Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/04—Polysulfides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/307—Handling of material to be used in additive manufacturing
  • B29C64/314—Preparation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/06—Fibrous reinforcements only
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D99/00—Subject matter not provided for in other groups of this subclass
  • B29D99/0078—Producing filamentary materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
  • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/04—Particle-shaped
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
  • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
• • 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
  • B29K2021/00—Use of unspecified rubbers as moulding material
  • B29K2021/003—Thermoplastic elastomers
• • 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
  • B29K2021/00—Use of unspecified rubbers as moulding material
  • B29K2021/006—Thermosetting elastomers
• • 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
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
• • 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
• • 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
  • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
  • B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
• • 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
  • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
  • B29K2101/12—Thermoplastic materials
• • 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
• • 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
• • 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
  • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
  • B29K2309/08—Glass
• • 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
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0077—Yield strength; Tensile strength
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/16—Fibres; Fibrils
• • 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
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a thermoplastic resin filament that has suitable mechanical properties and can be wound, and a modeled article that is modeled using the filament.
• filaments are manufactured using resins such as polyphenylene sulfide (PPS) resin, polyetherimide (PEI) resin, polyether sulfone (PES) resin, polyether ether ketone (PPEK) resin, etc.
• PPS polyphenylene sulfide
• PEI polyetherimide
• PES polyether sulfone
• PPEK polyether ether ketone
• the inventors of the present invention have an object to manufacture a thermoplastic resin filament for 3D printing that can be wound and that can obtain suitable mechanical properties after modeling.
• thermoplastic resin (A) a fibrous reinforcing material (B) having a fiber length of 3 to 9 mm and a fiber diameter of 5 to 20 ⁇ m, and an elastomer
• a fiber-reinforced resin filament characterized by containing (C) provides a windable thermoplastic resin filament for 3D printing, and a modeled object that can be modeled by a hot melt lamination method using this is preferable.
• the present inventors have found that it exhibits excellent mechanical properties, and have completed the present invention.
• the present invention includes the following aspects.
• a fiber-reinforced thermoplastic resin characterized by containing a thermoplastic resin (A), a fibrous reinforcing material (B) having a fiber length of 3 to 9 mm and a fiber diameter of 5 to 20 ⁇ m, and an elastomer (C). filament.
• thermoplastic resin (A) is one or more resins selected from polyarylene sulfide resins, polyamide resins, and polyester resins. fiber reinforced thermoplastic filaments.
• thermoplastic resin (A) 5 to 35% by weight of fibrous reinforcing material (B) having a fiber length of 3 to 9 mm and a fiber diameter of 5 to 20 ⁇ m, and elastomer (C) of 2 to 35 % by weight of the fiber-reinforced thermoplastic resin filament according to any one of [1] to [4].
• thermoplastic resin filament for 3D printing that can be wound and that can obtain suitable mechanical properties after modeling using it.
• thermoplastic resin (A) The fiber-reinforced thermoplastic resin filaments of the present invention contain a thermoplastic resin (A) as an essential component.
• the thermoplastic resin (A) in the present invention is a resin that exhibits plasticity when heated and solidifies when cooled, and is not particularly limited within the range in which the effects of the present invention can be obtained, but a resin having a melting point of 150° C. or higher is preferred. A resin with a melting point of 170° C. or higher is more preferable because the durability after molding is improved, and a resin with a melting point of 270° C. or higher is most preferable.
• the thermoplastic resin used in the present invention specifically includes polyamide resins having an aliphatic skeleton such as polyamide 6 (6-nylon), polyamide 66 (6,6-nylon) or polyamide 12 (12-nylon), and , Polyamide 6T (6T-nylon), Polyamide 9T (9T-nylon), etc.
• Polyamide resins having an aromatic skeleton such as a melting point of 170 ° C. or higher, preferably in the range of 170 to 310 ° C., polybutylene terephthalate, poly Polyester resins such as isobutylene terephthalate, polyethylene terephthalate or polycyclohexene terephthalate having a melting point of 220° C.
• Polyarylene sulfide resin typified by polyphenylene sulfide with a melting point in the range of ⁇ 300°C, polyetheretherketone with a melting point in the range of 300 to 390°C, polyaryletherketone, and parahydroxybenzoic acid having a melting point in the skeleton Liquid crystal polymers having a melting point of 300° C. or higher, preferably 300° C. to less than the thermal decomposition temperature (380° C.), syndiotactic polystyrene having a melting point of 220° C.
• thermoplastic resins in the range of ° C., selected from polyarylene sulfide resins, polyamide resins, and polyester resins having excellent flame retardancy and dimensional stability. Thermoplastic resins are preferred, and polyarylene sulfide resins are particularly preferred.
• the thermoplastic resin preferably contains 30 to 93% by weight when the entire fiber-reinforced thermoplastic resin filament is 100% by weight. is obtained, it is preferably contained in an amount of 45 to 80% by weight.
• the polyarylene sulfide resin suitably used as a thermoplastic resin in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the following formula (1 )
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group or an ethoxy group).
• the trifunctional structural site represented by the following formula (8) is preferably 0.001 to 3 mol%, and preferably 0.01 to 1 mol%, relative to the total number of moles with other structural sites. is more preferred.
• the structural moiety represented by the formula (1) is preferably a hydrogen atom from the viewpoint of the mechanical strength of the polyarylene sulfide resin.
• the structure in which the sulfur atom is bonded to the aromatic ring in the repeating unit at the para position represented by the structural formula (3) is particularly desirable for the heat resistance and crystallinity of the polyarylene sulfide resin.
• polyarylene sulfide resin has not only the structural sites represented by the formulas (1) and (2), but also the following structural formulas (5) to (8)
• the structural sites represented by the above formulas (5) to (8) are 10 mol % or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin.
• the binding mode thereof may be either a random copolymer or a block copolymer. .
• the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but it is preferably 3 mol % or less, particularly 1 It is preferably mol % or less.
• the method for producing the polyarylene sulfide resin is not particularly limited. For example, 1) adding a dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, and if necessary adding a polyhalogenoaromatic compound or other copolymer components, 2) a method of polymerizing a dihalogeno aromatic compound in a polar solvent in the presence of a sulfidating agent or the like, and if necessary, a polyhalogeno aromatic compound or other copolymerization components are added; A method of self-condensing luthiophenol by adding other copolymerization components, if necessary, and the like. Among these methods, method 2) is versatile and preferred.
• an alkali metal salt of carboxylic acid or sulfonic acid, or an alkali hydroxide may be added in order to adjust the degree of polymerization.
• a hydrous sulfidation agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound is produced in the organic polar solvent.
• a sulfidating agent if necessary, are added to the polyhalogenoaromatic compound to react, and the amount of water in the reaction system is adjusted to the range of 0.02 to 0.5 mol per 1 mol of the organic polar solvent.
• a method for producing a polyarylene sulfide resin by controlling see JP-A-07-228699), or a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, if necessary.
• a polyhalogeno aromatic compound or other copolymer components are added, an alkali metal hydrosulfide and an organic acid alkali metal salt are added to 0.01 to 0.9 mol of an organic acid alkali metal salt per 1 mol of the sulfur source, and the reaction system.
• dihalogenoaromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4′-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalo
• the post-treatment method of the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization step is not particularly limited, but for example, (1) after the completion of the polymerization reaction, the reaction mixture is first treated as it is, or with an acid or base is added, the solvent is distilled off under reduced pressure or normal pressure, and the solid matter after the solvent is distilled off is treated with water, a reaction solvent (or an organic solvent having an equivalent solubility for the low-molecular-weight polymer), acetone, methyl ethyl ketone.
• the drying of the polyarylene sulfide resin may be carried out in a vacuum, in the air, or in an atmosphere of an inert gas such as nitrogen.
• melt viscosity is not particularly limited as long as it is within a range that allows molding by the hot melt lamination method. It preferably has a melt viscosity of 10 to 500 Pa ⁇ s, more preferably 25 to 450 Pa ⁇ s, even more preferably 40 to 350 Pa ⁇ s.
• the non-Newtonian index of the polyarylene sulfide resin is not particularly limited as long as it is in a range suitable for molding by the hot melt lamination method, but preferably in the range of 0.9 to 1.2. .
• the polyarylene sulfide resin used in the present invention has a melt viscosity suitable for molding by the hot melt lamination method.
• it prevents the melt viscosity of the melt-kneaded product from reacting with the fiber-reinforced bundle and excessively increasing, and has excellent moldability without thickness unevenness. can be exhibited, and the mechanical strength of the blow hollow molded product, especially the impact resistance, tends to be improved.
• the fiber-reinforced thermoplastic resin filament of the present invention contains as an essential component a fibrous reinforcing material (B) having a fiber length of 3-9 mm and a fiber diameter of 5-20 ⁇ m.
• Inorganic fibers and/or organic fibers can be used as the fibrous reinforcing material used in the present invention, and these fibers may be processed so as to have a fiber length of 3 to 9 mm and a fiber diameter of 5 to 20 ⁇ m.
• fibrous reinforcing materials examples include glass fiber reinforcing material, metal fiber reinforcing material, basalt fiber reinforcing material, carbon fiber (carbon fiber) reinforcing material, aramid fiber (wholly aromatic polyamide fiber) reinforcing material, nylon MXD6 fiber (m- It is possible to use a fibrous reinforcing material such as a fiber reinforcing material made of a cocondensation polymer of xylylenediamine and adipic acid, a PET fiber reinforcing material, a PBT fiber reinforcing material, and a wholly aromatic polyester fiber (Kevlar fiber) reinforcing material.
• a glass fiber reinforcing material and a carbon fiber reinforcing material are preferable because suitable toughness can be obtained when made into a filament.
• the fibrous reinforcing material (B) can also be a fiber reinforced bundle within the range where the effects of the present invention can be obtained.
• These fiber reinforced bundles include single fiber bundles of fibrous reinforcing materials containing one or more selected from maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, and copolymers of these compounds. Rovings converged by agents can also be used.
• the method for producing these fibrous reinforcing materials is not particularly limited as long as the effects of the present invention can be obtained. , melt homogenization, and then the resulting molten glass is fed to a bushing device and continuously drawn out in filaments from the bushing nozzle to form glass fibers. Chopped strands obtained by cutting the glass fiber thus formed into a predetermined length, yarn obtained by twisting the strands, roving obtained by combining a plurality of strands, etc. are coated with various processing agents (sizing), and bundled in units of a predetermined number. A fiber-reinforced bundle glass fiber may be obtained by doing so.
• the PAN-based precursor fiber bundle is subjected to a flame-proof heat treatment in an inert atmosphere at 200 to 300 ° C., and the obtained flame-proof fiber bundle is carbonized.
• carbonization is performed in an inert atmosphere at 300° C. or higher to obtain carbon fibers.
• the content of the fibrous reinforcing material is not particularly limited as long as the effect of the present invention can be obtained, but it is 5 to 35% by weight when the entire fiber-reinforced thermoplastic resin filaments are 100% by weight. %, and preferably 10 to 30% by weight because suitable mechanical strength can be obtained when modeling is performed by the hot melt lamination method.
• thermoplastic resin filaments of the present invention contain an elastomer (C) as an essential component.
• elastomer (C) used in the present invention known elastomers can be used as long as the effects of the present invention can be obtained.
• Thermoplastic elastomers are preferred as these elastomers.
• These thermoplastic elastomers preferably have functional groups capable of reacting with at least one group selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups and salts of carboxyl groups. Thereby, it is possible to obtain a resin composition which is particularly excellent in terms of adhesiveness, impact resistance, etc., and which can suppress the amount of gas generated by heating.
• Such functional groups include epoxy group, amino group, hydroxyl group, carboxyl group, mercapto group, isocyanate group, oxazoline group, and formula: R (CO) O (CO) - or R (CO) O - (in the formula, R represents an alkyl group having 1 to 8 carbon atoms.).
• a thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an ⁇ -olefin and a vinyl polymerizable compound having the functional group.
• ⁇ -olefins include ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1, and acid-modified ethylene- ⁇ -olefin copolymers.
• Examples of the vinyl polymerizable compound having a functional group include ⁇ , ⁇ -unsaturated carboxylic acids and their alkyl esters such as (meth)acrylic acid and (meth)acrylic acid esters, maleic acid, fumaric acid, itaconic acid and Other examples include ⁇ , ⁇ -unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters, acid anhydrides thereof, etc.), and glycidyl (meth)acrylates such as ethylene-glycidyl methacrylate copolymers.
• acid-modified ethylene- ⁇ -olefin copolymers ethylene-glycidyl methacrylate copolymers, epoxy groups, carboxyl groups, and formulas: R(CO)O(CO)— or R(CO)O— (wherein R represents an alkyl group having 1 to 8 carbon atoms.)
• R(CO)O(CO)— or R(CO)O— wherein R represents an alkyl group having 1 to 8 carbon atoms.
• the content of the elastomer is not particularly limited as long as the effects of the present invention can be obtained, but it is contained in an amount of 2 to 35% by weight when the entire fiber-reinforced thermoplastic resin filament is taken as 100% by weight.
• the content is 10 to 20% by weight because suitable mechanical strength can be obtained when modeling is performed by the hot-melt lamination method.
• the present invention relates to fiber-reinforced thermoplastic resin filaments containing the components (A) to (C) as essential components.
• the fiber-reinforced thermoplastic resin filaments may contain known additives other than the components (A) to (C) as long as the effects of the present invention are not impaired. These additives include release agents, colorants, heat stabilizers, ultraviolet stabilizers, foaming agents, rust inhibitors, crystal modifiers, lubricants, coupling agents, fiber lengths and fiber diameters different from those of component (B).
• Various fibrous fillers such as fibrous reinforcing materials, bead-shaped, flake-shaped fillers, and roving-treated fillers can be added and used.
• the fiber-reinforced thermoplastic resin filament of the present invention is not limited in its shape as long as the effect of the present invention can be obtained, but the diameter of the cross section provided perpendicular to the stretching direction of the filament is preferably 1 to 4 mm ⁇ . is preferably from 1.5 mm ⁇ to 3.5 mm ⁇ , and more preferably from 1.75 mm ⁇ to 3.0 mm ⁇ for ease of handling during winding and molding. Also, the length of the filament in the drawing direction is not particularly limited, and may be appropriately set according to the desired application.
• the fiber-reinforced thermoplastic resin filament of the present invention is not particularly limited in its flexural modulus as long as the effect of the present invention can be obtained.
• the flexural modulus of the filament is preferably 2 to 25 GPa, more preferably 5 to 20 GPa, because the filament can be easily handled.
• the thickness of the test piece is affected, so the measurement was performed using an injection-molded product for the purpose of measuring the flexural modulus of the filament itself.
• the fiber-reinforced thermoplastic resin filament of the present invention is not particularly limited in its tensile strength within the range where the effects of the present invention can be obtained. One is preferable, and 60 to 150 is more preferable because the moldability is improved.
• the measurement was performed using an injection-molded product for the purpose of measuring the tensile strength of the filament itself.
• the use of the fiber-reinforced thermoplastic resin filament of the present invention is not limited, but it is used for purposes such as providing it to a modeling apparatus for modeling.
• a modeling apparatus a chamber type that can heat the inside of the modeling chamber, a top heating type that has a heating device near the modeling nozzle, and a modeling apparatus that can heat the modeling table are selected. It is preferable because the effect of the present invention is exhibited particularly when it is provided for.
• thermoplastic resin (A) which is the base resin
• fibrous reinforcing material (B) having a fiber length of 3 to 6 mm and a fiber diameter of 5 to 20 ⁇ m
• elastomer (C) are mixed with a processing stabilizer
• Melt-kneading is carried out within a temperature range of +10°C to +100°C of melting point, more preferably +20°C to +50°C of melting point. After melt-kneading, additional components may be added as required, and the mixture may be further kneaded with a single-screw or twin-screw extruder to form filaments, or may be made into filaments as they are after melt-kneading.
• a PAN-based precursor fiber bundle is heat-treated for flameproofing in an inert atmosphere at 200 to 300°C, and the obtained flameproof fiber bundle is carbonized in an inert atmosphere at 300°C or higher in a carbonization step to obtain carbon fibers. Got a bunch. Subsequent steps were the same as for the glass fiber, followed by a sizing step to produce a carbon fiber chopped strand cut to a length of 6 mm.
• Examples 2 to 9 Fiber-reinforced thermoplastic resin filaments of Examples 2 to 9 were produced in the same manner as in Example 1 except that the types and blending amounts of each component were changed to those shown in Tables 1 and 2.
• Comparative Examples 1 to 7 Thermoplastic resin filaments of Comparative Examples 1 to 7 were produced in the same manner as in Example 1 except that the types and blending amounts of each component were changed to those shown in Table 2.
• the fragility and surface condition of each filament were evaluated by the following bending test and filament condition observation.
• the filament diameter is within ⁇ 0.05 mm of the set diameter
• the filament diameter is greater than ⁇ 0.05 mm of the set diameter and within ⁇ 0.10 mm .15 mm or less
• filament diameter is larger than the set diameter ⁇ 0.15 mm
• Tables 1 and 2 show the compositions of the above examples and the results obtained in the bending test, tensile test, bending test, and filament state observation.
• the fiber-reinforced thermoplastic resin filaments of Examples 1 to 9 according to the present invention are superior in tensile strength and bending strength to the thermoplastic resin filaments of Comparative Examples 1 to 7, and can be wound. Met.
• the filaments of Examples 1 to 9 were excellent in dimensional stability during filament production.
• thermoplastic resin filaments of Examples 1 to 9 and Comparative Examples 1 to 7 were subjected to P220 manufactured by Apium Co., Ltd., and modeled by a hot-melt lamination method.
• the nozzle temperature setting at the time of modeling was set in the range of 320°C to 380°C, the table temperature in the range of 60°C to 150°C, and the external heater in the range of 100°C to 200°C.
• the thermoplastic resin filaments of Examples 1 to 9 and Comparative Examples 5 and 6 were used, shaped objects could be produced. The shape became abnormal and the desired model could not be obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Mechanical Engineering (AREA)
• Composite Materials (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Ceramic Engineering (AREA)
• Civil Engineering (AREA)
• Structural Engineering (AREA)
• Reinforced Plastic Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84543916

Family Applications (1)

Country Status (6)

Cited By (1)

Citations (9)

• 2022
  • 2022-06-09 KR KR1020247001703A patent/KR20240025605A/ko not_active Abandoned
  • 2022-06-09 CN CN202280044334.1A patent/CN117561151A/zh active Pending
  • 2022-06-09 EP EP22828237.2A patent/EP4360842A4/en active Pending
  • 2022-06-09 JP JP2022574375A patent/JP7294547B2/ja active Active
  • 2022-06-09 US US18/572,919 patent/US20240294755A1/en active Pending
  • 2022-06-09 WO PCT/JP2022/023219 patent/WO2022270320A1/ja not_active Ceased

Patent Citations (9)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events