JPH05214263A - Pigment of high adsorbing power - Google Patents
Pigment of high adsorbing powerInfo
- Publication number
- JPH05214263A JPH05214263A JP4755992A JP4755992A JPH05214263A JP H05214263 A JPH05214263 A JP H05214263A JP 4755992 A JP4755992 A JP 4755992A JP 4755992 A JP4755992 A JP 4755992A JP H05214263 A JPH05214263 A JP H05214263A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- transition metal
- aqueous solution
- silica
- surface area
- 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.)
- Withdrawn
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- -1 transition metal salt Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 7
- 238000004438 BET method Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000003349 gelling agent Substances 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 28
- 239000000377 silicon dioxide Substances 0.000 abstract description 13
- 230000001877 deodorizing effect Effects 0.000 abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 102200150779 rs200154873 Human genes 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Paper (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高吸着能を有する顔料
に関する。FIELD OF THE INVENTION The present invention relates to a pigment having a high adsorption capacity.
【０００２】[0002]
【従来の技術】従来、種々の顔料が知られているが、比
表面積が100m2 /g以上であるものも、吸着能が高いため
に脱臭性を有する顔料も知られていない。2. Description of the Related Art Heretofore, various pigments have been known, but neither a pigment having a specific surface area of 100 m 2 / g or more nor a pigment having a deodorizing property due to its high adsorption capacity is known.
【０００３】[0003]
【発明が解決しようとする課題】顔料に高い吸着能を付
与することができれば、壁紙、塗料、壁への吹きつけな
どに使用した際に、顔料としての色彩効果ばかりでなく
自然の脱臭作用、有害気体成分の吸着除去の作用を期待
することができる。そこで、本発明の課題は、高吸着能
を有する顔料を提供することである。If it is possible to impart a high adsorption capacity to a pigment, when it is used for wallpaper, paint, spraying on a wall, etc., not only the color effect as a pigment but also a natural deodorizing effect, It is possible to expect an action of adsorbing and removing harmful gas components. Then, the subject of this invention is providing the pigment which has high adsorption capacity.
【０００４】[0004]
【課題を解決するための手段】本発明によると、担体化
合物に担持された遷移金属酸化物からなり、 BET法によ
り測定された比表面積が100m2 /g以上である顔料が提供
される。顔料を構成する遷移金属酸化物としては、例え
ば次のものが挙げられ、これらと色彩の関係も以下に示
す通りである。Ti（白）, Ni（黄）, Fe（赤茶）Mn（こ
げ茶）, Co（緑）, Cu（オリーブ色）。According to the present invention, there is provided a pigment comprising a transition metal oxide supported on a carrier compound and having a specific surface area of 100 m 2 / g or more as measured by the BET method. Examples of transition metal oxides constituting the pigment include the following, and the relationship between these and colors is also as shown below. Ti (white), Ni (yellow), Fe (red brown) Mn (dark brown), Co (green), Cu (olive).
【０００５】これらの遷移金属酸化物は、担体化合物に
担持されるが、担体としては、シリカ、アルミナ、ジル
コニア等の金属酸化物があげられる。この場合、遷移金
属酸化物の顔料中に占める割合は、顔料の色合い、彩度
に影響するので目的に応じて設定される。通常、遷移金
属化合物と担体化合物との合計に対し、５〜80モル％が
好ましく、さらには10〜70モル％が好ましい。本発明の
顔料は100m2 /g以上の比表面積を有するため、吸着能が
高く、脱臭性能に優れている。These transition metal oxides are supported on a carrier compound, and examples of the carrier include metal oxides such as silica, alumina and zirconia. In this case, the proportion of the transition metal oxide in the pigment affects the hue and saturation of the pigment and is set according to the purpose. Usually, it is preferably from 5 to 80 mol%, more preferably from 10 to 70 mol%, based on the total of the transition metal compound and the carrier compound. Since the pigment of the present invention has a specific surface area of 100 m 2 / g or more, it has high adsorption ability and excellent deodorizing performance.
【０００６】この顔料の製造は、例えば、予め担体とな
る金属酸化物又は金属水酸化物、例えば、水酸化アル
ミ、水酸化ジルコニウム等のコロイド水溶液と、遷移金
属塩の水溶液とを混合し、さらにこの混合物にゲル化
剤、例えばアンモニア水、炭酸アンモニウム等の水溶液
を加えて担体成分と遷移金属塩との共沈物を作成し、そ
の共沈物を固液分離した後、 200〜800 ℃で焼成するこ
とにより、行うことができる。For the production of this pigment, for example, a metal oxide or metal hydroxide serving as a carrier, for example, an aqueous colloidal solution of aluminum hydroxide, zirconium hydroxide or the like is mixed with an aqueous solution of a transition metal salt, and further, A gelling agent such as aqueous ammonia or ammonium carbonate is added to this mixture to form a coprecipitate of the carrier component and the transition metal salt, and the coprecipitate is subjected to solid-liquid separation, and then at 200 to 800 ° C. It can be performed by firing.
【０００７】シリカを担体とする場合についてより具体
的に説明すると、コロイダルシリカの水溶液と、所定の
遷移金属塩、例えば硝酸塩、硫酸塩、塩化物、炭酸塩等
の水溶液とを、好ましくはシリカ（ SiO2 ）分５〜95モ
ル％、遷移金属分５〜95、より好ましくはシリカ分10〜
90モル％、遷移金属分10〜90モル％となる割合で混合す
る。シリカ分が少なすぎると得られる顔料の比表面積が
大きくならず、吸着能が高まらないし、シリカ分が多過
ぎると彩度が低く顔料として実用的でないことがある。
次に得られた混合液に沈澱剤、例えばアンモニア水を添
加して溶液のpHを７以上に変化させてシリカと遷移金属
とを共沈させたのち、共沈物を 200〜800 ℃で焼成す
る。こうして、シリカを担体とする顔料が得られる。共
沈物の焼成は、一般に、酸素、空気等の酸化性雰囲気中
において 450〜700℃程度の温度で行えばよい。焼成時
間は、通常、 0.5〜２時間程度でよい。The case where silica is used as a carrier will be described more specifically. An aqueous solution of colloidal silica and an aqueous solution of a predetermined transition metal salt such as nitrate, sulfate, chloride, carbonate, etc., preferably silica ( SiO 2 ) content 5 to 95 mol%, transition metal content 5 to 95, more preferably silica content 10 to
90 mol% and a transition metal content of 10 to 90 mol% are mixed. If the silica content is too low, the specific surface area of the resulting pigment does not increase, and the adsorption capacity does not increase. If the silica content is too high, the chroma is low and it may not be practical as a pigment.
Next, a precipitating agent such as aqueous ammonia is added to the obtained mixed solution to change the pH of the solution to 7 or more to coprecipitate silica and transition metal, and then the coprecipitate is calcined at 200 to 800 ° C. To do. In this way, a silica-based pigment is obtained. The coprecipitate may be generally baked at a temperature of about 450 to 700 ° C. in an oxidizing atmosphere such as oxygen or air. The firing time is usually about 0.5 to 2 hours.
【０００８】[0008]
実施例１〜６ 64.8重量％のTiCl4 水溶液（Ti分として４モル) ( 1170
ｇ）と20重量％のコロダルシリカ水溶液（Si分として１
モル) (300ｇ）を混合し、水溶液1470ｇを調製した。こ
の水溶液に、濃度約10％のアンモニア水を添加後のpHが
７〜９になるように添加し、チタン−シリカ共沈物を得
た。共沈物を遠心分離により固液分離し、得られた固形
物を 500℃で１時間焼成し、チタニア−シリカ複合酸化
物 380ｇを得た。これを粉砕して目的の顔料を得た。得
られた顔料の色合い、 BET法による比表面積、代表的な
臭気成分であるトリメチルアミン (TMA)に対する飽和吸
着量を測定した。結果を表１に示す。Examples 1 to 6 64.8 wt% TiCl 4 aqueous solution (4 mol as Ti content) (1170
g) and a 20 wt% aqueous solution of corrodal silica (Si content is 1
(300 g) was mixed to prepare 1470 g of an aqueous solution. Ammonia water having a concentration of about 10% was added to this aqueous solution so that the pH after the addition was 7 to 9 to obtain a titanium-silica coprecipitate. The coprecipitate was subjected to solid-liquid separation by centrifugation, and the obtained solid was calcined at 500 ° C for 1 hour to obtain 380 g of a titania-silica composite oxide. This was crushed to obtain the desired pigment. The hue of the obtained pigment, the specific surface area by the BET method, and the saturated adsorption amount for trimethylamine (TMA), which is a typical odor component, were measured. The results are shown in Table 1.
【０００９】実施例２〜６ 原料として64.8重量％、TiCl4 水溶液（Ti分として４モ
ル) ( 1170ｇ）と20重量％コロダルシリカ水溶液（Si分
として１モル) (300ｇ）の他に、表１に示した顔料組成
に応じて、第三の化合物として硝酸ニッケル、塩化鉄、
塩化マンガン、塩化コバルト又は硝酸銅を１モルを使用
し、焼成温度を表１に記載の温度に変えた以外は、実施
例１と同様にして顔料を製造した。得られた顔料につい
て実施例１と同様の測定を行った。結果を表１に示す。Examples 2 to 6 In addition to 64.8% by weight as a raw material, a TiCl 4 aqueous solution (4 mol as Ti content) (1170 g) and a 20% by weight collodal silica aqueous solution (1 mol as Si content) (300 g), Table 1 Depending on the pigment composition shown, nickel nitrate as a third compound, iron chloride,
A pigment was produced in the same manner as in Example 1 except that 1 mol of manganese chloride, cobalt chloride or copper nitrate was used and the firing temperature was changed to the temperature shown in Table 1. The same measurement as in Example 1 was performed on the obtained pigment. The results are shown in Table 1.
【００１０】実施例７ 64.8重量％のTiCl4 水溶液（Ti分として1.71モル) (502
ｇ）、20重量％コロイダルシリカ水溶液（Si分として0.
43モル) (123ｇ) と塩化マンガン・４水和物0.43モル
（86ｇ）を混合し、水溶液２リットルを調製した。この
水溶液に20重量％炭酸アンモニウム水溶液を添加した以
外は実施例１と同様にして顔料を製造した。得られた顔
料について実施例１と同様の測定を行った。結果を表１
に示す。Example 7 64.8% by weight TiCl 4 aqueous solution (1.71 mol as Ti content) (502
g), 20% by weight colloidal silica aqueous solution (Si content of 0.
43 mol) (123 g) and 0.43 mol (86 g) of manganese chloride tetrahydrate were mixed to prepare 2 liters of an aqueous solution. A pigment was produced in the same manner as in Example 1 except that a 20 wt% ammonium carbonate aqueous solution was added to this aqueous solution. The same measurement as in Example 1 was performed on the obtained pigment. The results are shown in Table 1.
Shown in.
【００１１】実施例８ 64.8重量％のTiCl4 水溶液（Ti分として0.43モル) (125
ｇ）、20重量％コロイダルシリカ水溶液（Si分として0.
11モル) ( 31ｇ) 及び塩化コバルト・６水和物0.11モル
（26ｇ）を混合し、水溶液１リットルを調製した。アル
カリ性の水溶液として炭酸アンモニウム ( 153ｇ）と28
重量％アンモニア水（55ｇ）を混合し水溶液１リットル
とした。実施例１と同様にして前者の水溶液に後者のア
ルカリ性水溶液を混合して共沈を起させ、顔料を製造し
た。得られた顔料について実施例１と同様の測定を行っ
た。結果を表１に示す。Example 8 64.8 wt% TiCl 4 aqueous solution (0.43 mol as Ti content) (125
g), 20% by weight colloidal silica aqueous solution (Si content of 0.
11 mol) (31 g) and 0.11 mol (26 g) of cobalt chloride hexahydrate were mixed to prepare 1 liter of an aqueous solution. 28 with ammonium carbonate (153g) as an alkaline aqueous solution
Aqueous water (55 g) was mixed by weight to prepare an aqueous solution of 1 liter. In the same manner as in Example 1, the former aqueous solution was mixed with the latter aqueous alkaline solution to cause coprecipitation to produce a pigment. The same measurement as in Example 1 was performed on the obtained pigment. The results are shown in Table 1.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】本発明の顔料は吸着能が高いため、例え
ば脱臭能も優れている。壁紙、塗料に使用することによ
り自然な脱臭効果を得ることができる。Since the pigment of the present invention has a high adsorption ability, it has an excellent deodorizing ability, for example. A natural deodorizing effect can be obtained by using it for wallpaper and paint.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 5/00 ＰＳＤ 6904−4Ｊ Ｄ２１Ｈ 19/38 17/67 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C09D 5/00 PSD 6904-4J D21H 19/38 17/67
Claims (2)
からなり、 BET法により測定された比表面積が100m2 /g
以上である、高吸着能を有する顔料。1. A specific surface area as measured by the BET method of 100 m 2 / g, which is composed of a transition metal oxide supported on a carrier compound.
The above is a pigment having a high adsorption ability.
水溶液と遷移金属塩の水溶液を混合し、さらにこの混合
物にゲル化剤を加えて担体成分と遷移金属塩との共沈物
を得、その共沈物を固液分離した後、 200〜800 ℃で焼
成することよりなる請求項１に記載の顔料の製造方法。2. A colloidal aqueous solution of a metal oxide or a metal hydroxide is mixed with an aqueous solution of a transition metal salt, and a gelling agent is added to the mixture to obtain a coprecipitate of a carrier component and a transition metal salt. The method for producing a pigment according to claim 1, wherein the coprecipitate is subjected to solid-liquid separation and then calcined at 200 to 800 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4755992A JPH05214263A (en) | 1992-02-03 | 1992-02-03 | Pigment of high adsorbing power |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4755992A JPH05214263A (en) | 1992-02-03 | 1992-02-03 | Pigment of high adsorbing power |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05214263A true JPH05214263A (en) | 1993-08-24 |
Family
ID=12778558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4755992A Withdrawn JPH05214263A (en) | 1992-02-03 | 1992-02-03 | Pigment of high adsorbing power |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05214263A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861741A (en) * | 2015-03-27 | 2015-08-26 | 浙江树人大学 | Brown porous inorganic solid pigment synthesis method |
-
1992
- 1992-02-03 JP JP4755992A patent/JPH05214263A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861741A (en) * | 2015-03-27 | 2015-08-26 | 浙江树人大学 | Brown porous inorganic solid pigment synthesis method |
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