Metal component, movement, watch, and method for producing metal component

Abstract

To provide: a metal component having excellent magnetic resistance; a movement and a watch that include the metal component; and a method for producing a metal component having excellent magnetic resistance.SOLUTION: A metal component comprises an alloy of nickel, phosphorus, and cobalt, where the full width at half maximum of the maximum peak observed in the range of 2θ=35°-55° in an X-ray diffraction pattern is 6.0° or greater, or the cobalt content is 6 mass% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a metal part, a movement, a timepiece, and a method for manufacturing a metal part. [Background technology]

[0002] Various metal materials are used for the parts of mechanical watches. For example, Patent Document 1 lists a nickel-cobalt-phosphorus alloy as an example of a metal material suitable for use in the parts of mechanical watches. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-80699 Summary of the Invention [Problem to be solved by the invention]

[0004] Mechanical watch components require excellent anti-magnetic properties to prevent malfunctions due to the effects of magnetism. Metal components made from alloys of nickel, phosphorus, and cobalt (hereinafter referred to as nickel-phosphorus-cobalt alloys) are required to have even better anti-magnetic properties. In view of the above circumstances, an object of the present disclosure is to provide a metal part with excellent magnetic resistance, a movement and a timepiece including the metal part, and a method for manufacturing a metal part with excellent magnetic resistance. [Means for solving the problem]

[0005] The means for solving the above problems include the following embodiments. <1> Contains alloys of nickel, phosphorus and cobalt, A metal part in which the half-width of the maximum peak observed in the range of 2θ=35° to 55° in an X-ray diffraction pattern is 6.0° or more. <2> Contains alloys of nickel, phosphorus and cobalt, A metal part, wherein the alloy contains cobalt at a content of 6% by mass or less. <3> <1> or <2> A movement including the metal parts described in . <4> <1> or <2> A watch comprising the metal part described in item 1. <5> forming a metal part from a feedstock of an alloy of nickel, phosphorus and cobalt; The method for manufacturing a metal part includes adjusting the composition of the raw materials so that the alloy contains 6 mass % or less of cobalt, and forming the metal part. <6> The raw material is an aqueous solution containing nickel ions, phosphorus ions, and cobalt ions. <5> A method for manufacturing a metal part according to claim 1. <7> performing an X-ray diffraction measurement of the metal part; and determining the magnetic properties of the metal part based on the results of the X-ray diffraction measurement. [Effects of the Invention]

[0006] According to the present disclosure, there are provided metal parts with excellent magnetic resistance, movements and timepieces including these metal parts, and methods for manufacturing metal parts with excellent magnetic resistance. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a plan view schematically illustrating an example of a movement according to an embodiment of the present disclosure. [Figure 2] FIG. 1 is a diagram schematically illustrating an example of a timepiece according to an embodiment of the present disclosure. [Figure 3] 1A to 1C are diagrams schematically illustrating an example of a method for manufacturing a metal member according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present disclosure will be described. In this specification, when a numerical range is expressed using "to", the numerical range means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits.

[0009] First Embodiment A first embodiment of the present disclosure includes an alloy of nickel, phosphorus, and cobalt, The metal part has an X-ray diffraction pattern in which the half-width of the maximum peak observed in the range of 2θ=35° to 55° is 6.0° or more.

[0010] As shown in the examples described below, metal parts containing a nickel-phosphorus-cobalt alloy and having a half-width of the maximum peak observed in the range of 2θ=35° to 55° in an X-ray diffraction pattern of 6.0° or more have superior magnetic resistance compared to metal parts having a half-width of less than 6.0°. Metal parts having a half-value width of the maximum peak observed in the range of 2θ=35° to 55° in an X-ray diffraction pattern of 6.0° or more exhibit excellent magnetic resistance, for example, because the crystalline state of metal parts having a half-value width of 6.0° or more is more amorphous than the crystalline state of metal parts having a half-value width of less than 6.0°.

[0011] In this disclosure, the X-ray diffraction pattern of a metal part is obtained by the 2θ / θ method, where θ is the diffraction angle of the X-ray. The half-width of the maximum peak is the difference in 2θ values ​​on both sides of the peak when the intensity (height) of the maximum peak is half (full width at half maximum, FWHM).

[0012] From the viewpoint of magnetic resistance of metal parts, the half-width of the maximum peak observed in the range of 2θ=35° to 55° is preferably 6.2° or more, more preferably 6.4° or more, and even more preferably 6.6° or more. The upper limit of the half width is not particularly limited, but may be, for example, 10.0° or less, 9.0° or less, or 8.0° or less.

[0013] In the present disclosure, the term "nickel-phosphorus-cobalt alloy" refers to an alloy containing nickel, phosphorus, and cobalt, with the total content of nickel, phosphorus, and cobalt being 99 mass % or more. The total content of nickel, phosphorus, and cobalt in the nickel-phosphorus-cobalt alloy may be 99.5 mass % or more, 99.9 mass % or more, or 100 mass %.

[0014] From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the nickel content in the nickel-phosphorus-cobalt alloy is preferably 70 mass% or more, more preferably 75 mass% or more, and even more preferably 80 mass% or more. From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the nickel content in the nickel-phosphorus-cobalt alloy is preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 88 mass% or less.

[0015] From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the phosphorus content in the nickel-phosphorus-cobalt alloy is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the phosphorus content in the nickel-phosphorus-cobalt alloy is preferably 25 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less.

[0016] From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the cobalt content in the nickel-phosphorus-cobalt alloy is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and even more preferably 0.4 mass% or more. From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the cobalt content in the nickel-phosphorus-cobalt alloy is preferably 10 mass% or less, more preferably 8 mass% or less, and even more preferably 6 mass% or less.

[0017] The metal part of the first embodiment may be made entirely of a nickel-phosphorus-cobalt alloy, or may be made partially of a nickel-phosphorus-cobalt alloy. A metal part partially made of a nickel-phosphorus-cobalt alloy may have a portion made of the nickel-phosphorus-cobalt alloy and a portion made of a material other than the nickel-phosphorus-cobalt alloy, such as a metal part having a substrate and a layer made of the nickel-phosphorus-cobalt alloy disposed on the surface of the substrate. When a metal part includes a portion made of a material other than a nickel-phosphorus-cobalt alloy, the material may be either a metal or a non-metal material.

[0018] The method for manufacturing the metal part of the first embodiment is not particularly limited and can be selected depending on the application, shape, etc. Specific examples of methods for manufacturing the metal part include plating, vacuum deposition, sputtering, CVD, ALD, 3D modeling, casting, forging, cutting, pressing, and combinations thereof. From the viewpoint of the magnetic resistance of metal parts, plating is a preferred method for manufacturing metal parts.

[0019] The crystalline state of the nickel-phosphorus-cobalt alloy contained in the metal part is easily affected by heat and strain. For this reason, for example, the crystallization of the nickel-phosphorus-cobalt alloy may progress due to processing performed in the manufacturing process of the metal part. The crystallization of the nickel-phosphorus-cobalt alloy may cause the alloy to become magnetic. Therefore, it is preferable to select a manufacturing method for the metal part taking into consideration changes in the crystalline state of the metal part.

[0020] The dimensions of the metal part are not particularly limited and can be selected depending on the application and manufacturing method of the metal part. For example, the dimension of the metal member in the thickness direction may be in the range of 0.1 μm to 10,000 μm. When a portion of a metal part contains a nickel-phosphorus-cobalt alloy, the above dimensions refer to the dimensions of the portion of the metal member that contains the nickel-phosphorus-cobalt alloy.

[0021] The use of the metal parts is not particularly limited. Examples of uses for metal parts include those requiring excellent magnetic resistance, such as parts for mechanical watches. There are no particular restrictions on the type of watch part to which the metal parts are applied, and the part may be a movement, case, dial (display face), crown, hand, etc. The watch part to which the metal parts are applied is preferably a part built into the case, and more preferably a movement.

[0022] Second Embodiment A second embodiment of the present disclosure includes an alloy of nickel, phosphorus, and cobalt, The metal part is such that the alloy contains cobalt at a content of 6 mass % or less.

[0023] The definition and preferred aspects of the nickel-phosphorus-cobalt alloy in the second embodiment are the same as the definition and preferred aspects of the nickel-phosphorus-cobalt alloy in the first embodiment.

[0024] As shown in the examples described below, metal parts in which the cobalt content in the nickel-phosphorus-cobalt alloy is 6% by mass or less have superior magnetic resistance compared to metal parts in which the cobalt content in the nickel-phosphorus-cobalt alloy is greater than 6% by mass. One reason why metal parts with a nickel-phosphorus-cobalt alloy containing 6% or less cobalt by mass exhibit excellent magnetic resistance is that the crystalline state of metal parts with a nickel-phosphorus-cobalt alloy containing 6% or less cobalt by mass is more amorphous than the crystalline state of metal parts with a nickel-phosphorus-cobalt alloy containing more than 6% cobalt by mass.

[0025] From the viewpoint of magnetic resistance of the metal member, the cobalt content in the nickel-phosphorus-cobalt alloy is preferably 5 mass % or less, more preferably 4 mass % or less, and even more preferably 3 mass % or less. From the viewpoint of the balance of the various properties of the nickel-phosphorus-cobalt alloy, the cobalt content in the nickel-phosphorus-cobalt alloy is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and even more preferably 0.4 mass% or more.

[0026] In the metal part of the second embodiment, the half width of the maximum peak observed in the range of 2θ=35° to 55° in the X-ray diffraction pattern may be 6.0° or more, 6.2° or more, 6.4° or more, or 6.6° or more. The half width may be 10.0° or less, 9.0° or less, or 8.0° or less.

[0027] The preferred aspects of the metal part in the second embodiment are the same as the preferred aspects of the metal part in the first embodiment.

[0028] Third Embodiment A third embodiment of the present disclosure is a movement including the metal part of the first or second embodiment. In this disclosure, the term "movement" refers to the parts involved in driving a mechanical timepiece. Specific examples of metal parts included in the movement include an escape wheel, an anchor, a rotor, a balance wheel, gears, a hairspring, a main plate, and screws.

[0029] As an example of a movement, Figure 1 shows the structure of a movement including an escape wheel and anchor, which function as parts (escapement) to keep the speed of the watch constant.

[0030] The movement 24 shown in FIG. 1 includes an escape wheel 26 and an anchor 28 . The escape wheel 26 has a plurality of arms 32 that extend obliquely radially from the rotation axis 30. The arms 32 are capable of contacting the pallet fork 28 at sliding surfaces 42 at their tips. The escape wheel 26 is held rotatably in the direction of arrow R1 around the rotation axis 30.

[0031] The pallet fork 28 is held so as to be able to swing in the direction of arrow Y1 and the opposite direction, that is, in the direction of arrow Y2, around the pallet fork shaft 36. The pallet fork 28 swings by repeatedly rotating a predetermined angle in the direction of arrow Y1 and a predetermined angle in the direction of arrow Y2, due to an impulse jewel (not shown).

[0032] The pallet fork 28 has two angular pieces 38, one of which holds an inward claw 40A and the other of which holds an outward claw 40B. The inward claw 40A and the outward claw 40B are capable of coming into contact with the arm 32 at an opposed surface 44 that faces the sliding surface 42 of the arm 32. Hereinafter, when there is no need to distinguish between the recessed claws 40A and the protruding claws 40B, they will be simply referred to as the pallet claws 40.

[0033] The escape wheel 26 receives a rotational driving force from a driving source (not shown) in the direction of arrow R1. Rotation of the escape wheel 26 in the direction of arrow R1 is temporarily blocked when one of the arms 32 comes into contact with the recessed pawl 40A or the projecting pawl 40B. For example, as shown in FIG. 1, a state can be adopted in which rotation in the direction of arrow R1 is blocked when one of the arms 32 comes into contact with the projecting pawl 40B. Here, when the impulse jewel (not shown) rotates the pallet fork 28 in the direction of arrow Y1, the projecting pawl 40B moves away from the arm 32, and the escape wheel 26 becomes rotatable in the direction of arrow R1.

[0034] While the projecting claw 40B is moving away from the arm 32, the sliding surface 42 slides against the opposed surface 44 of the projecting claw 40B, and the escape wheel 26 rotates.

[0035] While the escape wheel and pinion 26 rotates in the direction of arrow R1, the pallet fork 28 rotates a predetermined angle in the direction of arrow Y1, and when the rotation angle of the escape wheel and pinion 26 reaches a predetermined angle, the recessed pawl 40A comes into contact with the arm 32 of the escape wheel and pinion 26 (an arm different from the arm with which the projecting pawl 40B was in contact). This again prevents the escape wheel and pinion 26 from rotating. Next, when the pallet fork 28 rotates in the direction of arrow Y2, the recessed pawl 40A moves away from the arm 32. This again allows the escape wheel and pinion 26 to rotate in the direction of arrow R1.

[0036] In this way, even while the inserting claw 40A is moving away from the arm 32, the sliding surface 42 slides against the opposed surface of the inserting claw 40A, and the escape wheel 26 rotates.

[0037] When the escape wheel 26 rotates a predetermined angle in the direction of arrow R1, the outgoing pawl 40B comes into contact with the arm 32 of the escape wheel 26 (an arm different from the arm that the incoming pawl 40A was in contact with), preventing the rotation of the escape wheel 26. The escape wheel 26 functions to mark a fixed time by performing such intermittent rotation (rotating a fixed angle and stopping rotation).

[0038] <Fourth embodiment> A fourth embodiment of the present disclosure is a timepiece that includes the metal part of the first or second embodiment. That is, at least one of the parts that make up the timepiece of the fourth embodiment is the metal part of the first or second embodiment.

[0039] An example of the configuration of a timepiece according to the fourth embodiment is shown in FIG. In the watch 10 shown in Figure 2, the type of parts to which the metal parts of the first or second embodiment are applied is not particularly limited, and may be a movement, case 12, dial (display) 14, crown 16, hands 18, etc., which are not shown. The part to which the metal part of the first or second embodiment is applied is preferably a part to be built into a watch case, and more preferably a movement.

[0040] Fifth Embodiment A fifth embodiment of the present disclosure is forming a metal part from a feedstock of an alloy of nickel, phosphorus and cobalt; The method for producing the metal part includes adjusting the composition of the raw materials so that the alloy contains 6 mass % or less of cobalt.

[0041] According to the method of the fifth embodiment, it is possible to more reliably manufacture metal members in which the cobalt content in the nickel-phosphorus-cobalt alloy is 6 mass % or less, compared to when the composition of the raw material of the nickel-phosphorus-cobalt alloy is not adjusted. As a result, it is possible to improve the yield of metal parts that satisfy predetermined standards of magnetic properties, for example.

[0042] From the viewpoint of the magnetic resistance of the metal component, it is preferable to adjust the composition of the alloy raw materials so that the cobalt content in the nickel-phosphorus-cobalt alloy is 5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less. From the viewpoint of balancing the various properties of the nickel-phosphorus-cobalt alloy, the composition of the alloy raw materials is preferably adjusted so that the cobalt content in the nickel-phosphorus-cobalt alloy is 0.1 mass% or more, more preferably 0.2 mass% or more, and even more preferably 0.4 mass% or more.

[0043] The type of raw material for the nickel-phosphorus-cobalt alloy used in the method of the fifth embodiment is not particularly limited. From the viewpoint of the magnetic resistance of the metal part, the raw material of the nickel-phosphorus-cobalt alloy may be an aqueous solution containing nickel ions, phosphorus ions, and cobalt ions. An example of a method using an aqueous solution containing nickel ions, phosphorus ions, and cobalt ions as a raw material is plating.

[0044] In this disclosure, "plating" refers to a method of forming a metal layer by reducing metal ions on the surface of a substrate. Plating may be either electrolytic plating or electroless plating.

[0045] The method for carrying out the plating may be electroforming (electroforming). In the present disclosure, electroforming refers to a method in which the substrate is removed from a metal layer formed on the surface of the substrate by electrolytic plating, and the metal layer from which the substrate has been removed is used as a product.

[0046] Metal components manufactured by electroforming may have any desired shape, and such metal components can be obtained, for example, by a method called LIGA, which combines photolithography and electroplating. Specifically, a metal member having a desired shape can be obtained by carrying out steps (A) to (D) shown in FIG.

[0047] 3(A), a photoresist layer 32 is formed on the surface of a substrate 30, at least the surface of which is conductive. The photoresist used to form the photoresist layer 32 can be either a negative photoresist, which becomes less soluble in a developer upon exposure (i.e., becomes irremovable by development), or a positive photoresist, which becomes more soluble in a developer upon exposure (i.e., becomes removable by development). The following describes the use of a negative photoresist.

[0048] 3(B), the photoresist layer 32 is exposed to light in a pattern, and the unexposed portions of the photoresist layer 32 are removed with a developer. The light used for exposure can be X-rays, ultraviolet rays, or the like, without any particular limitation.

[0049] 3(C), the developed substrate 30 is immersed in an aqueous solution of metal ions to perform electroplating, thereby forming a metal layer 34 in the area where the unexposed portions of the photoresist layer 32 have been removed. If necessary, treatments such as grinding and polishing may be performed after the electroplating to adjust the thickness of the metal layer 34.

[0050] In the step of Figure 3(D), the substrate 30 and photoresist layer 32 are removed from the metal layer 34 formed by electrolytic plating, and the metal layer 34 having a shape corresponding to the unexposed portion of the photoresist layer 32 is obtained as a metal member 36.

[0051] Sixth Embodiment A sixth embodiment of the present disclosure is performing an X-ray diffraction measurement of the metal part; and determining the magnetic properties of the metal part based on the results of the X-ray diffraction measurement.

[0052] In the method of the sixth embodiment, X-ray diffraction measurement is performed on a metal part, and the magnetic properties of the metal part are determined based on the results. Therefore, for example, it is possible to determine whether a metal part meets predetermined magnetic property standards before manufacturing a product that includes the metal part. Furthermore, the metal part can be inspected efficiently using a non-destructive method. As a result, for example, it is possible to effectively reduce the cost of quality control of metal parts.

[0053] The determination based on the results of X-ray diffraction measurements may be made based on, for example, the value of the half-width of a predetermined peak observed in the X-ray diffraction pattern.

[0054] There are no particular limitations on the metal parts manufactured by the method of the sixth embodiment, as long as the magnetic properties can be determined based on the results of X-ray diffraction measurement. Metal parts whose magnetic properties can be determined based on the results of X-ray diffraction measurement include metal parts whose X-ray diffraction patterns reflect differences in the crystalline state of the metal material.

[0055] Specific examples of materials for metal parts to which the method of the sixth embodiment can be applied include alloys containing nickel as a main component, such as nickel-phosphorus alloys and nickel-phosphorus-cobalt alloys, and austenitic stainless steel.

[0056] The method for manufacturing a metal part by the method of the sixth embodiment is not particularly limited and can be selected depending on the application, shape, etc. of the metal part. Specific methods for manufacturing a metal part include plating, vacuum deposition, sputtering, CVD, ALD, 3D modeling, casting, forging, cutting, pressing, and combinations of these.

[0057] The crystalline state of a metal component can change due to the effects of heat and strain, so it is preferable to perform X-ray diffraction measurements of the metal component after all processes that apply heat or strain to the metal component have been completed. [Example]

[0058] Hereinafter, the present disclosure will be described based on examples, but the present disclosure is not limited to these examples.

[0059] (Preparation of test specimens) Using an aqueous solution containing nickel ions, phosphorus ions, and cobalt ions as the raw material, a test piece (thickness: 100 μm) made of a nickel-phosphorus-cobalt alloy was produced by electroforming. The concentrations of nickel ions, phosphorus ions, and cobalt ions in the aqueous solution were adjusted so that the nickel, phosphorus, and cobalt contents in the test piece were the values ​​shown in Table 1. The nickel (Ni) content shown in Table 1 is a value obtained by analysis using EDTA titration, and the phosphorus (P) and cobalt (Co) contents are values ​​obtained by analysis using acid decomposition-ICP atomic emission spectrometry.

[0060] (X-ray diffraction measurement) The prepared test specimens were subjected to X-ray diffraction measurement (2θ / θ method) to obtain X-ray diffraction patterns. The half-width of the maximum peak observed in the X-ray diffraction pattern in the range of 2θ = 35° to 55° was measured. The results are shown in Table 1.

[0061] (Measurement of magnetic properties) The magnetic moment of the test piece was measured in an applied magnetic field of 2000 Oe using a superconducting quantum interference magnetometer (SQUID magnetometer). The measured value was divided by the volume of the test piece to calculate the magnetization (A / m). The smaller the magnetization of the test piece, the better its magnetic resistance performance can be determined. The results are shown in Table 1.

[0062] [Table 1]

[0063] As shown in the results in Table 1, test specimens 1 to 4, in which the cobalt content in the nickel-phosphorus-cobalt alloy is 6 mass% or less, exhibit superior antimagnetic performance compared to test specimen 5, in which the cobalt content is greater than 6 mass%. This result also suggests that adjusting the composition of the raw materials so that the cobalt content is 6 mass% or less is an effective means of improving the antimagnetic performance of metal parts containing nickel-phosphorus-cobalt alloys. Furthermore, test specimens 1 to 4, in which the half-width of the maximum peak observed in the 2θ = 35° to 55° range in the X-ray diffraction pattern is 6.0° or more, exhibit superior magnetic resistance compared to test specimen 5, in which the half-width is smaller than 6.0°. This result also suggests that performing X-ray diffraction measurements on metal parts containing nickel-phosphorus-cobalt alloys is useful as a means of reducing quality control costs in the manufacture of metal parts. [Explanation of symbols]

[0064] 10. Clock 12 cases 14 Dial 16 Crown 18 needles 24 Movement 26 Escape wheel 28 Uncle 30 Rotation axis 32 Arm 36 Ankle shaft 40 Ankle Nails 42 sliding surface 44 Opposed surface

Claims

1. Contains alloys of nickel, phosphorus and cobalt, A metal part having an X-ray diffraction pattern in which the half-width of the maximum peak observed in the range of 2θ=35° to 55° is 6.0° or more.

2. Contains alloys of nickel, phosphorus and cobalt, The metal part, wherein the alloy contains cobalt at a content of 6% by mass or less.

3. A movement comprising the metal part according to claim 1 or 2.

4. A timepiece comprising the metal part according to claim 1 or 2.

5. forming a metal part from a feedstock of an alloy of nickel, phosphorus and cobalt; The method for manufacturing a metal part, wherein the formation of the metal part comprises adjusting the composition of the raw materials so that the alloy contains 6 mass % or less of cobalt.

6. 6. The method for manufacturing a metal part according to claim 5, wherein the raw material is an aqueous solution containing nickel ions, phosphorus ions, and cobalt ions.

7. performing an X-ray diffraction measurement of the metal part; and determining the magnetic properties of the metal part based on the results of the X-ray diffraction measurement.

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