Patent Application
20210381145
The present invention relates to a continuous-fiber nonwoven fabric (or continuous long-fiber nonwoven fabric), a composite material including the same, and a method for producing the composite material.
Composite material including reinforcing fibers (such as carbon fibers and glass fibers) and a matrix resin is lightweight and has excellent specific strength and specific rigidity. For these reasons, composite material is used in a wide range of fields: such as electrical and electronic industries, civil engineering and construction, aircrafts, automobiles, railways and ships, etc. It is known that composite material used in such fields generally includes continuous fibers (e.g. carbon fibers) as reinforcing fibers so as to exhibit high mechanical properties. It is also known that such composite material includes a thermosetting resin (such as an epoxy resin and a phenol resin) as a matrix resin of the composite material; among others, epoxy resins are often used.
A known technology for producing such composite material includes overlaying a pre-material containing reinforcing fibers and a matrix resin, and a meltable material different from the reinforcing fibers and the matrix resin, and melting the meltable material by heating or the like to uniformly distribute the meltable material in the composite material.
For example, Patent Document 1 (U.S. Pat. No. 8,409,486) describes combining a fiber material including a thermoplastic phenoxy resin having a certain weight-average molecular weight and a certain glass transition temperature with a preform including reinforcing fibers and a matrix resin, and further subjecting the combined body to curing treatment to produce a composite material.
Patent Document 1, however, describes that fiber materials including certain thermoplastic phenoxy resins include fibers such as monofilaments, multifilaments and staples, as well as two-dimensional textile products such as woven fabrics obtained by processing the fibers. Such fiber materials, however, tend to be poor in denseness as compared with continuous-fiber nonwoven fabrics. Patent Document 1 also describes that the obtained fiber material is used in combination with reinforcing fibers and a matrix resin to produce a composite material. However, since fibers such as monofilaments, multifilaments and staples and textile products obtained by processing these fibers tend to have gaps between the fibers, the obtained composite material tends to have poor appearance due to air entrainment or the like.
Therefore, in view of such conventional problems, an object of the present invention is to provide a continuous-fiber nonwoven fabric having excellent denseness, a composite material having good appearance, and a method for producing the composite material.
The inventors of the present invention have made intensive studies in order to achieve the object and finally achieved the present invention.
That is, the present invention may include the following preferred aspects.
Aspect 1
A continuous-fiber nonwoven fabric comprising fibers containing an amorphous thermoplastic phenoxy resin as a main component, wherein the thermoplastic phenoxy resin has a weight-average molecular weight in a range of from 10,000 to 100,000 (preferably from 12,000 to 80,000 and more preferably from 15,000 to 60,000) and a glass transition temperature equal to or lower than 100° C.
Aspect 2
The continuous-fiber nonwoven fabric according to aspect 1, wherein the continuous-fiber nonwoven fabric is a melt-blown nonwoven fabric or a spunbonded nonwoven fabric.
Aspect 3
The continuous-fiber nonwoven fabric according to aspect 1 or 2, wherein the fibers have an average fiber diameter equal to or smaller than 20 μm (preferably equal to or smaller than 15 μm, and more preferably equal to or smaller than 10 μm).
Aspect 4
The continuous-fiber nonwoven fabric according to any of aspects 1 to 3, wherein the continuous-fiber nonwoven fabric has a basis weight (A) equal to or lower than 100 g/m2 (preferably equal to or lower than 80 g/m2, more preferably equal to or lower than 50 g/m2, further preferably equal to or lower than 30 g/m2).
Aspect 5
The continuous-fiber nonwoven fabric according to any of aspects 1 to 4, wherein the continuous-fiber nonwoven fabric has a ratio of a permeability (B) to a basis weight (A) [permeability (B)/basis weight (A)] equal to or lower than 100 (preferably equal to or lower than 95, more preferably equal to or lower than 90, and further preferably equal to or lower than 85).
Aspect 6
A layered body comprising: the continuous-fiber nonwoven fabric as recited in any of aspects 1 to 5; and a preform containing reinforcing fibers and a matrix resin, the preform being overlaid on the continuous-fiber nonwoven fabric.
Aspect 7
The layered body according to aspect 6, wherein the reinforcing fibers are at least one selected from a group consisting of glass fibers, carbon fibers, liquid crystal polyester fibers, high-strength polyethylene fibers, aramid fibers, polyparaphenylene benzobisoxazole fibers, polyparaphenylene benzobisimidazole fibers, polyparaphenylene benzobisthiazole fibers, ceramic fibers, and metal fibers.
Aspect 8
The layered body according to aspect 6 or 7, wherein the matrix resin is at least one selected from a group consisting of an epoxy resin, a phenol resin, an unsaturated polyester resin, a cyanate ester resins, a phenol-formaldehyde resin, and a melamine resin.
Aspect 9
A composite material comprising: a melt of the continuous-fiber nonwoven fabric as recited in any of aspects 1 to 5; reinforcing fibers; and a matrix resin.
Aspect 10
The composite material according to aspect 9, wherein the reinforcing fibers are fixed by the melt of the continuous-fiber nonwoven fabric.
Aspect 11
A method for producing the composite material as recited in aspect 9 or 10, the method comprising subjecting the layered body as recited in any of aspects 6 to 8 to curing treatment.
Any combination of at least two features disclosed in the appended claims and/or the specification should be construed as included within the scope of the present invention. In particular, any combination of two or more of the appended claims should be equally construed as included within the scope of the present invention.
According to the present invention, it is possible to provide a continuous-fiber nonwoven fabric having excellent denseness, a composite material including the nonwoven fabric and having good appearance thanks to reduced cloudiness and reduced air entrainment, as well as a method for producing the composite material.
Hereinafter, the present invention will be described with reference to the embodiments. However, the present invention will not be limited to the embodiments.
Continuous-Fiber Nonwoven Fabric
The present invention relates to a continuous-fiber nonwoven fabric including fibers containing an amorphous thermoplastic phenoxy resin as a main component, wherein the thermoplastic phenoxy resin has a weight-average molecular weight in a range of from 10,000 to 100,000 and a glass transition temperature equal to or lower than 100° C. Use of a thermoplastic phenoxy resin having a specific weight-average molecular weight and a specific glass transition temperature makes it possible to provide the continuous-fiber nonwoven fabric having excellent denseness and to further provide a composite material combinedly including such a nonwoven fabric, reinforcing fibers and a matrix resin and having good appearance thanks to reduced cloudiness and reduced air entrainment.
In the present invention, it is important that the continuous-fiber nonwoven fabric comprises fibers containing a specific thermoplastic phenoxy resin as a main component. Where the fibers containing a thermoplastic phenoxy resin as a main component are short fibers, they tend to have insufficient strength in a machine direction (flow direction) as compared with that of long fibers, and a resultant composite material tends to have poor appearance because the composite material is likely to have air entrainment due to gaps between the short fibers. As used herein, the term “short fibers” means fibers cut to a length of 20 mm or shorter. The continuous-fiber nonwoven fabric according to the present invention is substantially free of such intentionally cut short fibers.
The form of the continuous-fiber nonwoven fabric according to the present invention is not particularly limited to a specific one, and the continuous-fiber nonwoven fabric may preferably be a melt-blown nonwoven fabric or a spunbonded nonwoven fabric obtained in accordance with a production method as described later. In particular, the continuous-fiber nonwoven fabric may preferably be a melt-blown nonwoven fabric in that the denseness of the continuous-fiber nonwoven fabric can be more easily enhanced thanks to a smaller average fiber diameter of the fibers.
Thermoplastic Phenoxy Resin
The thermoplastic phenoxy resin used in the present invention may be obtained by a conventionally known method in solution or in the absence of a solvent, such as a condensation reaction between a bivalent phenol compound and an epihalohydrin and a polyaddition reaction between a bivalent phenol compound and a bifunctional epoxy resin.
Examples of the bivalent phenol compound used for producing the thermoplastic phenoxy resin may include: hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylketone, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,3-bis(2-(4-hydroxyphenyl)propyl)benzene, 1,4-bis(2-(4-hydroxyphenyl)propyl)benzene, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 9,9-bis(4-hydroxyphenyl)fluorene. Among them, in terms of physical properties and costs, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylketone, 2,2-bis(4-hydroxyphenyl)propane, or 9,9-bis(4-hydroxyphenyl)fluorene is particularly preferred.
Examples of the bifunctional epoxy resin used for producing the thermoplastic phenoxy resin may include: epoxy oligomers obtained by a condensation reaction between a bivalent phenol compound as mentioned above and an epihalohydrin, such as hydroquinone diglycidyl ether, resorcin diglycidyl ether, a bisphenol S type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, methylhydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4′-dihydroxydiphenyloxide diglycidyl ether, 2,6-dihydroxy naphthalene diglycidyl ether, dichlorobisphenol A diglycidyl ether, a tetrabromobisphenol A type epoxy resin, and 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether. Among them, in terms of physical properties and costs, a bisphenol A type epoxy resin, a bisphenol S type epoxy resin, hydroquinone diglycidyl ether, a bisphenol F type epoxy resin, a tetrabromobisphenol A type epoxy resin, or 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether is particularly preferred.
The thermoplastic phenoxy resin may be produced in the absence of a solvent or in the presence of a reaction solvent. The following reaction solvents may be suitably used: aprotic organic solvents such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, and sulfolane. Further, a phenoxy resin obtained by solvent reaction may be subjected to desolvation treatment using an evaporator or the like to obtain a solid resin free of a solvent.
Conventionally known polymerization catalysts may be suitably used as reaction catalysts in the production of the thermoplastic phenoxy resin, such as alkali metal hydroxides, tertiary amine compounds, quaternary ammonium compounds, tertiary phosphine compounds, and quaternary phosphonium compounds.
It is important that the thermoplastic phenoxy resin used in the present invention is amorphous. In the present specification, a resin is determined as “amorphous” on the basis of whether or not an endothermic peak is observed when resultant fibers are placed in a differential scanning calorimeter (DSC) and are subjected as a resin to temperature rise at a rate of 10° C./min in nitrogen atmosphere. Where a resin exhibits an endothermic peak which is too broad to clearly determine the endothermic peak, the resin may be determined as substantially amorphous because the resin would still be applicable for practical use.
It is important that the thermoplastic phenoxy resin used in the present invention has a weight-average molecular weight in a range of from 10,000 to 100,000. The weight-average molecular weight may preferably be from 12,000 to 80,000, and even from about 15,000 to 60,000. Where the weight-average molecular weight is lower than 10,000, the resin does not stably flow through a nozzle because the viscosity of the resin is too low, so that it is difficult to obtain fibers from such a resin. Where the weight-average molecular weight exceeds 100,000, it is difficult to produce a nonwoven fabric having a small fiber diameter because the viscosity of the resin is too high, so that a continuous-fiber nonwoven fabric having desired denseness cannot be obtained. The weight-average molecular weight of the thermoplastic phenoxy resin is determined in accordance with the method described in Examples.
It is important that the thermoplastic phenoxy resin used in the present invention has a glass transition temperature equal to or lower than 100° C. The glass transition temperature may preferably be equal to or lower than 98° C., and even equal to or lower than about 95° C. Where the glass transition temperature of the thermoplastic phenoxy resin constituting the continuous-fiber nonwoven fabric exceeds 100° C., the continuous-fiber nonwoven fabric may not be sufficiently heated on the whole during the production of the composite material, possibly causing a problem in appearance such as cloudiness due to unmelted residues. A lower limit of the glass transition temperature of the thermoplastic phenoxy resin is not particularly limited to a specific one and may be, for example, equal to or higher than 30° C., preferably equal to or higher than 50° C., and more preferably equal to or higher than 60° C. in terms of heat resistance of the obtained nonwoven fabric. The glass transition temperature of the thermoplastic phenoxy resin is measured by differential scanning calorimetry (DSC) and is determined in accordance with the method described in Examples.
Fibers containing a thermoplastic phenoxy resin as a main component preferably contain the thermoplastic phenoxy resin in a proportion of 50 mass % or higher, more preferably 80 to 100 mass %, and further preferably 90 to 100 mass %.
As long as the effects of the present invention are not impaired, the fibers constituting the continuous-fiber nonwoven fabric according to the present invention may contain a component other than the thermoplastic phenoxy resin. Examples of the component other than the thermoplastic phenoxy resin may include: polypropylene, polyester, polyamide, liquid crystal polyester, antioxidant, antistatic agent, radical inhibitor, matting agent, ultraviolet absorber, flame retardant, and inorganic substance.
Examples of the inorganic substance may include: carbon nanotubes; fullerene; silicates such as talc, wallastinite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, and alumina silicate; metal oxides such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; glass beads; glass flakes; glass powder; ceramic beads; boron nitride; silicon carbide; carbon black; and graphite.
As long as the effects of the present invention are not impaired, the continuous-fiber nonwoven fabric according to the present invention may include fibers other than the fibers containing a thermoplastic phenoxy resin as a main component. Examples of the fibers other than the fibers containing a thermoplastic phenoxy resin as a main component may include non-conductive fibers and glass fibers. Examples of the non-conductive fibers may include: polypropylene fibers, polyethylene fibers, polyethylene terephthalate fibers, polybutylene terephthalate fibers, and 6-nylon fibers.
Method for Producing Continuous-Fiber Nonwoven Fabric
The method for producing a continuous-fiber nonwoven fabric according to the present invention is not particularly limited to a specific one and may suitably be carried out by melt blowing, spunbonding, flash spinning or electrospinning. Use of such a method makes it possible to easily obtain a continuous-fiber nonwoven fabric formed of fibers having a small average fiber diameter and thus having excellent denseness. Among others, melt blowing or spunbonding is preferably used in that these processes do not require a solvent in spinning, so that environmental impact can be minimized. p In the case of melt blowing, a conventionally known melt-blowing machine may be used as a spinning machine. The spinning temperature is not particularly limited to a specific one and may be, for example, from 250 to 380° C., preferably 270 to 360° C., and more preferably about 290 to 350° C. The temperature of hot air applied to the fibers immediately after discharge from nozzle holes (primary air temperature) is not limited to a specific one either and may be, for example, from 260 to 400° C., preferably about 270 to 380° C., and more preferably about 290 to 360° C. Further, the blowing amount (air amount) per meter of a nozzle width is not limited to a specific one either and may be, for example, from 5 to 50 Nm3, preferably 6 to 40 Nm3, and more preferably about 7 to 30 Nm3.
In the case of spunbonding, a conventionally known spunbonding machine may be used as a spinning machine. The spinning temperature is not particularly limited to a specific one and may be, for example, from 250 to 350° C., preferably 260 to 340° C., and more preferably about 280 to 330° C. The temperature of hot air applied to the fibers immediately after spinning (drawing air temperature) is not limited to a specific one either and may be, for example, from 260 to 370° C., preferably 270 to 350° C., and more preferably about 290 to 340° C. Further, the drawing air is not particularly limited to a specific one and may be applied at a rate of, for example, from 500 to 5000 m/min, preferably 600 to 4000 m/min, and more preferably about 800 to 3000 m/min.
The continuous-fiber nonwoven fabric obtained by the production method may be subjected to three-dimensional interlacing treatment by spunlacing, needle punching, or steam jetting or the like in order to further improve the mechanical strength.
Physical Properties of Continuous-Fiber Nonwoven Fabric
The average fiber diameter of the fibers constituting the continuous-fiber nonwoven fabric according to the present invention is not particularly limited to a specific one and may preferably be 20 μm or smaller, more preferably be 15 μm or smaller, and even about 10 μm or smaller. Where the average fiber diameter exceeds 20 μm, a resultant continuous-fiber nonwoven fabric tends to have a lower denseness, and a resultant composite material tends to have a lower surface smoothness. A lower limit of the average fiber diameter is not particularly limited to a specific one and may preferably be 1 μm or larger in terms of suppressed generation of fly waste, as well as ease of forming and ease of handling of the nonwoven fabric.
A basis weight (A) of the continuous-fiber nonwoven fabric according to the present invention is not particularly limited to a specific one and may preferably be 100 g/m2 or lower, more preferably 80 g/m2 or lower, further preferably 50 g/m2 or lower, and even about 30 g/m2 or lower. Where the basis weight (A) exceeds 100 g/m2, due to an excessive fiber amount in the fabric, only a part of the fibers tends to be melted during the production process of the composite material in which curing treatment is performed by heating. This often inhibits impregnation of the melt fibers into a preform including a matrix resin and reinforcing fibers or results in poor appearance such as cloudiness and/or air entrainment. A lower limit of the basis weight (A) is not particularly limited to a specific one and may preferably be 4 g/m2 or higher in terms of ease of forming of the nonwoven fabric.
An upper limit of a permeability (B) of the continuous-fiber nonwoven fabric according to the present invention is not particularly limited to a specific one and may preferably be 1,000 cm3/cm2·s or lower, more preferably 900 cm3/cm2·s or lower, more preferably 800 cm3/cm2·s or lower, and even about 500 cm3/cm2·s or lower. Where the permeability (B) exceeds 1,000 cm3/cm2 ·s, it tends to be impossible to ensure the denseness of the continuous-fiber nonwoven fabric. This often results in uneven impregnation of the melt fibers into a preform including a matrix resin and reinforcing fibers, so that a target surface smoothness cannot be achieved. A lower limit of the permeability (B) is not particularly limited to a specific one and may preferably be 50 cm3/cm2·s or higher, and even about 70 cm3/cm2·s or higher. Where the permeability (B) is lower than 50 cm3/cm2·s, only a part of the fibers tends to be melted during the production process of the composite material in which curing treatment is performed by heating. This often inhibits impregnation of the melt fibers into a preform including a matrix resin and reinforcing fibers or results in poor appearance such as cloudiness and/or air entrainment.
An upper limit of the ratio of the permeability (B) to the basis weight (A) [permeability (B)/basis weight (A)] is not particularly limited to a specific one and may preferably be 100 or lower, more preferably 95 or lower, further preferably 90 or lower, and even about 85 or lower. Where the ratio [the permeability (B)/the basis weight (A)] exceeds 100, the continuous-fiber nonwoven fabric tends to have reduced denseness, or impregnation of the melt fibers into a preform including a matrix resin and reinforcing fibers tends to be prevented at some locations due to the non-uniform fiber amount. A lower limit of the ratio [the permeability (B)/the basis weight (A)] is not particularly limited to a specific one and may preferably be 5 or higher in order to achieve uniform impregnation of the melt fibers into the preform including the matrix resin and the reinforcing fibers and prevent poor appearance due to air entrainment or the like.
A thickness of a single sheet of the continuous-fiber nonwoven fabric according to the present invention is not particularly limited to a specific one and may preferably be from 0.01 to 3 mm, more preferably 0.05 to 2 mm, further preferably 0.10 to 1 mm, and even about 0.10 to 0.50 mm in terms of denseness and ease of handling.
Layered Body
The continuous-fiber nonwoven fabric according to the present invention has excellent denseness and is useful as a material for producing a composite material as described later. Accordingly, the continuous-fiber nonwoven fabric may be overlaid on a preform including reinforcing fibers and a matrix resin to obtain a layered body which is used as an intermediate in producing the composite material. As used herein, the “preform” means an intermediate material including a matrix resin and a fiber substrate constituted by reinforcing fibers. As long as the preform includes a matrix resin and a fiber substrate, the form of the preform is not particularly limited to a specific one.
For example, the preform may have a form in which the matrix resin is impregnated into the fiber substrate, or in which particles and/or fibers made of the matrix resin are dispersed in the fiber substrate, or in which a film(s) and/or a sheet(s) made of the matrix resin is(are) overlaid on the fiber substrate. In the case where a preform has a form in which the matrix resin is impregnated into the fiber substrate, the preform may be, for example, preformed into a predetermined shape of a molded product or be shaped into the form of a prepreg (e.g. a sheet shape).
The type of the reinforcing fibers is not particularly limited to a specific one and may be, in terms of mechanical strength of a resultant composite material, at least one selected from a group consisting of glass fibers, carbon fibers, liquid crystal polyester fibers, high-strength polyethylene fibers, aramid fibers, polyparaphenylene benzobisoxazole fibers, polyparaphenylene benzobisimidazole fibers, polyparaphenylene benzobisthiazole fibers, ceramic fibers, and metal fibers. These reinforcing fibers may be used singly or in combination. The reinforcing fibers are selected such that the fibers do not melt during the production of the composite material. Among others, carbon fibers are preferable in order to enhance mechanical properties.
The shape of the fiber substrate is not particularly limited to a specific one and may be suitably adapted according to the intended use or the like. For example, the fiber substrate may be the form of a woven fabric, a non-crimp fabric (NCF), a unidirectional material (UD material), a knitted fabric, a nonwoven fabric, etc.
The type of the matrix resin is not particularly limited to a specific one as long as it is a thermosetting resin. For example, the matrix resin may be at least one selected from a group consisting of an epoxy resin, a phenol resin, an unsaturated polyester resin, a cyanate ester resins, a phenol-formaldehyde resin, and a melamine resin. Among others, an epoxy resin is preferable in terms of compatibility with the thermoplastic phenoxy resin.
The matrix resin may contain any of various known curing agents depending on the various types of the resin. For example, where the matrix resin is an epoxy resin, examples of the curing agent may include: amines, amides, imidazoles, acid anhydrides and the like.
The layered body may include at least one layer of a preform and at least one layer of a continuous-fiber nonwoven fabric. The layered body may include at least two layers of each. In terms of mechanical strength of a resultant composite material, the layered body includes preferably 5 or more layers of preforms and preferably 5 or more layers of continuous-fiber nonwoven fabrics. In order to ensure surface smoothness and to further enhance appearance, the layered body preferably includes a continuous-fiber nonwoven fabric disposed as an outermost layer on either side of the layered body, and more preferably includes continuous-fiber nonwoven fabrics disposed as outermost layers on both sides of the layered body.
A method for overlaying a preform and a continuous-fiber nonwoven fabric is not particularly limited to a specific one. For example, (i) a continuous-fiber nonwoven fabric and a preform including a matrix resin and reinforcing fibers may be separately prepared and overlaid on each other, or (ii) a continuous-fiber nonwoven fabric may be directly spun by melt blowing, spunbonding, flash spinning or electrospinning so as to be overlaid on a preform including a matrix resin and reinforcing fibers.
Composite Material
The present invention also includes a preferred embodiment of a composite material including a melt of the continuous-fiber nonwoven fabric, reinforcing fibers, and a matrix resin. Since the continuous-fiber nonwoven fabric according to the present invention has excellent denseness, the composite material, in which such a nonwoven fabric is melted so as to be integrated with the reinforcing fibers and the matrix resin, is unlikely to have cloudiness and/or air entrainment and thus has good appearance.
A method for producing the composite material is not particularly limited to a specific one and preferably includes subjecting the layered body to curing treatment. The layered body can be obtained by overlaying the continuous-fiber nonwoven fabric on the preform including the matrix resin and the reinforcing fibers, as described above. In the composite material obtained by such a method, the continuous-fiber nonwoven fabric and the matrix resin are once melted during the curing treatment, giving the composite material good appearance and excellent mechanical strength. Specifically, the continuous-fiber nonwoven fabric having good denseness is melted during the curing treatment, so that the thermoplastic phenoxy resin constituting the continuous-fiber nonwoven fabric can be uniformly impregnated into the surface of the composite material and throughout the composite material to fix the reinforcing fibers. Thus, irregularity of orientation of the reinforcing fibers is alleviated, so that bending strength and the like can be improved. In addition, the matrix resin is melted during the curing treatment, so that the mechanical strength of the reinforcing fibers can be improved.
The composite material preferably has a form in which the reinforcing fibers are fixed by a melt of the continuous-fiber nonwoven fabric.
As used herein, the “form in which the reinforcing fibers are fixed by a melt of the continuous-fiber nonwoven fabric” means a state in which the thermoplastic phenoxy resin constituting the continuous-fiber nonwoven fabric, which is melted and is mixed with the matrix resin during the curing treatment, is uniformly impregnated into the surface of the composite material and throughout the composite material and is cured to fix the reinforcing fibers in place. The reinforcing fibers in the composite material may be fixed by a mixture of the melt of the continuous-fiber nonwoven fabric and the matrix resin. In the composite material, the thermoplastic phenoxy resin constituting the continuous-fiber nonwoven fabric may be chemically bonded to the matrix resin.
The conditions for the curing treatment are not particularly limited to a specific one, and the curing treatment may be carried out by overlaying the continuous-fiber nonwoven fabric and the preform and then applying heat and pressure to them using a hot press or the like. The heating temperature is not particularly limited to a specific one and may be, for example, from 120 to 300° C., preferably from 130 to 250° C., and more preferably from about 140 to 200° C. The pressure is not particularly limited to a specific one and may be, for example, from 5 to 100 MPa, preferably from 7 to 80 MPa, and more preferably from about 10 to 50 MPa. The time for applying heat and pressure is not particularly limited to a specific one and may be, for example, from 10 seconds to 30 minutes, preferably from 30 seconds to 20 minutes, and more preferably from about 1 minute to 10 minutes.
The composite material according to the present invention may be formed into a desired shape according to the intended use or the like. In such a case, in the curing treatment, the composite material may be heated by various thermoforming processes (such as air-pressure forming, vacuum forming and press forming) to be melted and cured in a desired shape.
The composite material according to the present invention may have a multilayered structure including, in a thickness direction of the composite material, a plurality of layers each having the reinforcing fibers oriented horizontally. Where the composite material is produced by the production method as described above, it is possible to increase a content of the reinforcing fibers in a resultant composite material. For example, the basis weight of the reinforcing fibers in the composite material may be in a range of from 100 to 5000 g/m2, preferably from 500 to 4500 g/m2, and more preferably from 800 to 4000 g/m2.
Hereinafter, the present invention will be described in more detail with reference to the Examples and Comparative Examples. However, the present invention will not be limited by the Examples whatsoever. In the Examples and Comparative Examples below, various physical properties were determined in the following manner.
Weight-Average Molecular Weight of Thermoplastic Phenoxy Resin
A weight-average molecular weight (Mw) of a thermoplastic phenoxy resin was measured in terms of standard polystyrene by gel permeation chromatography (GPC). A measurement instrument and conditions used are listed below.
Glass Transition Temperature (° C.) of Thermoplastic Phenoxy Resin
In accordance with JIS K 7121, 10 mg of a thermoplastic phenoxy resin was collected in an aluminum pan and was subjected to temperature rise at a rate of 10° C./min using a differential scanning calorimeter (DSC) to produce a thermogram and determine a glass transition temperature.
Basis Weight (A) (g/m2) of Continuous-fiber nonwoven fabric
In accordance with JIS L 1906, three sample pieces (20 cm long×20 cm wide) were taken per meter of a width of a continuous-fiber nonwoven fabric, and a mass of each sample piece was measured using an electronic balance. An average of the masses of the three sample pieces was calculated and was divided by a sample piece area of 400 cm2 to obtain a mass per unit area as a basis weight (A) of the nonwoven fabric.
Permeability (B) (cm3/cm2·s) of Continuous-fiber nonwoven fabric
In accordance with JIS L 1096, 6.27.1 (method A: Frazier method), same sample pieces were prepared as those for the basis weight measurement, and a permeability of each sample piece was measured using a permeability tester (manufactured by TEXTEST (Switzerland): FX3300) with a measurement area set to 38 cm2 and under a measurement pressure of 125 Pa. An average of measurements of the three sample pieces was calculated as a permeability (B) of the nonwoven fabric.
Average Fiber Diameter (μm) of Fibers Constituting Continuous-fiber nonwoven fabric
An image of a prepared nonwoven fabric was taken at an arbitrary point using a scanning electron microscope at a magnification of 1000 times. Fiber diameters of randomly selected 100 fibers were measured, and an average of the measurements was calculated as an average fiber diameter of the fibers.
Denseness of Continuous-Fiber Nonwoven Fabric
A denseness of a continuous-fiber nonwoven fabric was calculated by the following formula. A smaller value represents a higher denseness.
Denseness=Permeability (B)/Basis weight (A)
Appearance of Composite Material
Appearance of a composite material, in view of the presence or absence of cloudiness and air entrainment, was observed by visual inspection and was determined in accordance with the following standards:
Good: good appearance without cloudiness or air entrainment,
Moderate: applicable for practical use with small cloudiness and/or air entrainment,
Poor: poor appearance with a lot of cloudiness and/or air entrainment
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 30,000 and a glass transition temperature of 90° C. was prepared and was blown at a rate of 10 Nm3 per meter of a nozzle width at a spinning temperature of 340° C. and a hot air temperature of 340° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 7.6 g/m2, a permeability (B) of 637 cm3/cm2·s, an average fiber diameter of 8.6 μm, and a thickness of 0.18 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] of 100 or lower and was excellent in denseness.
Preparation of Composite Material
On a preform including a carbon fiber woven fabric (“W-3101” manufactured by Toho Tenax Co., Ltd.: 3K woven fabric, basis weight of 200 g/m2) impregnated with an epoxy resin, was overlaid the continuous-fiber nonwoven fabric to give a unit of a layered body. Twelve of such units of the layered bodies were prepared and were overlaid on one another such that the preforms and the continuous-fiber nonwoven fabrics were alternately arranged, and then as an outermost layer, a continuous-fiber nonwoven fabric was placed on a preform to give a multilayered body. This multilayered body was thermocompression molded for 3 minutes at a temperature of 160° C. and under a pressure of 20 MPa to obtain a composite material in the form of a flat plate. The obtained composite material had good appearance.
A same thermoplastic phenoxy resin as the resin used in Example 1 was prepared and was blown at a rate of 10 Nm3 per meter of a nozzle width at a spinning temperature of 340° C. and a hot air temperature of 340° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 12.2 g/m2, a permeability (B) of 243 cm3/cm2·s, an average fiber diameter of 7.9 μm, and a thickness of 0.26 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] of 100 or lower and was excellent in denseness. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had good appearance.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 50,000 and a glass transition temperature of 95° C. was prepared and was blown at a rate of 20 Nm3 per meter of a nozzle width at a spinning temperature of 340° C. and a hot air temperature of 340° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 12.3 g/m2, a permeability (B) of 496 cm3/cm2·s, an average fiber diameter of 8.8 μm, and a thickness of 0.31 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] of 100 or lower and was excellent in denseness. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had good appearance.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane and epichlorohydrin) having a weight-average molecular weight of 20,000 and a glass transition temperature of 70° C. was prepared and was blown at a rate of 22 Nm3 per meter of a nozzle width at a spinning temperature of 300° C. and a hot air temperature of 300° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 12.3 g/m2, a permeability (B) of 87 cm3/cm2·an average fiber diameter of 7.2 μm and a thickness of 0.13 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] of 100 or lower and was excellent in denseness. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had good appearance.
A same thermoplastic phenoxy resin as the resin used in Example 1 was prepared and was used to produce a spunbonded nonwoven fabric at a drawing air rate of 1200 m/min and at a spinning temperature of 300° C. and a hot air temperature (drawing air temperature) of 300° C., as a continuous-fiber nonwoven fabric having a basis weight (A) of 20.4 g/m2, a permeability (B) of 745 cm3/cm2·s, an average fiber diameter of 12.7 μm, and a thickness of 0.47 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] of 100 or lower and was excellent in denseness. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had good appearance.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 90,000 and a glass transition temperature of 90° C. was prepared and was blown at a rate of 22 Nm3 per meter of a nozzle width at a spinning temperature of 360° C. and a hot air temperature of 360° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 12.2 g/m2, a permeability (B) of 912 cm3/cm2·s, an average fiber diameter of 13.3 μm, and a thickness of 0.44 min/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] of 100 or lower and was excellent in denseness. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had small cloudiness and air entrainment but was still applicable for practical use.
A same thermoplastic phenoxy resin as the resin used in Example 1 was prepared and was blown at a rate of 18 Nm3 per meter of a nozzle width at a spinning temperature of 300° C. and a hot air temperature of 300° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 12.0 g/m2, a permeability (B) of 1318 cm3/cm2·s, an average fiber diameter of 11.2 μm, and a thickness of 0.35 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] exceeding 100. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had small cloudiness and air entrainment but was still applicable for practical use.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 8,000 and a glass transition temperature of 90° C. was prepared and was blown at a rate of 18 Nm3 per meter of a nozzle width at a spinning temperature of 300° C. and a hot air temperature of 300° C. Due to frequent fiber breakage immediately below the nozzle and a large amount of fly waste scattering, an intended continuous-fiber nonwoven fabric was not obtained.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 200,000 and a glass transition temperature of 90° C. was prepared and was blown at a rate of 18 Nm3 per meter of a nozzle width at a spinning temperature of 340° C. and a hot air temperature of 340° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 12.9 g/m2, a permeability (13) of 2187 cm3/cm2·s, an average fiber diameter of 21.3 μm, and a thickness of 0.59 mm/sheet. The obtained nonwoven fabric had a ratio [the permeability (B)/the basis weight (A)] exceeding 100 and had insufficient denseness. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had poor appearance.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 30,000 and a glass transition temperature of 140° C. was prepared and was blown at a rate of 18 Nm3 per meter of a nozzle width at a spinning temperature of 340° C. and a hot air temperature of 340° C. to obtain a melt-blown nonwoven fabric having a basis weight (A) of 12.5 g/m2, a permeability (B) of 712 cm3/cm2·s, an average fiber diameter of 9.7 μm, and a thickness of 0.37 mm/sheet. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had poor appearance because of cloudiness caused by unmelted residues.
A thermoplastic phenoxy resin (a condensation reaction product of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin) having a weight-average molecular weight of 120,000 and a glass transition temperature of 90° C. was prepared and was blown at a rate of 22 Nm3 per meter of a nozzle width at a spinning temperature of 360° C. and a hot air temperature of 360° C. to obtain a melt-blown nonwoven fabric as a continuous-fiber nonwoven fabric having a basis weight (A) of 11.9 g/m2, a permeability (B) of 1512 cm3/cm2·s, an average fiber diameter of 17.1 μm, and a thickness of 0.49 mm/sheet. Except for using the nonwoven fabric obtained by this procedure, a composite material was prepared in a same manner as that of Example 1. The obtained composite material had poor appearance.
Since the continuous-fiber nonwoven fabric according to the present invention has excellent denseness, the continuous-fiber nonwoven fabric may be used in combination with reinforcing fibers and a matrix resin to form a composite material, so that the resultant composite material has good appearance. Such a composite material may be shaped into a form such as a board form and be suitably used as a heat insulating material, a protective material, an insulating material, or the like.
Although the present invention has been described in terms of the preferred Examples thereof, those skilled in the art would readily arrive at various changes and modifications in view of the present specification without departing from the scope of the invention.
Accordingly, such changes and modifications are included within the scope of the present invention defined by the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-041245 | Mar 2019 | JP | national |
This application is a continuation application, under 35 U.S.C §111(a) of international application No. PCT/JP2020/007840, filed Feb. 26, 2020, which claims priority to Japanese patent application No. 2019-041245, filed Mar. 7, 2019, the entire disclosures of all of which are herein incorporated by reference as a part of this application.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2020/007840 | Feb 2020 | US |
| Child | 17408676 | US |
