WO2014021084A1 - 耐熱性樹脂複合体およびその製造方法、ならびに耐熱性樹脂複合体用不織布 - Google Patents
耐熱性樹脂複合体およびその製造方法、ならびに耐熱性樹脂複合体用不織布 Download PDFInfo
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- WO2014021084A1 WO2014021084A1 PCT/JP2013/069108 JP2013069108W WO2014021084A1 WO 2014021084 A1 WO2014021084 A1 WO 2014021084A1 JP 2013069108 W JP2013069108 W JP 2013069108W WO 2014021084 A1 WO2014021084 A1 WO 2014021084A1
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- fiber
- heat
- resin composite
- nonwoven fabric
- resistant resin
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- 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
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- B29C70/40—Shaping or impregnating by compression not applied
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- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- Y10T442/642—Strand or fiber material is a blend of polymeric material and a filler material
Definitions
- the present invention relates to a heat resistant resin composite having excellent mechanical properties and heat resistance, and a method for producing the same, and also relates to a nonwoven fabric for a heat resistant resin composite useful for producing the composite. is there. Furthermore, the present invention relates to a heat-resistant resin composite excellent in heat resistance, flame retardancy, dimensional stability, and process passability.
- a heat-resistant resin composite is used in the general industrial materials field, electrical / electronic field, In the civil engineering / architecture field, aircraft / automobile / railway / ship field, agricultural material field, optical material field, medical material field, etc., it should be used extremely effectively for applications that are exposed to a high temperature environment. Can do.
- Fiber reinforced resin composites consisting of carbon fiber, glass fiber and other reinforced fibers and thermoplastic resins are lightweight and have excellent specific strength and specific rigidity, so they can be used in electrical / electronic applications, civil engineering / architecture applications, automotive applications, Widely used for aircraft applications.
- reinforcing fibers may be used as continuous fibers in order to improve mechanical properties.
- continuous fibers have poor shapeability and are not suitable for fiber reinforced resin composites having complicated shapes. Manufacture may be difficult. Therefore, Patent Document 1 (Japanese Patent Laid-Open No. 61-130345) and Patent Document 2 (Japanese Patent Laid-Open No. 6-107808) describe a fiber-reinforced resin having a complicated shape by making the reinforcing fibers discontinuous. It has been proposed to produce a composite.
- Patent Document 3 Japanese Patent Publication No. 3-25537
- heat-resistant fibers and unstretched polyphenylene sulfide fibers are blended in a weight ratio of 92: 8 to 20:80 to form a web
- a method for producing a heat-resistant nonwoven fabric is disclosed in which thermocompression bonding is performed under a temperature condition in which unstretched fibers are plasticized under pressure and cause a fusing action.
- Patent Document 4 International Publication No. 2007/097436 pamphlet discloses a molding material composed of 20 to 65% by weight of thermoplastic resin fibers such as nylon 6 and polypropylene and 35 to 80% by weight of carbon fibers, which is a single fiber.
- thermoplastic resin fibers such as nylon 6 and polypropylene
- carbon fiber and single fiber thermoplastic resin fiber the weight average fiber length (Lw) of the carbon fiber is in the range of 1 to 15 mm
- the orientation parameter (fp) of the carbon fiber is ⁇ 0.25. Molding materials in the range of ⁇ 0.25 are disclosed.
- Patent Document 5 Japanese Patent Publication No. 2006-524755 discloses at least one first fiber as a molten fiber made of a high-performance thermoplastic material, and has higher temperature stability than the molten fiber.
- a fiber composite is disclosed that is manufactured from a nonwoven mat that includes at least one second reinforcing fiber of high performance material and a PVA binder.
- the glass transition temperatures of polyphenylene sulfide fiber, nylon 6 fiber, and polypropylene fiber used in Patent Document 3 or 4 are less than 100 ° C. Since the glass transition temperature is a temperature at which the micro-brown motion of the polymer chain begins, when the temperature is exceeded, molecules in the amorphous part start to move. Therefore, since the physical properties of the polymer greatly change at 100 ° C. or higher, use at high temperatures is limited.
- the fiber composite material is formed in the Example from the nonwoven mat comprised by the PPS (polyphenylene sulfide) fiber, the carbon fiber, and the PVA binder fiber at the compression temperature of 350 degreeC
- the polyphenylene sulfide fiber has a glass transition temperature of less than 100 ° C. and is practically limited.
- the present inventors have obtained a thermoplastic fiber constituting a matrix by heat fusion in order to obtain a molded product having high heat resistance even in actual use. It was found that the glass transition temperature of the glass must be 100 ° C. or higher.
- the first embodiment of the present invention is a nonwoven fabric used for producing a heat-resistant resin composite
- the nonwoven fabric includes a heat-resistant thermoplastic fiber, a reinforcing fiber, and a polyester binder fiber
- the heat-resistant thermoplastic fiber has a glass transition temperature of 100 ° C. or higher, an average fineness of 0.1 to 10 dtex, and an average fiber length of 0.5 to 60 mm.
- Composed of polymer The nonwoven fabric for heat resistant resin composites, wherein the proportion of thermoplastic fibers constituting the nonwoven fabric is 30 to 80 wt%.
- the crystallinity of the polyester binder fiber may be 50% or less.
- the heat-resistant thermoplastic fiber may be a fiber that has not been substantially stretched after spinning.
- the heat-resistant thermoplastic fiber may be composed of at least one selected from the group consisting of polyetherimide fiber, semi-aromatic polyamide fiber, polyether ether ketone fiber, and polycarbonate fiber, for example.
- the reinforcing fiber may be composed of at least one selected from the group consisting of carbon fiber, glass fiber, wholly aromatic polyester fiber, and para-aramid fiber, for example.
- the nonwoven fabric may have a basis weight of 5 to 1500 g / m 2 , for example.
- the second embodiment of the present invention comprises a preparation step of preparing the nonwoven fabric, One or more sheets of the non-woven fabric, a heat forming step of heating and compressing at or above the flow start temperature of the heat-resistant thermoplastic fiber, Is a method for producing a heat resistant resin composite.
- a third embodiment of the present invention is a heat resistant resin composite composed of a matrix resin and reinforcing fibers dispersed in the matrix resin,
- the bending strength at 24 ° C. may be 150 MPa or more, and the retention rate of the bending strength at 100 ° C. with respect to 24 ° C. may be 70% or more.
- the bending elastic modulus at 24 ° C. may be 5 GPa or more, and the retention rate of the bending elastic modulus at 100 ° C. with respect to 24 ° C. may be 70% or more.
- the heat-resistant resin composite may have a density of 2.00 g / cm 3 or less and a thickness of 0.3 mm or more.
- the heat-resistant resin composite of the present invention does not require a special thermoforming process, and can be manufactured at a low cost by a normal thermoforming process such as compression molding or GMT molding.
- the shape can also be designed freely, including many fields such as general industrial materials field, electrical / electronic field, civil engineering / architecture field, aircraft / automobile / railway / ship field, agricultural material field, optical material field, medical material field, etc. It can be used very effectively for applications.
- the first embodiment of the present invention is a non-woven fabric that is used to produce a heat-resistant resin composite and includes heat-resistant thermoplastic fibers, reinforcing fibers, and polyester-based binder fibers.
- thermoplastic fiber Since the heat-resistant thermoplastic fiber used in the present invention has high heat resistance, its glass transition temperature is 100 ° C. or higher. Moreover, since it is a thermoplastic fiber, it can be heated and melted or heated and flowed by increasing the temperature. In general, it is well known that the mechanical properties of macromolecules greatly drop at the glass transition temperature at which the amorphous part molecules move. For example, even if a thermoplastic fiber having a melting point of 200 ° C. or higher, such as polyethylene terephthalate (PET) or nylon 6, its mechanical properties are drastically lowered at a glass transition temperature of 60 to 80 ° C. It is hard to say that it is excellent in performance.
- PET polyethylene terephthalate
- the glass transition temperature of the heat-resistant thermoplastic fiber used in the present invention is preferably 105 ° C. or higher, more preferably 110 ° C. or higher.
- the upper limit of the glass transition temperature of a heat resistant thermoplastic fiber is suitably set according to the kind of fiber, about 200 degreeC may be sufficient from a viewpoint of a moldability.
- the glass transition temperature in the present invention depends on the temperature dependence of the loss tangent (tan ⁇ ) at a frequency of 10 Hz and a heating rate of 10 ° C./min using a solid dynamic viscoelastic device “Rheospectra DVE-V4” manufactured by Rheology. Is measured from the peak temperature.
- the peak temperature of tan ⁇ is a temperature at which the first derivative of the amount of change with respect to the temperature of the value of tan ⁇ becomes zero.
- the heat-resistant thermoplastic fiber used in the present invention is not particularly limited as long as the glass transition temperature is 100 ° C. or higher, and may be used alone or in combination of two or more.
- Fluorine fibers such as tetrafluoroethylene fibers; polyimide fibers such as semi-aromatic polyimide fibers, polyamideimide fibers, and polyetherimide fibers; polysulfone fibers such as polysulfone fibers and polyethersulfone fibers Semi-aromatic polyamide fiber; polyetherketone fiber such as polyetherketone fiber, polyetheretherketone fiber and polyetherketoneketone fiber; polycarbonate fiber; polyarylate fiber; wholly aromatic polyester fiber Etc.
- polyetherimide fiber semi-aromatic polyamide fiber
- polyether ether ketone fiber polycarbonate fiber
- semi-aromatic polyamide fibers wholly aromatic polyester fibers, polysulfone fibers, polycarbonate fibers and the like are preferably used.
- the heat-resistant thermoplastic fiber used in the present invention includes an antioxidant, an antistatic agent, a radical inhibitor, a matting agent, an ultraviolet absorber, a flame retardant, various inorganic substances and the like as long as the effects of the present invention are not impaired. You may go out.
- specific examples of such inorganic substances include carbon materials such as carbon nanotubes, fullerenes, carbon black, graphite, and silicon carbide; talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, and alumina.
- Silicate materials such as silicate
- Metal beads such as ceramic beads, silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, iron oxide
- carbonates such as calcium carbonate, magnesium carbonate, dolomite
- Sulfates of calcium hydroxide such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide
- Glasses such as glass beads, glass flakes and glass powders; Ceramic beads; Boron nitride and the like are used.
- the production of the heat-resistant thermoplastic fiber used in the present invention is not particularly limited as long as the fiber shape can be obtained, and a known melt spinning apparatus can be used. That is, it is obtained by melting and kneading at least thermoplastic polymer pellets and powders with a melt extruder, introducing the molten polymer into a spinning cylinder, measuring it with a gear pump, and winding the yarn discharged from the spinning nozzle.
- the take-up speed at that time is not particularly limited, but from the viewpoint of reducing the occurrence of molecular orientation on the spinning line, the take-up speed is preferably 500 m / min to 4000 m / min.
- the heat-resistant thermoplastic fiber of the present invention is substantially stretched in order to improve the process passability in the production process of the heat-resistant resin composite and the dimensional stability and appearance of the resulting resin composite.
- the term “stretching” refers to a process of drawing a cooled fiber using a tensioning means such as a roller after melt spinning, and the molten raw yarn is discharged in a winding process after being discharged from a nozzle. The stretched process is not included.
- the average fineness of the single fiber of the heat-resistant thermoplastic fiber used in the present invention is 0.1 to 15 dtex.
- the thinner the average fineness the greater the number of heat-resistant thermoplastic fibers constituting the nonwoven fabric and the more uniformly the reinforcing fibers can be dispersed.
- the average fineness is less than 0.1 dtex, they are entangled with each other in the nonwoven fabric manufacturing process. There is a possibility that the reinforcing fibers cannot be uniformly dispersed.
- process passability is greatly deteriorated, for example, drainage in the process is deteriorated.
- the average fineness of the heat-resistant thermoplastic fiber is preferably 0.1 to 10 dtex, more preferably 0.2 to 9 dtex, still more preferably 0.3 to 8 dtex (for example, 0.3 to 5 dtex).
- the average fiber length of the single fiber of the heat-resistant thermoplastic fiber used in the present invention is essential to be 0.5 to 60 mm. If the average fiber length is less than 0.5 mm, the fibers fall off during the nonwoven fabric manufacturing process, and especially when the nonwoven fabric is manufactured by wet papermaking, the drainage in the process becomes worse and the process passability is greatly improved. It is not preferable because it may deteriorate. If the average fiber length is larger than 60 mm, it may be entangled in the nonwoven fabric manufacturing process and the reinforcing fibers may not be uniformly dispersed, which is not preferable.
- the thickness is preferably 1 to 55 mm, more preferably 3 to 50 mm.
- a circular shape may be sufficient, A hollow, flatness, a polygon, T shape, L shape, I shape, a cross shape, a multileaf shape, a star shape, etc. It may be a modified cross section.
- the reinforcing fiber used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, and may be an organic fiber or an inorganic fiber, and may be used alone or in combination of two or more. Also good.
- examples of inorganic fibers include glass fibers, carbon fibers, silicon carbide fibers, alumina fibers, ceramic fibers, basalt fibers, and various metal fibers (for example, gold, silver, copper, iron, nickel, titanium, stainless steel, etc.).
- organic fibers examples include wholly aromatic polyester fibers, polyphenylene sulfide fibers, para aramid fibers, polysulfonamide fibers, phenol resin fibers, wholly aromatic polyimide fibers, and fluorine fibers. can do.
- the organic fiber may be a stretched fiber that has been stretched as necessary.
- the flow start temperature of such an organic fiber is preferably higher than the flow start temperature of the heat-resistant thermoplastic fiber.
- carbon fibers are preferably used from the viewpoint of mechanical properties, flame retardancy, heat resistance, and availability.
- glass fibers wholly aromatic polyester fibers, and para aramid fibers are preferably used from the viewpoint of mechanical properties, flame retardancy, heat resistance, and availability.
- para aramid fibers are preferably used from the viewpoint of mechanical properties, flame retardancy, heat resistance, and availability.
- the average fineness of the single fiber of the reinforcing fiber used in the present invention can be appropriately set within a range that can be suitably dispersed in the heat-resistant thermoplastic fiber, and may be, for example, 10 to 0.01 dtex, preferably May be 8 to 0.1 dtex, more preferably 6 to 1 dtex.
- the average fiber length of the single fibers of the reinforcing fiber used in the present invention can be appropriately set according to the required strength of the composite, and may be, for example, 1 to 40 mm, preferably 5 to 35 mm, More preferably, it may be 10 to 30 mm.
- the cross-sectional shape of the fiber is not particularly limited, and may be circular or hollow, flat, polygonal, T-shaped, L-shaped, I-shaped, cross-shaped, multi-lobed, star-shaped, etc. It doesn't matter.
- polyester binder fiber The polyester-based binder fiber used in the present invention improves the dispersibility of the heat-resistant thermoplastic fiber and the reinforcing fiber by combining with the heat-resistant thermoplastic fiber in the nonwoven fabric, and molded the nonwoven fabric into a resin composite. At this time, the heat resistance of the resin composite can be exhibited without impairing the heat resistance exhibited by the heat-resistant thermoplastic resin.
- the polyester polymer may contain a small amount of other dicarboxylic acid components other than terephthalic acid and isophthalic acid in combination of one kind or plural kinds as long as the effects of the present invention are not impaired.
- other dicarboxylic acid components include naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, benzophenone dicarboxylic acid, aromatic dicarboxylic acid such as 4,4′-diphenyldicarboxylic acid, 3,3′-diphenyldicarboxylic acid; adipic acid, Examples thereof include aliphatic dicarboxylic acids such as succinic acid, azelaic acid, sebacic acid and dodecanedioic acid; and alicyclic dicarboxylic acids such as hexahydroterephthalic acid and 1,3-adamantanedicarboxylic acid.
- ethylene glycol can be used as the diol component.
- the diol component include chlorohydroquinone, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, Examples thereof include aromatic diols such as p-xylene glycol; aliphatic diols such as diethylene glycol, propane diol, butane diol, hexane diol, and neopentyl glycol, and alicyclic diols such as cyclohexane dimethanol. These diol components may be used alone or in combination of two or more.
- the production method of the polyester polymer constituting the polyester binder fiber used in the present invention is not particularly limited, and a known method can be applied. That is, it can be produced by a method of melt polymerization through a transesterification reaction using a dicarboxylic acid component and a diol component as starting materials, or a method of melt polymerization after directly esterifying the dicarboxylic component and the diol component.
- the intrinsic viscosity of the polyester polymer constituting the polyester binder fiber used in the present invention is not particularly limited. However, from the viewpoint of mechanical properties, process passability, and cost of the obtained fiber, for example, 0.4 to 1. It may be in the range of 5, and is preferably in the range of 0.6 to 1.3.
- the intrinsic viscosity is a viscosity obtained from a viscosity measured at 30 ° C. after being dissolved in a mixed solution of phenol / chloroethane (weight ratio 1/1), and is represented by “ ⁇ ”.
- a polyester-based binder fiber can be obtained by melt spinning the polyester-based polymer thus obtained by a known or conventional method.
- melt spinning a polyester polymer melted by heating is discharged into the air from a pore nozzle, cooled and solidified in the air while the discharged molten yarn is thinned, and then taken up at a constant speed. Can be made into fibers.
- the polyester-based binder fiber used in the present invention may have a crystallinity of, for example, 50% or less, preferably 45% or less, more preferably 40% or less, from the viewpoint of exhibiting good binder performance.
- the crystallinity can be set to a desired value by adjusting the copolymerization ratio of the dicarboxylic acid component, the stretching ratio in the fiberizing step, and the like. From the viewpoint of molding the heat-resistant resin composite, the degree of crystallinity of the polyester-based binder fiber may be 5% or more.
- the single fiber fineness of the polyester binder fiber used in the present invention is not particularly limited, and fibers having an average fineness of, for example, 0.1 to 50 dtex, preferably 0.5 to 20 dtex can be widely used. What is necessary is just to adjust the fineness of a fiber suitably from a nozzle diameter or discharge amount.
- the average fiber length of single fibers of the polyester binder fiber used in the present invention can be appropriately set according to the required strength of the composite, and may be, for example, 1 to 40 mm, preferably 5 to It may be 35 mm, more preferably 10 to 30 mm.
- the cross-sectional shape of the polyester-based binder fiber used in the present invention is not particularly limited, and may be circular, hollow, flat, polygonal, T-shaped, L-shaped, I-shaped, cruciform, multileaf, star An irregular cross section such as a shape may be used.
- the polyester-based binder fiber may be a composite fiber such as a core-sheath type, a sea-island type, or a side-by-side type as necessary as long as a heat-resistant resin composite can be formed. In this case, the predetermined degree of crystallinity only needs to be possessed by the polyester polymer on the side exhibiting the fusibility.
- the nonwoven fabric of the present invention is a porous sheet in which discontinuous fibers are intertwined with each other in a three-dimensional structure, and includes at least heat-resistant thermoplastic fibers, reinforcing fibers, and polyester-based binder fibers.
- the ratio of heat-resistant thermoplastic fibers constituting the nonwoven fabric used in the present invention is 30 to 80 wt%.
- the proportion of thermoplastic fibers is less than 30 wt%, the reinforcing fibers cannot be uniformly dispersed, and the resin composite obtained by thermoforming this does not only cause poor appearance but also has low mechanical properties.
- the ratio of the thermoplastic fiber is 80 wt% or more, the mixing amount of the reinforcing fiber is reduced, and a resin composite having sufficient mechanical properties cannot be obtained.
- it is 35 to 75 wt%, more preferably 40 to 70 wt%.
- (the former) / (the latter) 35/65 to 75/25, more preferably 40/60 to 70/30.
- the method for producing the nonwoven fabric of the present invention is not particularly limited, and examples thereof include known or conventional methods for producing nonwoven fabrics such as spunlace nonwoven fabric, needle punched nonwoven fabric, steam jet nonwoven fabric, dry papermaking method and wet papermaking method.
- wet papermaking is preferred from the viewpoint of production efficiency and uniform dispersion of reinforcing fibers in the nonwoven fabric.
- an aqueous slurry containing at least the heat-resistant thermoplastic fiber, the reinforcing fiber, and the polyester-based binder fiber is prepared, and then this slurry is subjected to a normal papermaking process.
- a drying process under heating for drying the slurry is performed.
- the heating temperature at this time is equal to or higher than the softening point of the polyester-based binder fiber, and in this drying process, the polyester-based binder fiber in the slurry fuses the heat-resistant thermoplastic resin and the reinforcing fiber to form a paper or web shape.
- the nonwoven fabric which has can be formed.
- the binder may be applied by spray drying.
- the basis weight of the nonwoven fabric used in the present invention is preferably 5 to 1500 g / m 2 , more preferably 6 to 1400 g / m 2 , and even more preferably 7 to 1300 g / m 2 . If the basis weight is too small or too large, the formation of spots may increase and the process passability may deteriorate.
- the method for producing a heat-resistant resin composite of the present invention includes a step of preparing the non-woven fabric, a heat forming step of superimposing one or many of the non-woven fabrics, and heating and compressing at or above the flow start temperature of the heat-resistant thermoplastic fiber.
- a single kind of nonwoven fabric may be used in multiple numbers, and a different kind of nonwoven fabric may be used in combination.
- the flow starting temperature is the melting point in the case of a crystalline resin, and the glass transition temperature in the case of an amorphous resin.
- the heat molding method there is no particular limitation on the heat molding method, and general compression molding such as stampable molding, pressure molding, vacuum pressure molding, and GMT molding is preferably used. What is necessary is just to set the shaping
- the molding temperature is preferably in the range of not less than the melting point of the heat-resistant thermoplastic fiber and not more than (melting point + 100) ° C.
- the heat-resistant thermoplastic fiber is non-crystalline, the molding temperature is preferably in the range of not less than the glass transition temperature of the heat-resistant thermoplastic fiber and not more than (glass transition temperature + 200) ° C. If necessary, it can be preheated with an IR heater or the like before the heat molding.
- the pressure at the time of heat molding is not particularly limited, but is usually 0.05 N / mm 2 or more (for example, 0.05 to 15 N / mm 2 ).
- the time for thermoforming is not particularly limited, but the polymer may be deteriorated when exposed to a high temperature for a long time. Therefore, it is usually preferably within 30 minutes.
- the thickness and density of the resulting heat-resistant resin composite material can be appropriately set depending on the type of reinforcing fiber and the applied pressure. Furthermore, there is no restriction
- a plurality of non-woven fabrics having different specifications can be laminated, or non-woven fabrics having different specifications can be separately placed in a mold of a certain size and heat-molded. In some cases, it can be molded together with other reinforcing fiber fabrics or resin composites. And according to the objective, it is also possible to heat-mold again the heat resistant resin composite obtained by heat-molding once.
- the obtained heat-resistant resin composite is thermoformed using a nonwoven fabric containing thermoplastic fibers and reinforcing fibers as a precursor, it can contain reinforcing fibers having a long fiber length at a high content, and reinforcing fibers Can be arranged at random, which is excellent in mechanical characteristics and isotropy. Moreover, the outstanding shaping property can also be achieved by heat-molding a nonwoven fabric.
- the heat-resistant resin composite of the present invention is a heat-resistant resin composite composed of a matrix resin and reinforcing fibers dispersed in the matrix resin,
- the bending strength at 24 ° C. may be, for example, 150 MPa or more, preferably 160 MPa or more, and more preferably 170 MPa or more.
- the flexural modulus at 24 ° C. may be, for example, 5 GPa or more, preferably 5.5 GPa or more, and more preferably 6 GPa or more.
- the heat-resistant resin composite obtained as described above has a bending strength retention at 100 ° C. with respect to a bending strength at 24 ° C. and a bending elastic modulus at 100 ° C. with respect to a bending elastic modulus at 24 ° C. It is preferable that all of these retention rates are 70% or more. If the retention rate of either bending strength or flexural modulus is less than 70%, it cannot be said that it has heat resistance. Preferably it is 74% or more, More preferably, it is 78% or more.
- the density of the heat resistant resin composite of the present invention is preferably 2.00 g / cm 3 or less. If the density is greater than 2.00 g / m 3 , it cannot be said to be a heat-resistant resin composite that contributes to weight reduction, and its use may be limited. Preferably it is 1.95 g / cm 3 or less, more preferably 1.90 g / cm 3 or less.
- the lower limit of the density is appropriately determined according to the selection of the material and the like, but may be, for example, about 0.5 g / cm 3 .
- the heat-resistant resin composite of the present invention preferably has a thickness of 0.3 mm or more (preferably 0.5 mm or more).
- the thickness is too thin, the strength of the resulting heat-resistant resin composite is lowered and the production cost is increased, which is not preferable. More preferably, it is 0.7 mm or more, More preferably, it is 1 mm or more.
- the upper limit of thickness can be suitably set according to the thickness calculated
- the heat-resistant resin composite of the present invention not only has excellent mechanical properties and heat resistance, but also can be manufactured at low cost without requiring a special process.
- a personal computer, a display, an OA device, a mobile phone Cases such as portable information terminals, digital video cameras, optical equipment, audio, air conditioners, lighting equipment, toy products, and other household appliances, electrical and electronic equipment parts such as trays, chassis, interior members, or cases, columns, panels Civil engineering such as reinforcing materials, building materials parts, various members, various frames, various hinges, various arms, various axles, various wheel bearings, various beams, various pillars, various members, various frames, various beams, various supports, various Rails, various hinges, outer panels or body parts, bumpers, moldings, under covers, engine covers, Exterior parts such as flow plates, spoilers, cowl louvers, aero parts, interior parts such as instrument panels, seat frames, door trims, pillar trims, handles, various modules, or motor parts, CNG tanks, gasoline tanks, fuel pumps, air intake
- Glass transition temperature of heat-resistant thermoplastic fiber in ° C The glass transition temperature of the fiber was measured for the temperature dependence of the loss tangent (tan ⁇ ) at a frequency of 10 Hz and a heating rate of 10 ° C./min using a solid dynamic viscoelastic device “RheoSpectra DVE-V4” manufactured by Rheology. It calculated
- Average fiber length mm 100 pieces were randomly extracted from the cut yarn, the fiber lengths of each were measured, and the average fiber length was determined.
- the intrinsic viscosity of the PET binder fiber was calculated from the solution viscosity measured at 30 ° C. after being dissolved in a mixed solution of phenol / chloroethane (weight ratio 1/1).
- the obtained fiber had a crystallinity of 20%, an intrinsic viscosity of 0.8, an average fineness of 2.2 dtex, and a circular cross-sectional shape.
- Example 1 A polyetherimide polymer (“ULTEM 9001” manufactured by Servic Innovative Plastics) was vacuum-dried at 150 ° C. for 12 hours. (2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 390 ° C., a spinning speed of 1500 m / min, and a discharge amount of 50 g / min to obtain a 2640 dtex / 1200 f multifilament. Subsequently, the obtained fiber was cut into 10 mm. (3) The appearance of the obtained fiber was good without fluff and the like, the average fineness of the single fiber was 2.2 dtex, the average fiber length was 10.1 mm, and the glass transition temperature was 213 ° C.
- ULTEM 9001 manufactured by Servic Innovative Plastics
- the appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 250 MPa, 12 GPa, the bending strength at 100 ° C. and the bending elastic modulus are 215 MPa and 10 GPa, respectively. They were 86% and 83%, respectively, and were excellent in heat resistance.
- Example 3 In Example 1 (4), a flat plate (density: 1.5) was obtained in the same manner as in Example 1 except that the PEI fiber was 80 wt% (heat-resistant thermoplastic fiber) and the glass fiber was 17 wt% (reinforced fiber). 41 g / cm 3 , thickness: 1.5 mm). The appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 181 MPa, 8 GPa, the bending strength at 100 ° C., the bending elastic modulus are 157 MPa and 7 GPa, respectively, and the retention rate is They were 87% and 88%, respectively, and were excellent in heat resistance.
- the PEI fiber was 80 wt% (heat-resistant thermoplastic fiber) and the glass fiber was 17 wt% (reinforced fiber). 41 g / cm 3 , thickness: 1.5 mm).
- the appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 181 MPa,
- Example 4 In Example 1 (4), a PAN-based carbon fiber having a cut length of 13 mm (manufactured by Toho Tenax; average fiber diameter: 7 ⁇ m, average fiber length: 13 mm) was used as the reinforcing fiber in the same manner as in Example 1 to obtain a flat plate. (Density: 1.49 g / cm 3 , thickness: 1.5 mm) was obtained. The appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 360 MPa, 22 GPa, the bending strength at 100 ° C. and the bending elastic modulus are 318 MPa and 20 GPa, respectively. They were 88% and 91%, respectively, and were excellent in heat resistance.
- Example 5 A semi-aromatic polyamide polymer (“Genesta PA9MT” manufactured by Kuraray Co., Ltd.) was vacuum-dried at 80 ° C. for 12 hours. (2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 310 ° C., a spinning speed of 1500 m / min, and a discharge rate of 50 g / min to obtain a multifilament. Subsequently, the obtained fiber was cut into 5 mm. (3) The appearance of the obtained fiber was good without fluff and the like, the average fineness of the single fiber was 0.7 dtex, the average fiber length was 5.2 mm, and the glass transition temperature was 121 ° C.
- Example 6 (1) In Example 5 (4), the heat-resistant thermoplastic fiber is 50 wt%, and a 13 mm-cut para-aramid fiber as a reinforcing fiber (manufactured by Toray DuPont Co., Ltd., Kevlar; average fineness 2.2 dtex, A flat plate was obtained in the same manner as in Example 5 except that 40 wt% of the average fiber length (10 mm) and 10 wt% of the PET binder fiber were used. The density of the obtained flat plate was 1.31 g / cm 3 and the thickness was 1.5 mm.
- the appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 300 MPa, 18 GPa, the bending strength at 100 ° C., the bending elastic modulus are 226 MPa and 15 GPa, respectively, and the retention rate is They were 75% and 83%, respectively, and were excellent in heat resistance.
- Example 7 A PEEK polymer (“90G” manufactured by Victrex) was vacuum-dried at 80 ° C. for 12 hours. (2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 400 ° C., a spinning speed of 1500 m / min, and a discharge rate of 50 g / min to obtain a multifilament. Subsequently, the obtained fiber was cut into 5 mm. (3) The appearance of the obtained fiber was good without fluff and the like, the average fineness of the single fiber was 8.8 dtex, the average fiber length was 5.1 mm, and the glass transition temperature was 146 ° C.
- Example 8 (1) In Example 7 (4), a flat plate (density: 1.0.5) was used in the same manner as in Example 7 except that 30 wt% heat-resistant thermoplastic fiber, 65 wt% reinforcing fiber, and 5 wt% binder fiber were used. 40 g / cm 3 , thickness: 1.5 mm). The appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 325 MPa, 20 GPa, the bending strength at 100 ° C. and the bending elastic modulus are 235 MPa and 15 GPa, respectively. They were 72% and 75%, respectively, and were excellent in heat resistance.
- Example 9 A PC polymer (“FST Polyca” manufactured by SABIC) was vacuum-dried at 80 ° C. for 12 hours. (2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 300 ° C., a spinning speed of 1500 m / min, and a discharge rate of 50 g / min to obtain a multifilament. Subsequently, the obtained fiber was cut into 50 mm. (3) The appearance of the obtained fiber was good without fluff and the like, the average fineness of the single fiber was 2.2 dtex, the average fiber length was 50 mm, and the glass transition temperature was 132 ° C.
- PET fiber Karl Fischer “N701Y” having an average fineness of 2.2 dtex, an average fiber length of 10.3 mm, and a glass transition temperature of 75 ° C., 50 wt% (thermoplastic fiber), 13 mm cut length PAN system
- 47 wt% of carbon fibers average fiber diameter of 7 ⁇ m, average fiber length of 13 mm
- 3 wt% of PET binder fibers average fiber length of 10 mm
- Example 1 except that PEI fiber was changed to 10 wt% (heat-resistant thermoplastic fiber), glass fiber was set to 80 wt% (reinforced fiber), and PET binder fiber was set to 10 wt% in Example 1 (4).
- a flat plate (density: 2.01 g / cm 3 , thickness: 1.3 mm) was obtained by the same method as above. The appearance of the obtained flat plate is good, the bending strength at room temperature and the bending elastic modulus are 120 MPa, 8 GPa, the bending strength at 100 ° C., the bending elastic modulus are 60 MPa and 5 GPa, respectively, and the retention rate is They were 50% and 63%, respectively, and were inferior in heat resistance. It was thought that this was because the amount of thermoplastic resin in the molded product was small and impregnation was poor.
- Example 3 (1) In Example 1 (3), except that the average fineness of the heat-resistant thermoplastic fiber was changed to 20 dtex, an attempt was made to produce a nonwoven fabric by wet papermaking in the same manner as in Example 1, but the heat-resistant thermoplastic Since the fineness of the fibers is large, the number of heat-resistant thermoplastic fibers constituting the nonwoven fabric is small, and the eyes are rough. Therefore, the dispersibility of the glass fibers during the paper making process was poor, and the glass fibers dropped out from the gaps between the nonwoven fabrics. Therefore, the processability was extremely poor, and the nonwoven fabric could not be prototyped with good reproducibility.
- Example 4 (1) In Example 1 (3), except that the average fiber length of the heat-resistant thermoplastic fiber was changed to 70.8 mm, trial production of a nonwoven fabric by wet papermaking was attempted in the same manner as in Example 1, but the heat resistance Since the heat-resistant thermoplastic fibers have a large fiber length, the heat-resistant thermoplastic fibers are entangled with each other, the dispersibility of the glass fibers is poor, the process passability is extremely poor, and a nonwoven fabric cannot be produced with good reproducibility.
- Example 5 (1) In Example 1, a flat plate was obtained in the same manner as in Example 1 except that the binder fiber was a PVA binder fiber (manufactured by Kuraray Co., Ltd., SPG05611). It was out. As guessed from the fact that there was an odor during thermoforming, it was considered that the PVA fiber as the binder fiber decomposed and generated gas in the hot compression process at a high temperature, resulting in poor appearance.
- PVA binder fiber manufactured by Kuraray Co., Ltd., SPG05611. It was out. As guessed from the fact that there was an odor during thermoforming, it was considered that the PVA fiber as the binder fiber decomposed and generated gas in the hot compression process at a high temperature, resulting in poor appearance.
- the bending strength at room temperature and the bending elastic modulus of the obtained molded product are 220 MPa, 9 GPa, bending strength at 100 ° C., the bending elastic modulus are 150 MPa and 6 GPa, respectively, and the holding ratio is respectively They were 68% and 67%, and were inferior in heat resistance.
- Example 6 A flat plate (density: 1.29 g / cm 3 , thickness: 1.5 mm) was obtained in the same manner as in Example except that PE binder fiber was used as the binder fiber in Example 1. The appearance of the obtained flat plate was good, the bending strength and bending elastic modulus at room temperature were 200 MPa and 8 GPa, respectively, but the bending strength and bending elastic modulus at 100 ° C. were 100 MPa and 4 GPa, respectively. Each of the retention rates was 50%, which was inferior in heat resistance.
- a heat resistant resin composite formed from a nonwoven fabric containing a heat resistant thermoplastic fiber having a glass transition temperature of 100 ° C. or higher and a reinforcing fiber in a specific ratio is: It can be seen that not only the bending characteristics are excellent, but also the heat resistance is excellent.
- the heat-resistant resin composite of the present invention does not require a special thermoforming process, and can be manufactured at a low cost by a normal thermoforming process such as compression molding or GMT molding.
- the shape can also be designed freely, including many fields such as general industrial materials field, electrical / electronic field, civil engineering / architecture field, aircraft / automobile / railway / ship field, agricultural material field, optical material field, medical material field, etc. It can be used very effectively for applications.
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Abstract
Description
そこで、特許文献3(特公平3-25537号公報)には、耐熱性繊維と未延伸ポリフェニレンサルファイド繊維とを重量比で92:8~20:80の割合で混綿してウェブを形成し、該未延伸繊維が加圧下で可塑化し融着作用を生じる温度条件で熱圧着を行う耐熱性不織布の製造方法が開示されている。
本発明の別の目的は、前記目的に加えて、高温でも使用に耐えうる耐熱性はもとより、使用温度下における耐久性を有する耐熱性樹脂複合体を提供することにある。
本発明のさらに別の目的は、このような耐熱性樹脂複合体を効率よく製造できる製造方法および製造に好適に用いることができる耐熱性樹脂複合体用不織布を提供することにある。
前記不織布は、耐熱性熱可塑性繊維と強化繊維とポリエステル系バインダー繊維とを含み、
前記耐熱性熱可塑性繊維は、ガラス転移温度が100℃以上、平均繊度が0.1~10dtex、及び平均繊維長が0.5~60mmであり、
前記ポリエステル系バインダー繊維は、テレフタル酸成分(A)とイソフタル酸成分(B)を、その共重合割合(モル比)が(A)/(B)=100/0~40/60として含むポリエステル系ポリマーで構成され、
前記不織布を構成する熱可塑性繊維の割合が30~80wt%である、耐熱性樹脂複合体用不織布である。
前記不織布を一枚ないしは多数枚重ね合わせ、耐熱性熱可塑性繊維の流動開始温度以上で加熱圧縮する加熱成形工程と、
を少なくとも備える耐熱性樹脂複合体の製造方法である。
前記マトリックス樹脂は、ガラス転移温度が100℃以上の耐熱性熱可塑性ポリマーと、テレフタル酸成分(A)とイソフタル酸成分(B)を、その共重合割合(モル比)が(A)/(B)=100/0~40/60として含むポリエステル系ポリマーとで構成され、
前記耐熱性熱可塑性ポリマーの複合体中の割合が30~80wt%である、耐熱性樹脂複合体である。
本発明で用いる耐熱性熱可塑性繊維は、高い耐熱性を有しているため、そのガラス転移温度が100℃以上である。また熱可塑性繊維であるため、温度上昇により加熱溶融あるいは加熱流動が可能である。一般に、高分子の力学物性は非晶部の分子が動き出すガラス転移温度で大きく落ち込むことがよく知られている。例えば、ポリエチレンテレフタレート(PET)やナイロン6などのような200℃以上の融点を持つ熱可塑性繊維であっても、その力学物性は60~80℃付近のガラス転移温度で大きく落ち込んでしまうため、耐熱性に優れているとは言い難い。従って、ガラス転移温度が100℃未満の熱可塑性繊維を用いると、得られる樹脂複合体の耐熱性が高いとは言えず、実使用に制限がかかるものとなる。本発明で用いる耐熱性熱可塑性繊維のガラス転移温度は、好ましくは105℃以上、更に好ましくは110℃以上である。なお、耐熱性熱可塑性繊維のガラス転移温度の上限値は繊維の種類に応じて適宜設定されるが、成形性の観点から200℃程度であってもよい。
なお、「延伸」とは、溶融紡糸後、冷却された繊維に対して、ローラなどの引張手段を用いて繊維を引き伸ばす工程を意味し、ノズルからの吐出後、巻き取る工程において溶融原糸が引き伸ばされる工程は含まれない。
本発明で用いる強化繊維については、本発明の効果を損なわない限り特に制限されず、有機繊維であっても無機繊維であってもよく、また、単独で、あるいは二種以上を組み合わせて用いてもよい。例えば、無機繊維としては、ガラス繊維、炭素繊維、炭化ケイ素繊維、アルミナ繊維、セラミックファイバー、玄武岩繊維、各種金属繊維(例えば、金、銀、銅、鉄、ニッケル、チタン、ステンレス等)を例示することができ、また、有機繊維としては、全芳香族ポリエステル系繊維、ポリフェニレンサルファイド系繊維、パラ系アラミド繊維、ポリスルフォンアミド系繊維、フェノール樹脂繊維、全芳香族ポリイミド繊維、フッ素系繊維等を例示することができる。なお、有機繊維は、必要に応じて延伸処理された延伸繊維であってもよい。
強化繊維として用いられる有機繊維が熱可塑性繊維である場合、このような有機繊維の流動開始温度は、耐熱性熱可塑性繊維の流動開始温度よりも高いのが好ましい。
なお、繊維の断面形状に関しても特に制限はなく、円形であってもよいし、中空、扁平、多角形、T字形、L字形、I字形、十字形、多葉形、星形等の異形断面であってもかまわない。
本発明で用いられるポリエステル系バインダー繊維は、不織布中において、耐熱性熱可塑性繊維と組み合わせることによって、耐熱性熱可塑性繊維と強化繊維との分散性を向上させるとともに、不織布を樹脂複合体に成形した際に、耐熱性熱可塑性樹脂が発揮する耐熱性を損なうことなく、樹脂複合体への耐熱性を発揮させることができる。
ポリエステル系バインダー繊維は、テレフタル酸成分(A)とイソフタル酸成分(B)を、その共重合割合(モル比)が(A)/(B)=100/0~40/60(好ましくは99/1~40/60)として含むポリエステル系ポリマーで構成されている。
さらに、ポリエステル系バインダー繊維は、耐熱性樹脂複合体を形成できる限り、必要に応じて、芯鞘型、海島型、サイドバイサイド型などの複合繊維であってもよい。この場合、所定の結晶化度は、融着性を発揮する側のポリエステル系ポリマーが有していればよい。
本発明の不織布は、不連続繊維が3次元構造に絡み合って結合している多孔質のシートであり、耐熱性熱可塑性繊維と強化繊維とポリエステル系バインダー繊維とを少なくとも含んでいる。
また、不織布を製造する際、ポリエステル系バインダー繊維による接着性を向上させるため、一旦得られたウェブに対して、さらに熱プレス、スルーエアボンドなどのサーマルボンド工程を行うのが好ましい。
また、不織布の均一性や圧着性を高めるために、スプレードライによりバインダーを塗布してもよい。
本発明の耐熱樹脂複合体の製造方法は、前記不織布を準備する工程と、前記不織布を一枚ないしは多数枚重ね合わせ、前記耐熱性熱可塑性繊維の流動開始温度以上で加熱圧縮する加熱成形工程と、を少なくとも備えている。なお、不織布は、単一の種類の不織布を複数用いてもよいし、異なる種類の不織布を組み合わせて用いてもよい。
なお、ここで流動開始温度とは、結晶性樹脂の場合はその融点であり、非結晶性樹脂の場合はそのガラス転移温度を意味している。
本発明の耐熱性樹脂複合体は、マトリックス樹脂と、このマトリックス樹脂中に分散された強化繊維とで構成された耐熱性樹脂複合体であって、
前記マトリックスは、ガラス転移温度が100℃以上の耐熱性熱可塑性ポリマーと、テレフタル酸成分(A)とイソフタル酸成分(B)を、その共重合割合(モル比)が(A)/(B)=100/0~40/60として含むポリエステル系ポリマーとで構成され、
前記耐熱性熱可塑性ポリマーの複合体中の割合が30~80wt%である樹脂複合体である。
また、耐熱性樹脂複合体では、24℃での曲げ弾性率が、例えば5GPa以上であってもよく、好ましくは5.5GPa以上、更に好ましくは6GPa以上であってもよい。
繊維のガラス転移温度は、レオロジー社製固体動的粘弾性装置「レオスペクトラDVE-V4」を用い、周波数10Hz、昇温速度10℃/minで損失正接(tanδ)の温度依存性を測定し、そのピーク温度から求めた。
マルチフィラメントから無作為に100本抜き出し、夫々の単繊維の繊度を測定し、平均繊度を求めた。
カット糸から無作為に100本抜き出し、夫々の繊維長を測定し、平均繊維長を求めた。
PET系バインダー繊維の結晶化度は、広角X線回折法により求めた。すなわち、(株)リガク製X線発生装置(RAD-3A型)を用い、ニッケルフィルターで単色化したCu-Kα線で[010]の散乱強度を測定し、次式により結晶化度を算出した。
(結晶化度Xc)=(結晶部の散乱強度)/(全散乱強度)×100(%)
PET系バインダー繊維の固有粘度は、フェノール/クロロエタン(重量比1/1)の混合溶液に溶解させ、30℃で測定した溶液粘度から算出した。
JIS L1913試験法に準じて測定し、n=3の平均値を採用した。
24℃ならびに100℃における複合体の曲げ強度ならびに曲げ弾性率は、ASTM790に準拠して測定した。
(1)重合反応装置を用い、常法により280℃で重縮合反応を行い、テレフタル酸とイソフタル酸の共重合割合(モル比)が70/30、エチレングリコール100モル%からなる、固有粘度(η)が0.81であるPET系ポリマーを製造した。製造されたポリマーは、重合機底部よりストランド状に水中に押し出し、ペレット状に切断した。
(2)上記で得られたPET系ポリマーを、270℃に加熱された同方向回転タイプのベント式2軸押出し機に供給し、滞留時間2分を経て280℃に加熱された紡糸ヘッドに導き、吐出量45g/分の条件で丸孔ノズルより吐出し、紡糸速度1200m/分で引取り、2640dtex/1200fのPET系ポリマー単独からなるマルチフィラメントを得た。次いで得られた繊維を10mmにカットした。
得られた繊維は、結晶化度20%、極限粘度0.8、平均繊度2.2dtex、および円形の断面形状を有していた。
(1)ポリエーテルイミド系ポリマー(サービックイノベイティブプラスチックス社製「ULTEM9001」)を150℃で12時間真空乾燥した。
(2)上記(1)のポリマーを紡糸ヘッド温度390℃、紡糸速度1500m/分、吐出量50g/分の条件で丸孔ノズルより吐出し、2640dtex/1200fのマルチフィラメントを得た。次いで、得られた繊維を10mmにカットした。
(3)得られた繊維の外観は毛羽等なく良好で、単繊維の平均繊度は2.2dtex、平均繊維長は10.1mmで、ガラス転移温度は213℃であった。
(4)上記(3)で得られたPEI繊維50wt%、15mmのカット長のガラス繊維47wt%(平均繊度2.2dtex、平均繊維長15mm)、および参考例1で得られたPET系バインダー繊維3wt%(平均繊維長10mm)を水中に分散したスラリーを用いて湿式抄紙し、100℃で熱風乾燥後、目付け500g/m2の紙を得た。
(5)得られた紙を6枚重ね合わせ(総目付け=3000g/m2)、PEI繊維が全て溶ける温度である360℃で、圧力10N/mm2の下、3分間圧縮成形して平板を成形した。
得られた平板の密度は1.68g/cm3であり、厚さは1.5mmであった。
(6)得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、260MPa、12GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、220MPa、10GPaであり、その保持率はそれぞれ、85%、83%であり、耐熱性に優れるものであった。
実施例1の(2)において、PEI繊維のカット長を3mm(平均繊維長=3.2mm)にした以外は実施例1と同様な方法で平板(密度:1.69g/cm3、厚さ:1.3mm)を得た。得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、250MPa、12GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、215MPa、10GPaであり、その保持率はそれぞれ、86%、83%であり、耐熱性に優れるものであった。
実施例1の(4)において、PEI繊維を80wt%(耐熱性熱可塑性繊維)、ガラス繊維を17wt%(強化繊維)にした以外は、実施例1と同様の方法で平板(密度:1.41g/cm3、厚さ:1.5mm)を得た。
得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、181MPa、8GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、157MPa、7GPaであり、その保持率はそれぞれ、87%、88%であり、耐熱性に優れるものであった。
実施例1の(4)において、強化繊維として13mmのカット長のPAN系炭素繊維(東邦テナックス製;平均繊維径7μm、平均繊維長13mm)を用いた以外は実施例1と同様な方法で平板(密度:1.49g/cm3、厚さ:1.5mm)を得た。
得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、360MPa、22GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、318MPa、20GPaであり、その保持率はそれぞれ、88%、91%であり、耐熱性に優れるものであった。
(1)半芳香族ポリアミド系ポリマー(クラレ社製「ジェネスタPA9MT」)を80℃で12時間真空乾燥した。
(2)上記(1)のポリマーを紡糸ヘッド温度310℃、紡糸速度1500m/分、吐出量50g/分の条件で丸孔ノズルより吐出し、マルチフィラメントを得た。次いで、得られた繊維を5mmにカットした。
(3)得られた繊維の外観は毛羽等なく良好で、単繊維の平均繊度は0.7dtex、平均繊維長は5.2mmで、ガラス転移温度は121℃であった。
(4)上記(3)で得られた繊維60wt%(耐熱性熱可塑性繊維)、13mmのカット長のPAN系炭素繊維37wt%(平均繊維径7μm、平均繊維長13mm)、および参考例1で得られたPET系バインダー繊維(平均繊維長10mm)3wt%を水中に分散したスラリーを用いて湿式抄紙し、目付け500g/m2の紙を得た。
(5)得られた紙を6枚重ね合わせ(総目付け=3000g/m2)、半芳香族ポリアミド系ポリマー繊維が全て溶ける温度である330℃で、圧力10N/mm2の下、5分間圧縮成形して平板を成形した。
得られた平板の密度は1.46g/cm3であり、厚さは1.5mmであった。
(6)得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、372MPa、24GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、310MPa、21GPaであり、その保持率はそれぞれ、83%、88%であり、耐熱性に優れるものであった。
(1)実施例5の(4)において、耐熱性熱可塑性繊維を50wt%、強化繊維として13mmのカット長のパラ系アラミド繊維(東レ・デュポン(株)製、ケブラー;平均繊度2.2dtex、平均繊維長10mm)を40wt%、PET系バインダー繊維を10wt%用いた以外は実施例5と同様な方法で平板を得た。
得られた平板の密度は1.31g/cm3であり、厚さは1.5mmであった。
得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、300MPa、18GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、226MPa、15GPaであり、その保持率はそれぞれ、75%、83%であり、耐熱性に優れるものであった。
(1)PEEK系ポリマー(Victrex社製「90G」)を80℃で12時間真空乾燥した。
(2)上記(1)のポリマーを紡糸ヘッド温度400℃、紡糸速度1500m/分、吐出量50g/分の条件で丸孔ノズルより吐出し、マルチフィラメントを得た。次いで、得られた繊維を5mmにカットした。
(3)得られた繊維の外観は毛羽等なく良好で、単繊維の平均繊度は8.8dtex、平均繊維長は5.1mmで、ガラス転移温度は146℃であった。
(4)上記(3)で得られた繊維を50wt%(耐熱性熱可塑性繊維)、13mmのカット長のPAN系炭素繊維を47wt%(平均繊維径7μm、平均繊維長13mm)、および参考例1で得られたPET系バインダー繊維(平均繊維長10mm)3wt%水中に分散したスラリーを用いて湿式抄紙し、100℃で熱風乾燥後、目付け500g/m2の紙を得た。
(5)得られた紙を6枚重ね合わせ(総目付け=3000g/m2)、PEEK繊維が全て溶ける温度である430℃で、圧力10N/mm2の下、5分間圧縮成形して平板を成形した。
得られた平板の密度は1.50g/cm3であり、厚さは1.5mmであった。
(6)得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、352MPa、22GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、275MPa、19GPaであり、その保持率はそれぞれ、78%、86%であり、耐熱性に優れるものであった。
(1)実施例7の(4)において、耐熱性熱可塑性繊維を30wt%、強化繊維を65wt%、バインダー繊維を5wt%用いた以外は実施例7と同様の方法で平板(密度:1.40g/cm3、厚さ:1.5mm)を得た。得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、325MPa、20GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、235MPa、15GPaであり、その保持率はそれぞれ、72%、75%であり、耐熱性に優れるものであった。
(1)PC系ポリマー(SABIC社製「FSTポリカ」)を80℃で12時間真空乾燥した。
(2)上記(1)のポリマーを紡糸ヘッド温度300℃、紡糸速度1500m/分、吐出量50g/分の条件で丸孔ノズルより吐出し、マルチフィラメントを得た。次いで、得られた繊維を50mmにカットした。
(3)得られた繊維の外観は毛羽等なく良好で、単繊維の平均繊度は2.2dtex、平均繊維長は50mmで、ガラス転移温度は132℃であった。
(4)上記(3)で得られた繊維を65wt%(耐熱性熱可塑性繊維)、13mmのカット長のPAN系炭素繊維を30wt%(平均繊維径7μm、平均繊維長13mm)、および参考例1で得られたPET系バインダー繊維(平均繊維長20mm)5wt%を混綿してエアレイド成形し、180℃の熱風乾燥器中で2分間熱処理して、目付100g/m2のエアレイドウェブを得た。
(5)得られた紙を30枚重ね合わせ(総目付け=3000g/m2)、PC繊維が全て溶ける温度である330℃で圧縮成形して平板を成形した。
得られた平板の密度は1.37g/cm3であり、厚さは1.5mmであった。
(6)得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、220MPa、18GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、162MPa、16GPaであり、その保持率はそれぞれ、74%、89%であり、耐熱性に優れるものであった。
(1)平均繊度が2.2dtex、平均繊維長が10.3mm、ガラス転移温度が75℃のPET繊維(クラレ製「N701Y」)を50wt%(熱可塑性繊維)、13mmのカット長のPAN系炭素繊維を47wt%(平均繊維径7μm、平均繊維長13mm)、および参考例1で得られたPET系バインダー繊維(平均繊維長10mm)3wt%を水中に分散したスラリーを用いて湿式抄紙し、100℃で熱風乾燥後、目付け500g/m2の紙を得た。
(2)得られた紙を6枚重ね合わせ(総目付け=3000g/m2)、PET繊維が全て溶ける温度である200℃で、圧力10N/mm2の下、5分間圧縮成形して平板を成形した。
得られた平板の密度は1.39g/cm3であり、厚さは1.5mmであった。
(3)得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、200MPa、20GPaであったが、曲げ特性は熱可塑性繊維のガラス転移温度である75℃で大きく落ち込み、100℃での曲げ強度、曲げ弾性率はそれぞれ、50MPa、4GPaであり、その保持率はそれぞれ、25%、20%であり、耐熱性に劣るものであった。
(1)実施例1の(4)において、PEI繊維を10wt%(耐熱性熱可塑性繊維)、ガラス繊維を80wt%(強化繊維)、PET系バインダー繊維を10wt%にした以外は、実施例1と同様な方法で平板(密度:2.01g/cm3、厚さ:1.3mm)を得た。得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、120MPa、8GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、60MPa、5GPaであり、その保持率はそれぞれ、50%、63%であり、耐熱性に劣るものであった。成形品に占める熱可塑性樹脂の量が少なく、含浸性が悪いためであると考えられた。
(1)実施例1の(3)において、耐熱性熱可塑性繊維の平均繊度を20dtexに変えた以外は、実施例1と同様な方法で湿式抄紙による不織布試作を試みたが、耐熱性熱可塑性繊維の繊度が大きいため、不織布を構成する耐熱性熱可塑性繊維の構成本数が少なく、目が粗いものになった。そのため、抄紙工程中でのガラス繊維の分散性が悪く、さらに不織布の隙間からガラス繊維が脱落したため、極めて工程通過性が悪く、再現性良く不織布を試作することが出来なかった。
(1)実施例1の(3)において、耐熱性熱可塑性繊維の平均繊維長を70.8mmに変えた以外は、実施例1と同様な方法で湿式抄紙による不織布試作を試みたが、耐熱性熱可塑性繊維の繊維長が大きいため、耐熱性熱可塑性繊維同士が絡まったり、ガラス繊維の分散性が悪く、極めて工程通過性が悪く、再現性良く不織布を試作することが出来なかった。
(1)実施例1において、バインダー繊維をPVA系バインダー繊維((株)クラレ製、SPG05611)にした以外は、実施例1と同様の方法で平板を得たが平板には多くの気泡が噛んでいた。熱成形中に臭気があったことから推測されるように、高温での熱圧縮工程でバインダー繊維となるPVA系繊維が分解しガスを発生したため、概観不良をおこしたものと考えられる。それゆえ、得られた成形品の室温での曲げ強度、曲げ弾性率はそれぞれ、220MPa、9GPa、100℃での曲げ強度、曲げ弾性率はそれぞれ、150MPa、6GPaであり、その保持率はそれぞれ、68%、67%であり、耐熱性に劣るものであった。
(1)実施例1において、バインダー繊維をPE系バインダー繊維にした以外は、実施例と同様な方法で平板(密度:1.29g/cm3、厚さ:1.5mm)を得た。得られた平板の外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、200MPa、8GPaであったが、100℃での曲げ強度、曲げ弾性率はそれぞれ、100MPa、4GPaであり、その保持率はそれぞれ50%であり、耐熱性に劣るものであった。
Claims (12)
- 耐熱性樹脂複合体を作製するために用いられる不織布であって、
前記不織布は、耐熱性熱可塑性繊維と強化繊維とポリエステル系バインダー繊維とを含み、
前記耐熱性熱可塑性繊維は、ガラス転移温度が100℃以上、平均繊度が0.1~10dtex、及び平均繊維長が0.5~60mmであり、
前記ポリエステル系バインダー繊維は、テレフタル酸成分(A)とイソフタル酸成分(B)を、その共重合割合(モル比)が(A)/(B)=100/0~40/60として含むポリエステル系ポリマーで構成され、
前記不織布を構成する熱可塑性繊維の割合が30~80wt%である、耐熱性樹脂複合体用不織布。 - 請求項1の不織布において、ポリエステル系バインダー繊維の結晶化度が50%以下である、耐熱性樹脂複合体用不織布。
- 請求項1または2の不織布において、前記耐熱性熱可塑性繊維と前記ポリエステル系バインダー繊維との割合(重量比)が(前者)/(後者)=60/40~99/1である耐熱性樹脂複合体用不織布。
- 請求項1~3のいずれか一項に記載の不織布において、耐熱性熱可塑性繊維が、紡糸後、実質的に延伸を施されていない繊維である、耐熱性樹脂複合体用不織布。
- 請求項1~4のいずれか一項に記載の不織布において、耐熱性熱可塑性繊維が、ポリエーテルイミド系繊維、半芳香族ポリアミド系繊維、ポリエーテルエーテルケトン系繊維、及びポリカーボネート系繊維からなる群から選択された少なくとも一種で構成される、耐熱性樹脂複合体用不織布。
- 請求項1~5のいずれか一項に記載の不織布において、強化繊維が、炭素繊維、ガラス繊維、全芳香族ポリエステル系繊維、及びパラ系アラミド繊維からなる群から選択された少なくとも一種で構成される、耐熱性樹脂複合体用不織布。
- 請求項1~6のいずれか一項に記載の不織布において、目付けが5~1500g/m2である、耐熱性樹脂複合体用不織布。
- 請求項1~7のいずれか一項に記載された不織布を準備する準備工程と、
前記不織布を一枚ないしは多数枚重ね合わせ、耐熱性熱可塑性繊維の流動開始温度以上で加熱圧縮する加熱成形工程と、
を少なくとも備える耐熱性樹脂複合体の製造方法。 - マトリックス樹脂と、このマトリックス樹脂中に分散された強化繊維とで構成された耐熱性樹脂複合体であって、
前記マトリックス樹脂は、ガラス転移温度が100℃以上の耐熱性熱可塑性ポリマーと、テレフタル酸成分(A)とイソフタル酸成分(B)を、その共重合割合(モル比)が(A)/(B)=100/0~40/60として含むポリエステル系ポリマーとで構成され、
前記耐熱性熱可塑性ポリマーの複合体中の割合が30~80wt%である、耐熱性樹脂複合体。 - 請求項9の耐熱性樹脂複合体において、24℃での曲げ強度が150MPa以上であり、且つ24℃に対する100℃の曲げ強度の保持率が70%以上である、耐熱性樹脂複合体。
- 請求項9または10の耐熱性樹脂複合体において、24℃での曲げ弾性率が5GPa以上であり、且つ24℃に対する100℃の曲げ弾性率の保持率が70%以上である、耐熱性樹脂複合体。
- 請求項9~11のいずれか一項に記載の耐熱性樹脂複合体において、密度が2.00g/cm3以下、且つ厚さが0.3mm以上である、耐熱性樹脂複合体。
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Also Published As
Publication number | Publication date |
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EP2881421A1 (en) | 2015-06-10 |
TW201413084A (zh) | 2014-04-01 |
KR20150040867A (ko) | 2015-04-15 |
TWI592534B (zh) | 2017-07-21 |
US20220033595A1 (en) | 2022-02-03 |
JP2018111914A (ja) | 2018-07-19 |
EP2881421B1 (en) | 2018-06-06 |
KR102199889B1 (ko) | 2021-01-07 |
CN107254057B (zh) | 2021-01-05 |
US20150140306A1 (en) | 2015-05-21 |
CN104508018B (zh) | 2017-10-20 |
JP6771504B2 (ja) | 2020-10-21 |
EP2881421A4 (en) | 2016-04-06 |
CN107254057A (zh) | 2017-10-17 |
JP6420663B2 (ja) | 2018-11-07 |
CN104508018A (zh) | 2015-04-08 |
JPWO2014021084A1 (ja) | 2016-07-21 |
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