JPH06256011A - Inorganic pigment composition and its production - Google Patents
Inorganic pigment composition and its productionInfo
- Publication number
- JPH06256011A JPH06256011A JP6764993A JP6764993A JPH06256011A JP H06256011 A JPH06256011 A JP H06256011A JP 6764993 A JP6764993 A JP 6764993A JP 6764993 A JP6764993 A JP 6764993A JP H06256011 A JPH06256011 A JP H06256011A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic pigment
- pigment composition
- cordierite
- composition
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はガラスやセラミック等の
着色に用いる無機顔料組成物及びその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic pigment composition used for coloring glass, ceramics and the like and a method for producing the same.
【０００２】[0002]
【従来の技術】ガラスやセラミック等の一部又は全部を
着色することは従来より行われている。例えば、透明な
ガラス表面に、意匠や遮蔽等を目的として、ある色の顔
料を含有した低融点ガラスフリットベースを塗布、焼付
けして、着色層を形成し、ガラスの着色を行うことがあ
る。ここで用いられる顔料としては、スピネルなどの結
晶構造を有し、熱膨張率が大きかった。2. Description of the Related Art Coloring a part or all of glass, ceramics or the like has been conventionally performed. For example, a low-melting-point glass frit base containing a pigment of a certain color may be applied and baked on a transparent glass surface for the purpose of designing, shielding, or the like to form a colored layer, thereby coloring the glass. The pigment used here had a crystal structure such as spinel and had a large coefficient of thermal expansion.
【０００３】[0003]
【発明が解決しようとする課題】従来用いられている顔
料は、いずれも熱膨張が大きいため、着色層の熱膨張率
がガラスのそれよりも大きくなる傾向があった。そのた
め、ガラスに引っ張り応力がはたらき、ガラスの強度が
低下するという課題が有った。一方、コーディエライト
は２ＭｇＯ・２Ａｌ2 Ｏ3 ・５ＳｉＯ2 の化学式を有
し、低熱膨張のセラミック材料として知られている。し
かし、その粉末は白色を呈し、このままでは、白色以外
の無機顔料として使用することは困難であった。Since the pigments used conventionally have large thermal expansion, the coefficient of thermal expansion of the colored layer tends to be larger than that of glass. Therefore, there is a problem that tensile stress acts on the glass and the strength of the glass decreases. On the other hand, cordierite has a chemical formula of 2MgO.2Al 2 O 3 .5SiO 2 and is known as a ceramic material having low thermal expansion. However, the powder had a white color, and as it was, it was difficult to use it as an inorganic pigment other than white.
【０００４】本発明は、従来の技術の上記課題を解消
し、低熱膨張でかつ高温度で安定な無機顔料組成物及び
その製造法の提供を目的とする。An object of the present invention is to solve the above problems of the prior art and to provide an inorganic pigment composition having a low thermal expansion and stable at high temperature, and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明は、主にコーディ
エライトからなり、２（Ｍｇ1-x ・Ｍ’x ）Ｏ・２（Ａ
ｌ2(1-y)・Ｍ”2y）Ｏ3 ・５ＳｉＯ2 と表したとき、
ｘ、ｙがそれぞれ０．０３≦ｘ≦０．５０、０．０３≦
ｙ≦０．５０を満たし、かつＭ’がＣｕ、Ｃｏ、Ｎｉ及
びＭｎから選ばれる少なくとも１種であり、Ｍ”がＦｅ
及びＣｒから選ばれる少なくとも１種である無機顔料組
成物及びその製造法である。The present invention is mainly composed of cordierite and is composed of 2 (Mg 1-x · M ′ x ) O · 2 (A
When expressed as l 2 (1-y) · M ″ 2y ) O 3 / 5SiO 2 ,
x and y are 0.03 ≦ x ≦ 0.50 and 0.03 ≦, respectively.
y ≦ 0.50 is satisfied, M ′ is at least one selected from Cu, Co, Ni and Mn, and M ″ is Fe.
And at least one inorganic pigment composition selected from Cr and a method for producing the same.
【０００６】以下、本発明について、詳細に説明する。
まず、化学式で２（Ｍｇ1-x ・Ｍ’x ）Ｏ・２（Ａｌ
2(1-y)・Ｍ”2y）Ｏ3 ・５ＳｉＯ2 と表したとき、Ｍ’
をＣｕ、Ｃｏ、Ｎｉ、Ｍｎから、Ｍ”をＦｅ、Ｃｒから
選び、調合を行う。ここでＭ’、Ｍ”はそれぞれ、２、
３価の金属イオンを表しコーディエライトを着色する。
またｘ、ｙは０．０３より小さいと、着色が不十分であ
り、０．５０より大きいとコーディエライト以外の結晶
構造を有する化合物が増えて、熱膨張が大きくなり過ぎ
る。The present invention will be described in detail below.
First, in the chemical formula, 2 (Mg 1-x・ M ' x ) O ・ 2 (Al
2 (1-y) · M "2y) when expressed as O 3 · 5SiO 2, M '
Is selected from Cu, Co, Ni, and Mn, and M ″ is selected from Fe and Cr, and mixing is performed. Here, M ′ and M ″ are 2, and 2, respectively.
Represents a trivalent metal ion and colors cordierite.
When x and y are smaller than 0.03, coloring is insufficient, and when larger than 0.50, compounds having a crystal structure other than cordierite increase, and thermal expansion becomes too large.
【０００７】かかる無機顔料組成物を製造するにあたっ
ては、調合した粉末を混合し、ついで焼成し、添加した
２、３価の金属イオンを、それぞれＭｇ、Ａｌサイトに
一部固溶させることにより、コーディエライト構造の無
機顔料組成物が得られる。また、混合後、ガラス化して
から再度熱処理することによってもコーディエライト構
造の無機顔料組成物が得られる。In the production of such an inorganic pigment composition, the prepared powders are mixed and then fired, and the added divalent and trivalent metal ions are partially solid-dissolved in Mg and Al sites, respectively. An inorganic pigment composition having a cordierite structure is obtained. In addition, the inorganic pigment composition having a cordierite structure can also be obtained by heat-treating again after mixing and vitrifying.
【０００８】前者の製造法の場合、焼成温度は、１００
０℃以上の温度が好ましい。焼成温度が１０００℃より
低いと、添加した２、３価の金属イオンが十分固溶せ
ず、着色が不十分となる。In the former manufacturing method, the firing temperature is 100.
Temperatures above 0 ° C are preferred. If the firing temperature is lower than 1000 ° C., the added divalent and trivalent metal ions do not sufficiently form a solid solution, resulting in insufficient coloring.
【０００９】後者の製造法の場合、添加した２、３価の
金属イオンの種類、量にもよるが、まず、１２００℃以
上の温度で加熱溶融し、急冷してコーディエライト系の
ガラスをつくる。ついでこのガラスを８００℃以上の温
度で加熱し、結晶化させてコーディエライト構造の無機
顔料組成物を析出させる。結晶を析出させる前に、ガラ
スを粉砕しておいてもよい。In the latter production method, although depending on the type and amount of the added divalent and trivalent metal ions, first, the mixture is heated and melted at a temperature of 1200 ° C. or higher and then rapidly cooled to form a cordierite glass. to make. Then, the glass is heated at a temperature of 800 ° C. or higher to crystallize the inorganic pigment composition having a cordierite structure. The glass may be crushed before the crystals are precipitated.
【００１０】なお、原料としてのＭ’、Ｍ”は金属の状
態で添加してもよく、化合物の状態で添加してもよい。The raw materials M'and M "may be added in the form of a metal or in the form of a compound.
【００１１】[0011]
【作用】本発明において、添加した２、３価の金属イオ
ンが、それぞれＭｇ、Ａｌサイトに一部固溶することに
より、本来白色であるコーディエライトが着色したもの
と思われる。In the present invention, it is considered that the originally white cordierite is colored by the solid solution of the added divalent and trivalent metal ions in the Mg and Al sites, respectively.
【００１２】[0012]
［実施例１〜９］２（Ｍｇ1-x ・Ｍ’x Ｏ・２（Ａｌ
2(1-y)・Ｍ”2y）Ｏ3 ・５ＳｉＯ2 において、表１に示
した割合（単位：原子比）で調合し、混合した。その
後、外径２０ｍｍ、長さ３０ｍｍに１０００ｋｇ／ｃｍ
2 で成形し、表１の焼成温度（単位：℃）で２時間焼成
し、焼結体を得た。得られた焼結体の色を肉眼にて観察
してから、外径５ｍｍ、長さ１５ｍｍの試料を切り出
し、室温から７００℃までの熱膨張率（単位：１０-7／
℃）を測定した。それらの結果を表１に示した。表１に
は、比較例１〜２も示した。表１より明らかなように、
本発明による無機顔料組成物は、熱膨張率が小さく、
黒、青、緑などに着色している。[Examples 1 to 9] 2 (Mg 1-x · M ′ x O · 2 (Al
2 (1-y) · M ″ 2y ) O 3 · 5SiO 2 was mixed and mixed in the proportions (unit: atomic ratio) shown in Table 1. After that, 1000 kg / cm in an outer diameter of 20 mm and a length of 30 mm.
Molded in 2 and fired for 2 hours at the firing temperature (unit: ° C) shown in Table 1 to obtain a sintered body. After observing the color of the obtained sintered body with the naked eye, a sample having an outer diameter of 5 mm and a length of 15 mm was cut out, and the coefficient of thermal expansion from room temperature to 700 ° C. (unit: 10 −7 /
C) was measured. The results are shown in Table 1. Table 1 also shows Comparative Examples 1 and 2. As is clear from Table 1,
The inorganic pigment composition according to the present invention has a small coefficient of thermal expansion,
It is colored black, blue, green, etc.
【００１３】[0013]
【表１】 [Table 1]
【００１４】［比較例１〜２］表１に示した条件で調
合、混合、焼成を行い、実施例１と同様に評価したとこ
ろ、比較例１では熱膨張率は小さいものの、白っぽく着
色が不十分であった。比較例２では十分黒く着色してい
たものの、熱膨張率が大きかった。[Comparative Examples 1 and 2] Preparation, mixing and firing were carried out under the conditions shown in Table 1 and evaluated in the same manner as in Example 1. In Comparative Example 1, although the coefficient of thermal expansion was small, whitish coloring was not observed. Was enough. Comparative Example 2 was colored sufficiently black, but had a large coefficient of thermal expansion.
【００１５】［実施例１０］コーディエライト粉末１０
０ｇに対してＣｕ粉末１０ｇの割合で添加、混合し、実
施例１と同様に成形、焼成したところ、黒く着色してお
り、熱膨張率は２３×１０-7／℃であった。[Example 10] Cordierite powder 10
When Cu powder was added and mixed in a ratio of 0 g to 0 g, and the mixture was molded and fired in the same manner as in Example 1, it was colored black and had a thermal expansion coefficient of 23 × 10 −7 / ° C.
【００１６】［実施例１１］実施例１の組成で調合し、
混合後、１６００℃で加熱溶融し、急冷してガラス化し
た。ついで１２００℃に２時間保持し、結晶化処理を行
った。その結果、黒く着色し、熱膨張率は２４×１０-7
／℃であった。[Example 11] The composition of Example 1 was prepared,
After mixing, the mixture was heated and melted at 1600 ° C., and rapidly cooled to vitrify. Then, it was kept at 1200 ° C. for 2 hours to carry out a crystallization treatment. As a result, it was colored black and had a coefficient of thermal expansion of 24 × 10 −7.
/ ° C.
【００１７】［実施例１２］実施例１１で、ガラス化
後、粉砕し、外径２０ｍｍ、長さ３０ｍｍに１０００ｋ
ｇ／ｃｍ2 で成形した。ついで実施例１１と同様に結晶
化処理を行った。その結果、黒く着色し、熱膨張率は２
３×１０-7／℃であった。[Embodiment 12] In Embodiment 11, after vitrification, it is crushed to have an outer diameter of 20 mm and a length of 30 mm of 1000 k.
Molded at g / cm 2 . Then, crystallization treatment was performed in the same manner as in Example 11. As a result, it is colored black and has a coefficient of thermal expansion of 2
It was 3 × 10 −7 / ° C.
【００１８】[0018]
【発明の効果】本発明によれば、低膨張で、高温で安定
な無機顔料組成物が得られる。According to the present invention, an inorganic pigment composition having a low expansion and stable at high temperature can be obtained.
Claims (4)
1-x ・Ｍ’x ）Ｏ・２（Ａｌ2(1-y)・Ｍ”2y）Ｏ3 ・５
ＳｉＯ2 と表したとき、ｘ、ｙがそれぞれ０．０３≦ｘ
≦０．５０、０．０３≦ｙ≦０．５０を満たし、かつ
Ｍ’がＣｕ、Ｃｏ、Ｎｉ及びＭｎから選ばれる少なくと
も１種であり、Ｍ”がＦｅ及びＣｒから選ばれる少なく
とも１種である無機顔料組成物。1. Mainly composed of cordierite, 2 (Mg
1-x · M 'x) O · 2 (Al 2 (1-y) · M "2y) O 3 · 5
When expressed as SiO 2 , x and y are each 0.03 ≦ x
≦ 0.50, 0.03 ≦ y ≦ 0.50, and M ′ is at least one selected from Cu, Co, Ni, and Mn, and M ″ is at least one selected from Fe and Cr. An inorganic pigment composition.
後、１０００℃以上の温度で焼成することを特徴とする
請求項１記載の無機顔料組成物の製造法。2. The method for producing an inorganic pigment composition according to claim 1, wherein the chemical composition is adjusted to the above chemical composition, the mixture is mixed, and then the composition is baked at a temperature of 1000 ° C. or higher.
後、１２００℃以上の温度で加熱溶融し急冷してガラス
を得、８００℃以上の温度でコーディエライトを結晶化
させることを特徴とする請求項１記載の無機顔料組成物
の製造法。3. The composition is prepared to have the above chemical composition, and after mixing, heated and melted at a temperature of 1200 ° C. or higher and rapidly cooled to obtain glass, and cordierite is crystallized at a temperature of 800 ° C. or higher. The method for producing the inorganic pigment composition according to claim 1.
後、１２００℃以上の温度で加熱溶融し急冷してガラス
を得、粉砕後８００℃以上の温度でコーディエライトを
結晶化させることを特徴とする請求項１記載の無機顔料
組成物の製造法。4. Mixing to have the above chemical composition, mixing, heating and melting at a temperature of 1200 ° C. or higher and quenching to obtain glass, and crushing cordierite at a temperature of 800 ° C. or higher after crushing. The method for producing the inorganic pigment composition according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6764993A JPH06256011A (en) | 1993-03-03 | 1993-03-03 | Inorganic pigment composition and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6764993A JPH06256011A (en) | 1993-03-03 | 1993-03-03 | Inorganic pigment composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06256011A true JPH06256011A (en) | 1994-09-13 |
Family
ID=13351088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6764993A Pending JPH06256011A (en) | 1993-03-03 | 1993-03-03 | Inorganic pigment composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06256011A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222151A (en) * | 2009-03-19 | 2010-10-07 | Asahi Kasei Chemicals Corp | Silica-based material and method for producing the same and metal supporting material |
| US9120085B2 (en) | 2010-09-16 | 2015-09-01 | Asahi Kasei Chemicals Corporation | Silica-based material and process for producing the same, noble metal supported material and process for producing carboxylic acids by using the same as catalyst |
| CN113905994A (en) * | 2019-06-05 | 2022-01-07 | 费罗公司 | Dark low expansion fillers |
-
1993
- 1993-03-03 JP JP6764993A patent/JPH06256011A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222151A (en) * | 2009-03-19 | 2010-10-07 | Asahi Kasei Chemicals Corp | Silica-based material and method for producing the same and metal supporting material |
| US9120085B2 (en) | 2010-09-16 | 2015-09-01 | Asahi Kasei Chemicals Corporation | Silica-based material and process for producing the same, noble metal supported material and process for producing carboxylic acids by using the same as catalyst |
| JP5794993B2 (en) * | 2010-09-16 | 2015-10-14 | 旭化成ケミカルズ株式会社 | Silica-based material and method for producing the same, noble metal support and method for producing carboxylic acids using the same as a catalyst |
| US9480973B2 (en) | 2010-09-16 | 2016-11-01 | Asahi Kasei Kabushiki Kaisha | Silica-based material and process for producing the same, noble metal supported material and process for producing carboxylic acids by using the same as catalyst |
| CN113905994A (en) * | 2019-06-05 | 2022-01-07 | 费罗公司 | Dark low expansion fillers |
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