阅读说明：本技术 黑色混合氧化物材料及其制造方法 (Black mixed oxide material and method for producing same ) 是由 中岛干夫 加东隆 于 2018-06-07 设计创作，主要内容包括：本发明提供一种黑色混合氧化物材料及其制造方法,并且提供使用该黑色混合氧化物材料的各种产品,该黑色混合氧化物材料与铬的价数无关,主要成分中不含有铬本身,而且主要成分中也不含有钴,具备高安全性、良好的色调及经济性。含有以La、Mn和Cu为主要成分的氧化物,并且是作为主要成分不含有Cr和Co的混合氧化物,以将以下氧化物的整体重量设为100重量％的氧化物换算量计,所述混合氧化物中的La、Mn和Cu的含量满足以下比例：以La<Sub>2</Sub>O<Sub>3</Sub>计,La为35～70重量％；以MnO<Sub>2</Sub>计,Mn为25～60重量％；以CuO计,Cu为0.5～10重量％。(The present invention provides a black mixed oxide material which does not contain chromium itself as a main component and does not contain cobalt as a main component regardless of the valence of chromium, and which has high safety, good color tone and economy, a method for producing the same, and various products using the black mixed oxide material. An oxide containing La, Mn and Cu as main components and being a mixed oxide containing Cr and Co as main components, the mixed oxide containing La, Mn and Cu in a content satisfying the following proportions in terms of oxides, taking the total weight of the following oxides as 100 wt%: with La 2 O 3 In terms of La, 35-70 wt%; in MnO 2 In terms of Mn, the Mn content is 25-60 wt%; cu is 0.5 to 10 wt% in terms of CuO.)

1. A black mixed oxide material characterized by containing an oxide having La, Mn and Cu as main components and not containing Cr and Co as the main components.

2. The black mixed oxide material according to claim 1, wherein the mixed oxide has a perovskite phase showing a diffraction peak of maximum intensity in a range of 31 ° to 34 ° of a diffraction angle 2 θ when measured by X-ray diffraction using CuK α rays as an X-ray source,

and the mixed oxide contains Mn having a spinel structure₃O₄As an oxide of Mn.

3. The black mixed oxide material according to claim 1, wherein the contents of La, Mn, and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the entire weight of the following oxides as 100 wt%:

with La₂O₃In terms of La, 35-70 wt%;

in MnO₂In terms of Mn, the Mn content is 25-60 wt%;

cu is 0.5 to 10 wt% in terms of CuO.

4. The black mixed oxide material according to claim 1, wherein the mixed oxide further contains an oxide of Mo as the main component,

adding La to La₂O₃Mn is calculated as MnO₂In terms of oxide, the total weight of the 3 oxides is 100 wt% in terms of Cu as CuO,

relative to 100 weight of the oxide equivalent% of Mo in MoO₃The mixed oxide contains Mo in a proportion of 5 wt% or less.

5. The black mixed oxide material according to claim 1, wherein the mixed oxide further contains, as a subcomponent, one or more of Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Fe, Zn, Sr, Y, Zr, Nb, Sn, Sb, Ba, Ta, W, Bi, Ce, Pr, Nd, or Er in addition to the main component,

adding La to La₂O₃Mn is calculated as MnO₂In terms of oxide, the total weight of the 3 oxides is 100 wt% in terms of Cu as CuO,

the subcomponents are represented by Li with respect to 100 wt% of the oxide equivalent₂O、B₂O₃、Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、V₂O₅、Fe₃O₃、ZnO、SrO、Y₂O₃、ZrO₂、Nb₂O₃、SnO₂、Sb₂O₃、BaO、Ta₂O₅、WO₃、Bi₂O₃、CeO₂、Pr₆O₁₁、Nd₂O₅Or Er₂O₃The mixed oxide contains the subcomponents in a proportion of 20 wt% or less.

6. The black mixed oxide material according to claim 1, wherein the mixed oxide is a black pigment.

7. The black mixed oxide material according to claim 1, wherein the mixed oxide is a non-magnetic material.

8. The black mixed oxide material according to claim 1, wherein the mixed oxide is an insulating material.

9. A method for producing a black mixed oxide material according to claim 1, comprising:

a primary grinding step of mixing and grinding oxide raw materials of La, Mn and Cu to obtain a primary ground product with an average particle size of 5 [ mu ] m or less;

a raw material firing step of firing the primary pulverized material at 700 to 1200 ℃ to obtain a raw material fired material; and

a secondary grinding step of grinding the fired raw material to an average particle diameter of 50 μm or less,

thereby obtaining a mixed oxide.

10. The method for producing a black mixed oxide material according to claim 9, wherein the contents of La, Mn, and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the entire weight of the following oxides as 100 wt%:

with La₂O₃In terms of La, 35-70 wt%;

in MnO₂In terms of Mn, the Mn content is 25-60 wt%;

cu is 0.5 to 10 wt% in terms of CuO.

11. The method for producing a black mixed oxide material according to claim 9, wherein the mixed oxide further contains an oxide of Mo as the main component,

adding La to La₂O₃Mn is calculated as MnO₂In terms of oxide, the total weight of the 3 oxides is 100 wt% in terms of Cu as CuO,

mo is MoO based on 100 wt% of the oxide equivalent₃The mixed oxide contains Mo in a proportion of 5 wt% or less.

12. A method for producing a black mixed oxide material according to claim 1, comprising:

a first pulverization step of mixing and pulverizing oxide raw materials of La, Mn and Cu to obtain a first pulverized product having an average particle diameter of 5 [ mu ] m or less;

a first firing step of firing the first pulverized material at 700 to 1200 ℃ to obtain a first fired material;

a second pulverization step of pulverizing the first fired product to obtain a second pulverized product having an average particle size of 50 μm or less;

a second firing step of firing the second pulverized material at 600 to 1100 ℃ to obtain a second fired material; and

a third grinding step of grinding the second fired powder to an average particle diameter of 20 μm or less,

thereby obtaining a mixed oxide.

13. The method for producing a black mixed oxide material according to claim 12, wherein the contents of La, Mn, and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the entire weight of the following oxides as 100 wt%:

with La₂O₃In terms of La, 35-70 wt%;

in MnO₂In terms of Mn, the Mn content is 25-60 wt%;

cu is 0.5 to 10 wt% in terms of CuO.

14. The method for producing a black mixed oxide material according to claim 12, wherein the mixed oxide further contains an oxide of Mo as the main component,

adding La to La₂O₃Mn is calculated as MnO₂In terms of oxide, the total weight of the 3 oxides is 100 wt% in terms of Cu as CuO,

mo is MoO based on 100 wt% of the oxide equivalent₃The mixed oxide contains Mo in a proportion of 5 wt% or less.

15. An inorganic ceramic material comprising the black mixed oxide material according to claim 1 and a ceramic agent.

16. An inorganic glass paste comprising the black mixed oxide material according to claim 1 and a glass agent.

17. A fired product obtained by firing the inorganic glass slurry according to claim 16 on a glass part, a metal part, a ceramic or a porcelain.

18. A resin paste comprising the black mixed oxide material according to claim 1 and a resin agent.

19. A coated product obtained by coating the resin paste according to claim 18 on a support.

20. The coated product of claim 19, wherein the support is glass, metal, ceramic, porcelain, a resinous article, or a carbon material.

21. A resin member comprising the black mixed oxide material according to claim 1 and a resin agent.

Technical Field

The present invention relates to a black mixed oxide material containing no chromium and no cobalt as main components, a method for producing the same, and a product using the black mixed oxide material.

Background

Inorganic black pigments are used in various fields such as kiln industry, paints, coloring of resins, and pigment components of glass pastes. For example, glass paste using a black pigment is used for ceramic paste constituting a coating film on the edge of an automobile window glass (see patent document 1), insulating paste for an insulating barrier of a plasma display, and the like (see patent document 2). Most black pigments so far contain chromium (Cr) as a constituent. Cr containing chromium compound for improving heat resistance and adjusting color tone of pigment₂O₃Etc. as raw material oxides indispensable for the production of black pigmentsOne of which is widely used.

However, currently, in all stages from production to distribution of electrical and electronic devices within the european union area, for the purpose of minimizing risks to the environment and human body, "european parliament and council directive on the restriction of the use of certain harmful substances in electrical and electronic devices" is implemented. This is commonly referred to as the RoHS instruction (short for Restriction of Hazardous substations). The RoHS directive prohibits in principle the use of hazardous substances, 6 substances being specified being lead (Pb), mercury (Hg), cadmium (Cd), chromium (Cr) 6 in valence⁶⁺) Polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs).

In the development of products complying with the RoHS directive, it is necessary to thoroughly manage the raw material components used up to the parts, materials, and the like constituting the products so that the products do not contain the 6 substances prohibited from being used. The restriction of harmful chemicals considering such environmental problems is spread not only in countries of the european union but also in countries of the world.

Cr contained as a raw material oxide of a general pigment is converted into 6-valent chromium (Cr) having strong toxicity by heating or the like⁶⁺). In the pigment production step, the 6-valent chromium produced is removed by washing with water or the like as necessary. However, there is a possibility that the chromium oxide partially changes to 6-valent chromium again after the drying step at about 180 ℃. Therefore, the black pigment itself as a product may become a problem. On this basis, depending on the use of the pigment, there may be heat or ultraviolet exposure depending on the conditions of use. In this case, it cannot be completely denied that Cr contained in the black pigment has a valence of 3 (Cr) due to a change with time³⁺) To 6 (Cr)⁶⁺) The danger of (2).

Current RoHS directive has only 6-valent chromium as subject of restrictions. However, when products using black pigments containing chromium are discarded, safety problems accompanying the change in the valence number are becoming more important. Finally, attention has been paid to a black pigment containing no chromium component itself (see patent document 3). The black pigment of patent document 3 uses a strontium compound and iron oxide as its main components. Since strontium has high solubility in water, the practical production method is limited to a nonaqueous liquid or ethanol. Therefore, the production cost of the pigment is increased, and the range of use and the use thereof are also extremely limited.

Further, blending and methods used for producing black pigments have been repeatedly improved, and new black pigments containing no chromium per se have been proposed (see patent documents 4 and 5). The black pigment of patent document 4 is a pigment containing oxides of Mn, Co, Ni, and Fe as main components. The black pigment of patent document 5 is a pigment containing oxides of Mn, Fe, Cu, and Co as main components. In particular, a black color of good quality is obtained by the black pigment of patent document 5.

As described above, with the necessity of managing harmful chemical substances contained in the product, a pigment of a component class not containing chromium can be obtained. However, as shown by the main component, cobalt is contained as one of the main components. Cobalt is known to be a cause of allergic symptoms, and is expected to be reduced as much as possible from the composition of the main component. Therefore, from the viewpoint of environmental compatibility, a new component class in which chromium is not contained in the main component and cobalt is not contained is strongly desired on the premise that a good black color required for a black pigment is exhibited.

Patent document 1 Japanese patent laid-open No. Hei 6-340447

Patent document 2 Japanese patent laid-open No. Hei 6-144871

Patent document 3 Japanese patent laid-open No. 2000-264639

Patent document 4 Japanese patent laid-open No. 2007-217544

Patent document 5 Japanese patent No. 5131664

Based on such a history, the inventors have conducted intensive studies while newly adjusting the main component of the black pigment. As a result, a black pigment composed of a main component containing neither chromium nor cobalt as a main component has been developed. Further, it was confirmed that the pigment had other physical properties in addition to the desired performance as a black pigment.

Disclosure of Invention

In view of the above, the present invention provides a black mixed oxide material which does not contain chromium itself as a main component and does not contain cobalt as a main component regardless of the valence of chromium, and which has high safety, good color tone and economy, and a method for producing the same, and provides various products in view of the physical properties of the black mixed oxide material.

First, a black mixed oxide material is characterized by containing an oxide containing La, Mn, and Cu as main components and not containing Cr and Co as the main components.

Second, a black mixed oxide material, characterized in that the mixed oxide has a perovskite phase showing a diffraction peak of maximum intensity in a range of 31 ° to 34 ° of a diffraction angle 2 θ in an X-ray diffraction measurement using CuK α ray as an X-ray source, and the mixed oxide contains Mn having a spinel structure₃O₄As an oxide of Mn.

Third, a black mixed oxide material, characterized in that the contents of La, Mn and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the total weight of the following oxides as 100 wt%: with La₂O₃In terms of La, 35-70 wt%; in MnO₂In terms of Mn, the Mn content is 25-60 wt%; cu is 0.5 to 10 wt% in terms of CuO.

Fourth, a black mixed oxide material, wherein the mixed oxide further contains an oxide of Mo as the main component, and La is La₂O₃Mn is calculated as MnO₂In terms of oxides, wherein Cu is calculated as CuO and the total weight of the 3 oxides is 100 wt%, Mo is calculated as MoO with respect to 100 wt% of the oxides₃The mixed oxide contains Mo in a proportion of 5 wt% or less.

Fifth, a black mixed oxide material, characterized in that the mixed oxide contains Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Fe, Zn, Sr, Y, Zr, Nb, Sn, Sb, Ba, Ta, W, Bi, Ce, B, Ti, B,One or more of Pr, Nd or Er as accessory components, La is La₂O₃Mn is calculated as MnO₂In terms of oxides, Cu is calculated as CuO, and the total weight of the 3 oxides is 100 wt%, and the subcomponents are Li in 100 wt% of the oxides₂O、B₂O₃、Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、V₂O₅、Fe₃O₃、ZnO、SrO、Y₂O₃、ZrO₂、Nb₂O₃、SnO₂、Sb₂O₃、BaO、Ta₂O₅、WO₃、Bi₂O₃、CeO₂、Pr₆O₁₁、Nd₂O₅Or Er₂O₃The mixed oxide contains the subcomponents in a proportion of 20 wt% or less.

Sixth, a black mixed oxide material, characterized in that the mixed oxide is a black pigment.

Seventh, a black mixed oxide material, wherein the mixed oxide is a non-magnetic material.

Eighth, a black mixed oxide material, wherein the mixed oxide is an insulating material.

Ninth, a method for producing a black mixed oxide material, comprising: a primary grinding step of mixing and grinding oxide raw materials of La, Mn and Cu to obtain a primary ground product with an average particle size of 5 [ mu ] m or less; a raw material firing step of firing the primary pulverized material at 700 to 1200 ℃ to obtain a raw material fired material; and a secondary grinding step of grinding the fired raw material to an average particle diameter of 50 μm or less to obtain a mixed oxide.

Tenth, a method for producing a black mixed oxide material, characterized in that La, Mn and Mn in the mixed oxide are contained in amounts converted to oxides, taking the total weight of the following oxides as 100 wt%The content of Cu satisfies the following ratio: with La₂O₃In terms of La, 35-70 wt%; in MnO₂In terms of Mn, the Mn content is 25-60 wt%; cu is 0.5 to 10 wt% in terms of CuO.

Eleventh, a method for producing a black mixed oxide material, wherein the mixed oxide further contains an oxide of Mo as the main component, and La is La₂O₃Mn is calculated as MnO₂In terms of oxides, wherein Cu is calculated as CuO and the total weight of the 3 oxides is 100 wt%, Mo is calculated as MoO with respect to 100 wt% of the oxides₃The mixed oxide contains Mo in a proportion of 5 wt% or less.

Twelfth, a method for producing a black mixed oxide material, comprising: a first pulverization step of mixing and pulverizing oxide raw materials of La, Mn and Cu to obtain a first pulverized product having an average particle diameter of 5 [ mu ] m or less; a first firing step of firing the first pulverized material at 700 to 1200 ℃ to obtain a first fired material; a second pulverization step of pulverizing the first fired product to obtain a second pulverized product having an average particle size of 50 μm or less; a second firing step of firing the second pulverized material at 600 to 1100 ℃ to obtain a second fired material; and a third grinding step of grinding the second fired material to an average particle diameter of 20 μm or less to obtain a mixed oxide.

Thirteenth, a method for producing a black mixed oxide material, characterized in that the contents of La, Mn and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the total weight of the following oxides as 100 wt%: with La₂O₃In terms of La, 35-70 wt%; in MnO₂In terms of Mn, the Mn content is 25-60 wt%; cu is 0.5 to 10 wt% in terms of CuO.

Fourteenth, a method for producing a black mixed oxide material, characterized in that the mixed oxide further contains an oxide of Mo as the main component, and La is La₂O₃Mn is calculated as MnO₂Calculating Cu as CuO, and calculating the 3 oxidesIn terms of oxide(s) in which the total weight of (a) is 100 wt%, Mo is represented by MoO with respect to 100 wt% of the oxide(s) in terms of oxide(s)₃The mixed oxide contains Mo in a proportion of 5 wt% or less.

Fifteenth, an inorganic ceramic material, characterized by containing a black mixed oxide material and a ceramic agent.

Sixteenth, an inorganic glass paste characterized by containing a black mixed oxide material and a glass agent.

Seventeenth, a fired product, characterized in that it is obtained by firing an inorganic glass slurry on a glass member, a metal member, a pottery or a porcelain.

Eighteenth, a resin paste characterized by containing a black mixed oxide material and a resin agent.

Nineteenth is a coated product characterized by being obtained by coating a resin slurry on a support.

Twentieth, a coated product, characterized in that the support is glass, metal, pottery, porcelain, a resin product, or a carbon material.

Twenty-first, a resin member, characterized by containing a black mixed oxide material and a resin agent.

According to the black mixed oxide material, since the black mixed oxide material contains an oxide containing La, Mn, and Cu as main components and does not contain Cr and Co as the main components, chromium itself is not contained in the main components regardless of the valence number of chromium and cobalt is not contained in the main components, and the black mixed oxide material has high safety, a good color tone, and economical efficiency.

Since the mixed oxide has a perovskite phase showing a diffraction peak of maximum intensity in a range of 31 DEG to 34 DEG of a diffraction angle 2 theta in X-ray diffraction measurement using CuK alpha rays as an X-ray source, and contains Mn having a spinel structure₃O₄The Mn oxide is in the form of a sintered mixed oxide.

Due to the following oxidesThe contents of La, Mn and Cu in the mixed oxide satisfy the following ratios, given as oxide conversion amounts of 100 wt% in total weight: with La₂O₃In terms of La, 35-70 wt%; in MnO₂In terms of Mn, the Mn content is 25-60 wt%; since Cu is 0.5 to 10 wt% in terms of CuO, chromium itself is not contained in the main component, and cobalt is not contained in the main component, and a good black color is exhibited.

Since the mixed oxide further contains an oxide of Mo as the main component, La is taken as La₂O₃Mn is calculated as MnO₂In terms of oxides, wherein Cu is calculated as CuO and the total weight of the 3 oxides is 100 wt%, Mo is calculated as MoO with respect to 100 wt% of the oxides₃The mixed oxide contains Mo at a ratio of 5 wt% or less, and therefore exhibits a black color of better quality.

The mixed oxide contains, in addition to the main component, at least one of Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Fe, Zn, Sr, Y, Zr, Nb, Sn, Sb, Ba, Ta, W, Bi, Ce, Pr, Nd, or Er as a subcomponent, and La is La₂O₃Mn is calculated as MnO₂In terms of oxides, Cu is calculated as CuO, and the total weight of the 3 oxides is 100 wt%, and the subcomponents are Li in 100 wt% of the oxides₂O、B₂O₃、Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、V₂O₅、Fe₃O₃、ZnO、SrO、Y₂O₃、ZrO₂、Nb₂O₃、SnO₂、Sb₂O₃、BaO、Ta₂O₅、WO₃、Bi₂O₃、CeO₂、Pr₆O₁₁、Nd₂O₅Or Er₂O₃Since the mixed oxide contains the subcomponents at a ratio of 20 wt% or less, it is not necessary to use a high-purity raw material or to use a high-purity raw materialThe person uses special manufacturing management and methods for avoiding the inclusion of impurities, and the raw materials and manufacturing costs can be relatively inexpensive.

Since the mixed oxide is a black pigment, a non-magnetic material, or an insulating material, the black mixed oxide material has a wide range of applications.

The method for producing a black mixed oxide material includes: a primary grinding step of mixing and grinding oxide raw materials of La, Mn and Cu to obtain a primary ground product with an average particle size of 5 [ mu ] m or less; a raw material firing step of firing the primary pulverized material at 700 to 1200 ℃ to obtain a raw material fired material; and a secondary grinding step of obtaining a mixed oxide by grinding the fired raw material to an average particle diameter of 50 μm or less, wherein the mixed oxide contains no chromium per se as a main component and no cobalt as a main component regardless of the valence of chromium, and is highly safe, excellent in color tone, and economical.

Since the contents of La, Mn and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the entire weight of the following oxides as 100 wt%: with La₂O₃In terms of La, 35-70 wt%; in MnO₂In terms of Mn, the Mn content is 25-60 wt%; since Cu is 0.5 to 10 wt% in terms of CuO, chromium itself is not contained in the main component, and cobalt is not contained in the main component, and a good black color is exhibited.

Since the mixed oxide further contains an oxide of Mo as the main component, La is taken as La₂O₃Mn is calculated as MnO₂In terms of oxides, wherein Cu is calculated as CuO and the total weight of the 3 oxides is 100 wt%, Mo is calculated as MoO with respect to 100 wt% of the oxides₃The mixed oxide contains Mo at a ratio of 5 wt% or less, and therefore exhibits a black color of better quality.

The method for producing a black mixed oxide material includes: a first pulverization step of mixing and pulverizing oxide raw materials of La, Mn and Cu to obtain a first pulverized product having an average particle diameter of 5 [ mu ] m or less; a first firing step of firing the first pulverized material at 700 to 1200 ℃ to obtain a first fired material; a second pulverization step of pulverizing the first fired product to obtain a second pulverized product having an average particle size of 50 μm or less; a second firing step of firing the second pulverized material at 600 to 1100 ℃ to obtain a second fired material; and a third grinding step of grinding the second fired material to an average particle diameter of 20 μm or less to obtain a mixed oxide, wherein the second fired material contains no chromium itself as a main component and no cobalt as a main component regardless of the valence of chromium, and is highly safe, excellent in color tone, and economical.

Since the contents of La, Mn and Cu in the mixed oxide satisfy the following ratios in terms of oxides, taking the entire weight of the following oxides as 100 wt%: with La₂O₃In terms of La, 35-70 wt%; in MnO₂In terms of Mn, the Mn content is 25-60 wt%; since Cu is 0.5 to 10 wt% in terms of CuO, chromium itself is not contained in the main component, and cobalt is not contained in the main component, and a good black color is exhibited.

Since the mixed oxide further contains an oxide of Mo as the main component, La is taken as La₂O₃Mn is calculated as MnO₂In terms of oxides, wherein Cu is calculated as CuO and the total weight of the 3 oxides is 100 wt%, Mo is calculated as MoO with respect to 100 wt% of the oxides₃Since the mixed oxide contains Mo in an amount of 5 wt% or less, a black color of better quality can be obtained.

The black mixed oxide material can be used for a wide range of products by being applied to a black inorganic ceramic material, a black inorganic glass paste, a black resin paste, and the like. Therefore, the material containing neither chromium nor cobalt can be used in place of the conventional material.

Drawings

Fig. 1 is a schematic process diagram of a method for producing a black mixed oxide material according to a first embodiment.

Fig. 2 is a schematic process diagram of a method for producing a black mixed oxide material according to a second embodiment.

Fig. 3 is a triangular diagram in which the main components in the black mixed oxide material are converted into oxides.

Fig. 4 is an enlarged view of a main portion of fig. 3.

FIG. 5 is an X-ray diffraction pattern of sample preparation example 29.

FIG. 6 is an X-ray diffraction pattern of sample preparation example 35.

FIG. 7 is an X-ray diffraction pattern of sample preparation 51.

Fig. 8 is a graph of the magnetization curve of sample preparation example 51.

Fig. 9 is a diagram partially enlarging the graph of fig. 8.

Detailed Description

The black mixed oxide material of the present invention is a black mixed oxide material of a composition type which does not contain Cr itself as a main component and does not contain Co as a main component, regardless of the valence of Cr. That is, the black mixed oxide material contains 3 kinds of La, Mn, and Cu as main components. Wherein Cr and Co are not contained in the main component. And is a mixed oxide of oxides of 3 main components of metal elements. Further, for the purpose of using the black mixed oxide material as a black pigment, Mo is also blended in the main component of 3 kinds of metal elements to prepare a mixed oxide in order to improve good color development. As shown in examples described later, the pigment composition has properties of a nonmagnetic material and an insulating material in addition to its performance as a pigment.

The mixed oxide shows, for example, X-ray diffraction patterns of fig. 5 to 7 as later-described examples in X-ray diffraction (XRD) measurement using CuK α rays as an X-ray source. The sequence of fig. 5, 6, 7 corresponds to the subsequent sample preparation examples 29, 35, 51. As can be seen from the illustrated pattern, a characteristic peak was confirmed for the mixed oxide. The diffraction peak having the maximum intensity exists in a range of 31 DEG to 34 DEG which is defined as a diffraction angle 2 theta. Considering the above peaks and the like, it is assumed that the mixed oxide has a perovskite phase. In addition, it is also assumed that the mixed oxide contains Mn having a spinel structure from the black-colored positions at four corners in the illustrated pattern₃O₄As an oxide of Mn.

The form of the raw materials of La, Mn, and Cu as the main components is not particularly limited, and metal compounds such as carbonates and hydroxides may be used in addition to the respective metal oxides. Specifically, from La₂O₃、La(OH)₃、La₂(CO₃)₃、MnO₂、Mn₃O₄、MnCO₃、Mn(OH)₂Natural manganese dioxide powder (containing MnO)₂+Fe₂O₃)、CuO、Cu₂O₃、CuCO₂、Cu(OH)₂And the like are appropriately selected. In the composition containing Mo as the main component, from MoO₂、MoO₃、Mo(CO)₆And the like are appropriately selected. Further, these may be combined as necessary.

The black mixed oxide material shows the peaks of the illustrated X-ray diffraction pattern, and is also confirmed as the morphology of the sintered mixed oxide. Therefore, the amount of the metal elements contained in the mixed oxide, which is established among the main components La, Mn, and Cu, can be expressed by the relative ratio of the amounts of the metal elements in terms of oxides in the following oxide forms.

In the oxide equivalent, the mixing ratio of the oxides of La, Mn, and Cu as the main components is derived from the triangular chart of fig. 3 in the subsequent example. The triangular chart shows the balance of the amounts established between the respective oxides of the black pigment, which is a mixed oxide of the sample preparation example described later. Specifically, La is well understood as La₂O₃Mn is expressed as MnO₂In terms of CuO, Cu is in the form of an oxide. The total weight of the 3 oxides is calculated as 100 wt%. On the basis of the above, La is formed₂O₃In the range of 35 to 70 wt%, MnO₂In the range of 25 to 60 wt%, and CuO in the range of 0.5 to 10 wt%. When the oxide of each metal element is controlled within the above range, a favorable black color appears. Thus, the pigment use of black mixed oxide materials is most powerful.

The ratio of each main component metal element is a convenient calculation value as the kind of the oxide. Therefore, in reality, the sum of the weight percentages of the oxides of the main components La, Mn, and Cu may exceed 100 or fall below 100. This is because the purity of the raw material as the main component element, the mixing of the later-described subcomponents, the change in the oxidation number (the number of oxygen elements) in the pigment, and the like are considered. By converting the main component metal element into the weight of the oxide, it is easy to grasp whether the black color is acceptable or not and the balance of the amounts of the metal elements to be mixed with each other. In addition, the amount and ratio of the other components to be added can be easily determined.

La as an oxide of La₂O₃The more the amount of (A) is, the thicker the concentration is, and the degree of blackness is increased. When La₂O₃When the reduced weight of (3) is less than 35% by weight, the desired degree of blackness is lowered. When La₂O₃When the reduced weight of (2) exceeds 70% by weight, La is removed₂O₃The amount of other raw materials is reduced, and the quality stability cannot be maintained by other components. Thus, La₂O₃The content is preferably 35 to 70 wt%, and more preferably 40 to 70 wt%.

MnO as Mn oxide₂The larger the amount of (A) is, the thicker the concentration becomes, and the degree of blackness as a black pigment increases. When MnO is present₂When the reduced weight of (b) is less than 25% by weight, a good black color cannot be obtained as in La. When MnO is present₂When the reduced weight of (2) exceeds 60% by weight, MnO is present₂The amount of the other raw materials is reduced, and the quality stability based on the other components cannot be maintained. Thus, MnO₂Preferably 25 to 60% by weight.

CuO, which is an oxide of Cu, can achieve good black color development together with the above-described oxides of La and Mn. When the equivalent weight of CuO is less than 0.5 wt%, the color tone other than black increases, and the density of the pigment and the feeling of black hardly occur. When the equivalent weight of CuO exceeds 10 wt%, the red color increases and the concentration cannot be obtained when the application of the black pigment is assumed from the relationship with other components. In addition, the melting temperature of the ceramic slurry containing the mixed oxide material rises. Further, acid resistance is also reduced. Therefore, Cu is added in a balance of conditions, and CuO is preferably 0.5 to 10 wt%.

As for mixed oxides of La, Mn and Cu (3 main component groups), and one kind of oxide containing Mo as a main component (4 main component groups) as well. With the addition of Mo, the mixed oxide can become a better quality black pigment. Of the 4 main component classes of mixed oxides, Mo is in MoO₃Relative to La₂O₃、MnO₂And CuO (La) as a whole₂O₃、MnO₂And CuO) is 100 wt%, and contains MoO in a proportion of 5 wt% or less₃. When MoO₃When the reduced weight of (2) exceeds 5% by weight, the black color concentration rather begins to decrease. Therefore, 5% by weight is the upper limit. For MoO₃The lower limit of the converted weight of (c) is not particularly limited. Among them, from the viewpoint of clarifying the effect of Mo addition, it is preferably 0.01% by weight or more.

In a black mixed oxide material containing a mixed oxide (3 main component groups) containing La, Mn and Cu as main components or a mixed oxide (4 main component groups) containing Mo as a main component, one or more of Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Fe, Zn, Sr, Y, Zr, Nb, Sn, Sb, Ba, Ta, W, Bi, Ce, Pr, Nd and Er are selectively contained as subcomponents in addition to the main component.

With respect to the contents of the listed subcomponents, the content is relative to La₂O₃、MnO₂And CuO (La) as a whole₂O₃、MnO₂And CuO) is 100 wt% in terms of oxide, in the case of Li₂O、B₂O₃、Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、V₂O₅、Fe₃O₃、ZnO、SrO、Y₂O₃、ZrO₂、Nb₂O₃、SnO₂、Sb₂O₃、BaO、Ta₂O₅、WO₃、Bi₂O₃、CeO₂、Pr₆O₁₁、Nd₂O₅Or Er₂O₃The content of (b) is defined to be 20 wt% or less in terms of oxide.

By containing these subcomponents, an effect of promoting crystal growth of a mixed oxide generated by a reaction of an oxide of a raw material and the like can be expected. Further, it is also useful for adjustment of sintering temperature, stabilization of color of pigment, and the like. Thus, the use of extremely high purity raw materials, special manufacturing management and methods for avoiding the incorporation of impurities are also reduced. Thus, raw material and manufacturing costs may be relatively inexpensive. The practical problem is that it is extremely difficult to remove the mixture of the side materials in mass production. When the amount of the subcomponent exceeds 20% by weight, it is not preferable to lower the desired property of the black pigment, and the content of the subcomponent is preferably as small as possible. However, although the effect of the side component contribution is unknown, there are also examples in which the performance is improved by addition as will be clear from the later-described embodiments.

Thus, the method for producing the black mixed oxide material according to the first embodiment will be described with reference to the schematic process diagram of fig. 1. First, an oxide raw material M of La, Mn, and Cu (may contain Mo) satisfying the oxide equivalent amounts described above is prepared. The oxide raw material M is mixed and pulverized to obtain a primary pulverized product 11 having an average particle diameter of 5 μ M or less (S11: primary pulverization step). The primary pulverized material 11 is fired in an oxidizing atmosphere at 700 to 1200 ℃ to obtain a raw material fired material 12 (S12: raw material firing step). The raw material fired product 12 was pulverized again to an average particle diameter of 50 μm or less to prepare a mixed oxide P1 of a black mixed oxide material (S13: secondary pulverization step).

Next, a method for producing a black mixed oxide material according to a second embodiment will be described with reference to the schematic process diagram of fig. 2. Oxide raw materials M of La, Mn and Cu (which may contain Mo) satisfying the oxide equivalent amounts described above are prepared. The oxide raw materials M are mixed and pulverized to obtain a first pulverized material 21 having an average particle diameter of 5 μ M or less (S21: first pulverization step). The first pulverized material 21 is fired in an oxidizing atmosphere at 700 to 1200 ℃ to obtain a first fired material 22 (S22: first firing step). The first calcined product 22 is pulverized to an average particle size of 50 μm or less to obtain a second pulverized product 23 (S23: second pulverization step). The second pulverized material 23 is fired in an oxidizing atmosphere at 60 to 1100 ℃ to obtain a second fired material 24 (S24: second firing step). Thereafter, the second fired material 24 was pulverized to an average particle size of 5 μm or less to prepare a mixed oxide P2 of a black mixed oxide material (S25: third pulverization step).

In the pulverization (S11, S13, S21, S23, S25) shown in the schematic process diagrams of fig. 1 and 2, a pulverization device such as a ball mill, a vibration mill, an attritor, a bead mill, a jet mill, a tube mill, a spray mill, a refiner, or a pulverizer is used. In the case of pulverization, since pulverization can be carried out by mixing both wet and dry pulverization, productivity is high and treatment cost is also advantageous. For example, a wet mixing and pulverizing method in a ball mill is described, and an oxide raw material, water, balls, a pulverizing aid (a dispersant, an antifoaming agent, or the like), and the like are put into a ball mill and mixed and pulverized. The raw material oxides can be uniformly mixed and pulverized by appropriately selecting and using known materials as the pulverization aid such as an antifoaming agent and a dispersant. The amount of the oxide is adjusted according to the oxide raw material.

The inner surface of the ball mill is laid with lining materials such as alumina, zirconia, rubber, polyurethane, nylon, silica and the like. Alumina and zirconia are preferred because they have higher hardness than other lining materials, and can reduce the mixing of the lining material into the pigment and shorten the pulverization time.

The grinding balls are alumina balls, zirconia balls, porcelain balls, steel balls, etc. In addition, zirconia balls may be used as the inner liner of polyurethane or nylon. Since polyurethane and nylon are carbonized and disappeared during firing, there is less possibility of mixing impurities. The particle size of the grinding balls is appropriately changed according to the size of the particle size of the raw material oxide.

The dispersant, which is one of the grinding aids, is selected from sodium polycarboxylate, sulfonic acid polymer (sodium salt), and the like, in addition to the polycarboxylic acid compound and ammonium polyacrylate or sodium polyacrylate, which are polyacrylic acid compounds. By adding the grinding aid appropriately, the dispersibility in the raw material oxide liquid becomes good, and the grinding can be carried out very finely in a short time. It is known that the specific gravity of the raw material oxide of each main component is different. Therefore, in order to prevent variation in pulverization, uniform pulverization of any component is required. In particular, ammonium polyacrylate is preferably used because it is decomposed by firing and does not leave sodium as compared with other grinding aids.

In the pulverization (S11, S13), the average particle diameter of the raw material oxide after pulverization is pulverized to 5 μm or less, further pulverized to 2 μm or less, preferably to 1 μm or less, and more preferably to 0.7 μm or less. This is to promote the growth of sintered particles of the mixed oxide generated during firing by reducing the average particle diameter as much as possible. In addition, since the reactivity of the oxide raw material having a smaller average particle diameter is improved, a mixed oxide having a preferable crystal structure is easily obtained. Since the smaller the average particle size is, the longer the pulverization time is, the average particle size is defined in consideration of the performance required of the pigment, the firing time, and the like.

The "average particle diameter" in the present specification means a particle diameter (cumulative average diameter) of 50% of the integrated value in the particle size distribution obtained by the laser diffraction/scattering method using the laser diffraction/scattering particle diameter/particle size distribution measuring apparatus of the following example.

The pulverized product obtained by wet pulverization is put into a slurry tank and dried by a spray dryer, a filter press (dehydration dryer), a decanter (centrifugal separation dehydration dryer), or the like. The moisture content is 1.0% or less, preferably 0.5% or less. When a filter press, a decanter or the like is used for drying, it is necessary to re-dry and pulverize, and a spray dryer is preferably used for convenience of the production method. The drying step is also omitted depending on the state of the water content after the mixing and pulverization.

In the pulverization after firing in FIGS. 1 and 2 (S13, S23), the powder is pulverized to an average particle size of 50 μm or less. Of course, the particle size during the pulverization may be smaller than 50 μm as necessary. In the first embodiment, the pulverization of S13 is finally completed. Therefore, in the pulverization of S13, the average particle size is selected according to the intended use. The pulverization (S23) of fig. 2 (second embodiment) is adjusted by intentionally enlarging the crystals of the mixed oxide in consideration of the heat exposure at the time of the subsequent firing.

In the pulverization after firing in the process diagram of FIG. 2 (S25), the powder is pulverized to an average particle size of 20 μm or less, further pulverized to an average particle size of 5 to 10 μm or less, preferably to an average particle size of 0.5 to 2 μm, and further preferably to an average particle size of 0.8 to 1 μm. The average particle size of the black mixed oxide material is reduced by pulverization after firing. As a result, the specific surface area becomes large, the density becomes dense, and the color tone becomes more uniform, and a pigment with good reproducibility can be produced. In the pulverization after the firing, a pulverization device is used by the same method as the above pulverization. When the ball mill grinding or the like is performed by a wet method, drying may be performed by a spray dryer or the like as necessary. When the pigment is coagulated by drying, the pigment may be pulverized by using an impact pulverizer such as a jet mill, a vibration mill, or a hammer mill.

The firing of S12, S22, and S24 in process diagrams 1 and 2 is also referred to as calcination (calcination). In this firing, the oxide raw material (pulverized material) is put into a pot made of mullite, cordierite, alumina or the like. The mixed oxide is produced from the oxide raw material by firing. The hue and concentration of the black mixed oxide material may vary depending on the degree of crystal growth and densification of its mixed oxide. When the black mixed oxide material is a black pigment, the firing temperature, the firing time, and the like are appropriately selected depending on each raw material oxide contained, in consideration of the use and performance thereof.

In addition, in the firing (S12, S22) in the method for producing a black mixed oxide material according to the first and second embodiments, a relatively large firing apparatus such as a tunnel kiln, a roller kiln, a rotary kiln, or a shuttle kiln is also used for mass production. In general, when a large-sized firing apparatus is used, unevenness is likely to occur in the sintering of the oxide material. Therefore, by introducing heated air, heated oxygen, or the like into each of the above-described kilns, the firing stage can be brought into an oxidizing atmosphere. Therefore, it is very convenient to produce a large amount of black pigment having a satisfactory quality at a low cost. When a rotary kiln is used, the mixed pulverized material is directly introduced into the kiln. The firing is performed at a temperature of 700 to 1200 ℃ for 1 to 8 hours, although the firing is different depending on the scale of the firing apparatus and the amount of the raw material oxide. The firing time is the maximum temperature holding time. In order to complete the treatment by one firing, a temperature gradient may be provided in the firing apparatus.

In the method for producing a black mixed oxide material according to the second embodiment, an electric furnace is used in addition to a tunnel furnace or the like for firing the raw material oxide (S24). Since the temperature of the electric furnace can be controlled more easily than in the above-described kilns, the amount of heat applied to the oxide raw material during firing can be accurately controlled. For example, when a metal oxide of a raw material is sintered to grow a crystal of a mixed oxide, it is convenient to adjust the thermal history (heating temperature, heating time) of the raw material. When an electric furnace is used, the oxide raw material and the like are heated in a static state. Therefore, the contact amount of the raw material with oxygen may become uneven, and thus the oxidation may be sufficient by repeating the firing twice.

In the case where the black mixed oxide material is a black pigment, the quality thereof is influenced by the crystal structure that rapidly develops during sintering, and therefore, in the case where stabilization of the properties is prioritized, the production method of the second embodiment is preferably employed. The first firing step is performed at 600 to 1200 ℃ for 1 to 6 hours, and the second firing step is performed at 600 to 1100 ℃ for 1 to 4 hours, taking into consideration the composition of the oxide raw material to be fired, the sintering performance accompanying the composition, and the like, in each temperature range and time. The time for the first firing step and the second firing step is the holding time of the respective maximum temperatures.

As can be understood from the description of the main components so far, the black mixed oxide material is not dependent on the valence number of chromium, and does not contain chromium itself in the main component, and is very economical and extremely safe. In the conventional production process of pigment, etc., 6-valent chromium (Cr) is generated for removal⁶⁺) The water washing step is required, but may be omitted. The additional drying and pulverizing steps can also be omitted. Therefore, the manufacturing time can be greatly shortened, and alsoThe manufacturing cost can be greatly reduced. In addition, the use of extremely high-purity and expensive raw materials is not required for the raw material oxide, and relatively inexpensive raw materials can be used, which is very advantageous in terms of raw material cost.

Further, since the black mixed oxide material (black pigment) which does not contain a chromium component and a cobalt component in the main component is a nonmagnetic material and an insulating material, 6-valent chromium which generates a harmful substance depending on the use and the use environment is not generated. In addition, the allergy caused by cobalt can be reduced. Examples of the use of such a black mixed oxide material include resin pigments, paint pigments, coloring pigments for ceramics (including ultraviolet absorbing and reflecting pigments for automobile window glasses), heat-radiating pigments, infrared reflecting pigments, colored ceramics, and other various products.

As the black mixed oxide material described in detail so far, when the black mixed oxide material is a black pigment, an inorganic glass paste (black inorganic glass paste) containing a black mixed oxide material (black pigment) and a glass agent is used. For example, inorganic glass paste is fired on the surface of a glass plate as a glass plate product. Specific glass sheet products include window glasses such as a front glass, a rear glass, and a roof glass of an automobile. Inorganic glass paste is applied to the surface of these glasses. The inorganic glass paste protects the adhesive and the cushion resin body present between the above glass sheet product and the vehicle body from ultraviolet rays, and prevents the aging of the adhesive and the cushion resin body. Of course, inorganic glass pastes are used for glass windows (glass plate products) of various transportation machines such as heavy vehicles, ships, and airplanes, as well as glass plate products for display screens, in addition to automobiles. In addition, the coating can also be used for coating and coating the metal surface. In addition, the seven-treasure painting can be used for painting on pottery or porcelain products and processing seven-treasure.

The composition of the inorganic glass paste is disclosed in Japanese patent laid-open Nos. 2002-20140 and 4035673, and is made of SiO₂、B₂O₃、ZnO、TiO₂、Li₂O、Na₂O、K₂O、ZrO₂Etc. formThe glass of (2) is the main component. The vitreous material is pulverized in advance to 0.1 to 30 μm, preferably to an average particle diameter of 0.5 to 20 μm, and is finely processed to a powder. To the mixture, a thermally decomposable resin such as a cellulose resin or an acrylic resin, a high-boiling-point solvent oil such as pine oil, the black mixed oxide material (black pigment) and other inorganic fillers are added, and the mixture is kneaded sufficiently and finished into a slurry.

The inorganic glass paste containing the black mixed oxide material (black pigment) thus produced is applied to, for example, the edge portion of a glass plate cut out in an appropriate shape. The inorganic glass paste may be applied to the surface of the glass plate by screen printing, spray coating, roll coating, or the like. Among them, screen printing is relatively simple. And the glass plate coated with the inorganic glass slurry is dried and then fixed on the surface of the glass plate by firing.

The glass sheets are bent by pressing the glass sheets between a mold and a mold in a furnace, and the glass sheets are bent by evacuating the glass sheets to the mold in the furnace. The glass sheet is formed by a tunnel furnace for preheating at room temperature to about 660 ℃ and a batch furnace for bending at 640-720 ℃ and passing through the two furnaces. The inorganic glass paste is fired on the surface of the glass sheet in a preliminary heating stage. Therefore, in molding glass plate, a glass plate product coated with an inorganic glass paste having an aspherical surface such as a window glass can be obtained.

Instead of the glass frit, a black mixed oxide material may be added to the ceramic frit to obtain an inorganic ceramic material. Examples of the ceramic agent include known ceramic materials such as alumina, partially stabilized zirconia, and stabilized zirconia. The partially stabilized zirconia and the stabilized zirconia contain calcium oxide, magnesium oxide, cesium oxide, aluminum oxide, yttrium oxide, or the like as a component. This result can appear as a black ceramic material.

Further, a resin agent may be added to the black mixed oxide material to prepare a resin slurry. The resin slurry is applied to the surface of a support such as glass, metal, ceramics, resin products, or carbon materials. The result is that a black color and pattern can be drawn on the surface of the listed support. The usage is the same as that of a general black pigment.

Further, the black mixed oxide material-containing resin can also be prepared by mixing the black mixed oxide material and the resin agent. This is so-called resin coloring. The black degree of the resin product is adjusted according to the addition amount. In addition, the color tone of the resin can be controlled with the addition of the transparent resin. The resin used for the resin paste and the black mixed oxide material-containing resin is a known resin such as a thermoplastic resin and a thermosetting resin, and is not particularly limited. Is appropriately selected in consideration of the use, place of use, durability, and the like of the product. The black mixed oxide material-containing resin is processed into pellets and used as a raw material for molded articles such as injection molding and extrusion molding. As described above, the black pigment of the present invention can replace the conventional black material as a mixed oxide material containing neither chromium nor cobalt.

It has been described so far that the mixed oxide further has a function as a nonmagnetic material. Therefore, the mixed oxide may be a black mixed oxide material having a non-magnetic function. The mixed oxide is non-magnetic and is preferably used for applications avoiding excitation and shielding by magnetic force. For example, protective applications for electronic components and the like are envisaged. In addition, the mixed oxide itself also presents black color, so the application of the product is also wide.

In addition, the mixed oxide further has a function as an insulating material. Therefore, the mixed oxide can be used as a black mixed oxide material having an insulating function. The mixed oxide is expected to have an electrically shielding effect by having an insulating property. For example, protective applications for electronic components and the like are envisaged. In addition, the mixed oxide itself also presents black color, so the application of the product is also wide.