Ceramic for decorative piece and decorative piece

The present invention relates to decorative parts for fishing thread guidance, decorative parts for watches, decorative parts for portable terminals, decorative parts for daily necessities, decorative parts for accessories, decorative parts for building materials, decorative parts for kitchens, decorative parts for automobiles, and home appliances. It is related to ceramics for decorative parts that bring out a beautiful golden color tone used for decorative parts and religious crafts, especially for decorative parts for fishing thread guides such as guide rings for fishing threads, for watches such as wristwatch cases and band pieces. It relates to decorative parts, decorative parts for portable terminals such as various operation keys and cases to be pressed, and decorative parts for daily necessities such as soap cases and scissors.

Conventionally, metal-based materials have been used for decorative parts used for guides for fishing threads, watches, etc. However, decorative parts made of metal-based materials have insufficient wear resistance and hardness, so that they are decorative parts. There is a problem that the surface is easily damaged and the decorativeness is gradually impaired.

In addition, a base layer is formed on the surface of the base material, and a DLC (Diamond Like Carbon) film is formed by CVD (Chemical Vapor Deposition) that excites the gas into a plasma state, resulting in abrasion resistance on the surface. However, some of them are not suitable for decorative parts because the coating layer is easily peeled off or the coating layer is damaged.

Therefore, in order to solve such a problem, ceramics having high hardness are being used for decorative parts used for guides for fishing threads, watches, etc., and the present inventor has shown in Patent Document 1. He has proposed a ceramic sintered body composed of a first hard phase containing a nitride of titanium, a second hard phase containing at least one of alumina or zirconia, and a bonded phase containing nickel. According to this ceramic sintered body, in sliding under wet conditions, the surface layer of the first hard phase containing titanium nitride becomes an oxide and expands in volume, but the second hard phase causes the first hard phase. Is protected and the first hard phase does not desorb, so that it can exhibit excellent wear resistance and high hardness, and this ceramic sintered body can be used as a decorative part for fishing thread guides. It is stated that it can be applied to decorative parts for watches.<patcit num="1"><text>International Publication No. 05/0931 10 Pamphlet</text></patcit>

<p> However, in the ceramic sintered body proposed by the present inventor in Patent Document 1, when this ceramic sintered body is used as a guide member for a fishing thread and slid with the fishing thread under a dry method, a titanium nitride is produced. Although the surface layer of the first hard phase containing the oxide becomes an oxide and expands in volume, the second hard phase protects the first hard phase and prevents the first hard phase from desorbing, which is excellent. Although it can exhibit abrasion resistance and high hardness, it has recently been attempted to use such a ceramic sintered body not only for decorative parts for watches but also for various operation keys of mobile terminals. Therefore, the decorative parts worn or carried by consumers are required to be further improved in hardness so as to withstand mechanical impact. In addition, such decorative parts are required to have a golden color tone that can give a sense of quality, aesthetic satisfaction and mental comfort.</p><p> The present invention has been devised to solve the above problems, and has a high hardness and a golden color tone that can give consumers a sense of luxury, aesthetic satisfaction and mental comfort for a long period of time. An object of the present invention is to provide ceramics for decorative parts, decorative parts for guiding fishing threads using the same, decorative parts for watches, decorative parts for mobile terminals, and decorative parts for daily necessities.</p>

<p> The ceramic for decorative parts of the present invention is characterized by containing titanium nitride as a main component and zirconium oxide, tantalum nitride and nickel.</p><p> Further, in the above configuration, the ceramic for decorative parts of the present invention has the zirconium oxide content of 9% by mass or more and 30% by mass or less, and the tantalum nitride content of 9% by mass or more and 23% by mass or less. , The nickel content is 3% by mass or more and 10% by mass or less.</p><p> Further, the ceramics for decorative parts of the present invention are characterized in that they further contain chromium in any of the above configurations.</p><p> Further, the ceramics for decorative parts of the present invention are characterized by further containing manganese in any of the above configurations.</p><p> Further, in any of the above configurations, the ceramics for decorative parts of the present invention have a CIE1976 L * a * b * color space brightness index L * of 60 or more and 70 or less, and a chromaticity index a *, b *. Is 4.5 or more and 6.5 or less, and 10 or more and 20 or less, respectively.</p><p> Further, the decorative part for guiding the fishing thread of the present invention is characterized by being made of the ceramic for the decorative part of the present invention having any of the above configurations.</p><p> Further, the decorative parts for watches of the present invention are characterized by being made of the ceramics for decorative parts of the present invention having any of the above configurations.</p><p> Further, the decorative parts for mobile terminals of the present invention are characterized by being made of ceramics for decorative parts having any of the above configurations.</p><p> Further, the decorative parts for daily necessities of the present invention are characterized by being made of ceramics for decorative parts having any of the above configurations.</p>

<p> According to the ceramics for decorative parts of the present invention, since titanium nitride is the main component and contains zirconium oxide, tantalum nitride and nickel, each crystal particle of titanium nitride and tantalum nitride on the surface layer of the ceramics for decorative parts is oxidized. Since zirconium oxide suppresses the volume expansion at that time, it is possible to suppress the degranulation of each crystal particle of titanium nitride and tantalum nitride. Further, by including tantalum nitride, the hardness of ceramics for decorative parts can be improved. Further, by containing nickel, it acts as a binder that firmly binds the crystal particles of titanium nitride and tantalum nitride to each other and the crystal particles of titanium nitride and the crystal particles of tantalum nitride, so that the fracture toughness can be improved. .. In addition, the golden color tone of titanium nitride is exquisitely fused with the glossy brownish color tone of tantalum nitride and the silver color tone of nickel, so it is a golden color with extremely high decorative value. Can bring out the color tone of.</p><p> Further, according to the ceramics for decorative parts of the present invention, the content of zirconium oxide is 9% by mass or more and 30% by mass or less, the content of tantalum nitride is 9% by mass or more and 23% by mass or less, and the content of nickel is contained. When the amount is 3% by mass or more and 10% by mass or less, the volume expansion when the surface layer of the ceramic for decorative parts is oxidized is suppressed, and the crystal particles of titanium nitride and tantalum nitride are more difficult to degrease and become high temperature. After heating and sintering, when cooled to room temperature, the volume expansion that occurs with the phase transition of zirconium oxide is suppressed, so cracks are less likely to occur in the bonded phase formed by nickel, so polishing resistance Abrasion can be improved. Further, since the content of tantalum nitride is 9% by mass or more and 23% by mass or less, the hardness of the ceramics for decorative parts can be increased without impairing the vividness of the color tone of the ceramics for decorative parts. Further, since the nickel content is 3% by mass or more and 10% by mass or less, the crystal particles of titanium nitride and tantalum nitride and the crystal particles of titanium nitride can be used without reducing the hardness of the ceramics for decorative parts. Since it acts as a binder that firmly binds the crystal particles of tantalum nitride, the fracture toughness becomes higher, so that the abrasion resistance can be improved.</p><p> Further, according to the ceramics for decorative parts of the present invention, when chromium is further contained, it combines with oxygen in the air to form a dense oxide film on the surface, so that corrosion resistance can be improved, so that it has a high-class feeling and aesthetics. It can continue to provide satisfaction and mental comfort for a long period of time.</p><p> Further, according to the ceramics for decorative parts of the present invention, when manganese is further contained, the granules obtained by spray drying are suppressed from oxidation by containing manganese having a high ionization tendency and a strong oxygen adsorption action, and the decoration is performed. It is possible to suppress variations in the color tone of the surface.</p><p> Further, according to the ceramics for decorative parts of the present invention, the CIE1976 L * a * b * color space of the decorative surface has a brightness index L * of 60 or more and 70 or less, and a chromaticity index a * and b * of 4.5 or more and 6.5, respectively. Below, when it is 10 or more and 20 or less, it becomes a golden color tone having moderate brightness and vividness, and it is possible to continue to give a sense of luxury, aesthetic satisfaction and mental comfort for a long period of time.</p><p> Further, according to the decorative part for guiding the fishing thread of the present invention made of the ceramic for the decorative part of the present invention, the surface has high hardness even if it is rubbed by fine sand or the like adhering to the fishing thread when guiding the fishing thread. It is hard to be scratched and can withstand long-term use while maintaining a golden color tone.</p><p> Further, according to the decorative parts for watches of the present invention made of the ceramics for decorative parts of the present invention, a golden color tone having a high decorative value can be obtained, and the wear resistance is excellent and the hardness is high. Therefore, it is possible to continue to give the consumer a sense of luxury, aesthetic satisfaction and mental comfort through the visual sense for a long period of time.</p><p> Further, according to the decorative parts for mobile terminals of the present invention made of the ceramics for decorative parts of the present invention, a golden color tone having a high decorative value can be obtained, and the wear resistance is excellent and the hardness is high. Therefore, it can be suitably used for a mobile terminal in which fashionability is important as well as function.</p><p> Further, according to the decorative parts for daily necessities of the present invention made of the ceramics for decorative parts of the present invention, when the soap case, the handle of a brush or razor, the ear pad, the scissors, etc. are formed of the ceramics for decorative parts of the present invention, they are decorated. It becomes a golden color tone with high value, and when used, it can give a sense of luxury, aesthetic satisfaction and mental comfort through the eyes.</p>

Hereinafter, examples of embodiments of the ceramics for decorative parts of the present invention will be described. First, the ceramics for decorative parts of the present invention contain titanium nitride as a main component, and zirconium oxide, tantalum nitride, and nickel. The main component referred to here is a component that occupies 50% by mass or more with respect to 100% by mass of all the components constituting the ceramics for decorative parts. Titanium nitride, which is the main component, exhibits a good golden color tone as a decorative part and has features such as high mechanical properties such as strength and hardness. Therefore, in the ceramics for decorative parts of the present invention. Is preferably contained in a content of 70% by mass or more of titanium nitride.

Zirconium oxide also affects wear resistance. When sweat, muddy water, etc. adhere to ceramics containing titanium nitride as the main component and containing tantalum nitride and nickel and not containing zirconium oxide, the surface layer is oxidized and tantalum nitride and tantalum nitride become titanium oxide and tantalum oxide, respectively. Occasionally, the volume expands and the crystal particles of titanium nitride and tantalum nitride are easily degranulated. On the other hand, even if sweat, muddy water, etc. adhere to ceramics containing titanium nitride as a main component and containing zirconium oxide, tantalum nitride, and nickel, the crystal particles of zirconium oxide expand in volume when the surface layer of the ceramics is oxidized. It is possible to suppress the degranulation of each crystal particle of titanium nitride and tantalum nitride.

Further, by including tantalum nitride, the hardness of ceramics for decorative parts can be improved. Further, by containing nickel, it can act as a binder to firmly bond the crystal particles of titanium nitride and tantalum nitride, and the crystal particles of titanium nitride and the crystal particles of tantalum nitride, and can improve the fracture toughness. Titanium nitride, zirconium oxide, tantalum nitride and nickel constituting the ceramics for decorative parts of the present invention can be identified by X-ray diffraction.

As described above, since the ceramic for decorative parts of the present invention contains titanium nitride as a main component and contains zirconium oxide, tantalum nitride and nickel, the surface layer of each crystal particle of titanium nitride and tantalum nitride is oxidized and expanded in volume. However, since these crystal particles are protected by zirconium oxide, these crystal particles are rarely degranulated, and in addition to the golden color tone of titanium nitride, the glossy brownish color tone of tantalum nitride and the silver color of nickel. Since the color tone of the system is exquisitely fused, it is possible to create a golden color tone with extremely high decorative value. As described above, since titanium nitride is the main component and contains zirconium oxide, tantalum nitride, and nickel, the ceramics for decorative parts have excellent wear resistance, fracture toughness, and high hardness while producing a color tone having high decorative value. Can be.

Further, the ceramics for decorative parts of the present invention have a zirconium oxide content of 9% by mass or more and 30% by mass or less, a tantalum nitride content of 9% by mass or more and 23% by mass or less, and a nickel content of 9% by mass or more and 23% by mass or less. It is preferably 3% by mass or more and 10% by mass or less.

When the content of zirconium oxide is 9% by mass or more and 30% by mass or less, the crystal particles of titanium nitride and tantalum nitride are more difficult to degrease due to the above-mentioned reasons, and after being heated to a high temperature and sintered, the temperature is normal. Since the volume expansion generated by the phase transition of zirconium oxide when cooled to the above level is suppressed, cracks are less likely to occur in the bonded phase formed by nickel, so that wear resistance can be improved.

In the ceramics for decorative parts of the present invention, most of the crystal structure of zirconium oxide at room temperature is monoclinic crystal, and the phase transitions to tetragonal crystal and cubic crystal in order with volume shrinkage due to heating during sintering. When cooled, the phase transitions to tetragonal and monoclinic in order with volume expansion.

Further, when the content of tantalum nitride is 9% by mass or more and 23% by mass or less, the hardness of the ceramics for decorative parts can be increased without impairing the vividness of the color tone of the ceramics for decorative parts.

When the nickel content is 3% by mass or more and 10% by mass or less, the crystal particles of titanium nitride and tantalum nitride and the crystal particles of titanium nitride and nitride are nitrided with almost no decrease in the hardness of the ceramics for decorative parts. Since it acts as a binder that firmly binds the crystal particles of tantalum and has higher breaking toughness, wear resistance can be improved.

The contents of titanium nitride, zirconium oxide, tantalum nitride, and nickel constituting the ceramics for decorative parts of the present invention can be determined by a fluorescent X-ray analysis method or an ICP (Inductivity Coupled Plasma) emission analysis method. Specifically, for titanium nitride and tantalum nitride, the content of the metal element of Ti and Ta is measured and converted into a nitride, and for zirconium oxide, the content of the metal element of Zr is measured and oxidized. It can be converted into a thing. For nickel, the measured value of the metal element of Ni is the content.

Further, the ceramics for decorative parts of the present invention preferably further contain chromium. Chromium combines with oxygen in the air to form a dense oxide film on the surface, which can improve corrosion resistance, and with nickel surrounding the chromium, titanium nitride and tantalum nitride crystal particles and each other. By forming a bonding phase that bonds the crystal particles of titanium nitride and the crystal particles of tantalum nitride, nickel reacts with chromium to form a nickel-chromium compound, and it is possible to suppress the ionization and outflow of nickel. .. However, since the content of chromium affects the vividness of color, in order to suppress the outflow of nickel and to have both corrosion resistance and vividness, in particular, the content of chromium is 1.5% by mass or more and 5% by mass or less. It is preferable to include it.

The state in which nickel surrounds chromium means a state in which chromium is surrounded by a bonding phase without contacting with crystal particles of titanium nitride. In this state, a decorative surface obtained by a scanning electron microscope is used. It can be confirmed by comparing the image of the above with the image of the decorative surface showing the distribution state of nickel and chromium detected by the energy dispersive (EDS) X-ray microscope.

Here, the decorative surface in the ceramics for decorative parts of the present invention refers to a surface on which the decorative value of the decorative part is required, and does not need to include a surface on which the decorative value is not required, and thus refers to all surfaces. is not it. For example, when the ceramics for decorative parts of the present invention are used for a watch case, the outer surface of the watch case is a decorative surface because it is an object of appreciation and a decorative value is required. The inner surface or the like into which the drive mechanism of the watch is fitted is not a decorative surface because usually no decorative value is required.

Further, the ceramics for decorative parts of the present invention preferably further contain manganese. This is because manganese has a high ionization tendency and has a strong oxygen adsorption action. Therefore, by containing manganese, it is possible to suppress the oxidation of the granules obtained by spray drying and suppress the variation in the color tone of the decorative surface.

Whether or not chromium and manganese are contained in the ceramics for decorative parts and their contents can be determined by a fluorescent X-ray analysis method or an ICP (Inductivity Coupled Plasma) emission analysis method.

Further, in the ceramics for decorative parts of the present invention, the value of the brightness index L * in the CIE1976 L * a * b * color space of the decorative surface is 60 or more and 70 or less, and the values of the chromaticity indexes a * and b * are 4.5, respectively. It is preferably 6.5 or more and 10 or more and 20 or less. Within this range, the golden color tone has moderate brightness and vividness, and it is possible to continue to give a sense of luxury, aesthetic satisfaction and mental comfort for a long period of time.

Here, the lightness index L * is an index indicating the lightness and darkness of the color tone. When the value of the lightness index L * is large, the color tone is bright, and when the value of the lightness index L * is small, the color tone is dark. The chromaticity index a * is an index that indicates the degree of color tone from red to green. When the value of a * is large in the positive direction, the color tone becomes red, and as the absolute value decreases, the color tone lacks vividness. The color tone becomes dull, and when the value of a * is large in the negative direction, the color tone becomes green. Furthermore, the chromaticity index b * is an index showing the degree of yellow to blue of the color tone, and when the value of b * is large in the positive direction, the color tone becomes yellow, and as the absolute value becomes smaller, the color tone lacks vividness. The color tone becomes dull, and when the value of b * is large in the negative direction, the color tone becomes blue.

The values of the brightness index L * and the chromaticity indexes a * and b * in the CIE1976 L * a * b * color space of such a decorative surface are obtained by measuring in accordance with JIS Z 8722-2000. Be done. For example, using a spectrophotometer (CM-3700d manufactured by Konica Minolta Holdings Co., Ltd.), the light source can be set to CIE standard light source D65, the viewing angle can be set to 10 °, and the measurement range can be set to 5 mm x 7 mm. ..

Further, since the arithmetic average height Ra of the decorative surface affects the reflectance of light and the color tone changes, it is preferable to set the arithmetic average height Ra of the decorative surface to 0.03 μm or less. As a result, the reflectance of light is increased, and the value of the brightness index L * can be increased. If the arithmetic mean height Ra exceeds 0.03 μm, the value of the brightness index L * may decrease, the color tone may become dark, and the sense of quality may decrease.

This light is a set of visible light in the wavelength range of 380 to 780 nm. By setting the arithmetic average height Ra to 0.03 μm or less, the visible light is dispersed and the light in the wavelength range of 450 to 500 nm showing blue is reflected. It acts to increase the reflection of light in the wavelength range of 570 to 590 nm, which indicates yellow, so that it can exhibit a golden color that gives a sense of luxury, aesthetic satisfaction, and mental comfort. In particular, the reflectance of the decorative surface to light in the wavelength range of 570 to 700 nm is preferably 50% or more.

The arithmetic mean height Ra may be measured in accordance with JIS B 0601-2001, and the measurement length and cutoff value shall be 5 mm and 0.8 mm, respectively, and measured using a stylus type surface roughness meter. In some cases, for example, a stylus with a stylus tip radius of 2 μm was applied to the decorative surface of ceramics for decorative parts, and the scanning speed of the stylus was set to 0.5 mm / sec. Let the average value of be the value of the arithmetic mean height Ra.

Further, in the ceramics for decorative parts of the present invention, the open porosity on the decorative surface affects the value of the lightness index L *, and when the open porosity is high, the value of the lightness index L * becomes small and the open porosity is low. And the value of the brightness index L * becomes large. Therefore, the open porosity on the decorative surface is preferably 2.5% or less, and more preferably 1.1% or less.

For the porosity of the decorative surface, use a metallurgical microscope at a magnification of 200 times, capture the image of the decorative surface with a CCD camera, and use an image analyzer (LUZEX-FS, etc. manufactured by NIRECO CORPORATION) to capture the image in the image. Measured area of 1 field of view is 2.25 x 10^-2mm², The number of measurement fields is 20, that is, the total measurement area is 4.5 × 10.^-1mm²The area of the open pores in the above can be obtained, and the ratio to the total measured area may be the open porosity of the decorative surface.

Further, in the ceramics for decorative parts of the present invention, the composition formula of titanium nitride, which is the main component, is TiN._xWhen, it is preferable that 0.8 x 0.96. Composition formula is TiN_xThe color tone is affected by the value of the number of atoms x when. When the number of atoms x becomes small, the color tone changes from golden to light golden, and when the number of atoms x becomes large, the color tone becomes dull and dark golden. From this point of view, the composition formula is TiN._xThe value of the number of atoms x is preferably 0.8 or more and 0.96 or less, and when the value of the number of atoms x is in this range, the glossy color tone is further increased, resulting in a higher sense of quality and aesthetic satisfaction. You can get a feeling.

The decorative part for guiding the fishing thread of the present invention is characterized by being made of the ceramic for the decorative part of the present invention having the above configuration, and specific examples thereof include a guide ring for fishing thread and a guide for fishing thread provided with the guide ring for fishing thread. is there.

FIG. 1 shows an example of a guide ring for fishing thread, which is a decorative part for guiding fishing thread of the present invention, and a guide ring for fishing thread provided with the guide ring for fishing thread, and FIG. 1A is a plan view of the guide ring for fishing thread. , (B) are perspective views of a fishing thread guide provided with the fishing thread guide ring of (a).

The fishing rod guide ring 1 of the example shown in FIG. 1 is for guiding by inserting a fishing thread (not shown) on the inner peripheral side thereof, and the fishing thread guide 6 is a holding portion 2 for holding the fishing thread guide ring 1. A guide ring 1 for fishing thread is provided on a frame body 5 in which a support portion 3 of the holding portion 2 and a fixing portion 4 fixed to a fishing rod (not shown) are integrally formed. By forming the fishing thread guide ring 1 with the ceramics for decorative parts of the present invention, it is possible to give the consumer a sense of luxury, aesthetic satisfaction and mental comfort.

Further, since the guide ring 1 for fishing thread having a golden color and the guide 6 for fishing thread and the color tone of the fishing rod are in good harmony, it can be suitably used for fishing tackle. In particular, since it exhibits a golden color tone, it can be used as a fishing tackle preferred by those who seek a high-class feeling from their luxury items. The surface of the fishing guide ring 1 may be coated with a transparent film having high wear resistance, for example, a film made of amorphous hard carbon to further improve the wear resistance.

FIG. 2 shows an example of a watch case which is a decorative part for a watch of the present invention, (a) is a perspective view of the watch case as viewed from the front side, and (b) is a watch case of (a). Is a perspective view seen from the back side. Further, FIG. 3 is a perspective view showing another example of the watch case, which is a decorative component for the watch of the present invention. Further, FIG. 4 is a schematic view showing an example of the configuration of a watch band, which is a decorative part for a watch of the present invention. In these figures, when the same parts are shown, the same reference numerals are given.

The watch case 10A of the example shown in FIG. 2 includes a recess 11 for accommodating a movement (drive mechanism) (not shown) and a foot portion 12 for fixing a watch band (not shown) for attaching the watch to the arm. The recess 11 is composed of a thin bottom portion 13 and a thick body portion 14. Further, the watch case 10B of the example shown in FIG. 3 has a hole 15 for inserting a movement (drive mechanism) (not shown) and a watch band (not shown) for attaching the watch to the arm formed on the body 14. It is equipped with a foot 12 to fix the watch.

Then, the band pieces constituting the watch band 50 of the example shown in FIG. 4 are arranged so as to sandwich the middle piece 20 having the through hole 21 into which the pin 40 is inserted and the middle piece 20, and both ends of the pin 40 are inserted. It is composed of an outer piece 30 having a pin hole 31 to be inserted, and the pin 40 is inserted into the through hole 21 of the middle piece 20, and both ends of the inserted pin 40 are inserted into the pin hole 31 of the outer piece 30. , The middle piece 20 and the outer piece 30 are sequentially connected to form a watch band 50.

Further, since the middle piece 20 is frequently subjected to a tensile load, a tensile strength of 196 N or more is required. To obtain this tensile strength, insert a cemented carbide pin (not shown) longer than the length of the through hole 21 into the through holes 21a and 21b of the middle piece 20, and then pull the pin in the pulling direction to separate the middle piece. The strength at the time when 20 is broken can be read by the load cell.

Since the decorative parts for the watch of the present invention used as the band pieces constituting the watch cases 10A and 10B and the band 50 for the watch are made of the ceramics for the decorative parts of the present invention, they have a high-class feeling as a watch. You can get enough aesthetic satisfaction and get mental comfort through your eyes.

FIG. 5 is a perspective view showing an example of a mobile phone using the decorative parts for a mobile terminal of the present invention, and FIG. 6 is a perspective view showing a state in which the housing of the mobile phone of the example shown in FIG. 5 is open. Is. The decorative parts for mobile terminals of the present invention are characterized by being made of the ceramics for decorative parts of the present invention, and specific examples thereof include various operation keys and cases to be pressed in the examples shown in FIGS. 5 and 6.

The mobile phone 60 in the example shown in FIG. 5 has a mode key 61a that changes the mode of the mobile phone 60 to a radio mode that is a radio listening mode, a music mode that is a music listening mode, and the manner mode of the mobile phone 60. The first housing 62 is equipped with a manner key 61b to be used, and a touch sensor 63 that detects contact with a finger or the like and inputs by this contact, a camera 64 that captures a subject, a light 65, and a touch sensor. The second housing 67 is provided with a slide switch 66 for setting valid or invalid input of 63 or the like.

Next, the mobile phone 60 of the example shown in FIG. 6 shows a state in which the second housing 67 is open, and the first housing 62 and the second housing 67 are connected to each other via the hinge 68. The second housing 67 can be freely opened and closed. Further, the second housing 67 has a front case 69a and a rear case 69b, and the front case 69a is provided with a liquid crystal display unit 70.

The first housing 62 also has a front case 71a and a rear case 71b, and the front case 71a is provided with various operation keys. These operation keys include a numeric keypad 72a for entering a phone number, a cursor movement key 72b for moving the cursor about menus of various functions, a call key 72c for starting a call by pressing when receiving a call, power on / off and during a call. There are power / end call keys 72d, function keys 73L, 73R, etc. located on the left and right of the center key 72f located in the center of the cursor movement key 72b.

The above cases are front case 69a and 71a, rear case 69b and 71b, operation key numeric keypad 72a, cursor movement key 72b, call key 72c, power / end call key 72d, center key 72f, function key 73L and R, etc. By forming at least one of the above ceramics for decorative parts of the present invention, the consumer is given a sense of luxury, aesthetic satisfaction and mental comfort for a long period of time, and owning a mobile phone exhibiting such a color tone. You can feel the satisfaction of. Further, since the ceramics for decorative parts of the present invention have good compatibility with other color tones, they can be used in combination with members of various color tones, so that it is possible to meet the diversification of consumers' tastes.

Although a mobile phone has been described as an example of a mobile terminal, the mobile terminal on which the mobile terminal of the present invention is used is not limited to the mobile phone, and is a mobile information terminal (PDA) or a portable type. Various mobile terminals are applicable as long as they are portable terminals such as car navigation systems and audio players and the parts are required to be decorative.

FIG. 7 is a schematic view showing an example of the configuration of a soap case using the decorative parts for daily necessities of the present invention. The soap case 80 is composed of a main body 83 and a lid 82, and a discharge hole 85 for draining water adhering to the surface of the soap 81 is formed on the mounting surface 84 of the soap 81 of the main body 83. .. When the soap 81 is not used, the soap 81 is placed on the mounting surface 84 of the main body 83 and is stored by fitting the lid 82 to the main body 83. When the soap 81 is used, the main body 83 to the lid 82 are moved. Remove and take out soap 81 for use. Then, by placing the used soap 81 on the mounting surface 84 of the main body 83, the water adhering to the surface of the soap 81 can be drained by the discharge hole 85, and the soap 81 can be prevented from melting. Can be done.

By forming the main body 83 and the lid 82 of the soap case 80 with the ceramics for decorative parts of the present invention, a feeling of satisfaction by having many consumers and a feeling of luxury and aesthetic satisfaction through the eyes when using the soap case 80. And can give mental comfort. Further, it can be suitably used not only for the soap case 80 but also for decorative parts for daily necessities such as toothbrushes, razor handles, earpicks and scissors. In particular, in bathrooms and washrooms of luxury hotels, by using the ceramics for decorative parts of the present invention for amenity goods marked with various logos, etc., a sense of luxury, aesthetic satisfaction and spirituality are strongly produced. It can give you peace of mind.

The Vickers hardness of the ceramics for decorative parts of the present invention can be measured in accordance with JIS R 1610-2003. Further, the wear resistance of the ceramics for decorative parts of the present invention can be evaluated by producing an wear resistance evaluation device having the configuration shown below and using the device.

FIG. 8 is a schematic configuration diagram of an abrasion resistance evaluation device used for evaluating the abrasion resistance of the ceramics for decorative parts of the present invention. The wear resistance evaluation device 100 connects the nylon thread 102, a plurality of pulleys 103 that apply tension to the thread 102 at a predetermined position, and the pulley 103a, which is one of the pulleys 103, to connect the thread 102 to the arrow. It consists of a motor (not shown) that runs in a direction and a water tank 104 that attaches muddy water to the thread 102. A load corresponding to the mass of the weight 105 is applied, and the thread 102 to which muddy water adheres through the water tank 104 is placed at a predetermined position. It has a structure that slides on the outer peripheral surface of the columnar ceramics 101 for decorative parts fixed with a jig (not shown) or the like, and the number of the nylon thread 102 may be, for example, 3. ..

The conditions for evaluating the wear resistance of the decorative parts ceramics 101 using this wear resistance evaluation device 100 are, for example, a weight 105 having a mass of 500 g and a thread 102 having a columnar decorative parts 101. The speed of sliding on the outer circumference of the ceramic is set to 60 m / min, and the mileage of the thread 102 may be set to 3000 m or more. Then, after driving the motor and sliding the thread 102, the surface shape measuring microscope (Keyence measuring unit VF-7510 / controller VF) is used to remove the deepest part of the scratch caused by the wear of the columnar decorative ceramics 101. Abrasion resistance can be evaluated by measuring using -7500) and comparing these measured values.

Next, an example of the method for manufacturing the ceramics for decorative parts of the present invention will be described. In order to obtain the ceramics for decorative parts of the present invention, first, titanium nitride as a main component and zirconium oxide, tantalum carbide or tantalum nitride and nickel powders are weighed in a predetermined amount, pulverized and mixed to prepare a blending raw material. To do. More specifically, a titanium nitride powder having an average particle size of 10 μm or more and 30 μm or less, a zirconium oxide powder having an average particle size of 1 μm or more and 2 μm or less, and a tantalum carbide powder having an average particle size of 1 μm or more and 3 μm or less. Prepare tantalum nitride powder with an average particle size of 1 μm or more and 3 μm or less and nickel powder with an average particle size of 10 μm or more and 20 μm or less. The tantalum nitride powder may be 8% by mass or more and 25% by mass or less, the nickel powder may be 2% by mass or more and 12% by mass or less, and the balance may be weighed and crushed / mixed so as to be titanium nitride powder.

When the content of zirconium oxide is 9% by mass or more and 30% by mass or less, the content of tantalum nitride is 9% by mass or more and 23% by mass or less, and the content of nickel is 3% by mass or more and 10% by mass or less. In order to obtain a certain ceramic for decorative parts, the ratio of each component in the compounding raw material may be the same as the content of each component in the sintered body.

Further, in order to obtain ceramics for decorative parts containing chromium, a chromium powder having an average particle size of 3 μm or more and 10 μm or less or a composition formula of Cr is used.₃C₂Chromium carbide powder with an average particle size of 3 μm or more and 10 μm or less is used as a part of the compounding raw material, and when chromium powder is used, the ratio is 1.5% by mass or more and 5% by mass or less, and chromium carbide is used. When the powder of No. 1 is used, the ratio may be 1.8% by mass or more and 6.2% by mass or less.

Further, in order to obtain ceramics for decorative parts containing manganese, a manganese powder having an average particle size of 13 μm or more and 23 μm or less or a composition formula of MnCO is used.₃Manganese carbonate powder with an average particle size of 13 μm or more and 23 μm or less is used as a part of the compounding raw material, and when manganese powder is used, the ratio is 0.2% by mass or more and 0.4% by mass or less, and manganese carbonate is used. When the powder of No. 1 is used, the ratio may be 0.4% by mass or more and 0.8% by mass or less.

In order to form a bonding phase in which the crystal particles of titanium nitride and tantalum nitride and the crystal particles of titanium nitride and the crystal particles of tantalum nitride are bonded to each other while nickel surrounds chromium, the nickel powder and chromium are used. It is necessary to increase the frequency of contact with the powder or chromium carbide powder. In order to increase this frequency, the crushing / mixing time may be lengthened, for example, the crushing / mixing time may be 150 hours or more. At this time, examples of unavoidable impurities in this compounding raw material include silicon, phosphorus, sulfur, iron, etc., but since these may adversely affect the color tone of the decorative surface, it is preferable that each of them is less than 0.5% by mass. is there.

Also, the titanium nitride powder may have a stoichiometric composition of TiN or a non-stoichiometric composition of TiN._xAlthough it may be (0 &lt;x &lt;1), the purity of each powder is preferably 99% or more, and the titanium nitride powder is one, from the viewpoint of abrasion resistance and color tone having high decorative value. There is no problem even if a small amount of TiNi is produced by reacting with the partial nickel powder. In particular, the composition formula of titanium nitride, which is the main component of ceramics for decorative parts, is TiN._xTo make 0.8 x 0.96, the composition formula of the titanium nitride powder should be TiN._xWhen, 0.7 x 0.9 may be used.

Next, isopropanol, for example, as an organic solvent is added to the compounding raw material, mixed and pulverized using a mill, and then a predetermined amount of paraffin wax is added as a binder, and a desired molding method, for example, a dry pressure molding method, cold stilling, is performed. It is molded into a desired shape such as a disk, flat plate, or ring by a hydraulic pressure molding method, an extrusion molding method, or the like.

When dry pressurization is selected as the molding method, the molding pressure affects the open porosity and Vickers hardness (Hv) on the decorative surface, so it is preferable to set the molding pressure to 49 MPa or more and 196 MPa or less. .. By setting the molding pressure to 49 MPa or more and 196 MPa or less, the life of the molding mold can be extended, the relative density is 95% or more, the open porosity is 2.5% or less, and the Vickers hardness (Hv) is 13 GPa. The above sintered body can be obtained.

Then, the obtained molded product is degreased in a non-oxidizing atmosphere such as a nitrogen atmosphere or an inert gas atmosphere as necessary, and then fired in a nitrogen atmosphere, and sintered having a relative density of 95% or more with respect to the theoretical density. Get the body. In addition, when firing in a nitrogen atmosphere, when firing in an oxidizing atmosphere, titanium is oxidized and most of it is composed of TiO.₂This is because the titanium oxide is represented by, and is affected by the white color tone inherent in this titanium oxide, and the overall color tone of the ceramics for decorative parts becomes whitish and hazy.

Further, it is preferable that the firing temperature is 1400 ° C or higher and 1550 ° C or lower. This is because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and the firing cost can be reduced.

Then, the surface of the obtained sintered body for which the decorative value is required is wrapped by using a lapping machine and then barrel-polished, so that the surface of the sintered body is decorated with a golden color tone. As a surface, the ceramics for decorative parts of the present invention can be obtained. It is preferable that the maximum diameter of the pores appearing on such a decorative surface is 30 μm or less, and by setting the maximum diameter within this range, germs, foreign substances, contaminants, etc. may adhere to the pores. Can be reduced.

If the shape of the product made of ceramics for decorative parts is complicated, it is close to the block shape or product shape by the dry pressure molding method, cold hydrostatic pressure molding method, extrusion molding method, injection molding method, etc. in advance. It may be molded into a shape, sintered, then ground to form a product shape, and then lapped and barrel-polished in sequence, or it may be formed into a product shape by an injection molding method from the beginning, and after firing, it is sequentially formed. Lapping and barrel polishing may be performed.

Here, in order to reduce the arithmetic mean height Ra of the surface to be the decorative surface to 0.03 μm or less, diamond abrasive grains having a small average particle size may be supplied to a tin lapping machine for lapping, for example, the average grain. Diamond abrasive grains having a diameter of 1 μm or less may be used. Further, in barrel polishing, a rotating barrel polishing machine may be used, and Green Carborundum (GC) may be put into the rotating barrel polishing machine as a medium and performed wet for 24 hours.

The ceramics for decorative parts of the present invention obtained as described above have a high hardness and a golden color tone that can give the consumer a sense of luxury, aesthetic satisfaction and mental comfort for a long period of time. Decorative parts for fishing thread guides such as guide rings for fishing threads, decorative parts for watches such as watch cases and band pieces for watches, decorative parts for portable terminals such as various operation keys and cases to be pressed, and life such as soap cases and scissors. For decorative parts such as brooches, necklaces, earrings, rings, bracelets, anklets, tie pins, tie tacks, medals, buttons, etc. It can be suitably used as decorative parts, kitchen decorative parts such as spoons, knives and forks, and religious crafts. Further, it can be suitably used for hobbies and tastes such as initial logos and brand logos for decorating accessories, decorative parts for automobiles such as emblems, decorative parts for other home appliances, poker chips and golf putters.

Examples of the present invention are shown below, but the present invention is not limited to the following examples.

(Example 1) First, titanium nitride (TiN), zirconium oxide (ZrO)₂), Tantalum nitride (TaN) and nickel (Ni) powders were weighed so that the contents in the ceramics for decorative parts had the contents shown in Table 1, and mixed to prepare a blending raw material.

Next, isopropanol was added as an organic solvent to each of the above-mentioned compounding raw materials, and after crushing and mixing for 72 hours using a vibration mill, 3% by mass of a binder such as polyethylene glycol was added to the compounding raw materials and mixed, and a spray dryer was used. Was spray-dried to obtain granules. Then, the obtained granules were filled in a molding die and pressure-molded at a pressure of 98 MPa to prepare 6 columnar molded bodies for each sample and 1 disk-shaped molded body for each sample. .. These compacts were degreased at 600 ° C in a nitrogen atmosphere and then held at 1450 ° C for 2 hours in a nitrogen atmosphere to obtain sintered bodies. After that, the columnar sintered body is barrel-polished using a rotary barrel grinding machine, and the sample No. has a surface having an arithmetic mean height (Ra) of 0.05 to 0.23 μm specified in JIS B 0601-2001. Ceramics for decorative parts 1 to 15 were obtained.

For disc-shaped sintered bodies, diamond abrasive grains with an average particle size of 1 μm are supplied to a tin lapping machine, and the surface of the sintered body is wrapped for 1 hour, according to JIS B 0601-2001. Ceramics for decorative parts of Samples No. 1 to 15 having a surface with a specified arithmetic mean height (Ra) of 0.05 to 0.23 μm were obtained.

The contents of titanium nitride, zirconium oxide, tantalum nitride, and nickel that make up this ceramic for decorative parts are measured by ICP emission spectroscopic analysis, and Ni is the measured value, and Ti and Ta was converted to nitride and Zr was converted to oxide. The Vickers hardness was measured in accordance with JIS R 1610-2003, and the fracture toughness was measured by the indenter press-fitting method (IF method) specified in JIS R 1607-1995.

Regarding the evaluation of wear resistance, the ceramics for columnar decorative parts of Samples Nos. 1 to 15 were placed at predetermined positions (decorated in FIG. 8) using the wear resistance evaluation device of the example shown in FIG. After fixing with a jig to the position of ceramics 101 for parts), water 0.001m³On the other hand, 10 g of semi-porcelain soil (clay containing porcelain soil (porcelain stone) in clay) was added and mixed to prepare muddy water in the water tank 104. Then, the weight 105 is set to 500 g, the speed at which the thread 102 slides on the outer peripheral side of the cylindrical ceramics for decorative parts is set to 60 m / min, and the mileage of the thread 102 is set to 3000 m. The attached nylon (Toray silver scale Σ3) thread 102 was slid on the outer peripheral side of the cylindrical ceramic for decorative parts. After that, using a surface shape measuring microscope (Keyence measuring unit VF-7510 / controller VF-7500), the deepest part of the scratch caused by the abrasion of the ceramics for columnar decorative parts by sliding the thread 102. Was measured, and the average value of each of the 6 samples was calculated as the wear depth.

In addition, a spectrophotometer (CM-3700d manufactured by Konica Minolta Holdings) is used in accordance with JIS Z 8722-2000, a CIE standard light source D65 is used as the light source, and the viewing angle is set to 10 ° to form a disk. The color tone of the surface of ceramics for decorative parts was measured.

Furthermore, regarding color tones, a questionnaire survey was conducted on a total of 40 monitors, 5 males and 5 females, for each age group in their 20s to 50s, with three items: luxury, aesthetic satisfaction, and mental comfort. Of the three survey results of luxury, aesthetic satisfaction, and mental comfort, those with 90% or more of the monitors who answered "obtainable" were "excellent", and one of the above three items. However, those with 70% or more and less than 90% were evaluated as "good", and those with even one item less than 70% were evaluated as "poor".

The results are shown in Table 1.

<tables num="1"><img file="JP2010030833A_D0001.tif" /></tables>

As can be seen from the results shown in Table 1, Samples Nos. 1 to 14 of the present invention contain titanium nitride as a main component and zirconium oxide, tantalum nitride and nickel, and therefore have higher hardness than Sample No. 15 which is a comparative example. High, low wear, and excellent wear resistance. According to the results of the monitor questionnaire survey, the three items of luxury, aesthetic satisfaction, and mental comfort were 85% or more, indicating that the monitor was satisfied. Do you get it.

In addition, the content of zirconium oxide is 9% by mass or more and 30% by mass or less, and the content of tantalum nitride is 9% by mass or more and 23% by mass or less, as compared with Sample Nos. 1,3,5,9,11,14. Sample Nos. 2,4,6 to 8,10,12,13 having a nickel content of 3% by mass or more and 10% by mass or less have hardness, abrasion resistance (wear depth), and fracture toughness. It was found that the ceramics for decorative parts were excellent in any or all of the color tone evaluations and were particularly satisfying.

(Example 2) A test was conducted to confirm the change in characteristics due to the difference in chromium content. First, the same titanium nitride (TiN) and zirconium oxide (ZrO) as in Example 1₂), Tantalum nitride (TaN) and nickel (Ni) powder and chromium (Cr) powder are prepared, and for sample No. 16, the content in ceramics for decorative parts is the same as that of sample No. 7. Samples Nos. 17 to 20 are weighed so that the content in the ceramics for decorative parts is as shown in Table 2 by adding chromium, and then crushed and mixed to prepare the raw material. did. Next, disk-shaped ceramics for decorative parts of Sample Nos. 16 to 20 were obtained by the same manufacturing method as in Example 1.

Then, the contents and color tones of titanium nitride, zirconium oxide, tantalum nitride, nickel and chromium were measured in the same manner as in Example 1. Next, among the corrosion resistance tests specified in JIS B 7001-1995, an artificial sweat semi-immersion test (40 ± 2 ° C, left for 24 hours) was performed, the color tone of each sample after the test was measured, and the brightness before and after the test was measured. The difference between the index L * and the chromaticity index a * and b * was calculated. The results are shown in Table 2.

<tables num="2"><img file="JP2010030833A_D0002.tif" /></tables>

As shown in Table 2, compared to sample No. 16 which does not contain chromium, samples No. 17 to 20 contain chromium and therefore combine with oxygen in the air to form a dense oxide film on the decorative surface. It was found that the corrosion resistance was improved, and the lightness index L * and the chromaticness index a * and b * had little change before and after the test, and the corrosion resistance was good.

In addition, since samples Nos. 17 to 19 have a chromium content of 1.5% by mass or more and 5% by mass or less, the chromaticity index a is higher than that of sample No. 20 having a chromium content of more than 5% by mass. The value of * was large and the color tone was bright golden, which was found to be good.

(Example 3) A test was conducted to confirm the change in characteristics due to the difference in manganese content. First, the same titanium nitride (TiN) and zirconium oxide (ZrO) as in Example 2₂), Tantalum nitride (TaN), nickel (Ni) and chromium (Cr) powder and manganese (Mn) powder are prepared. For sample No. 21, the content in ceramics for decorative parts is sample No. 18. Weighed so that the content is the same as that of the above, and for samples Nos. 22 to 24, weighed so that the content in the ceramics for decorative parts would be the content shown in Table 3 by adding manganese, and crushed and mixed. And used as a compounding raw material. Next, disk-shaped ceramics for decorative parts of Sample Nos. 21 to 24 were obtained by the same manufacturing method as in Example 1.

Then, the contents of titanium nitride, zirconium oxide, tantalum nitride, nickel, chromium and manganese were measured in the same manner as in Example 1. In addition, the color tones were measured at one location in the center of the surface and four locations at the periphery of the surface, and the average value and standard deviation were calculated. The results are shown in Table 3.

<tables num="3"><img file="JP2010030833A_D0003.tif" /></tables>

As shown in Table 3, compared to sample No. 21 which does not contain manganese, samples No. 22 to 24 contain manganese, so that the granules obtained by spray drying are hardly oxidized, so that the color tone on the surface is toned. It was found that there was little variation in the sample and it was good.

Further, using the ceramics for decorative parts of the present invention, a guide ring for fishing threads, which is a decorative part for guiding fishing threads, a watch case or watch band piece, which is a decorative part for watches, and a mobile phone, which is a decorative part for mobile terminals. When we made various operation keys and cases, soap cases and scissors that are decorative parts for daily necessities, they have excellent wear resistance and high hardness, so the surface is not easily scratched and the golden color tone is long-term. It has been found that these decorative parts can be used to construct attractive products that continue to provide luxury, aesthetic satisfaction and mental comfort for a long period of time, as they can be maintained over time.

<figref num="1">An example of a guide ring for fishing thread, which is a decorative part for guiding fishing thread of the present invention, and a guide for fishing thread provided with the guide ring for fishing thread is shown. FIG. It is a perspective view of the guide for fishing thread provided with the guide ring for fishing thread of a).</figref><figref num="2">An example of a watch case, which is a decorative component for a watch of the present invention, is shown in (a) is a perspective view of the watch case viewed from the front side, and (b) is a view of the watch case of (a) from the back side. It is a perspective view.</figref><figref num="3">It is a perspective view which shows another example of the timepiece case which is a decorative part for a timepiece of this invention.</figref><figref num="4">It is a schematic diagram which shows an example of the structure of the timepiece band which is a decorative part for a timepiece of this invention.</figref><figref num="5">It is a perspective view which shows an example of the mobile phone using the decorative part for a mobile terminal of this invention.</figref><figref num="6">It is a perspective view which shows an example of the state which the housing of the mobile phone using the decorative part for a mobile terminal of this invention is opened.</figref><figref num="7">It is a schematic diagram which shows an example of the structure of the soap case using the decorative part for daily necessities of this invention.</figref><figref num="8">It is a schematic block diagram of the abrasion resistance evaluation apparatus used for the evaluation of the abrasion resistance of the ceramic for decorative parts of this invention.</figref>

Code description

1: Guide ring for fishing thread 6: Fishing thread guide 10A, 10B: Watch case 20: Nakakoma 30: Outer piece 40: Pin 50: Watch band 60: Mobile phone 80: Soap case