JPH0610101B2 - Colored ceramic decorative material - Google Patents

Description

The present invention relates to a colored ceramic decorative member.

"Prior Art" Conventionally, for example, colored ceramic decorative members that have been prized for watch cases, lighter cases, tie pins, etc.
It has a structure in which an inorganic pigment such as Cr ₂ O ₃ , MnO ₂ or Co ₃ O ₄ is introduced into the matrix of a polycrystalline alumina sintered body or a polycrystalline zirconia sintered body.

"Problems to be solved by the invention" By the way, the decorative member has a long-lasting elegant appearance, has various color tones, is excellent in corrosion resistance, and is excellent in abrasion resistance. Excellent mechanical properties are essential conditions. However, in the conventional colored ceramics decorative member, it is difficult to color the substrate in various colors, and it is inevitable that mechanical strength such as segregation strength, abrasion resistance (hardness), fracture toughness, etc. They were not excellent in various properties, and were poor in prize value and practical strength. That is, in the conventional colored ceramics decorative member, as described above, Cr ₂ O ₃ , Mn is contained in the matrix of the sintered body such as alumina or zirconia.
Since the structure has introduced an inorganic pigment with high heat resistance such as O ₂ and Co ₃ O ₄ , there is a natural limit to the type of color, and heat resistance is required to make it a color that can be endured for a prize as a decorative member. There is a drawback in that the amount of the inorganic pigment having a high property is added, and therefore the mechanical properties of the matrix are sometimes greatly reduced.

The present invention has been made in view of the above circumstances, and is a colored ceramic decoration that exhibits a novel color tone that has never existed before and that prevents deterioration of mechanical properties such as segregation strength, abrasion resistance (hardness), and fracture toughness. It is intended to provide a member.

"Means for Solving Problems" The present invention has been accomplished by the present inventors as a result of earnest research to achieve the above-mentioned object, and as a result, the following findings have been obtained and the present invention has been completed. . That is, A ₂ O ₃ , TiO ₂ , S
at least one selected from the group consisting of iO ₂ and Pr ₆
A compound having a coloring ability obtained by sintering and pulverizing a mixed powder of at least one selected from the group consisting of inorganic pigments such as O ₁₁ , V ₂ O ₅ , MnO ₂ and Co ₃ O ₄ , A ₂
By introducing a raw material powder consisting of ceramic powder such as O ₃ and ZrO ₂ , unavoidable impurities, and sintering aid powder which is added as necessary, into a green matrix obtained by sintering, We have obtained the knowledge that the purpose can be achieved. Where A ₂ O ₃ and Ti
O ₂ and SiO ₂ do not have coloring ability alone, but should be called coloring aids (hereinafter, these compounds are referred to as coloring aids in the present specification). However, at least one and _{Pr 6 O 11, V 2 O} 5, MnO 2, Co 3 O 4 or the like of the solid-phase chemical reaction at elevated temperature to a mixture of at least one inorganic pigment of these compounds, such as solid When a solubilization reaction, a spinelization reaction or the like is caused, a compound having a coloring ability that can be significantly used in the present invention is obtained (hereinafter, the compound having this coloring ability is referred to as a coloring component in the present specification). ). For example, A ₂ O ₃
For -fe ₂ O ₃ system is a solid solution in which a solid solution Fe ₂ O ₃ in the A ₂ O _3, in the case of A ₂ O ₃ -Co ₃ O ₄ system A ₂ O ₃ ·
The majority of the spinel is CoO.

The production conditions of the colored ceramics decorative member according to the present invention will be described below.

(1) Coloring component At least one compound selected from coloring aids and at least one inorganic pigment are pulverized by a suitable means to a particle size of about 1 to 10 μm, and uniformly mixed by a suitable means. , Usually at a temperature of 1000-1400 ° C in an oxidizing atmosphere,
Allow solid phase chemical reaction to occur for 0.1 to 2 hours. The compound thus obtained is usually pulverized by a suitable means to a size of about 1 μm.

(2) Other raw material powders No particular mention is made of ceramic powders such as alumina and zirconia.
Generally, it may be about 1 μm or less. When using zirconia as the ceramic powder, use zirconia powder that is already partially stabilized or stabilized with a known stabilizer such as yttrium oxide, calcium oxide, or magnesium oxide, or zirconia powder. In addition, a stabilizer powder having a particle size of 1.0 μm or less may be added in an amount capable of partially stabilizing or stabilizing.

If necessary, a sintering aid is added in a range not impairing the effects of the present invention, usually 0.3 to 3% by weight based on the ceramic powder.
You may add. As the sintering aid, magnesium oxide, calcium oxide and the like can be listed.

(3) Raw material mixed powder A raw material mixed powder is obtained by mixing the above-mentioned various powders in a specific ratio.

(4) Molding and Sintering The above raw material mixed powder is molded into a desired shape by an appropriate method and then sintered. As the sintering conditions, it depends on the properties of each raw material mixed powder, but usually the sintering temperature is 1400 to 1700.
℃, preferably 1500 to 1650 ℃ for alumina system, 1400 to 1500 ℃ for zirconia system, sintering time 0.5 to 6 hours, preferably 2 to 4 hours, normal pressure or pressure sintering To do. There are no particular restrictions on the atmosphere.

(5) Mirror polishing The sintered body obtained as described above is colored with a coloring component, and the surface of this sintered body is mirror-polished by an appropriate method to provide a smooth and deep surface. It has a glossy mirror surface and is a suitable decorative member.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example First, as the coloring component 1, high purity TiO ₂ powder (average particle size 10 μm) and high purity V ₂ O ₅ powder (average particle size 10 μm) were used.
m) is uniformly mixed at a molar ratio of 100: 1 to obtain a mixed powder, and the mixed powder is mixed in an oxidizing atmosphere at a temperature of 1100 ° C.
A reaction product is obtained by causing a solid phase chemical reaction for 0.5 hours,
The reaction product was first roughly crushed with a ball mill, then wet crushed with a planetary mill for 24 hours, dried, and further crushed with a planetary mill until an average particle size of about 1 μm was obtained.
Got

Next, as coloring component 2, high-purity SiO ₂ powder (average particle size 10 μm) and high-purity Pr ₆ O ₁₁ (average particle size 10 μm)
And high-purity V ₂ O ₅ (average particle size 10 μm) in a molar ratio of 8:
The mixed powder is uniformly mixed in a ratio of 1: 1 to obtain a mixed powder, and a solid-state chemical reaction is caused to occur in the mixed powder in an oxidizing atmosphere at a temperature of 1400 ° C. for 0.5 hour to obtain a reaction product. The product is crushed and crushed by a method similar to the above method to give a coloring component 2
Got

Furthermore, as the coloring component 3, high-purity A ₂ O ₃ powder (average particle size 10 μm) and high-purity MnO ₂ powder (average particle size 10 μm)
m) is uniformly mixed in a molar ratio of 4: 1 to obtain a mixed powder, and the mixed powder is mixed in an oxidizing atmosphere at a temperature of 1200 ° C.
A reaction product is obtained by causing a solid phase chemical reaction for 0.5 hours,
The reaction product was crushed and crushed in the same manner as the above method to obtain a colored component 3.

Further, as the coloring component 4, high-purity A ₂ O ₃ (average particle size)
10 μm) and high-purity Co ₃ O ₄ (average particle size 10 μm) are uniformly mixed in a molar ratio of 4: 1 to obtain a mixed powder, and the mixed powder is heated in an oxidizing atmosphere at a temperature of 1200 ° C. A solid-state chemical reaction was allowed to occur for 0.5 hours to obtain a reaction product, and the reaction product was crushed and crushed by the same method as the above method to obtain a colored component 4.

Various coloring components thus obtained, high-purity zirconia powder partially stabilized with Y ₂ O ₃ (average particle size 0.1 μm
m) or high-purity alumina powder (average particle size 0.4 μm),
Further, if necessary, sintering aids were mixed in the proportions shown in the table, followed by wet mixing and pulverization in a planetary mill for 24 hours, which was then dried and pulverized. Coarse particles were removed from this by a 0.3 mm sieve to obtain a raw material mixed powder. This raw material mixed powder was subjected to primary molding at a press molding pressure of 300 kg / cm ² into a cubic shape of 55 mm × ²⁰ mm × 5 mm, and then secondary molding by cold isostatic pressing at 4000 kg / cm ² to obtain a molded body. Was sintered under normal pressure for 4 hours under the atmosphere and sintering temperature shown in the table to obtain a sintered body.

When the thus obtained sintered body was mirror-polished to a surface roughness of 1 μm or less by lapping, it was found that each of them became a mirror surface having a smooth, deep, and fresh luster, and a suitable decorative member. . The color tone was changed depending on the coloring component, and a difference in color tone was recognized due to the difference in the base material.

Next, the segregation strength, fracture toughness, and hardness of the obtained sintered body were measured. The method for measuring the electro-deposition strength is JIS-R1601-3.
According to the point bending test method, the fracture toughness was measured by S.P. as the toughness characteristic of the sintered body by using the critical stress intensity factor when the sintered body was broken by the growth of microcracks. E. N. B (Single
The edge hardness was measured according to the Edge Notched Beam method, and the hardness was measured with a Vickus hardness meter. The measurement results are as shown in the table.

Now, as it is clear from Table, the mechanical properties of the colored ceramic decorative member according to the present invention, flexural resistance of 60~90kg / mm ² in zirconia, fracture toughness 7~8MN / m ^3/2, the hardness ( Abrasion resistance) 1240 to 1310, and alumina-based anti-sedimentation strength 26 to
39 kg / mm ^2, a fracture toughness 5~6MN / mm ^3/2, a hardness (wear resistance) from 1530 to 1830. Such mechanical properties exceed those of conventional ceramic decorative members colored in colors close to yellow, green, red, pink and blue.

Further, it was also clarified that the colored ceramics decorative member according to the present invention exhibits a novel color tone which has never been seen and has a beautiful appearance.

"Effect of the Invention" As described above, the colored ceramic decorative member according to the present invention, A ₂ O _3, at least one selected from TiO _2, the group consisting of SiO ₂ and Pr ₆ O _11, V ₂ O ₅ , M
A compound having a coloring ability obtained by sintering and crushing a mixed powder of at least one selected from the group consisting of inorganic pigments such as nO ₂ and Co ₃ O ₄ is a ceramic powder such as alumina or zirconia, It is characterized in that it is introduced into a matrix matrix obtained by sintering a matrix raw material powder consisting of unavoidable impurities and a sintering aid powder added as necessary, and exhibits a new color tone. Since it has a beautiful appearance and a small amount of a coloring component needs to be added, it is possible to effectively prevent deterioration of various mechanical properties.

Therefore, it is possible to provide a colored ceramics decorative member which is rich in prize value and practical strength.

Claims (1)

[Claims] 1. A A ₂ O _3, TiO _2, at least one selected from the group consisting of SiO ₂ and _{Pr 6 O 11, V 2 O} 5, M
A compound having a coloring ability obtained by sintering and pulverizing a mixed powder of at least one selected from the group consisting of inorganic pigments such as nO ₂ and Co ₃ O ₄ is A ₂ O ₃ , ZrO ₂ etc. A colored ceramics decorative member, characterized in that it is introduced into a matrix matrix obtained by sintering a matrix raw material powder consisting of the ceramics powder, the unavoidable impurities and a sintering aid powder which is added if necessary.