JP7265471B2 - clock - Google Patents

Description

The present invention relates to timepieces.

Patent Literature 1 describes a cover member for a timepiece provided with a translucent base material. In this watch cover member, an antireflection layer formed by alternately laminating a layer made of silicon oxide (SiO ₂ ) and a layer made of silicon nitride (SiN) is formed on one surface of the base material. It is An antistatic layer having at least a transparent conductive film layer is formed on the other surface of the base material. The antistatic layer is formed using ITO (Indium Tin Oxide).

JP 2017-128494 A

In watch windshields, it is desirable to be able to achieve antireflection or antistatic functions at low cost.

SUMMARY OF THE INVENTION An object of the present invention is to provide a timepiece capable of realizing antireflection or antistatic function at low cost.

A timepiece according to the present invention includes a dial, an exterior case that houses the dial and has an opening facing the dial, and a transparent windshield that closes the opening, wherein the windshield is made of transparent material. and a transparent organic layer formed on the side of the base facing the dial and exposed to the internal space of the exterior case, wherein the organic layer comprises an antireflection layer and a conductive layer. It is characterized by having at least one of the layers.

The windshield of the timepiece according to the present invention has a transparent organic layer formed on the side of the substrate facing the dial and exposed to the inner space of the exterior case. The organic layer has at least one of an antireflection layer and a conductive layer. According to the timepiece of the present invention, the antireflection function or the antistatic function can be achieved at low cost.

FIG. 1 is a diagram showing a timepiece according to the first embodiment. FIG. 2 is a cross-sectional view of the timepiece according to the first embodiment. FIG. 3 is a diagram showing the rotor and stator of the electrostatic motor according to the first embodiment. FIG. 4 is a perspective view of the electrostatic motor according to the first embodiment. FIG. 5 is a cross-sectional view of the windshield according to the first embodiment. FIG. 6 is a cross-sectional view of the vicinity of the packing in the timepiece of the first embodiment. FIG. 7 is a cross-sectional view of the windshield according to the second embodiment. FIG. 8 is a cross-sectional view of the windshield according to the third embodiment. FIG. 9 is a cross-sectional view of another windshield according to the third embodiment.

A timepiece according to an embodiment of the present invention will be described in detail below with reference to the drawings. In addition, this invention is not limited by this embodiment. In addition, components in the following embodiments include those that can be easily assumed by those skilled in the art or substantially the same components.

[First embodiment]
A first embodiment will be described with reference to FIGS. 1 to 6. FIG. This embodiment relates to a timepiece. 1 is a diagram showing a timepiece according to the first embodiment, FIG. 2 is a sectional view of the timepiece according to the first embodiment, and FIG. 3 is a rotor and stator of an electrostatic motor according to the first embodiment. 4 is a perspective view of the electrostatic motor according to the first embodiment; FIG. 5 is a cross-sectional view of the windshield according to the first embodiment; FIG. It is a sectional view.

As shown in FIGS. 1 and 2, the timepiece 1 of this embodiment is an analog electronic timepiece that displays the time with hands 36. As shown in FIG. The illustrated watch 1 is a watch worn on the wrist of the user. The watch 1 has a watch case 20 , a windshield 10 , a dial 31 , a movement 34 and hands 36 . The hands 36 have a second hand 36a, a minute hand 36b and an hour hand 36c.

As shown in FIG. 2 , the watch case 20 has an exterior case 21 and a back cover 22 . The exterior case 21 is made of a conductive metal. The outer case 21 has a tubular shape, for example, a substantially cylindrical shape. The exterior case 21 houses a dial 31, a movement 34, and pointers 36. As shown in FIG. In the following description, the axial direction of the exterior case 21 is simply referred to as "axial direction Z". Further, one side in the axial direction Z is called "front side Fz", and the other side in the axial direction Z is called "back side Rz". A needle main body 36 m of the pointer 36 is arranged on the front side Fz of the dial 31 . That is, the front side Fz is the side facing the user when the user checks the time. The back side Rz is the side facing the user's arm when the watch 1 is worn on the user's arm.

The dial 31 has a front surface 31a and a back surface 31b. The front surface 31a is a surface on which scales and hour characters are arranged. The back surface 31 b is the back surface of the dial 31 and faces the movement 34 . The dial 31 is fixed to the exterior case 21 with the front surface 31a facing the front side Fz.

The movement 34 is arranged on the back side Rz with respect to the dial 31 . The movement 34 is fixed to the exterior case 21 via the middle frame 35 . A parting 37 is arranged on the periphery of the dial 31 . The parting 37 is arranged on the front side Fz of the dial 31 and fixed to the exterior case 21 . The parting 37 is a dial ring. The inner peripheral surface of the parting 37 is inclined with respect to the axial direction Z. As shown in FIG.

The exterior case 21 has openings 21a and 21b. The opening 21 a is an opening on the front side Fz of the exterior case 21 . The opening 21a faces the front surface 31a of the dial 31 in the axial direction Z. As shown in FIG. The opening 21b is an opening on the back side Rz of the exterior case 21 . The opening 21b faces the rear surface 31b of the dial 31 in the Z-axis direction.

The windshield 10 closes the opening 21 a of the exterior case 21 . Windshield 10 has substrate 11 and coating 12 . The base material 11 is a transparent member made of, for example, glass or plastic. Examples of glass include sapphire glass, soda glass, and tempered crystal glass. Examples of plastics include acrylic resins and polycarbonates. The coating 12 of this embodiment has an inorganic layer 6 and an organic layer 7 . The coating 12 is formed on the rear surface side Rz of the base material 11, and is formed on the side of the base material facing the dial. Coating 12 is a transparent layer exposed to the interior space of the outer case. Details of the coating 12 will be described later.

The packing 32 is interposed between the windshield 10 and the exterior case 21 . The packing 32 seals between the windshield 10 and the inner peripheral surface of the exterior case 21 . The packing 32 may seal between the windshield 10 and the front face of the parting 37 . The packing 32 is an annular sealing member, and is made of resin such as rubber, for example.

The back cover 22 closes the opening 21b of the exterior case 21 . The back cover 22 is made of, for example, a conductive metal. A packing 33 is interposed between the exterior case 21 and the back cover 22 . The illustrated packing 33 is a face seal and seals between the rear surface of the exterior case 21 and the front surface of the back cover 22 . The packings 32 and 33 form an airtight structure that prevents dust, dirt, moisture, and the like from entering the internal space 23 of the exterior case 21 .

The movement 34 of this embodiment has the electrostatic motor 4 shown in FIGS. The electrostatic motor 4 has a rotor 40 , a rotating shaft 41 and a stator 50 . The rotor 40 and the stator 50 of the present embodiment each have a disc shape, but the stator 50 is not limited to a disc shape, and may have a square shape or the like. The stator 50 of this embodiment is fixed to the housing or the like so as not to rotate. The rotating shaft 41 is fixed with respect to the rotor 40 . The rotating shaft 41 is rotatably supported by a stone or the like. The rotor 40 is coaxial with the stator 50 and faces the stator 50 with a gap therebetween.

The rotor 40 is a disk-shaped member formed of a substrate material such as a silicon substrate, a glass epoxy substrate provided with an electrode surface for charging, or an aluminum plate. A plurality of electret films 42 are formed on the surface of the rotor 40 facing the stator 50 . The electret films 42 are arranged at regular intervals along the direction of rotation about the rotation shaft 41 . The electret film 42 is a thin film made of an electret material. The electret film 42 of this embodiment is charged to a negative potential. Through holes 43 are formed between adjacent electret films 42 in the rotor 40 .

A plurality of fixed electrodes 51 , 52 , 53 are arranged on the surface of the stator 50 facing the rotor 40 . The illustrated electrostatic motor 4 is a three-phase motor of U-phase, V-phase, and W-phase. The fixed electrode 51 is an electrode corresponding to the U phase, the fixed electrode 52 is an electrode corresponding to the V phase, and the fixed electrode 53 is an electrode corresponding to the W phase. A plurality of electrode groups 54 each including fixed electrodes 51 , 52 and 53 are arranged on the stator 50 . The fixed electrodes 51 , 52 , 53 are arranged at regular intervals along the rotation direction CW of the rotor 40 . The electrostatic motor 4 rotates the rotor 40 by electrostatic force acting on the electret film 42 from the fixed electrodes 51 , 52 , 53 .

The rotating shaft 41 of the electrostatic motor 4 is connected to the rotating shaft of the hands 36 via, for example, a train wheel. In the timepiece 1 of this embodiment, the rotating shaft 41 is connected to the rotating shaft of the second hand 36a. That is, the electrostatic motor 4 rotates the second hand 36a. In this case, the movement 34 may have a motor different from the electrostatic motor 4 as a motor for driving the minute hand 36b and the hour hand 36c. In the movement 34, the second hand 36a, the minute hand 36b, and the hour hand 36c may all be driven by the electrostatic motor 4.

FIG. 5 shows a cross section of the windshield 10 according to this embodiment. As shown in FIG. 5, coating 12 has transparent inorganic layer 6 and transparent organic layer 7 . Inorganic layer 6 is interposed between organic layer 7 and substrate 11 . In other words, the inorganic layer 6 is formed on the back surface 11 b of the substrate 11 , and the organic layer 7 is formed on the back surface 6 b of the inorganic layer 6 . When the inorganic layer 6 is formed on the base material 11, the base material 11 may be made of an inorganic material such as glass.

The inorganic layer 6 has a first inorganic layer 61 and a second inorganic layer 62 . The refractive index n1 of the first inorganic layer 61 is greater than the refractive index n2 of the second inorganic layer 62 . That is, the first inorganic layer 61 is a high refractive index layer, and the second inorganic layer 62 is a low refractive index layer. The inorganic layer 6 is formed by alternately stacking first inorganic layers 61 and second inorganic layers 62 . The first inorganic layer 61 is the layer closest to the front side Fz in the inorganic layer 6 . That is, the inorganic layer 6 is formed by forming the first inorganic layer 61 on the back surface 11b of the base material 11 and then alternately overlapping the second inorganic layer 62 and the first inorganic layer 61 . The first inorganic layer 61 is the outermost layer of the inorganic layer 6 , that is, the layer located on the rearmost side Rz. The illustrated inorganic layer 6 has three first inorganic layers 61 and two second inorganic layers 62 .

The first inorganic layer 61 is made of, for example, aluminum oxide (AL ₂ O ₃ ). The second inorganic layer 62 is made of magnesium fluoride (MGF ₂ ), for example. In addition, the inorganic material forming the first inorganic layer 61 is not limited to aluminum oxide (AL ₂ O ₃ ), and may be, for example, silicon nitride (SiN). The inorganic material forming the second inorganic layer 62 is not limited to magnesium fluoride (MGF ₂ ), and may be, for example, silicon oxide (SiO ₂ ).

The illustrated organic layer 7 consists of a single-layer first conductive layer 70 . The first conductive layer 70 is a layer containing an organic material having conductivity, and contains, for example, a conductive polymer. The first conductive layer 70 covers the inorganic layer 6 from the dial 31 side. The first conductive layer 70 is exposed to the internal space 23 of the exterior case 21 . In other words, the back surface 70b of the first conductive layer 70 is an exposed surface facing the dial 31 in the axial direction Z. As shown in FIG.

In the film 12 of this embodiment, the inorganic layer 6 and the organic layer 7 constitute an antireflection layer. The refractive index n3 of the first conductive layer 70 is smaller than the refractive index n1 of the first inorganic layer 61 . That is, the coating 12 is formed by alternately laminating the first inorganic layer 61 having a relatively high refractive index and the layer having a relatively low refractive index (the second inorganic layer 62 or the first conductive layer 70). configured as follows. The thickness t1 of the first inorganic layer 61, the thickness t2 of the second inorganic layer 62, and the thickness t3 of the first conductive layer 70 are determined so that the coating 12 has an antireflection function. Coating 12 is configured to cancel reflected light by optical interference.

In the timepiece 1 of this embodiment, the first conductive layer 70 exposed to the internal space 23 of the windshield 10 has electrical conductivity. In other words, potential localization is less likely to occur in the first conductive layer 70 . In other words, on the back surface 70b of the first conductive layer 70, the potential tends to be made uniform. As a result, in the timepiece 1 of the present embodiment, problems caused by potential localization are suppressed. For example, the timepiece 1 of this embodiment can stabilize the movement of the hands 36 .

As a comparative example for the windshield 10 of the present embodiment, a windshield not provided with the first conductive layer 70 will be considered. In the windshield of the comparative example, potential localization is likely to occur on the exposed surface facing the dial 31 . If the electric potential is localized, for example, the movement of the pointer 36 may become unstable due to variations in the electrostatic force acting on the pointer 36 . In addition, localization of the potential on the exposed surface of the windshield may act as an electrostatic force that destabilizes the rotation of the rotor 40 . On the other hand, the timepiece 1 of this embodiment can stabilize the movement of the hands 36 .

As shown in FIG. 6, in the timepiece 1 of this embodiment, the packing 32 is provided with a conductive film 32a. The conductive film 32a is formed to cover the entire packing 32, for example. The conductive film 32a is formed by applying a conductive paint to the surface of the packing 32, for example. The conductive film 32 a is in contact with the first conductive layer 70 and the exterior case 21 . That is, the first conductive layer 70 is grounded to the exterior case 21 through the packing 32 . Since the first conductive layer 70 is grounded, the first conductive layer 70 is less likely to be charged. Therefore, electrostatic force is less likely to occur between the first conductive layer 70 and the pointer 36 or rotor 40 . As a result, the movement of the hands 36 is stabilized. In addition, since the first conductive layer 70 is difficult to be charged, stains are less likely to adhere to the first conductive layer 70 .

Also, the conductive film 32 a grounds the base material 11 to the exterior case 21 . Therefore, the base material 11 is less likely to be charged and dirt is less likely to adhere to the base material 11 . For example, when the base material 11 is made of plastic, adhesion of dirt to the base material 11 is preferably suppressed. A conductive film may be formed on the surface of the parting 37 .

In addition, in the windshield 10 of the present embodiment, the first conductive layer 70 may be directly formed on the base material 11 without providing the inorganic layer 6 . The first conductive layer 70 of the present embodiment is an antistatic film, and is formed of a composition for forming an antistatic film for a windshield, which will be described below.

<Composition for forming antistatic film for windshield>
The windshield antistatic film-forming composition of the present embodiment contains at least one selected from a conductive polymer, an acetylenic surfactant, a water-soluble organic solvent having a boiling point of 180° C. or higher, isopropyl alcohol and ethanol. Contains alcohol and water. The composition for forming an antistatic film for watches according to the present embodiment contains the conductive polymer in an amount of 0.03% by mass or more and 5.0% by mass or less, and the acetylenic surfactant in an amount of 0.01% by mass. % or more and 1.0 mass % or less, and the water-soluble organic solvent having a boiling point of 180° C. or more is contained in an amount of 0.1 mass % or more and 10.0 mass % or less. From the viewpoint of solubility, it is preferable to contain the conductive polymer in an amount of 0.03% by mass or more and 1.0% by mass or less.

The windshield antistatic film-forming composition of the present embodiment can form an antistatic film on the surface of the base material 11 constituting the windshield 10 of a timepiece, for example. For example, the composition for forming an antistatic film for the windshield of the present embodiment can be applied by coating or the like to the surface of the base material 11 constituting the windshield 10 of the watch, and heated to form the antistatic film. The formed antistatic film is a conductive polymer film containing at least a conductive polymer because the water-soluble organic solvent having a boiling point of 180° C. or higher, alcohol, and water evaporate during heating. By the way, as in Patent Document 1, the antistatic film can also be formed from an inorganic compound such as ITO (Indium Tin Oxide). However, the ITO film needs to be formed using a vacuum deposition apparatus, which is complicated and expensive. Also, the ITO film may crack due to temperature changes. On the other hand, the conductive polymer film can be formed through adhesion such as coating and heating as described above. That is, it can be formed easily and the cost can be reduced. Moreover, even if the base material 11 is plastic, a conductive polymer film can be formed. Furthermore, the conductive polymer film is resistant to cracking due to temperature changes and has excellent antistatic properties.

Conventionally, when the substrate 11 is made of plastic, an antistatic film may be formed using a surfactant. An antistatic film formed of a surfactant prevents static electricity by using moisture in the air to lower the surface resistance. Therefore, when the humidity is low, it is difficult to exhibit the antistatic performance. In contrast, the antistatic film formed using the composition for forming an antistatic film for a windshield of the present embodiment prevents charging due to the function of the conductive polymer. Therefore, antistatic performance can be exhibited regardless of humidity. Therefore, even when an antistatic film is provided on the surface of the base material 11 on the dial 31 side, the antistatic performance can be exhibited.

In addition, since a watch using an electrostatic motor 4 is activated by an electrostatic induction force, it is necessary to keep the inside of the watch case 20 at low humidity. Electrostatic attraction is likely to occur between the part and the hands 36 that display the time and the like. As a result, uneven hand movement may occur. Even in such a timepiece, the composition for forming an antistatic film for a windshield according to the present embodiment can form an antistatic film with excellent antistatic performance, so that uneven movement of the hands can be suppressed.

As described above, the formed antistatic film contains a conductive polymer, and therefore exhibits excellent antistatic performance. In addition, when the composition for forming an antistatic film for a windshield of the present embodiment contains the conductive polymer in the above amount, an antistatic film capable of exhibiting excellent antistatic performance can be obtained. In addition, when the conductive polymer is contained in the above amount, it hardly affects the appearance of the windshield 10 .

Examples of conductive polymers include poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT/PSS; Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)), polyaniline, polyacetylene, and polythiophene. , polypyrrole, polyphenylene vinylene, polythienylene vinylene, and derivatives thereof. The conductive polymer may be used singly or in combination of two or more.

Among these, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) is preferably used as the conductive polymer from the viewpoint of antistatic performance.

When the acetylenic surfactant is used, when the composition for forming a windshield antistatic film of the present embodiment adheres to the substrate 11 or the inorganic layer 6, the composition for forming the windshield antistatic film of the present embodiment repels. He becomes difficult. Therefore, it can adhere thinly and uniformly. Further, when the composition for forming a windshield antistatic film of the present embodiment contains the acetylenic surfactant in the above amount, the above functions are sufficiently exhibited.

Acetylene surfactants include acetylene alcohol, acetylene diol, and compounds obtained by adding alkylene oxide thereto. Acetylene-based surfactants may be used singly or in combination of two or more.

Acetylene alcohols include compounds represented by HOCR ₁ R ₂ —C≡CH (R ₁ and R ₂ each represent an alkyl group having 1 to 8 carbon atoms). Specific examples include compounds in which R ₁ is a methyl group and R ₂ is an isobutyl group, compounds in which R ₁ and R ₂ are methyl groups, and compounds in which R ₁ is a methyl group and R ₂ is an ethyl group.

The acetylenediol is represented by HOCR ₁ R ₂ —C≡C—CR ₁ R ₂ OH (R ₁ and R ₂ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms). compounds that are Specifically, compounds where R ₁ is a methyl group and R ₂ is an isobutyl group, compounds where R ₁ and R ₂ are methyl groups, compounds where R ₁ is a methyl group and R ₂ is an ethyl group, compounds where R ₁ is Examples include methyl groups and compounds in which R ₂ is an isopentyl group.

Compounds obtained by adding alkylene oxide thereto include compounds obtained by adding ethylene oxide or propylene oxide to the above acetylene alcohol or acetylenediol.

Among these, 2,5,8,11-tetramethyl-6-dodecine-5,8-diol and ethoxylate are preferably used as the acetylenic surfactant from the viewpoint of ease of film formation. .

The water-soluble organic solvent having a boiling point of 180° C. or higher evaporates gradually and slowly when the composition for forming an antistatic film for a windshield according to the present embodiment adhered to the base material 11 and the inorganic layer 6 is heated. As the water-soluble organic solvent slowly evaporates, an intermolecular path of the conductive polymer (in other words, a path through which electrons can move to develop conductivity) is formed. Therefore, an antistatic film capable of exhibiting excellent antistatic performance can be obtained. Further, when the composition for forming an antistatic film for a windshield of the present embodiment contains a water-soluble organic solvent having a boiling point of 180° C. or higher in the above amount, the above functions are sufficiently exhibited.

Water-soluble organic solvents having a boiling point of 180° C. or higher include dimethylsulfoxide (boiling point of 189° C.), ethylene glycol (boiling point of 197.6° C.), and N-methylpyrrolidone (boiling point of 202° C.). The water-soluble organic solvents having a boiling point of 180° C. or higher may be used singly or in combination of two or more.

Among these, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) is preferably used as dimethylsulfoxide from the viewpoint of ease of path formation.

In the windshield antistatic film-forming composition of the present embodiment, the balance is at least one alcohol selected from isopropyl alcohol and ethanol, and water. In addition, in this specification, at least one alcohol selected from isopropyl alcohol and ethanol is simply referred to as an alcohol component. As the alcohol component, isopropyl alcohol and ethanol may be used alone, or both may be used in combination. The alcohol component and water serve to dissolve both the acetylenic surfactant and the conductive polymer in the windshield antistatic film-forming composition of the present embodiment.

As the alcohol component, isopropyl alcohol is preferably used from the viewpoint of compatibility.

The windshield antistatic film-forming composition of the present embodiment may further contain a silane coupling agent having an epoxy group. When the silane coupling agent having an epoxy group is used, the antistatic film can be firmly adhered to the base material 11 especially when the base material 11 is glass. In addition, the stability of the composition for forming a windshield antistatic film of the present embodiment is also improved.

A silane coupling agent having an epoxy group is, specifically, a silicon compound having a hydrolyzable group (X) that has affinity and reactivity with an inorganic material and an epoxy group (Y) that chemically bonds with an organic material. be. For example, the silane coupling agent is X _{3-n Men} Si-RY (X is a hydrolyzable group, Y is an epoxy group, Me is a methyl group, R is an alkylene group having 2 to 3 carbon atoms, n is 0 or 1.). Examples of the hydrolyzable group (X) include CH ₃ O--(methoxy group), CH ₃ CH ₂ O--(ethoxy group) and CH ₃ OCH ₂ CH ₂ O--(2-methoxyethoxy group). Moreover, an ethylene group and a propylene group are mentioned as R (alkylene group).

Silane coupling agents having an epoxy group include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4 -epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiisopropenoxysilane. Silane coupling agents having an epoxy group may be used singly or in combination of two or more.

When the composition for forming a windshield antistatic film of the present embodiment contains a silane coupling agent having an epoxy group, the silane coupling agent having an epoxy group is contained in an amount of 0.01% by mass or more and 0.5% by mass. It is preferably included in the following amounts.

When a silane coupling agent having an epoxy group is used, the composition for forming an antistatic film for a windshield comprises a conductive polymer, an acetylenic surfactant, a water-soluble organic solvent having a boiling point of 180° C. or higher, and a silane coupling agent having an epoxy group, and the balance is an alcohol component and water.

The windshield antistatic film-forming composition of the present embodiment may further contain at least one water-soluble resin selected from water-soluble polyurethanes and water-soluble polyesters. As the water-soluble resin, water-soluble polyurethane or water-soluble polyester may be used alone, or both may be used in combination. The use of a water-soluble resin can improve the adhesion of the antistatic film. Therefore, the antistatic film can be more preferably formed not only on the base material 11 but also on the packing 32 or the external parts coated with an organic coating.

When the composition for forming a windshield antistatic film of the present embodiment contains a water-soluble resin, it preferably contains the water-soluble resin in an amount of 0.01% by mass or more and 2.5% by mass or less.

When a water-soluble resin is used, the windshield antistatic film-forming composition comprises a conductive polymer, an acetylenic surfactant, a water-soluble organic solvent having a boiling point of 180° C. or higher, and a water-soluble resin. with the balance being the alcohol component and water.

The windshield antistatic film-forming composition of the present embodiment can be prepared, for example, by the following procedure. First, an aqueous solution containing a conductive polymer is prepared, an alcohol component is added little by little while stirring, and then other components are added. Furthermore, an alcohol component and/or water may be added for final concentration adjustment. In this manner, the composition for forming a windshield antistatic film of the present embodiment can be obtained.

The first conductive layer 70 of this embodiment contains a conductive polymer. The conductive polymer is, for example, the conductive polymer exemplified in the windshield antistatic film-forming composition of the present embodiment. As the conductive polymer, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) is preferably used from the viewpoint of antistatic performance.

The thickness of the base material 11 is usually 0.5 mm or more and 8 mm or less. The thickness of the first conductive layer 70 is usually 4 nm or more and 1 μm or less.

The first conductive layer 70 is formed, for example, by applying a composition for forming a windshield antistatic film to the back surface 6b of the inorganic layer 6 or the back surface 11b of the substrate 11 and heating the composition to 60° C. or more and 130° C. or less. The formed first conductive layer 70 contains at least a conductive polymer and may contain an acetylenic surfactant. In addition, when the windshield antistatic film-forming composition contains a silane coupling agent having an epoxy group, the first conductive layer 70 may contain a compound derived from the silane coupling agent. Moreover, when the composition for forming an antistatic film for a windshield contains a water-based resin, the first conductive layer 70 may contain the water-based resin.

The conductive film 32a of the packing 32 may be formed from the windshield antistatic film-forming composition of the present embodiment. Further, a conductive film may be formed on the packing 33 using the windshield antistatic film-forming composition of the present embodiment.

As described above, the timepiece 1 of this embodiment has the dial 31 , the exterior case 21 , and the transparent windshield 10 . The exterior case 21 is a member that accommodates the dial 31 and has an opening 21 a facing the dial 31 . The windshield 10 closes the opening 21 a of the exterior case 21 . The windshield 10 has a transparent substrate 11 and a transparent organic layer 7 . The organic layer 7 is formed on the side of the substrate 11 facing the dial 31 and is exposed to the internal space 23 of the outer case 21 . The organic layer 7 has at least one of an antireflection layer and a conductive layer. The organic layer 7 of this embodiment has a first conductive layer 70 . The organic layer 7 can be formed at a lower cost than inorganic layers. By using the organic layer 7, the antireflection function and the antistatic function can be realized in the windshield 10 at low cost.

The windshield 10 of this embodiment has an inorganic layer 6 interposed between the organic layer 7 and the substrate 11 . The first conductive layer 70 covers the inorganic layer 6 from the dial 31 side. By covering the inorganic layer 6 with the first conductive layer having conductivity, the antistatic performance of the windshield 10 is improved.

In addition, the first conductive layer 70 of this embodiment constitutes an antireflection layer together with the inorganic layer 6 . The first conductive layer 70 provides antireflection and antistatic functions.

Moreover, the first conductive layer 70 of the present embodiment is positioned at the outermost layer of the organic layer 7 . Therefore, the first conductive layer 70 can suppress localization of potential on the surface of the windshield 10 .

The timepiece 1 of this embodiment also has a packing 32 interposed between the windshield 10 and the outer case 21 and having a conductive film 32a formed on the surface thereof. A first conductive layer 70 of the organic layer 7 is grounded to the exterior case 21 through the packing 32 . This configuration improves the antistatic performance of the first conductive layer 70 .

The timepiece 1 of this embodiment has an electrostatic motor 4 and hands 36 driven by the electrostatic motor 4 . Therefore, in the timepiece 1 having the electrostatic motor 4, at least one of the antireflection function and the stabilization of the movement of the hands 36 is realized.

[Second embodiment]
A second embodiment will be described with reference to FIG. In the second embodiment, constituent elements having functions similar to those described in the first embodiment are denoted by the same reference numerals, and overlapping descriptions are omitted. FIG. 7 is a cross-sectional view of the windshield according to the second embodiment. The windshield 10 of the second embodiment differs from the windshield 10 of the first embodiment in that the film 12 does not have the inorganic layer 6, for example.

As shown in FIG. 7, the coating 12 of the second embodiment is the organic layer 7 . The organic layer 7 is configured to function as an antireflection layer and has a conductive layer. The organic layer 7 has high refractive index layers 71 , 73 and 75 and low refractive index layers 72 , 74 and 76 . The refractive index of the high refractive index layers 71, 73, 75 is higher than the refractive index of the low refractive index layers 72, 74, 76.

The organic layer 7 is a six-layer laminated film in which high refractive index layers 71, 73, 75 and low refractive index layers 72, 74, 76 are alternately laminated. More specifically, the organic layer 7 includes, from the substrate 11 side, a high refractive index layer 71, a low refractive index layer 72, a high refractive index layer 73, a low refractive index layer 74, a high refractive index layer 75, and a low refractive index layer. Layers 76 are stacked in sequence. That is, the outermost layer of the organic layer 7 is the low refractive index layer 76 . In the organic layer 7 of this embodiment, the high refractive index layer 71 is in contact with the rear surface 11b of the substrate 11 . Further, since the low refractive index layer 76 is arranged as the outermost layer of the organic layer 7, the gap between the refractive index of the outermost layer and the refractive index of air is reduced.

The high refractive index layers 71, 73, 75 and the low refractive index layers 72, 74, 76 of this embodiment are each formed using a polymer. Therefore, the windshield 10 of this embodiment can be manufactured at low cost by a simple method without using a vapor deposition device.

The high refractive index layers 71, 73, 75 contain a high refractive index polymer with a refractive index exceeding 1.5. High refractive index polymers include, for example, Poly(pentabromophenyl methacrylate) (refractive index: 1.7) and Poly(vinylphenylsulfide) (refractive index: 1.7). Alternatively, poly(2-vinylthiophene) (refractive index: 1.6) can be used. The high refractive index polymer may be used singly or in combination of two or more.

The low refractive index layers 72, 74, 76 contain a low refractive index polymer having a refractive index of 1.5 or less. Low refractive index polymers include, for example, Poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), index: 1.4) or poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT/PSS; Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate), refractive index: 1.47 ). The low refractive index polymer may be used singly or in combination of two or more.

The plurality of high refractive index layers 71, 73, and 75 may each contain the same high refractive index polymer, or may contain different high refractive index polymers. Further, the plurality of low refractive index layers 72, 74, 76 may contain the same low refractive index polymer or may contain different low refractive index polymers. The type of polymer can be appropriately selected so as to obtain the desired antireflection performance.

In addition, when the low refractive index layers 72, 74, 76 contain PEDOT/PSS, the low refractive index layers are also excellent in antistatic performance and can be called an antistatic film. Therefore, the film 12 including such a low refractive index layer exhibits antistatic performance as well as antireflection performance when the timepiece 1 is constructed. In particular, from the viewpoint of antistatic performance, it is preferable that the outermost surface low refractive index layer 76 of the coating 12 contains PEDOT/PSS.

The thicknesses of the high refractive index layers 71, 73, 75 and the low refractive index layers 72, 74, 76 and the thickness of the entire coating 12 can be appropriately set so as to obtain desired antireflection performance. The thicknesses of the high refractive index layers 71, 73, 75 and the low refractive index layers 72, 74, 76 are, for example, 0.1 μm or more and 0.4 μm or less.

Furthermore, the film 12 is formed on the back surface 11b of the base material 11, which is on the dial 31 side when the timepiece 1 is constructed. This case is more preferable from the viewpoint of antireflection performance, visibility and scratch resistance.

Note that the number of layers of the coating 12 is not limited to six. As long as the high refractive index layer is in contact with the surface of the base material 11 and the outermost surface of the coating 12 is the low refractive index layer, the coating 12 may be a laminated film other than 6 layers, such as 2 layers, 4 layers, or 8 layers. It may be a film or the like. From the viewpoint of antireflection performance, the number of layers is preferably as large as possible, but from the viewpoint of cost, the number of layers is preferably as small as possible.

The coating 12 may further have another antistatic film on the back side Rz of the antireflection layer. Other antistatic films include, for example, conductive polymers other than PEDOT/PSS. Examples of conductive polymers include polyaniline, polyacetylene, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, and derivatives thereof. The conductive polymer may be used singly or in combination of two or more.

The manufacturing method for manufacturing the windshield 10 of the present embodiment includes, for example, a high refractive index layer forming step (I), a low refractive index layer forming step (II), a high refractive index layer forming step (III), and a low refractive index layer forming. It includes step (IV), high refractive index layer forming step (V), and low refractive index layer forming step (VI).

In the high refractive index layer forming step (I), a composition for forming a high refractive index layer containing a high refractive index polymer having a refractive index exceeding 1.5 is attached to the surface of the substrate 11 and heated to obtain a high refractive index layer. A high refractive index layer 71 containing a refractive index polymer is formed.

Substrate 11 includes glass or plastic. The details of the base material 11 are as described in the windshield 10 of the first embodiment.

The composition for forming a high refractive index layer contains a high refractive index polymer. The details of the high refractive index polymer are as described in the watch windshield of the present embodiment.

The composition for forming a high refractive index layer usually further contains an organic solvent. Examples of organic solvents include chloroform, dichloromethane, dimethylsulfoxide and the like.

Moreover, the composition for forming a high refractive index layer may further contain a silane coupling agent having an epoxy group. When a silane coupling agent having an epoxy group is used, the non-reflection film can be firmly adhered to the base material, especially when the base material is glass. Moreover, the stability of the composition for forming a high refractive index layer is also improved.

Details of the silane coupling agent having an epoxy group are, for example, the same as those described for the windshield 10 of the first embodiment.

In the composition for forming a high refractive index layer, the concentration of the high refractive index polymer can be appropriately adjusted depending on the thickness of the high refractive index layer to be formed. Also, the concentration of the silane coupling agent having an epoxy group can be appropriately adjusted depending on the thickness of the high refractive index layer to be formed.

The high refractive index layer-forming composition may be applied, for example, by spray coating or the like, or by dipping. The composition for forming a high refractive index layer adhered to the substrate may be heated until the organic solvent evaporates. Moreover, heating may be performed in the air or in an inert gas such as nitrogen gas.

Thereby, a high refractive index layer 71 containing a high refractive index polymer having a refractive index exceeding 1.5 can be formed on the surface of the substrate 11 . The high refractive index layer 71 contains at least a high refractive index polymer and may contain a compound derived from a silane coupling agent having an epoxy group.

Next, in the low refractive index layer forming step (II), a low refractive index polymer having a refractive index of 1.5 or less is applied to the surface of the high refractive index layer 71 formed in the high refractive index layer forming step (I). is applied and heated to form a low refractive index layer 72 containing a low refractive index polymer.

The composition for forming a low refractive index layer contains a low refractive index polymer. The details of the low refractive index polymer are as described in the windshield 10 of the present embodiment.

When poly(2,2,3,3,4,4-heptafluorobutyl methacrylate) is used as the low refractive index polymer, the low refractive index layer-forming composition (low refractive index layer-forming composition (A)) typically further comprises an organic solvent. Examples of organic solvents include chloroform, dichloromethane, dimethylsulfoxide, fluorine-based organic solvents, and the like. Among these, fluorine-based organic solvents are preferably used.

The low refractive index layer-forming composition (A) may further contain a silane coupling agent having an epoxy group. Details of the silane coupling agent having an epoxy group in the composition for forming a low refractive index layer (A) are as described for the composition for forming a high refractive index layer.

In the low refractive index layer-forming composition (A), the concentration of the low refractive index polymer can be appropriately adjusted depending on the thickness of the low refractive index layer 72 to be formed. Also, the concentration of the silane coupling agent having an epoxy group can be appropriately adjusted depending on the thickness of the low refractive index layer 72 to be formed.

When PEDOT/PSS is used as the low refractive index polymer, the composition for forming a low refractive index layer (composition for forming a low refractive index layer (B)) is usually combined with the low refractive index polymer to form an acetylenic surfactant. agent, a water-soluble organic solvent having a boiling point of 180° C. or higher, at least one alcohol selected from isopropyl alcohol and ethanol, and water.

When an acetylenic surfactant is used, the low refractive index layer-forming composition (B) is less likely to be repelled during layer formation. Therefore, it can adhere thinly and uniformly.

Acetylene surfactants include acetylene alcohol, acetylene diol, and compounds obtained by adding alkylene oxide thereto. Acetylene-based surfactants may be used singly or in combination of two or more. Details of acetylene alcohol, acetylene diol, and alkylene oxide are the same as those described for the windshield 10 of the first embodiment.

The water-soluble organic solvent having a boiling point of 180° C. or higher slowly evaporates when the low refractive index layer-forming composition (B) is heated during layer formation. As the water-soluble organic solvent slowly evaporates, an intermolecular path (in other words, a path along which conductive electrons can move) of the low refractive index polymer, which is also a conductive polymer, is formed in the meantime. Therefore, an antistatic film capable of exhibiting excellent antistatic performance can be obtained.

Details of the water-soluble organic solvent having a boiling point of 180° C. or more are the same as those described in the windshield 10 of the first embodiment, for example.

In the low refractive index layer-forming composition (B), the balance is at least one alcohol selected from isopropyl alcohol and ethanol, and water. In addition, in this specification, at least one alcohol selected from isopropyl alcohol and ethanol is simply referred to as an alcohol component. As the alcohol component, isopropyl alcohol and ethanol may be used alone, or both may be used in combination. The alcohol component and water have the role of dissolving both the acetylenic surfactant and the low refractive index polymer, which is also a conductive polymer, in the low refractive index layer-forming composition (B).

As the alcohol component, isopropyl alcohol is preferably used from the viewpoint of compatibility.

The low refractive index layer-forming composition (B) may further contain a silane coupling agent having an epoxy group. Details of the silane coupling agent having an epoxy group in the composition for forming a low refractive index layer (B) are as described for the composition for forming a high refractive index layer.

When a silane coupling agent having an epoxy group is used, the composition for forming a low refractive index layer (B) comprises a low refractive index polymer, an acetylenic surfactant, and a water-soluble organic compound having a boiling point of 180°C or higher. It contains a solvent and a silane coupling agent having an epoxy group, and the balance is an alcohol component and water.

In the low refractive index layer-forming composition (B), the concentration of the low refractive index polymer can be appropriately adjusted depending on the thickness of the low refractive index layer 72 to be formed. Also, the concentration of the acetylenic surfactant, the water-soluble organic solvent having a boiling point of 180° C. or higher, or the silane coupling agent having an epoxy group can be appropriately adjusted depending on the thickness of the low refractive index layer 72 to be formed.

The adhesion of the composition for forming a low refractive index layer may be carried out by coating such as spray coating, or may be carried out by dipping. The adhered composition for forming a low refractive index layer may be heated until the solvent evaporates. Moreover, heating may be performed in the air or in an inert gas such as nitrogen gas.

Thereby, a low refractive index layer 72 containing a low refractive index polymer having a refractive index of 1.5 or less can be formed on the surface of the high refractive index layer 71 . The low refractive index layer 72 contains at least a low refractive index polymer and may contain a compound derived from an acetylenic surfactant or a silane coupling agent having an epoxy group.

Furthermore, following the low refractive index layer forming step (II), the high refractive index layer forming step (III), the low refractive index layer forming step (IV), the high refractive index layer forming step (V), and the low refractive index layer A forming step (VI) is performed. The high refractive index layer forming step (III) is the high refractive index layer forming step except for forming the high refractive index layer 73 on the surface of the low refractive index layer 72 formed in the low refractive index layer forming step (II). Same as (I). In addition, the low refractive index layer forming step (IV) includes forming the low refractive index layer 74 on the surface of the high refractive index layer 73 formed in the high refractive index layer forming step (III). It is the same as the formation step (II).

The high refractive index layer forming step (V) is the high refractive index layer forming step except for forming the high refractive index layer 75 on the surface of the low refractive index layer 74 formed in the low refractive index layer forming step (IV). Same as (I). The low refractive index layer forming step (VI) is the low refractive index layer forming step except for forming the low refractive index layer 76 on the surface of the high refractive index layer 75 formed in the high refractive index layer forming step (V). Same as (IV).

By the above manufacturing method, the coating 12 in which the high refractive index layer 71 is in contact with the surface of the substrate 11 and the low refractive index layer 76 is the outermost surface of the non-reflective coating is obtained. When PEDOT/PSS is used as the low refractive index polymer, it is preferably used in the low refractive index layer forming step (VI) from the viewpoint of antistatic performance.

In addition, in the windshield 10 of the present embodiment, when the surface of the coating 12 further has another antistatic film, the step of forming another antistatic film is performed following the low refractive index layer forming step (VI). Do it. Also in this case, it can be manufactured at low cost by a simple method.

As described above, the organic layer 7 of the second embodiment has an antireflection layer in which the high refractive index layers 71, 73, 75 and the low refractive index layers 72, 74, 76 are alternately laminated. The refractive index of the low refractive index layers 72, 74, 76 is lower than the refractive index of the high refractive index layers. Since the organic layer 7 constitutes the antireflection layer, the cost of the windshield 10 can be reduced. In the organic layer 7, the layer closest to the dial 31 may be the conductive layer. In this case, antistatic performance is improved.

[Third Embodiment]
A third embodiment will be described with reference to FIGS. 8 and 9. FIG. In the third embodiment, constituent elements having functions similar to those described in the first and second embodiments are denoted by the same reference numerals, and overlapping descriptions are omitted. 8 is a cross-sectional view of a windshield according to the third embodiment, and FIG. 9 is a cross-sectional view of another windshield according to the third embodiment. The windshield 10 of the third embodiment differs from the windshield 10 of each of the embodiments described above in that, for example, an inorganic layer 8 is formed on the front side Fz of the substrate 11 .

In the windshield 10 shown in FIG. 8, the base material 11, the inorganic layer 6, and the organic layer 7 are the same as the base material 11, the inorganic layer 6, and the organic layer 7 of the first embodiment. The inorganic layer 8 is formed on the front surface 11 a of the substrate 11 .

The inorganic layer 8 has a first inorganic layer 81 and a second inorganic layer 82 . The refractive index n4 of the first inorganic layer 81 is greater than the refractive index n5 of the second inorganic layer 82 . That is, the first inorganic layer 81 is a high refractive index layer, and the second inorganic layer 82 is a low refractive index layer. The inorganic layer 8 is formed by alternately stacking first inorganic layers 81 and second inorganic layers 82 . The illustrated inorganic layer 8 has two first inorganic layers 81 and two second inorganic layers 82 . The first inorganic layer 81 is the layer closest to the rear side Rz in the inorganic layer 8 . That is, the inorganic layer 8 is formed by forming the first inorganic layer 81 on the front surface 11a of the base material 11 and then alternately overlapping the second inorganic layer 82 and the first inorganic layer 81 . The outermost layer of the inorganic layer 8 is the second inorganic layer 82 .

The first inorganic layer 81 is made of silicon nitride (SiN), for example. The second inorganic layer 82 is made of silicon oxide (SiO ₂ ), for example. The inorganic material forming the first inorganic layer 81 is not limited to silicon nitride (SiN), and may be, for example, aluminum oxide (AL ₂ O ₃ ). The inorganic material forming the second inorganic layer 82 is not limited to silicon oxide (SiO ₂ ), and may be, for example, magnesium fluoride (MGF ₂ ). Also, the number of layers of the inorganic layers 8 is not limited to four. The inorganic layer 8 may be, for example, a 2-layer, 6-layer, or 8-layer laminated film.

In the windshield 10 shown in FIG. 9, the substrate 11 and the organic layer 7 are the same as the substrate 11 and the organic layer 7 of the second embodiment. The inorganic layer 8 is formed on the front surface 11 a of the substrate 11 . The structure of the inorganic layer 8 is, for example, the same as that of the inorganic layer 8 described with reference to FIG.

According to the timepiece 1 according to the third embodiment, the antireflection layer is provided on both the front side Fz and the rear side Rz of the substrate 11, thereby improving visibility.

[Modified example of each embodiment]
The timepiece 1 is not limited to an analog wristwatch. The clock 1 may be a digital clock, a wall clock, a table clock, a pocket watch, or the like.

The contents disclosed in the above embodiments and modifications can be executed in combination as appropriate.

REFERENCE SIGNS LIST 1 watch 4 electrostatic motor 6 inorganic layer 7 organic layer 8 inorganic layer 10 windshield 11 base material 11a: front surface 11b: back surface 12 coating 20 watch case 21 outer case 21a, 21b opening 22 back cover 23 internal space 31 dial 31a: Front 31b: Back 32, 33 Packing 32a Conductive film 34 Movement 35 Middle frame 36 Pointer 36a: Second hand 36b: Minute hand 36c: Hour hand 36m: Hand body 37 Parting line 40 Rotor 41 Rotating shaft 42 Electret film 43 Through hole 50 Stator 51: first electrode 52: second electrode 53: third electrode 61 first inorganic layer 62 second inorganic layer 70 first conductive layer 71, 73, 75 high refractive index layer 72, 74, 76 low refractive index Index layer 81 First inorganic layer 82 Second inorganic layer Z-axis direction Fz: front side, Rz: back side

Claims (10)

a dial;
an exterior case containing the dial and having an opening facing the dial;
a transparent windshield that closes the opening;
with
The windshield includes a transparent base material, a transparent organic layer formed on a side of the base material facing the dial and exposed to an internal space of the exterior case,
with
A timepiece, wherein the organic layer has at least a conductive layer out of an antireflection layer and a conductive layer. The organic layer has an antireflection layer in which a high refractive index layer and a low refractive index layer are alternately laminated,
The timepiece according to claim 1 , wherein the refractive index of the low refractive index layer is lower than the refractive index of the high refractive index layer. The windshield has an inorganic layer interposed between the organic layer and the base material,
The organic layer has a first conductive layer that is a conductive layer,
3. The timepiece according to claim 1 , wherein the first conductive layer covers the inorganic layer from the dial side. 4. The timepiece according to claim 3 , wherein the first conductive layer forms an antireflection layer together with the inorganic layer. 4. The timepiece according to any one of claims 1 to 3 , wherein the organic layer has a conductive layer positioned as the outermost layer of the organic layer. a packing interposed between the windshield and the outer case and having a conductive film formed on the surface thereof;
The exterior case is made of a conductive metal,
The timepiece according to any one of claims 1 to 4 , wherein the organic layer has a conductive layer grounded to the exterior case through the packing. an electrostatic motor;
a pointer driven by the electrostatic motor;
The timepiece according to any one of claims 1 to 6 , comprising: a dial;
an exterior case containing the dial and having an opening facing the dial;
a transparent windshield that closes the opening;
with
The windshield includes a transparent base material, a transparent organic layer formed on a side of the base material facing the dial and exposed to an internal space of the exterior case,
with
The organic layer has at least one of an antireflection layer and a conductive layer,
The windshield has an inorganic layer interposed between the organic layer and the base material,
The organic layer has a first conductive layer that is a conductive layer,
The first conductive layer covers the inorganic layer from the dial side.
A clock characterized by: a dial;
an exterior case containing the dial and having an opening facing the dial;
a transparent windshield that closes the opening;
with
The windshield includes a transparent base material, a transparent organic layer formed on a side of the base material facing the dial and exposed to an internal space of the exterior case,
with
The organic layer has at least one of an antireflection layer and a conductive layer,
The organic layer has a conductive layer positioned as the outermost layer of the organic layer.
A clock characterized by: a dial;
an exterior case containing the dial and having an opening facing the dial;
a transparent windshield that closes the opening;
a packing interposed between the windshield and the exterior case and having a conductive film formed on its surface;
with
The windshield includes a transparent base material, a transparent organic layer formed on a side of the base material facing the dial and exposed to an internal space of the exterior case,
with
The organic layer has at least one of an antireflection layer and a conductive layer,
The exterior case is made of a conductive metal,
The organic layer has a conductive layer grounded to the exterior case through the packing.
A clock characterized by:

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