WO2015115408A1 - 繊維強化多層ペレット、それを成形してなる成形品、および繊維強化多層ペレットの製造方法 - Google Patents
繊維強化多層ペレット、それを成形してなる成形品、および繊維強化多層ペレットの製造方法 Download PDFInfo
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- WO2015115408A1 WO2015115408A1 PCT/JP2015/052157 JP2015052157W WO2015115408A1 WO 2015115408 A1 WO2015115408 A1 WO 2015115408A1 JP 2015052157 W JP2015052157 W JP 2015052157W WO 2015115408 A1 WO2015115408 A1 WO 2015115408A1
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- fibrous filler
- fiber
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- fiber length
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- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/10—Extrusion moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
- B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/728—Measuring data of the driving system, e.g. torque, speed, power, vibration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
- B29K2105/122—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles microfibres or nanofibers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
Definitions
- the present invention relates to a fiber-reinforced multilayer pellet, a molded product formed by molding the fiber-reinforced multilayer pellet, and a method for manufacturing the fiber-reinforced multilayer pellet.
- a fiber filler such as glass fiber or carbon fiber is blended as a means for improving the mechanical properties of the thermoplastic resin.
- a general blending method of the fibrous filler there is a method of melt-kneading a thermoplastic resin and a chopped strand (short fiber) of a fiber in an extruder.
- thermoplastic resin in which continuous fibers of carbon fibers are impregnated with thermoplastic resin as a matrix resin, molded, cooled, and aligned in the longitudinal direction
- pultrusion method for example, patents
- a resin-impregnated fiber bundle obtained by impregnating a fiber bundle selected from metal fibers, metal-coated non-metal fibers and carbon fibers with a shaping nozzle at the exit of the crosshead die, and a pelletizer.
- pultrusion method for example, patents
- Patent Document 1 has a problem that the mechanical properties are insufficient although the flowability and the surface appearance are improved by using short glass fibers.
- both methods are methods in which the continuous long fiber bundle is covered with a thermoplastic resin while being drawn from the die. It was easy to protrude from the coating, and there was a problem in productivity.
- Patent Document 4 has a problem that although the fiber length can remain long, the dispersibility of the fiber is low and the mechanical properties are insufficient.
- An object of the present invention is to solve the above-mentioned problems and to provide a fiber-reinforced multilayer pellet that is excellent in productivity, fluidity, and mechanical properties of a molded product to be obtained and can be highly filled with a fibrous filler. It is.
- the fiber-reinforced multilayer pellet of the present invention has the following constitution (1) or (2). That is, (1) A fiber-reinforced multilayer pellet having a sheath layer and a core layer, wherein the sheath layer includes the thermoplastic resin (a1) and the fibrous filler (b1), and the weight average fiber length (Lw) of the fibrous filler ) Is 0.1 mm or more and less than 0.5 mm, and the weight average fiber length / number average fiber length ratio (Lw / Ln) is 1.0 or more and less than 1.8, and the core layer Includes a thermoplastic resin (a2) and a fibrous filler (b2), and the weight average fiber length (Lw) of the fibrous filler (b2) is 0.5 mm or more and less than 15.0 mm, and the weight average fiber A fiber-reinforced multilayer pellet composed of a resin composition having a length / number average fiber length ratio (Lw / Ln) of 1.8 or more and less than
- the ratio of the weight average fiber length / number average fiber length (Lw / Ln) is 1.0 or more and less than 1.8, and the weight average fiber length (Lw) of the fibrous filler in the center of the pellet is A fiber-reinforced multilayer pellet having a weight average fiber length / number average fiber length ratio (Lw / Ln) of 1.8 or more and less than 5.0, which is 0.5 mm or more and less than 15.0 mm.
- the molded product of the present invention has the following configuration. That is, A molded product formed by molding the fiber-reinforced multilayer pellet.
- the manufacturing method of the fiber reinforced multilayer pellet of this invention has the following structure. That is, Production of the fiber-reinforced multilayer pellet (1) forming a multilayer structure by melt-kneading the resin composition constituting the sheath layer and the resin composition constituting the core layer, respectively, and discharging them using a crosshead die Method.
- the resin composition constituting the sheath layer contains 40 to 95% by weight of the thermoplastic resin (a1) and 5 to 60% by weight of the fibrous filler (b1). It is preferable.
- the resin composition constituting the core layer contains 40 to 95% by weight of the thermoplastic resin (a2) and 5 to 60% by weight of the fibrous filler (b2). It is preferable.
- the fibrous filler (b1) contained in the sheath layer and / or the fibrous filler (b2) contained in the core layer is made of glass fiber or polyacrylonitrile.
- at least one selected from the group consisting of pitch-based carbon fibers and stainless fibers is preferable.
- the fibrous filler is preferably at least one selected from the group consisting of glass fiber, polyacrylonitrile-based or pitch-based carbon fiber, and stainless steel fiber.
- a multilayer structure in which a resin composition having a specific fiber length distribution is disposed in a core layer or a pellet central portion, and a resin composition having a specific fiber length distribution is disposed in a sheath layer or a pellet surface layer portion.
- the fiber-reinforced multilayer pellet of the first aspect of the present invention has a weight average fiber length (Lw) of 0.1 mm or more and less than 0.5 mm, and a ratio of weight average fiber length / number average fiber length (Lw / Ln).
- a core layer having excellent mechanical properties including a fibrous filler having a large Lw and Lw / Ln is coated with a sheath layer having excellent fluidity and productivity including a fibrous filler having a small Lw and Lw / Ln.
- the shape of the fiber-reinforced multilayer pellet of the present invention is not particularly limited, but is preferably a cylindrical shape having a diameter of 1 to 7 mm and a pellet length of 3 to 30 mm. If a diameter is 1 mm or more, a pellet can be manufactured more easily. If the diameter is 7 mm or less, the biting property to the molding machine at the time of molding is excellent, and the supply can be performed stably. On the other hand, if the pellet length is 3 mm or more, the mechanical properties of the molded product can be further improved. If the pellet length is 30 mm or less, supply to the molding machine during molding can be performed stably.
- the composition of the sheath layer and the core layer is preferably such that the core layer is 10% by weight or more and 90% by weight or less and the sheath layer is 10% by weight or more and 90% by weight or less with respect to 100% by weight in total of both layers.
- the core layer is more preferably 20% by weight or more, further preferably 40% by weight or more, and particularly preferably 60% by weight or more.
- the sheath layer is more preferably 80% by weight or less, further preferably 60% by weight or less, and particularly preferably 40% by weight or less.
- the productivity of the fiber-reinforced multilayer pellet can be further improved.
- the core layer is more preferably 87.5% by weight or less, further preferably 85% by weight or less, and particularly preferably 80% by weight or less.
- the sheath layer is more preferably 12.5% by weight or more, further preferably 15% by weight or more, and particularly preferably 20% by weight or more.
- the fiber reinforced multilayer pellet of this invention may have 2 or more core layers, and may have 2 or more sheath layers. When two or more core layers or sheath layers are provided, the total weight of each layer is preferably within the above range.
- the sheath layer includes the thermoplastic resin (a1) and the fibrous filler (b1), the weight average fiber length (Lw) of the fibrous filler is 0.1 mm or more and less than 0.5 mm, and the weight average fiber length /
- the number average fiber length ratio (Lw / Ln) is composed of a resin composition having a ratio of 1.0 to less than 1.8. That is, the weight average fiber length (Lw) of the fibrous filler in the sheath layer of the fiber reinforced multilayer pellet is 0.1 mm or more and less than 0.5 mm, and the ratio of the weight average fiber length / number average fiber length (Lw / Ln). Is 1.0 or more and less than 1.8.
- the thermoplastic resin (a1) used in the resin composition constituting the sheath layer is not particularly limited as long as it is a resin exhibiting thermoplasticity.
- a styrene resin or an olefin resin is used.
- styrene resins examples include PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile / styrene copolymer), AES (acrylonitrile / ethylene / propylene / non-conjugated diene rubber / styrene copolymer), ABS (acrylonitrile / Butadiene / styrene copolymer), MBS (methyl methacrylate / butadiene / styrene copolymer), and the like.
- “/” represents a copolymer, and the same applies hereinafter. Two or more of these may be contained. Among these, ABS is particularly preferable.
- the olefin resin examples include polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / nonconjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / methacrylic acid.
- examples include glycidyl copolymers, ethylene / vinyl acetate / glycidyl methacrylate copolymers, ethylene / propylene-g-maleic anhydride copolymers, methacrylic acid / methyl methacrylate / glutaric anhydride copolymers, etc. May contain two or more.
- polypropylene is particularly preferable from the viewpoint of further improving the fluidity and the mechanical strength of the molded product.
- polypropylene examples include homopolymers obtained by homopolymerizing propylene, random copolymers obtained by copolymerizing propylene and ethylene, block copolymers obtained by blending polyethylene and ethylene / propylene rubber with polypropylene, and the like. Preferably used.
- structure of polypropylene there is no particular limitation on the structure of polypropylene, and any structure of atactic structure having a random structure, syndiotactic structure having a regular alternating structure, and isotactic structure having a regular arrangement in one direction may be adopted. Good.
- the molecular weight of the olefin resin is MFR (melt flow rate), and the value measured at 230 ° C.-2.16 kg load is in the range of 0.1 to 200 g / 10 min in accordance with ISO 1133. Preferably there is.
- MFR melt flow rate
- productivity can be improved more by making MFR into 200 g / 10min or less. 100 g / 10 min or less is more preferable, and 50 g / 10 min or less is more preferable.
- the intrinsic viscosity measured in a decahydronaphthalene or tetrahydronaphthalene solvent can also be used as a basic index.
- thermoplastic elastomers examples include polyester polyether elastomers, polyester polyester elastomers, thermoplastic polyurethane elastomers, thermoplastic styrene butadiene elastomers, thermoplastic olefin elastomers, and thermoplastic polyamide elastomers. Two or more of these may be contained.
- the polyamide is not particularly limited as long as it has an amide bond in a repeating structure obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like.
- lactams include ⁇ -caprolactam, enantolactam, and ⁇ -laurolactam.
- diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 1,9-nonane diamine, 1,10-decane diamine, and 2-methyl-1,8-octane.
- Aliphatic diamines such as diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bis Examples include alicyclic diamines such as aminomethylcyclohexane, aromatic diamines such as m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.
- dicarboxylic acid examples include aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, etc.
- aromatic dicarboxylic acids such as alicyclic dicarboxylic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.
- aminocarboxylic acids examples include ⁇ -aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid. Is mentioned.
- polyamides include, for example, nylon 6, nylon 46, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 6/612, nylon MXD (m-xylylenediamine ) 6, nylon 9T, nylon 10T, nylon 6T / 66, nylon 6T / 6I, nylon 6T / M5T, nylon 6T / 12, nylon 66 / 6T / 6I, nylon 6T / 6, and the like. Two or more of these may be contained. Among these, nylon 6, nylon 66, nylon 610, and nylon 9T are preferable.
- the degree of polymerization of the polyamide is not particularly limited, but a polyamide having a relative viscosity of 1.5 to 7.0 measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml is preferable.
- the relative viscosity is more preferably 2.0 or more, and further preferably 2.2 or more.
- the relative viscosity is more preferably 5.0 or less, and further preferably 3.0 or less.
- polyester a polymer or copolymer having a main structural unit as a residue of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable.
- the polyester may contain one or more residues selected from hydroxycarboxylic acids or ester-forming derivatives thereof and lactones.
- hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, and 6-hydroxy-2-naphthoic acid.
- lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.
- Examples of the polymer or copolymer having these residues as structural units include fats such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / ⁇ -hydroxybutyric acid / ⁇ -hydroxyvaleric acid, and the like. Group polyester resin. Two or more of these may be contained.
- the melting point of the polyester is not particularly limited, but is preferably 120 ° C. or higher and more preferably 220 ° C. or higher from the viewpoint of heat resistance. Although an upper limit is not specifically limited, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less.
- the melting point of the polyester is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.
- the amount of the carboxyl terminal group of the polyester is not particularly limited, but is preferably 50 eq / t or less and more preferably 10 eq / t or less in terms of fluidity, hydrolysis resistance, and heat resistance. The lower limit is 0 eq / t.
- the amount of carboxyl end groups of the polyester resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.
- the viscosity of the polyester is not particularly limited as long as it can be melt kneaded, but in terms of moldability, the intrinsic viscosity when the o-chlorophenol solution is measured at 25 ° C. is in the range of 0.36 to 1.60 dl / g. It is preferable that By setting the intrinsic viscosity to 0.36 dl / g or more, not only the coating power when forming into a multi-layer pellet is high and the productivity is improved, but also the mechanical strength of the molded product obtained by molding the fiber-reinforced multi-layer pellet is increased. Can be further improved.
- the intrinsic viscosity is more preferably 0.50 dl / g or more, and further preferably 0.70 dl / g or more.
- the intrinsic viscosity is more preferably 1.25 dl / g or less, and further preferably 1.0 dl / g or less.
- the molecular weight of the polyester resin is not particularly limited, but in terms of heat resistance, the weight average molecular weight (Mw) is preferably in the range of 50,000 to 500,000, and more preferably in the range of 150,000 to 250,000.
- the molecular weight of the polyester is a value measured by gel permeation chromatography (GPC).
- the production method of the polyester is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization may be used, and any of transesterification and direct polymerization can be applied.
- Polycarbonate can be obtained by a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of caustic alkali and a solvent, or a transesterification method in which a bifunctional phenolic compound and diethyl carbonate are transesterified in the presence of a catalyst.
- the polycarbonate include aromatic homopolycarbonate and aromatic copolycarbonate.
- the viscosity average molecular weight of these aromatic polycarbonates is preferably 10,000 or more, and more preferably 15,000 or more.
- the upper limit is preferably 100,000 or less, more preferably 50,000 or less, from the viewpoint of reducing breakage of the fibrous filler and production stability.
- Bifunctional phenol compounds include 2,2′-bis (4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4-hydroxyphenyl) methane. 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3,5-diphenyl) butane, 2, 2'-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1'-bis (4-hydroxyphenyl) ethane Etc. Two or more of these may be used.
- polyarylene sulfide examples include polyphenylene sulfide (PPS), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and the like. Two or more of these may be contained. Of these, polyphenylene sulfide is particularly preferably used.
- Polyarylene sulfide is a method for obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368, a comparison described in JP-B-52-12240 and JP-A-61-7332. It can be produced by a generally known method such as a method for obtaining a polymer having a large molecular weight.
- the resulting polyarylene sulfide is subjected to crosslinking / high molecular weight by heating, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, washing with an organic solvent, hot water, aqueous acid solution, etc., acid anhydride, amine, isocyanate
- an inert gas atmosphere such as nitrogen or reduced pressure
- a functional group-containing compound such as a functional group-containing disulfide compound.
- Specific methods for crosslinking / high molecular weight polyarylene sulfide by heating include an atmosphere of an oxidizing gas such as air and oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen and argon.
- the heat treatment temperature is preferably in the range of 200 to 270 ° C.
- the treatment time is preferably in the range of 2 to 50 hours. From the viewpoint of efficiently and more uniformly heat-treating, it is preferable to heat in a heating vessel with a rotary type or a stirring blade.
- a specific method for heat-treating polyarylene sulfide under an inert gas atmosphere such as nitrogen or under reduced pressure is as follows: under an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm -2 or less). Examples of the heat treatment method include a heat treatment temperature of 200 to 270 ° C.
- Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade, but from the viewpoint of efficiently and more uniformly heating the heating container with a rotary or stirring blade. It is more preferable to heat in.
- N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are preferably used as the organic solvent.
- a method of washing with an organic solvent for example, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed.
- the washing temperature is preferably from room temperature to 150 ° C.
- the polyarylene sulfide resin that has been subjected to organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.
- the water used is preferably distilled water or deionized water.
- the operation of the hot water treatment is usually performed by charging a predetermined amount of polyarylene sulfide into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel.
- the ratio of the polyarylene sulfide resin to water is preferably used at a bath ratio of 200 g or less of polyarylene sulfide with respect to 1 liter of water.
- a specific method for acid-treating polyarylene sulfide for example, there is a method of immersing polyarylene sulfide resin in an acid or an aqueous solution of acid, and stirring or heating can be appropriately performed as necessary.
- the acid acetic acid and hydrochloric acid are preferably used.
- the polyarylene sulfide subjected to the acid treatment is preferably washed several times with water or warm water in order to remove the remaining acid or salt.
- the water used for washing is preferably distilled water or deionized water.
- the melt viscosity of polyarylene sulfide is preferably 80 Pa ⁇ s or less, more preferably 20 Pa ⁇ s or less under conditions of 310 ° C. and a shear rate of 1000 / sec. Although there is no restriction
- the melt viscosity can be measured using a capillograph (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.
- cellulose derivatives include cellulose acetate, cellulose acetate butyrate, and ethyl cellulose. Two or more of these may be contained.
- thermoplastic resins polyamide, styrene resin, olefin resin, polycarbonate, polyarylene sulfide, and the like are preferable. Since these thermoplastic resins are excellent in affinity with the fibrous filler, they are excellent in molding processability and can further improve the mechanical properties and surface appearance of the molded product.
- nylon 6, nylon 66, nylon 610, nylon 9T, ABS (acrylonitrile / butadiene / styrene copolymer), polypropylene, polycarbonate, polyphenylene sulfide and the like can be used more preferably.
- any filler having a fibrous shape can be used as the fibrous filler (b1) used in the resin composition constituting the sheath layer.
- a fibrous filler in addition to mechanical properties such as strength and rigidity, a molded product having excellent dimensional stability can be obtained.
- glass fibers polyacrylonitrile (PAN) -based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, Asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, silicon nitride whisker, wollastonite, alumina silicate fiber, whisker-like filler, metal (nickel , Copper, cobalt, silver, aluminum, iron, and alloys thereof), and the like, and the like (glass fiber, aramid fiber, polyester fiber, carbon fiber, etc.).
- PAN polyacrylonitrile
- metal fibers such as aluminum fibers and brass fibers
- organic fibers such as aromatic polyamide fibers
- gypsum fibers ceramic fibers
- Asbestos fiber zirconia fiber
- alumina fiber silica fiber
- fibrous filler (b1) glass fiber, PAN-based or pitch-based carbon fiber, and stainless steel fiber are more preferable from the viewpoint of balance between mechanical properties such as strength and rigidity of the molded product and fluidity, and PAN-based carbon. More preferred are fibers. PAN-based carbon fibers can be preferably used because they have a large effect of improving mechanical properties and are difficult to break during melt-kneading.
- the surface of the fibrous filler (b1) may be used with a coupling agent or sizing agent attached thereto.
- the coupling agent include amino-based, epoxy-based, chlor-based, mercapto-based, and cationic silane coupling agents, and amino-based silane coupling agents can be suitably used.
- the sizing agent include a sizing agent containing a maleic anhydride compound, a urethane compound, an acrylic compound, an epoxy compound, a phenol compound and / or a derivative of these compounds, and contains a urethane compound.
- a sizing agent can be suitably used.
- the content of the sizing agent in the fibrous filler (b1) is preferably 0.1 to 10.0% by weight, more preferably 0.3 to 8.0% by weight, and 0.5 to 6.0% by weight. Is particularly preferred.
- the fiber-reinforced multilayer pellet of the present invention has a weight average fiber length (Lw) of the fibrous filler (b1) in the resin composition constituting the sheath layer in the range of 0.1 mm or more and less than 0.5 mm.
- the ratio of fiber length / number average fiber length (Lw / Ln: degree of dispersion) is in the range of 1.0 or more and less than 1.8.
- Lw of the fibrous filler (b1) in the sheath layer is 0.5 mm or more, the surface appearance of the fiber-reinforced multilayer pellet is lowered, and the productivity is lowered. Less than 0.45 mm is more preferable, and less than 0.40 mm is even more preferable. If the Lw / Ln (dispersion degree) of the fibrous filler (b1) in the sheath layer is less than 1.0, the mechanical properties, particularly the flexural modulus, of the molded product obtained from the fiber-reinforced multilayer pellets are lowered. 1.05 or more is preferable and 1.1 or more is more preferable.
- the Lw / Ln (dispersion degree) of the fibrous filler (b1) in the sheath layer is 1.8 or more, the surface appearance of the fiber-reinforced multilayer pellet is lowered, and the productivity is lowered. Less than 1.7 is preferable, and less than 1.6 is more preferable.
- the weight average fiber length (Lw) and the number average fiber length (Ln) of the fibrous filler (b1) in the resin composition can be determined as follows, for example. First, when manufacturing fiber-reinforced multilayer pellets, the sheath layer is sampled by stopping the supply of the core layer and supplying only the sheath layer.
- the sheath layer can be sampled by cutting the outer peripheral surface layer of the fiber-reinforced multilayer pellet. If the sheath layer and the core layer can be distinguished at this time, it is preferable to sample by cutting only the outer sheath layer, but if the discrimination is difficult, the outer peripheral surface layer is made of the fiber-reinforced multilayer pellet. Sampling is defined as a portion within 10% by weight from the outermost layer. The sample is dissolved in a solvent in which the thermoplastic resin dissolves, and then filtered and washed on a filter paper. The fibrous filler that is a residue on the filter paper is observed at a magnification of 50 times using an optical microscope. The length of 1000 fibrous fillers was measured, and the weight value (Lw), number average fiber length (Ln), and dispersity (Lw / Ln) from the measured value (mm) (2 decimal places are significant figures). ) Is calculated.
- Number average fiber length (Ln) ⁇ (Li ⁇ ni) / ⁇ ni
- the above expression is simplified and becomes the following expression.
- Weight average fiber length (Lw) ⁇ (Li 2 ⁇ ni) / ⁇ (Li ⁇ ni)
- Li Fiber length of fibrous filler ni: Number of fibrous fillers of fiber length Li
- Wi Weight of fibrous filler ri: Fiber diameter of fibrous filler
- ⁇ Density of fibrous filler Fibrous filler (B1) is not limited as long as it can be added to the melt-kneading apparatus, and examples thereof include chopped strands, crushed fibers, and continuous long fibers that have been cut in advance. Chopped strand can be preferably used from the viewpoint of productivity.
- a means for adjusting the fiber length distribution of the fibrous filler (b1) in the sheath layer to the above range for example, a method using a fibrous filler having an arbitrary fiber length distribution as a raw material in accordance with the target fiber length distribution , A method of adjusting the shearing imparted to the fibrous filler by adjusting the melt viscosity of the thermoplastic resin used, a method of adjusting the screw rotation speed, cylinder temperature, and discharge rate during melt kneading of the resin composition described later Etc.
- the content of the thermoplastic resin (a1) is preferably 40% by weight or more and 95% by weight or less, and the content of the fibrous filler (b1) is 5% by weight or more and 60% by weight or less. Is preferred.
- the content of the thermoplastic resin (a1) is more preferably 45% by weight or more, and more preferably 50% by weight or more.
- the content of the fibrous filler (b1) is more preferably 55% by weight or less, and further preferably 50% by weight or less.
- the content of the thermoplastic resin (a1) is more preferably 90% by weight or less, and more preferably 85% by weight or less.
- the content of the fibrous filler (b1) is more preferably 10% by weight or more, and more preferably 15% by weight or more.
- the resin composition constituting the sheath layer may further contain an arbitrary component.
- a copper compound is preferably used as an additive for improving long-term heat resistance.
- a copper compound a monovalent
- the amount of copper compound added is preferably 0.015 to 1 part by weight per 100 parts by weight of polyamide.
- an alkali halide may be added together with the copper compound.
- potassium iodide and sodium iodide are preferable.
- a non-fibrous filler can be used in combination with the fibrous filler (b1).
- the non-fibrous filler is not particularly limited, and any filler such as a plate shape, a powder shape, and a granular shape can be used.
- silicates such as talc, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, metal compounds such as magnesium oxide, alumina, zirconium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite Carbonates such as calcium sulfate, sulfate such as barium sulfate, glass beads, ceramic beads, boron nitride, calcium phosphate, hydroxide such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass flakes, glass powder,
- Non-fibrous fillers such as glass balloons, carbon black and silica, graphite, and smectite clay minerals such as montmorillonite, beidellite
- the layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions.
- these non-fibrous fillers are preferably treated with a coupling agent such as silane or titanate, or other surface treatment agent, and preferably treated with an epoxy silane or aminosilane coupling agent. More preferred.
- glass flakes and glass beads are more preferably used.
- the content of the non-fibrous filler is 0.01 to 20% by weight in 100% by weight of the resin composition, preferably 0.02 to 15% by weight, more preferably 0.05 to 10% by weight.
- the content of the non-fibrous filler is 0.01% by weight or more, the mechanical properties of the molded product can be further improved. On the other hand, if it is 20% by weight or less, the surface appearance and moldability of the fiber-reinforced multilayer pellet can be further improved.
- the core layer includes the thermoplastic resin (a2) and the fibrous filler (b2), the weight average fiber length (Lw) of the fibrous filler is 0.5 mm or more and less than 15.0 mm, and the weight average fiber length /
- the number average fiber length ratio (Lw / Ln) is composed of a resin composition having a ratio of 1.8 to less than 5.0. That is, the weight average fiber length (Lw) of the fibrous filler in the core layer of the fiber reinforced multilayer pellet is 0.5 mm or more and less than 15.0 mm, and the ratio of the weight average fiber length / number average fiber length (Lw / Ln). Is 1.8 or more and less than 5.0.
- the thermoplastic resin (a2) used for the resin composition constituting the core layer is not particularly limited as long as it is a resin exhibiting thermoplasticity.
- the resin composition constituting the sheath layer What was illustrated as a thermoplastic resin (a1) used for a thing can be mentioned.
- thermoplastic resin (a2) polyamide, styrene resin, olefin resin, polycarbonate, polyarylene sulfide and the like are preferable.
- nylon 6, nylon 66, nylon 610, nylon 9T, ABS (acrylonitrile / butadiene / styrene copolymer), polypropylene, polycarbonate, polyphenylene sulfide and the like can be preferably used.
- any filler having a fibrous shape can be used as the fibrous filler (b2) used in the resin composition constituting the core layer.
- a fibrous filler (b1) used for the resin composition which comprises a sheath layer can be mentioned.
- PAN-based carbon fibers are particularly preferable. PAN-based carbon fibers can be preferably used because they have a large effect of improving mechanical properties and are difficult to break during melt-kneading.
- the surface of the fibrous filler (b2) may be used with a coupling agent or sizing agent attached thereto.
- the coupling agent and sizing agent include those exemplified above as the coupling agent and sizing agent used in (b1).
- the content of the sizing agent in the fibrous filler (b2) is preferably from 0.1 to 10.0% by weight, more preferably from 0.3 to 8.0% by weight, and from 0.5 to 6.0% by weight. Is particularly preferred.
- the fiber-reinforced multilayer pellet of the present invention has a weight average fiber length (Lw) of the fibrous filler (b2) in the resin composition constituting the core layer in the range of 0.5 mm or more and less than 15.0 mm, and the weight average The ratio of the fiber length / number average fiber length (Lw / Ln: degree of dispersion) is in the range of 1.8 or more and less than 5.0.
- Lw of the fibrous filler (b2) in the core layer is less than 0.5 mm, the mechanical properties, particularly the impact strength, of the molded product obtained from the fiber-reinforced multilayer pellet is lowered. 0.55 mm or more is preferable, and 0.6 mm or more is more preferable.
- Lw of the fibrous filler (b2) in the core layer is 15.0 mm or more
- the pellet surface appearance of the fiber-reinforced multilayer pellet is deteriorated. 10.0 mm or less is preferable and 6.0 mm or less is more preferable.
- the Lw / Ln (dispersion degree) of the fibrous filler (b2) in the core layer is less than 1.8, the mechanical properties, particularly the impact strength, of the molded product obtained from the fiber-reinforced multilayer pellet is lowered. 1.9 or more is preferable and 2.0 or more is more preferable.
- the Lw / Ln (dispersion degree) of the fibrous filler (b2) in the core layer is 5.0 or more, the surface appearance of the fiber-reinforced multilayer pellet is deteriorated. 4.5 or less is preferable and 4.0 or less is more preferable.
- the weight average fiber length (Lw) and the number average fiber length (Ln) of the fibrous filler (b2) in the resin composition can be determined as follows, for example.
- the core layer is sampled by stopping the supply of the sheath layer and supplying only the core layer.
- the core layer can also be sampled by cutting the fiber reinforced multilayer pellet along the flow direction at the center and cutting the center along the flow direction.
- the sheath layer and the core layer can be distinguished, it is preferable to sample by cutting only the central core layer, but if the identification is difficult, the central portion is the center of the fiber-reinforced multilayer pellet. Is defined as a portion within 10% by weight and sampled.
- the sample is dissolved in a solvent in which the thermoplastic resin dissolves, and then filtered and washed on a filter paper.
- the fibrous filler that is a residue on the filter paper is observed at a magnification of 50 times using an optical microscope.
- the length of 1,000 fibrous fillers is measured, and the weight average fiber length (Lw), number average fiber length (Ln), dispersity (Lw) from the measured value (mm) (2 decimal places are significant figures) / Ln) is calculated.
- Number average fiber length (Ln) ⁇ (Li ⁇ ni) / ⁇ ni
- the above expression is simplified and becomes the following expression.
- Weight average fiber length (Lw) ⁇ (Li 2 ⁇ ni) / ⁇ (Li ⁇ ni)
- Li Fiber length of fibrous filler ni: Number of fibrous fillers of fiber length
- Wi Weight of fibrous filler ri: Fiber diameter of fibrous filler
- ⁇ Density of fibrous filler Fibrous filler (B2) is not limited as long as it can be added to the melt-kneading apparatus, and examples thereof include chopped strands, crushed fibers, and continuous long fibers that have been cut in advance. Chopped strand can be preferably used from the viewpoint of productivity.
- a means for adjusting the fiber length distribution of the fibrous filler (b2) in the core layer to the above range for example, a method using a fibrous filler having an arbitrary fiber length distribution as a raw material in accordance with the target fiber length distribution , A method of adjusting the shearing imparted to the fibrous filler by adjusting the melt viscosity of the thermoplastic resin used, a method of adjusting the screw rotation speed, cylinder temperature, and discharge rate during melt kneading of the resin composition described later Etc.
- the resin composition constituting the core layer may further contain any component.
- any component As an arbitrary component, what was illustrated as an arbitrary component in the resin composition which comprises a sheath layer can be mentioned.
- the content of the thermoplastic resin (a2) is preferably 40% by weight or more and 95% by weight or less, and the content of the fibrous filler (b2) is 5% by weight or more and 60% by weight or less. Is preferred.
- the content of the thermoplastic resin (a2) is more preferably 45% by weight or more, and more preferably 50% by weight or more.
- the content of the fibrous filler (b2) is more preferably 55% by weight or less, and further preferably 50% by weight or less.
- the content of the thermoplastic resin (a2) is 95% by weight or less and the content of the fibrous filler (b2) is 5% by weight or more, the mechanical properties of the molded product obtained from the fiber-reinforced multilayer pellets In particular, the bending elastic modulus can be further improved.
- the content of the thermoplastic resin (a2) is more preferably 90% by weight or less, and more preferably 85% by weight or less.
- the content of the fibrous filler (b2) is more preferably 10% by weight or more, and more preferably 15% by weight or more.
- the fiber-reinforced multilayer pellet of the present invention is a fiber-reinforced pellet containing a thermoplastic resin (a3) and a fibrous filler (b3) as well as the two-layer pellet made of the above-mentioned sheath layer / core layer.
- the weight average fiber length (Lw) of the fibrous filler in the part is 0.1 mm or more and less than 0.5 mm, and the ratio of the weight average fiber length / number average fiber length (Lw / Ln) is 1.0 or more.
- the weight average fiber length (Lw) of the fibrous filler in the center of the pellet is 0.5 mm or more and less than 15.0 mm, and the ratio of the weight average fiber length / number average fiber length (Lw / Ln) Also included are fiber reinforced multilayer pellets having a thickness of 1.8 to less than 5.0.
- a fiber filler having a large Lw and Lw / Ln is contained in the center of the pellet to exhibit excellent mechanical properties, and a fiber having a small Lw and Lw / Ln.
- thermoplastic resin (a3) used for the fiber-reinforced multilayer pellet of the present invention is not particularly limited as long as it is a resin exhibiting thermoplasticity.
- thermoplastic resin (a1) used for the resin composition constituting the sheath layer. ) Can be mentioned as examples.
- thermoplastic resin (a3) polyamide, styrene resin, olefin resin, polycarbonate, polyarylene sulfide and the like are preferable.
- nylon 6, nylon 66, nylon 610, nylon 9T, ABS (acrylonitrile / butadiene / styrene copolymer), polypropylene, polycarbonate, polyphenylene sulfide and the like can be preferably used.
- any filler having a fibrous shape can be used as the fibrous filler (b3) used in the fiber-reinforced multilayer pellet of the present invention.
- a fibrous filler (b1) used for the resin composition which comprises a sheath layer can be mentioned.
- PAN-based carbon fibers are particularly preferable. PAN-based carbon fibers can be preferably used because they have a large effect of improving mechanical properties and are difficult to break during melt-kneading.
- a material obtained by attaching a coupling agent or a sizing agent may be used.
- the coupling agent and sizing agent include those exemplified above as the coupling agent and sizing agent used in (b1).
- the content of the sizing agent in the fibrous filler (b3) is preferably 0.1 to 10.0% by weight, more preferably 0.3 to 8.0% by weight, and 0.5 to 6.0% by weight. Is particularly preferred.
- the weight average fiber length (Lw) of the fibrous filler in the pellet surface layer portion and the central portion, and the weight average fiber length / number average fiber length ratio (Lw / Ln) are: It is a value obtained from the outermost layer and the portion within 10% by weight from the center.
- the weight average fiber length (Lw) of the fibrous filler (b3) in the pellet surface layer is in the range of 0.1 mm or more and less than 0.5 mm, and the weight average fiber length / number average fiber
- the length ratio (Lw / Ln) is in the range of 1.0 or more and less than 1.8.
- the Lw of the fibrous filler (b3) in the pellet surface layer portion is 0.5 mm or more, the surface appearance of the fiber-reinforced multilayer pellet is lowered and the productivity is lowered. Less than 0.45 mm is more preferable, and less than 0.40 mm is even more preferable. Further, if the Lw / Ln (dispersion degree) of the fibrous filler (b3) in the pellet surface layer portion is less than 1.0, the mechanical properties, particularly the bending elastic modulus, of the molded product obtained from the fiber-reinforced multilayer pellet is lowered. . 1.05 or more is preferable and 1.1 or more is more preferable.
- the Lw / Ln (dispersion degree) of the fibrous filler (b3) in the pellet surface layer portion is 1.8 or more, the surface appearance of the fiber-reinforced multilayer pellet is lowered and the productivity is lowered. Less than 1.7 is preferable, and less than 1.6 is more preferable.
- the fiber-reinforced multilayer pellet of the present invention has a weight average fiber length (Lw) of the fibrous filler (b3) in the center of the pellet in the range of 0.5 mm or more and less than 15.0 mm, and the weight average fiber length / number average fiber.
- the length ratio (Lw / Ln) is in the range of 1.8 or more and less than 5.0. If the Lw of the fibrous filler (b3) at the center of the pellet is less than 0.5 mm, the mechanical properties, particularly the impact strength, of the molded product obtained from the fiber-reinforced multilayer pellet is lowered. 0.55 mm or more is preferable, and 0.6 mm or more is more preferable.
- the Lw of the fibrous filler (b3) in the center of the pellet is 15.0 mm or more, the pellet surface appearance of the fiber-reinforced multilayer pellet is lowered. 10.0 mm or less is preferable and 6.0 mm or less is more preferable. Further, if the Lw / Ln (dispersion degree) of the fibrous filler (b3) in the center of the pellet is less than 1.8, the mechanical properties, particularly the impact strength, of the molded product obtained from the fiber-reinforced multilayer pellet is lowered. 1.9 or more is preferable and 2.0 or more is more preferable.
- the Lw / Ln (dispersion degree) of the fibrous filler (b3) at the center of the pellet is 5.0 or more, the surface appearance of the fiber-reinforced multilayer pellet is deteriorated. 4.5 or less is preferable and 4.0 or less is more preferable.
- the weight average fiber length (Lw) and the number average fiber length (Ln) of the fibrous filler (b3) in the resin composition can be determined as follows, for example.
- the obtained fiber-reinforced multilayer pellet can be sampled by cutting at the center along the flow direction and cutting portions within 10% by weight from the surface layer and the center, respectively. The sample is dissolved in a solvent in which the thermoplastic resin is dissolved, and then filtered and washed on a filter paper. The fibrous filler that is a residue on the filter paper is observed at a magnification of 50 times using an optical microscope.
- the length of 1,000 fibrous fillers is measured, and the weight average fiber length (Lw), number average fiber length (Ln), dispersity (Lw) from the measured value (mm) (2 decimal places are significant figures) / Ln) is calculated.
- the calculation formula is the same as the formula shown for the fibrous filler (b1).
- the fibrous filler (b3) is not limited as long as it can be added to the melt-kneading apparatus, and includes chopped strands, crushed fibers, continuous long fibers, and the like that have been cut in advance, and these are used in combination of two or more. You can also. Chopped strand can be preferably used from the viewpoint of productivity.
- the fiber-reinforced multilayer pellet of the present invention as a means for adjusting the fiber length distribution of the fibrous filler (b3) to the above range, for example, fibrous filling having an arbitrary fiber length distribution according to the target fiber length distribution A method of using a material as a raw material, a method of adjusting breakage due to shear using fibrous fillers having different elastic moduli, a method of adjusting a screw rotation speed, a cylinder temperature, a discharge amount at the time of melt-kneading a resin composition described later, etc. Is mentioned.
- the thermoplastic resin (a3) content is preferably 40% by weight or more and 95% by weight or less, and the fibrous filler (b3) content is 5% by weight or more and 60% by weight or less. preferable.
- the content of the thermoplastic resin (a3) 40% by weight or more and the content of the fibrous filler (b3) 60% by weight or less, the moldability and the surface appearance of the fiber-reinforced multilayer pellet are further improved. be able to.
- the content of the thermoplastic resin (a3) is more preferably 45% by weight or more, and more preferably 50% by weight or more.
- the content of the fibrous filler (b3) is more preferably 55% by weight or less, and further preferably 50% by weight or less.
- the content of the thermoplastic resin (a3) is 95% by weight or less and the content of the fibrous filler (b3) is 5% by weight or more, the mechanical properties of the molded product obtained from the fiber-reinforced multilayer pellets In particular, the bending elastic modulus can be further improved.
- the content of the thermoplastic resin (a3) is more preferably 90% by weight or less, and more preferably 85% by weight or less.
- the content of the fibrous filler (b3) is more preferably 10% by weight or more, and more preferably 15% by weight or more.
- a method for producing the fiber-reinforced multilayer pellet of the present invention will be described.
- a manufacturing method for melt-kneading a fibrous filler having an arbitrary fiber length distribution as a raw material a manufacturing method for adjusting a screw rotation speed, a cylinder temperature, a discharge amount at the time of melt-kneading a resin composition, etc.
- thermoplastic resin and the fibrous filler to be used are not limited.
- the manufacturing method of the fiber reinforced multilayer pellet which has a sheath layer and a core layer using a crosshead die is demonstrated to an example.
- the resin composition constituting the sheath layer is obtained by melt-kneading the thermoplastic resin (a1), the fibrous filler (b1), and other components (for example, non-fibrous filler) as necessary using a melt-kneading apparatus.
- the set temperature of the melt-kneading apparatus is preferably the melting point (Tm) + 30 ° C. or higher of the thermoplastic resin used or the glass transition point (Tg) + 120 ° C. or higher.
- the raw material supply position for supplying the thermoplastic resin (a1) and the fibrous filler (b1) to the melt-kneading apparatus is not particularly limited, but if it is a twin screw extruder, the thermoplastic resin (a1) is supplied as the main raw material.
- the mouth is preferred.
- the fibrous filler (b1) is intermediate between the main raw material supply port and the discharge port, specifically, the seal zone or mixing zone closest to the main raw material supply port in the screw element design, and the seal zone or An intermediate position with respect to the mixing zone is preferable because the weight average fiber length can be easily controlled.
- melt-kneading apparatus there is no particular limitation on the melt-kneading apparatus, and it is possible to heat-melt and mix the thermoplastic resin (a1), the fibrous filler (b1) and other components as necessary under an appropriate shear field.
- Melt kneaders such as known extruders and continuous kneaders used for the above can be used. For example, a single screw extruder and kneader with one screw, a twin screw extruder and kneader with two screws, a multi-screw extruder and kneader with three or more screws, and two extruders and kneaders were connected.
- Examples thereof include a tandem extruder, an extruder and a kneader provided with a side feeder that can only supply raw materials without being melt-kneaded.
- a melting or non-melting conveyance zone having a full flight screw or the like
- a sealing zone having a seal ring or the like
- a mixing zone having unimelt, kneading or the like.
- a continuous melt-kneading device having two or more sealing zones and / or mixing zones and two or more raw material supply ports is preferable, and has two or more sealing zones and / or mixing zones and two or more raw material supply ports.
- a continuous melt-kneading apparatus having a biaxial screw portion is more preferred, and a biaxial extruder having two or more seal zones and / or mixing zones and two or more raw material supply ports is most preferred.
- a resin composition contains a non-fibrous filler
- the resin composition constituting the core layer is obtained by melt-kneading the thermoplastic resin (b2), the fibrous filler (b2) and, if necessary, other components (for example, non-fibrous filler) using a melt-kneader.
- the set temperature of the melt-kneading apparatus is preferably the melting point (Tm) + 30 ° C. or higher of the thermoplastic resin (b2) to be used or the glass transition point (Tg) + 120 ° C. or higher.
- the raw material supply position for supplying the thermoplastic resin (a2) and the fibrous filler (b2) to the melt-kneading apparatus is not particularly limited, but if it is a single screw extruder, the thermoplastic resin (a2) and the fibrous filler are used. It is preferable to introduce the material (b2) from the main raw material supply port.
- melt-kneading apparatus there is no particular limitation on the melt-kneading apparatus, and it is possible to heat-melt and mix the thermoplastic resin (a2), the fibrous filler (b2) and other components as necessary under a low shear field.
- Melt-kneading apparatuses such as known extruders and continuous kneaders used for the above can be used. For example, a single screw extruder and kneader with one screw, a twin screw extruder and kneader with two screws, a multi-screw extruder and kneader with three or more screws, and two extruders and kneaders were connected.
- Examples thereof include a tandem extruder, an extruder and a kneader provided with a side feeder that can only supply raw materials without being melt-kneaded.
- a melting or non-melting conveyance zone having a full flight screw or the like there is no particular limitation on the combination of a melting or non-melting conveyance zone having a full flight screw or the like, a sealing zone having a seal ring or the like, a mixing zone having unimelt, kneading or the like.
- a continuous melt kneader having a full flight screw without a sealing zone and / or a mixing zone is preferred.
- a resin composition contains a non-fibrous filler, it is preferable to supply a non-fibrous filler to a melt-kneading apparatus with a fibrous filler.
- the fiber reinforced multi-layer pellets of the present invention can be obtained by supplying the resin composition constituting each melt-kneaded layer to, for example, one crosshead die and discharging it.
- the thermoplastic resin (a1) and the fibrous filler (b1) are melt-kneaded by a melt-kneading apparatus, and the weight average fiber length (Lw) of the fibrous filler (b1) is 0.1 mm or more and less than 0.5 mm.
- a sheath composition by feeding a resin composition (A) controlled so that the ratio of weight average fiber length / number average fiber length (Lw / Ln) is in the range of 1.0 or more and less than 1.8 to the crosshead die.
- the thermoplastic resin (a2) and the fibrous filler (b2) are melt-kneaded with a melt-kneading apparatus, and the weight average fiber length (Lw) of the fibrous filler (b2) is 0.5 mm or more and 15.0 mm.
- the fiber-reinforced multilayer pellet of the present invention thus obtained is excellent in productivity, fluidity and surface appearance, and can be molded into a molded product having excellent mechanical properties.
- the fiber-reinforced multilayer pellet of the present invention can be processed into a molded product having excellent surface appearance (gloss) and mechanical properties by a molding method such as normal injection molding, extrusion molding, or press molding. Taking advantage of such characteristics, the fiber-reinforced multilayer pellets of the present invention are injection molded products such as automobile parts, electrical / electronic parts, sports equipment parts, etc., and molded products having a thin part with a thickness of 0.1 to 2.0 mm, This is useful for molded products that require dimensional accuracy.
- the above-mentioned various molded products can be used for various applications such as automobile parts, electric / electronic parts, building members, sporting goods parts, various containers, daily necessities, household goods and sanitary goods.
- Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer , Distributor cap, vapor canister Housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun
- VTR parts TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, optical recording media substrates such as Blu-ray disc, lighting parts and housing, chassis parts, refrigerator parts, air conditioner parts, type Home and office electrical product parts represented by lighter parts and word processor parts can be listed.
- video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, optical recording media substrates such as Blu-ray disc, lighting parts and housing, chassis parts, refrigerator parts, air conditioner parts, type Home and office electrical product parts represented by lighter parts and word processor parts can be listed.
- the fiber-reinforced resin pellets and molded products of the present invention can be recycled. For example, after pulverizing the fiber reinforced resin pellet and a molded product comprising the same, and preferably making it into a powder form, it can be used by adding an additive as necessary. It is difficult for the obtained resin composition to exhibit the same mechanical strength as the molded article of the present invention.
- Thermoplastic resin (A1) Thermoplastic resin for sheath layer (a1-1) Nylon 6 resin (relative viscosity 2.35 measured at 25 ° C. in 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml) was used.
- Nylon 6 resin (relative viscosity of 3.40 measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml) was used.
- A1-3 Polycarbonate resin “Taflon” (registered trademark) A1900 (manufactured by Idemitsu Kosan Co., Ltd.) was used.
- A2 Thermoplastic resin for core layer The same nylon 6 resin as (a2-1) and (a1-1) was used.
- (A2-2) The same polycarbonate resin as (a1-3) was used.
- [Fibrous filler] (B1) Fibrous filler for sheath layer (b1-1) Carbon fiber “Torayca” (registered trademark) cut fiber TV14-006 (chopped strand having a fiber length of 6 mm) (manufactured by Toray Industries, Inc., original yarn T700SC-12K: tensile Strength 4.90 GPa, tensile modulus 230 GPa, fiber diameter 6.8 ⁇ m).
- B2 Fibrous filler for core layer (b2-1) The same carbon fiber as (b1-1) was used.
- Carbon fiber reinforced pellets Carbon fiber reinforced nylon 6 resin “Torayca” (registered trademark) long fiber pellet TLP1060 (carbon fiber content 30 wt%, manufactured by Toray Industries, Inc.) (long fiber reinforced pellet) was used.
- C2 The carbon fiber reinforced nylon 6 resin (short fiber reinforced pellet) obtained in Comparative Example 1 in Table 1 was used.
- Examples 1 to 5, Comparative Examples 1 to 5 Using the sheath layer resin composition (A) described in Table 1 and the sheath layer twin screw extruder (TEX30 ⁇ manufactured by Nippon Steel Works) set to various conditions shown in the table, the thermoplastic resin (a1) was used.
- the fibrous filler (b1) was supplied into the molten resin using a side feeder, melted and kneaded, and supplied to the core-sheath forming crosshead die.
- the thermoplastic resin (a2) and the fibrous material were added to the single screw extruder for core layer ( ⁇ 40 mm, L / D30) set in the conditions shown in the table.
- the filler (b2) was supplied to the main hopper, melted and kneaded, and supplied to the core-sheath forming crosshead die.
- the multilayer strand discharged from the die with a diameter of 4 mm was cooled in water, cut into a length of 3.0 mm by a strand cutter, and pelletized to obtain a fiber-reinforced multilayer pellet.
- the composition ratio of the core layer / sheath layer was adjusted by the discharge amount of the melt kneader for the core layer and the sheath layer.
- the core layer resin composition (B) was not used in Comparative Examples 1 and 2
- the sheath layer resin composition (A) was not used in Comparative Example 3 were not multilayer pellets. .
- the fiber-reinforced multilayer pellet obtained above was vacuum-dried at 80 ° C. all day and night, using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions shown in Table 1, injection speed 50 mm / sec, injection pressure Each test piece was molded at the lower limit pressure + 1 MPa, and the physical properties were measured under the following conditions.
- the sheath layer resin composition is a sheath layer biaxial extruder
- the core layer resin composition is a core layer single screw extruder, each independently under the same extrusion conditions as the respective Examples and Comparative Examples.
- the strands melted and kneaded and discharged from the crosshead die were sampled.
- the fiber-reinforced multilayer pellets discharged from the crosshead die were cut at the center along the flow direction, and each was within 10% by weight from the outermost layer and the center.
- the sheath layer and the core layer were sampled by cutting the portion.
- the obtained sample was dissolved in formic acid, washed and filtered, and the length of 1,000 randomly selected samples was measured while observing the residue with an optical microscope at a magnification of 50 times. . From the obtained measured values, the weight average fiber length (Lw), the number average fiber length (Ln), and the dispersity (Lw / Ln) were calculated by the following formula.
- the flow length was an average value of 20 shots.
- [Appearance Evaluation] Fibrous filling existing on the surface of the molded product when molded with a square plate mold of 80 mm x 80 mm x 3 mm thickness, temperature conditions shown in the table, injection speed 50 mm / sec, and injection pressure at lower limit pressure + 1 MPa The number of material aggregates was counted visually. The number of aggregates was the average of the values counted for 10 square plates.
- Comparative Example 6 As shown in Table 1, only the long fiber reinforced pellets (c1) were supplied to the injection molding machine, test pieces were molded in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 5, and the physical properties were measured.
- Table 1 shows the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 8.
- the resin composition (A) of the sheath layer has a thermoplastic resin (a1) and a weight average fiber length (Lw) of 0.1 mm or more and less than 0.5 mm, and
- the composition includes a fibrous filler (b1) having a ratio of weight average fiber length / number average fiber length (Lw / Ln) of 1 or more and less than 1.8, and the resin composition (B) of the core layer is thermoplastic.
- Resin (a2) and weight average fiber length (Lw) are 0.5 mm or more and less than 15.0 mm, and ratio of weight average fiber length / number average fiber length (Lw / Ln) is 1.8 or more and less than 5.0
- the fiber reinforced multi-layer pellets including the fibrous filler (b2) are highly productive, have a significantly improved impact resistance, and are flowable despite being highly filled with the fibrous filler. It can be seen that it has excellent properties and appearance.
- the sheath layer composition alone is excellent in productivity but has no improvement in mechanical properties and particularly low impact strength.
- the core layer composition alone when used, the strands expand due to the fluff and the strands cannot be drawn and cannot be pelletized, or the productivity is poor.
- Comparative Example 4 when the fiber length of the sheath layer is 0.5 mm or more, the mechanical properties are excellent, but the strands expand due to the fluff and the strand breaks frequently, resulting in poor productivity.
- the productivity is excellent. Impact strength is low and inferior.
- Comparative Example 6 the long fiber reinforced pellets alone, in which carbon fibers are coated with nylon 6 resin, and the blended long fiber reinforced pellets and short fiber reinforced pellets in Comparative Example 7 have excellent mechanical properties but fluidity. The appearance of the molded product is lowered because it is low and the dispersibility of the fibrous filler is also low. Further, in Comparative Example 8, when a dry blend of a thermoplastic resin and a fibrous filler is directly mixed with a molding machine, all of mechanical properties, fluidity, and appearance are deteriorated.
- thermoplastic resin (a1) was used. After supplying to the main hopper, the fibrous filler (b1) was supplied into the molten resin using a side feeder, melted and kneaded, and supplied to the core-sheath forming crosshead die.
- thermoplastic resin (a2) was fed to the twin screw extruder for core layer (TEX30 ⁇ , L / D35 manufactured by Nippon Steel Works) set to various conditions shown in the table.
- fibrous filler (b2) were supplied to the main hopper, melted and kneaded, and supplied to the core-sheath forming crosshead die.
- the multilayer strand discharged with a diameter of 4 mm from the die was cooled in water, cut into a length of 3.0 mm by a strand cutter, and pelletized to obtain a fiber-reinforced multilayer pellet.
- the composition ratio of the core layer / sheath layer was adjusted by the discharge amount of the melt kneader for the core layer and the sheath layer.
- the sheath layer resin composition (A) was not used in Comparative Examples 9 and 12, and the core layer resin composition (B) was not used in Comparative Example 11, these Comparative Examples 9, 11, and 12 were multilayer pellets. is not.
- the fiber-reinforced multilayer pellet of the present invention can be used for various applications such as automobile interior parts, automobile exterior parts, sports equipment members, housings of various electric / electronic parts, chassis and internal parts.
Abstract
Description
(1)鞘層および芯層を有する繊維強化多層ペレットであって、鞘層が、熱可塑性樹脂(a1)および繊維状充填材(b1)を含み、繊維状充填材の重量平均繊維長(Lw)が0.1mm以上0.5mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.0以上1.8未満である樹脂組成物から構成され、芯層が、熱可塑性樹脂(a2)および繊維状充填材(b2)を含み、繊維状充填材(b2)の重量平均繊維長(Lw)が0.5mm以上15.0mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.8以上5.0未満である樹脂組成物から構成される繊維強化多層ペレット、
または、
(2)熱可塑性樹脂(a3)および繊維状充填材(b3)を含む繊維強化ペレットであって、ペレット表層部における繊維状充填材の重量平均繊維長(Lw)が0.1mm以上0.5mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.0以上1.8未満であり、ペレット中心部における繊維状充填材の重量平均繊維長(Lw)が0.5mm以上15.0mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.8以上5.0未満である繊維強化多層ペレット、である。
上記繊維強化多層ペレットを成形してなる成形品、である。
前記鞘層を構成する樹脂組成物および前記芯層を構成する樹脂組成物をそれぞれ溶融混練し、クロスヘッドダイを用いて吐出することにより多層構造を形成する前記繊維強化多層ペレット(1)の製造方法、である。
ここで、樹脂組成物中の繊維状充填材(b1)の重量平均繊維長(Lw)、数平均繊維長(Ln)は、例えば、次のようにして求めることができる。まず、繊維強化多層ペレットを製造する時に、芯層の供給を止めて鞘層のみを供給することにより、鞘層をサンプリングする。または、繊維強化多層ペレット外周部表層を切削することにより、鞘層をサンプリングすることもできる。この際の鞘層と芯層が識別可能であれば、外周部の鞘層のみを切削することによりサンプリングすることが好ましいが、識別が困難な場合には、外周部表層を繊維強化多層ペレットの最表層から10重量%以内の部分と定義してサンプリングするものである。そのサンプルを、熱可塑性樹脂が溶解する溶剤にて溶解させた後、濾紙上で濾過・洗浄を行う。その濾紙上の残渣である繊維状充填材を、光学顕微鏡を使用し50倍の倍率で観察する。繊維状充填材1000本の長さを測定し、その測定値(mm)(小数点2桁が有効数字)から重量平均繊維長(Lw)、数平均繊維長(Ln)、分散度(Lw/Ln)を算出する。
重量平均繊維長(Lw)=Σ(Wi×Li)/ΣWi=Σ(πri2×Li×ρ×ni×Li)/Σ(πri2×Li×ρ×ni)
繊維径ri、および密度ρが一定である場合、上式は簡略化され、以下の式となる。
Li:繊維状充填材の繊維長
ni:繊維長Liの繊維状充填材の本数
Wi:繊維状充填材の重量
ri:繊維状充填材の繊維径
ρ:繊維状充填材の密度
繊維状充填材(b1)としては、溶融混練装置に添加できる形態であれば制限はなく、予め裁断されているチョップドストランドや破砕繊維、連続長繊維等が挙げられる。生産性の観点からチョップドストランドが好ましく利用できる。
重量平均繊維長(Lw)=Σ(Wi×Li)/ΣWi=Σ(πri2×Li×ρ×ni×Li)/Σ(πri2×Li×ρ×ni)
繊維径ri、および密度ρが一定である場合、上式は簡略化され、以下の式となる。
Li:繊維状充填材の繊維長
ni:繊維長Liの繊維状充填材の本数
Wi:繊維状充填材の重量
ri:繊維状充填材の繊維径
ρ:繊維状充填材の密度
繊維状充填材(b2)としては、溶融混練装置に添加できる形態であれば制限はなく、予め裁断されているチョップドストランドや破砕繊維、連続長繊維等が挙げられる。生産性の観点からチョップドストランドが好ましく利用できる。
本発明の繊維強化多層ペレットは、前記の鞘層/芯層からなる2層ペレットのみならず、熱可塑性樹脂(a3)および繊維状充填剤(b3)を含む繊維強化ペレットであって、ペレット表層部における繊維状充填材の重量平均繊維長(Lw)が0.1mm以上0.5mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.0以上1.8未満であり、ペレット中心部における繊維状充填材の重量平均繊維長(Lw)が0.5mm以上15.0mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.8以上5.0未満である繊維強化多層ペレットも含む。前記、鞘層/芯層からなる2層ペレット同様に、LwおよびLw/Lnの大きい繊維状充填材をペレット中心部に含むことで優れた機械特性を発現し、LwおよびLw/Lnの小さい繊維状充填材をペレット表層部に含むことで流動性および生産性を併せ持つ繊維強化多層ペレットを得ることができる。
本発明の繊維強化多層ペレットに使用する熱可塑性樹脂(a3)は、熱可塑性を示す樹脂であれば特に限定されず、例えば、前記鞘層を構成する樹脂組成物に使用する熱可塑性樹脂(a1)として例示したものを挙げることができる。
本発明の繊維強化多層ペレットにおいて、ペレット表層部と中心部における繊維状充填材の重量平均繊維長(Lw)、および重量平均繊維長/数平均繊維長の比(Lw/Ln)とは、ペレットの最表層および中心からそれぞれ10重量%以内の部分より得られる値である。
ペレット表層部における繊維状充填材(b3)のLwが0.1mm未満であると、繊維強化多層ペレットから得られる成形品の機械特性、特に曲げ弾性率が低下する。0.125mm以上が好ましく、0.15mm以上がより好ましい。一方、ペレット表層部における繊維状充填材(b3)のLwが0.5mm以上であると、繊維強化多層ペレットの表面外観が低下し、生産性が低下する。0.45mm未満がより好ましく、0.40mm未満がさらに好ましい。また、ペレット表層部における繊維状充填材(b3)のLw/Ln(分散度)が1.0未満であると、繊維強化多層ペレットから得られる成形品の機械特性、特に曲げ弾性率が低下する。1.05以上が好ましく、1.1以上がより好ましい。一方、ペレット表層部における繊維状充填材(b3)のLw/Ln(分散度)が1.8以上であると、繊維強化多層ペレットの表面外観が低下し、生産性が低下する。1.7未満が好ましく、1.6未満がより好ましい。
ペレット中心部における繊維状充填材(b3)のLwが0.5mm未満であると、繊維強化多層ペレットから得られる成形品の機械特性、特に衝撃強度が低下する。0.55mm以上が好ましく、0.6mm以上がより好ましい。一方、ペレット中心部における繊維状充填材(b3)のLwが15.0mm以上であると、繊維強化多層ペレットのペレット表面外観が低下する。10.0mm以下が好ましく、6.0mm以下がより好ましい。また、ペレット中心部における繊維状充填材(b3)のLw/Ln(分散度)が1.8未満であると、繊維強化多層ペレットから得られる成形品の機械特性、特に衝撃強度が低下する。1.9以上が好ましく、2.0以上がより好ましい。一方、ペレット中心部における繊維状充填材(b3)のLw/Ln(分散度)が5.0以上であると、繊維強化多層ペレットの表面外観が低下する。4.5以下が好ましく、4.0以下がより好ましい。
[熱可塑性樹脂]
(a1)鞘層の熱可塑性樹脂
(a1-1)ナイロン6樹脂(樹脂濃度0.01g/mlの98%濃硫酸溶液中、25℃で測定した相対粘度2.35)を使用した。
(a2)芯層の熱可塑性樹脂
(a2-1)(a1-1)と同じナイロン6樹脂を使用した。
[繊維状充填材]
(b1)鞘層の繊維状充填材
(b1-1)炭素繊維“トレカ”(登録商標)カットファイバーTV14-006(繊維長6mmのチョップドストランド)(東レ株式会社製、原糸T700SC-12K:引張強度4.90GPa、引張弾性率230GPa、繊維径6.8μm)を使用した。
(b2)芯層の繊維状充填材
(b2-1)(b1-1)と同じ炭素繊維を使用した。[炭素繊維強化ペレット]
(c1)炭素繊維強化ナイロン6樹脂“トレカ”(登録商標)長繊維ペレットTLP1060(炭素繊維含有量30wt%、東レ株式会社製)(長繊維強化ペレット)を使用した。
(c2)表1中の比較例1にて得られた炭素繊維強化ナイロン6樹脂(短繊維強化ペレット)を使用した。
[実施例1~5、比較例1~5]
表1記載の鞘層樹脂組成物(A)の組成比で、表中に示す諸条件に設定した鞘層用2軸押出機(日本製鋼所製TEX30α)を用い、熱可塑性樹脂(a1)を主ホッパーに供給後、繊維状充填材(b1)をサイドフィーダーを用いて溶融樹脂中に供給して溶融混練し、芯鞘形成用クロスヘッドダイに供給した。表1記載の芯層樹脂組成物(B)の組成比で、表中に示す諸条件に設定した芯層用単軸押出機(φ40mm、L/D30)に熱可塑性樹脂(a2)および繊維状充填材(b2)を主ホッパーに供給して溶融混練し、芯鞘形成用クロスヘッドダイに供給した。ダイから直径4mmで吐出された多層ストランドを水中にて冷却し、ストランドカッターにより長さ3.0mm長にカットしてペレット化を実施し、繊維強化多層ペレットを得た。なお、芯層/鞘層の構成比は芯層および鞘層の溶融混練装置の吐出量により調整した。ただし、比較例1、2においては芯層樹脂組成物(B)を用いず、比較例3においては鞘層樹脂組成物(A)を用いなかったのでこれら比較例1~3は多層ペレットではない。
[繊維長]鞘層用樹脂組成物を鞘層用2軸押出機で、芯層用樹脂組成物を芯層用単軸押出機で、それぞれ単独で各実施例および比較例と同じ押出条件で溶融混練し、クロスヘッドダイより吐出されたストランドをサンプリングした。さらに、実施例1~5および比較例4~5については、クロスヘッドダイより吐出された繊維強化多層ペレットを、流れ方向に沿って中央部で切断し、最表層および中心からそれぞれ10重量%以内の部分を切削することにより、鞘層および芯層のサンプリングをした。得られたサンプルは、ギ酸にて溶かした後、洗浄・濾過を行い、その残渣を光学顕微鏡にて50倍の倍率で観察しながら、無作為に選んだ1,000本の長さを測定した。得られた測定値から、下記式により、重量平均繊維長(Lw)、数平均繊維長(Ln)および分散度(Lw/Ln)を算出した。
重量平均繊維長(Lw)=Σ(Li2×ni)/Σ(Li×ni)
Li:繊維状充填材の繊維長
ni:繊維長Liの繊維状充填材の本数。
[生産性(連続引き取り性)]クロスヘッドダイから10kg/hrの速度で30分間吐出し、ストランドの切れた回数を求めた。
[耐衝撃性]ISO3167タイプB試験片を使用し、ISO179に従い23℃でシャルピー衝撃強さ(ノッチ付き)を評価した。試験片12本について測定した値の平均値とした。
[引張強度]ISO3167タイプA試験片を使用し、ISO527に従い23℃で引張強度を評価した。いずれも試験片6本について測定した値の平均値とした。
[曲げ強度、曲げ弾性率]ISO3167タイプA試験片を使用し、ISO178に従い23℃で曲げ強度および曲げ弾性率を評価した。いずれも試験片6本について測定した値の平均値とした。
[スパイラルフロー長]幅10mm、2mmtの金型を用い、表中に示す温度条件、射出速度50mm/sec、射出圧力80MPaで成形した際の流動長を測定した。流動長は20ショットの平均の値とした。
[外観評価]80mm×80mm×3mm厚の角板金型を用い、表中に示す温度条件、射出速度50mm/sec、射出圧を下限圧+1MPaで成形した際の成形品表面に存在する繊維状充填材凝集物の個数を目視にて数えた。凝集物の個数は角板10枚について計数した値の平均値とした。
[比較例6]
表1記載のとおり、長繊維強化ペレット(c1)のみを射出成形機に供給し、実施例1~5および比較例1~5と同様に試験片を成形し、物性を測定した。
[比較例7]
表1記載のとおり、長繊維強化ペレット(c1)と短繊維強化ペレット(c2)を50重量部:50重量部の組成比でドライブレンドした混合ペレットを射出成形機に供給し、実施例1~5および比較例1~5と同様に試験片を成形し、物性を測定した。
[比較例8]
表1記載のとおり、ナイロン6樹脂(a1-1)と炭素繊維チョップドストランド(b1-1)を70重量部:30重量部の組成比でドライブレンドして射出成形機に供給し、実施例1~5および比較例1~5と同様に試験片を成形し、物性を測定した。
[実施例6~11、比較例9~12]
表2記載の鞘層樹脂組成物(A)の組成比で、表中に示す諸条件に設定した鞘層用2軸押出機(日本製鋼所製TEX30α)を用い、熱可塑性樹脂(a1)を主ホッパーに供給後、繊維状充填材(b1)をサイドフィーダーを用いて溶融樹脂中に供給して溶融混練し、芯鞘形成用クロスヘッドダイに供給した。表2記載の芯層樹脂組成物(B)の組成比で、表中に示す諸条件に設定した芯層用2軸押出機(日本製鋼所製TEX30α、L/D35)に熱可塑性樹脂(a2)および繊維状充填材(b2)を主ホッパーに供給して溶融混練し、芯鞘形成用クロスヘッドダイに供給した。ダイから直径4mmで吐出された多層ストランドを水中にて冷却、ストランドカッターにより長さ3.0mm長にカットしてペレット化を実施し、繊維強化多層ペレットを得た。なお、芯層/鞘層の構成比は芯層および鞘層の溶融混練装置の吐出量により調整した。ただし、比較例9、12においては鞘層樹脂組成物(A)を用いず、比較例11においては芯層樹脂組成物(B)を用いなかったのでこれら比較例9、11、12は多層ペレットではない。
Claims (8)
- 鞘層および芯層を有する繊維強化多層ペレットであって、鞘層が、熱可塑性樹脂(a1)および繊維状充填材(b1)を含み、繊維状充填材(b1)の重量平均繊維長(Lw)が0.1mm以上0.5mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.0以上1.8未満である樹脂組成物から構成され、芯層が、熱可塑性樹脂(a2)および繊維状充填材(b2)を含み、繊維状充填材(b2)の重量平均繊維長(Lw)が0.5mm以上15.0mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.8以上5.0未満である樹脂組成物から構成される繊維強化多層ペレット。
- 前記鞘層を構成する樹脂組成物が、熱可塑性樹脂(a1)40~95重量%および繊維状充填材(b1)5~60重量%を含む請求項1に記載の繊維強化多層ペレット。
- 前記芯層を構成する樹脂組成物が、熱可塑性樹脂(a2)40~95重量%および繊維状充填材(b2)5~60重量%を含む請求項1または2に記載の繊維強化多層ペレット。
- 前記鞘層に含まれる繊維状充填材(b1)および/または前記芯層に含まれる繊維状充填材(b2)が、ガラス繊維、ポリアクリロニトリル系またはピッチ系炭素繊維およびステンレス繊維からなる群より選ばれる少なくとも1種である請求項1~3のいずれかに記載の繊維強化多層ペレット。
- 熱可塑性樹脂(a3)および繊維状充填材(b3)を含む繊維強化ペレットであって、ペレット表層部における繊維状充填材の重量平均繊維長(Lw)が0.1mm以上0.5mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.0以上1.8未満であり、ペレット中心部における繊維状充填材の重量平均繊維長(Lw)が0.5mm以上15.0mm未満であり、且つ重量平均繊維長/数平均繊維長の比(Lw/Ln)が1.8以上5.0未満である繊維強化多層ペレット。
- 前記繊維状充填材が、ガラス繊維、ポリアクリロニトリル系またはピッチ系炭素繊維およびステンレス繊維からなる群より選ばれる少なくとも1種である請求項5に記載の繊維強化多層ペレット。
- 請求項1~6のいずれかに記載の繊維強化多層ペレットを成形してなる成形品。
- 前記鞘層を構成する樹脂組成物および前記芯層を構成する樹脂組成物をそれぞれ溶融混練し、クロスヘッドダイを用いて吐出することにより多層構造を形成する請求項1~4のいずれかに記載の繊維強化多層ペレットの製造方法。
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CN201580006954.6A CN105960315B (zh) | 2014-02-03 | 2015-01-27 | 纤维增强多层颗粒、将其成型而成的成型品、及纤维增强多层颗粒的制造方法 |
KR1020167019965A KR20160115919A (ko) | 2014-02-03 | 2015-01-27 | 섬유 강화 다층 펠릿, 그것을 성형하여 이루어지는 성형품, 및 섬유 강화 다층 펠릿의 제조 방법 |
US15/115,298 US10391676B2 (en) | 2014-02-03 | 2015-01-27 | Fiber-reinforced multilayered pellet, molded article molded therefrom, and method of producing fiber-reinforced multilayered pellet |
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JP7360579B2 (ja) * | 2017-10-30 | 2023-10-13 | ダイセルミライズ株式会社 | 電磁波遮蔽吸収性成形体 |
JP6937385B2 (ja) * | 2017-12-05 | 2021-09-22 | 大塚化学株式会社 | 複合積層体及びその製造方法 |
JP6752935B1 (ja) | 2019-05-28 | 2020-09-09 | 旭化成株式会社 | 樹脂成形体の製造方法 |
US10703030B1 (en) * | 2019-09-12 | 2020-07-07 | Coretech System Co., Ltd. | Molding system for preparing fiberless thermoplastic composite article |
JP2021194798A (ja) * | 2020-06-10 | 2021-12-27 | 古河電気工業株式会社 | 繊維分散樹脂複合材、成形体、及び複合部材 |
CN114437456B (zh) * | 2020-10-30 | 2024-02-13 | 中国石油化工股份有限公司 | 一种热塑性复合材料及其制备方法和应用 |
KR102311536B1 (ko) * | 2021-04-22 | 2021-10-13 | 주식회사 성원 | 폐분체도료를 활용한 재생펠렛의 제조방법 및 이를 이용하여 제조한 폐분체도료를 활용한 재생펠렛 |
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