CN1186400C - 氧化铁颜料的制备方法 - Google Patents
氧化铁颜料的制备方法 Download PDFInfo
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- CN1186400C CN1186400C CNB001344404A CN00134440A CN1186400C CN 1186400 C CN1186400 C CN 1186400C CN B001344404 A CNB001344404 A CN B001344404A CN 00134440 A CN00134440 A CN 00134440A CN 1186400 C CN1186400 C CN 1186400C
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- 239000000049 pigment Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 239000000725 suspension Substances 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 229960005191 ferric oxide Drugs 0.000 claims description 9
- 239000001062 red colorant Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000004922 lacquer Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 2
- 239000001054 red pigment Substances 0.000 abstract description 2
- 229910052595 hematite Inorganic materials 0.000 abstract 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 abstract 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001034 iron oxide pigment Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compounds Of Iron (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明涉及纯色氧化铁红颜料的制备方法以及这些纯色颜料及其应用，所述制备方法包括通过稀硝酸与元素铁在大于90℃的温度进行反应形成赤铁矿核的悬浮液的步骤。
Description
本发明涉及纯色氧化铁红颜料的制备方法以及这些颜料及其应用。
制备红色氧化铁颜料的方法已经公开于下列文献中：T.C.Patton，Pigment Handbook，Vol 1，New York 1988。此外，SHEN，Qing；SUN，Fengzhi在Wujiyan Gongye 1997，(6)，5-6(CH)，Wujiyan GongyeBianjib，(CA 128：218378n)中报道了一种方法，其中在升高的温度下将稀硝酸作用于元素铁，形成赤铁矿核的悬浮液。如何将该悬浮液转化为红色颜料的悬浮液并回收该颜料是已知的。然而，由该方法产生的红颜料颜色饱和度比较低，因此主要用于建材工业。
因此，本发明的目的是提供改善的氧化铁红颜料，它具有Shen等所述产生核的简单方法的优点，而不具有不适当的颜色纯度的缺点。
现已发现，通过保持核形成的反应温度高于90℃、而不是Shen等推荐的86℃，可以满足氧化铁红颜料市场销售的较高要求。
本发明涉及氧化铁红颜料的生产方法，该方法是将稀硝酸与元素铁在大于90℃的温度进行反应形成赤铁矿核的悬浮液，然后将该赤铁矿核的悬浮液转化成赤铁矿颜料悬浮液，并任选地回收固体颜料。
本发明还涉及在颜色试验中颜色饱和度(C*)大于39 CIELAB单位的颜料。
本发明还涉及这些颜料在使混凝土、塑料、涂料、漆着色中的应用和如此着色或涂覆后的底物。
在本发明方法的优选实施方案中，通过以下方法制备核的悬浮液：
a)将元素铁置于反应温度为90℃-99℃的水中，特别优选的是95℃-99℃。
在本发明方法的另一优选实施方案中，
b)将元素铁与2-6％(重量)HNO3浓度的硝酸反应，
在本发明方法的另一优选实施方案中，将铁与硝酸以下述比例反应，
c)Fe∶HNO3的摩尔比为1.5-16。
由此得到核的红色悬浮液。X-射线相分析显示悬浮的颗粒仅仅由赤铁矿组成。
元素铁优选废铁、特别优选铁皮。
转化方法还可以包括通过与铁(II)盐和碱金属氢氧化物反应并暴露于含氧气体而使赤铁矿核悬浮液转化成赤铁矿颜料悬浮液的步骤。
转化方法还可以包括用元素铁、铁(II)盐和含氧气体将赤铁矿核悬浮液转化为赤铁矿颜料悬浮液的步骤。
颜料形成优选以两种方式进行。将金属离子和铁(II)盐加入核悬浮液中，将整个混合物加热至70℃-100℃、优选75℃-90℃，并且每小时、每升悬浮液用0.2-50升空气进行氧化，直至达到所需的色度，或者将核悬浮液加热至70℃-100℃、优选75℃-90℃，加入铁(II)盐和碱溶液，并且将整个混合物以每小时、每升悬浮液1-400升空气氧化，直至达到所需的色度。
分离出盐水后，可以将红色的膏转化为浆或者干燥和研磨以形成粉状颜料。由此得到软的纯色氧化铁颜料。经X-射线相分析确定所得产物为α-Fe2O3(ASTM No.：33.0664)。
优选的是，在颜色试验中，该氧化铁红颜料的颜色饱和度C*大于40CIELAB单位。
优选用本发明颜料对混凝土和塑料挤塑制品以及汽车漆着色。按照本发明，塑料挤塑制品还包括电动机械打印方法中使用的色粉以及用这些颜料着色；涂料包括乳化漆和喷墨打印机的墨。
本发明的颜料可以采用已知方式造粒，并以此形式使用。
在含有63％亚麻子油和23％邻苯二甲酸酐的醇酸树脂(Alkydal L 64，Bayer AG，Leverkusen，DE)中进行颜料在涂层领域中应用的颜色试验，在醇酸树脂中加有5％ Luvotix HT添加剂(Lehmann & Voss)以增加粘度。颜料的体积浓度为10％。
使用Ulbricht球形光度计(照明条件为d/8°，标准光源C/2°)测定CIELAB数据(DIN6174)，包括表面反射。颜色的饱和度(C*)被视为颜料的颜色纯度的量度。
实施例1
在300l/h的氮气氛下，将1773g铁皮置于24升水中，并加热至95℃。用1小时，向其中加入1445.1g 34.6％(重量)的硝酸。然后使该混合物反应30分钟。形成赤铁矿核悬浮液。无需回收该核，并随后以其获得的状态使用该悬浮液。
实施例2
将685g铁皮、70g实施例1得到的Fe2O3核(固体物质)、4升水和175g FeCl3在100l/h的氮气氛下、以200转/分钟的速度搅拌，并加热至70℃。然后使气体处理改为100l/h空气，并通气100小时。
实施例3
将0.26mol实施例1的Fe2O3核(固体物质)、4.94mol FeCl2和6.3升水置于100l/h氮气氛下，并加热至90℃。经5分钟，用氢氧化钠溶液将pH值调节为2.0，并在此pH值以150l/h的量通气15小时进行氧化。
表1 L 64纯色度的绝对值
类型说明 L* a* b* C*
实施例2 42.2 30.6 26.9 40.8
实施例3 41.1 31.7 26.1 41.1
750/99/11) 41.2 28.8 22.2 36.4
Bayferrox 41002) 39.7 29.6 23.7 37.9
1)赤铁矿颜料，普通的中国市售产品
2)Bayferrox 4100，赤铁矿颜料，Bayer AG，Leverkusen，DE
尽管前面对本发明进行了说明性的详细描述，但是应该理解，该详细说明仅仅是说明的目的，在不背离本发明精神和范围的条件下，本领域专业人员可以对其进行改变，除非受到权利要求的限制。
Claims (9)
1.制备氧化铁红颜料的方法，包括将稀硝酸与元素铁在90-99℃的温度进行反应形成赤铁矿核的悬浮液，然后将该赤铁矿核的悬浮液转化为赤铁矿颜料悬浮液，并任选地回收固体颜料。
2.权利要求1的方法，其中反应温度为95-99℃。
3.权利要求1的方法，其中硝酸的浓度为2-6％重量HNO3。
4.权利要求1的方法，其中Fe∶HNO3的摩尔比为1.5-16。
5.权利要求1的方法，其中通过与二价铁盐和碱金属氢氧化物反应并暴露于含氧气体，将赤铁矿核悬浮液转化为赤铁矿颜料悬浮液。
6.权利要求1的方法，其中用元素铁、二价铁盐和含氧气体将赤铁矿核悬浮液转化为赤铁矿颜料悬浮液。
7.按权利要求1所述方法制得的氧化铁红颜料，其中在涂料试验中颜色饱和度大于39CIELAB单位。
8.权利要求7的氧化铁红颜料，其中在涂料试验中颜色饱和度大于40CIELAB单位。
9.权利要求7所述的氧化铁红颜料在混凝土、塑料、涂料或漆中的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19958168.1 | 1999-12-02 | ||
| DE19958168A DE19958168A1 (de) | 1999-12-02 | 1999-12-02 | Verfahren zur Herstellung von Eisenoxidpigmenten |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1297968A CN1297968A (zh) | 2001-06-06 |
| CN1186400C true CN1186400C (zh) | 2005-01-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001344404A Expired - Lifetime CN1186400C (zh) | 1999-12-02 | 2000-12-01 | 氧化铁颜料的制备方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6503315B1 (zh) |
| EP (1) | EP1106577B1 (zh) |
| JP (1) | JP4988983B2 (zh) |
| CN (1) | CN1186400C (zh) |
| AT (1) | ATE521575T1 (zh) |
| CA (1) | CA2326765A1 (zh) |
| DE (1) | DE19958168A1 (zh) |
| ES (1) | ES2369251T3 (zh) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406873A (zh) * | 2001-09-13 | 2003-04-02 | 户田工业株式会社 | 粒状赤铁矿微粒的制造方法 |
| DE10311550B4 (de) * | 2003-03-17 | 2006-08-10 | Lanxess Deutschland Gmbh | Eisenoxidpigmente |
| DE10311549B4 (de) | 2003-03-17 | 2006-08-10 | Lanxess Deutschland Gmbh | Eisenoxidpigmente |
| FR2856051B1 (fr) | 2003-06-11 | 2005-09-09 | Inertec | Procede de synthese de ferrates |
| US7399454B2 (en) * | 2004-04-29 | 2008-07-15 | Metalox International, Llc | Metallurgical dust reclamation process |
| US7124777B2 (en) * | 2004-09-03 | 2006-10-24 | Ranco Incorporated Of Delaware | Reversing valve with flowsplitter |
| JP2006124547A (ja) * | 2004-10-29 | 2006-05-18 | Jfe Chemical Corp | インクジェット用インクの着色材用酸化鉄微粒子、インクジェット用インク及びインクジェット用インクの製造方法 |
| DE102006023245A1 (de) * | 2006-05-18 | 2007-11-22 | Lanxess Deutschland Gmbh | Oxidationsstabile Eisenoxidpigmente, Verfahren zu ihrer Herstellung sowie deren Verwendung |
| US7347893B2 (en) * | 2006-06-02 | 2008-03-25 | Iop Specialists Sdn. Bhd. | Iron oxide pigments from mill scale |
| CN1903943B (zh) * | 2006-08-01 | 2010-11-17 | 上海一品颜料有限公司 | 一种氧化铁颜料的制备方法 |
| CN101811739B (zh) * | 2010-04-15 | 2012-04-18 | 升华集团德清华源颜料有限公司 | 低砷氧化铁红颜料的制备方法 |
| DK2760795T3 (da) * | 2011-09-30 | 2017-11-27 | Lanxess Deutschland Gmbh | Forbedret fremgangsmåde til fremstilling af findelt hæmatit og af røde jernoxid-pigmenter |
| RU2649430C2 (ru) * | 2013-11-08 | 2018-04-03 | Лэнксесс Спешалти Кемикалс Ко., Лтд. | Получение красного железоокисного пигмента |
| CN103788716A (zh) * | 2014-02-12 | 2014-05-14 | 铜陵瑞莱科技有限公司 | 一种含茜草提取物的氧化铁红颜料 |
| BR112017004214B1 (pt) | 2014-09-05 | 2022-02-08 | Lanxess Deutschland Gmbh | Processo para a preparação de pigmentos de hematita, e processo para a preparação de pigmentos vermelhos de óxido de ferro |
| WO2016034692A1 (de) | 2014-09-05 | 2016-03-10 | Lanxess Deutschland Gmbh | Herstellung von eisenoxid-rot-pigment |
| DK3191409T3 (da) | 2014-09-11 | 2019-05-06 | Lanxess Deutschland Gmbh | Røde jernoxidpigmenter med forbedrede farveværdier |
| EP3216764A1 (de) * | 2016-03-09 | 2017-09-13 | LANXESS Deutschland GmbH | Herstellung von eisenoxid-rot-pigmenten |
| EP3216765A1 (de) | 2016-03-09 | 2017-09-13 | LANXESS Deutschland GmbH | Herstellung von eisenoxid-rot-pigment |
| EP3219763B1 (de) | 2016-03-16 | 2018-11-28 | LANXESS Deutschland GmbH | Verwendung von eisenoxid-rot-pigmenten in wässrigen präparationen |
| RU2758643C2 (ru) * | 2017-12-01 | 2021-11-01 | ЛЕНКСЕСС Дойчланд ГмбХ | Получение суспензии красного железоокисного пигмента |
| EP3597602A1 (en) | 2018-07-18 | 2020-01-22 | LANXESS Deutschland GmbH | Hematite pigments |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2249274A1 (de) * | 1972-10-07 | 1974-04-18 | Bayer Ag | Herstellung von gefaelltem rotem eisen(iii)-oxid |
| DE3022875A1 (de) * | 1980-06-19 | 1982-01-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von eisenoxidpigmenten mit verbesserter reinheit sowie deren verwendung |
| DE3716300A1 (de) * | 1987-05-15 | 1988-11-24 | Bayer Ag | Neue farbreine eisenoxidpigmente, verfahren zu ihrer herstellung und deren verwendung |
| US5421878A (en) * | 1992-10-23 | 1995-06-06 | Bayer Ag | Pure-colored iron oxide direct red pigments, a process for their production and their use |
| ES2152470T3 (es) * | 1995-10-26 | 2001-02-01 | Bayer Ag | Pigmentos de oxido de hierro rojos de pureza cromatica y con matiz amarillo, procedimiento para su fabricacion y su uso. |
-
1999
- 1999-12-02 DE DE19958168A patent/DE19958168A1/de not_active Withdrawn
-
2000
- 2000-11-21 AT AT00125284T patent/ATE521575T1/de active
- 2000-11-21 ES ES00125284T patent/ES2369251T3/es not_active Expired - Lifetime
- 2000-11-21 EP EP00125284A patent/EP1106577B1/de not_active Expired - Lifetime
- 2000-11-22 US US09/718,272 patent/US6503315B1/en not_active Expired - Lifetime
- 2000-11-24 CA CA002326765A patent/CA2326765A1/en not_active Abandoned
- 2000-12-01 JP JP2000366952A patent/JP4988983B2/ja not_active Expired - Lifetime
- 2000-12-01 CN CNB001344404A patent/CN1186400C/zh not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE19958168A1 (de) | 2001-06-07 |
| CN1297968A (zh) | 2001-06-06 |
| JP4988983B2 (ja) | 2012-08-01 |
| CA2326765A1 (en) | 2001-06-02 |
| JP2001200177A (ja) | 2001-07-24 |
| ES2369251T3 (es) | 2011-11-28 |
| EP1106577A2 (de) | 2001-06-13 |
| EP1106577B1 (de) | 2011-08-24 |
| US6503315B1 (en) | 2003-01-07 |
| EP1106577A3 (de) | 2003-04-23 |
| ATE521575T1 (de) | 2011-09-15 |
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