Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
• • 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
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products

Definitions

• the present invention relates to an amorphous epoxy fiber and a fiber structure using the fiber, and further relates to a molded product obtained by melting the fiber.
• Amorphous epoxy resin is a thermoplastic resin that has excellent adhesion to various materials and can be molded at a relatively low temperature, so it is used for various purposes.
• Patent Document 1 a fiber material obtained by melt-spinning polyhydroxyether, which is an amorphous epoxy resin, is used as a binder fiber to fix reinforcing fibers.
• reinforcing fibers are fixed in a predetermined arrangement with a thermoplastic fiber material composed of a polyhydroxy ether having a specific weight average molecular weight and a glass transition temperature to form a preform, and a matrix material is injected into the preform.
• a composite material obtained by performing a curing treatment to crosslink the thermoplastic fiber material with the matrix material is described.
• Patent Document 1 only uses a fiber material made of polyhydroxy ether as a binder fiber, and uses a separately prepared thermosetting resin as the matrix resin of the composite material.
• thermoplastic resin as matrix resin
• the fiber structure containing the amorphous epoxy fibers is formed into a matrix resin of a thermoplastic composite material. If it can be used as a material, it is expected that a composite material having good adhesion to reinforcing fibers (for example, carbon fiber) can be easily formed.
• the fiber material made of polyhydroxy ether described in Patent Document 1 is inferior in dimensional stability, and there is a problem that the formability is inferior when such a fiber material is melted to form a molded product. ..
• an object of the present invention is to solve the above-mentioned problems and to provide an amorphous epoxy fiber having excellent dimensional stability.
• the inventors of the present invention obtained an amorphous epoxy resin when the spinning conditions and drawing conditions for fiberizing the amorphous epoxy resin are changed. It was found that there is a difference in the dry heat shrinkage rate of the fiber at high temperature. Then, it was found that the difference in the dry heat shrinkage rate was influenced by the orientation of the fibers, and as a result of further research, the birefringence value, which is an index showing the orientation, was in the non-crystalline range. It has been found that the epoxy fiber can sufficiently suppress the dry heat shrinkage rate at high temperature, that is, it is excellent in dimensional stability, and the present invention has been completed.
• Amorphous epoxy fiber having a birefringence value of 0.005 or less (preferably 0.004 or less, more preferably 0.003 or less, still more preferably 0.002 or less).
• Aspect 2 The amorphous epoxy fiber according to the first aspect, which comprises an amorphous epoxy resin represented by the following general formula. (In the formula, X is a divalent phenol residue and n is 20 or more (preferably 20 to 300, more preferably 40 to 280, still more preferably 50 to 250)).
• Aspect 3 The amorphous epoxy fiber according to the first or second aspect, wherein the average fiber diameter of the single fiber is 40 ⁇ m or less (preferably 38 ⁇ m or less, more preferably 35 ⁇ m or less).
• Aspect 4 The amorphous epoxy fiber according to any one of aspects 1 to 3, wherein the dry heat shrinkage rate at 100 ° C. is 40% or less (preferably 35% or less, more preferably 30% or less, still more preferable. Is 25% or less, particularly preferably 20% or less), an amorphous epoxy fiber.
• the fiber structure according to the fifth aspect which is a mixed fiber yarn, a woven or knitted fabric, or a non-woven fabric.
• a method for producing a molded product according to the seventh aspect wherein the amorphous epoxy fiber according to any one of the first to fourth aspects or the fiber structure according to the fifth or sixth aspect is used as the amorphous epoxy.
• a method for producing a molded product which is formed by heating an amorphous epoxy resin constituting a system fiber at a temperature equal to or higher than the glass transition temperature.
• the amorphous epoxy fiber of the present invention has excellent dimensional stability because the birefringence value is controlled within a specific range.
• the amorphous epoxy fiber of the present invention is composed of an amorphous epoxy resin.
• the amorphous epoxy resin used in the present invention is a thermoplastic resin that can be obtained from a condensation reaction between a dihydric phenol compound and epihalohydrin, or a polyaddition reaction between a divalent phenol compound and a bifunctional epoxy compound. May be good.
• divalent phenol compound used as a raw material for the amorphous epoxy resin examples include hydroquinone, resorcin, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenylketone, and 2,2-bis (4-hydroxyphenyl).
• divalent phenol compounds can be used alone or in combination of two or more. Further, as the dihydric phenol compound, it is preferable to use bisphenols, and in particular, it is more preferable to use at least one divalent phenol compound selected from the group consisting of bisphenol A, bisphenol F and bisphenol S.
• Examples of the bifunctional epoxy compound used as a raw material for the amorphous epoxy resin include epoxy oligomers obtained by the condensation reaction between the above divalent phenol compound and epihalohydrin, for example, hydroquinone diglycidyl ether, resorcin diglycidyl ether, and bisphenol S type.
• Epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, methylhydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyloxide diglycidyl ether, 2,6-dihydroxynaphthalenediglycidyl ether, dichloro Examples thereof include bisphenol A diglycidyl ether, tetrabromo bisphenol A type epoxy resin, and 9,9'-bis (4-hydroxyphenyl) full orange glycidyl ether.
• These bifunctional epoxy compounds can be used alone or in combination of two or more.
• the bifunctional epoxy compound it is more preferable to use at least one bifunctional epoxy compound selected from the group consisting of the bisphenol A type epoxy resin and the bisphenol F type epoxy resin.
• the amorphous epoxy resin can be produced in the absence of a solvent or in the presence of a reaction solvent, and the reaction solvent used is an aprotic organic solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetphenone, N-methyl. Pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, sulfolane and the like can be preferably used. Further, the amorphous epoxy resin obtained by the solvent reaction can be made into a solid resin containing no solvent by subjecting it to a solvent removal treatment using an evaporator or the like.
• polymerization catalysts can be used in the production of amorphous epoxy resins, for example, alkali metal hydroxides, tertiary amine compounds, quaternary ammonium compounds, tertiary phosphine compounds, and fourth.
• a quaternary phosphonium compound or the like can be preferably used.
• the amorphous epoxy fiber of the present invention may contain an amorphous epoxy resin represented by the following formula.
• X may be a divalent phenol residue and n may be 20 or more.
• the divalent phenol residue may have a chemical structure derived from the divalent phenol compound, or may contain one or more chemical structures.
• X may have a chemical structure derived from at least one divalent phenol compound selected from the group consisting of bisphenol A, bisphenol F and bisphenol S.
• n represents the average degree of polymerization, and may be, for example, in the range of 20 to 300, preferably in the range of 40 to 280, and more preferably in the range of 50 to 250.
• the amorphous epoxy resin may have a functional group such as a hydroxyl group (for example, a phenolic hydroxyl group) or an epoxy group at the terminal.
• a functional group such as a hydroxyl group (for example, a phenolic hydroxyl group) or an epoxy group at the terminal.
• amorphous is confirmed by the presence or absence of an endothermic peak when the sample is heated in nitrogen at a rate of 10 ° C./min with a differential scanning calorimeter (DSC). can do. If the endothermic peak is very broad and the endothermic peak cannot be clearly determined, it may be judged to be substantially amorphous because it is at a level that does not cause any problem in actual use.
• DSC differential scanning calorimeter
• the weight average molecular weight of the amorphous epoxy resin may be in the range of 10,000 to 100,000, preferably 20,000 to 90,000, more preferably 30,000, from the viewpoint of improving spinnability. It may be up to 80,000.
• the weight average molecular weight of the amorphous epoxy resin indicates a value measured by gel permeation chromatography (GPC).
• the glass transition temperature of the amorphous epoxy resin (hereinafter, may be referred to as Tg) may be 100 ° C. or lower, preferably 98 ° C. or lower, from the viewpoint of moldability of the amorphous epoxy fiber. More preferably, it may be 95 ° C. or lower.
• the lower limit of the glass transition temperature of the amorphous epoxy resin is not particularly limited, but from the viewpoint of the heat resistance of the obtained fiber, for example, it may be 30 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher. It may be above ° C.
• the glass transition temperature of the amorphous epoxy resin is measured by differential scanning calorimetry (DSC).
• the amorphous epoxy resin may have, for example, a melt viscosity of 600 to 4000 poise at 300 ° C. and a shear rate of 1000 sec -1 , preferably 700 to 3000 poise, and more preferably 800 to 2000 poise.
• the amorphous epoxy fiber of the present invention may contain a component other than the amorphous epoxy resin as long as the effect of the present invention is not impaired, and as a component other than the amorphous epoxy resin.
• a component other than the amorphous epoxy resin examples include antioxidants, plasticizers, antistatic agents, radical inhibitors, matting agents, ultraviolet absorbers, flame retardants, dyes, pigments, polymers other than amorphous epoxy resins and the like.
• the amorphous epoxy fiber of the present invention may contain 50% by weight or more of the amorphous epoxy resin, preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 98% by weight. As described above, even more preferably, it may be contained in an amount of 99.5% by weight or more.
• the amorphous epoxy fiber of the present invention has a birefringence value of 0.005 or less.
• the birefringence value is an index indicating the molecular orientation state of the amorphous epoxy resin, and the smaller the birefringence value, the lower the molecular orientation with respect to the fiber axis direction. Since the amorphous epoxy fiber of the present invention has a specific birefringence value, the shrinkage at high temperature can be reduced.
• the birefringence value of the amorphous epoxy fiber may be preferably 0.004 or less, more preferably 0.003 or less, still more preferably 0.002 or less.
• the lower limit of the birefringence value is not particularly limited, but may be, for example, about 0.0001.
• the birefringence value is a value measured by the method described in Examples described later.
• the average fiber diameter of the single fiber can be appropriately adjusted according to the application and the like, and the average fiber diameter of the single fiber may be 40 ⁇ m or less, preferably 38 ⁇ m or less. More preferably, it may be 35 ⁇ m or less.
• the average fiber diameter of the single fibers is in the above range, so that the fibers can be mixed well with the reinforcing fibers.
• the lower limit of the average fiber diameter of the single fiber is not particularly limited as long as it has a specific birefringence value, but may be, for example, 5 ⁇ m or more, preferably 12 ⁇ m or more, and more preferably 15 ⁇ m or more. good.
• the average fiber diameter of the single fiber may be a value measured by the circumscribed circle diameter of the fiber cross-sectional shape.
• the number of filaments of the amorphous epoxy fiber of the present invention can be appropriately adjusted according to the intended use, and may be monofilament or multifilament. In the case of a multifilament, for example, the number of filaments may be 5 to 3000, preferably 10 to 2000, more preferably 30 to 1500, and even more preferably 50 to 500.
• the total fineness of the amorphous epoxy fiber of the present invention can be appropriately adjusted depending on the intended use, for example, it may be 1 to 10000 dtex, preferably 10 to 5000 dtex, more preferably 50 to 3000 dtex, still more preferably. May be 100 to 1500 dtex.
• the dry heat shrinkage rate at 100 ° C. can be reduced.
• the dry heat shrinkage rate at 100 ° C. may be 40% or less, preferably 35% or less, more preferably 30% or less, still more preferably 25% or less, and particularly preferably 20% or less. ..
• the lower limit of the dry heat shrinkage rate is not particularly limited and is preferably 0%, but may be, for example, about 1%.
• the amorphous epoxy fiber of the present invention is excellent in dimensional stability and therefore excellent in moldability.
• the amorphous epoxy fiber of the present invention is composed of an amorphous epoxy resin, it can be molded at a relatively low temperature and is excellent in low temperature moldability.
• the dry heat shrinkage rate is a value measured by the method described in Examples described later.
• the method for producing an amorphous epoxy fiber of the present invention may include a spinning step of melt-spinning an amorphous epoxy resin, and adjusts spinning conditions (particularly, spinning temperature and spinning speed) in the spinning step. Thereby, the shear stress applied to the molten polymer at the time of spinning can be reduced, and an amorphous epoxy fiber satisfying a specific compound refraction value can be obtained.
• a known melt spinning device can be used for melt spinning of an amorphous epoxy resin.
• pellets of amorphous epoxy resin are melt-kneaded with a melt extruder to guide the molten polymer to a spinning cylinder.
• the amorphous epoxy fiber of the present invention can be produced by weighing the molten polymer with a gear pump, discharging a predetermined amount from the spinning nozzle, and winding the obtained yarn.
• the yarn wound after melt spinning can be used as it is without being stretched.
• the shear stress applied to the molten polymer can be reduced by lowering the melt viscosity at the spinning temperature, so that the orientation of the fibers can be suppressed.
• the spinning temperature may be adjusted so that the melt viscosity at a shear rate of 1000 sec -1 at the spinning temperature is 600 to 4000 poise, preferably 700 to 3000 poise, and more preferably 800 to 2000 poise.
• the melt viscosity of the amorphous epoxy resin can be lowered by increasing the spinning temperature, but the spinning temperature can be appropriately set according to the type of the amorphous epoxy resin, for example, spinning.
• the temperature may be 250 to 330 ° C., preferably 260 to 320 ° C., more preferably 280 to 315 ° C.
• the size of the spinning hole (single hole) in the spinneret can be appropriately set according to the desired fiber diameter, and is, for example, about 0.02 to 1 mm 2 , preferably about 0.03 to 0.5 mm 2 . More preferably, it may be about 0.03 to 0.15 mm 2.
• the shape of the spinning hole can be appropriately selected according to the required fiber cross-sectional shape, but is preferably a perfect circular shape.
• the discharge rate from the spinning nozzle can be appropriately set according to the viscosity of the molten polymer at the spinning temperature, the hole diameter of the nozzle, and the discharge amount, but by making it relatively low, the shear stress applied to the molten polymer in the nozzle is applied. Can be reduced.
• the discharge rate may be in the range of 2.54 m / min to 42.4 m / min, preferably 4.24 m / min to 33.9 m / min, more preferably 4.24 m / min to 25. It may be 4 m / min.
• the spinning speed (winding speed) at that time can be appropriately set according to the viscosity of the molten polymer at the spinning temperature, the pore diameter of the nozzle, and the discharge amount.
• the orientation can be reduced. For example, it is preferable to pick up in the range of 100 m / min to 2000 m / min, more preferably 100 m / min to 1500 m / min, still more preferably 100 m / min to 1000 m / min, and particularly preferably 100 m / min to 750 m / min. Most preferably, it may be 100 m / min to 500 m / min.
• the ratio of the discharge speed to the take-up speed may be, for example, in the range of 2 to 300, preferably 5 to 5 from the viewpoint of adjusting the orientation of the fibers. It may be in the range of 200, more preferably 10 to 100, and even more preferably 15 to 50.
• the fiber obtained after melt spinning may be used as it is as an undrawn yarn without being drawn, and the amorphous epoxy fiber is specific.
• it may include a drawing step of drawing the fibers obtained by the spinning step, for example, from the viewpoint of adjusting the fiber diameter. From the viewpoint of reducing shrinkage at high temperatures, it is preferable to use it as an undrawn yarn.
• the birefringence value of the undrawn yarn is preferably 0.0045 or less, more preferably 0.0035 or less, from the viewpoint of adjusting the birefringence value of the amorphous epoxy fiber.
• the stretching temperature is preferably Tg-30 ° C. or higher and Tg + 20 ° C. or lower based on the glass transition temperature (Tg) of the amorphous epoxy resin.
• Tg glass transition temperature
• the draw ratio is extremely low with respect to the yarn discharged from the spinning nozzle (for example, the draw ratio is about 1.01 to 1.3). It is preferable to set the draw ratio (preferably about 1.01 to 1.2) for drawing, but the draw ratio may be set according to the draw temperature in consideration of compatibility with the adjustment of the fiber diameter.
• the stretching ratio is preferably 1.01 to 1.2, and when the stretching temperature is Tg-20 ° C or higher and lower than Tg ° C, the stretching ratio is It is preferably 1.01 to 1.4, and when it is Tg ° C. or higher and Tg + 20 ° C. or lower, the draw ratio is preferably 1.01 to 1.7.
• the amorphous epoxy fiber of the present invention can be used as a fiber structure containing at least a part thereof.
• the amorphous epoxy fiber can be used in any fiber form such as staple fiber, shortcut fiber, filament yarn, spun yarn, string, rope and the like. Further, the amorphous epoxy fiber may be a non-composite fiber or a composite fiber.
• the fiber structure of the present invention may be a cloth.
• the shape of the cloth is not particularly limited as long as the amorphous epoxy fiber of the present invention is used, and the shape of the cloth includes various cloths such as non-woven fabric (including paper), woven fabric, and knitted fabric. Such fabrics can be produced using amorphous epoxy fibers by known or conventional methods.
• the fiber structure of the present invention may be combined with an amorphous epoxy fiber and another fiber as long as the effect of the present invention is not impaired.
• a mixed fiber yarn in which an amorphous epoxy fiber and another fiber are mixed can be used.
• the fabric contains, for example, the amorphous epoxy fiber according to the present invention as the main fiber, and the ratio thereof is 50% by mass or more, preferably 80% by mass or more, particularly 90% by mass, based on the whole. The above may be included.
• the fiber structure may be a mixed fiber yarn or a mixed fiber fabric containing reinforcing fibers as other fibers.
• Amorphous epoxy fibers and fiber structures containing them are available in various shapes, including industrial materials, agricultural materials, civil engineering materials, electrical and electronic fields, optical materials, aircraft, automobiles, and ships. It can be used extremely effectively for many purposes.
• the amorphous epoxy fiber of the present invention can be used as a molded product using it as a matrix.
• the molded body may be any as long as it can be obtained by molding an amorphous epoxy fiber or a fiber structure, for example, a reinforcing fiber obtained by molding an amorphous epoxy fiber or a fiber structure. It may be a molded body containing no reinforcing fibers, or a composite material containing reinforcing fibers obtained by molding an amorphous epoxy fiber or a fiber structure together with a reinforcing fiber.
• the method for producing a molded product of the present invention includes a step of preparing the amorphous epoxy fiber or fiber structure and the amorphous epoxy fiber or fiber structure at a temperature equal to or higher than the glass transition temperature of the amorphous epoxy resin. It may be provided with at least a heat forming step of heating.
• the heat molding method is not particularly limited as long as the amorphous epoxy fibers are melted and integrated, and a general molding method for a molded product can be used.
• the amorphous epoxy fiber can be melted and molded into a desired shape by heating at a temperature equal to or higher than the glass transition temperature of the amorphous epoxy resin.
• the heating temperature is 300. It may be below ° C., preferably below 280 ° C. Further, since the amorphous epoxy fiber can be molded even at a relatively low temperature, the heating temperature may be 250 ° C. or lower, preferably 230 ° C. or lower, from the viewpoint of preventing deterioration of the molded product. good.
• the molded product When the molded product is heat-molded, it may be molded under pressure.
• the pressure is not particularly limited, but is usually carried out at a pressure of 0.05 N / mm 2 or more (for example, 0.05 to 15 N / mm 2).
• the time for heat molding is not particularly limited, but it is usually preferably 30 minutes or less because the polymer may deteriorate when exposed to high temperature for a long time.
• the shape of the molded product is not particularly limited and can be appropriately set according to the application. It is also possible to heat-mold by stacking a plurality of fabrics having different specifications or separately arranging fabrics having different specifications in a mold of a certain size. In some cases, it can be molded together with other reinforcing fiber fabrics or composite materials. Then, depending on the purpose, it is also possible to heat-mold the molded product obtained by heat-molding once again.
• the molded body of the present invention is a composite material containing reinforcing fibers
• a method for producing the composite material a laminate obtained by laminating a fiber structure and a reinforcing fiber fabric (for example, a reinforcing fiber woven fabric) is heat-molded.
• a method and a manufacturing method in which a fiber structure containing reinforcing fibers is heat-molded include a method and a manufacturing method in which a fiber structure containing reinforcing fibers is heat-molded.
• the type of reinforcing fiber used for the composite material is not particularly limited, but from the viewpoint of the mechanical strength of the obtained composite material, glass fiber, carbon fiber, liquid crystal polyester fiber, aramid fiber, polyparaphenylene benzobisoxazole fiber, polyparaphenylene. Included is at least one selected from the group consisting of benzobis imidazole fibers, polyparaphenylene benzobisthiazole fibers, ceramic fibers, and metal fibers.
• One type of these reinforcing fibers may be used alone, or two or more types may be used in combination. Of these, carbon fiber or glass fiber is preferable from the viewpoint of enhancing mechanical properties.
• the shape of the reinforcing fiber fabric is not particularly limited and can be appropriately set according to the application, for example, woven fabric, non-crimp fabric (NCF), one-way pulling material (UD material), knitted fabric, non-woven fabric and the like. Can be mentioned.
• the molded product of the present invention preferably has a density of 2.00 g / cm 3 or less. It is preferably 1.95 g / cm 3 or less, and more preferably 1.90 g / cm 3 or less.
• the lower limit of the density is appropriately determined depending on the selection of the material and the like, but may be, for example, about 0.1 g / cm 3.
• the molded product of the present invention preferably has a thickness of 0.05 mm or more (preferably 0.1 mm or more). It may be more preferably 0.3 mm or more, still more preferably 0.5 mm or more.
• the upper limit of the thickness can be appropriately set according to the thickness required for the molded product, but may be, for example, about 10 mm.
• the molded product of the present invention can be manufactured at low cost without requiring a special process, for example, a personal computer, a display, an OA device, a mobile phone, a mobile information terminal, a digital video camera, an optical device, an audio system, an air conditioner, a lighting device, etc.
• Chassis for toy supplies, electrical and electronic equipment parts, and other home appliances include civil engineering and building material parts such as interior parts, exterior parts, columns, panels, reinforcements; various types of vehicles (automobiles, motorcycles, ships, aircraft, etc.)
• vehicles such as members, various frames, various hinges, various arms, various axles, various wheel bearings, various beams, various pillars, various supports, various rails; instrument panels, seat frames, door trims, pillar trims, handles, various modules, etc.
• melt viscosity The melt viscosity of the amorphous epoxy resin was measured at 300 ° C. and a shear rate of 1000 sec -1 using a capillograph "1C PMD-C” manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the fiber thickness indicates the fiber diameter.
• ⁇ n R / d ⁇ n: birefringence value, R: retardation (nm), d: fiber thickness (nm)
• a scanning electron microscope (SEM) was used to perform magnified imaging at a predetermined magnification, and the average value of the measured values of 100 randomly selected fiber diameters was taken as the average fiber diameter.
• a slurry consisting of 50 wt% of amorphous epoxy fiber and 50 wt% of carbon fiber with a cut length of 13 mm (manufactured by Teijin Limited: average fiber diameter 7 ⁇ m, specific gravity 1.8 g / cm 3) was used as the matrix of the molded body. Then, a mixed non-woven fabric (mixed paper) having a grain size of 254 g / m 2 was obtained by a wet raid process. Next, the obtained non-woven fabric was press-molded at 260 ° C. for 3 minutes under a pressure of 3 N / mm 2 to obtain a composite material having a thickness of 1 mm.
• the moldability was evaluated based on the following criteria based on the appearance of the composite material (roughness of the surface, uneven thickness, presence / absence of shrinkage, presence / absence of warpage).
• ⁇ There is no surface roughness, uneven thickness, shrinkage, or warpage.
• ⁇ Rough surface, uneven thickness, shrinkage, and warpage are slightly observed.
• X Rough surface, uneven thickness, shrinkage, and warpage are very large.
• a mixed non-woven fabric (mixed paper) having a grain size of 98 g / m 2 was obtained by a wet raid process. Next, the obtained non-woven fabric was press-molded at 200 ° C. for 1 minute under a pressure of 3 N / mm 2 to obtain a composite material having a thickness of 1 mm.
• the moldability was evaluated based on the following criteria based on the appearance of the composite material (roughness of the surface, uneven thickness, presence / absence of shrinkage, presence / absence of warpage).
• ⁇ There is no surface roughness, uneven thickness, shrinkage, or warpage.
• ⁇ Rough surface, uneven thickness, shrinkage, and warpage are slightly observed.
• X Rough surface, uneven thickness, shrinkage, and warpage are very large.
• Example 1 As an amorphous epoxy resin, a bisphenol A (BPA) type phenoxy resin having a weight average molecular weight of 60,000, a glass transition temperature of 84 ° C., and a melt viscosity of 890 poise at 300 ° C. (manufactured by Nittetsu Chemical & Materials Co., Ltd.) YP-50s ”) was used. This resin is melt-extruded with a twin-screw extruder and discharged from a round hole nozzle of 0.2 mm ⁇ ⁇ 100 holes at a spinning temperature of 300 ° C., the discharge speed is 4.5 m / min, the take-up speed is 167 m / min, and the discharge speed. The fiber was wound by adjusting the ratio (draft) of the speed to the winding speed to 37.1. The obtained fibers were evaluated and the results are shown in Table 1.
• BPA bisphenol A
• Example 2 Fibers were obtained in the same manner as in Example 1 except that the discharge speed was adjusted to 8.1 m / min, the take-up speed was adjusted to 300 m / min, and the ratio (draft) of the discharge speed to the take-up speed was adjusted to 37.0. The obtained fibers were evaluated and the results are shown in Table 1.
• Example 3 Fibers were obtained in the same manner as in Example 1 except that the discharge speed was adjusted to 12.1 m / min, the take-up speed was adjusted to 450 m / min, and the ratio (draft) of the discharge speed to the take-up speed was adjusted to 37.2. The obtained fibers were evaluated and the results are shown in Table 1.
• Example 4 Fibers were obtained in the same manner as in Example 1 except that the discharge speed was adjusted to 25.9 m / min, the take-up speed was adjusted to 1400 m / min, and the ratio (draft) of the discharge speed to the take-up speed was adjusted to 54.1. The obtained fibers were evaluated and the results are shown in Table 1.
• Example 5 Fibers were obtained in the same manner as in Example 1 except that the discharge speed was adjusted to 9.0 m / min, the take-up speed was adjusted to 167 m / min, and the ratio (draft) of the discharge speed to the take-up speed was adjusted to 18.6. Further, this fiber was drawn at a drawing temperature of 100 ° C., a drawing speed of 12 m / min, and a drawing ratio of 1.5 times to obtain a drawn fiber. The obtained fibers were evaluated and the results are shown in Table 1.
• Example 6 Stretched fibers were obtained in the same manner as in Example 5 except that the stretching temperature was 80 ° C., the stretching speed was 12 m / min, and the stretching ratio was 1.25 times. The obtained fibers were evaluated and the results are shown in Table 1.
• Example 7 Stretched fibers were obtained in the same manner as in Example 5 except that the stretching temperature was 60 ° C., the stretching speed was 12 m / min, and the stretching ratio was 1.05 times. The obtained fibers were evaluated and the results are shown in Table 1.
• Example 4 The fibers obtained in Example 4 were stretched at a stretching temperature of 60 ° C., a stretching speed of 12 m / min, and a stretching ratio of 1.1 times to obtain drawn fibers. The obtained fibers were evaluated and the results are shown in Table 1.
• amorphous epoxy fibers having a specific birefringence value can be obtained by adjusting the spinning conditions, and in Examples 5 to 7, the amorphous epoxy fibers can be obtained.
• the spinning conditions and the drawing conditions By adjusting the spinning conditions and the drawing conditions, an amorphous epoxy fiber having a specific birefringence value can be obtained, and the dimensional stability is excellent. Therefore, such an amorphous epoxy fiber has a good appearance of a composite material molded by using it as a matrix, and is excellent in moldability.
• the obtained fibers are inferior in dimensional stability because the birefringence value cannot be controlled. Therefore, the composite material formed by using the obtained fibers as a matrix has extremely large surface roughness, uneven thickness and shrinkage, and the obtained fibers are inferior in moldability.
• the amorphous epoxy fiber of the present invention and the fiber structure containing the same can be suitably used in various applications, and further, the amorphous epoxy fiber is melted and used as a matrixed molded product. be able to.
• Such amorphous epoxy fibers, fiber structures and molded bodies are used in the general industrial materials field, electrical / electronic field, civil engineering / building field, aircraft / automobile / railway / ship field, agricultural material field, and optical material field. , Medical material field, etc., can be used extremely effectively.

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• 2021
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