Methods for manufacturing blended yarns, fabrics and molded articles

Abstract

The object of this invention is to provide a method for manufacturing blended fibers, fabrics, and molded articles with excellent softness. The blended fibers of this invention comprise continuous thermoplastic resin fibers and continuous reinforcing fibers. The continuous thermoplastic resin fibers comprise a polyamide resin, said polyamide resin comprising diamine units and dicarboxylic acid units, wherein at least 70 mol% of the diamine units are derived from phenylenediamine, and at least 70 mol% of the dicarboxylic acid units are derived from α,ω-linear aliphatic dicarboxylic acids having 11 to 20 carbon atoms.

Description

Technical Field

[0001] This invention relates to methods for manufacturing blended filaments, fabrics, and molded articles. In particular, it relates to blended filaments using specific polyamide resins. Background Technology

[0002] Research has been conducted on blended filaments using thermoplastic resin fibers and continuous reinforcing fibers. These blended filaments, due to their softness, are suitable for molding complex shapes and for products requiring exceptional strength.

[0003] Furthermore, as an example of the application of blended fibers, blended fibers containing continuous thermoplastic resin fibers and continuous reinforcing fibers are known. Moreover, the use of these blended fibers for sewing (embroidery) has been investigated (Patent Documents 1 and 2). This sewing technique is called Custom Fiber Placement (TFP).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2016 / 159340

[0007] Patent Document 2: Japanese Patent Application Publication No. 2020-063342 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] In this patent document 1, the TFP processing using a blend of continuous thermoplastic resin fibers and continuous carbon fibers was studied, wherein the continuous thermoplastic resin fibers used a polyamide resin composed of sebacic acid and phenylenediamine.

[0010] The aforementioned blended fibers are excellent materials, but in recent years there has been a demand for blended fibers capable of more precise TFP processing. That is, in components requiring design flexibility, blended fibers with the ability to handle more complex shapes are needed.

[0011] The purpose of this invention is to solve this problem and to provide a method for manufacturing blended fibers, fabrics and molded articles with excellent softness.

[0012] Solution for solving the problem

[0013] Based on the above-mentioned issues, the inventors conducted research and found that the above-mentioned issues can be solved by using a specified polyamide resin.

[0014] <1> A blended filament comprising continuous thermoplastic resin fibers and continuous reinforcing fibers,

[0015] The continuous thermoplastic resin fiber comprises polyamide resin.

[0016] The polyamide resin comprises diamine units and dicarboxylic acid units.

[0017] More than 70 mol% of the diamine unit is derived from phenylenediamine.

[0018] More than 70 mol% of the dicarboxylic acid units are derived from α,ω-linear aliphatic dicarboxylic acids with 11 to 20 carbon atoms.

[0019] <2> according to <1> The blended fibers wherein more than 70 mol% of the dicarboxylic acid units are derived from dodecanoic acid and / or tetradecanoic acid.

[0020] <3> according to <1> The blended fiber wherein more than 70 mol% of the dicarboxylic acid unit is derived from dodecanoic acid.

[0021] <4> according to <1> ~ <3> In any one of the blended fibers, 20-100 mol% of the diamine unit is derived from m-phenylenediamine and 80-0 mol% is derived from p-phenylenediamine (wherein the total does not exceed 100 mol%).

[0022] <5> according to <1> The blended fibers, wherein more than 70 mol% of the dicarboxylic acid units are derived from dodecanoic acid and / or tetradecanoic acid,

[0023] 20-100 mol% of the diamine unit is derived from m-phenylenediamine, and 80-0 mol% is derived from p-phenylenediamine (wherein the total does not exceed 100 mol%).

[0024] <6> according to <1> ~ <5> The blended fiber in any one of the following methods, wherein the continuous reinforcing fiber comprises at least one selected from the group consisting of carbon fiber, glass fiber and aramid fiber.

[0025] <7> according to <1> ~ <6> The blended filaments in any one of the following methods, wherein the number-average fiber length of the continuous reinforcing fibers exceeds 10 mm.

[0026] <8> according to <1> ~ <7> The blended filaments described in any one of the following examples, wherein the continuous thermoplastic resin fiber is an unstretched fiber.

[0027] <9> according to <1> ~ <8> The blended fiber described in any one of the above is used for custom fiber layup processing.

[0028] <10> A fabric made of <1> ~ <9> The blended fibers formed as described in any one of the above.

[0029] <11> A method for manufacturing a molded article, comprising: <1> ~ <9> The blended fibers described in any one of the above are subjected to heat processing.

[0030] <12> A method for manufacturing a molded article, comprising: <1> ~ <9> The blended yarns described in any one of the above are subjected to customized fiber laying processing.

[0031] The effects of the invention

[0032] According to the present invention, a method for manufacturing blended fibers, fabrics, and molded articles with excellent softness can be provided. Attached Figure Description

[0033] Figure 1 This is a schematic diagram showing the state of stitching the blended fibers of the present invention together using conformal yarn.

[0034] Figure 2 This is a schematic diagram showing the completion of embroidery when the blended fiber (A) of the prior art and the blended fiber (B) of the present invention are sewn together.

[0035] Figure 3 This is a schematic diagram illustrating the method for measuring the shapeability of this embodiment. Detailed Implementation

[0036] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0037] It should be noted that in this specification, the "~" symbol is used to encompass the numerical values ​​described before and after it as lower and upper limits. Furthermore, any combination of the upper and lower limits mentioned in this specification can be used as an example of this embodiment.

[0038] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this manual are set at 23°C.

[0039] Where the measurement methods described in the standards shown in this specification differ from year to year, unless otherwise specified, they are assumed to be based on the standards as of January 1, 2024. Where the measurement methods described in the standards shown in this specification are abolished as of January 1, 2024, the standards as of the abolishment date are used.

[0040] Figures 1-3 Sometimes the scale and other parameters do not match reality.

[0041] The blended filament of this embodiment is characterized by comprising continuous thermoplastic resin fibers and continuous reinforcing fibers. The continuous thermoplastic resin fibers comprise a polyamide resin, which comprises diamine units and dicarboxylic acid units. At least 70 mol% of the diamine units are derived from phenylenediamine, and at least 70 mol% of the dicarboxylic acid units are derived from α,ω-linear aliphatic dicarboxylic acids having 11 to 20 carbon atoms. This configuration provides a blended filament with excellent softness.

[0042] Figure 1 This is a schematic diagram showing the state in which the blended fiber 1 in this embodiment is sewn together using conformal yarn 2. (See diagram below.) Figure 1 As shown, by using the blended fiber 1 of this embodiment, desired embroidery (stitching) can be performed using TFP. The stitching needle is mechanically controlled, and the conformal yarn 2 stitches the blended fiber 1, thereby maintaining the blended fiber 1 in the desired shape. Here, if the blended fiber is stiff, it will twist within the conformal yarn. In this embodiment, it has been found that by using a specified polyamide resin, even when performing stitches with complex shapes, the blended fiber is stitched in the desired position.

[0043] Figure 2 This refers to a blend of continuous thermoplastic resin fibers and continuous carbon fibers (…). Figure 2 (A) and the blended fibers of this embodiment Figure 2 (B) is a schematic diagram showing the completion of the embroidery during the stitching process, wherein the continuous thermoplastic resin fiber uses a polyamide resin composed of sebacic acid and phenylenediamine. Figure 2 Conformal wires are not shown in the diagram.

[0044] exist Figure 2 In (A), a blended filament 1 comprising continuous thermoplastic resin fibers and continuous carbon fibers is used for sewing, wherein the continuous thermoplastic resin fibers utilize a polyamide resin composed of sebacic acid and phenylenediamine. Figure 2 In (A), the mixed fiber 1 deviates from the designed desired pattern 3. Figure 2 The dotted portion of (A) is stitched together. This is because... Figure 2 Although the blended fiber 1 shown in (A) is a good blended fiber with excellent rigidity, it is hard due to its excellent rigidity. The blended fiber is twisted in the conformal fiber, and as a result, the blended fiber 1 is conformally maintained slightly deviating from the set desired pattern 3.

[0045] In contrast, such as Figure 2 As shown in (B), when using the blended fiber 1 of this embodiment, the blended fiber 1 is soft and thus the blended fiber 1 is arranged to follow the desired pattern. The desired pattern is formed by stitching.

[0046] It should be noted that, Figure 2This is a schematic diagram used to illustrate the differences between the prior art and this embodiment, and does not necessarily represent the actual stitching state. In fact, the effect of using the blended fibers of this embodiment becomes clear when stitching elliptical patterns with smaller radii of curvature (e.g., elliptical patterns with a horizontal radius of 3cm and a vertical radius of 10cm).

[0047] The following is a detailed description of this embodiment.

[0048] <Blended fibers>

[0049] In this embodiment, the blended filament preferably contains continuous reinforcing fibers dispersed within it, and the continuous reinforcing fibers and continuous thermoplastic resin fibers are bundled (preferably in the form of ribbons). When forming the bundles, it is preferable to use a binding agent and / or a surface treatment agent.

[0050] Furthermore, in the blended filaments of this embodiment, the continuous thermoplastic resin fiber preferably does not impregnate the continuous reinforcing fiber and maintains its fibrous state. Alternatively, in the blended filaments of this embodiment, a portion of the continuous thermoplastic resin fiber component may impregnate the continuous reinforcing fiber. Specifically, in the blended filaments of this embodiment, the impregnation rate of the continuous thermoplastic resin fiber component is less than 1%, preferably 0.5% or less. The lower limit of the impregnation rate is not particularly limited and can be 0%.

[0051] <<Methods for Determining Permeability>>

[0052] For the hybrid filaments, sections perpendicular to the length direction of the continuous reinforcing fibers were gathered and cut, embedded in epoxy resin, and the surface corresponding to the cross-section of the hybrid filament was ground. Cross-sectional images were captured using an ultra-deep color 3D shape measuring microscope. The cross-section of the epoxy resin-embedded hybrid filament was observed using a digital microscope. For the obtained cross-sectional images, the area where thermoplastic resin fibers were impregnated into the continuous reinforcing fibers (the area where thermoplastic resin fibers were melt-impregnated between the continuous reinforcing fibers) was selected using ImageJ image analysis software, and its area was measured. The impregnation rate is expressed as the area impregnated with thermoplastic resin fibers into the continuous reinforcing fibers divided by the cross-sectional area (in %).

[0053] The ultra-deep color 3D shape measuring microscope uses VK-9500 (control unit) / VK-9510 (measuring unit) (manufactured by KEYENCECORPORATION).

[0054] The blended fibers are preferably treated with agents such as bundlers or surface treatment agents. This configuration improves the dispersion of the continuous reinforcing fibers in the blended fibers and makes them easier to bundle. Examples of treatment agents include ester compounds, alkylene glycol compounds, polyolefin compounds, and phenyl ether compounds. Compounds that function as surfactants are particularly preferred.

[0055] Furthermore, the proportion of continuous reinforcing fibers in the blended fiber is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and may also be set to 55% by mass or more. The upper limit of the proportion of continuous reinforcing fibers in the blended fiber is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and may also be set to 65% by mass or less.

[0056] The blended fiber in this embodiment may contain only one type of continuous reinforcing fiber, or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0057] The proportion of continuous thermoplastic resin fiber in the blended filament is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and may also be set to 35% by mass or more. The upper limit of the proportion of continuous thermoplastic resin fiber is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, particularly preferably 50% by mass or less, and may also be set to 45% by mass or less.

[0058] The blended filaments of this embodiment may contain only one type of thermoplastic resin fiber, or they may contain two or more types. When containing two or more types, the total amount is preferably within the range described above.

[0059] Furthermore, in the blended filament of this embodiment, the total amount of continuous thermoplastic resin fiber and continuous reinforcing fiber preferably accounts for 90% or more by mass of the blended filament, more preferably 95% or more by mass, may account for 99% or more by mass, and may be 100% or less by mass.

[0060] The dispersion of the continuous reinforcing fibers in the blended filaments is preferably 60-100%, more preferably 63-100%, even more preferably 68-100%, and particularly preferably 70-100%. By setting it within this range, the blended filaments exhibit more uniform physical properties, thereby further improving the appearance of the molded articles. In addition, when using it to manufacture molded articles, molded articles with superior mechanical properties can be obtained.

[0061] <<Methods for Determining Dispersion>>

[0062] The blended fibers were embedded in epoxy resin, and the cross-section perpendicular to the length direction of the blended fibers was ground. Cross-sectional images were captured using an ultra-deep color 3D shape measuring microscope. In the captured images, six auxiliary lines were drawn radially at equal intervals. The lengths of the continuous reinforcing fiber regions located on each auxiliary line were measured as a1, a2, a3…ai (i=n). Additionally, the lengths of the continuous thermoplastic resin fiber regions located on each auxiliary line were measured as b1, b2, b3…bi (i=m). Based on these results, the dispersion was calculated using the following formula.

[0063] [Mathematical Expression 1]

[0064]

[0065] The ultra-deep color 3D shape measuring microscope can be used with VK-9500 (control unit) / VK-9510 (measuring unit) (KEYENCE CORPORATION).

[0066] Blended fibers are typically manufactured using continuous thermoplastic resin fiber bundles and continuous reinforcing fiber bundles.

[0067] The continuous reinforcing fibers and / or continuous thermoplastic resin fibers used in the blended filaments are preferably fibers that have undergone surface treatment with a treatment agent. By configuring it in this way, it is easy to obtain blended filaments in which the continuous reinforcing fibers and continuous thermoplastic resin fibers are more evenly dispersed. In addition, it is possible to improve the infiltration rate of the continuous thermoplastic resin fiber component into the continuous reinforcing fibers after molding.

[0068] For details on other blended fibers, please refer to paragraphs 0018 to 0039 of WO2016 / 159340, which are incorporated herein by reference.

[0069] <Continuous thermoplastic resin fiber>

[0070] The blended filaments of this embodiment comprise continuous thermoplastic resin fibers. Continuous thermoplastic resin fibers refer to thermoplastic resin fibers with an average fiber length exceeding 6 mm, preferably exceeding 10 mm, more preferably exceeding 12 mm, more preferably exceeding 30 mm, and even more preferably exceeding 10 cm. The average fiber length of the continuous thermoplastic resin fibers used in this embodiment is not particularly limited, but from the viewpoint of good molding processability, it is preferably 1 m or more, more preferably 100 m or more, even more preferably 1,000 m or more, and preferably 20,000 m or less, more preferably 10,000 m or less, and even more preferably 7,000 m or less.

[0071] The polyamide resin constituting the continuous thermoplastic resin fiber includes the following polyamide resin (hereinafter sometimes referred to as "phenylene dimethylamine polyamide resin"): it contains diamine units and dicarboxylic acid units, wherein more than 70 mol% of the diamine units are derived from phenylene dimethylamine, and more than 70 mol% of the dicarboxylic acid units are derived from α,ω-linear aliphatic dicarboxylic acids having 11 to 20 carbon atoms.

[0072] The diamine units in the phenylenediamine-based polyamide resin preferably account for 75 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 99 mol% or more derived from phenylenediamine (preferably p-phenylenediamine and / or m-phenylenediamine).

[0073] The phenylenediamine is preferably p-phenylenediamine and / or m-phenylenediamine. The phenylenediamine preferably comprises 0-100 mol% m-phenylenediamine and 100-0 mol% p-phenylenediamine (wherein the total amount of m-phenylenediamine and p-phenylenediamine does not exceed 100 mol%), more preferably comprising 20-100 mol% m-phenylenediamine and 80-0 mol% p-phenylenediamine.

[0074] In the diphenylene dimethylamine-based polyamide resin, the total percentage of p-phenylene dimethylamine units and m-phenylene dimethylamine units preferably accounts for 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 99 mol% or more of the diamine units. The maximum total percentage of the aforementioned p-phenylene dimethylamine units and m-phenylene dimethylamine units is 100 mol%.

[0075] Examples of diamines other than m-phenylenediamine and p-phenylenediamine that can be used as raw material components in diphenylenediamine-based polyamide resins include: tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. Aliphatic diamines; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decahydronaphthalene, and bis(aminomethyl)tricyclodecane; and diamines with aromatic rings such as bis(4-aminophenyl)ether, p-phenylenediamine, and bis(aminomethyl)naphthalene. One type or a mixture of two or more types may be used.

[0076] On the other hand, the dicarboxylic acid unit of the phenylenediamine polyamide resin preferably comprises 75 mol% or more, more preferably 80 mol% or more, further preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 99 mol% or more derived from α,ω-linear aliphatic dicarboxylic acids having a preferred number of carbons of 11 to 20.

[0077] The preferred dicarboxylic acid component used as a raw material for phenylenediamine polyamide resins is an α,ω-linear aliphatic dicarboxylic acid with 11 to 20 carbon atoms, preferably an α,ω-linear aliphatic dicarboxylic acid with 11 to 16 carbon atoms, and preferably an α,ω-linear aliphatic dicarboxylic acid with 12 to 14 carbon atoms.

[0078] The α,ω-linear aliphatic dicarboxylic acids with 11 to 20 carbon atoms are specifically dodecanoic acid, tridecanoic acid, tetradecanoic acid, etc. Among them, dodecanoic acid and / or tetradecanoic acid are preferred, and more preferably dodecanoic acid, based on the melting point of the polyamide resin being within the range suitable for molding and processing.

[0079] Examples of dicarboxylic acid components other than those mentioned above include: α,ω-linear aliphatic dicarboxylic acids with 10 or fewer carbon atoms, such as adipic acid and sebacic acid; phthalic acid compounds such as isophthalic acid, terephthalic acid, and phthalic acid; and isomers of naphthalic acid such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. One type or two or more types may be used in combination.

[0080] It should be noted that while phenylene dimethylamine-based polyamide resins are composed primarily of diamine units and dicarboxylic acid units, other structural units are not entirely excluded. They may also include structural units derived from lactams such as ε-caprolactam and laurolactam, as well as aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "primary component" refers to the structural unit constituting the phenylene dimethylamine-based polyamide resin in which the total number of diamine units and dicarboxylic acid units is the largest among all structural units. In this embodiment, the total number of diamine units and dicarboxylic acid units in the phenylene dimethylamine-based polyamide resin preferably accounts for 90% or more by mass, more preferably 95% or more by mass, further preferably 97% or more by mass, and even more preferably 99% or more by mass.

[0081] Phenylenediamine-based polyamide resins are also preferably polyamide resins manufactured using biomass raw materials (biomass polyamide resins). By using biomass polyamide resins, environmental impact can be reduced.

[0082] Raw material monomers that have undergone Quality Balance Certification (ISCC PLUS) can also be used. Quality Balance Certification refers to the quantification of the extent to which renewable raw materials and / or biological raw materials are used in each plant and / or production facility, and the extent to which finished products are produced and / or shipped, and this is guaranteed along with quality.

[0083] The melting point of the diphenylene diamine-based polyamide resin is preferably 150°C or higher, more preferably 160°C or higher, even more preferably 170°C or higher, and even more preferably 180°C or higher. It is also preferably 300°C or lower, more preferably 290°C or lower, even more preferably 280°C or lower, and even more preferably 275°C or lower. The melting point was determined according to the description in the examples described later.

[0084] In the case where the blended fiber in this embodiment contains two or more phenylenediamine-based polyamide resins, it is set as the weighted average of each polyamide resin.

[0085] The lower limit of the number average molecular weight (Mn) of the diphenylene diamine-based polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less. Within this range, the heat resistance, elastic modulus, dimensional stability, and processability are improved.

[0086] The number-average molecular weight is the converted value of polystyrene determined by GPC (gel permeation chromatography). More specifically, the number-average molecular weight can be determined according to the description in paragraph 0047 of Japanese Patent Application Publication No. 2018-165298, the contents of which are incorporated herein by reference.

[0087] In this embodiment, the content of compounds with a molecular weight of 310 or more and 1000 or less in the diphenylene diamine polyamide resin is preferably less than 0.1% by mass or more than 1.5% by mass.

[0088] In this embodiment, the content of compounds with a molecular weight of less than 310 in the phenylenediamine polyamide resin is preferably greater than 0.1% by mass.

[0089] Continuous thermoplastic resin fibers may contain polyamide resins other than diphenylene diamine-based polyamide resins. Examples of polyamide resins other than diphenylene diamine-based polyamide resins include aliphatic polyamide resins and semi-aromatic polyamide resins other than diphenylene diamine-based polyamide resins.

[0090] Examples of aliphatic polyamide resins include polyamide 4, polyamide 46, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 11, and polyamide 12.

[0091] Examples of semi-aromatic polyamide resins include terephthalic acid-based polyamide resins (polyamide 6T, polyamide 9T, and polyamide 10T).

[0092] When the continuous thermoplastic resin fiber contains polyamide resin other than diphenylene diamine polyamide resin, its content is preferably less than 10% by mass of the content of diphenylene diamine polyamide resin, more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0093] Continuous thermoplastic resin fibers can be surface treated with surface treatment agents.

[0094] Continuous thermoplastic resin fibers may or may not be stretched. In this embodiment, it is preferable to leave them unstretched. By leaving them unstretched, blended fibers with superior softness can be produced.

[0095] The aforementioned continuous thermoplastic resin fiber may contain other components besides polyamide resin, or it may not contain any.

[0096] Other components mentioned above may include thermoplastic resins other than polyamide resins, antioxidants, heat stabilizers and other stabilizers, hydrolysis resistance modifiers, weather stabilizers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, colorants, release agents and other additives. For details, please refer to paragraphs 0130-0155 of Japanese Patent No. 4894982 and paragraphs 0047-0103 of International Publication No. 2021 / 241471, the contents of which are incorporated herein by reference.

[0097] The content of components other than polyamide resin in these continuous thermoplastic resin fibers is preferably less than 10% by mass of the blended fibers, more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0098] The aforementioned continuous thermoplastic resin fibers are preferably free of cobalt stearate, and more preferably free of cobalt salts.

[0099] <Continuous reinforcing fiber>

[0100] The blended filaments of this embodiment include continuous reinforcing fibers. Continuous reinforcing fibers refer to reinforcing fibers with an average fiber length exceeding 6 mm, preferably exceeding 10 mm, more preferably exceeding 12 mm, even more preferably exceeding 30 mm, and even more preferably exceeding 10 cm. There is no particular limitation on the average fiber length of the continuous reinforcing fibers used in this embodiment. From the viewpoint of ensuring good molding processability, it is preferably 1 m or more, more preferably 100 m or more, even more preferably 1,000 m or more, and preferably 20,000 m or less, more preferably 10,000 m or less, and even more preferably 7,000 m or less.

[0101] Examples of continuous reinforcing fibers include: inorganic fibers such as glass fiber, carbon fiber, metal fiber, boron fiber, basalt fiber, and ceramic fiber; and organic fibers such as aramid fiber, polyoxymethylene fiber, aromatic polyamide fiber, poly(p-phenylenebenzodioxazole) fiber, and ultra-high molecular weight polyethylene fiber. Preferably, the fiber contains at least one fiber selected from the group consisting of carbon fiber, glass fiber, and aramid fiber; more preferably, carbon fiber and / or glass fiber; and even more preferably, carbon fiber.

[0102] Examples of carbon fibers include polyacrylonitrile-based carbon fibers and pitch-based carbon fibers.

[0103] As glass fiber, fibers are obtained by melting and spinning commonly supplied E glass, C glass, A glass, S glass, and alkali-resistant glass.

[0104] Continuous reinforcing fibers can be surface treated with surface treatment agents.

[0105] The cross-section of the continuous reinforcing fiber can be either circular or non-circular.

[0106] As for continuous carbon fibers, in addition to the above, reference can be made to paragraph 0074 of Japanese Patent No. 7398028, the contents of which are incorporated herein by reference.

[0107] In this embodiment, the continuous reinforcing fibers are typically oriented in one direction.

[0108] When the continuous reinforcing fiber is carbon fiber, the tensile strength is preferably 1500 MPa or more, more preferably 2500 MPa or more, and even more preferably 3500 MPa or more. There is no particular upper limit, but it is practically 8000 MPa or less. When glass fiber is used, the tensile strength is preferably 800 MPa or more, more preferably 1800 MPa or more, and even more preferably 2800 MPa or more. There is no particular upper limit, but it is practically 5000 MPa or less.

[0109] <Other Ingredients>

[0110] The blended filaments in this embodiment may contain other components besides continuous thermoplastic resin fibers and continuous reinforcing fibers, or they may not contain any of them.

[0111] Other components mentioned above may include thermoplastic resins other than polyamide resins, fillers other than continuous reinforcing fibers, nucleating agents, antioxidants, heat stabilizers and other stabilizers, hydrolysis resistance modifiers, weather stabilizers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, colorants, release agents and other additives. For details, please refer to paragraphs 0130-0155 of Japanese Patent No. 4894982 and paragraphs 0047-0103 of International Publication No. 2021 / 241471, the contents of which are incorporated herein by reference.

[0112] The content of these other components is preferably less than 10% by mass of the blended fibers, more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0113] The blended filaments of this embodiment are typically manufactured using continuous thermoplastic resin fiber bundles and continuous reinforcing fiber bundles. The continuous reinforcing fibers and / or continuous thermoplastic resin fibers used in the blended filaments are preferably fibers that have undergone surface treatment with a treatment agent. With this configuration, it is easy to obtain blended filaments in which the continuous reinforcing fibers and continuous thermoplastic resin fibers are more uniformly dispersed, and furthermore, the infiltration rate of the continuous thermoplastic resin fiber component into the continuous reinforcing fibers after molding can be improved. Detailed information regarding other blended filaments and their manufacturing methods can be found in paragraphs 0018 to 0039 of International Publication No. 2016 / 159340 and paragraph 0051 of Japanese Patent Application Publication No. 2020-063342, the contents of which are incorporated herein by reference.

[0114] Each blended filament in this embodiment typically contains 2 to 1000 (preferably 10 to 100) continuous thermoplastic resin fibers and 2 to 1000 (preferably 10 to 100) continuous reinforcing fibers.

[0115] The blended filaments of this embodiment can be heat-processed to manufacture molded articles. As molded articles, there are no particular limitations; they are widely used in automobile and aircraft parts, general machinery parts, precision machinery parts, electronic / electrical equipment parts, OA equipment parts, building materials / housing equipment related parts, medical devices, leisure sports goods, game equipment, medical products, food packaging films and other daily necessities, defense and aerospace products, etc. They are particularly suitable as molding materials for medical equipment (knee, ankle, and foot orthotics, etc.), window frames for automobiles, trains, and ships, frames for helmet visors, eyeglass frames, safety shoes, etc. In particular, the composite material of this invention has high utilization value as a material for forming medical equipment and for secondary structural components in automobiles. Furthermore, it is suitable for manufacturing molded articles with concave or convex portions.

[0116] The blended fiber yarn of this embodiment is preferably used for custom fiber layup processing (TFP applications). Additionally, the blended fiber yarn of this embodiment is preferably used as yarn in applications including yarn spinning, such as braiding machines, knitting machines, and looms.

[0117] Examples of applications using the blended fibers of this embodiment include customized fiber lay-up products, fabrics formed from the blended fibers of this embodiment, and woven fabrics formed from the blended fibers of this embodiment. Additionally, examples of applications including yarn spinning in this embodiment include braided tapes and twisted tapes.

[0118] Return again Figure 1 The following describes the case where the blended filaments of this embodiment are processed by custom fiber placement. Figure 1 This is an example of a customized fiber placement process using the blended filaments of this embodiment. 1 represents the blended filaments of this embodiment, and 2 represents the conformal fiber. In TFP processing, the blended filaments 1 are preferably arranged along the shape of the molded article, and then sewn together using the conformal fiber 2. The conformal fiber 2 is typically a continuous thermoplastic resin fiber, preferably within the same range as the continuous thermoplastic resin fibers described above. The blended filaments of this embodiment can preferably be used for... Figure 1 As shown, molded articles having two or more, preferably three or more, folded-back portions. In particular, they are preferably used for manufacturing... Figure 1 A molded product having a folding section with a folding angle of 90° or more, as shown.

[0119] The molded article of this embodiment is formed by heating the blended filaments.

[0120] In addition, the molded article of this embodiment is also formed by heating and processing a customized fiber-layout product of blended filaments.

[0121] Example

[0122] The following examples illustrate the present invention in more detail. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0123] If the measuring equipment used in the embodiments is difficult to obtain due to production stoppages or other reasons, other equipment with equivalent performance can be used for measurement.

[0124] <Ingredients>

[0125] Continuous carbon fiber: TR3523, PYROFIL (registered trademark) manufactured by Mitsubishi Chemical Corporation.

[0126] MP12(30): Polyamide resin synthesized according to the following synthesis example 1

[0127] MP12(40): Polyamide resin synthesized according to Synthesis Example 2 below

[0128] MP14(30): Polyamide resin synthesized according to the following synthesis example 3

[0129] MXD12: A polyamide resin synthesized according to Synthesis Example 4 below.

[0130] PXD12: A polyamide resin synthesized according to Synthesis Example 5 below.

[0131] MP10(30): Polyamide resin synthesized according to Synthesis Example 6 below

[0132] PXD10: A polyamide resin synthesized according to Synthesis Example 7 below.

[0133] <Synthetic Example 1: Synthesis of MP12(30)>

[0134] Dodecanoic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. After thorough nitrogen purging, the mixture was heated to 180°C until melted. While stirring the contents, a mixture of m-phenylenediamine and p-phenylenediamine (70:30) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MPXDA) was slowly added dropwise at a molar ratio of 1:1 to the dodecanoic acid, while the temperature was raised to 290°C. After the addition was complete, the liquid temperature was maintained at 290°C, and the reaction continued for 10 minutes. Then, the pressure inside the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for 20 minutes. During this period, the reaction temperature was continuously raised to 300°C. After the reaction was complete, a pressure of 0.3 MPa was applied to the reactor with nitrogen, and the polymer was extracted as a thread from a nozzle at the bottom of the polymerization tank. After water cooling, the polymer was granulated using a granulator to obtain the final product.

[0135] <Synthetic Example 2: Synthesis of MP12(40)>

[0136] Dodecanoic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. After thorough nitrogen purging, the mixture was heated to 180°C until melted. While stirring the contents, a mixture of m-phenylenediamine and p-phenylenediamine (60:40) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MXDA, Showa Denko Co., Ltd., PXDA) was slowly added dropwise at a molar ratio of 1:1 to the dodecanoic acid, while the temperature was raised to 290°C. After the addition was complete, the liquid temperature was maintained at 290°C, and the reaction continued for 10 minutes. Then, the pressure in the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for 20 minutes. During this period, the reaction temperature was continuously raised to 300°C. After the reaction is complete, nitrogen gas is applied to the reactor at 0.3 MPa. The polymer is then taken out from the nozzle at the bottom of the polymerization tank in the form of a wire. After water cooling, it is granulated using a granulator to obtain the final product.

[0137] <Synthesis Example 3: Synthesis of MP14(30)>

[0138] Tetradecanoic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. The reactor was then fully purged with nitrogen, and further heated to 180°C under a small nitrogen flow to dissolve the tetradecanoic acid and create a homogeneous flow. A mixture of m-phenylenediamine and p-phenylenediamine (70:30) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MXDA, Showa Denko Co., Ltd., PXDA) was slowly added dropwise over 160 minutes at a molar ratio of 1:1 with the tetradecanoic acid. During this time, the reaction system was kept at atmospheric pressure, and the internal temperature was continuously raised to 240°C. Water distilled off during the dropwise addition of p-phenylenediamine / m-phenylenediamine was removed from the system through the condenser and cooler. After the dropwise addition of p-phenylenediamine / m-phenylenediamine was completed, the liquid temperature was maintained at 240°C, and the reaction continued for 10 minutes. Then, the pressure inside the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for 20 minutes. During this period, the reaction temperature was continuously increased to 250°C. After the reaction was completed, a pressure of 0.3 MPa was applied to the reactor with nitrogen gas, and the polymer was taken out in the form of a wire from the nozzle at the bottom of the polymerization tank. After water cooling, it was cut into granules to obtain molten polymer granules.

[0139] <Synthesis Example 4: Synthesis of MXD12>

[0140] Dodecanoic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. After thorough nitrogen purging, the mixture was heated to 180°C until melted. While stirring the contents, m-phenylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., MXDA) was slowly added dropwise at a molar ratio of 1:1 with the dodecanoic acid, while the temperature was raised to 290°C. The liquid temperature was maintained at 290°C, and the reaction continued for 10 minutes. Then, the pressure inside the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for 20 minutes. During this period, the reaction temperature was continuously raised to 300°C. After the reaction was completed, a pressure of 0.3 MPa was applied to the reactor with nitrogen, and the polymer was extracted as a thread from a nozzle at the bottom of the polymerization tank. After water cooling, the polymer was granulated using a granulator to obtain the final product.

[0141] <Synthesis Example 5: Synthesis of PXD12>

[0142] Dodecanoic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. After thorough nitrogen purging, the mixture was heated to 180°C until melted. While stirring the contents, p-phenylenediamine (manufactured by Showa Denko Corporation, PXDA) was slowly added dropwise at a molar ratio of 1:1 to the dodecanoic acid, while the temperature was raised to 290°C. The liquid temperature was maintained at 290°C, and the reaction continued for 10 minutes. Then, the pressure in the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for 20 minutes. During this period, the reaction temperature was continuously raised to 300°C. After the reaction was completed, a pressure of 0.2 MPa was applied to the reactor with nitrogen, and the polymer was extracted as a thread from a nozzle at the bottom of the polymerization tank. After water cooling, the polymer was granulated using a granulator to obtain the final product.

[0143] <Synthesis Example 6: Synthesis of MP10(30)>

[0144] Sebacic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. After thorough nitrogen purging, the mixture was heated to 170°C until melted. While stirring the contents, a mixture of m-phenylenediamine and p-phenylenediamine (70:30) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MPXDA) was slowly added dropwise at a molar ratio of 1:1 to sebacic acid, while the temperature was raised to 240°C. After the addition was complete, the temperature was raised to 260°C and maintained for 20 minutes. Then, the pressure inside the reaction system was continuously reduced to 0.08 MPa, and the reaction continued. After the reaction was complete, a pressure of 0.2 MPa was applied to the reactor with nitrogen, and the polymer was extracted as a thread from a nozzle at the bottom of the polymerization tank. After water cooling, the polymer was granulated using a granulator to obtain the final product.

[0145] <Synthesis Example 7: Synthesis of PXD10>

[0146] Sebacic acid was added to a jacketed reactor equipped with a stirrer, condenser, cooler, thermometer, dropping tank, and nitrogen inlet pipe. After thorough nitrogen purging, the mixture was heated to 170°C until melted. While stirring the contents, p-phenylenediamine (manufactured by Showa Denko Corporation, PXDA) was slowly added dropwise at a molar ratio of 1:1 to sebacic acid, while the temperature was raised to 240°C. After the addition was complete, the temperature was increased to 260°C and maintained for 20 minutes. Then, the pressure inside the reaction system was continuously reduced to 0.08 MPa, and the reaction continued. After the reaction was complete, a pressure of 0.2 MPa was applied to the reactor with nitrogen, and the polymer was extracted as a thread from a nozzle at the bottom of the polymerization tank. After water cooling, the polymer was granulated using a granulator to obtain the final product.

[0147] Melting point of polyamide resin

[0148] Unless otherwise specified, the melting point (Tm) of polyamide resins shall be determined by differential scanning calorimetry (DSC) based on ISO 11357.

[0149] Specifically, using a differential scanning calorimeter (DSC), the resin is placed in the DSC measuring dish and pretreated under a nitrogen atmosphere by heating at a rate of 10°C / min to a temperature exceeding the melting point, followed by rapid cooling. The measurement conditions are as follows: heating rate of 10°C / min, held at 280°C for 5 minutes, then cooling at a rate of -5°C / min until reaching 100°C, to determine the melting point (Tm).

[0150] As a differential scanning calorimeter, the "DSC-60" manufactured by Shimadzu Corporation was used.

[0151] Table 1 lists the melting points of the polyamide resins used in each example and comparative example.

[0152] Manufacturing of Continuous Thermoplastic Resin Fibers

[0153] The thermoplastic resin shown in Table 1 was melt-extruded using a single-screw extruder with a screw diameter of 30 mm. The extrusion was performed through a 60-hole die to form a filament, which was simultaneously wound and stretched using rollers to wind 800 m of the continuous thermoplastic resin fiber bundle onto the winding body. The melting temperature was set to the melting point of the continuous thermoplastic resin + 15°C.

[0154] Example 1

[0155] <Manufacturing Method of Blended Fibers>

[0156] Fibers are drawn from a wound body of continuous thermoplastic resin fibers with a length of 1 m or more and a wound body of continuous carbon fibers with a length of 1 m or more, and are fibrillated by blowing while passing through a plurality of guides. While fibrillating, the continuous thermoplastic resin fibers and the continuous carbon fibers are made into a bundle, and further, blowing is applied while passing through a plurality of guides to promote homogenization.

[0157] The fineness of the obtained mixed fiber yarn is about 13000 dtex, the number of fibers is about 13500 f, the volume ratio of the continuous thermoplastic resin fibers to the continuous carbon fibers is 1:1, and the proportion of the continuous carbon fibers is 61% by mass.

[0158] <TFP performance>

[0159] Using a Tajima Industries Ltd. composite fiber sewing machine, TCWM-101, and using the obtained mixed fiber yarn, an ellipse with a transverse length of 3 cm and a longitudinal length of 10 cm is drawn on a film (thickness 50 μm) formed from MP10(30) obtained in Synthesis Example 6. The area of the deviation portion from the desired pattern is measured, and the ratio (unit: %) of the area to the area of the ellipse with a transverse length of 3 cm and a longitudinal length of 10 cm is calculated. Evaluation is carried out as follows.

[0160] A: The deviation from the desired pattern is 0.5% or less (for example, it is shifted inward within a range of 0.5% or less compared to the desired pattern, etc.)

[0161] B: The deviation from the desired pattern exceeds 0.5% and is 1% or less

[0162] C: The deviation from the desired pattern exceeds 1% and is 3% or less

[0163] D: The deviation from the desired pattern exceeds 3%

[0164] <Formability>

[0165] Using the obtained mixed fiber yarn, a twill fabric with a unit area mass of 300 GSM (grams per square meter, Gram per Square Meater) and a size of (a 70 cm × 70 cm square) is manufactured.

[0166] At room temperature, a 300 gsm twill fabric 5 is Figure 3 formed in a mold 4 having an inclination of 100° as shown in (A) of Figure 3 After 1 minute, as shown in (B) of , the distance X returned from the corner in the twill fabric 5 is measured. The measurement is carried out at 23°C.

[0167] A: 2 mm or less

[0168] B: Exceeds 2 mm and is 4 mm or less

[0169] C: More than 4mm

[0170] Examples 2-5, Comparative Example 1, Comparative Example 2

[0171] In Example 1, the changes are made as shown in Table 1, and otherwise the same applies.

[0172] [Table 1]

[0173]

[0174] In Table 1 above, the type of resin fiber indicates the type of thermoplastic resin that constitutes the continuous thermoplastic resin fiber.

[0175] In Table 1 above, the melting point of the resin indicates the melting point of the thermoplastic resin that constitutes the continuous thermoplastic resin fiber.

[0176] The resulting blended fibers all had an impregnation rate of less than 35% and a dispersion of more than 60%.

[0177] As can be seen from the above results, the blended fibers of the present invention have such excellent softness that they can be processed into more precise TFP (Examples 1-5). Furthermore, their shapeability is also excellent.

[0178] In contrast, although the TFP properties and shape properties of the comparative example blended fibers are excellent, they are not as good as the blended fibers of the present invention (Comparative Example 1 and Comparative Example 2).

[0179] Explanation of reference numerals in the attached figures

[0180] 1. Blended fibers

[0181] 2 Conformal yarn

[0182] 3. Desired Pattern

[0183] 4. Mold

[0184] 5. Twill fabric

Claims

1. A blended filament comprising continuous thermoplastic resin fibers and continuous reinforcing fibers, The continuous thermoplastic resin fiber comprises polyamide resin. The polyamide resin comprises diamine units and dicarboxylic acid units. More than 70 mol% of the diamine unit is derived from phenylenediamine. More than 70 mol% of the dicarboxylic acid units are derived from α,ω-linear aliphatic dicarboxylic acids with 11 to 20 carbon atoms.

2. The blended fiber according to claim 1, wherein, More than 70 mol% of the dicarboxylic acid unit is derived from dodecanoic acid and / or tetradecanoic acid.

3. The blended fiber according to claim 1, wherein, More than 70 mol% of the dicarboxylic acid unit is derived from dodecanoic acid.

4. The blended fiber according to any one of claims 1 to 3, wherein, 20-100 mol% of the diamine unit is derived from m-phenylenediamine, and 80-0 mol% is derived from p-phenylenediamine, wherein the total does not exceed 100 mol%.

5. The blended fiber according to claim 1, wherein, More than 70 mol% of the dicarboxylic acid unit is derived from dodecanoic acid and / or tetradecanoic acid. 20-100 mol% of the diamine unit is derived from m-phenylenediamine, and 80-0 mol% is derived from p-phenylenediamine, wherein the total does not exceed 100 mol%.

6. The blended fiber according to any one of claims 1 to 5, wherein, The continuous reinforcing fiber comprises at least one selected from the group consisting of carbon fiber, glass fiber and aramid fiber.

7. The blended fiber according to any one of claims 1 to 6, wherein, The number-average fiber length of the continuous reinforcing fiber exceeds 10 mm.

8. The blended fiber according to any one of claims 1 to 7, wherein, The continuous thermoplastic resin fiber is an unstretched fiber.

9. The blended fiber according to any one of claims 1 to 8, used for customized fiber laying processing.

10. A fabric formed from the blended filaments according to any one of claims 1 to 9.

11. A method for manufacturing a molded article, comprising heating the blended filaments according to any one of claims 1 to 9.

12. A method for manufacturing a molded article, comprising performing a customized fiber laying process on the blended filaments according to any one of claims 1 to 9.

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