• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    The object of the present invention is an electroformed element for an assembly part of a timepiece, for example a spring, and a timepiece using such an element. The electroformed element is composed of a nickel-iron alloy consisting of nickel, iron and unavoidable impurities, containing iron representing 5 to 25% by mass, and having a part roughly structured by layers (1 A) in which a stacked part (1a) having a gradual iron content in the thickness direction is repeatedly stacked several times. According to a preferred embodiment, the stacked part (1a) consists of crystal grains having an average grain diameter of 50 nm or less.
    公开号:CH715216A2
    申请号:CH00908/19
    申请日:2019-07-12
    公开日:2020-01-31
    发明作者:Kishi Matsuo；Takahama Miel
    申请人:Seiko Instr Inc；
    IPC主号:
    专利说明:

    Description
    BACKGROUND OF THE INVENTION
    1. Field of the invention The present invention relates to an element electroformed by an electroplating process and a timepiece using this process.
    2. Description of the Prior Art [0002] Conventionally, a watch, which is a small precision machine, particularly a mechanical watch, is equipped with a large number of small components such as gears and springs.
    A small component of this type is conventionally produced mainly by a machining process such as cutting or stamping; however, recently, a production method via an electroforming method has been adopted, and this is because there is an advantage in forming a component by the electroforming method due to their resulting smaller dimensional tolerance compared to a component formed by machining. On the other hand, even a complex shape can also be formed precisely. In particular, according to a technique called UVLIGA (according to the original German terminology "Lithography Galvanoformung Abformung") in which photolithography and an electroplating process are combined, an electroformed element can be produced with very high precision (see, for example, JP-A-11-15 126 (patent document 1)).
    On the other hand, as a material widely used for electroformed elements, electroformed nickel bodies are known; however, this material has poor creep and stress relieving properties, and therefore its use to form components such as springs has been considered difficult.
    In such circumstances, the application of an alloy composed of nickel and iron having excellent creep resistance and excellent resistance properties to stress relaxation to an electroformed element has been attempted, and a technique to improve properties by optimizing composition, grain size, hardness, etc. and further by performing heat treatment or the like has appeared (see, for example, JP-A-2014-198 897 (patent document 2)).
    However, in order to improve the property of creep resistance and the property of resistance to stress relaxation by the electroformed component of the nickel-iron alloy, it is necessary to increase the iron content; however, when the iron content exceeds 25%, the component is in an unstable state as an electroformed body, and the problem is that it is difficult to obtain a dense and hard electroformed body.
    This is due to the fact that, in addition to the deterioration of the stability of an electroforming solution during the formation of an electroformed body, iron is stably incorporated into a face-centered cubic structure which is a nickel crystal as a structure substituted by an iron content of about 25%, but when the iron content is increased to reach 25% or more, the distortion is increased and in addition, a centered cubic mesh phase, which is a type of iron structure is formed, and therefore, the problem that arises is that the structure becomes very unstable as an electroformed body, which causes friability and a decrease in its structural strength.
    SUMMARY OF THE INVENTION An object of the present patent application to provide an electroformed element having high precision and also having excellent hardness and an excellent Young's modulus, and also having excellent properties of resistance to relaxation constraints, and also to provide a timepiece using the electroformed element as an assembly part.
    [1] An electroformed element according to one aspect of the present patent application is an electroformed element composed of a nickel-iron alloy which consists of Ni, Fe and unavoidable impurities, the mass content of Fe of which is 5 to 25%, and has a coarsely structured layer part in which a stacked part having a gradual Fe content in the thickness direction is repeatedly stacked several times.
    [2] In the electroformed element according to the above aspect, it is preferred that the stacked part consists of crystal grains having an average grain diameter of 50 nm or less when the latter is measured by X-ray diffractometry .
    [3] In the electroformed element according to the above aspect, it is preferred that the crystal shape of the crystal grain constituting the stacked part is a single single cubic mesh layer with centered face, and a nickel atom is partially substituted by an iron atom.
    [4] In the electroformed element according to the above aspect, it is preferred that the gradient of Fe content in the stacked part is achieved by stacking the crystal grains having different Fe contents.
    CH 715 216 A2 [5] In the electroformed element according to the above aspect, it is preferred that the content of Fe in the individual crystal grains constituting the stacked part has a progressive gradient, and that the sizes of the grains of crystal in the stacked part are changed substantially in one direction.
    [6] In the electroformed element according to the above aspect, it is preferred that in the gradual composition of Fe in the stacked part, with respect to the intermediate concentration which is constituted by the value intermediate between the maximum concentration of Fe and the lowest concentration of Fe, the composition of Fe is gradual in a concentration range deviating from ± 15% to ± 50% relative to the intermediate concentration.
    [7] In the electroformed member according to the above aspect, it is preferred that the stacked part has a layer thickness of 500 nm or more, up to 10 μm or less.
    [8] In the electroformed element according to the above aspect, it is preferred that the direction substantially parallel to the layers constituting the stacked part is adjusted in the direction of a mechanical load.
    [9] A timepiece according to one aspect of this patent application in which an assembly part composed of the electroformed element according to one of the preceding points is provided.
    [10] In the timepiece according to this aspect, it is preferred that the assembly part is a spring.
    According to the electroformed element according to this aspect, a component consists of a nickel-iron alloy containing Fe at 5 to 25% as an average value and has a part roughly structured in layers in which a stacked part having a content gradual Fe in the thickness direction is repeatedly stacked several times, and therefore has excellent creep resistance and excellent stress resistance properties, and has high precision, and thus excellent elasticity properties can also be obtained.
    Therefore, the electroformed element with high precision can be applied to a spring, and the precision of a device (for example, a timepiece or the like) using the high precision component is also improved. Furthermore, since it is an electroformed element, the degree of freedom given with regard to the shape of the component is increased, and therefore this also contributes to a reduction in size of a mechanism or a part which was difficult to produce using a material formed by conventional machining.
    BRIEF DESCRIPTION OF THE DRAWINGS
    [0011]Figs. 1A and 1B show an electroformed body according to a first embodiment for the present invention, and FIG. 1A is a side view showing the complete shape of the electroformed body; fig. 1B is a partially enlarged sectional view taken along line A-A of the electroformed body. Figs. 2A and 2B represent a part of the structure of the electroformed body in an enlarged scale, and fig. 2A is an enlarged view showing a diagram of a stacked part having a gradual composition, and FIG. 2B is an enlarged view showing a diagram of a stacked part having a graded composition of Fe consisting of crystal grains having different compositions. Figs. 3A to 3F show an example of a method of producing the electroformed body, and fig. 3A is a sectional view showing a state where an electrode layer is formed on a substrate, FIG. 3B is a sectional view showing a state where a photoresist is formed on the electrode layer, FIG. 3C is a sectional view showing a state where an electroforming mold is formed by opening part of the photosensitive resin, FIG. 3D is a sectional view showing a state where an electroformed body is formed in the electroforming mold, fig. 3E is a sectional view showing a state where the surface of the electroformed body is flattened, and FIG. 3F is a sectional view showing an electroformed body taken out of the electroforming mold. Figs. 4A and 4B represent views to illustrate details of a state where the electroforming process using the electroforming mold is in progress; fig. 4A is a sectional view showing the electroforming mold, and FIG. 4B is a sectional view showing the state of the iron ions and the nickel ions immediately before their deposition while the electroforming process is in progress. Figs. 5A and 5B represent views to illustrate details of a state where the electroforming process using the electroforming mold is in progress; fig. 5A is a sectional view
    CH 715 216 A2
    showing a state where a stacked part having a gradual composition of iron is formed in the electroforming mold, and fig. 5B is a sectional view showing a state after an electroforming bath is stirred or shaken in the middle of the electroforming process. Fig. 6 is a graph representing an example of the measurement results of a composition of Fe in an electroformed body of Example 1 in the direction of the depth from its surface by an SEM ("scanning electron microscope", that is to say say scanning electron microscope). Figs. 7A and 7B represent measurement results for an electroformed body of Example 2, and fig. 7A is a graph showing an example of results of measurement of a composition of Fe in the direction of the depth from a surface of the body electroformed by an SEM, and FIG. 7B is an SEM image representing a measurement direction in a cross section of the electroformed body. Figs. 8A and 8B represent the measurement results for an electroformed body of Example 3, and fig. 8A is a graph showing an example of results of measurement of a composition of Fe in the direction of the depth from a surface of the body electroformed by an SEM, and FIG. 8B is an SEM image representing a measurement direction in a cross section of the electroformed body. Figs. 9A and 9B represent the measurement results for an electroformed body according to a conventional example, and FIG. 9A is a graph showing an example of the results of measuring a composition of Fe in the direction of the depth from a surface of the body electroformed by an SEM, and FIG. 9B is an SEM image representing a direction of measurement in a cross section of the electroformed body.
    DESCRIPTION OF THE EMBODIMENTS Hereinafter, showing an example of an electroformed body (electroformed element) according to is a first embodiment of the present invention, the configuration of the latter will be described in detail with reference to fig. 1A to fig. 2B. Incidentally, it should be noted that in the drawings used in the following description, in order to ensure that the respective parts have a recognizable size, the respective parts are represented by appropriately modifying their reproduction scales. Therefore, the relative sizes of the respective parts are not limited to those shown in the drawings.
    [Electroformed element] An electroformed body (electroformed element) 1 of this embodiment is, for example, a plate-shaped body as shown in FIG. 1 A, and it preferably has a composition containing a percentage of Fe at 5 to 25% in terms of mass, the remainder being Ni and unavoidable impurities. Incidentally, as being unavoidable impurities, we can find S which is inevitably introduced from the electroforming bath mentioned below; the latter can be contained in a range of about 0.005 to 0.2%.
    The electroformed body 1 according to this embodiment is composed of a roughly structured part in layers 1A in which a stacked part 1a having a gradual iron content in the direction of its thickness (the vertical direction in FIGS. 1 B, 2A and 2B) is stacked repeatedly several times as shown in cross section AA, shown in FIG. 1 B, and a cross section in FIG. 2A. The electroformed body 1 of the state shown in fig. 1A has, according to a plan view, a thin rectangular shape oriented vertically, which is composed of a long side 1A in the direction of its length, and a short side 1B in the direction of its width, and when a parallel direction at the short side 1B is defined as the direction X and the direction parallel to the long side 1A is defined as the direction Y, the direction Z is defined as being the direction of the thickness of the electroformed body 1.
    The electroformed body 1 according to this embodiment is a part to be used such as, for example, a flat spring, and is preferably used so that the direction in which a load is supposed to act is the direction indicated by the arrow “a”, that is to say, a bending or mechanical load acts in the direction ± X.
    In FIG. 2A, a diagram of the stacked part 1a constituting a structure of the electroformed body 1 is shown, and in FIG. 2B, a detailed enlarged partial transverse structure of the stacked part 1a is shown.
    The stacked part 1a constituting the electroformed body 1 is formed by the electroforming method mentioned below, and therefore, unlike a body stacked via a uniform stacked film consisting of a film with a single layer or the like, to be stacked by a deposition method such as a spray method, a film is produced by depositing crystal grains in deposition positions or various positions in the thickness direction, whereby the electroformed body 1 is produced . Therefore, as shown in FIG. 2A, it is not that the stacked part 1a is produced uniformly in the direction of the film thickness (vertical direction) and the planar direction (horizontal direction) in fig. 2A, but that the stacked part 1a is deposited, during the growth process, of
    CH 715 216 A2 so as to include certain displacement of positions in these directions. A schematic representation of such a state is shown in fig. 2A, however, when a plurality of contour lines 1 s each schematically representing a contour of a gradient of Fe content is drawn, the stacked part 1a is formed so that three zones S1 which can be divided so as to join the contour lines 1 s are arranged side by side in a first layer in fig. 2A, and the stacked part 1a as a second layer is formed by further stacking two different zones S1 arranged side by side thereon.
    In FIG. 2A, the empty parts drawn as interstices between the zones S1 do not mean that no crystal grain is present in these portions, but mean that crystal grains are certainly also present in these portions, but that these crystal grains deposited having an Fe content that does not meet the adjacent contour line 1 s, and therefore these portions are not shown as zones S1. Therefore, fig. 2A only shows a state where crystal grains present in each area S1 are deposited as a stacked part 1a so that the contour lines 1s can be drawn, and is illustrated as a schematic view showing a state where the roughly part structured in layers 1A is formed by depositing a plurality of these.
    According to this embodiment, the thickness of the stacked part 1a is approximately 500 nm to 10 μm.
    Moreover, when the upper limit and the lower limit of the numerical range in this text are described using "to", the range can include the upper limit and the lower limit unless something else is specified . Therefore, "500 nm to 10 μm" means a range of 500 nm or more and 10 μm or less.
    [0022] FIG. 2B is a schematic partial sectional view showing the structure of the electroformed body 1 on an even larger scale. The level of the Fe content in each zone delimited by a separation line 1t in an irregular granular form is expressed by the level of density of the diagonal lines. Among the respective zones, the zone with the highest density of diagonal lines is the crystal grain 1R having the highest Fe content, the zone with the second highest density of diagonal lines is the crystal grain 1R having the second highest high Fe content, the area with the third highest density of diagonal lines is the crystal grain 1R having the third highest Fe content, and the area with the fourth highest density of diagonal lines corresponds to the crystal grain 1R having the fourth highest Fe content.
    In FIG. 2B, for reasons of convenience and by convention, the layer composed of crystal grains 1R having the highest concentration of Fe is defined as being the first crystal layer 1b, the layer composed of crystal grains 1R having the second highest concentration of Fe is defined as the second crystal layer 1c, the layer composed of crystal grains 1R having the third highest concentration of Fe is defined as the third crystal layer 1d, and the layer composed of crystal grains 1R having the fourth highest concentration of Fe is defined as the fourth crystal layer 1e, and a state is shown where the stacked part 1a is formed from an assembly of four types of crystal layers.
    Also in FIG. 2B, in the same way as in the case of FIG. 2A, it is not that the crystal grains are not present in empty zones outside the respective zones delimited by the separation lines 1t; the crystal grains are also present in these empty zones, but the lines of separation 1t and the diagonal lines are simply not represented. Therefore, it can also be said that fig. 2A is a schematic view showing a state of the concentration of Fe only in the respective zones delimited by the separation lines 1t.
    Moreover, in FIG. 2B, in order to simplify the description, only four layers of the crystal layers from 1b to 1e are drawn, however, in the current electroformed body 1, the stacked part 1a is formed by more layers of crystal. The number of crystal layers in the stacked part 1a will be described later.
    In this embodiment, an area delimited by the separation line 1t and having an equal concentration of Fe is considered to correspond to a crystal grain 1 R. As for the size of this crystal grain 1 R, by example, the average grain diameter is assumed to be 50 nm or less, more specifically, 20 to 30 nm. Moreover, in relation to the specific size of the crystal grain 1 R, it has been confirmed that the average grain diameter is 50 nm or less, more specifically, from 20 to 30 nm by submitting samples of the examples below. mentioned in an X-ray analysis.
    As described above, the electroformed body 1 of this embodiment has the roughly structured part in layers 1A in which the stacked part 1a having a gradual content of Fe in the thickness direction is repeatedly stacked several times. Then, each stacked part 1a is composed of a stacked structure formed by the first crystal layer 1b composed of the crystal grains 1R having a substantially equal Fe concentration, the second crystal layer 1 c composed of the crystal grains 1R having a substantially equal concentration of Fe, the third crystal layer 1d composed of crystal grains 1R having a substantially equal concentration of Fe, and the fourth crystal layer 1 e composed of crystal grains 1R having a substantially equal concentration of Fe. Moreover, the number of crystal layers constituting each stacked part 1a is not specifically 4, but of an arbitrary number.
    CH 715 216 A2 As an example, the thickness of the stacked part 1 a is approximately 500 nm to 10 μm, and consequently, assuming that the average diameter of the crystal grain is 20 to 30 nm, the stacked part 1 a is formed from several tens to several hundred layers of crystal.
    In the electroformed body 1 according to this embodiment, it is desired that the crystal shapes of the individual crystal grains 1R are each a single cubic mesh layer with centered face, and a crystal shape in which an Ni atom is partially substituted by an Fe atom. In the Ni-Fe alloy, if the Fe content is in the range of 5 to 25% by mass, the crystal grain may have a crystal form in which an Ni atom is partially substituted by an Fe atom, and in such a case, the electroformed body 1, which can have excellent mechanical properties as described below, is obtained.
    It is preferred that the Fedans content in the individual crystal grains constituting the stacked part 1 has a progressive gradient, and also that the sizes of the crystal grains 1R in the stacked part 1a vary substantially in one direction.
    For example, the grain diameter of the crystal grain 1R increases while the Fe content decreases. Furthermore, when the stacked part 1a is formed, the grain diameter of the crystal grain 1R increases in a transverse direction (a vertical direction with respect to a growth direction of the stacked part 1a) while the stacking process is in progress (in the thickness direction).
    In addition, when the Fe content increases in the electroformed body 1, the grain diameter of the crystal grain 1R tends to decrease. Therefore, when the Fe content is low, the grain diameter of the 1R crystal grain tends to increase. Therefore, a layer (crystal grains) having a high Fe content is newly produced in a part where the grain diameter of crystal grain 1R is large, and the crystal grain is produced to become large. Therefore, the 1R crystal grain tends to become large in the direction of growth of the layer. In addition, in the thickness direction, the composition is controlled, and therefore the size of the crystal grain 1R hardly increases in the thickness direction along the stack, and tends to increase in the transverse direction. .
    [Method of manufacturing the electroformed body] In the following, a method will be described for the manufacture of an electroformed body configured as explained above.
    When the electroformed body 1 is produced, it is important to deposit the electroformed body having the composition mentioned above, and therefore, it is preferred to adjust and mix the composition of an electroforming solution, and perform electroforming in order to make the composition.
    As a source of Ni, nickel sulphate, nickel chloride, nickel sulfamate, or the like can be used, and as a source of Fe, ferrous sulfate, ferrous chloride, ferrous sulfamate, or can be used. similar. In addition, as a buffer solution, boric acid, acetic acid, citric acid, or the like can be added to the electroforming solution.
    In addition, as a core inhibitor, a surfactant such as a sulfate surfactant or an alkyl sulfonate surfactant can be added to the electroforming solution. Additionally, as a primary brightener, sodium saccharin, sodium naphthalene sulfonate, or p-toluene sulfonamide, and as a secondary brightener, butynediol, formaldehyde, or the like can be added to the electroforming solution. In addition, an antioxidant such as ascorbic acid or ascorbic isoacid or a complexing agent such as malonic acid, tartaric acid, or succinic acid can be added to the electroforming solution. .
    In the following, preferred examples of an electroforming bath composition and electroforming conditions according to this embodiment will be shown, however; the composition of the electroforming bath and the electroforming conditions can be appropriately modified as required within a range not detrimental to the advantageous effects of the present invention, i.e., as long as the composition of the bath and the conditions cause the deposition of an electroformed body containing 5 to 25% Fe, the remainder being Ni and inevitable impurities, and the present invention is not limited to the examples shown below.
    However, when the electroformed body 1 is produced as described below, it is necessary to mix the electroforming solution at each predetermined time or to stir, vibrate, or turn the electroforming mold immersed in the electroforming solution at each predetermined time while depositing grains by electroforming to produce the electroformed body 1.
    When the electroforming mold is turned, an electroforming step can be carried out by repeating a rotation at a frequency of 10 revolutions / minute over a period of 5 to 20 seconds, then leave to rest during a rest period d '' about 100 to 115 seconds.
    (Composition of the electroforming bath) nickel sulfamate tetrahydrate: 200 to 300 g / L
    CH 715 216 A2
    nickel chloride hexahydrate: 2 to 10 g / L ferrous sulfamate pentahydrate: 5 to 50 g / L boric acid: 10 to 50 g / L surfactant: 0.1 to 10 g / L primary gloss: 1 to 15 g / L secondary gloss: 0.05 to 5 g / L antioxidant: 0.1 to 10 g / L pH: 2 to 4 bath temperature: 40 to 60 ° C
    (Electroforming conditions) cathode current density: 1 to 10 A / dm 2 By carrying out the electroforming step using electroforming installations having an electroforming bath constituted as described above, the body electroformed 1 can be produced.
    Incidentally, in this embodiment, a percentage of sulfur S is defined between 0.005 to 0.2%. However, a source S according to this embodiment is included in the nickel sulfamate tetrahydrate, the ferrous sulfamate pentahydrate, the surfactant and the primary brightener in the composition of the electroforming bath mentioned above. In the electroforming step, metal ions react in the cathode, thereby depositing a metal, however, at this time, non-metallic ions, brighteners, etc. adhering to the surface of the cathode are incorporated with each other. Consequently, elements contained in the composition of the bath such as S, O and H which are generally seen as inevitable impurities cause an eutectoid. That is, in this embodiment, by adjusting the composition of nickel sulfamate tetrahydrate or the like described above, the amount of S can be controlled.
    In addition, S is an impurity, and it is preferred that its content be as low as possible from the point of view of the properties of the alloy; however, excessive reduction can increase the cost of electroforming, and therefore, in this embodiment, the content is adjusted to preferably be in the range of 0.005% to 0.2%.
    The electroformed body according to this embodiment has the composition mentioned above, but may contain other traces of elements included in a range which does not affect the advantageous effects of the present invention.
    In the following, we will describe an electrode for electroforming to be used for electroforming.
    Figs. 3A to 3F are views illustrating a step of forming an electrode for electroforming.
    First, as shown in FIG. 3A, an electrode 3 intended to become a cathode during an electroforming step is formed on a substrate 2.
    For the substrate, various materials such as stainless steel and titanium T1 other than silicon, quartz and sapphire can be used. As the material for electrode 3, Cu, Au, Cr, Tl, or the like can be used. Moreover, when a metallic material is adopted as the substrate 2, the electrode 3 may not be formed. In such a case, the substrate 2 can be fabricated to function as an electrode (cathode) for electroforming.
    The thickness of the substrate 2 is preferably fixed between 100 μm and 1 mm, so that it can be found independently in the next step. In addition, the thickness of the electrode 3 is preferably fixed at 10 nm or more in order to ensure stable conduction in the electroforming step mentioned below and the minimum resistance. On the other hand, when the thickness of the electrode 3 is too thick, the electrode may be peeled due to a stressing action or the deposit may take time, which is problematic; therefore, the thickness of the electrode is preferably fixed at 10 μm or less.
    FIG. 3B is a view illustrating a step of forming a layer of photoresist resin.
    As shown in FIG. 3B, a photosensitive resin 4 is deposited on the electrode 3. The photosensitive resin can be of a negative type or a positive type and can be deposited using a centrifugal coating method or an immersion coating method. Moreover, when a dry film is used as a photosensitive resin, the photosensitive resin 4 can be deposited using a laminating process.
    CH 715 216 A2 The thickness of the photosensitive resin 4 is equal to or greater than the thickness of the electroformed body 1 which must be formed in a subsequent step.
    In the following description, a case will be described where the photosensitive resin 4 is of the negative type.
    [0055] FIG. 3C is a view illustrating a development stage.
    As shown in FIG. 3C, firstly, the photosensitive resin 4 is irradiated with an ultraviolet ray using a photomask (not shown) having an outline pattern of the electroformed body 1 (see fig. 3F) to be formed in the next step, thereby polymerizing the photosensitive resin 4 elsewhere than in the part where the electroformed material is to be deposited in an electroforming step constituting the next step. Then, the photosensitive resin 4 (in the part in which the electroformed body is to be deposited) which has not polymerized is removed, thereby forming an electroforming mold 7 having a pattern P to form a shape of outline of the body electroformed 1 (see fig. 3F). The pattern P shown in the drawing includes a recess 6 to form the contour shape of the electroformed body 1. In addition, although not shown in the drawing, it is assumed that a plurality of P patterns described above are formed on along a matrix direction in the electroforming mold 7.
    Moreover, the method for forming the electroforming mold 7 according to this embodiment has been described by representing the step of forming the electroforming electrode at the time of the development step, as shown in fig. 3A to 3C, by way of example; however, the present invention is not limited to such a case, and another known method can be adopted as a method for forming the electroforming mold 7.
    The electroforming mold 7 is fixed in an electroforming device (not shown), and the electroformed body 1 composed of an Ni-Fe alloy is formed on the exposed electrode 3 as shown in FIG. 3D.
    The electroforming device has an electroforming tank, in which the above-mentioned electroforming solution containing Ni ions and Fe ions is stored, and it comprises an anode immersed in the solution electroforming as well as a power supply connected to both the anode and the electrode (cathode) 3 of the electroforming mold 7 through electrical wiring.
    After the electroforming mold 7 is immersed in the electroforming solution by being fixed to a template (not shown), the power supply is activated, and a voltage is applied between the anode and the cathode. Thus, Ni ions and Fe ions from the electroforming solution move towards the cathode, and are deposited as Ni-Fe alloy on the surface of cathode 3, and further, the alloy is produced so as to form a laminated metal body 10.
    In FIG. 4A, an enlarged structure of the electroforming mold 7 is shown, and in FIG. 4B, a state where the electroforming mold 7 is immersed in the electroforming solution and the Ni ions and the Fe ions in the electroforming solution are present around the recess 6 is shown diagrammatically. In fig. 4B, the white circles indicate ions of Ni 8, and the hatched circles indicate ions of Fe 9. In the state shown in fig. 4B, the Ni 8 ions and the Fe 9 ions are substantially evenly dispersed within the recess 6.
    When the power supply is activated and a voltage is applied between the anode and the electrode (cathode) 3 as described above in this state of the system, the Ni 8 ions and the Fe ions 9 are deposited on the surface of the electrode 3, and a stacked part 1 a composed of an Ni-Fe alloy is deposited; however, the Fe 9 ions are preferably deposited on the Ni 8 ions, and therefore 1R crystal grains having a high concentration of Fe are deposited in the stacked part 1 a. When the deposition is able to take place, the Fe ions present inside the recess 6 gradually decrease, and therefore, 1R crystal grains having a gradually reduced Fe concentration are deposited during the deposition process. Therefore, in the stacked part 1a, a concentration concentration of Fe is formed in the direction of its thickness.
    A state where the Fe 9 ions have decreased in the recess 6 by continuing the electroforming is shown in FIG. 5A. In the state shown in fig. 5A, only a layer of the stacked part 1a having an Fe gradient concentration is formed on the surface of the electrode 3 in the recess 6.
    After the deposition process continues while remaining in the state mentioned above for a predetermined period, for example, for about 100 to 120 seconds, an operation of mixing the electroforming solution, or of rotation or stirring of the electroforming mold 7 is carried out in the electroforming solution at each template.
    When the electroforming mold 7 is rotated, it is preferable to perform the rotation operation at a speed of about 10 revolutions / minute for a period of about 5 to 30 seconds.
    By any of these operations, the electroforming solution present in the recess 6 is replaced by an electroforming solution having an average ion concentration present around the electroforming mold 7. This state is shown in fig. 5B.
    In the state shown in FIG. 5A, a crystal layer 1b having a high concentration of Fe is deposited in an initial state on the electrode 3, and then, crystal layers 1c, 1d and 1e having a gradually decreasing concentration of Fe are deposited sequentially. When the state is changed to a state shown in fig. 5B by mixing the electroforming solution or rotating the electroforming mold 7, the crystal layer
    CH 715 216 A2 b having a high concentration of Fe is deposited in the initial state again from this time, and the crystal layers 1 c, 1 d and 1 e having a concentration of Fe which gradually decreases are deposited sequentially thereafter. By acting in this way, a part coarsely structured in layers 1A is formed in which the stacked part 1 has a gradual Fe content in the thickness direction is repeatedly stacked.
    As the difference in concentration of Fe in the stacked part 1a, with respect to an intermediate concentration of Fe which is the intermediate value between the crystal layer having the maximum concentration of Fe and the crystal layer having the concentration of Fe 1a. lower, it is preferred that the gradual concentration of Fe is included in a concentration difference range from ± 15% to ± 50% of the intermediate concentration.
    In addition, even if the concentration is within this range, it is desirable that the concentration is within a concentration range deviating from ± 20% to ± 45% relative to the intermediate concentration, and so even more desirable in a concentration range from ± 22% to ± 41% relative to the intermediate concentration.
    By repeatedly carrying out the deposition for approximately 100 to 120 seconds, and rotating the electroforming mold 7 (or mixing the electroforming solution or shaking the electroforming mold 7), it is possible to forming a laminated metal body 10 having a coarsely structured portion 1A with a predetermined thickness, wherein the stacked portion 1a having a gradual Fe content in the direction of the thickness is repeatedly stacked several times.
    When the electroforming is carried out at the cathodic current density mentioned above using the electroforming solution mentioned above, the stacking can be carried out according to a repetition cycle in which the thickness of the part stacked 1 a is fixed at approximately 1 to 2 μm under the conditions in which the thickness of the photosensitive resin is 100 to 300 μm, and the internal width of the opening is 50 to 100 μm.
    A laminated metal body 10 having a thickness equal to or greater than the thickness of the recess 6 is deposited. That is, the depth of the recess 6 is equal to the thickness of the electroformed body 1, and therefore the Ni-Fe alloy can grow until at least the recess 6 of the mold d 'electroforming 7 is completely filled by the laminated metal body 10. However, when a prepolishing and polishing step shown in FIG. 3E is omitted in the next step, the laminated metal body 10 is deposited so that the thickness of the laminated metal body 10 is the same as the thickness of the electroformed body 1.
    FIG. 3E is a view illustrating a step of grinding and polishing. The laminated metal body 10 obtained in the above-mentioned electroforming step is abraded so as to have the same thickness as the electroformed body 1, and its surface is polished and finished to have a surface with a mirror finish.
    Specifically, after the electroforming mold 7 in which the laminated metal body 10 is formed is taken out of the electroforming tank, the laminated metal body 10 is abraded with the electroforming mold 7 so as to have the same thickness dimension as the electroformed body 1. In this embodiment, the grinding is carried out in such a way that the surface part of the laminated metal body 10 formed above the surface of the electroforming mold 7 is eliminated (so that only the electroformed body 1 formed in the recess 6 remains).
    FIG. 3F is a view illustrating the step of extracting the electroformed body.
    In the step of extracting the electroformed body, the electroformed body is extracted by removing the substrate 2, the electrode 3, and the photosensitive resin 4; however, such a method of removal or removal is not particularly limited, and these members can be removed by, for example, engraving. In addition, a method for extracting the electroformed body 1 by applying physical force can be employed. By doing this, the electroformed body 1 composed of a desired alloy of Ni-Fe can be obtained.
    In addition, the crystal structures can be equalized by subjecting this electroformed body 1 to a heat treatment at 250 ° C for about 3 hours.
    According to the electroformed body 1 produced by the process mentioned above, an electroformed body 1 is obtained, which has a plate shape shown in FIG. 1A, and in which a plurality of stacked parts 1a are stacked in the thickness direction as shown in Fig. 1 B, that is to say in the growth direction of the electroforming, and each stacked part 1a has a Fe concentration gradient.
    According to this electroformed body 1, the electroformed body is composed of an Ni-Fe alloy containing Fe at 5 to 25%, and therefore, an electroformed body can be obtained having excellent mechanical properties such as the limit elastic is about 1500 MPa or more, and whose Young's modulus is 150 GPa or more, and which has excellent elasticity properties.
    In addition, when the recess 6 formed in the photosensitive resin 4 is produced by UV drying and by acid etching, the treatment can be carried out with higher precision compared to general machining, and therefore, the electroformed body 1 obtained is formed with high dimensional precision.
    It was revealed in the description of JP-A-2014-198 897 by the holder of the present patent application that, according to the electroformed body 1 of a Ni-Fe alloy having the composition mentioned above, the excellent properties
    CH 715 216 A2 mechanicals mentioned above are demonstrated, and it has been proven that the excellent Young's modulus, Vickers hardness, etc. for an assembly part such as a timepiece component can be obtained. For example, for an electroformed body 1 of a Ni-Fe alloy having the composition mentioned above, a Vickers hardness (Hv) of 580 or more, preferably about 620 to 630 can be obtained, and a body electroformed having an elastic limit of about 1400 MPa or more and a Young's modulus of about 150 to 170 GPa can be obtained.
    In addition to these excellent mechanical properties, the electroformed body 1 of this embodiment also has excellent hardness, and an excellent elastic limit and, stably, an excellent Young's Modulus. Consequently, such an element thus produced is particularly excellent for use as a spring material on which a load acts in the direction of the arrow "a" shown in FIG. 1 A, i.e. in a direction parallel to the layers of the stacked part 1a.
    For example, the electroformed body 1 having a hardness at a level between 670 and 720 Hv, an elastic limit at a level between 1500 and 1700 MPa, and a Young's modulus at a level of 170 MPa, and having excellent elasticity property can be obtained.
    Compared to the Ni-Fe alloy constituting the electroformed body 1, when the Fe content exceeds 25%, the alloy becomes brittle, and therefore, considering a possible variation for the Fe content, the limit higher to consider is substantially set at around 15 to 20%.
    The excellent mechanical properties previously revealed by the holder of this patent application in the description of JP-A-2014-198 897 are mechanical properties obtained in the Ni-Fe alloy produced to contain Fe at approximately 25 % massive.
    In the electroformed body 1 of this embodiment, the inclusion of the roughly structured part in layers 1A in which the stacked part 1a having a gradual Fe content in the direction of the thickness is repeatedly stacked times actually acts, and even if the Fe content is set at about 10 to 17%, on the electroformed body 1 which is not less than a Ni-Fe alloy having an Fe content of about 25%, can also stably demonstrating excellent mechanical properties at a high level as described above can be obtained.
    According to the electroformed body 1 of this embodiment, compared to an electroformed element Ni conventional or similar, the risk of magnification of the crystal grains is eliminated, and the mechanical properties such as a Young's modulus and a limit elastic are improved as described above, and therefore a technique for producing a small component with high precision can also be applied to a spring as an assembly part of a timepiece, and the precision of a device (for example, a timepiece or the like) using the high precision component is also improved. This technique can be applied to a spring such as a chronograph coupling lever as an assembly part for a timepiece.
    In addition, since an electroforming step using the photosensitive resin 4 described above is adopted in the process for producing the electroformed body 1, the degree of freedom in the choice of the shape of the component is increased, and by therefore, a mechanism which could not be realized with a conventional machined component can be realized; this contributes to a possible reduction in size of the mechanism, and also contributes to a reduction in size of a product such as a timepiece using small mechanisms.
    In passing, it will be specified that an electroformed body 1 of the embodiment described above can also have the same advantageous properties even if the structure does not consist entirely of the roughly structured part in layers 1A in which the stacked part 1a is filed.
    For example, even if crystal grains which cannot be represented as constituting the stacked part 1a are partially contained as illustrated in FIG. 2A, if the roughly structured layer part 1A in which the stacked part 1a is deposited is contained in the structure, an electroformed body capable of achieving the object of the present invention can be formed.
    As an example, it is desired to include the roughly structured part in layers 1A in which the stacked part 1a is deposited on 50% of volume or more of the structure.
    EXAMPLES In the following, the present invention will be described in more detail by means of examples; however, the present invention is not limited to the conditions used in the following examples.
    An electroforming mold was formed according to the method shown in Figs. 3A to 3C. During the formation of the electroforming mold, a substrate Si having a thickness of 525 μm was adopted as substrate and Au was adopted as electrode.
    Then, using the electroforming mold obtained, an electroformed body in a 10-cm2 plate form composed of an Ni-Fe alloy was produced by an electroforming device including an electroforming bath.
    [Composition of the electroforming bath, pH and temperature of the bath] As composition of the electroforming bath, the following composition was used.
    CH 715 216 A2 nickel sulfamate tetrahydrate: 200 to 300 g / L, nickel chloride hexahydrate: 2 to 10 g / L, ferrous sulfamate pentahydrate: 5 to 50 g / L, boric acid: 10 to 50 g / L, surfactant: 0.1 to 10 g / L, primary shine: 1 to 15 g / L, secondary shine: 0.05 to 5 g / L, and antioxidant: 0.1 to 10 g / L; pH: 2 to 4; bath temperature 40 to 60 ° C. [Electroforming conditions] [0100] The electroformed bodies of Examples 1 to 3 were produced by repeating an operation for authorizing an electric current to flow at a current density cathode of 4 A / dm2 (45 jum / hour) for 115 seconds and by carrying out below a rotation (speed of rotation of template: 10 revolutions / minute) for 5 seconds.
    As the electroformed body of a conventional example, a sample in a form such as a plate having a thickness of about 150 µm was produced by allowing an electric current to flow continuously at a cathode current density of 4 A / dm2 (45 jum / hour) for 3 hours and 30 minutes.
    Compared to the samples of Examples 1 to 3 and the sample of the conventional example, a cross section was cut from each sample in the form of a plate, and a component analysis was carried out in the direction of plate thickness by SEM (scanning electron microscopy).
    The results of the analysis of Example 1 are shown in FIG. 6, the results of the analysis of Example 2 are shown in Figs. 7A and 7B, the results of the analysis of Example 3 are shown in Figs. 8A and 8B, and the results of the analysis of conventional example 1 are shown in Figs. 9A and 9B.
    Moreover, in FIG. 7B, the direction of analysis of the cross section of the sample of Example 2 is shown in FIG. 8B, the direction of analysis of the cross section of the sample of Example 3 is shown, and in FIG. 9B, the direction of analysis of the cross section of the sample of the conventional example is shown.
    The sample of Example 1 is a sample which is an Ni-Fe alloy and has a composition aspiring to a composition of the electroforming bath having a Fe concentration of 5.3% by mass, the sample of l Example 2 is a sample which is a Ni-Fe alloy and has an electroforming bath composition targeting an Fe concentration of 9.6% by mass, and the sample of Example 3 is a sample which is a Ni alloy -Fe and has a composition of the electroforming bath aimed at an Fe concentration of 14.9% by mass. The sample of conventional example 1 is a sample which is an Ni-Fe alloy and has an electroforming bath composition aiming at an Fe concentration of 17% by mass.
    According to the results of the analysis of the Fe content in the thickness direction obtained from the samples of Examples 1 to 3, it was found that an increase and a decrease in the Fe content are repeated substantially periodic with the advancement of the measurement depth.
    Therefore, it is found that the samples of Examples 1 to 3 all have a roughly structured part in layers in which a stacked part having a gradual Fe content in the direction of the thickness is repeatedly stacked several times.
    Also in the conventional example 1, an increase and a decrease in the concentration of Fe were noted, however, the periodicity was blurred, and the difference between high and low concentrations was smaller in examples 1 to 3 .
    Consequently, compared with Examples 1 to 3, in order to check the variation of the Fe content, the numerical values of the maximum concentration of Fe and the lowest concentration of Fe were measured, and an intermediate concentration which is its intermediate value was determined by calculation, and with respect to each of examples 1 to 3, to what extent the range of variation lies with respect to the intermediate value of the Fe concentration was measured.
    In the measurement results of Example 1, the maximum concentration of Fe is 6.6% by mass when the depth is 6.6 μm, and the lowest concentration of Fe is 4.2% by mass when the depth is 3.6 μm.
    From these results, the intermediate concentration of Example 1 is 5.4% by mass, and the concentration of Fe falls in the range of 5.4% by mass ± 1.2% by mass.
    In the measurement results of Example 2, the maximum concentration of Fe is 13.4% by mass when the depth is 7.6 μm, and the lowest concentration of Fe is 5.6% by mass when the depth is of 5.0 μm.
    From these results, the intermediate concentration of Example 2 is 9.5% by mass and the concentration of Fe falls in the range of 9.5% by mass ± 3.9% by mass.
    In the measurement results of Example 3, the maximum concentration of Fe is 16.2% by mass when the depth is 4.0 μm, and the lowest concentration of Fe is 8.4% by mass when the depth is 6.5 μm.
    From these results, the intermediate concentration of Example 3 is 12.3% by mass and the concentration of Fe falls in the range of 12.3% by mass ± 3.9% by mass.
    Next, a ratio between the level of variation of each example relative to the value of the intermediate concentration of each example was determined by a calculation.
    CH 715 216 A2 [0117] The variation of 1.2% by mass in Example 1 corresponds to 22% of the intermediate concentration.
    The variation of 3.9% by mass in Example 2 corresponds to 41% of the intermediate concentration.
    The variation of 3.9% by mass in Example 3 corresponds to 31% of the intermediate concentration.
    On the other hand, in the measurement results of conventional example 1, the maximum concentration of Fe is 18.5% by mass when the depth is 6.5 μm, and the lowest concentration of Fe is 15.5 % mass when the depth is 0.2 μm.
    From these results, the intermediate concentration of conventional example 1 is 17.0% by mass, and the Fe concentration falls in the range of 17.0% by mass ± 1.5% by mass.
    The variation of 1.5% in mass of the conventional example 1 corresponds to 9% of the intermediate concentration.
    When comparing the calculation results of examples 1 to 3 with the calculation results of conventional example 1, it was found that with respect to the intermediate concentration, which is an intermediate value between the maximum concentration of Fe and the lowest Fe concentration in a structure having a coarsely structured portion in layers in which a stacked portion having a gradual Fe content in the thickness direction is repeatedly stacked several times according to the present invention, the composition of Fe is preferably gradual in a concentration difference range from ± 15% to ± 50% relative to the intermediate concentration.
    Even if it is in this range, it is desirable that the concentration is in a range deviating from ± 20% to ± 45% relative to the intermediate concentration, and more preferably in a range of concentration deviating from ± 22% to ± 41% compared to the intermediate concentration.
    Compared to the samples of Examples 1 to 3 and to the sample of the conventional example, the results of measurement of the hardness (Hv), of the Young's modulus (GPa), and the elastic limit are represented in the following table 1.
    Table 1 [0126]
    properties Example 1 Example 2 Example 3 Conventional example 1 Composition of Fe (mass%) 5.3 9.6 14.9 16.7 Hardness (Hv) (kg / mm 2 ) 720 685 674 634 Young's module (GPa) 172 174 170 176 Elastic limit (MPa) 1412 1729 1756 1437
    As shown in Table 1, the electroformed bodies of Examples 1,2 and 3 demonstrated excellent mechanical properties equal to or better than those of the electroformed body of the conventional example. In particular, when the Fe content in the Ni-Fe alloy is increased, excellent values are obtained for the Young's modulus and the elastic limit, however, it has been found that while Fe is contained at 16.7% of mass in the conventional example, in example 1, even if the Fe content is 5.3% by mass, an equivalent Young's modulus and elastic limit are always obtained. In examples 2 and 3, although the content of F is lower than in the conventional example, the electroformed body according to the invention shows a higher elastic limit, and an excellent value of a class of 1700 MPa could be obtained.
    From these results, it has been found that according to an electroformed body having a roughly structured part in layers in which a stacked part having a gradual Fe content in the thickness direction is repeatedly stacked several times as in the examples of this patent application, even if the Fe content is lower than for a conventional element, excellent mechanical properties are always obtained.
    Then, a plurality of samples were produced using electroforming baths targeting compositions similar to those of Examples 1,2 and 3 and the conventional example under the same manufacturing conditions as those of Examples 1, 2 and 3 and under the same manufacturing conditions as those of the conventional example, and the results of measurement of the hardness (Hv), the Young's modulus (GPa), and the elastic limit are shown in tables 2 to Next 4 4.
    Table 2 [0130]
    properties Example 4 Example 5 Example 6 Example 7 Example 8 Composition of Fe (mass%) 6.3 9.4 9.7 9.7 9.0
    CH 715 216 A2
    properties Example 4 Example 5 Example 6 Example 7 Example 8 Hardness (Hv) (kg / mm 2 ) 728 692 704 692 695Young's module (GPa) 180 176 170 180 175Elastic limit (MPa) 1550 1742 1621 1700 1694Table 3 [0131] propertiesExample 9 Example 10 Example 11 Example 12 Example 13 Composition of Fe (mass%) 14.1 14.1 14.3 13.8 17.9Hardness (Hv) (kg / mm 2 ) 670 675 674 674 666Young's module (GPa) 172 170 169 169 171Elastic limit (MPa) 1774 1704 1683 1683 1677Table 4 [0132] propertiesExample 14 Conventional example 2 ExampleI conventional3 Conventional example 4 Conventional example 5 Composition of Fe (mass%) 17.3 16.0 17.016.2 17.4 Hardness (Hv) (kg / mm 2 ) 663 637 638638 648 Young's module (GPa) 167 176 175175 176 Elastic limit (MPa) 1654 1501 15721572 1567
    Examples 4 to 14 showed the same trend as Examples 1 to 33 and the conventional examples 2 to 5 showed the same trend as the conventional example 1.
    From these results, in Examples 4 to 12, although the Fe content is lower than the conventional examples, a higher elastic limit has been demonstrated, and an excellent value of a class of 1700 MPa has been obtained. .
    From these results, it has been found that for an electroformed body having a roughly structured part in layers in which a stacked part having a gradual Fe content in the thickness direction is repeatedly stacked several times as in the examples From this request, even if the Fe content is lower than for a conventional element, excellent mechanical properties are always obtained.
    In addition, compared to the samples of Examples 1 to 14, the average crystal grain diameters of the crystal grains constituting the stacked part were measured by X-ray diffractometry and fell in the range of 20 to 30 nm in all samples.
    权利要求:
    Claims (10)
    [1]
    claims
    1. Electroformed element, which is composed of a nickel-iron alloy [Ni-Fe] consisting of nickel, iron and unavoidable impurities, the mass content of Fe is 5 to 25%, and having a roughly structured by layers (1 A) in which a stacked part (1a) having a gradual Fe content in the thickness direction is repeatedly stacked several times.
    [2]
    2. An electroformed element according to claim 1, in which the stacked part (1a) consists of crystal grains having an average grain diameter of 50 nm or less when the latter is measured by X-ray diffractometry.
    [3]
    3. Electroformed element according to claim 1 or 2, in which the crystal shape of the crystal grain constituting the stacked part (1a) is a single cubic mesh layer with centered face, and a nickel atom is partially substituted by an atom of iron.
    [4]
    4. Electroformed element according to one of claims 1 to 3, in which a Fe content gradient in the stacked part (1a) is produced by stacking the crystal grains having different Fe contents.
    CH 715 216 A2
    [5]
    5. Electroformed element according to one of claims 1 to 4, in which the content of Fe in the individual crystal grains constituting the stacked part (1a) has a progressive gradient, and the sizes of the crystal grains in the stacked part ( 1a) are changed substantially in one direction.
    [6]
    6. Electroformed element according to one of claims 1 to 5, in which the gradual composition of Fe of the stacked part (1a) is gradual in a concentration range deviating from ± 15% to ± 50% relative to the intermediate concentration, which is the intermediate value between the maximum concentration of Fe and the lowest concentration of Fe.
    [7]
    7. Electroformed element according to one of claims 1 to 6, in which the stacked part (1a) has a layer thickness ranging from 500 nm or more to 10 μm or less.
    [8]
    8. Electroformed element according to one of claims 1 to 7, wherein the direction substantially parallel to the layers constituting the stacked part (1a) is adjusted in the direction of a mechanical load.
    [9]
    9. Timepiece, in which an assembly part composed of the electroformed element according to one of claims 1 to 8 is provided.
    [10]
    10. Timepiece according to claim 9, wherein the assembly part is a spring.
    CH 715 216 A2
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    同族专利:
    公开号 | 公开日
    US20200024710A1|2020-01-23|
    US11053573B2|2021-07-06|
    CN110724978A|2020-01-24|
    JP2020012140A|2020-01-23|
    引用文献:
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    JPH1115126A|1997-06-23|1999-01-22|Sumitomo Heavy Ind Ltd|Mask for multiple exposure and manufacture of micromachine using the same|
    US9005420B2|2007-12-20|2015-04-14|Integran Technologies Inc.|Variable property electrodepositing of metallic structures|
    JP6296491B2|2013-03-14|2018-03-20|セイコーインスツル株式会社|Metal structure, method for manufacturing metal structure, spring component, start / stop lever for watch, and watch|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2018133920A|JP2020012140A|2018-07-17|2018-07-17|Electrocast component, and watch|
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