることができる。分繊処理割合の多い繊維束とは、繊維束内における分繊処理された長さを長くした繊維束もしくは、分繊処理された区間と未分繊処理の区間との発生頻度を高めた繊維束のことである。また、1つの回転分繊手段に設けられた突出部210の数が多いほど、繊維束100と接触して突出部210が磨耗する頻度を減らすことにより、寿命を長くすることができる。突出部210を設ける数としては、円盤状の外縁に等間隔に3~12個配置することが好ましく、より好ましくは4~8個である。
By arranging a large number of projecting parts 210 in the rotary separating means 220, it is possible to obtain the fiber bundle 100 having a large separation processing ratio, and to prolong the life of the rotary separating means 220. A fiber bundle with a high proportion of fiber division means a fiber bundle with a long fiber division length in the fiber bundle, or a fiber with an increased frequency of generation between a part subjected to fiber division treatment and a part without fiber division treatment It is a bunch. In addition, as the number of the protrusions 210 provided in one rotational separating unit increases, the life can be extended by reducing the frequency with which the protrusions 210 come into contact with the fiber bundle 100 and wear. The number of the projections 210 is preferably 3 to 12 and more preferably 4 to 8 at equal intervals on the outer edge of the disk.
このように、分繊処理割合と突出部の寿命とを優先させつつ、繊維束幅が安定した繊維束100を得ようとする場合、回転分繊手段220には、撚りを検知する撮像手段を有していることが好ましい。具体的には、撮像手段が撚りを検知するまでの通常時は、回転分繊手段220は回転および停止を間欠的に繰り返すことで分繊処理を行い、撚りを検知した場合には、回転分繊手段220の回転速度を通常時より上げる、および/または停止時間を短くすることで、繊維束幅を安定させることができる。前記停止時間をゼロに、つまり、停止せず連続して回転し続けることもできる。
As described above, in order to obtain the fiber bundle 100 having a stable fiber bundle width while giving priority to the division processing ratio and the life of the projecting portion, the rotational separation unit 220 is an imaging unit that detects twist. It is preferable to have. Specifically, when the imaging means normally detects a twist, the rotation separating means 220 intermittently repeats rotation and stop to perform the separation process, and when the twist is detected, the rotation amount is detected. The fiber bundle width can be stabilized by increasing the rotation speed of the fiber means 220 from normal and / or shortening the stop time. It is also possible to keep the stop time at zero, i.e. continuously rotating without stopping.
また、回転分繊手段220の間欠的な回転と停止を繰り返す方法以外にも、常に回転分繊手段220を回転し続けてもよい。その際、繊維束100の走行速度と回転分繊手段220の回転速度とを、相対的にいずれか一方を早くする、もしくは遅くすることが好ましい。速度が同じ場合には、突出部210を繊維束100に突き刺す/抜き出す、の動作が行われるため、分繊処理区間は形成できるものの、繊維束100に対する分繊作用が弱いため、分繊処理が十分に行われない場合がある。またいずれか一方の速度が相対的に早過ぎる、もしくは遅すぎる場合には、繊維束100と突出部210とが接触する回数が多くなり、擦過によって糸切れする恐れがあり、連続生産性に劣ることがある。
In addition to the method of repeating the intermittent rotation and stop of the rotational separation means 220, the rotational separation means 220 may always be kept rotating. At that time, it is preferable to make either one of the traveling speed of the fiber bundle 100 and the rotational speed of the rotational separation means 220 relatively faster or slower. In the case of the same speed, the operation of piercing / extracting the protruding portion 210 into / from the fiber bundle 100 is performed, and although the separation processing section can be formed, the separation effect on the fiber bundle 100 is weak. It may not be done enough. Also, if either one of the speeds is relatively too fast or too slow, the number of contact between the fiber bundle 100 and the projecting portion 210 increases, which may cause breakage due to abrasion, resulting in poor continuous productivity. Sometimes.
本発明では、分繊手段200、回転分繊手段220の突き入れと抜き取りを、分繊手段200、回転分繊手段220の往復移動によって行う往復移動機構を更に有してもよい。また、分繊手段200、回転分繊手段220を繊維束100の繰り出し方向に沿って往復移動させるための往復移動機構を更に有することも好ましい態様である。往復移動機構には、圧空や電動のシリンダやスライダなどの直動アクチュエータを用いることができる。
In the present invention, a reciprocation mechanism may be further provided, in which the separating means 200 and the rotary separating means 220 are pushed in and out by reciprocating movement of the separating means 200 and the rotary separating means 220. In addition, it is also preferable to further include a reciprocating mechanism for reciprocating the separating means 200 and the rotational separating means 220 along the delivery direction of the fiber bundle 100. As the reciprocating mechanism, linear actuators such as pneumatic and electric cylinders and sliders can be used.
繊維束に強化繊維を用いる場合の分繊処理区間の数は、ある幅方向の領域において少なくとも(F/10,000-1)箇所以上(F/50-1)箇所未満の分繊処理区間数を有することが好ましい。ここで、Fは分繊処理を行う繊維束を構成する総単糸本数(本)である。分繊処理区間の数は、ある幅方向の領域において少なくとも(F/10,000-1)箇所以上分繊処理区間を有することで、分繊繊維束を所定の長さにカットし不連続繊維強化複合材料にした際に、不連続繊維強化複合材料中の強化繊維束端部が細かく分割されるため、力学特性に優れた不連続繊維強化複合材料を得ることができる。また、分繊繊維束をカットせず連続繊維として用いる際は、後工程で樹脂等を含浸し強化繊維複合材料とする際に、分繊処理区間が多く含まれる領域から、強化繊維束内に樹脂が含浸する起点となり、成形時間が短縮できるとともに、強化繊維複合材料中のボイド等を低減させることができる。分繊処理区間数を(F/50-1)箇所未満とすることで、得られる分繊繊維束が糸切れを起こしにくく、繊維強化複合材料とした際の力学特性の低下を抑制できる。
When reinforcing fibers are used for the fiber bundle, the number of separation processing sections is at least the number of (F / 10,000-1) or more and (F / 50-1) or less in the area in the width direction. It is preferable to have Here, F is the total number of single yarns (pieces) constituting the fiber bundle to be subjected to the separation treatment. By having at least (F / 10,000-1) or more splitting treatment sections in a region in a width direction, the number of splitting treatment sections cuts the split fiber bundle into a predetermined length and discontinuous fibers In forming the reinforced composite material, since the reinforcing fiber bundle end in the discontinuous fiber reinforced composite material is finely divided, the discontinuous fiber reinforced composite material having excellent mechanical properties can be obtained. In addition, when using split fiber bundles as continuous fibers without cutting them, when impregnating a resin or the like in a later step to form a reinforced fiber composite material, from a region where a large number of split treatment sections are included, within the reinforcing fiber bundles While becoming a starting point which resin impregnates, and being able to shorten molding time, a void etc. in reinforcing fiber composite material can be reduced. By setting the number of division processing sections to less than (F / 50-1), it is difficult for the obtained divided fiber bundle to cause yarn breakage, and it is possible to suppress a decrease in mechanical properties when the fiber-reinforced composite material is formed.
分繊処理区間を、繊維束100の長手方向に周期性や規則性を持たせて設けると、後工程で分繊繊維束を所定の長さにカットした不連続繊維とする場合、所定の分繊繊維束本数へ制御しやすくすることができる。
If the separation processing section is provided with periodicity or regularity in the longitudinal direction of the fiber bundle 100, a predetermined amount can be obtained if the separation fiber bundle is cut into a predetermined length in a later step. The number of fiber bundles can be easily controlled.
次に本発明におけるサイジング剤付与のタイミングについて説明する。図6は、本発明に係る強化繊維束の製造方法において、強化繊維束の製造工程中におけるサイジング剤付与工程のタイミング例を示している。図6には、繊維束100が分繊処理工程300を経て分繊繊維束180に形成される工程中において、サイジング剤付与工程400が、分繊処理工程300よりも前に行われるパターンAと、分繊処理工程300よりも後に行われるパターンBとが示されている。パターンA、パターンBのいずれのタイミングも可能である。
Next, the timing of the sizing agent application in the present invention will be described. FIG. 6 shows an example of the timing of the sizing agent application process in the process of manufacturing a reinforcing fiber bundle in the method of manufacturing a reinforcing fiber bundle according to the present invention. In FIG. 6, in the process in which the fiber bundle 100 is formed into the split fiber bundle 180 through the split treatment process 300, the sizing agent application process 400 is performed with the pattern A performed before the split treatment process 300. And a pattern B to be performed after the fiber separation treatment process 300 is shown. Both timings of pattern A and pattern B are possible.
図7は、本発明に係る繊維束拡幅工程301を含む強化繊維束の製造方法において、強化繊維束の製造工程中におけるサイジング剤付与工程400のタイミング例を示している。図7には、繊維束100が繊維束拡幅工程301と分繊処理工程300とをこの順に経て分繊繊維束180に形成される工程中において、サイジング剤付与工程400が、繊維束拡幅工程301よりも前に行われるパターンCと、繊維束拡幅工程301と分繊処理工程300との間で行われるパターンDと、分繊処理工程300よりも後に行われるパターンEとが示されている。パターンC、パターンD、パターンEのいずれのタイミングも可能であるが、最適な分繊処理を達成できる観点から、パターンDのタイミングが最も好ましい。
FIG. 7 shows a timing example of the sizing agent application process 400 during the process of manufacturing the reinforcing fiber bundle in the method of manufacturing a reinforcing fiber bundle including the fiber bundle widening process 301 according to the present invention. In FIG. 7, in the process in which the fiber bundle 100 is formed into the divided fiber bundle 180 through the fiber bundle widening step 301 and the fiber dividing treatment step 300 in this order, the sizing agent applying step 400 is the fiber bundle widening step 301. A pattern C which is performed before the above, a pattern D which is performed between the fiber bundle widening step 301 and the separation processing step 300, and a pattern E which is performed after the separation processing step 300 are shown. Although any timing of the pattern C, the pattern D, and the pattern E is possible, the timing of the pattern D is most preferable from the viewpoint of achieving the optimum separation processing.
図8は、本発明に係る繊維強化熱可塑性樹脂成形材料を構成する強化繊維束の製造方法において、強化繊維束の製造工程中における、サイジング剤塗布工程と乾燥工程を含むサイジング剤付与工程のタイミング例を示している。サイジング剤付与工程400は、サイジング剤塗布工程401と乾燥工程402を含むが、図8には、これらサイジング剤塗布工程401と乾燥工程402を含むサイジング剤付与工程400が、繊維束100が分繊処理工程300を経て分繊繊維束180に形成される工程中において、分繊処理工程300よりも前に行われるパターンFと、分繊処理工程300よりも後に行われるパターンGとが示されている。パターンF、パターンGのいずれのタイミングも可能である。パターンFは、図6におけるパターンAと、パターンGは、図6におけるパターンBと実質的に同一である。
FIG. 8 is the timing of the sizing agent application process including the sizing agent application process and the drying process in the manufacturing process of the reinforcing fiber bundle in the manufacturing method of the reinforcing fiber bundle which constitutes the fiber reinforced thermoplastic resin molding material according to the present invention. An example is shown. The sizing agent applying process 400 includes a sizing agent applying process 401 and a drying process 402. In FIG. 8, the sizing agent applying process 400 including the sizing agent applying process 401 and the drying process 402 is performed. A pattern F performed prior to the separation processing step 300 and a pattern G performed after the separation processing step 300 are shown in the process of forming the separation fiber bundle 180 through the processing step 300. There is. Either timing of pattern F or pattern G is possible. The pattern F is substantially the same as the pattern A in FIG. 6 and the pattern G is substantially the same as the pattern B in FIG.
図9は、本発明に係る繊維強化熱可塑性樹脂成形材料を構成する強化繊維束の製造方法において、強化繊維束の製造工程中における、サイジング剤塗布工程と乾燥工程を含むサイジング剤付与工程の別のタイミング例を示している。図9に示すタイミング例におけるパターンHでは、サイジング剤付与工程400におけるサイジング剤塗布工程401と乾燥工程402とが分離されてそれぞれ別のタイミングで行われる。サイジング剤塗布工程401は、分繊処理工程300よりも前に行われ、乾燥工程402は、分繊処理工程300よりも後に行われる。
FIG. 9 is another manufacturing method of the reinforced fiber bundle which comprises the fiber reinforced thermoplastic resin molding material based on this invention WHEREIN: In the manufacturing process of a reinforced fiber bundle, another sizing agent provision process including a sizing agent application process and a drying process The timing example of is shown. In the pattern H in the timing example shown in FIG. 9, the sizing agent application process 401 and the drying process 402 in the sizing agent application process 400 are separated and performed at different timings. The sizing agent application step 401 is performed before the fiber separation treatment step 300, and the drying step 402 is performed after the fiber separation treatment step 300.
図10は、本発明に係る繊維束拡幅工程を含む強化繊維束の製造方法における、サイジング剤塗布工程と乾燥工程を含むサイジング剤付与工程のタイミング例を示しており、繊維束100が繊維束拡幅工程301と分繊処理工程300とをこの順に経て分繊繊維束180に形成される工程中において、サイジング剤付与工程のサイジング剤塗布工程401が、繊維束拡幅工程301よりも前に行われ、乾燥工程402については、繊維束拡幅工程301と分繊処理工程300との間で行われるパターンIと、分繊処理工程300よりも後に行われるパターンJが示されている。
FIG. 10 shows a timing example of a sizing agent application process including a sizing agent application process and a drying process in the method for producing a reinforced fiber bundle including the fiber bundle widening process according to the present invention, and the fiber bundle 100 is fiber bundle widening. During the step of forming the split fiber bundle 180 through the step 301 and the splitting treatment step 300 in this order, the sizing agent applying step 401 of the sizing agent applying step is performed prior to the fiber bundle widening step 301, As for the drying step 402, a pattern I performed between the fiber bundle widening step 301 and the separation processing step 300 and a pattern J performed after the separation processing step 300 are shown.
図11は、本発明に係る繊維束拡幅工程を含む強化繊維束の製造方法における、サイジング剤塗布工程と乾燥工程を含むサイジング剤付与工程の別のタイミング例を示しており、繊維束100が繊維束拡幅工程301と分繊処理工程300とをこの順に経て分繊繊維束180に形成される工程中において、サイジング剤付与工程のサイジング剤塗布工程401が、繊維束拡幅工程301と分繊処理工程300との間で行われ、乾燥工程402が、分繊処理工程300よりも後に行われるパターンKが示されている。
FIG. 11 shows another timing example of the sizing agent application process including the sizing agent application process and the drying process in the method for producing a reinforced fiber bundle including the fiber bundle widening process according to the present invention, and the fiber bundle 100 is a fiber In the process of forming the split fiber bundle 180 through the bundle spreading step 301 and the splitting treatment step 300 in this order, the sizing agent application step 401 of the sizing agent application step comprises the fiber bundle widening step 301 and the splitting treatment step A pattern K is shown which is performed between 300 and 300, and the drying step 402 is performed after the separation processing step 300.
このように、本発明に係る強化繊維束の製造方法においては、各種のタイミングでサイジング剤を付与することが可能である。
Thus, in the method for producing a reinforcing fiber bundle according to the present invention, it is possible to apply the sizing agent at various timings.
本発明の繊維強化熱可塑性樹脂成形材料を構成するチョップド強化繊維束の平均束幅は0.03mm以上が好ましく、0.05mm以上がより好ましく、0.07mm以上がさらに好ましい。0.03mm未満の場合、成形材料の流動性に劣る懸念がある。繊維強化熱可塑性樹脂成形材料を構成する強化繊維束の平均束幅は3mm以下が好ましく、2mm以下がより好ましく、1mm以下がさらに好ましい。3mmを超える場合、成形品の力学特性が劣る懸念がある。
The average bundle width of the chopped reinforcing fiber bundle constituting the fiber-reinforced thermoplastic resin molding material of the present invention is preferably 0.03 mm or more, more preferably 0.05 mm or more, and still more preferably 0.07 mm or more. If it is less than 0.03 mm, there is a concern that the flowability of the molding material may be poor. 3 mm or less is preferable, as for the average bundle | flux width | variety of the reinforced fiber bundle which comprises a fiber reinforced thermoplastic resin molding material, 2 mm or less is more preferable, and 1 mm or less is more preferable. If it exceeds 3 mm, there is a concern that the mechanical properties of the molded article may be inferior.
本発明で使用されるチョップド強化繊維束内の平均繊維数の上限は4,000本以下が好ましく、3,000本以下がより好ましく、2,000本以下がさらに好ましい。この範囲であれば成形品の力学特性を高めることができる。また束内平均繊維数下限は50本以上が好ましく、100本以上がより好ましく、200本以上がさらに好ましい。この範囲であれば成形材料の流動性を高めることができる。平均繊維数の導出方法は後述する。
The upper limit of the average number of fibers in the chopped reinforcing fiber bundle used in the present invention is preferably 4,000 or less, more preferably 3,000 or less, and still more preferably 2,000 or less. Within this range, the mechanical properties of the molded article can be enhanced. The lower limit of the number of fibers in the bundle is preferably 50 or more, more preferably 100 or more, and still more preferably 200 or more. Within this range, the flowability of the molding material can be enhanced. The method of deriving the average number of fibers will be described later.
本発明に係る、サイジング剤塗布後のチョップド強化繊維束を水へ浸漬する前の幅をW3、強化繊維束を25℃の水に、5分間浸漬した後、取り出し、1分間水を切った後における幅をW4とすると、強化繊維束の幅変化率W4/W3は0.6以上が好ましく、0.7以上がより好ましく、0.8以上がさらに好ましい。強化繊維束の幅変化率W4/W3が0.6より小さいと強化繊維束に付着されているサイジング剤の水可溶の物性が残っていることにより、繊維束が再凝集することがあり、再凝集すると、最適な単糸数に調整された繊維束の形態を保持することが困難になる。最適な単糸数に調整された繊維束の形態に保持できないと、最適な形態の中間基材にすることができず、成形の際の流動性と成形品の力学特性をバランスよく発現させることが困難となる。また幅変化率W4/W3は1.1以下であることが好ましい。幅変化率W4/W3が1.1を超えると繊維束の柔軟性が欠けてきて硬くなりすぎ、ボビンの巻き取り、巻き出しがスムーズにいかなくなる可能性がある。また、カット時に単糸割れを引き起こし、理想のチョップド繊維束形態が得られない可能性が生じる。強化繊維束の幅変化率W4/W3の導出方法は後述する。
The width before immersing the chopped reinforcing fiber bundle after applying a sizing agent to water according to the present invention is W3 and the reinforcing fiber bundle is immersed in water at 25 ° C. for 5 minutes, then taken out and drained for 1 minute Assuming that the width of the reinforcing fiber bundle is W4, the width change ratio W4 / W3 of the reinforcing fiber bundle is preferably 0.6 or more, more preferably 0.7 or more, and still more preferably 0.8 or more. If the width change ratio W4 / W3 of the reinforcing fiber bundle is smaller than 0.6, the water-soluble physical properties of the sizing agent attached to the reinforcing fiber bundle remain, and the fiber bundle may reaggregate, Reaggregation makes it difficult to maintain the form of the fiber bundle adjusted to the optimum number of single yarns. If it can not be maintained in the form of a fiber bundle adjusted to the optimum number of single yarns, it can not be made an intermediate substrate of the optimum form, and it is possible to balance the flowability during molding and the mechanical properties of the molded article in a balanced manner. It will be difficult. The width change ratio W4 / W3 is preferably 1.1 or less. If the width change ratio W4 / W3 exceeds 1.1, the flexibility of the fiber bundle is lacking and the fiber bundle becomes too hard, and the bobbin may not be smoothly wound and unwound. In addition, single yarn breakage may occur at the time of cutting, which may result in failure to obtain an ideal chopped fiber bundle form. The method of deriving the width change ratio W4 / W3 of the reinforcing fiber bundle will be described later.
本発明において、チョップド繊維束の束状集合体に含浸するマトリックス熱可塑性樹脂としては特に限定されず、例えば、ポリアミド樹脂、ポリアセタール、ポリアクリレート、ポリスルフォン、ABS、ポリエステル、アクリル、ポリブチレンテレフタラート(PBT)、ポリエチレンテレフタレート(PET)、ポリエチレン、ポリプロピレン、ポリフェニレンスルフィド(PPS)、ポリエーテルエーテルケトン(PEEK)、液晶ポリマー、塩ビ、ポリテトラフルオロエチレンなどのフッ素系樹脂、シリコーンなどが挙げられる。特に、上記熱可塑性樹脂としてポリアミド系樹脂を使用することが好ましく、さらにポリアミドに無機系の酸化防止剤を配合させることが好ましい。本発明に用いる熱可塑性ポリアミド樹脂としては、例えば、環状ラクタムの開環重合またはω-アミノカルボン酸の重縮合で得られるナイロン6、ナイロン11、ナイロン12やジアミンとジカルボン酸の重縮合で得られるナイロン66、ナイロン610、ナイロン612、ナイロン6T、ナイロン6I、ナイロン9T、ナイロンM5T、ナイロンMFD6、2種以上のジアミンとジカルボン酸の重縮合で得られるナイロン66・6・6I、ナイロン66・6・12などの共重合ナイロンなどが好適に使用することができる。特にナイロン6、66、610は機械的特性とコストの観点から好ましい。
In the present invention, the matrix thermoplastic resin to be impregnated into the bundle of chopped fiber bundles is not particularly limited. For example, polyamide resin, polyacetal, polyacrylate, polysulfone, ABS, polyester, acrylic, polybutylene terephthalate ( PBT), polyethylene terephthalate (PET), polyethylene, polypropylene, polyphenylene sulfide (PPS), polyetheretherketone (PEEK), liquid crystal polymer, polyvinyl chloride, fluorine resin such as polytetrafluoroethylene, silicone, and the like. In particular, it is preferable to use a polyamide-based resin as the above-mentioned thermoplastic resin, and it is more preferable to blend an inorganic antioxidant with the polyamide. The thermoplastic polyamide resin used in the present invention can be obtained, for example, by polycondensation of nylon 6, nylon 11, nylon 12 or diamine and diamine with dicarboxylic acid obtained by ring-opening polymerization of cyclic lactam or polycondensation of ω-aminocarboxylic acid. Nylon 66, nylon 610, nylon 612, nylon 6T, nylon 6I, nylon 9T, nylon M5T, nylon MFD 6, nylon 66.6-6I obtained by polycondensation of two or more diamines and dicarboxylic acids, nylon 66.6.6. Copolymerized nylon such as 12 can be suitably used. In particular, nylon 6, 66, 610 is preferred in view of mechanical properties and cost.
また、本発明に用いるハロゲン化銅あるいはその誘導体としては、ヨウ化銅、臭化銅、塩化銅、メルカプトベンズイミダゾールとヨウ化銅との錯塩などが挙げられる。なかでもヨウ化銅、メルカプトベンズイミダゾールとヨウ化銅との錯塩を好適に使用できる。ハロゲン化銅あるいはその誘導体の添加量としては、熱可塑性ポリアミド樹脂100重量部に対し0.001~5重量部の範囲にあることが好ましい。添加量が0.001部未満では予熱時の樹脂分解や発煙、臭気を抑えることができず、5重量部以上では改善効果の向上が見られなくなる。更に0.002~1重量部が熱安定化効果とコストのバランスから好ましい。
Further, as copper halide or derivatives thereof used in the present invention, copper iodide, copper bromide, copper chloride, a complex salt of mercaptobenzimidazole and copper iodide, and the like can be mentioned. Among them, copper iodide and a complex salt of mercaptobenzimidazole and copper iodide can be suitably used. The addition amount of the copper halide or its derivative is preferably in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyamide resin. If the addition amount is less than 0.001 part, it is not possible to suppress resin decomposition, smoke and odor during preheating, and if it is 5 parts by weight or more, improvement of the improvement effect can not be observed. Furthermore, 0.002 to 1 part by weight is preferable because of the balance between the heat stabilization effect and the cost.
本発明において、チョップド繊維束の束状集合体にマトリックス樹脂を含浸する方法は特に限定するものではなく、上記熱可塑性樹脂を含浸する方法を例示すると、熱可塑性樹脂繊維を含有する束状集合体を作製し、束状集合体に含まれる熱可塑性樹脂繊維をそのままマトリックス樹脂として使用してもかまわないし、熱可塑性樹脂繊維を含まない束状集合体を原料として用い、繊維強化熱可塑性樹脂成形材料を製造する任意の段階でマトリックス樹脂を含浸してもかまわない。
In the present invention, the method for impregnating the bundle of chopped fiber bundles with the matrix resin is not particularly limited, and the method for impregnating the thermoplastic resin may be exemplified by a bundle of thermoplastic resin fibers. The thermoplastic resin fibers contained in the bundle-like aggregate may be used as it is as a matrix resin, or a bundle-like aggregate containing no thermoplastic resin fiber as a raw material, a fiber-reinforced thermoplastic resin molding material The matrix resin may be impregnated at any stage of production of.
また、熱可塑性樹脂繊維を含有する束状集合体を原料として用いる場合であっても、繊維強化熱可塑性樹脂成形材料を製造する任意の段階でマトリックス樹脂を含浸することもできる。このような場合、熱可塑性樹脂繊維を構成する樹脂とマトリックス樹脂は同一の樹脂であってもかまわないし、異なる樹脂であってもかまわない。熱可塑性樹脂繊維を構成する樹脂とマトリックス樹脂が異なる場合は、両者は相溶性を有するか、あるいは、親和性が高い方が好ましい。
Further, even in the case of using a bundle-like aggregate containing thermoplastic resin fibers as a raw material, the matrix resin can be impregnated at any stage of producing a fiber-reinforced thermoplastic resin molding material. In such a case, the resin constituting the thermoplastic resin fiber and the matrix resin may be the same resin or different resins. When the resin constituting the thermoplastic resin fiber is different from the matrix resin, it is preferable that the two have compatibility or high affinity.
繊維強化熱可塑性樹脂成形材料を製造するに際し、束状集合体への、マトリックス樹脂である熱可塑性樹脂の含浸を、含浸プレス機を用いて実施することができる。プレス機としてはマトリックス樹脂の含浸に必要な温度、圧力を実現できるものであれば特に制限はなく、上下する平面状のプラテンを有する通常のプレス機や、1対のエンドレススチールベルトが走行する機構を有するいわゆるダブルベルトプレス機を用いることができる。かかる含浸工程においてはマトリックス樹脂を、フィルム、不織布又は織物等のシート状とした後、不連続繊維マットと積層し、その状態で上記プレス機等を用いてマトリックス樹脂を溶融・含浸することができるし、粒子状のマトリックス樹脂を束状集合体上に散布し積層体としてもよいし、もしくはチョップド繊維束を散布する際に同時に散布し、束状集合体内部に混ぜてもよい。
When manufacturing a fiber-reinforced thermoplastic resin molding material, impregnation of the bundle-like aggregate with the thermoplastic resin which is a matrix resin can be carried out using an impregnation press. The press is not particularly limited as long as it can realize the temperature and pressure necessary for the impregnation of the matrix resin, and a normal press having a flat platen which moves up and down, and a mechanism on which a pair of endless steel belts travel So-called double belt presses can be used. In the impregnation step, the matrix resin is formed into a sheet form such as a film, nonwoven fabric or woven fabric and then laminated with a discontinuous fiber mat, and the matrix resin can be melted and impregnated using the above-mentioned press or the like in that state. Alternatively, the particulate matrix resin may be dispersed on the bundle assembly to form a laminate, or the chopped fiber bundle may be dispersed at the same time as the dispersion and may be mixed inside the bundle assembly.
繊維強化樹脂成形材料に占める強化繊維の体積含有量としては、全体体積の20体積%以上が好ましく、25体積%以上がより好ましく、30体積%以上がさらに好ましい。強化繊維の体積含有量が20体積%未満になると、繊維強化樹脂成形材料の力学特性も低下する傾向にある。一方、また、繊維強化樹脂成形材料に占める強化繊維の体積含有量は70体積%以下が好ましく、65体積%以下がより好ましく、60体積%以下がさらに好ましい。強化繊維の体積含有量が70体積%を超えると、繊維強化樹脂成形材料の力学特性は向上しやすいものの、成形性が低下する傾向にある。
The volume content of reinforcing fibers in the fiber-reinforced resin molding material is preferably 20% by volume or more of the total volume, more preferably 25% by volume or more, and still more preferably 30% by volume or more. If the volume content of reinforcing fibers is less than 20% by volume, the mechanical properties of the fiber-reinforced resin molding material also tend to decrease. On the other hand, the volume content of reinforcing fibers in the fiber-reinforced resin molding material is preferably 70% by volume or less, more preferably 65% by volume or less, and still more preferably 60% by volume or less. If the volume content of reinforcing fibers exceeds 70% by volume, the mechanical properties of the fiber-reinforced resin molding material are likely to be improved, but the moldability tends to be reduced.
次に、本発明の実施例、比較例について説明する。なお、本発明は本実施例や比較例によって何ら制限されるものではない。
Next, Examples and Comparative Examples of the present invention will be described. The present invention is not limited at all by the examples and comparative examples.
(1)使用原料
・強化繊維束(1):炭素繊維束(ZOLTEK社製“PX35”、単糸数50,000本、“13”(エポキシ)サイジング剤、サイジング剤付着量1.5重量%)を用いた。
・強化繊維束(2):炭素繊維束(ZOLTEK社製“PX35”、単糸数50,000本、サイジング剤なし)を用いた。
・強化繊維束(3):ガラス繊維束(日東紡績製240TEX、単糸数1,600本)を用いた。
・強化繊維束(4):炭素繊維束(ZOLTEK社製“PX35”、単糸数50,000本、サイジング剤なし)を用いた。
・樹脂シート(1): ポリアミド6樹脂(東レ(株)社製、“アミラン”(登録商標)CM1001)からなるポリアミドマスターバッチを用いて、目付150g/m2のシートを作製した。
・樹脂シート(2): 未変性ポリプロピレン樹脂(プライムポリマー(株)社製、“プライムポリプロ”(登録商標)J106MG)90質量%と、酸変性ポリプロピレン樹脂(三井化学(株)製、“アドマー”(登録商標)QE800)10質量%とからなるポリプロピレンマスターバッチを用いて、シートを作製した。
・サイジング剤(1): 水溶性ポリアミド(東レ(株)社製、“T-70”)を用いた。
・サイジング剤(2): 水溶性ポリアミド(東レ(株)社製、“A-90”)を用いた。
・サイジング剤(3): 水溶性ポリアミド(東レ(株)社製、“P-70”)を用いた。
・サイジング剤(4): 水溶性ポリアミド(東レ(株)社製、“P-95”)を用いた。 (1) Raw materials used · Reinforcing fiber bundle (1): Carbon fiber bundle ("PX35" manufactured by ZOLTEK, 50,000 single yarns, "13" (epoxy) sizing agent, sizing agent adhesion amount 1.5% by weight) Was used.
Reinforcing fiber bundle (2): A carbon fiber bundle ("PX35" manufactured by ZOLTEK, 50,000 single yarns, no sizing agent) was used.
Reinforcing fiber bundle (3): A glass fiber bundle (240 TEX manufactured by Nitto Boshoku, 1,600 single yarns) was used.
Reinforcing fiber bundle (4): A carbon fiber bundle ("PX35" manufactured by ZOLTEK, 50,000 single yarns, no sizing agent) was used.
Resin Sheet (1): A sheet having a basis weight of 150 g / m 2 was produced using a polyamide masterbatch consisting ofpolyamide 6 resin ("Amilan" (registered trademark) CM 1001, manufactured by Toray Industries, Inc.).
Resin sheet (2): 90% by mass of unmodified polypropylene resin (Prime Polymer Co., Ltd., “Prime PolyPro” (registered trademark) J106MG) and acid-modified polypropylene resin (Mitsui Chemical Co., Ltd., “Admar” Sheets were made using a polypropylene masterbatch consisting of 10% by weight (registered trademark) QE 800).
Sizing agent (1): A water-soluble polyamide ("T-70" manufactured by Toray Industries, Inc.) was used.
Sizing agent (2): A water-soluble polyamide ("A-90" manufactured by Toray Industries, Inc.) was used.
Sizing agent (3): A water-soluble polyamide ("P-70" manufactured by Toray Industries, Inc.) was used.
Sizing agent (4): A water-soluble polyamide ("P-95" manufactured by Toray Industries, Inc.) was used.
・強化繊維束(1):炭素繊維束(ZOLTEK社製“PX35”、単糸数50,000本、“13”(エポキシ)サイジング剤、サイジング剤付着量1.5重量%)を用いた。
・強化繊維束(2):炭素繊維束(ZOLTEK社製“PX35”、単糸数50,000本、サイジング剤なし)を用いた。
・強化繊維束(3):ガラス繊維束(日東紡績製240TEX、単糸数1,600本)を用いた。
・強化繊維束(4):炭素繊維束(ZOLTEK社製“PX35”、単糸数50,000本、サイジング剤なし)を用いた。
・樹脂シート(1): ポリアミド6樹脂(東レ(株)社製、“アミラン”(登録商標)CM1001)からなるポリアミドマスターバッチを用いて、目付150g/m2のシートを作製した。
・樹脂シート(2): 未変性ポリプロピレン樹脂(プライムポリマー(株)社製、“プライムポリプロ”(登録商標)J106MG)90質量%と、酸変性ポリプロピレン樹脂(三井化学(株)製、“アドマー”(登録商標)QE800)10質量%とからなるポリプロピレンマスターバッチを用いて、シートを作製した。
・サイジング剤(1): 水溶性ポリアミド(東レ(株)社製、“T-70”)を用いた。
・サイジング剤(2): 水溶性ポリアミド(東レ(株)社製、“A-90”)を用いた。
・サイジング剤(3): 水溶性ポリアミド(東レ(株)社製、“P-70”)を用いた。
・サイジング剤(4): 水溶性ポリアミド(東レ(株)社製、“P-95”)を用いた。 (1) Raw materials used · Reinforcing fiber bundle (1): Carbon fiber bundle ("PX35" manufactured by ZOLTEK, 50,000 single yarns, "13" (epoxy) sizing agent, sizing agent adhesion amount 1.5% by weight) Was used.
Reinforcing fiber bundle (2): A carbon fiber bundle ("PX35" manufactured by ZOLTEK, 50,000 single yarns, no sizing agent) was used.
Reinforcing fiber bundle (3): A glass fiber bundle (240 TEX manufactured by Nitto Boshoku, 1,600 single yarns) was used.
Reinforcing fiber bundle (4): A carbon fiber bundle ("PX35" manufactured by ZOLTEK, 50,000 single yarns, no sizing agent) was used.
Resin Sheet (1): A sheet having a basis weight of 150 g / m 2 was produced using a polyamide masterbatch consisting of
Resin sheet (2): 90% by mass of unmodified polypropylene resin (Prime Polymer Co., Ltd., “Prime PolyPro” (registered trademark) J106MG) and acid-modified polypropylene resin (Mitsui Chemical Co., Ltd., “Admar” Sheets were made using a polypropylene masterbatch consisting of 10% by weight (registered trademark) QE 800).
Sizing agent (1): A water-soluble polyamide ("T-70" manufactured by Toray Industries, Inc.) was used.
Sizing agent (2): A water-soluble polyamide ("A-90" manufactured by Toray Industries, Inc.) was used.
Sizing agent (3): A water-soluble polyamide ("P-70" manufactured by Toray Industries, Inc.) was used.
Sizing agent (4): A water-soluble polyamide ("P-95" manufactured by Toray Industries, Inc.) was used.
(2)サイジング剤または水溶性ポリアミドの付着量の測定方法
サイジング剤または水溶性ポリアミドが付着している炭素繊維束を5gほど採取し、耐熱製の容器に投入した。次にこの容器を80℃、真空条件下で24時間乾燥し、吸湿しないように注意しながら室温まで冷却後、秤量した炭素繊維の重量をm1(g)とし、続いて容器ごと、窒素雰囲気中、450℃で灰化処理を行った。吸湿しないように注意しながら室温まで冷却し、秤量した炭素繊維の重量をm2(g)とした。以上の処理を経て、炭素繊維へのサイジング剤または水溶性ポリアミドの付着量を次式により求めた。測定は10本の繊維束について行い、その平均値を算出した。
付着量(重量%)=100×{(m1-m2)/m1} (2) Measuring Method of Adhered Amount of Sizing Agent or Water-Soluble Polyamide About 5 g of a carbon fiber bundle to which the sizing agent or the water-soluble polyamide was adhered was collected and placed in a heat resistant container. Next, the container is dried at 80 ° C. under vacuum conditions for 24 hours, and after cooling to room temperature while taking care not to absorb moisture, the weighed carbon fiber weight is m1 (g), and then the whole container, in a nitrogen atmosphere The ashing treatment was performed at 450 ° C. It cooled to room temperature paying attention so as not to absorb moisture, and the weight of the weighed carbon fiber was set to m2 (g). After the above treatment, the adhesion amount of the sizing agent or the water-soluble polyamide to the carbon fiber was determined by the following equation. The measurement was performed on ten fiber bundles, and the average value was calculated.
Adhesion amount (% by weight) = 100 × {(m1-m2) / m1}
サイジング剤または水溶性ポリアミドが付着している炭素繊維束を5gほど採取し、耐熱製の容器に投入した。次にこの容器を80℃、真空条件下で24時間乾燥し、吸湿しないように注意しながら室温まで冷却後、秤量した炭素繊維の重量をm1(g)とし、続いて容器ごと、窒素雰囲気中、450℃で灰化処理を行った。吸湿しないように注意しながら室温まで冷却し、秤量した炭素繊維の重量をm2(g)とした。以上の処理を経て、炭素繊維へのサイジング剤または水溶性ポリアミドの付着量を次式により求めた。測定は10本の繊維束について行い、その平均値を算出した。
付着量(重量%)=100×{(m1-m2)/m1} (2) Measuring Method of Adhered Amount of Sizing Agent or Water-Soluble Polyamide About 5 g of a carbon fiber bundle to which the sizing agent or the water-soluble polyamide was adhered was collected and placed in a heat resistant container. Next, the container is dried at 80 ° C. under vacuum conditions for 24 hours, and after cooling to room temperature while taking care not to absorb moisture, the weighed carbon fiber weight is m1 (g), and then the whole container, in a nitrogen atmosphere The ashing treatment was performed at 450 ° C. It cooled to room temperature paying attention so as not to absorb moisture, and the weight of the weighed carbon fiber was set to m2 (g). After the above treatment, the adhesion amount of the sizing agent or the water-soluble polyamide to the carbon fiber was determined by the following equation. The measurement was performed on ten fiber bundles, and the average value was calculated.
Adhesion amount (% by weight) = 100 × {(m1-m2) / m1}
(3)ドレープ値の測定
30cmに切断した強化繊維束をまっすぐ伸ばして平らな台に載せ、湾曲したり撚れたりしないことを確認する。湾曲あるいは撚れが発生した場合、100℃以下の加熱、あるいは、0.1MPa以下の加圧によって除くことが好ましい。図12に示すように、23±5℃の雰囲気下、直方体の台の端に、30cmに切断した強化繊維束を固定し、この時、強化繊維束は台の端から25cm突き出るように固定した。すなわち、強化繊維束の端から5cmの部分が、台の端に来るようにした。この状態で5分間静置した後、台に固定していない方の強化繊維束の先端と、台の側面との最短距離を測定し、ドレープ値D1とした。測定した前記強化繊維束を25℃の水に、5分間浸漬した後、取り出し、水を切った。次に強化繊維束を80℃、真空条件下で24時間乾燥し、絶乾した後、前記方法と同様の方法で浸漬処理後ドレープ値D2とした。測定本数はn=5とし、平均値を採用した。 (3) Measurement of drape value Stretch the reinforcing fiber bundle cut to 30 cm and place it on a flat table, and make sure that it does not bend or twist. When bending or twisting occurs, it is preferable to remove by heating at 100 ° C. or less or pressurization at 0.1 MPa or less. As shown in FIG. 12, under the atmosphere of 23 ± 5 ° C., the reinforcing fiber bundle cut to 30 cm was fixed to the end of the rectangular parallelepiped base, and at this time, the reinforcing fiber bundle was fixed so as to project 25 cm from the base end . That is, theportion 5 cm from the end of the reinforcing fiber bundle was made to come to the end of the platform. After standing for 5 minutes in this state, the shortest distance between the tip of the reinforcing fiber bundle not fixed to the table and the side surface of the table was measured, and this was taken as the drape value D1. The measured reinforcing fiber bundle was immersed in water at 25 ° C. for 5 minutes, then taken out, and the water was removed. Next, the reinforcing fiber bundle is dried at 80 ° C. under vacuum conditions for 24 hours, is absolutely dried, and is taken as a post-immersion treatment drape value D2 in the same manner as the above method. The number of measurements was n = 5, and the average value was adopted.
30cmに切断した強化繊維束をまっすぐ伸ばして平らな台に載せ、湾曲したり撚れたりしないことを確認する。湾曲あるいは撚れが発生した場合、100℃以下の加熱、あるいは、0.1MPa以下の加圧によって除くことが好ましい。図12に示すように、23±5℃の雰囲気下、直方体の台の端に、30cmに切断した強化繊維束を固定し、この時、強化繊維束は台の端から25cm突き出るように固定した。すなわち、強化繊維束の端から5cmの部分が、台の端に来るようにした。この状態で5分間静置した後、台に固定していない方の強化繊維束の先端と、台の側面との最短距離を測定し、ドレープ値D1とした。測定した前記強化繊維束を25℃の水に、5分間浸漬した後、取り出し、水を切った。次に強化繊維束を80℃、真空条件下で24時間乾燥し、絶乾した後、前記方法と同様の方法で浸漬処理後ドレープ値D2とした。測定本数はn=5とし、平均値を採用した。 (3) Measurement of drape value Stretch the reinforcing fiber bundle cut to 30 cm and place it on a flat table, and make sure that it does not bend or twist. When bending or twisting occurs, it is preferable to remove by heating at 100 ° C. or less or pressurization at 0.1 MPa or less. As shown in FIG. 12, under the atmosphere of 23 ± 5 ° C., the reinforcing fiber bundle cut to 30 cm was fixed to the end of the rectangular parallelepiped base, and at this time, the reinforcing fiber bundle was fixed so as to project 25 cm from the base end . That is, the
(4)硬度の測定
強化繊維束の硬度は、JIS L-1096 E法(ハンドルオメータ法)に準じ、HANDLE-O-Meter(大栄科学精機製作所製「CAN-1MCB」)を用いて測定した。硬度測定に用いる試験片の長さは10cm、幅はフィラメント数1,700本~550本で1mmとなるように強化繊維束を開繊調整した。また、スリット幅は20mmに設定した。このスリット溝が設けられた試験台に試験片となる強化繊維束を1本乗せ、ブレードにて溝の所定深さ(8mm)まで試験片を押し込むときに発生する抵抗力(g)を測定した。強化繊維束の硬度は3回の測定の平均値から得た。 (4) Measurement of Hardness The hardness of the reinforcing fiber bundle was measured using HANDLE-O-Meter ("CAN-1 MCB" manufactured by Daiei Kagaku Seiki, Ltd.) according to JIS L-1096 E method (handle ohm method). . The reinforcing fiber bundle was opened and adjusted so that the length of the test piece used for hardness measurement was 10 cm, and the width was 1 mm with 1,700 to 550 filaments. The slit width was set to 20 mm. One reinforcing fiber bundle as a test piece was placed on the test table provided with the slit groove, and the resistance (g) generated when the test piece was pushed into the groove to a predetermined depth (8 mm) with a blade was measured. . The hardness of the reinforcing fiber bundle was obtained from the average value of three measurements.
強化繊維束の硬度は、JIS L-1096 E法(ハンドルオメータ法)に準じ、HANDLE-O-Meter(大栄科学精機製作所製「CAN-1MCB」)を用いて測定した。硬度測定に用いる試験片の長さは10cm、幅はフィラメント数1,700本~550本で1mmとなるように強化繊維束を開繊調整した。また、スリット幅は20mmに設定した。このスリット溝が設けられた試験台に試験片となる強化繊維束を1本乗せ、ブレードにて溝の所定深さ(8mm)まで試験片を押し込むときに発生する抵抗力(g)を測定した。強化繊維束の硬度は3回の測定の平均値から得た。 (4) Measurement of Hardness The hardness of the reinforcing fiber bundle was measured using HANDLE-O-Meter ("CAN-1 MCB" manufactured by Daiei Kagaku Seiki, Ltd.) according to JIS L-1096 E method (handle ohm method). . The reinforcing fiber bundle was opened and adjusted so that the length of the test piece used for hardness measurement was 10 cm, and the width was 1 mm with 1,700 to 550 filaments. The slit width was set to 20 mm. One reinforcing fiber bundle as a test piece was placed on the test table provided with the slit groove, and the resistance (g) generated when the test piece was pushed into the groove to a predetermined depth (8 mm) with a blade was measured. . The hardness of the reinforcing fiber bundle was obtained from the average value of three measurements.
(5)サイジング剤が塗布された強化繊維束の幅変化率測定
強化繊維束の分繊処理を施す前の幅30mmから85mmに拡幅され、サイジング剤が塗布された強化繊維束を長さ230mmにカットし、その一端の端から30mmの位置をクリップで挟み、逆端から100mmの間で幅を5点測定し、その平均値を浸漬前におけるW1とした。その後、25℃の水に、5分間浸漬した後、取り出し、クリップで挟んだ側が上に来るように吊るした状態で1分間水を切った後、クリップで挟んだ逆端から100mmの間における幅を5点測定し、その平均値を浸漬後におけるW2とした。以上の処理を経て、樹脂含有強化繊維束の幅変化率を次式により求めた。
幅変化率=W2/W1 (5) Measurement of width change rate of reinforcing fiber bundle coated with sizing agent Width of reinforcing fiber bundle expanded from 30 mm to 85 mm before subjected to reinforcing treatment of reinforcing fiber bundle, length is 230 mm It cut, pinched the position of 30 mm from the end of one end with a clip, measured five points of width between 100 mm from an opposite end, and made the average value W1 before immersion. Then, immerse in water at 25 ° C for 5 minutes, then take it out and hang it up so that the clipped side is up for 1 minute, then remove the water for 1 minute, and then the width between 100mm from the opposite end pinched by the clip Was measured at five points, and the average value was taken as W2 after immersion. After the above processing, the width change rate of the resin-containing reinforcing fiber bundle was determined by the following equation.
Width change rate = W2 / W1
強化繊維束の分繊処理を施す前の幅30mmから85mmに拡幅され、サイジング剤が塗布された強化繊維束を長さ230mmにカットし、その一端の端から30mmの位置をクリップで挟み、逆端から100mmの間で幅を5点測定し、その平均値を浸漬前におけるW1とした。その後、25℃の水に、5分間浸漬した後、取り出し、クリップで挟んだ側が上に来るように吊るした状態で1分間水を切った後、クリップで挟んだ逆端から100mmの間における幅を5点測定し、その平均値を浸漬後におけるW2とした。以上の処理を経て、樹脂含有強化繊維束の幅変化率を次式により求めた。
幅変化率=W2/W1 (5) Measurement of width change rate of reinforcing fiber bundle coated with sizing agent Width of reinforcing fiber bundle expanded from 30 mm to 85 mm before subjected to reinforcing treatment of reinforcing fiber bundle, length is 230 mm It cut, pinched the position of 30 mm from the end of one end with a clip, measured five points of width between 100 mm from an opposite end, and made the average value W1 before immersion. Then, immerse in water at 25 ° C for 5 minutes, then take it out and hang it up so that the clipped side is up for 1 minute, then remove the water for 1 minute, and then the width between 100mm from the opposite end pinched by the clip Was measured at five points, and the average value was taken as W2 after immersion. After the above processing, the width change rate of the resin-containing reinforcing fiber bundle was determined by the following equation.
Width change rate = W2 / W1
(6)チョップド繊維束の幅変化率測定
強化繊維束をカットし得られた、チョップド繊維束の幅を顕微鏡を用いて測定し、浸漬前におけるW3とした。その後、25℃の水に、5分間浸漬した後、ピンセットを用いて取り出し、形態がずれないように慎重にキムワイプ上に配置し、1分間水を切った後、幅を測定し、浸漬後におけるW4とした。以上の処理を経て、チョップド繊維束の幅変化率を次式により求めた。
幅変化率=W4/W3 (6) Measurement of Width Change Rate of Chopped Fiber Bundle The width of the chopped fiber bundle obtained by cutting the reinforcing fiber bundle was measured using a microscope and was defined as W3 before immersion. After soaking in 25 ° C. water for 5 minutes, take out with tweezers and carefully place on Kimwipe so that the form does not shift, and after 1 minute of water draining, measure the width, and after immersion It was W4. After the above processing, the width change rate of the chopped fiber bundle was determined by the following equation.
Width change rate = W4 / W3
強化繊維束をカットし得られた、チョップド繊維束の幅を顕微鏡を用いて測定し、浸漬前におけるW3とした。その後、25℃の水に、5分間浸漬した後、ピンセットを用いて取り出し、形態がずれないように慎重にキムワイプ上に配置し、1分間水を切った後、幅を測定し、浸漬後におけるW4とした。以上の処理を経て、チョップド繊維束の幅変化率を次式により求めた。
幅変化率=W4/W3 (6) Measurement of Width Change Rate of Chopped Fiber Bundle The width of the chopped fiber bundle obtained by cutting the reinforcing fiber bundle was measured using a microscope and was defined as W3 before immersion. After soaking in 25 ° C. water for 5 minutes, take out with tweezers and carefully place on Kimwipe so that the form does not shift, and after 1 minute of water draining, measure the width, and after immersion It was W4. After the above processing, the width change rate of the chopped fiber bundle was determined by the following equation.
Width change rate = W4 / W3
(7)Wf(繊維強化樹脂成形材料中の強化繊維の重量含有率)
繊維強化樹脂成形材料から約2gのサンプルを切り出し、その質量を測定した。その後、サンプルを500℃に加熱した電気炉の中で1時間加熱してマトリックス樹脂等の有機物を焼き飛ばした。室温まで冷却してから、残った強化繊維の質量を測定した。強化繊維の質量に対する、マトリックス樹脂等の有機物を焼き飛ばす前のサンプルの質量に対する比率を測定し、強化繊維の重量含有率Wf(重量%)を算出した。 (7) Wf (weight content of reinforcing fibers in fiber-reinforced resin molding material)
About 2 g of a sample was cut out of the fiber-reinforced resin molding material, and its mass was measured. Thereafter, the sample was heated in an electric furnace heated to 500 ° C. for 1 hour to burn off organic substances such as matrix resin. After cooling to room temperature, the weight of the remaining reinforcing fibers was measured. The ratio to the mass of the sample before burning off the organic matter such as the matrix resin with respect to the mass of the reinforcing fiber was measured, and the weight content Wf (% by weight) of the reinforcing fiber was calculated.
繊維強化樹脂成形材料から約2gのサンプルを切り出し、その質量を測定した。その後、サンプルを500℃に加熱した電気炉の中で1時間加熱してマトリックス樹脂等の有機物を焼き飛ばした。室温まで冷却してから、残った強化繊維の質量を測定した。強化繊維の質量に対する、マトリックス樹脂等の有機物を焼き飛ばす前のサンプルの質量に対する比率を測定し、強化繊維の重量含有率Wf(重量%)を算出した。 (7) Wf (weight content of reinforcing fibers in fiber-reinforced resin molding material)
About 2 g of a sample was cut out of the fiber-reinforced resin molding material, and its mass was measured. Thereafter, the sample was heated in an electric furnace heated to 500 ° C. for 1 hour to burn off organic substances such as matrix resin. After cooling to room temperature, the weight of the remaining reinforcing fibers was measured. The ratio to the mass of the sample before burning off the organic matter such as the matrix resin with respect to the mass of the reinforcing fiber was measured, and the weight content Wf (% by weight) of the reinforcing fiber was calculated.
(8)力学特性の評価方法
繊維強化樹脂成形材料を後記する方法により成形し、500×400mmの平板成形品を得た。平板長手方向を0°とし、得られた平板より0°と90°方向から、それぞれ100×25×2mmの試験片を16片(合計32片)を切り出し、JIS K7074(1988年)に準拠し、曲げ強度を求めた。曲げ強度が350MPa以上をA、350MPa未満をBと判定した。 (8) Evaluation Method of Mechanical Properties The fiber-reinforced resin molding material was molded by a method described later to obtain a flat molded article of 500 × 400 mm. With the flat plate longitudinal direction set to 0 °, 16 pieces (total 32 pieces) of 100 × 25 × 2 mm test pieces are cut out from the obtained flat plate from 0 ° and 90 ° directions, respectively, according to JIS K 7074 (1988) , Bending strength was determined. The bending strength was determined to be A at 350 MPa or more and B at less than 350 MPa.
繊維強化樹脂成形材料を後記する方法により成形し、500×400mmの平板成形品を得た。平板長手方向を0°とし、得られた平板より0°と90°方向から、それぞれ100×25×2mmの試験片を16片(合計32片)を切り出し、JIS K7074(1988年)に準拠し、曲げ強度を求めた。曲げ強度が350MPa以上をA、350MPa未満をBと判定した。 (8) Evaluation Method of Mechanical Properties The fiber-reinforced resin molding material was molded by a method described later to obtain a flat molded article of 500 × 400 mm. With the flat plate longitudinal direction set to 0 °, 16 pieces (total 32 pieces) of 100 × 25 × 2 mm test pieces are cut out from the obtained flat plate from 0 ° and 90 ° directions, respectively, according to JIS K 7074 (1988) , Bending strength was determined. The bending strength was determined to be A at 350 MPa or more and B at less than 350 MPa.
(9)流動性試験(スタンピング成形)
寸法150mm×150mm×2mmの繊維強化樹脂成形材料を2枚重ねた状態で、基材中心温度(二枚重ねた間の温度)が260℃となるように予熱後、150℃に昇温したプレス盤に配し、10MPaで30秒間加圧した。この圧縮後の面積A2(mm2)と、プレス前の繊維強化樹脂成形材料の面積A1(mm2)を測定し、A2/A1×100を流動率(%)とした。流動率が250%以上をA、250%未満をBと判定した。
・樹脂シート2の場合
寸法150mm×150mm×2mmの繊維強化樹脂成形材料を2枚重ねた状態で、基材中心温度(二枚重ねた間の温度)が220℃となるように予熱後、120℃に昇温したプレス盤に配し、10MPaで30秒間加圧した。この圧縮後の面積A2(mm2)と、プレス前の基材の面積A1(mm2)を測定し、A2/A1×100を流動率(%)とした。流動率が200%未満をC、200%以上300%未満をB、300%以上をAと判定した。 (9) Fluidity test (stamping)
A press machine heated to 150 ° C after preheating so that the substrate center temperature (temperature between two sheets overlap) becomes 260 ° C in a state where two fiber reinforced resin molding materials ofdimensions 150 mm × 150 mm × 2 mm are stacked Distribute and pressurize at 10 MPa for 30 seconds. This area after compression A2 (mm 2), measuring the area A1 (mm 2) of the press prior to the fiber-reinforced resin molding material was the A2 / A1 × 100 and the flow rate (%). The flow rate was determined to be 250% or more as A, and less than 250% as B.
In the case ofresin sheet 2, in a state where two fiber reinforced resin molding materials of dimensions 150 mm × 150 mm × 2 mm are stacked, the temperature is raised to 120 ° C. after preheating so that the substrate center temperature (temperature between two sheets stacked) becomes 220 ° C. It was placed on a heated press platen and pressurized at 10 MPa for 30 seconds. The area A2 (mm 2 ) after this compression and the area A1 (mm 2 ) of the substrate before pressing were measured, and A2 / A1 × 100 was taken as the flow rate (%). The fluidity was determined to be less than 200% C, 200% or more and less than 300% B, and 300% or more A.
寸法150mm×150mm×2mmの繊維強化樹脂成形材料を2枚重ねた状態で、基材中心温度(二枚重ねた間の温度)が260℃となるように予熱後、150℃に昇温したプレス盤に配し、10MPaで30秒間加圧した。この圧縮後の面積A2(mm2)と、プレス前の繊維強化樹脂成形材料の面積A1(mm2)を測定し、A2/A1×100を流動率(%)とした。流動率が250%以上をA、250%未満をBと判定した。
・樹脂シート2の場合
寸法150mm×150mm×2mmの繊維強化樹脂成形材料を2枚重ねた状態で、基材中心温度(二枚重ねた間の温度)が220℃となるように予熱後、120℃に昇温したプレス盤に配し、10MPaで30秒間加圧した。この圧縮後の面積A2(mm2)と、プレス前の基材の面積A1(mm2)を測定し、A2/A1×100を流動率(%)とした。流動率が200%未満をC、200%以上300%未満をB、300%以上をAと判定した。 (9) Fluidity test (stamping)
A press machine heated to 150 ° C after preheating so that the substrate center temperature (temperature between two sheets overlap) becomes 260 ° C in a state where two fiber reinforced resin molding materials of
In the case of
(10)工程通過性
強化繊維束を分繊する工程、および、分繊した強化繊維束を連続でカットし散布する工程通過性について下記の通り判定した。
A:強化繊維束を分繊できる。分繊した強化繊維束をボビンから巻き出し、問題なくカット、散布できる。
B:強化繊維束を分繊できる。しかし、分繊した強化繊維束がボビンやカッター部で10回に1~7回、巻き付く。
C:強化繊維束を分繊できない。あるいは、分繊繊維できるが、分繊した強化繊維束がボビンやカッター部で10回に8回以上巻き付く。 (10) Process Passability The step of separating the reinforcing fiber bundle and the step passing property of continuously cutting and dispersing the divided reinforcing fiber bundle were determined as follows.
A: Reinforcing fiber bundle can be separated. The divided reinforcing fiber bundle can be unwound from a bobbin and cut and dispersed without any problem.
B: The reinforcing fiber bundle can be separated. However, the divided reinforcing fiber bundle is wound 1 to 7 times in 10 times at the bobbin or cutter portion.
C: The reinforcing fiber bundle can not be separated. Alternatively, separation fibers can be used, but the separated reinforcing fiber bundle is wound eight times or more in ten times at the bobbin or cutter portion.
強化繊維束を分繊する工程、および、分繊した強化繊維束を連続でカットし散布する工程通過性について下記の通り判定した。
A:強化繊維束を分繊できる。分繊した強化繊維束をボビンから巻き出し、問題なくカット、散布できる。
B:強化繊維束を分繊できる。しかし、分繊した強化繊維束がボビンやカッター部で10回に1~7回、巻き付く。
C:強化繊維束を分繊できない。あるいは、分繊繊維できるが、分繊した強化繊維束がボビンやカッター部で10回に8回以上巻き付く。 (10) Process Passability The step of separating the reinforcing fiber bundle and the step passing property of continuously cutting and dispersing the divided reinforcing fiber bundle were determined as follows.
A: Reinforcing fiber bundle can be separated. The divided reinforcing fiber bundle can be unwound from a bobbin and cut and dispersed without any problem.
B: The reinforcing fiber bundle can be separated. However, the divided reinforcing fiber bundle is wound 1 to 7 times in 10 times at the bobbin or cutter portion.
C: The reinforcing fiber bundle can not be separated. Alternatively, separation fibers can be used, but the separated reinforcing fiber bundle is wound eight times or more in ten times at the bobbin or cutter portion.
(実施例1)
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、50mm幅の幅規制ロールを通すことで50mmへ拡幅した強化繊維束を得た。 Example 1
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll oscillating in the axial direction at 10 Hz, apply a widening treatment, and then pass a 50 mm wide width regulating roll To obtain a reinforced fiber bundle expanded to 50 mm.
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、50mm幅の幅規制ロールを通すことで50mmへ拡幅した強化繊維束を得た。 Example 1
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll oscillating in the axial direction at 10 Hz, apply a widening treatment, and then pass a 50 mm wide width regulating roll To obtain a reinforced fiber bundle expanded to 50 mm.
次に2次サイジング剤(サイジング剤(1))を精製水で希釈した樹脂処理液に、拡幅した強化繊維束を連続で浸漬させて、次いで250℃のホットローラと250℃の乾燥炉(大気雰囲気下)を通させ、1.5分間の熱処理を施した。強化繊維束のサイジング剤付着量は0.1重量%であった。なお、これは1次サイジング剤を含まない総付着量である。
Next, the expanded reinforcing fiber bundle is continuously immersed in a resin treatment solution in which a secondary sizing agent (sizing agent (1)) is diluted with purified water, and then a 250 ° C. hot roller and a 250 ° C. drying oven (air) Under the atmosphere) and heat treatment for 1.5 minutes. The sizing agent adhesion amount of the reinforcing fiber bundle was 0.1% by weight. In addition, this is the total adhesion amount which does not contain a primary sizing agent.
得られた強化繊維束に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を強化繊維束に対して、間欠的に抜き挿しした。この時、一定速度10m/分で走行する強化繊維束に対して、3秒間分繊処理手段を突き刺し、0.2秒間で分繊処理手段を抜き、再度突き刺す工程を繰り返し行なった。表1に示す通り、得られたれ繊維束幅W3は1mm程度となった。
An iron plate for separation processing equipped with a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained reinforcing fiber bundle is parallel to the reinforcing fiber bundle width direction at 1 mm intervals. The set separation processing means was prepared. This separation processing means was intermittently pulled out and inserted into the reinforcing fiber bundle. At this time, the reinforcing fiber bundle traveling at a constant speed of 10 m / min was pierced with the separating treatment means for 3 seconds, the separating treatment means was removed in 0.2 seconds, and the process of piercing again was repeated. As shown in Table 1, the obtained fiber bundle width W3 was about 1 mm.
続いて、得られた強化繊維束を、ロータリーカッターへ連続で投入して繊維長25mm、切断角度20°に切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は250g/m2であった。
Subsequently, the obtained reinforcing fiber bundle is continuously charged into a rotary cutter, cut at a fiber length of 25 mm, a cutting angle of 20 °, and dispersed so as to disperse uniformly, so that the fiber orientation is isotropic. A fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 250 g / m 2 .
次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように、不連続繊維不織布5枚と樹脂シート(1)10枚(樹脂シートを不織布最表層に1枚、不織布の層間に2枚配置。)を積層した後に、全体をステンレス板で挟み、240℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mm、強化繊維重量含有率46重量%の繊維強化樹脂成形材料を得た。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。
Next, 5 sheets of the discontinuous fiber non-woven fabric and 10 sheets of the resin sheet (1) (one resin sheet as the outermost layer of the non-woven fabric, so that the weight ratio of the discontinuous fiber non-woven fabric to the resin sheet (1) is 45: 55 After laminating two sheets between the layers of the non-woven fabric), the whole was sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and then hot pressed at 240 ° C. for 180 seconds while applying a pressure of 2.0 MPa. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm and a reinforcing fiber weight content of 46% by weight. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例2)
サイジング剤(1)の付着量を2重量%とした以外は実施例1と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 2)
The evaluation was performed in the same manner as Example 1 except that the adhesion amount of the sizing agent (1) was 2% by weight. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
サイジング剤(1)の付着量を2重量%とした以外は実施例1と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 2)
The evaluation was performed in the same manner as Example 1 except that the adhesion amount of the sizing agent (1) was 2% by weight. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例3)
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、30mm幅の幅規制ロールを通すことで30mmへ拡幅した拡幅繊維束を得た。 (Example 3)
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a 30 mm wide width regulating roll To obtain a widened fiber bundle widened to 30 mm.
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、30mm幅の幅規制ロールを通すことで30mmへ拡幅した拡幅繊維束を得た。 (Example 3)
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a 30 mm wide width regulating roll To obtain a widened fiber bundle widened to 30 mm.
拡幅幅を30mmとする以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。
The evaluation was performed in the same manner as in Example 2 except that the widening width was set to 30 mm. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例4)
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、90mm幅の幅規制ロールを通すことで85mmへ拡幅した拡幅繊維束を得た。 (Example 4)
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a 90 mm width regulating roll To obtain an expanded fiber bundle expanded to 85 mm.
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、90mm幅の幅規制ロールを通すことで85mmへ拡幅した拡幅繊維束を得た。 (Example 4)
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a 90 mm width regulating roll To obtain an expanded fiber bundle expanded to 85 mm.
拡幅幅を85mmとする以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。
The evaluation was performed in the same manner as in Example 2 except that the widening width was 85 mm. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例5)
2次サイジング剤の熱処理温度、時間を350℃、16分とすること以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 5)
Evaluation was performed in the same manner as in Example 2 except that the heat treatment temperature and time of the secondary sizing agent were set to 350 ° C. and 16 minutes. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
2次サイジング剤の熱処理温度、時間を350℃、16分とすること以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 5)
Evaluation was performed in the same manner as in Example 2 except that the heat treatment temperature and time of the secondary sizing agent were set to 350 ° C. and 16 minutes. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例6)
2次サイジング剤のサイジング剤(1)をサイジング剤(2)とした以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 6)
Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (2). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
2次サイジング剤のサイジング剤(1)をサイジング剤(2)とした以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 6)
Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (2). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例7)
2次サイジング剤のサイジング剤(1)をサイジング剤(3)とした以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 7)
Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (3). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
2次サイジング剤のサイジング剤(1)をサイジング剤(3)とした以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 7)
Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (3). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例8)
2次サイジング剤のサイジング剤(1)をサイジング剤(4)とした以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 8)
Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (4). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
2次サイジング剤のサイジング剤(1)をサイジング剤(4)とした以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 8)
Evaluation was performed in the same manner as in Example 2 except that the sizing agent (1) of the secondary sizing agent was changed to the sizing agent (4). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(比較例1)
2次サイジング剤を付与しない以外は実施例1と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Comparative example 1)
The evaluation was performed in the same manner as in Example 1 except that the secondary sizing agent was not applied. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
2次サイジング剤を付与しない以外は実施例1と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Comparative example 1)
The evaluation was performed in the same manner as in Example 1 except that the secondary sizing agent was not applied. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例9)
2次サイジング剤の熱処理温度、時間を100℃、0.3分とすること以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 9)
The evaluation was performed in the same manner as in Example 2 except that the heat treatment temperature and time of the secondary sizing agent were set to 100 ° C. and 0.3 minutes. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
2次サイジング剤の熱処理温度、時間を100℃、0.3分とすること以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Example 9)
The evaluation was performed in the same manner as in Example 2 except that the heat treatment temperature and time of the secondary sizing agent were set to 100 ° C. and 0.3 minutes. Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(比較例2)
強化繊維束(1)を強化繊維束(2)にすること以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Comparative example 2)
Evaluation was performed in the same manner as in Example 2 except that the reinforcing fiber bundle (1) was changed to the reinforcing fiber bundle (2). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
強化繊維束(1)を強化繊維束(2)にすること以外は実施例2と同様にして評価を行った。強化繊維束の特性、プロセス通過性や力学特性、流動性の結果を表1に示す。 (Comparative example 2)
Evaluation was performed in the same manner as in Example 2 except that the reinforcing fiber bundle (1) was changed to the reinforcing fiber bundle (2). Table 1 shows the properties of the reinforced fiber bundle, process passability, mechanical properties, and flowability.
(実施例10)
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで39mm幅へ拡幅した繊維束を得た。 (Example 10)
The reinforcing fiber bundle (1) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 39 mm width A wide fiber bundle was obtained.
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで39mm幅へ拡幅した繊維束を得た。 (Example 10)
The reinforcing fiber bundle (1) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 39 mm width A wide fiber bundle was obtained.
サイジング剤(1)を水に溶解させた母液を調整し、4.1重量%の付着量になるよう、浸漬法により架橋剤であるエポキシサイジング剤を含む強化繊維束(1)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(1)の単位幅あたりの繊維数1,290本/mm、束厚み0.07mm、ドレープ値135mm、束硬度78gであった。
A mother liquor in which the sizing agent (1) is dissolved in water is prepared and applied to a reinforcing fiber bundle (1) containing an epoxy sizing agent which is a crosslinking agent by a dipping method so as to obtain a coverage of 4.1% by weight. Drying was carried out with a hot roller at 250 ° C. for 0.5 minutes. As shown in Table 1, the fiber number per unit width of the reinforcing fiber bundle (1) was 1,290 fibers / mm, the bundle thickness was 0.07 mm, the drape value was 135 mm, and the bundle hardness was 78 g.
得られたサイジング剤付与済み拡幅強化繊維束(1)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、束内平均繊維数が1,120本、平均束幅が0.6mmの強化繊維束(1)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (1) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to obtain a reinforced fiber bundle (1) having an average number of fibers in the bundle of 1,120 and an average bundle width of 0.6 mm.
続いて、得られた強化繊維束(1)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Then, the fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (1) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例11)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで32mm幅へ拡幅した繊維束を得た。 (Example 11)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to a width of 32 mm. A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで32mm幅へ拡幅した繊維束を得た。 (Example 11)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to a width of 32 mm. A wide fiber bundle was obtained.
架橋剤であるメラミンと追サイジング剤(1)の比0.22となるように水に溶解させた母液を調整し、3.2重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,540本/mm、束厚み0.08mm、ドレープ値138mm、束硬度81gであった。
Adjust the mother liquor dissolved in water so that the ratio of melamine, which is a crosslinking agent, to the sizing agent (1) is 0.22, and adjust the reinforcing fiber bundle by an immersion method so that the adhesion amount is 3.2% by weight. 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,540, the bundle thickness was 0.08 mm, the drape value was 138 mm, and the bundle hardness was 81 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が990本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated again to divide the expanded reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 990 and an average bundle width of 0.6 mm.
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(2)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、240℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、210℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (2) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 210 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例12)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 12)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 12)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
架橋剤であるユリアと追サイジング剤(2)の比0.04となるように水に溶解させた母液を調整し、4.0重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,480本/mm、束厚み0.08mm、ドレープ値142mm、束硬度89gであった。
Adjust the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (2) is 0.04, and so that the adhesion amount is 4.0% by weight, by the immersion method 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,480, the bundle thickness was 0.08 mm, the drape value was 142 mm, and the bundle hardness was 89 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,030本、平均束幅が0.7mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,030 and an average bundle width of 0.7 mm .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例13)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで41mm幅へ拡幅した繊維束を得た。 (Example 13)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll of 41 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで41mm幅へ拡幅した繊維束を得た。 (Example 13)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll of 41 mm width A wide fiber bundle was obtained.
架橋剤であるフェノールと追サイジング剤(2)の比0.38となるように水に溶解させた母液を調整し、3.1重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,220本/mm、束厚み0.07mm、ドレープ値233mm、束硬度195gであった。
Adjust the mother liquor dissolved in water so that the ratio of phenol, which is a crosslinking agent, to the additional sizing agent (2) is 0.38, and soak the reinforcing fiber bundle by an immersion method so that the adhesion amount is 3.1% by weight. 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the fiber number per unit width of the reinforcing fiber bundle (4) was 1,220 fibers / mm, the bundle thickness was 0.07 mm, the drape value was 233 mm, and the bundle hardness was 195 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,880本、平均束幅が0.4mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,880 and an average bundle width of 0.4 mm .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例14)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで37mm幅へ拡幅した繊維束を得た。 (Example 14)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 37 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで37mm幅へ拡幅した繊維束を得た。 (Example 14)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 37 mm width A wide fiber bundle was obtained.
架橋剤であるユリアと追サイジング剤(2)の比0.04となるように水に溶解させた母液を調整し、2.8重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,350本/mm、束厚み0.07mm、ドレープ値133mm、束硬度78gであった。
Adjust the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (2) is 0.04, and so that the adhesion amount is 2.8% by weight, the reinforcing fiber bundle 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,350 fibers / mm, the bundle thickness was 0.07 mm, the drape value was 133 mm, and the bundle hardness was 78 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が5,230本、平均束幅が3.4mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 5,230 and an average bundle width of 3.4 mm. .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例15)
強化繊維束(3)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで3mm幅へ拡幅した繊維束を得た。 (Example 15)
Unwind the reinforcing fiber bundle (3) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening treatment, and then pass a width regulating roll to 3 mm width A wide fiber bundle was obtained.
強化繊維束(3)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで3mm幅へ拡幅した繊維束を得た。 (Example 15)
Unwind the reinforcing fiber bundle (3) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening treatment, and then pass a width regulating roll to 3 mm width A wide fiber bundle was obtained.
架橋剤であるメラミンと追サイジング剤(2)の比0.22となるように水に溶解させた母液を調整し、3.3重量%の付着量になるよう、浸漬法により強化繊維束(3)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(3)の単位幅あたりの繊維数550本/mm、束厚み0.07mm、ドレープ値127mm、束硬度76gであった。
Adjust the mother liquor dissolved in water so that the ratio of melamine, which is a crosslinking agent, and the sizing agent (2) is 0.22, and soak the reinforcing fiber bundle by an immersion method so that the adhesion amount is 3.3% by weight. 3) and dried for 0.5 minutes with a 250 ° C. hot roller. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (3) was 550, the bundle thickness was 0.07 mm, the drape value was 127 mm, and the bundle hardness was 76 g.
得られたサイジング剤付与済み拡幅強化繊維束(3)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(3)を分繊し、束内平均繊維数が410本、平均束幅が0.7mmの強化繊維束(3)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (3) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (3) to obtain a reinforcing fiber bundle (3) having an average number of fibers in the bundle of 410 and an average bundle width of 0.7 mm.
続いて、得られた強化繊維束(3)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(2)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、240℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、210℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (3) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (2) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 210 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例16)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 16)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 16)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
架橋剤であるユリアと追サイジング剤(3)の比0.22となるように水に溶解させた母液を調整し、5.5重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,480本/mm、束厚み0.08mm、ドレープ値180mm、束硬度123gであった。
Adjust the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (3) is 0.22, and so that the adhesion amount is 5.5% by weight, by the immersion method 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,480, the bundle thickness was 0.08 mm, the drape value was 180 mm, and the bundle hardness was 123 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が930本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 930 and an average bundle width of 0.6 mm.
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例17)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで28mm幅へ拡幅した繊維束を得た。 (Example 17)
The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 28 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで28mm幅へ拡幅した繊維束を得た。 (Example 17)
The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 28 mm width A wide fiber bundle was obtained.
架橋剤であるメラミンと追サイジング剤(3)の比0.22となるように水に溶解させた母液を調整し、3.3重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,780本/mm、束厚み0.1mm、ドレープ値204mm、束硬度163gであった。
Adjust the mother liquor dissolved in water so that the ratio of melamine, which is a crosslinking agent, to the sizing agent (3) is 0.22, and use a dipping method to obtain an adhesion amount of 3.3% by weight ( 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,780, the bundle thickness was 0.1 mm, the drape value was 204 mm, and the bundle hardness was 163 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,540本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to divide the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 1,540 and an average bundle width of 0.6 mm .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例18)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで13mm幅へ拡幅した繊維束を得た。 (Example 18)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 13 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで13mm幅へ拡幅した繊維束を得た。 (Example 18)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 13 mm width A wide fiber bundle was obtained.
架橋剤であるユリアと追サイジング剤(4)の比0.22となるように水に溶解させた母液を調整し、4.7重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数3,940本/mm、束厚み0.21mm、ドレープ値243mm、束硬度220gであった。
Adjust the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (4) is 0.22, and so that the adhesion amount is 4.7% by weight, by the immersion method 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 3,940, the bundle thickness was 0.21 mm, the drape value was 243 mm, and the bundle hardness was 220 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,120本、平均束幅が0.3mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,120 and an average bundle width of 0.3 mm .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(2)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、240℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、210℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (2) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 240 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 210 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例19)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで11mm幅へ拡幅した繊維束を得た。 (Example 19)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to a width of 11 mm. A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで11mm幅へ拡幅した繊維束を得た。 (Example 19)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to a width of 11 mm. A wide fiber bundle was obtained.
架橋剤であるメラミンと追サイジング剤(4)の比0.22となるように水に溶解させた母液を調整し、3.1重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数4,380本/mm、束厚み0.24mm、ドレープ値145mm、束硬度84gであった。
Adjust the mother liquor dissolved in water so that the ratio of melamine, which is a cross-linking agent, to the additional sizing agent (4) is 0.22, and make sure that the adhesion amount is 3.1% by weight. 4) and dried for 0.5 minutes with a hot roller at 250 ° C. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 4,380, the bundle thickness was 0.24 mm, the drape value was 145 mm, and the bundle hardness was 84 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が930本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 930 and an average bundle width of 0.6 mm.
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例20)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで36mm幅へ拡幅した繊維束を得た。 Example 20
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll. A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで36mm幅へ拡幅した繊維束を得た。 Example 20
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll. A wide fiber bundle was obtained.
架橋剤であるユリアと追サイジング剤(4)の比0.22となるように水に溶解させた母液を調整し、3.4重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、350℃のホットローラで11分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,380本/mm、束厚み0.07mm、ドレープ値136mm、束硬度80gであった。
Adjust the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (4) is 0.22, and so that the adhesion amount is 3.4% by weight, by a dipping method 4) and drying was carried out with a hot roller at 350 ° C. for 11 minutes. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,380, the bundle thickness was 0.07 mm, the drape value was 136 mm, and the bundle hardness was 80 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が2,330本、平均束幅が0.7mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 2,330 and an average bundle width of 0.7 mm. .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例21)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで33mm幅へ拡幅した繊維束を得た。 (Example 21)
The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 33 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで33mm幅へ拡幅した繊維束を得た。 (Example 21)
The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 33 mm width A wide fiber bundle was obtained.
架橋剤であるユリアと追サイジング剤(4)の比0.22となるように水に溶解させた母液を調整し、2.9重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.2分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,520本/mm、束厚み0.08mm、ドレープ値54mm、束硬度28gであった。
Adjust the mother liquor dissolved in water so that the ratio of urea, which is a crosslinking agent, to the additional sizing agent (4) is 0.22, and so that the adhesion amount is 2.9% by weight, by the immersion method 4) and drying was carried out with a hot roller at 250 ° C. for 0.2 minutes. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,520, the bundle thickness was 0.08 mm, the drape value was 54 mm, and the bundle hardness was 28 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が2,110本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 2,110 and an average bundle width of 0.6 mm .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例22)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで33mm幅へ拡幅した繊維束を得た。 (Example 22)
The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 33 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで33mm幅へ拡幅した繊維束を得た。 (Example 22)
The reinforcing fiber bundle (4) is unwound using a winder at a constant speed of 10 m / min, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 33 mm width A wide fiber bundle was obtained.
架橋剤であるメラミンと追サイジング剤(2)の比0.01となるように水に溶解させた母液を調整し、3.6重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.2分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,510本/mm、束厚み0.08mm、ドレープ値46mm、束硬度21gであった。
Adjust the mother liquor dissolved in water so that the ratio of melamine, which is a crosslinking agent, to the additional sizing agent (2) is 0.01, and use a dipping method to obtain an adhesion amount of 3.6% by weight ( 4) and drying was carried out with a hot roller at 250 ° C. for 0.2 minutes. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,510 fibers / mm, the bundle thickness was 0.08 mm, the drape value was 46 mm, and the bundle hardness was 21 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,140本、平均束幅が0.7mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to divide the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,140 and an average bundle width of 0.7 mm. .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例23)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで15mm幅へ拡幅した繊維束を得た。 (Example 23)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 15 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで15mm幅へ拡幅した繊維束を得た。 (Example 23)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 15 mm width A wide fiber bundle was obtained.
架橋剤であるメラミンと追サイジング剤(2)の比0.04となるように水に溶解させた母液を調整し、3.8重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.2分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,440本/mm、束厚み0.08mm、ドレープ値35mm、束硬度24gであった。
Adjust the mother liquor dissolved in water so that the ratio of melamine, which is a crosslinking agent, to the additional sizing agent (2) is 0.04, and use a dipping method to obtain an adhesion amount of 3.8% by weight ( 4) and drying was carried out with a hot roller at 250 ° C. for 0.2 minutes. As shown in Table 1, the fiber number per unit width of the reinforcing fiber bundle (4) was 1,440 fibers / mm, the bundle thickness was 0.08 mm, the drape value was 35 mm, and the bundle hardness was 24 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,280本、平均束幅が0.7mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to divide the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 1,280 and an average bundle width of 0.7 mm. .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例24)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 24)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 24)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
架橋剤であるフェノールと追サイジング剤(2)の比0.04となるように水に溶解させた母液を調整し、3.7重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.2分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,450本/mm、束厚み0.08mm、ドレープ値131mm、束硬度73gであった。
Adjust the mother liquor dissolved in water so that the ratio of phenol, which is a cross-linking agent, to the additional sizing agent (2) is 0.04, and immerse the reinforced fiber bundle so that the adhesion amount is 3.7% by weight 4) and drying was carried out with a hot roller at 250 ° C. for 0.2 minutes. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,450 fibers / mm, the bundle thickness was 0.08 mm, the drape value was 131 mm, and the bundle hardness was 73 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,180本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) and obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,180 and an average bundle width of 0.6 mm .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(実施例25)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 25)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで34mm幅へ拡幅した繊維束を得た。 (Example 25)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 34 mm width A wide fiber bundle was obtained.
架橋剤であるフェノールと追サイジング剤(2)の比0.04となるように水に溶解させた母液を調整し、3.6重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.2分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,480本/mm、束厚み0.08mm、ドレープ値142mm、束硬度89gであった。
Adjust the mother liquor dissolved in water so that the ratio of phenol, which is a cross-linking agent, to the additional sizing agent (2) is 0.04, and so that the adhesion amount is 3.6% by weight, 4) and drying was carried out with a hot roller at 250 ° C. for 0.2 minutes. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,480, the bundle thickness was 0.08 mm, the drape value was 142 mm, and the bundle hardness was 89 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が1,320本、平均束幅が0.02mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. Repeat the piercing operation again to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) with an average number of fibers in the bundle of 1,320 and an average bundle width of 0.02 mm. .
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を繊維長15mmに切断、均一分散するように散布することにより、繊維配向が等方的である不連続繊維不織布を得た。得られた不連続繊維不織布の目付は0.25kg/m2であった。次に、不連続繊維不織布と樹脂シート(1)の重量比が45:55となるように積層した後に、全体をステンレス板で挟み、270℃で90秒間予熱後、2.0MPaの圧力をかけながら180秒間、240℃にてホットプレスした。ついで、加圧状態で50℃まで冷却し、厚さ2mmの繊維強化樹脂成形材料を得た。この時、繊維強化樹脂成形材料の強化繊維重量含有率が46重量%になるように、樹脂シート作製の段階で樹脂の塗布量を調整した。得られた繊維強化樹脂成形材料の力学特性、流動性試験の評価を行った。結果を表2に示す。
Subsequently, fiber orientation is isotropic by continuously inserting the obtained reinforcing fiber bundle (4) into a rotary cutter, cutting the fiber bundle to a fiber length of 15 mm, and dispersing it so as to be uniformly dispersed. A discontinuous fiber non-woven fabric was obtained. The basis weight of the obtained discontinuous fiber non-woven fabric was 0.25 kg / m 2 . Next, after laminating so that the weight ratio of the discontinuous fiber non-woven fabric and the resin sheet (1) becomes 45: 55, the whole is sandwiched with a stainless steel plate, preheated at 270 ° C. for 90 seconds, and a pressure of 2.0 MPa is applied. While hot pressing at 240 ° C. for 180 seconds. Then, it was cooled to 50 ° C. in a pressurized state to obtain a fiber-reinforced resin molding material having a thickness of 2 mm. At this time, the application amount of resin was adjusted at the stage of resin sheet preparation so that the reinforcing fiber weight content of the fiber reinforced resin molding material would be 46% by weight. The mechanical properties of the obtained fiber-reinforced resin molding material and the flowability test were evaluated. The results are shown in Table 2.
(比較例4)
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで39mm幅へ拡幅した繊維束を得た。 (Comparative example 4)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 39 mm width A wide fiber bundle was obtained.
強化繊維束(4)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで39mm幅へ拡幅した繊維束を得た。 (Comparative example 4)
The reinforcing fiber bundle (4) is unwound at a constant speed of 10 m / min using a winder, passed through a vibration widening roll oscillating in an axial direction at 10 Hz, subjected to a widening treatment, and then passed through a width regulating roll to 39 mm width A wide fiber bundle was obtained.
追サイジング剤(4)を水に溶解させた母液を調整し、2.7重量%の付着量になるよう、浸漬法により強化繊維束(4)に付与し、250℃のホットローラで0.5分間、乾燥を行った。表1に示す通り、強化繊維束(4)の単位幅あたりの繊維数1,270本/mm、束厚み0.07mm、ドレープ値112mm、束硬度38gであった。
A mother liquor in which the additional sizing agent (4) is dissolved in water is prepared, applied to the reinforcing fiber bundle (4) by the immersion method so as to obtain an adhesion amount of 2.7% by weight, 0. 2 by a hot roller at 250 ° C. Drying was performed for 5 minutes. As shown in Table 1, the number of fibers per unit width of the reinforcing fiber bundle (4) was 1,270, the bundle thickness was 0.07 mm, the drape value was 112 mm, and the bundle hardness was 38 g.
得られたサイジング剤付与済み拡幅強化繊維束(4)に対して、厚み0.2mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(4)を分繊し、束内平均繊維数が970本、平均束幅が0.6mmの強化繊維束(4)を得た。
A split iron plate having a projecting shape with a thickness of 0.2 mm, a width of 3 mm, and a height of 20 mm with respect to the obtained sizing agent-applied widening reinforcing fiber bundle (4) in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The piercing operation was repeated to separate the widened reinforcing fiber bundle (4) to obtain a reinforcing fiber bundle (4) having an average number of fibers in the bundle of 970 and an average bundle width of 0.6 mm.
続いて、得られた強化繊維束(4)を、ロータリーカッターへ連続的に挿入して繊維束を切断しようとしたが、ボビンやカッター部への巻き付きが生じ成形材料を作製できなかった。
Subsequently, although it was tried to cut the fiber bundle by continuously inserting the obtained reinforced fiber bundle (4) into a rotary cutter, winding on the bobbin and the cutter portion occurred, and a molding material could not be prepared.
(比較例5)
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで41mm幅へ拡幅した繊維束を得た。 (Comparative example 5)
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a width regulating roll to 41 mm width A wide fiber bundle was obtained.
強化繊維束(1)を、ワインダーを用いて一定速度10m/分で巻き出し、10Hzで軸方向へ振動する振動拡幅ロールに通し、拡幅処理を施した後に、幅規制ロールを通すことで41mm幅へ拡幅した繊維束を得た。 (Comparative example 5)
Unwind the reinforcing fiber bundle (1) at a constant speed of 10 m / min using a winder, pass it through a vibration widening roll that vibrates in the axial direction at 10 Hz, apply a widening process, and then pass a width regulating roll to 41 mm width A wide fiber bundle was obtained.
表1に示す通り、強化繊維束(1)の単位幅あたりの繊維数1,230本/mm、束厚み0.07mm、ドレープ値54mm、束硬度27gであった。
As shown in Table 1, the fiber number per unit width of the reinforcing fiber bundle (1) was 1,230 fibers / mm, the bundle thickness was 0.07 mm, the drape value was 54 mm, and the bundle hardness was 27 g.
得られたサイジング剤付与済み拡幅強化繊維束(1)に対して、厚み0.07mm、幅3mm、高さ20mmの突出形状を具備する分繊処理用鉄製プレートを、強化繊維束の幅方向に対して1mm等間隔に並行にセットした分繊処理手段を準備した。この分繊処理手段を拡幅繊維束に対して、間欠的に抜き挿しし、分繊繊維束を得た。この時、分繊処理手段は一定速度10m/分で走行する拡幅繊維束に対して、3秒間分繊処理手段を突き刺し分繊処理区間を生成し、0.2秒間で分繊処理手段を抜き、再度突き刺す動作を繰り返し行い、拡幅された強化繊維束(1)を分繊し、束内平均繊維数が930本、平均束幅が0.6mmの強化繊維束(1)を得た。
With respect to the obtained sizing agent-applied widening reinforcing fiber bundle (1), a separation iron plate having a projecting shape with a thickness of 0.07 mm, a width of 3 mm and a height of 20 mm is provided in the width direction of the reinforcing fiber bundle On the other hand, separation processing means set in parallel at equal intervals of 1 mm were prepared. This separation processing means was intermittently pulled out and inserted from the widening fiber bundle to obtain a separation fiber bundle. At this time, the separation processing means pierces the separation processing means for 3 seconds against the widening fiber bundle traveling at a constant speed of 10 m / min to generate a separation processing section, and the separation processing means is removed in 0.2 seconds. The operation of piercing again was repeated, and the widened reinforcing fiber bundle (1) was separated to obtain a reinforcing fiber bundle (1) having an average number of fibers in the bundle of 930 and an average bundle width of 0.6 mm.
続いて、得られた強化繊維束(1)をロータリーカッターへ連続的に挿入して繊維束を切断しようとしたが、ボビンやカッター部への巻き付きが生じ成形材料を作製できなかった。
Subsequently, although it was tried to cut the fiber bundle by continuously inserting the obtained reinforced fiber bundle (1) into a rotary cutter, winding on the bobbin and the cutter portion occurred, and a molding material could not be produced.
本発明は、生産性や成形の際の流動性、成形品の力学特性に優れる強化繊維束とそのチョップド繊維束、およびその製造方法、ならびにそれを用いた繊維強化樹脂成形材料を提供できる。本発明の製造方法で得られる強化繊維束は不連続強化繊維コンポジットの材料であり、主に自動車内外装、電気・電子機器筐体、自転車、航空機内装材、輸送用箱体など等に好適に用いられる。
The present invention can provide a reinforced fiber bundle and a chopped fiber bundle thereof which are excellent in productivity, flowability in molding, and mechanical characteristics of a molded article, a method of producing the same, and a fiber-reinforced resin molding material using the same. The reinforcing fiber bundle obtained by the manufacturing method of the present invention is a material of the discontinuous reinforcing fiber composite, and is mainly suitable for automobile interior and exterior, electric / electronic equipment housing, bicycle, aircraft interior material, transport box etc. Used.
100 繊維束
110 分繊処理区間
120 絡合蓄積部
130 未分繊処理区間
140 毛羽溜まり
150 分繊処理部
160 絡合部
170 分繊距離
180 分繊繊維束
200 分繊手段
210 突出部
211 接触部
220 回転分繊手段
240 回転軸
300 分繊処理工程
301 繊維束拡幅工程
400 サイジング剤付与工程
401 サイジング剤塗布工程
402 乾燥工程
501 切断面
(1)~(4) 分繊手段移動方向
A~J パターン
a、b 繊維束走行方向 DESCRIPTION OFSYMBOLS 100 fiber bundle 110 division processing area 120 intertwining accumulation part 130 unseparating processing section 140 fluff accumulation 150 division processing part 160 entangled part 170 division distance 180 division fiber bundle 200 division means 210 projection part 211 contact part 220 Rotational dispersing means 240 Rotating shaft 300 Splitting process 301 Fiber bundle widening process 400 Sizing agent application process 401 Sizing agent application process 402 Drying process 501 Cutting plane (1) to (4) Separation means moving direction A to J pattern a, b Fiber bundle running direction
110 分繊処理区間
120 絡合蓄積部
130 未分繊処理区間
140 毛羽溜まり
150 分繊処理部
160 絡合部
170 分繊距離
180 分繊繊維束
200 分繊手段
210 突出部
211 接触部
220 回転分繊手段
240 回転軸
300 分繊処理工程
301 繊維束拡幅工程
400 サイジング剤付与工程
401 サイジング剤塗布工程
402 乾燥工程
501 切断面
(1)~(4) 分繊手段移動方向
A~J パターン
a、b 繊維束走行方向 DESCRIPTION OF
Claims (27)
- 強化繊維表面に、エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、または、それらを混合したものを含む第1のサイジング剤と、ポリアミド系樹脂を含む第2のサイジング剤とが付着していることを特徴とする強化繊維束。 The first sizing agent containing a compound having a functional group such as an epoxy group, a urethane group, an amino group, a carboxyl group or the like, or a mixture thereof on the surface of a reinforcing fiber, and a polyamide resin A reinforcing fiber bundle characterized in that a sizing agent is attached thereto.
- 単位幅当りの繊維本数が600本/mm以上1,600本/mm未満であり、強化繊維束のドレープ値が120mm以上240mm以下であることを特徴とする、請求項1に記載の強化繊維束。 The reinforcing fiber bundle according to claim 1, characterized in that the number of fibers per unit width is 600 / mm or more and less than 1,600 / mm and the drape value of the reinforcing fiber bundle is 120 mm or more and 240 mm or less. .
- 硬度が39g以上200g以下であることを特徴とする請求項1または2に記載の強化繊維束。 The reinforcing fiber bundle according to claim 1 or 2, wherein the hardness is 39 g or more and 200 g or less.
- ポリアミド系樹脂の付着量が0.1重量%以上5重量%以下であることを特徴とする請求項1~3のいずれかに記載の強化繊維束。 The reinforcing fiber bundle according to any one of claims 1 to 3, wherein the adhesion amount of the polyamide resin is 0.1% by weight or more and 5% by weight or less.
- 前記強化繊維束を25℃、5分間水に浸漬後、水から取り出した後における幅をW2とし、浸漬前における幅をW1とした場合の幅変化率W2/W1が0.5以上1.1以下であることを特徴とする請求項1~4のいずれかに記載の強化繊維束。 After immersing the reinforcing fiber bundle in water at 25 ° C. for 5 minutes, the width after taking out from water is W2, and the width change ratio W2 / W1 is 0.5 or more and 1.1 when the width before immersion is W1. The reinforcing fiber bundle according to any one of claims 1 to 4, which is as follows.
- 前記強化繊維束を25℃、5分間水に浸漬し、絶乾した後の空気中でのドレープ値D2が、110mm以上240mm以下であることを特徴とする請求項1~5のいずれかに記載の強化繊維束。 The drape value D2 in air after immersing the reinforcing fiber bundle in water at 25 ° C. for 5 minutes and drying completely is 110 mm or more and 240 mm or less according to any one of claims 1 to 5. Reinforcing fiber bundle.
- 複数の束に分繊された分繊処理区間と、未分繊処理区間とが交互に形成されている請求項1~6のいずれかに記載の強化繊維束。 The reinforced fiber bundle according to any one of claims 1 to 6, wherein a separation processing section divided into a plurality of bundles and an undivision processing section are alternately formed.
- 1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さが異なる長さを含むことを特徴とする、請求項1~7のいずれかに記載の強化繊維束。 The reinforcing fiber bundle according to any one of claims 1 to 7, characterized in that the lengths of adjacent division processing sections including one undivided processing section include different lengths.
- 請求項1~8のいずれかに記載の強化繊維束を切断してなるチョップド繊維束であって、前記チョップド繊維束を25℃、5分間水に浸漬後、取り出した後における幅をW4とし、浸漬前における幅をW3とした場合の幅変化率W4/W3が0.6以上1.1以下であることを特徴とするチョップド繊維束。 A chopped fiber bundle formed by cutting the reinforcing fiber bundle according to any one of claims 1 to 8, wherein the chopped fiber bundle is immersed in water at 25 ° C for 5 minutes, and the width after taking it out is W4. A chopped fiber bundle characterized in that a width change ratio W4 / W3 when the width before immersion is W3 is 0.6 or more and 1.1 or less.
- 前記強化繊繊維束を長手方向に対して所定角度θ(0°<θ<90°)で切断してなる請求項9に記載のチョップド繊維束。 10. The chopped fiber bundle according to claim 9, which is obtained by cutting the reinforcing fiber bundle at a predetermined angle θ (0 ° <θ <90 °) with respect to the longitudinal direction.
- 請求項9または10に記載のチョップド繊維束とマトリックス樹脂とを含む繊維強化樹脂成形材料。 A fiber-reinforced resin molding material comprising the chopped fiber bundle according to claim 9 and a matrix resin.
- 前記マトリックス樹脂がポリアミドであることを特徴とする、請求項11に記載の繊維強化樹脂成形材料。 The fiber-reinforced resin molding material according to claim 11, wherein the matrix resin is a polyamide.
- エポキシ基、ウレタン基、アミノ基、カルボキシル基等の官能基を有する化合物のいずれか、または、それらを混合したものを含む第1のサイジング剤が付着した強化繊維に水溶性ポリアミドを付与することを特徴とする強化繊維束の製造方法。 Providing a water-soluble polyamide to a reinforcing fiber to which a first sizing agent including any of compounds having functional groups such as an epoxy group, a urethane group, an amino group, and a carboxyl group or a mixture thereof is attached A method of producing a reinforced fiber bundle characterized by the present invention.
- 前記強化繊維束を開繊、拡幅する拡幅工程(I)を含むことを特徴とする、請求項13に記載の強化繊維束の製造方法 The method for producing a reinforced fiber bundle according to claim 13, characterized by comprising a widening step (I) of opening and widening the reinforced fiber bundle.
- 拡幅した前記強化繊維束にサイジング剤を塗布した後に架橋剤と反応させて強化繊維束を作製するサイジング剤付与工程(II)をさらに含むことを特徴とする請求項14に記載の強化繊維束の製造方法。 The reinforcing fiber bundle according to claim 14, further comprising a sizing agent applying step (II) of applying a sizing agent to the expanded reinforcing fiber bundle and then reacting it with a crosslinking agent to produce a reinforcing fiber bundle. Production method.
- 前記架橋剤がメラミン樹脂、ユリア樹脂、フェノール樹脂、エポキシ樹脂から選ばれる少なくとも1種の樹脂からなることを特徴とする、請求項15に記載の強化繊維束の製造方法。 The method for producing a reinforced fiber bundle according to claim 15, wherein the crosslinking agent comprises at least one resin selected from melamine resin, urea resin, phenol resin and epoxy resin.
- 前記架橋剤と前記サイジング剤の重量比が0.02以上1以下であることを特徴とする請求項14~16のいずれかに記載の強化繊維束の製造方法。 The method for producing a reinforcing fiber bundle according to any one of claims 14 to 16, wherein a weight ratio of the crosslinking agent to the sizing agent is 0.02 or more and 1 or less.
- 前記サイジング剤付与工程(II)において、強化繊維束の全サイジング剤付着量が0.5重量%以上5重量%以下となるように前記サイジング剤を塗布することを特徴とする、請求項14~17のいずれかに記載の強化繊維束の製造方法。 The sizing agent application step (II) is characterized in that the sizing agent is applied such that the total sizing agent adhesion amount of the reinforcing fiber bundle is 0.5% by weight or more and 5% by weight or less. The manufacturing method of the reinforced fiber bundle in any one of 17.
- 前記拡幅工程(I)において、強化繊維束の単位幅あたりの単糸数が1,600本/mm以下になるように拡幅することを特徴とする、請求項14~18のいずれかに記載の強化繊維束の製造方法。 The reinforcement according to any one of claims 14 to 18, characterized in that in the widening step (I), the width is increased so that the number of single yarns per unit width of the reinforcing fiber bundle is 1,600 / mm or less. Method of manufacturing fiber bundle.
- 水溶性ポリアミドが付与された前記強化繊維を熱処理する工程を含むことを特徴とする、請求項13~19のいずれかに記載の強化繊維束の製造方法。 The method for producing a reinforcing fiber bundle according to any one of claims 13 to 19, comprising the step of heat treating the reinforcing fiber to which a water-soluble polyamide is imparted.
- 前記熱処理の温度が130~350℃であることを特徴とする、請求項20に記載の強化繊維束の製造方法。 The method for producing a reinforced fiber bundle according to claim 20, wherein the temperature of the heat treatment is 130 to 350 属 C.
- 前記熱処理の時間が0.33~15分であることを特徴とする、請求項20または21に記載の強化繊維束の製造方法。 The method for producing a reinforcing fiber bundle according to claim 20 or 21, wherein the heat treatment time is 0.33 to 15 minutes.
- 前記熱処理後の水溶性ポリアミドがエステル結合、および/または、炭素-炭素の二重結合を有することを特徴とする、請求項20~22のいずれかに記載の強化繊維束の製造方法。 The method for producing a reinforcing fiber bundle according to any one of claims 20 to 22, wherein the water-soluble polyamide after the heat treatment has an ester bond and / or a carbon-carbon double bond.
- 前記水溶性ポリアミドが、主鎖中に三級アミノ基および/またはオキシエチレン基を有するジアミンとジカルボン酸とを重合して得られたものからなることを特徴とする、請求項13~23のいずれかに記載の強化繊維束の製造方法。 The water-soluble polyamide according to any one of claims 13 to 23, characterized in that it is obtained by polymerizing a diamine having a tertiary amino group and / or an oxyethylene group in its main chain and a dicarboxylic acid. The manufacturing method of the reinforced fiber bundle as described in.
- 前記強化繊維を分繊処理する工程を含むことを特徴とする、請求項13~24のいずれかに記載の強化繊維束の製造方法。 The method for producing a reinforcing fiber bundle according to any one of claims 13 to 24, comprising the step of separating the reinforcing fibers.
- 前記強化繊維束を長手方向に沿って走行させながら、複数の突出部を具備する分繊手段を前記強化繊維束に突き入れて分繊処理部を生成する分繊工程(III)と、
少なくとも1つの前記分繊処理部における前記突出部と前記強化繊維束との接触部に単糸が交絡する絡合部を形成する絡合工程(IV)と、
前記分繊手段を前記強化繊維束から抜き取り、前記絡合部を含む絡合蓄積部を通過させた後、前記分繊手段を前記強化繊維束に再度突き入れる再突き入れ工程(V)と、
複数の束に分割された分繊処理区間と未分繊処理区間とを交互に形成する分繊処理工程(VI)とをさらに含むことを特徴とする、請求項13~25のいずれかに記載の強化繊維束の製造方法。 A separating step (III) of inserting a separating means having a plurality of projecting portions into the reinforcing fiber bundle to generate a separating treatment part while traveling the reinforcing fiber bundle along the longitudinal direction;
An intertwining step (IV) of forming an intertwining portion in which a single yarn is intertwined in a contact portion between the protruding portion and the reinforcing fiber bundle in at least one of the separation processing portions;
Re-piercing step (V) in which the separating means is extracted from the reinforcing fiber bundle, passed through the entanglement storage part including the entangled part, and then the separating means is reinserted into the reinforcing fiber bundle;
26. The method according to any one of claims 13 to 25, further comprising a fiber separation treatment step (VI) alternately forming a fiber separation treated section divided into a plurality of bundles and an unsorted fiber processing section. Method of reinforcing fiber bundle of - 前記分繊処理工程(VI)において、1つの未分繊処理区間を挟んで隣接する分繊処理区間の長さが異なる長さを含むことを特徴とする請求項26に記載の強化繊維束の製造方法。
27. The reinforcing fiber bundle according to claim 26, wherein in the separation treatment step (VI), lengths of adjacent separation treatment sections sandwiching one undivided treatment section include different lengths. Production method.
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JP2002138370A (en) * | 2000-10-27 | 2002-05-14 | Toray Ind Inc | Chopped carbon fiber strand and fiber-reinforced thermoplastic resin composition |
JP2003105676A (en) * | 2001-09-28 | 2003-04-09 | Toray Ind Inc | Carbon fiber, carbon fiber-reinforced thermoplastic resin composition, molding material and molded product |
JP2005526163A (en) * | 2002-05-14 | 2005-09-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Crosslinkable polyamide compositions for paint applications, methods of using such compositions and articles made from such compositions |
WO2012081407A1 (en) * | 2010-12-13 | 2012-06-21 | 東レ株式会社 | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
JP2016194175A (en) * | 2015-04-01 | 2016-11-17 | トヨタ自動車株式会社 | Resin-coated carbon fiber and carbon fiber reinforced composite material of the same |
WO2017221657A1 (en) * | 2016-06-21 | 2017-12-28 | 東レ株式会社 | Partially separated fiber bundle, production method for partially separated fiber bundle, fiber-reinforced resin molding material using partially separated fiber bundle, and production method for fiber-reinforced resin molding material using partially separated fiber bundle |
WO2018143067A1 (en) * | 2017-02-02 | 2018-08-09 | 東レ株式会社 | Partially separated fiber bundle and method for manufacturing same, chopped-fiber bundle using same, and fiber-reinforced resin molding material |
-
2019
- 2019-01-17 JP JP2019512692A patent/JP7259740B2/en active Active
- 2019-01-17 WO PCT/JP2019/001221 patent/WO2019146486A1/en active Application Filing
Patent Citations (8)
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JPH01292038A (en) * | 1988-05-19 | 1989-11-24 | Toray Ind Inc | Non-twisted carbon fiber bundle having excellent openability, production of said bundle and apparatus therefor |
JP2002138370A (en) * | 2000-10-27 | 2002-05-14 | Toray Ind Inc | Chopped carbon fiber strand and fiber-reinforced thermoplastic resin composition |
JP2003105676A (en) * | 2001-09-28 | 2003-04-09 | Toray Ind Inc | Carbon fiber, carbon fiber-reinforced thermoplastic resin composition, molding material and molded product |
JP2005526163A (en) * | 2002-05-14 | 2005-09-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Crosslinkable polyamide compositions for paint applications, methods of using such compositions and articles made from such compositions |
WO2012081407A1 (en) * | 2010-12-13 | 2012-06-21 | 東レ株式会社 | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
JP2016194175A (en) * | 2015-04-01 | 2016-11-17 | トヨタ自動車株式会社 | Resin-coated carbon fiber and carbon fiber reinforced composite material of the same |
WO2017221657A1 (en) * | 2016-06-21 | 2017-12-28 | 東レ株式会社 | Partially separated fiber bundle, production method for partially separated fiber bundle, fiber-reinforced resin molding material using partially separated fiber bundle, and production method for fiber-reinforced resin molding material using partially separated fiber bundle |
WO2018143067A1 (en) * | 2017-02-02 | 2018-08-09 | 東レ株式会社 | Partially separated fiber bundle and method for manufacturing same, chopped-fiber bundle using same, and fiber-reinforced resin molding material |
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