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CN-122029128-A - Silicate blue pigment and method for producing same

CN122029128ACN 122029128 ACN122029128 ACN 122029128ACN-122029128-A

Abstract

The present invention provides a silicate blue pigment which is inexpensive, has low toxicity, exhibits vivid blue color, and has high-temperature durability, and a method for producing the same. The silicate blue pigment of the present invention has Mn doped at Si sites of a silicate represented by the following formula (A), and the Mn doped amount of 100% of the total atomic number of Si and Mn in the Si sites is 0.01 to 50%. Na 2 M 6 Si 4 O 15 (A) (in the formula (A), M represents at least 1 selected from the group consisting of Ca, sr and Ba.)

Inventors

  • NITTA KENJI
  • KATO TAKAAKI
  • KUWANA YASUHIRO
  • Kayane Ryo
  • YUAN JIANJUN
  • Indra Kusuma

Assignees

  • DIC株式会社
  • 国立大学法人新潟大学

Dates

Publication Date
20260512
Application Date
20241025
Priority Date
20231101

Claims (10)

  1. 1. A silicate blue pigment which comprises a silicate represented by the following formula (A) and Mn doped at Si sites, The doping amount of Mn in 100% of the total atomic number of Si and Mn in the Si site is 0.01-50%, Na 2 M 6 Si 4 O 15 (A) In the formula (A), M represents at least 1 selected from the group consisting of Ca, sr and Ba.
  2. 2. The silicate-based blue pigment according to claim 1, which is represented by the following general formula (1), Na 2 M 6 (Si 1-x Mn x ) 4 O 15 (1) In the formula (1), M represents at least 1 selected from the group consisting of Ca, sr and Ba, and x is 0.001-0.5.
  3. 3. The silicate-based blue pigment according to claim 1, having a crystal structure of the silicate represented by the formula (a).
  4. 4. The silicate-based blue pigment according to claim 1, which is represented by the following formula (1 a), Na 2 Ba 6 (Si 1-x Mn x ) 4 O 15 (1a) In the formula (1 a), x is 0.001 to 0.5.
  5. 5. The silicate-based blue pigment according to claim 1, which is represented by the following formula (1 b), Na 2 Ca 6 (Si 1-x Mn x ) 4 O 15 (1b) In the formula (1 a), x is 0.001 to 0.3.
  6. 6. A method for producing a silicate blue pigment according to any one of claims 1 to 5, comprising: A mixing step of mixing a Na compound, an M compound, an oxide of Si, and an Mn compound, and And a firing step of firing the mixture obtained in the mixing step.
  7. 7. The method for producing a silicate-based blue pigment according to claim 6, wherein the Na compound is at least 1 selected from the group consisting of NaCl and NaOH.
  8. 8. The method for producing a silicate-based blue pigment according to claim 6, wherein the Mn compound is an oxide of Mn.
  9. 9. The method for producing a silicate-based blue pigment according to claim 6, wherein the amount of the Na compound is 5 to 30 mass% greater than the stoichiometric ratio represented by the general formula (A).
  10. 10. The method for producing a blue silicate pigment according to claim 6, further comprising a washing step using water after said firing step.

Description

Silicate blue pigment and method for producing same Technical Field The present invention relates to a silicate blue pigment and a method for producing the same. The present application is based on the priority claimed in japanese patent application No. 2023-187572 of the application in japan at 11/2023, month 1, the contents of which are incorporated herein by reference. Background Inorganic pigments are used as coloring materials for ceramics, glass, plastics, paints, and the like. However, the existing inorganic pigments mostly contain metals exhibiting strong toxicity, and development of novel pigments for environmental protection instead of these inorganic pigments is required. For example, the earliest known vivid Blue pigment was cobalt Blue (CI pigment Blue 28 (CI PIGMENT Blue 28): coAl 2O4 spinel), but the possibility of being limited in the future due to the carcinogenicity of cobalt compounds is high. As blue pigments of similar concept there are YInMn blue (yttrium indium manganese blue, english: YInMn blue, Y stands for yttrium, in stands for indium, mn stands for manganese.). For example, non-patent document 1 reports L in CIE color system of blue pigment represented by YIn 0.8Mn0.2O3 having an optimal composition(. About.34) and bA value of (-39). Further, a blue pigment Ba 3(P1-xMnxO4)2 (x≤0.25) using inexpensive transition metal manganese, which is not pointed out as carcinogenicity, has been reported (non-patent document 2). On the other hand, non-patent document 3 reports a single crystal structure of Na 2Ca6Si4O15 obtained in a solid phase reaction performed at 1300 ℃. Prior art literature Non-patent literature Non-patent literature 1：Andrew E. Smith, Matthew C. Comstock, M.A. Subramanian: Spectral properties of the UV absorbing and near-IR reflecting blue pigment, YIn1-xMnxO3, DYES AND PIGMENTS, Volume 133, 2016, Pages 214-221. Non-patent literature 2：LAHA, S., SHARMA, R., BHAT, S.V. et al.: Ba3(P1-xMnxO4)2: Blue/green inorganic materials based on tetrahedral Mn(V), Bull. Mater. Sci.,Volume 34,2011, Pages 1257-1262. Non-patent literature 3：Volker Kahlenberg,Matthias Maier: MINERALOGY AND PETROLOGY, On the existence of a high-temperature polymorph of Na2Ca6Si4O15-implications for the phase equilibria in the system Na2O-CaO-SiO2, Volume110, 2016,pages 905-915. Disclosure of Invention Problems to be solved by the invention However, YInMn blue disclosed in non-patent document 1 is extremely expensive and is also a concern about carcinogenicity, and thus is hardly utilized. On the other hand, a blue pigment having a better hue than the blue pigment disclosed in non-patent document 2 is demanded. Namely, a blue pigment having low cost, low toxicity, color tone and high temperature durability is required. The purpose of the present invention is to provide a silicate-based blue pigment which is inexpensive, has low toxicity, exhibits vivid blue color, and has high-temperature durability, and a method for producing the same. Solution for solving the problem In order to solve these problems, the present inventors succeeded in synthesizing a novel blue pigment exhibiting vivid blue color and having high-temperature durability by doping a silicon (Si) site of a silicate system such as Na2Ba6Si4O15、Na2Sr6Si4O15、Na2Ca6Si4O15 with manganese as a coloring ion, which is inexpensive and has low toxicity. The following illustrates embodiments of the present invention. [1] A silicate blue pigment which comprises a silicate represented by the following formula (A) and Mn doped at Si sites, And the doping amount of Mn in 100% of the total atomic number of Si and Mn in the Si site is 0.01-50%. Na2M6Si4O15 (A) (In the formula (A), M represents at least 1 selected from the group consisting of Ca, sr and Ba.) [2] The silicate-based blue pigment according to [1], which is represented by the following general formula (1). Na2M6(Si1-xMnx)4O15 (1) ( In the formula (1), M represents at least 1 selected from the group consisting of Ca, sr and Ba. x is 0.001 to 0.5. ) [3] The silicate-based blue pigment according to [1] or [2], which has the crystal structure of the silicate represented by the formula (A). [4] The silicate-based blue pigment according to any one of [1] to [3], which is represented by the following formula (1 a). Na2Ba6(Si1-xMnx)4O15 (1a) (In the formula (1 a), x is 0.001-0.5.) [5] The silicate-based blue pigment according to any one of [1] to [3], which is represented by the following formula (1 b). Na2Ca6(Si1-xMnx)4O15 (1b) (In the formula (1 a), x is 0.001-0.3.) [6] A method for producing the silicate-based blue pigment according to any one of [1] to [5], comprising: A mixing step of mixing a Na compound, an M compound, an oxide of Si, and an Mn compound, and And a firing step of firing the mixture obtained in the mixing step. [7] The method for producing a silicate-based blue pigment according to [6], wherein the Na compound is at least 1 selected from the group consisting of NaCl and NaOH. [8] The