Graphene fiber with core-shell structure and oral care product comprising graphene fiber

Abstract

The utility model provides a graphene fiber with a core-shell structure. The graphene fiber with the core-shell structure comprises a core part and a shell part, wherein the core part is composed of polymer fibers, and the shell part is composed of a graphene-polymer fiber composite material and surrounds the core part. According to the present invention, the fiber has the structure, such that the fiber has the good physical property such as rebound resilience under the condition of the antibacterial property brought by the graphene, or has the good sharpened filament tip molding;

Description

Technical Field

[0001] The present application relates to the field of fibers, and more specifically to a core-shell structured graphene fiber and an oral care product comprising the same. Background Art

[0002] Graphene is a two-dimensional carbon material composed of a layer of carbon atoms periodically and tightly stacked in a benzene ring structure (i.e., a hexagonal honeycomb structure). Graphene can inactivate bacteria through various means such as physical cutting, oxidative stress, and interference with lipid molecules, and has a highly effective antibacterial effect.

[0003] In the prior art, graphene is added as an additive to fiber slices for co-spinning to obtain composite fibers containing graphene with antibacterial properties. Graphene is distributed inside and outside the fiber. Graphene distributed on the outside of the fiber can act on bacteria and make them inactive, thus making the fiber antibacterial.

[0004] However, the graphene distributed inside the fiber cannot come into contact with bacteria and cannot play an antibacterial role; therefore, more graphene needs to be added to make the fiber have a certain antibacterial property, and its antibacterial property is still unstable. In addition, as the amount of graphene added increases, the physical properties of the fiber, such as resilience, will decrease, resulting in a decrease in the overall performance of the fiber.

[0005] The sharpened wire is formed by hydrolyzing the polyester fiber material with a strong base (such as sodium hydroxide) to form a tip (sharpened). However, when such a fiber is used as a sharpened wire, graphene will also affect the tip formation of the sharpened wire.

[0006] new content

[0007] In order to make the fiber have good physical properties in addition to antibacterial properties, especially resilience (single filament recovery rate), or also have good sharpened filament tip molding, the fiber of the present application having the following structure is provided.

[0008] The present application provides a core-shell structured graphene fiber, comprising:

[0009] a core composed of polymer fibers; and

[0010] The shell part is composed of a graphene-polymer fiber composite material and surrounds the core part.

[0011] The fiber of the present application has the above-mentioned structure, so that in addition to having the antibacterial properties brought by graphene, it also has good physical properties, especially resilience (single-filament recovery rate), or also has good sharpened wire tip molding.

[0012] In some embodiments, the diameter of the core is 40% to 90% of the diameter of the shell.

[0013] In some embodiments, the cross-sectional area of ​​the shell is 20% to 90% of the cross-sectional area of ​​the fiber.

[0014] In some embodiments, the core portion includes a protrusion protruding from the shell portion in an extending direction of the fiber.

[0015] In some embodiments, the length of the protrusion in the extension direction is at least 5% of the length of the core in the extension direction.

[0016] In some embodiments, the fiber includes a tip portion having a cross-sectional area perpendicular to the extending direction of the fiber that decreases in the extending direction of the fiber.

[0017] In some embodiments, the length of the tip portion in the extension direction is at least 5% of the length of the fiber in the extension direction.

[0018] In some embodiments, the diameter of the tip portion at a distance of 0.01 mm from one end thereof is less than 0.04 mm.

[0019] In some embodiments, the diameter of the tip portion at a distance of 0.5 mm from one end thereof is less than 0.08 mm.

[0020] In some embodiments, the fiber has a length of 10 mm to 35.0 mm.

[0021] In some embodiments, the fiber has a diameter of 0.075 mm to 0.25 mm.

[0022] In some embodiments, the cross section of the fiber perpendicular to its extension direction is circular, elliptical, convex polygonal, or concave polygonal.

[0023] In one aspect, the present application provides an oral care product, characterized in that it includes the core-shell structured graphene fiber of the present application.

[0024] In some embodiments, the oral care product is a toothbrush. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] By describing the exemplary embodiments in detail with reference to the accompanying drawings, the features will become apparent to those skilled in the art. However, the various technical features in the accompanying drawings are not drawn to scale. For the purpose of clearly illustrating the present application, the size of each feature in the accompanying drawings may be arbitrarily enlarged or reduced. The size of each element or its proportional relationship in the accompanying drawings is not intended to limit the size of each element or its proportional relationship in the present application.

[0026] Figure 1 This is a schematic diagram of a partial structure of a fiber in some embodiments of the present application.

[0027] Figure 2 This is a schematic cross-sectional view of a fiber along a cross section perpendicular to its extending direction (ie, axial direction) in some embodiments of the present application.

[0028] Figure 3 Schematic diagram of a cross-section of a fiber along a cross section perpendicular to its extending direction in some other embodiments of the present application.

[0029] Figure 4 The ends of the fibers in some embodiments of the present application are shown.

[0030] Figure 5 The ends of fibers in other embodiments of the present application are shown.

[0031] Figure 6 An oral care product of the present application is shown, including the fiber of the present application.

[0032] The following are the descriptions of the reference numerals:

[0033] 100: fiber; 101: tip; 110: core; 111: protrusion; 112: radial protrusion; 120: shell; 200: toothbrush; 210: toothbrush body; 300: dental floss; z: extension direction (axial direction); ρ: radial direction; Circumferential direction; D1, D2: diameter; L, L′: length. DETAILED DESCRIPTION

[0034] In order to further explain the technical means and effects adopted by the present application to achieve the predetermined purpose, the specific implementation methods, structures, features and effects of the present application are described in detail below in combination with the accompanying drawings and embodiments.

[0035] The following will describe specific embodiments or implementations of the elements and their structural relationships to simplify the content of this application, and use specific language to describe the embodiments or implementations of the present application as exemplified in the accompanying drawings, so that those skilled in the art can implement the different features of the technical solutions of this application. However, it should be understood that these embodiments are merely exemplary and are not intended to limit the scope of this application. For those skilled in the art, any changes or modifications to the described embodiments and any further application of the principles described in this application can be regarded as generally common situations.

[0036] Terms and Definitions

[0037] The content of this application repeats the reference numerals in each embodiment. This repetition is for the purpose of simplicity and clarity, and is not intended to limit the relationship between the elements and their structural relationships of the various embodiments of this application. Even if the same reference numerals are shared, it does not necessarily mean that the features of one embodiment must be used in another embodiment.

[0038] For ease of description, spatially relative terms (such as "lower", "below", "below", "lower", "upper", "above", "above", "upper" or similar terms) may be used herein to describe the relationship between one element or feature and another element (or multiple elements) or feature (or multiple features) shown in each figure. In addition to the directions depicted in each figure, such spatially relative terms should be deemed to include different orientations of the device in use or operation. The technical solutions of the present application can be oriented in other ways (rotated 90 degrees, 180 degrees, mirrored, etc.) and the spatially relative terms used herein can be interpreted similarly.

[0039] As used herein, a cylindrical coordinate system is used to describe the spatial relativity of the structure of the fiber of the present application. The term "axial direction" can be understood in its usual sense in the art and means the direction in which the fiber of the present application extends, but is not intended to limit the fiber of the present application to being hard and only extending in one direction. The fiber of the present application, depending on its material, should have a certain plasticity and bendability. The terms "radial direction" and "circumferential direction" can be understood in their usual sense in the art.

[0040] As used herein, descriptions such as "forming a first feature 'above' or 'on' a second feature" may include an embodiment in which the first feature and the second feature are formed in direct contact, and may also include an embodiment in which an additional feature may be formed between the first feature and the second feature so that the first feature and the second feature may not be in direct contact. Unless otherwise specified, it should be deemed that the present application discloses an embodiment in which the first feature and the second feature are formed in direct contact and an embodiment in which the first feature and the second feature are not in direct contact, respectively.

[0041] As used herein, singular terms refer to one or more than one. For example, "element" or "an element" refers to one element or more than one element. As used herein, the term "plurality" refers to at least two.

[0042] As used herein, the term "about" refers to approximation, in the range of about or near. When the term "about" is used in conjunction with a numerical range, it modifies the range by expanding the limit above or below the provided numerical value. In general, the term "about" is used herein to make the numerical value change 10% above and below the provided value. On the one hand, the term "about" refers to adding or subtracting 20% ​​of the numerical value of the number modified by it. For example, "about 50%" refers to within the range of 45%-55%. The numerical ranges mentioned herein by endpoints include all integers and fractions contained in the range (e.g., "1 to 5" includes 1, 1.5, 2, 2.75, 3, 3.90, 4 and 5). It should also be understood that all integers and fractions thereof are considered to be modified by the term "about".

[0043] As used herein, the term "comprising", "including", or "containing", as a non-exclusive or open term, is intended to indicate that a combination (e.g., a device, a composition, a method, etc.) includes the listed elements (e.g., each unit of the device, each component of the composition, the substantial steps of the method, etc.), but does not exclude other elements. As used herein, the term "substantially consisting of..." when used to define compositions and methods means excluding other elements that have any substantial impact on the combination of the stated purpose, but does not exclude other elements that do not substantially affect the basic and novel features of the present application. As used herein, the term "consisting of..." refers to excluding a combination of other elements (units, components, substantial steps, etc.), but unless otherwise specified, it is not intended to exclude trace amounts of unavoidable impurities. The embodiments defined by each of these connecting terms are within the scope of the present application. As a specific embodiment thereof, the technical solution disclosed including the terms "comprising", "including", or "containing" should also be deemed to simultaneously disclose the corresponding technical solutions including the terms "substantially consisting of..." and "consisting of...".

[0044] As used herein, the term "and / or" refers to and encompasses any and all possible combinations of one or more associated listed items. When used in a list of two or more items, the term "and / or" means that any one of the listed items may be included alone, or may include any combination of two or more listed items. For example, if a group, combination, or composition, etc., is described as including (or containing) components A, B, C, and / or D, the composition may include A alone; B alone; C alone; D alone; a combination of A and B; a combination of A and C; a combination of A and D; a combination of B and C; a combination of B and D; a combination of C and D; a combination of A, B and C; a combination of A, B and D; a combination of A, C and D; a combination of B, C and D; or a combination of A, B, C, and D.

[0045] If not otherwise defined and not causing contextual conflict, the content ratio used herein shall be preferentially regarded as weight ratio, and the content percentage shall be preferentially regarded as weight percentage (wt %).

[0046] As used herein, the term "core-shell" or "core-sheath" means that in the fiber of the present application, at least a portion of the core in its extension direction, i.e., the axial direction (e.g., at least 50%, in particular, at least 60%, 70%, 75%, 80%, 85%, 90% or 95%, more particularly 100%) is surrounded by the shell (sheath). As used herein, the term "surrounding" means that the shell (sheath) is formed on at least a portion of the core in the radial direction (e.g., at least 50%, in particular, at least 60%, 70%, 75%, 80%, 85%, 90% or 95%, more particularly 100%), and the core portion on which the shell (sheath) is formed is covered by the shell without being exposed. As used herein, the terms "shell" and "sheath" should be understood the same and can be interchangeable when used to describe the fiber of the present application.

[0047] Implementation

[0048] Fiber (brush wire)

[0049] Figure 1 A schematic diagram of a partial structure of a fiber 100 in some embodiments of the present application; Figure 2 This is a cross-sectional view of the fiber 100 along the section AA perpendicular to the extension direction z (ie, the axial direction) thereof in some embodiments of the present application.

[0050] like Figure 2 As shown, the fiber 100 may include a core 110 and a shell 120 surrounding the core 110 (formed (covered) on at least a portion of the core 110 in the radial direction, for example, at least 50%, particularly at least 60%, 70%, 75%, 80%, 85%, 90% or 95%, more particularly 100%). In some embodiments, the fiber 100 is composed of the core 110 and the shell 120. In some embodiments, the fiber 100 may include a core 110 composed of a polymer fiber, and a shell 120 composed of a graphene polymer fiber and surrounding the core 110.

[0051] In some embodiments, the surrounding is contact surrounding or non-contact surrounding, in particular contact surrounding. In some embodiments, the shell 120 contact-surrounds the core 110, that is, the shell 120 is directly formed (contact-covered) on at least a portion of the core 110 in the radial direction.

[0052] In some embodiments, the core 110 may have a further core-shell structure.

[0053] In some embodiments, the core 110 may include polymer fibers. In some embodiments, the core 110 may include or consist of polyolefin fibers, polyfluoroolefin fibers, polyester fibers, or polyamide fibers. In some embodiments, the core 110 may include or consist of polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), nylon (such as nylon N6, nylon N66, nylon 610, nylon 612, nylon 1010, etc.), or a combination thereof.

[0054] In some embodiments, the core 110 may be composed of a single polyolefin fiber, a polyfluoroolefin fiber, a polyester fiber, or a polyamide fiber, or a combination of multiple polyolefin fibers, polyfluoroolefin fibers, polyester fibers, or polyamide fibers.

[0055] In some embodiments, the shell 120 may include polymer fibers. In some embodiments, the shell 120 may include polyolefin fibers, polyfluoroolefin fibers, polyester fibers, or polyamide fibers. In some embodiments, the shell 120 may include polyethylene, polypropylene, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, nylon (such as nylon N6, nylon N66, nylon 610, nylon 612, nylon 1010, etc.), or a combination thereof, but is not limited thereto.

[0056] In some embodiments, the shell 120 may be composed of graphene polyolefin fibers, graphene polyfluoroolefin fibers, graphene polyester fibers, or graphene polyamide fibers.

[0057] Graphene

[0058] In some embodiments, the core 110 and / or the shell 120 may include graphene. In some embodiments, the weight ratio of graphene in the shell 120 is greater than the weight ratio of graphene in the core 110. In some embodiments, the weight ratio of graphene in the shell 120 may be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 2, 2.5, 3, 4, 5, 6, 8, or 10 times the weight ratio of graphene in the core 110. In some embodiments, the weight ratio of graphene in the core 110 may be 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 times or less of the weight ratio of graphene in the shell 120.

[0059] In some embodiments, the core 110 may include 0.6 wt % or less, specifically 0.5 wt %, 0.4 wt %, 0.3 wt %, 0.2 wt %, or 0.1 wt % or less of graphene.

[0060] In some embodiments, core 110 may not include graphene.

[0061] In some embodiments, the shell 120 may include more than 0.4wt%, particularly 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3.0wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, or more than 4.0wt% of graphene. In some embodiments, the shell 120 may include 0.4-4.0wt%, specifically 0.6-4.0wt%, 0.8-4.0wt%, 0.4-3.0wt%, 0.6-3.0wt%, 0.8-3.0wt%, 0.4-2.4wt%, 0.6-2.4wt%, 0.8-2.4wt%, 0.4-1.6wt%, 0.6-1.6wt%, or 0.8-1.6wt% graphene.

[0062] In some embodiments, the fiber 100 may include more than 0.2 wt%, particularly 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, or 3.0 wt% or more of graphene. In some embodiments, the fiber 100 may include less than 3.0 wt%, particularly 2.9 wt%, 2.8 wt%, 2.7 wt%, 2.6 wt%, 2.5 wt%, 2.4 wt%, 2.3 wt%, 2.2 wt%, 2.1 wt%, 1.0 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1.0 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.45 wt%, 0.4 wt%, 0.35 wt%, 0.3 wt%, 0.25 wt%, or less than 0.2 wt% of graphene. In some embodiments, the fiber 100 may include 0.2-2.0 wt%, particularly 0.3-2.0 wt%, 0.4-2.0 wt%, 0.5-2.0 wt%, 0.2-1.7 wt%, 0.3-1.7 wt%, 0.4-1.7 wt%, 0.5-1.7 wt%, 0.2-1.3 wt%, 0.3-1.3 wt%, 0.4-1.3 wt%, 0.5-1.3 wt%, 0.2-0.8 wt%, 0.3-0.8 wt%, 0.4-0.8 wt%, or 0.5-0.8 wt% graphene.

[0063] In some embodiments, the graphene may be graphene oxide, reduced graphene, or a combination thereof.

[0064] In some embodiments, the core 110 and / or the shell 120, in particular the shell 120, may further include an antimicrobial agent. In some embodiments, the antimicrobial agent may be, for example, silver ions, zinc ions, or activated carbon.

[0065] Fiber proportions, shapes, and sizes

[0066] Figure 3 This is a cross-sectional view of the fiber 100 along a cross section perpendicular to the extending direction z thereof in some embodiments of the present application.

[0067] Please refer to Figure 3 (a)–(b). Figure 3 In (a), the cross-sectional area of ​​the core 110a occupies a larger proportion of the cross-sectional area of ​​the entire fiber 100a. In other words, the cross-sectional area of ​​the shell 120a occupies a smaller proportion of the cross-sectional area of ​​the entire fiber 100a. On the contrary, Figure 3 In (b), the cross-sectional area of ​​the core 110b occupies a smaller proportion of the cross-sectional area of ​​the entire fiber 100b. In other words, the cross-sectional area of ​​the shell 120b occupies a larger proportion of the cross-sectional area of ​​the entire fiber 100b. By adjusting the cross-sectional area ratio of the core 110 / shell 120 to the cross-sectional area of ​​the entire fiber 100, the weight percentage of the core 110 / shell 120 in the entire fiber 100 can be adjusted, and the weight percentage of the components of the core 110 / shell 120 in the entire fiber can be further adjusted.

[0068] In some embodiments, in a radial direction p perpendicular to the extension direction z, the diameter of the core 110 may be more than 10% of the diameter of the shell 120 (or the diameter of the fiber 100), in particular 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% or more. In some embodiments, in a radial direction p perpendicular to the extension direction z, the diameter of the core 110 may be less than 90% of the diameter of the shell 120 (or the diameter of the fiber 100), in particular 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, or 10% or less. In some embodiments, in the radial direction ρ perpendicular to the extension direction z, the diameter of the core 110 may be 40% to 90% of the diameter of the shell 120 (or the diameter of the fiber 100), in particular 45% to 90%, 50% to 90%, 55% to 90%, 40% to 80%, 45% to 80%, 50% to 80%, 55% to 80%, 40% to 75%, 45% to 75%, 50% to 75%, or 55% to 75%.

[0069] In some embodiments, in the radial direction ρ perpendicular to the extension direction z, the cross-sectional area of ​​the shell 120 may be more than 10% of the cross-sectional area of ​​the fiber 100 (or in particular the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), in particular 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% or more. In some embodiments, in the radial direction ρ perpendicular to the extension direction z, the cross-sectional area of ​​the shell 120 may be less than 90% of the cross-sectional area of ​​the fiber 100 (or in particular the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), in particular 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, or 10% or less. In some embodiments, in the radial direction ρ perpendicular to the extension direction z, the cross-sectional area of ​​the shell 120 may be 20% to 90% of the cross-sectional area of ​​the fiber 100 (or in particular the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), in particular 30% to 90%, 35% to 90%, 40% to 90%, 20% to 80%, 30% to 80%, 35% to 80%, 40% to 80%, 20% to 75%, 30% to 75%, 35% to 75%, or 40% to 75%.

[0070] In some embodiments, the weight of the shell 120 may be more than 20% of the weight of the fiber 100 (or in particular the sum of the weight of the shell 120 and the weight of the core 110), in particular 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% or more. In some embodiments, the weight of the shell 120 may be less than 90% of the weight of the fiber 100 (or in particular the sum of the weight of the shell 120 and the weight of the core 110), in particular 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, or 20% or less. In some embodiments, the weight of the shell 120 may be 20% to 90%, particularly 30% to 90%, 35% to 90%, 40% to 90%, 20% to 80%, 30% to 80%, 35% to 80%, 40% to 80%, 20% to 75%, 30% to 75%, 35% to 75%, or 40% to 75% of the weight of the fiber 100 (or particularly the sum of the weight of the shell 120 and the weight of the core 110).

[0071] In some embodiments, the diameter of the core 110 may be more than 50% of the diameter of the shell 120 (or the diameter of the fiber 100), and the shell 120 may include more than 0.8wt% of graphene. In some embodiments, the diameter of the core 110 may be more than 50% of the diameter of the shell 120 (or the diameter of the fiber 100), and the fiber 100 may include more than 0.6wt% of graphene. In some embodiments, the diameter of the core 110 may be more than 55% of the diameter of the shell 120 (or the diameter of the fiber 100), and the shell 120 may include more than 2.4wt% of graphene. In some embodiments, the diameter of the core 110 may be more than 55% of the diameter of the shell 120 (or the diameter of the fiber 100), and the shell 100 may include more than 1.6wt% of graphene.

[0072] In some embodiments, the cross-sectional area of ​​the shell 120 may be less than 75% of the cross-sectional area of ​​the fiber 100 (or in particular, the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), and the shell 120 may include more than 0.8 wt% of graphene. In some embodiments, the cross-sectional area of ​​the shell 120 may be less than 75% of the cross-sectional area of ​​the fiber 100 (or in particular, the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), and the fiber 100 may include more than 0.6 wt% of graphene. In some embodiments, the cross-sectional area of ​​the shell 120 may be less than 70% of the cross-sectional area of ​​the fiber 100 (or in particular, the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), and the shell 120 may include more than 2.4 wt% of graphene. In some embodiments, the cross-sectional area of ​​shell 120 may be less than 70% of the cross-sectional area of ​​fiber 100 (or in particular the sum of the cross-sectional area of ​​shell 120 and the cross-sectional area of ​​core 110), and shell 100 may include more than 1.6 wt % graphene.

[0073] In some embodiments, the diameter of the core 110 may be 45% to 90%, in particular 50% to 90%, of the diameter of the shell 120 (or the diameter of the fiber 100), and the shell 120 may include 0.8wt% to 4.0wt% graphene; in particular, the percentage of the diameter of the core 110 relative to the diameter of the shell 120 minus 40% may be more than about 6.25 times the weight percentage of the graphene in the shell 120.

[0074] In some embodiments, the cross-sectional area of ​​the shell 120 may be 20% to 80%, in particular 20% to 75%, of the cross-sectional area of ​​the fiber 100 (or in particular the sum of the cross-sectional area of ​​the shell 120 and the cross-sectional area of ​​the core 110), and the shell 120 may include 0.8 wt % to 4.0 wt % of graphene; in particular, 85% minus the percentage of the cross-sectional area of ​​the shell 120 relative to the cross-sectional area of ​​the fiber 100 may be more than about 6.25 times the weight percentage of the graphene in the shell 120.

[0075] In some embodiments, the cross-section of the fiber 100 in the vertical extension direction z may be circular or non-circular, for example, circular, elliptical, convex polygonal (for example, triangle, quadrilateral, pentagon, hexagon, heptagon, octagon, etc.) or concave polygonal (for example, star-shaped, such as a five-pointed star, a six-pointed star, a seven-pointed star, or an eight-pointed star, etc.).

[0076] Please refer to Figure 3 (a)-(d) show the shape of the fiber 100 or a portion thereof (i.e., the appearance shape of the shell 120) or the shape of the core 110 in some embodiments of the present application. Figure 3 As shown in (a)–(d), Figure 3 The fiber 100 (shell portion 120) in (a) and (b) may include a cylinder (i.e., its cross section is circular), Figure 3 The fiber 100 (shell portion 120) in (c) may include a pentagonal column (ie, its cross section is a pentagon), Figure 3 The fiber 100 (shell 120) in (d) may include a triangular prism (i.e., its cross section is triangular). However, the present application is not limited thereto, and the shape of the fiber 100 (i.e., the appearance shape of the shell 120) or the shape of the core 110 may be any shape feasible in the art.

[0077] In some embodiments, the length L of the fiber 100 may be 10 mm to 34 mm, particularly 15 mm to 20 mm, more particularly 16 mm to 17 mm, or particularly 10 mm to 15 mm, more particularly 11 mm to 13 mm, or particularly 20 mm to 34 mm, more particularly 26 mm to 30 mm.

[0078] In some embodiments, the diameter (e.g., the thickest diameter) D of the fiber 100 may be 0.50 mm or less, particularly 0.35 mm or less, more particularly 0.30 mm, 0.25 mm, 0.22 mm, 0.20 mm, 0.19 mm, 0.18 mm, 0.17 mm, 0.16 mm, 0.15 mm, 0.14 mm, 0.13 mm, 0.12 mm, 0.11 mm, 0.10 mm, 0.09 mm, 0.08 mm, 0.075 mm, 0.07 mm, 0.06 mm, 0.05 mm, 0.04 mm, 0.06 mm, 0.08 mm, 0.09 mm, 0.08 ... .03mm, or 0.02mm or less; and / or may be 0.01mm or more, in particular 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.075mm, 0.08mm, 0.09mm, 0.10mm, 0.11mm, 0.12mm, 0.13mm, 0.14mm, 0.15mm, 0.16mm, 0.17mm, 0.18mm, 0.19mm, 0.20mm, 0.22mm, 0.25mm, 0.30mm, or 0.35mm or more.

[0079] In some embodiments, the diameter (e.g., the diameter at the thickest point) D of the fiber 100 may be 0.075 mm to 0.25 mm, particularly 0.10 mm to 0.18 mm, more particularly 0.11 mm to 0.14 mm, more particularly 0.12 mm to 0.13 mm, or particularly 0.14 mm to 0.16 mm, more particularly 0.145 mm to 0.155 mm, or particularly 0.16 mm to 0.18 mm, more particularly 0.17 mm to 0.18 mm.

[0080] Fiber end

[0081] Please refer to Figure 4 , shows the end of the fiber 100 in some embodiments of the present application. In some embodiments, the core 110 of the fiber 100 (for example, a sharpened wire) may include a protrusion 111, which protrudes from the shell 120 in the extension direction z (i.e., the axial direction). That is, the protrusion 111 belongs to the portion of the core 110 that is not covered by the shell 120 in the radial direction. In some embodiments, the length of the protrusion 111 in the extension direction z may be at least 5%, in particular at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% of the length of the core 110 in the extension direction z. In some embodiments, the shape of the protrusion 111 may be cylindrical, conical, truncated cone, or a combination thereof. In some embodiments, the shape of the protrusion 111 may be cylindrical, conical, truncated cone, or a combination thereof.

[0082] In some embodiments, the fiber 100 (e.g., a sharpened wire) may include a tip portion 101. In some embodiments, the tip portion 101 has a cross-sectional area perpendicular to the extension direction z that decreases in the extension direction z. In some embodiments, the length of the tip portion 101 in the extension direction z may be at least 5%, in particular at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% of the length of the fiber 100 in the extension direction z. In some embodiments, the shape of the tip portion 101 may be conical, truncated cone, or a combination thereof. In some embodiments, the shape of the tip portion 101 may be a cone, a truncated cone, or a combination thereof.

[0083] In some embodiments, tip portion 101 may include protrusion 111; in other words, protrusion 111 constitutes at least a portion of tip portion 101. In some embodiments, protrusion 111 may include tip portion 101; in other words, tip portion 101 constitutes at least a portion of protrusion 111.

[0084] In some embodiments, Figure 4 As shown, the tip portion 101 may include a protrusion 111; and the tip portion 101 may include a portion of the shell 120 and a portion of the core 110, and in particular may include a portion of the shell 120, a portion of the core 110 that does not belong to the protrusion 111, and (the entire) protrusion 111.

[0085] Please refer to Figure 5 , showing the end of the fiber 100 in some embodiments of the present application.

[0086] In some embodiments, Figure 5 As shown in (a), the protrusion 111 may include the tip portion 101, and in particular, the protrusion 111 may include the (entire) tip portion 101 and a portion of the core 110 that does not belong to the tip portion 101. The tip portion 101 may be in the shape of a cone, a truncated cone, or a combination thereof, in particular, in the shape of a cone, a truncated cone, or a combination thereof.

[0087] In some embodiments, Figure 5 As shown in (b), the protrusion 111 may be columnar, in particular cylindrical. In some embodiments, the protrusion 111 may not have the tip 101.

[0088] In some embodiments, Figure 5As shown in (c), the protrusion 111 may be composed of the tip portion 101, and / or the tip portion 101 may be composed of the protrusion 111. In some embodiments, the core 110 may include a radial protrusion 112, wherein the cross-sectional area of ​​the core 110 perpendicular to the extension direction z of the radial protrusion 112 is greater than the cross-sectional area of ​​the core 110 outside the protrusion 111 perpendicular to the extension direction z. In some embodiments, the core 110 and the shell 120 are in contact with each other in the extension direction z.

[0089] In some embodiments, Figure 5 As shown in (d), the fiber 100 may not include the protrusion 111, and / or the fiber 100 may not include the tip 101. In some embodiments, one end of the core 110 and the shell 120 in the extension direction z (for example, the end away from the toothbrush body 210) is flush with each other. In some embodiments, both ends of the core 110 and the shell 120 in the extension direction z are flush with each other.

[0090] In some embodiments, the core 110 does not protrude beyond the shell 120 in the extension direction z. In some embodiments, the shell 120 does not protrude beyond the core 110 in the extension direction z.

[0091] In some embodiments, the diameter of the fiber 100, especially the tip 101, at 0.01 mm from one end thereof is less than 0.04 mm. In some embodiments, the diameter of the fiber 100, especially the tip 101, at 0.5 mm from one end thereof is less than 0.08 mm.

[0092] Application and characteristics of fiber

[0093] In some embodiments, the fiber 100 is a brush filament, more particularly a toothbrush filament, and more particularly a toothbrush sharpened filament. In some embodiments, the fiber 100 is used in oral care products, particularly oral hygiene products, more particularly tooth cleaning products, and more particularly a toothbrush. In some embodiments, the fiber 100 is an oral care fiber, particularly an oral hygiene fiber, more particularly a tooth cleaning fiber, and more particularly a toothbrush filament, and especially a toothbrush sharpened filament. In some embodiments, an oral care product, particularly an oral hygiene product, more particularly a tooth cleaning product, and more particularly a toothbrush, is provided, comprising the fiber 100, and an optional oral care product body. In some embodiments, the fiber 100 is used in hygiene products, particularly oral hygiene products.

[0094] Please refer to Figure 6 , showing oral care products in some embodiments of the present application.

[0095] Figure 6(a) shows a toothbrush 200 in some embodiments of the present application. In some embodiments, the toothbrush 200 may include the fiber 100 of the present application as a filament. In some embodiments, more than 50% of the filaments in the toothbrush 200 are the fiber 100 of the present application. In some embodiments, the toothbrush 200 may also include a toothbrush body 210, wherein the fiber 100 is disposed on the toothbrush body 210. In some embodiments, the length L′ of the fiber 100 protruding from the toothbrush body 210 may be 10 mm to 15 mm, in particular 11 mm to 13 mm.

[0096] Figure 6 (b) shows a dental floss 300 in some embodiments of the present application. In some embodiments, the dental floss 300 may include the fiber 100 of the present application, or may be composed thereof.

[0097] In some embodiments, the toothbrush 200 includes sharpened wires disposed on the toothbrush body 210. In some embodiments, more than 50%, especially more than 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the sharpened wires in the toothbrush 200 may be the fibers 100 of the present application, and the diameter of the fiber 100 at 0.01 mm from one end thereof (especially the end away from the toothbrush body 210) may be less than 0.04 mm. In some embodiments, more than 50%, especially more than 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the sharpened wires in the toothbrush 200 may be the fibers 100 of the present application, and the diameter of the fiber 100 at 0.5 mm from one end thereof (especially the end away from the toothbrush body 210) may be less than 0.08 mm.

[0098] In some embodiments, the single fiber recovery rate of the fiber 100 detected according to the method of GB 19342-2013 is greater than 60%.

[0099] In some embodiments, the antibacterial rate of fiber 100 against Escherichia coli 8099 is 90% or more according to the method of GB / T 36391-2018. In some embodiments, the antibacterial rate of fiber 100 against Staphylococcus aureus ATCC 6538 is 90% or more according to the method of GB / T 36391-2018. In some embodiments, the antibacterial rate of fiber 100 against Candida albicans ATC 10231 is 90% or more according to the method of GB / T 36391-2018. In some embodiments, the antibacterial rate of fiber 100 against beta-hemolytic Streptococcus CMCC 32210 is 90% or more according to the method of GB / T 36391-2018. In some embodiments, the antibacterial rate of fiber 100 against Klebsiella pneumoniae ATCC 4352 is 90% or more according to the method of GB / T 36391-2018.

[0100] In some embodiments, the fiber having the structure of the present application has good physical properties, especially resilience (single-filament recovery rate), while having the antibacterial properties brought by graphene.

[0101] In some embodiments, fibers having the core-to-shell ratio and / or graphene addition amount of the present application, fibers having the structure of the present application, in addition to having the antibacterial properties brought by graphene, also have good physical properties, especially resilience (single filament recovery rate).

[0102] In some embodiments, the fiber having the structure of the present application has the antibacterial properties brought by graphene and also has good sharpened wire tip shaping.

[0103] In some embodiments, fibers having the core-to-shell ratio and / or graphene addition amount of the present application, fibers having the structure of the present application, in addition to having the antibacterial properties brought by graphene, also have good sharpened wire tip molding.

[0104] Example

[0105] In the following examples and comparative examples:

[0106] - The test of the single-filament recovery rate is carried out in accordance with the test method of 5.5.5 (single-filament bending recovery rate) in the Chinese national standard GB 19342-2013 "Toothbrush". The standard stipulates that the single-filament recovery rate ≥ 60% meets the requirements.

[0107] - The antibacterial performance test refers to the provisions of 5.3.1 (antibacterial performance) in the Chinese national standard GB / T 36391-2018 "Antibacterial Toothbrush", and is tested according to the method specified in Appendix B (Material Antibacterial Performance Test Method Oscillation Method) in the Chinese national standard GB / T 21510-2008 "Nano-inorganic Antibacterial Performance Test Method". The standard stipulates that for Escherichia coli, an antibacterial rate ≥ 90% meets the requirements; for Staphylococcus aureus, an antibacterial rate ≥ 90% meets the requirements.

[0108] -Detection of the end diameter of the sharpened wire: Observe the end of the sharpened wire under an electronic magnifying glass at 400-500 times, and the fibers with a diameter of ≤0.08mm at 0.5mm from the tip reach more than 90%, which meets the requirements of the following embodiments and comparative examples of this application. The Chinese national standard GB / T 36391-2018 "Antibacterial Toothbrush" stipulates that: Fibers with a diameter of ≤0.04mm at 0.01mm from the tip reach more than 70% and meet the requirements; Fibers with a diameter of ≤0.08mm at 0.5mm from the tip reach more than 90% and meet the requirements.

[0109] Comparative Example 1

[0110] Fiber preparation

[0111] 8 wt % of graphene is added to PBT raw material particles, mixed and granulated to obtain graphene masterbatch.

[0112] 5 wt % of graphene masterbatch was added to the PBT raw material particles, and the mixture was extruded and spun to obtain fibers with an actual added graphene content of 0.4 wt %, which is the fiber of Comparative Example 1.

[0113] The tip of the fiber of Comparative Example 1 was immersed in a sodium hydroxide aqueous solution with a concentration of 30% to 70% for 20 to 30 minutes to obtain the sharpened wire of Comparative Example 1.

[0114] Fiber test results

[0115] The detection showed that the percentage of the fibers with a diameter of ≤0.08 mm at a distance of 0.5 mm from the tip of the sharpened wire in comparative example 1 reached more than 90%, which met the requirements.

[0116] The single fiber recovery rate of the fiber of comparative example 1 was tested to be 66.56%, which meets the requirements of GB 19342-2013.

[0117] The antibacterial performance test results are shown in Tables 1A and 1B. Tables 1A and 1B show that the antibacterial rates of the fiber of Comparative Example 1 against Escherichia coli 8099 and Staphylococcus aureus ATCC 6538 are 33% and 41%, respectively, which do not meet the requirements of GB / T 36391-2018.

[0118] Table 1A Antibacterial rate test results of the fiber of comparative example 1 against Escherichia coli 8099

[0119]

[0120] Table 1B Test results of antibacterial rate of the fiber of comparative example 1 against Staphylococcus aureus ATCC 6538

[0121]

[0122]

[0123] Comparative Example 2

[0124] Fiber preparation

[0125] The graphene masterbatch was prepared using the same method as in Comparative Example 1.

[0126] 10 wt % of graphene masterbatch was added to the PBT raw material particles, mixed and extruded and spun to obtain fibers with an actual added graphene content of 0.8 wt %, which is the fiber of Comparative Example 2.

[0127] The Comparative Example 2 sharpened wire was prepared from the Comparative Example 2 fibers using the same method as that used to prepare the Comparative Example 1 sharpened wire from the Comparative Example 1 fibers.

[0128] Fiber test results

[0129] The test showed that the percentage of the fibers with a diameter of ≤0.08 mm at a distance of 0.5 mm from the tip of the sharpened wire in Comparative Example 2 did not reach more than 90%, which did not meet the requirements.

[0130] The single fiber recovery rate of the fiber of comparative example 2 was tested to be 57.56%, which did not meet the requirements of GB 19342-2013.

[0131] The antibacterial performance test results are shown in Tables 2A to 2E. Tables 2A to 2E show that the antibacterial rate of the fiber of Comparative Example 2 against Escherichia coli 8099 is 62%, and the antibacterial rate against Staphylococcus aureus ATCC 6538 is 99%, wherein the antibacterial rate against Staphylococcus aureus meets the requirements of GB / T 36391-2018; the antibacterial rate against Candida albicans ATC 10231 is 74%, the antibacterial rate against beta-hemolytic Streptococcus CMCC 32210 is 77%, and the antibacterial rate against Klebsiella pneumoniae ATCC 4352 is 36%.

[0132] Table 2A Antibacterial rate test results of the fiber of comparative example 2 against Escherichia coli 8099

[0133]

[0134] Table 2B Antibacterial rate test results of the fiber of comparative example 2 against Staphylococcus aureus ATCC 6538

[0135]

[0136] Table 2C Antibacterial rate test results of the fiber of comparative example 2 against Candida albicans ATCC 10231

[0137]

[0138]

[0139] Table 2D Antibacterial rate test results of the fiber of comparative example 2 against beta-hemolytic streptococcus CMCC 32210

[0140]

[0141] Table 2E Antibacterial rate test results of the fiber of comparative example 2 against Klebsiella pneumoniae ATCC 4352

[0142]

[0143] Comparative Example 3

[0144] Fiber preparation

[0145] The graphene masterbatch was prepared using the same method as in Comparative Example 1.

[0146] 15 wt % of graphene masterbatch was added to the PBT raw material particles, mixed and extruded and spun to obtain fibers with an actual graphene content of 1.2 wt %, which is the fiber of Comparative Example 3.

[0147] The Comparative Example 3 sharpened wire was prepared from the Comparative Example 3 fibers using the same method as that used to prepare the Comparative Example 1 sharpened wire from the Comparative Example 1 fibers.

[0148] Fiber test results

[0149] The test showed that the percentage of the fibers with a diameter of ≤0.08 mm at a distance of 0.5 mm from the tip of the sharpened wire in Comparative Example 3 did not reach more than 90%, which did not meet the requirements.

[0150] The single fiber recovery rate of the fiber of comparative example 3 was tested to be 53.78%, which did not meet the requirements of GB 19342-2013.

[0151] The antibacterial performance test results are shown in Tables 3A to 3E. Tables 3A to 3E show that the antibacterial rate of the fiber of Comparative Example 3 against Escherichia coli 8099 is 58%, and the antibacterial rate against Staphylococcus aureus ATCC 6538 is 99%, wherein the antibacterial rate against Staphylococcus aureus meets the requirements of GB / T 36391-2018; the antibacterial rate against Candida albicans ATC 10231 is 78%, the antibacterial rate against beta-hemolytic Streptococcus CMCC 32210 is 76%, and the antibacterial rate against Klebsiella pneumoniae ATCC 4352 is 40%.

[0152] Table 3A Antibacterial rate test results of the fiber of comparative example 3 against Escherichia coli 8099

[0153]

[0154] Table 3B Antibacterial rate test results of the fiber of comparative example 3 against Staphylococcus aureus ATCC 6538

[0155]

[0156]

[0157] Table 3C Antibacterial rate test results of the fiber of comparative example 3 against Candida albicans ATCC 10231

[0158]

[0159] Table 3D Antibacterial rate test results of the fiber of comparative example 3 against beta-hemolytic streptococcus CMCC 32210

[0160]

[0161] Table 3E Antibacterial rate test results of the fiber of comparative example 3 against Klebsiella pneumoniae ATCC 4352

[0162]

[0163] It can be seen that although 1.2 wt% of graphene is added in Comparative Example 3, the overall antibacterial rate of the fiber is not significantly improved compared to Comparative Example 2 in which 0.8 wt% of graphene is added.

[0164] Example 1

[0165] Fiber preparation

[0166] The graphene masterbatch was prepared using the same method as in Comparative Example 1.

[0167] 10 wt% of graphene masterbatch was added to the PBT raw material particles as the shell raw material; and the PBT raw material without graphene masterbatch was used as the core raw material. The shell raw material and the core raw material were extruded and spun through a double barrel extruder to obtain a core-shell structure fiber with a shell graphene content of 0.8 wt%, which is the fiber of Example 1.

[0168] The sharpened wire of Example 1 was prepared from the fibers of Example 1 using the same method as that used to prepare the sharpened wire of Comparative Example 1 from the fibers of Comparative Example 1.

[0169] Fiber test results

[0170] The fiber of Example 1 exhibits an obvious double-layer structure, which is composed of a core 110 and a shell 120, wherein the cross-sectional shape of the core 110 is close to a circle. Five fibers of Example 1 were selected, and the diameter D′ of the core 110 and the diameter D of the shell 120 (also the diameter of the fiber 100) were measured. Figure 2 The ratio D' / D of the core diameter D' and the shell diameter D was calculated. The results are shown in Table 4. It can be seen that the average value of the ratio of the core diameter / shell diameter of the fiber of Example 1 is 0.695.

[0171] Table 4 Measurement results of the core diameter and shell diameter of the fiber of Example 1

[0172] Serial number Core diameter D'(mm) Shell diameter D(mm) The ratio of the core diameter to the shell diameter is D' / D 1 0.1256 0.1800 0.698 2 0.1256 0.1868 0.672 3 0.1256 0.1800 0.698 4 0.1290 0.1834 0.703 5 0.1290 0.1834 0.703 average value 0.695

[0173] Based on this, the ratio of the core diameter to the shell diameter of Example 1, D′ / D, can be used to estimate the cross-sectional area of ​​the shell of the fiber of Example 1 as 1–(D′ / D) based on the circular cross-section of the fiber and the core of Example 1. 2 , and further estimated that the mass ratio of the shell of the fiber of Example 1 is also about 1-(D′ / D) 2 , the graphene content of the entire fiber of Example 1 is calculated to be approximately (0.8 wt% × (1 – (D′ / D) 2 ))≈0.41%.

[0174] After testing, the percentage of fibers with a diameter of ≤0.08 mm at a distance of 0.5 mm from the tip of the sharpened wire in Example 1 reached more than 90%, which met the requirements.

[0175] After testing, the single fiber recovery rate of the fiber of Example 1 is 64.34%, which meets the requirements of GB 19342-2013.

[0176] The antibacterial performance test results are shown in Tables 5A and 5B. Tables 5A and 5B show that the antibacterial rate of the fiber of Example 1 against Escherichia coli 8099 is 99%, and the antibacterial rate against Staphylococcus aureus ATCC 6538 is >99%, both of which meet the requirements of GB / T 36391-2018.

[0177] Table 5A Antibacterial rate test results of the fiber of Example 1 against Escherichia coli 8099

[0178]

[0179] Table 5B Test results of antibacterial rate of the fiber of Example 1 against Staphylococcus aureus ATCC 6538

[0180]

[0181] Example 2

[0182] Fiber preparation

[0183] The graphene masterbatch was prepared using the same method as in Comparative Example 1.

[0184] 20 wt% of graphene masterbatch was added to the PBT raw material particles as the shell raw material; and the PBT raw material without graphene masterbatch was used as the core raw material. Using the same method as that for preparing the fiber of Example 1 from the shell raw material and the core raw material of Example 1, a core-shell structure fiber with a shell graphene content of 1.6 wt% (the graphene content of the entire fiber is about 0.83%) was prepared from the shell raw material and the core raw material of Example 2, which is the fiber of Example 2.

[0185] The sharpened wire of Example 2 was prepared from the fibers of Example 2 using the same method as that used to prepare the sharpened wire of Comparative Example 1 from the fibers of Comparative Example 1.

[0186] Fiber test results

[0187] After testing, the percentage of fibers with a diameter of ≤0.08 mm at a distance of 0.5 mm from the tip of the sharpened wire in Example 2 reached more than 90%, meeting the requirements.

[0188] After testing, the single fiber recovery rate of the fiber of Example 2 is 61.56%, which meets the requirements of GB 19342-2013.

[0189] The antibacterial performance test results are shown in Tables 6A and 6B. Tables 6A and 6B show that the antibacterial rate of the fiber of Example 2 against Escherichia coli 8099 is >99%, and the antibacterial rate against Staphylococcus aureus ATCC 6538 is >99%, both of which meet the requirements of GB / T 36391-2018.

[0190] Table 6A Antibacterial rate test results of the fiber of Example 2 against Escherichia coli 8099

[0191]

[0192] Table 6B Antibacterial rate test results of the fiber of Example 2 against Staphylococcus aureus ATCC 6538

[0193]

[0194] Example 3

[0195] Fiber preparation

[0196] The graphene masterbatch was prepared using the same method as in Comparative Example 1.

[0197] 5wt% of graphene masterbatch was added to the PBT raw material particles as the shell raw material; and the PBT raw material without graphene masterbatch was used as the core raw material. Using the same method as that for preparing the fiber of Example 1 from the shell raw material and the core raw material of Example 1, a core-shell structure fiber with a shell graphene content of 0.4wt% (the graphene content of the entire fiber is about 0.21%) was prepared from the shell raw material and the core raw material of Example 3, which is the fiber of Example 3.

[0198] The sharpened wire of Example 3 was prepared from the fibers of Example 3 using the same method as that used to prepare the sharpened wire of Comparative Example 1 from the fibers of Comparative Example 1.

[0199] Fiber test results

[0200] After testing, the percentage of fibers with a diameter of ≤0.08 mm at a distance of 0.5 mm from the tip of the sharpened wire in Example 3 reached more than 90%, which met the requirements.

[0201] After testing, the single fiber recovery rate of the fiber of Example 3 is 67.12%, which meets the requirements of GB 19342-2013.

[0202] The antibacterial performance test results are shown in Tables 6A and 6B. Tables 6A and 6B show that the antibacterial rate of the fiber of Example 3 against Escherichia coli 8099 is 72%, and the antibacterial rate against Staphylococcus aureus ATCC 6538 is 99%, wherein the antibacterial rate against Staphylococcus aureus meets the requirements of GB / T 36391-2018.

[0203] Example 4 Effect of core and shell diameters on fiber properties

[0204] As shown in Comparative Examples 1-3 and Examples 1-3, as the amount of graphene added increases, the single fiber recovery rate of the fiber decreases.

[0205] Example 4 studies the lower limit of the fiber shell cross-sectional area ratio (i.e., the upper limit of the core diameter to shell diameter ratio) if the single fiber recovery rate is to be above 60% when the addition ratio of graphene masterbatch in the shell is 10%, 20%, and 30%, respectively.

[0206] In Example 4, graphene masterbatch was prepared using the same method as Comparative Examples 1-3 and Examples 1-3.

[0207] In Example 4, various proportions of graphene masterbatch as described in Table 7 were added to the PBT raw material particles as the shell raw material of Examples 4A-4D; and the PBT raw material without graphene masterbatch was used as the core raw material of Examples 4A-4D. Using a method similar to the method of preparing the fibers of Examples 1-3 from the shell raw materials and core raw materials of Examples 1-3, the ratio of the core diameter to the shell diameter was adjusted, and core-shell structure fibers with different graphene contents and different core diameter-shell diameter ratios were prepared from the shell raw materials and core raw materials of Examples 4A-4D, i.e., the fibers of Examples 4A-4D.

[0208] The test results of the single fiber recovery rate of the fibers of Examples 4A-4D are shown in Table 7.

[0209] Table 7

[0210]

[0211] As shown in Table 7, as the ratio of the core diameter to the shell diameter increases (the fiber shell cross-sectional area ratio decreases), the addition ratio of the graphene masterbatch can be increased accordingly to obtain a fiber with sufficient single-filament recovery rate; conversely, if the addition ratio of the graphene masterbatch needs to be reduced, a lower ratio of the core diameter to the shell diameter (a higher fiber shell cross-sectional area ratio) can be selected to make the fiber have a sufficient single-filament recovery rate.

[0212] Specifically:

[0213] - In terms of the relationship between the core diameter / shell diameter ratio D′ / D and the shell graphene content w, as shown in Examples 4A and 4B, for example, the core diameter / shell diameter ratio D′ / D is about 0.5, and / or the shell graphene content w is about 1.6wt% or less, for example, 0.8wt% to 1.6wt%, and sufficient single filament recovery rate can be obtained; as shown in Example 4C, for example, the core diameter / shell diameter ratio D′ / D is about 0.5, and / or the shell graphene content w is about 2.4wt% or less, for example, 0.8wt% to 2.4wt%, and sufficient single filament recovery rate can be obtained; or based on Examples 4B and 4C, the core diameter / shell diameter ratio D′ / D minus 40% is about 6.25 times or more of the shell graphene content w, and sufficient single filament recovery rate can be obtained;

[0214] - The cross-sectional area of ​​the fiber shell accounts for 1-(D' / D) 2 In terms of the relationship between the graphene content w in the shell, as shown in Examples 4A and 4B, for example, the cross-sectional area of ​​the fiber shell accounts for 1-(D′ / D) 2 The ratio of the graphene content w in the shell is about 0.75, and / or the graphene content w in the shell is about 1.6 wt% or less, for example, 0.8 wt% to 1.6 wt%, to obtain a sufficient single fiber recovery rate; as shown in Example 4C, for example, the cross-sectional area of ​​the fiber shell accounts for 1-(D′ / D) 2 The graphene content w of the shell is about 0.7, and / or the graphene content w of the shell is about 2.4wt% or less, for example, 0.8wt% to 2.4wt%, to obtain a sufficient single fiber recovery rate; or according to the comprehensive embodiment 4B and 4C, 85% minus the fiber shell cross-sectional area ratio 1-(D′ / D) 2 When the content w of the graphene in the shell is about 6.25 times or more, a sufficient single-filament recovery rate can be obtained.

[0215] The above-mentioned implementation modes are only preferred implementation modes of the present application and cannot be used to limit the scope of protection of the present application. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present application shall fall within the scope of protection required by the present application.

Claims

1. A core-shell structured graphene fiber, characterized in that: include: a core, composed of polymer fibers; as well as The shell part is composed of a graphene-polymer fiber composite material and surrounds the core part.

2. The core-shell structured graphene fiber according to claim 1, characterized in that: The diameter of the core is 40% to 90% of the diameter of the shell; and / or The cross-sectional area of ​​the shell portion is 20% to 90% of the cross-sectional area of ​​the fiber.

3. The core-shell structured graphene fiber according to claim 1, characterized in that: The core portion includes a protrusion that protrudes beyond the shell portion in an extending direction of the fiber.

4. The core-shell structured graphene fiber according to claim 3, characterized in that: The length of the protrusion in the extending direction is at least 5% of the length of the core in the extending direction.

5. The core-shell structured graphene fiber according to claim 1, characterized in that: The fiber includes a tip portion having a cross-sectional area perpendicular to the extending direction and decreasing in the extending direction of the fiber.

6. The core-shell structured graphene fiber according to claim 5, characterized in that: The length of the tip portion in the extension direction is at least 5% of the length of the fiber in the extension direction.

7. The core-shell structured graphene fiber according to claim 5 or 6, characterized in that: The diameter of the tip portion at a distance of 0.01 mm from one end thereof is less than 0.04 mm; and / or The diameter of the tip portion at a distance of 0.5 mm from one end thereof is less than 0.08 mm.

8. The core-shell structured graphene fiber according to claim 1, characterized in that: The length of the fiber is 10 mm to 35.0 mm; and / or The fiber has a diameter of 0.075 mm to 0.25 mm; and / or The cross section of the fiber perpendicular to its extension direction is circular, elliptical, convex polygonal, or concave polygonal.

9. An oral care product, characterized in that: The invention comprises the core-shell structured graphene fiber according to any one of claims 1 to 8.

10. The oral care product according to claim 9, characterized in that: The oral care product is a toothbrush.

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