JP3651919B2 - Coloring of lacquers and plastics with iron oxide direct red pigment - Google Patents
Coloring of lacquers and plastics with iron oxide direct red pigment Download PDFInfo
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- JP3651919B2 JP3651919B2 JP28212093A JP28212093A JP3651919B2 JP 3651919 B2 JP3651919 B2 JP 3651919B2 JP 28212093 A JP28212093 A JP 28212093A JP 28212093 A JP28212093 A JP 28212093A JP 3651919 B2 JP3651919 B2 JP 3651919B2
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- iron
- suspension
- iron oxide
- seed
- red pigment
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 54
- 239000001054 red pigment Substances 0.000 title claims description 28
- 239000004922 lacquer Substances 0.000 title claims description 17
- 238000004040 coloring Methods 0.000 title claims description 4
- 239000004033 plastic Substances 0.000 title claims description 4
- 229920003023 plastic Polymers 0.000 title claims description 4
- 239000000725 suspension Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 229910052598 goethite Inorganic materials 0.000 claims description 11
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 241000231392 Gymnosiphon Species 0.000 description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 235000014413 iron hydroxide Nutrition 0.000 description 6
- 239000004277 Ferrous carbonate Substances 0.000 description 5
- 235000019268 ferrous carbonate Nutrition 0.000 description 5
- 239000001034 iron oxide pigment Substances 0.000 description 5
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 5
- 238000005273 aeration Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000001052 yellow pigment Substances 0.000 description 3
- 229910006540 α-FeOOH Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- 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
- C01P2006/12—Surface area
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- 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
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- 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)
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- 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
- 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
- C01P2006/65—Chroma (C*)
Description
【0001】
本発明は新規な純色酸化鉄直接赤色顔料を使用してラッカーおよびプラスチックを彩色する方法に関するものである。酸化鉄「直接」赤色顔料とは、下記の実施例において例示されているような沈澱法によって製造される酸化鉄赤色顔料を意味する。
【0002】
赤色酸化鉄顔料の製造には 4 種の公知の方法が存在する(パットン(T. C. Patton),顔料ハンドブック(Pigment Handbook),1 巻,ニューヨーク(New York)1988,288 ページ)。これらの方法の一つは、US-A 2,716,595 に記載されている赤色酸化鉄の直接沈澱である。この方法においては、鉄(II)塩溶液とアルカリ溶液とを実質的に等当量で混合し、得られる水酸化鉄(II)または炭酸鉄(II)の懸濁液に空気を流通させる。このようにして形成させた酸化水酸化鉄(III)種懸濁液を、鉄(II)塩の存在下に金属鉄を添加し、加熱し、酸素含有気体で酸化して赤色顔料に作り上げる。
【0003】
赤色顔料が赤色種懸濁液からのみ、また黄色顔料が黄色種懸濁液からのみ製造し得ることは DE-B 1 084 405 より公知である。したがって、最終生成物の色は使用する種により明確に決定される。
【0004】
黄色酸化鉄顔料と赤色酸化鉄顔料との混合物は褐色の、魅力的でない色調を与えるに過ぎない。US-A-3,946,103 は、微細な δ-FeOOH 粒子よりなる純粋な赤色種懸濁液の製造を可能にする種改質剤を用いる方法を開示している。
【0005】
この方法により製造した顔料は、その柔軟性のために、特にラッカー系に使用した場合に、黄色酸化鉄および黒色酸化鉄のか焼により製造した顔料との比較で分散性、光沢および凝集挙動に関して改良された性質を示す。しかし、ラッカーの応用面においては、US-A-3,946,103 に従って直接沈澱により製造した酸化鉄赤色顔料の色純度は黒色酸化鉄および黄色酸化鉄のか焼により製造した赤色顔料のものに遠く及ばない。
【0006】
したがって、本発明が指向した問題は、上記の顕著な性能は有するが不十分な色純度という欠点は持たない、改良された酸化鉄直接赤色顔料を提供することであった。
【0007】
驚くべきことには、赤色種懸濁液から通常の方法で製造されたものではなく、替わりに黄色の種懸濁液から製造された、ラッカー試験において 37.5 シーラブ(CIELAB)単位を超える色飽和(C*)を有する新規な酸化鉄直接赤色顔料により、これらの要求が満たされることがここに見いだされたのである。
【0008】
したがって本発明は、ラッカー試験において 37.5 シーラブ単位を超える、好ましくは 38.9 シーラブ単位を超える色飽和(C*)を有することを特徴とする酸化鉄直接赤色顔料に関するものである。
【0009】
ラッカー試験において、本発明記載の顔料はこれまで公知の直接赤色顔料(US-A 3,946,103 に従って製造されたバイフェロックス(Bayferrox)510R、またはファイザークローマ(Pfizer Croma)赤 RO 3097R)および、黒色顔料のか焼により得た赤色顔料(たとえば DE-A 2 826 941 に従って製造されたもの)(バイフェロックス 105 MR)より高い色飽和を有する。
【0010】
特に高い赤色成分(a*)がラッカー試験で得られ、美的に印象的な色印象につながる。
【0011】
特に好ましい具体例の一つにおいて、本発明記載の酸化鉄直接赤色顔料は、ラッカー試験において赤色成分(a*)が 27.5 シーラブ単位を超え、黄色成分 (b*)が 23 シーラブ単位を超えることを特徴とするものである。
【0012】
本発明記載の酸化鉄直接赤色顔料は、黄色の針鉄鉱(α-FeOOH)種懸濁液の製造、鉄(II)塩溶液と金属鉄との添加または鉄(II)塩溶液とアルカリ溶液との添加、加熱、および酸素含有気体を用いる酸化により得られる。
【0013】
純色酸化鉄赤色顔料がこの方法により得られることは、先行技術によれば黄色の種懸濁液からは黄色酸化鉄顔料のみを製造し得るのであるから、驚くべきことと考えなければならない。
【0014】
したがって本発明は、基本的に、100 m2/g を超える比表面積と 0.2 μm 未満の平均粒子サイズとを有する星型に枝分かれした粒子よりなる黄色針鉄鉱種懸濁液を顔料の合成用の種懸濁液として使用することを特徴とする、アルカリ溶液を用いる鉄(II)塩の沈澱および酸素含有気体を用いる酸化、鉄(II)塩溶液と金属鉄との、または鉄(II)塩溶液とアルカリ溶液との種懸濁液への添加、ならびに酸素含有気体を用いる所要の色調が得られるまでの酸化による、純色飽和酸化鉄直接赤色顔料の製造方法に関するものである。
【0015】
BET 表面積は窒素 1 点法(DIN 66 131)により測定し、粒子サイズは電子顕微鏡写真から測定する。
【0016】
本発明記載の方法においては、適当な条件を構成して懸濁液の中に種懸濁体を直接に製造することも、個別に製造した種を使用することも可能である。
【0017】
本発明記載の方法に使用する種懸濁液の粒子は、酸化鉄黄色顔料の製造に使用する通常の種とは、形状において全く異なる。
【0018】
図1は、本発明記載の方法に使用する針鉄鉱の種の典型的な星状枝分かれ体を示す。比較のために、図2は枝分かれしていない針状の個々の粒子よりなる、顔料合成工程において黄色酸化鉄顔料に導く通常の黄色の種を示す。
【0019】
本件黄色針鉄鉱種懸濁液(α-FeOOH)は、アルカリ溶液を用いる鉄(II)塩の沈澱と引き続く酸素含有気体を用いる酸化とにより製造される。
【0020】
本発明記載の方法の好ましい具体例の一つにおいては、種懸濁液は
a) 約 10 ないし 80 g/l の、好ましくは 20 ないし 40 g/l の濃度を有する硫酸鉄(II)水溶液を形成させ、
b) 上記の硫酸鉄(II)水溶液に約 0.8 ないし 1.0 当量の、好ましくは 0.85 ないし 0.95 当量のアルカリ性沈澱剤を添加して水酸化鉄(II)または炭酸鉄(II)の懸濁体を沈澱させ;
c) 上記の懸濁液に酸素含有気体を強力に通気し、上記の水酸化鉄(II)または炭酸鉄(II)を酸化して α-FeOOH 変態の酸化水酸化鉄(III)の懸濁液を形成させる
ことにより製造する。
【0021】
鉄鋼酸洗い工程からの、および/または二酸化チタニウムの製造工程からの鉄(II)塩を、本件硫酸鉄(II)の製造に特に有利に使用することができる。
【0022】
種の形成中に有力な温度は、好ましくは 15 ないし 35℃ の範囲、より好ましくは 20 ないし 35℃ の範囲である。
【0023】
水酸化鉄(II)または炭酸鉄(II)の懸濁液は、0.8 ないし 1.0 当量の、好ましくは 0.85 ないし 0.95 当量の沈澱剤を使用して沈澱させるが、NaOH、Na2CO3、NH3、MgO および/または MgCO3 が好適に使用される。
【0024】
沈澱に続いて、好ましくは空気を酸化剤として用いて酸化を行う。この目的には、懸濁液 1 リットルあたり毎時 20 ないし 300 リットル の空気を導入する。ここで、このようにして得られる種懸濁液を有利には 70 ないし 100℃ で 1 ないし 4 時間熟成させることができる。
【0025】
ラジオグラフィー相分析(ジーメンス(Siemens)D-500)(ASTM 第 29.0713)により測定して針鉄鉱(α-FeOOH)のみよりなる黄色種懸濁液が得られる。
【0026】
顔料形成には Fe2O3 として計算して 4 ないし 30 g/l の量の種が好適に使用され、7 ないし 20 g/l の量が特に好ましい。
【0027】
顔料形成は 2 種の方法により有利に実施することができる。第 1 の方法においては、金属鉄と鉄(II)塩溶液とを種懸濁液に添加し、ついで、これを 70 ないし 100℃ に、好ましくは 75 ないし 90℃ に加熱し、懸濁液 1 リットルあたり毎時 0.2 ないし 50 l の空気を懸濁液に通気して、ほぼ所要の色調が得られるまで酸化する。これは、種が 3 ないし 15 倍に、好ましくは 4 ないし 10 倍に増加したのちの場合である。
【0028】
第 2 の方法においては、種懸濁液を 70 ないし 100℃ に、好ましくは 75 ないし 90℃ に加熱し、ついで、鉄(II)塩溶液とアルカリ溶液とを添加し、pH 値を 4 ないし 5 の範囲にし、この懸濁液に懸濁液 1 リットルあたり毎時約 1 ないし 400 l の空気を懸濁液に通気して、所要の色調が得られるまで酸化する。所要の色調は、ここでも、3 ないし 15 倍の、好ましくは 4 ないし 10 倍の種の増加ののちに得られる。
【0029】
塩液は濾過と洗浄とにより、または沈降法により除去することができる。この赤色のペーストはスラリーに加工することも、乾燥、磨砕して粉末形状の顔料を形成させることもできる。
【0030】
柔軟な純色酸化鉄顔料が得られる。X-線相分析(ASTM 第 33.0664)により α-Fe2O3 が検出される。
【0031】
本発明におけるラッカー試験は、アルキダール(Alkydal)L64(バイエル社(Bayer AG)の製品、粘性を増加させるために 5 %のルボチックス(Luvotix)HT(レーマン・ウント・フォス(Lehman & Voss)の製品)を添加した、63 %のアマニ油と 23 %の無水フタル酸とを含有するアルキド樹脂)中で実施され、顔料の体積濃度は 10 %である。
【0032】
シーラブ単位(DIN 6174)は、ウルブリヒト球(照明条件 d/8° 、C/2°型標準光)を有する色測定装置を使用して測定し、表面反射も含まれている。
【0033】
表 1 は、本発明記載の若干の顔料の測色計データ、および比較のための若干の市販製品の対応するデータを示している。
【0034】
色飽和(C*)は顔料の色純度の尺度である。
【0035】
本発明はまた、本発明に従って製造した酸化鉄赤色顔料の、粉末形状の顔料としての、また、ペーストまたはスラリーの形状でのラッカーおよびプラスチックの彩色用の使用に関するものでもある。
【0036】
図1は、本発明記載の方法により製造した、顔料合成工程において純色赤色顔料につながる酸化鉄の種(針鉄鉱)を示している、比較のために、図2は顔料合成工程において黄色顔料につながる通常の黄色酸化鉄の種(針鉄鉱)を示している。図3は、建築材料試験における若干の酸化鉄赤色顔料のシーラブデータ(a* − b* 面内で点描したもの)を示している。
【0037】
本発明をいかなる様式においても限定することなく説明することを意図した以下の実施例は、黄色種懸濁液の形成と本発明記載の赤色形成の合成とを記述するものである。
【0038】
【実施例】
実施例1
二酸化チタニウムの製造よりの硫酸鉄溶液(FeSO4 濃度 25 g/l)22.3 l を最初に導入する。温度は 31℃ である。4.75 N の NaOH 溶液 1.325 lを添加し、続いて、この懸濁液を懸濁液 1 l あたり毎時 52 l の空気を用いて 28分間酸化する。得られる黄色種懸濁液を 80℃ に加熱し、2 時間撹拌する。
【0039】
実施例2
二酸化チタニウムの製造よりの硫酸鉄溶液(FeSO4 濃度 24.6 g/l)44 m3 を最初に導入する。温度は 29℃ である。4.5 N の NaOH 溶液 2.85 m3 を添加し、続いて、この懸濁液を懸濁液 1 l あたり毎時 215 l の空気を用いて 30 分間酸化する。得られる黄色種懸濁液を 80℃ に加熱し、2 時間撹拌する。
【0040】
実施例3
実施例1に従って製造した種懸濁液 3271 ml に、126 ml の硫酸鉄(II)溶液(FeSO4 200 g/l)、1603 ml の水および 450 g の金属鉄を添加する。85℃ に加熱したのちに、この懸濁液を懸濁液 1 リットルあたり毎時 20 l の空気を用いて酸化する。40 時間後、黄色の種懸濁液が純色の赤色顔料に転化した。増加倍率は 11.5 である。この懸濁液を濾過し、塩がなくなるまで洗浄し、85℃で乾燥し、得られる顔料を磨砕する。
【0041】
実施例4
実施例2に従って製造した種懸濁液 14,000 ml に、336 ml の硫酸鉄(II)溶液(FeSO4 200 g/l)、6664 ml の水および 1600 g の金属鉄を添加する。85℃ に加熱したのちに、この懸濁液を懸濁液 1 リットルあたり毎時 0.5 l の空気を用いて酸化する。
【0042】
22 時間後、黄色の種懸濁液が純色の赤色顔料に転化した。増加倍率は 4.4 である。この懸濁液を濾過し、塩がなくなるまで洗浄し、 85℃ で乾燥し、得られる顔料を磨砕する。
【0043】
【表1】
本発明の主なる特徴および態様は以下のとおりである。
【0044】
1.37.5 シーラブ単位を超えるラッカー試験における色飽和を有する酸化鉄直接赤色顔料。
【0045】
2.ラッカー試験において赤色成分(a*)が 27.5 シーラブ単位を超え、黄色成分(b*)が 23 シーラブ単位を超えることを特徴とする上記1記載の酸化鉄直接赤色顔料。
【0046】
3.基本的に、100 m2/g を超える比表面積と 0.2 μm 未満の平均粒子サイズとを有する星型に枝分かれした粒子よりなる黄色針鉄鉱種懸濁液を顔料の合成用の種懸濁液として使用することを特徴とする、鉄(II)塩溶液と金属鉄とを、または鉄(II)塩溶液とアルカリ溶液とを種懸濁液に添加し、酸素含有気体を用いて所要の色調が得られるまで酸化することよりなる純色酸化鉄赤色顔料の製造方法。
【0047】
4.a) 約 10 ないし 80 g/l の濃度を有する硫酸鉄(II)水溶液を形成させ;
b) 上記の硫酸鉄(II)水溶液に約 0.8 ないし 1.0 当量のアルカリ性沈澱剤を添加して水酸化鉄(II)または炭酸鉄(II)の懸濁体を沈澱させ;
c) 上記の懸濁液に酸素含有気体を強力に通気し、上記の水酸化鉄(II)または炭酸鉄(II)を酸化して上記の種懸濁液を形成させる
ことにより種懸濁液を製造することを特徴とする上記3記載の方法。
【0048】
5.上記の沈澱段階および酸化段階を約 15 ないし 40℃ の温度で実施することを特徴とする上記4記載の方法。
【0049】
6.上記の沈澱剤が NaOH、Na2CO3、NH3、MgO および MgCO3 よりなるグループから選択した少なくとも 1 種の物質を含有することを特徴とする上記4記載の方法。
【0050】
7.上記の種懸濁液を約 70 ないし 100℃ の温度で 1 ないし 4 時間熟成させることを特徴とする上記4記載の方法。
【0051】
8.上記の種懸濁液中の種の濃度が約 4 ないし 30 g/l であることを特徴とする上記3記載の方法。
【0052】
9.金属鉄と鉄(II)塩溶液とを種懸濁液に添加し、ついで、この懸濁液を約70 ないし 100℃ の温度に加熱し、ついで、この懸濁液に懸濁液 1 リットルあたり毎時約 0.2 ないし 50 l の空気を通気して所要の色調が得られるまで酸化することを特徴とする上記3記載の方法。
【0053】
10.上記の種懸濁液を約 70 ないし 100℃ の温度に加熱し、ついで上記の鉄(II)塩溶液とアルカリ溶液とを添加し、ついで、この懸濁液に懸濁液 1 リットルあたり毎時約 1 ないし 400 l の空気を通気して所望の色調が得られるまで酸化することを特徴とする上記3記載の方法。
【0054】
11.ラッカー試験において 38.9 シーラブ単位を超える色飽和を有する上記1記載の酸化鉄直接赤色顔料。
【0055】
12.上記の硫酸鉄(II)水溶液が約 20 ないし 40 g/l の濃度を有するものであることを特徴とする上記4記載の方法。
【0056】
13.約 0.85 ないし 0.95 当量の上記のアルカリ性沈澱剤を段階 b)において添加することを特徴とする上記4記載の方法。
【0057】
14.上記の沈澱段階および酸化段階を約 20 ないし 35℃ の温度で実施することを特徴とする上記5記載の方法。
【0058】
15.上記の種懸濁液中の種の濃度が約 7 ないし 20 g/l であることを特徴とする上記8記載の方法。
【0059】
16.上記の懸濁液を約 75 ないし 90℃ の温度に加熱することを特徴とする上記9記載の方法。
【0060】
17.上記の懸濁液を約 75 ないし 90℃ の温度に加熱することを特徴とする上記10記載の方法。
【0061】
18.上記の酸素含有気体が空気であることを特徴とする上記4記載の方法。
【0062】
19.上記の空気を上記の水酸化鉄(II)または炭酸鉄(II)の懸濁液に、上記の懸濁液 1 リットルあたり毎時約 20 ないし 300 リットルの量導入することを特徴とする上記18記載の方法。
【図面の簡単な説明】
【図1】本発明記載の方法により製造した酸化鉄(針鉄鉱)の種の粒子構造電子顕微鏡写真である。
【図2】通常の黄色酸化鉄(針鉄鉱)の種の粒子構造電子顕微鏡写真である。
【図3】 赤色成分および黄色成分の量をそれぞれ横軸および縦軸にとって表示したラッカー試験におけるシーラブデータの図表である。[0001]
The present invention relates to a process for coloring lacquers and plastics using a novel pure color iron oxide direct red pigment. By iron oxide “direct” red pigment is meant an iron oxide red pigment produced by a precipitation process as illustrated in the examples below.
[0002]
There are four known methods for the production of red iron oxide pigments (TC Patton, Pigment Handbook, Volume 1, New York 1988, p. 288). One of these methods is the direct precipitation of red iron oxide as described in US-A 2,716,595. In this method, an iron (II) salt solution and an alkaline solution are mixed at substantially equal equivalents, and air is circulated through the obtained suspension of iron hydroxide (II) or iron carbonate (II). The iron oxide (III) oxide suspension thus formed is added with metallic iron in the presence of an iron (II) salt, heated and oxidized with an oxygen-containing gas to form a red pigment.
[0003]
It is known from DE-B 1 084 405 that red pigments can only be produced from red seed suspensions and yellow pigments only from yellow seed suspensions. Thus, the color of the final product is clearly determined by the species used.
[0004]
Mixtures of yellow and red iron oxide pigments only give a brown, unattractive shade. US-A-3,946,103 discloses a method using a seed modifier which makes it possible to produce a pure red seed suspension consisting of fine δ-FeOOH particles.
[0005]
The pigments produced by this method are due to their flexibility, especially when used in lacquer systems, in terms of dispersibility, gloss and agglomeration behavior compared to pigments produced by calcination of yellow iron oxide and black iron oxide. Shows improved properties. However, in lacquer applications, the color purity of iron oxide red pigments produced by direct precipitation according to US-A-3,946,103 is far from that of red pigments produced by calcination of black iron oxide and yellow iron oxide.
[0006]
Accordingly, the problem addressed by the present invention was to provide an improved iron oxide direct red pigment which has the above noted performance but does not have the disadvantage of insufficient color purity.
[0007]
Surprisingly, color saturation exceeding 37.5 CIELAB units in the lacquer test, which was not produced in the usual way from a red seed suspension but instead from a yellow seed suspension ( It has now been found that these requirements are met by a novel iron oxide direct red pigment with C *).
[0008]
The invention therefore relates to an iron oxide direct red pigment characterized in that it has a color saturation (C *) in the lacquer test of more than 37.5 slabs, preferably more than 38.9 slabs.
[0009]
In the lacquer test, the pigments according to the invention are the known direct red pigments (Bayferrox 510 R manufactured according to US Pat. No. 3,946,103, or Pfizer Croma red RO 3097 R ) and black It has a higher color saturation than red pigments obtained by calcination of the pigment (for example those prepared according to DE-A 2 826 941) (Baiferox 105 M R ).
[0010]
A particularly high red component (a *) is obtained in the lacquer test, leading to an aesthetically impressive color impression.
[0011]
In one particularly preferred embodiment, the iron oxide direct red pigment according to the present invention has a red component (a *) exceeding 27.5 slab units and a yellow component (b *) exceeding 23 slab units in the lacquer test. It is a feature.
[0012]
The iron oxide direct red pigment according to the present invention comprises the preparation of a yellow goethite (α-FeOOH) seed suspension, the addition of iron (II) salt solution and metallic iron, or the iron (II) salt solution and alkaline solution. And heating, and oxidation using an oxygen-containing gas.
[0013]
The fact that pure iron oxide red pigments are obtained by this method must be considered surprising, since according to the prior art only yellow iron oxide pigments can be produced from yellow seed suspensions.
[0014]
Therefore, the present invention basically provides a yellow goethite seed suspension consisting of star-branched particles having a specific surface area of more than 100 m 2 / g and an average particle size of less than 0.2 μm for the synthesis of pigments. Precipitation of iron (II) salt using alkaline solution and oxidation using oxygen-containing gas, iron (II) salt solution and metallic iron, or iron (II) salt, characterized in that it is used as a seed suspension The present invention relates to a method for producing a pure color saturated iron oxide direct red pigment by addition of a solution and an alkaline solution to a seed suspension and oxidation until a required color tone using an oxygen-containing gas is obtained.
[0015]
The BET surface area is measured by the nitrogen one-point method (DIN 66 131), and the particle size is measured from an electron micrograph.
[0016]
In the process according to the invention, the seed suspension can be produced directly in the suspension with suitable conditions, or individually produced seeds can be used.
[0017]
The particles of the seed suspension used in the process according to the invention are quite different in shape from the usual seeds used for the production of iron oxide yellow pigments.
[0018]
FIG. 1 shows a typical star branch of a goethite species used in the process according to the invention. For comparison, FIG. 2 shows a normal yellow seed consisting of unbranched needle-like individual particles leading to a yellow iron oxide pigment in the pigment synthesis process.
[0019]
The yellow goethite seed suspension (α-FeOOH) is produced by precipitation of iron (II) salt using an alkaline solution followed by oxidation using an oxygen-containing gas.
[0020]
In one preferred embodiment of the process according to the invention, the seed suspension is a) an aqueous iron (II) sulfate solution having a concentration of about 10 to 80 g / l, preferably 20 to 40 g / l. Formed,
b) About 0.8 to 1.0 equivalent, preferably 0.85 to 0.95 equivalent of alkaline precipitant is added to the aqueous iron (II) sulfate solution to precipitate a suspension of iron hydroxide (II) or iron (II) carbonate. Let;
c) Oxygen-containing gas is vigorously bubbled through the suspension, and the iron hydroxide (II) or iron carbonate (II) is oxidized to suspend the α-FeOOH-modified iron oxide hydroxide (III). Manufacture by forming a liquid.
[0021]
Iron (II) salts from the steel pickling process and / or from the production process of titanium dioxide can be used particularly advantageously in the production of the present iron (II) sulfate.
[0022]
The prevailing temperature during seed formation is preferably in the range of 15 to 35 ° C, more preferably in the range of 20 to 35 ° C.
[0023]
A suspension of iron (II) hydroxide or iron (II) carbonate is precipitated using 0.8 to 1.0 equivalent, preferably 0.85 to 0.95 equivalent of a precipitating agent, but NaOH, Na 2 CO 3 , NH 3 MgO and / or MgCO 3 are preferably used.
[0024]
Following precipitation, oxidation is preferably performed using air as the oxidant. For this purpose, 20 to 300 liters of air per hour are introduced per liter of suspension. Here, the seed suspension thus obtained can be advantageously aged at 70 to 100 ° C. for 1 to 4 hours.
[0025]
A yellow seed suspension consisting only of goethite (α-FeOOH) is obtained as determined by radiographic phase analysis (Siemens D-500) (ASTM 29.0713).
[0026]
For pigment formation, seeds with a quantity of 4 to 30 g / l, calculated as Fe 2 O 3 , are preferably used, with quantities of 7 to 20 g / l being particularly preferred.
[0027]
Pigment formation can be advantageously carried out by two methods. In the first method, metallic iron and an iron (II) salt solution are added to the seed suspension, which is then heated to 70 to 100 ° C., preferably 75 to 90 ° C., and the suspension 1 Aeration of 0.2 to 50 liters of air per liter per hour through the suspension is oxidized until the desired color tone is obtained. This is the case after the seed has increased 3 to 15 times, preferably 4 to 10 times.
[0028]
In the second method, the seed suspension is heated to 70 to 100 ° C., preferably 75 to 90 ° C., and then an iron (II) salt solution and an alkaline solution are added to adjust the pH value to 4 to 5 ° C. In this range, about 1 to 400 l of air per liter of suspension per hour is passed through the suspension and oxidized until the desired color is obtained. The required shade is again obtained after a 3 to 15 fold increase, preferably a 4 to 10 fold increase in seed.
[0029]
The salt solution can be removed by filtration and washing, or by precipitation. This red paste can be processed into a slurry or dried and ground to form a powdered pigment.
[0030]
A flexible pure color iron oxide pigment is obtained. Α-Fe 2 O 3 is detected by X-ray phase analysis (ASTM 33.0664).
[0031]
The lacquer test according to the invention is based on Alkydal L64 (a product of Bayer AG, 5% Luvotix HT (a product of Lehman & Voss) to increase viscosity) , An alkyd resin containing 63% linseed oil and 23% phthalic anhydride), and the volume concentration of the pigment is 10%.
[0032]
The Sealab unit (DIN 6174) is measured using a color measuring device with a Ulbricht sphere (illumination conditions d / 8 °, C / 2 ° type standard light) and includes surface reflection.
[0033]
Table 1 shows the colorimetric data for some pigments according to the present invention and the corresponding data for some commercial products for comparison.
[0034]
Color saturation (C *) is a measure of the color purity of a pigment.
[0035]
The invention also relates to the use of iron oxide red pigments prepared according to the invention as pigments in powder form and for coloring lacquers and plastics in the form of pastes or slurries.
[0036]
FIG. 1 shows the iron oxide species (goethite) produced by the method of the present invention that leads to a pure red pigment in the pigment synthesis process. For comparison, FIG. 2 shows the yellow pigment in the pigment synthesis process. It shows a normal yellow iron oxide seed (goethite) that leads to it. FIG. 3 shows sealab data (stipulated in the a * -b * plane) of some iron oxide red pigments in the building material test.
[0037]
The following examples, which are intended to illustrate the invention without limiting it in any manner, describe the formation of a yellow seed suspension and the synthesis of a red formation according to the invention.
[0038]
【Example】
Example 1
First, 22.3 l of iron sulfate solution (FeSO 4 concentration 25 g / l) from the production of titanium dioxide is introduced. The temperature is 31 ° C. 1.325 l of 4.75 N NaOH solution is added, and the suspension is subsequently oxidized for 28 minutes with 52 l of air per liter of suspension per hour. The resulting yellow seed suspension is heated to 80 ° C. and stirred for 2 hours.
[0039]
Example 2
First, 44 m 3 of iron sulfate solution (FeSO 4 concentration 24.6 g / l) from the production of titanium dioxide is introduced. The temperature is 29 ° C. 2.85 m 3 of 4.5 N NaOH solution are added, and the suspension is subsequently oxidized for 30 minutes with 215 l of air / l of suspension. The resulting yellow seed suspension is heated to 80 ° C. and stirred for 2 hours.
[0040]
Example 3
To 3271 ml of the seed suspension prepared according to Example 1, 126 ml of iron (II) sulfate solution (FeSO 4 200 g / l), 1603 ml of water and 450 g of metallic iron are added. After heating to 85 ° C, the suspension is oxidized using 20 l of air per hour per liter of suspension. After 40 hours, the yellow seed suspension was converted to a pure red pigment. The multiplication factor is 11.5. The suspension is filtered, washed until free of salt, dried at 85 ° C. and the resulting pigment is ground.
[0041]
Example 4
To 14,000 ml of the seed suspension prepared according to Example 2, 336 ml of iron (II) sulfate solution (FeSO 4 200 g / l), 6664 ml of water and 1600 g of metallic iron are added. After heating to 85 ° C, the suspension is oxidized with 0.5 l of air per liter of suspension per hour.
[0042]
After 22 hours, the yellow seed suspension was converted to a pure red pigment. The multiplication factor is 4.4. The suspension is filtered, washed until free of salt, dried at 85 ° C. and the resulting pigment is ground.
[0043]
[Table 1]
The main features and aspects of the present invention are as follows.
[0044]
1. 37.5 Iron oxide direct red pigment with color saturation in the lacquer test exceeding the Sealab unit.
[0045]
2. 2. The iron oxide direct red pigment according to 1 above, wherein the red component (a *) exceeds 27.5 slab units and the yellow component (b *) exceeds 23 slab units in the lacquer test.
[0046]
3. Basically, a yellow goethite seed suspension consisting of star-branched particles with a specific surface area of more than 100 m 2 / g and an average particle size of less than 0.2 μm is used as a seed suspension for pigment synthesis. The iron (II) salt solution and metallic iron, or the iron (II) salt solution and the alkaline solution, which are characterized by being used, are added to the seed suspension, and the required color tone is obtained using an oxygen-containing gas. A method for producing a pure-colored iron oxide red pigment comprising oxidation until obtained.
[0047]
Four. a) forming an aqueous iron (II) sulfate solution having a concentration of about 10 to 80 g / l;
b) adding about 0.8 to 1.0 equivalent of an alkaline precipitant to the aqueous iron (II) sulfate solution to precipitate a suspension of iron hydroxide (II) or iron (II) carbonate;
c) A seed suspension by vigorously venting an oxygen-containing gas into the suspension and oxidizing the iron hydroxide (II) or iron (II) carbonate to form the seed suspension. 4. The method as described in 3 above, wherein
[0048]
Five. The method of claim 4 wherein the precipitation and oxidation steps are carried out at a temperature of about 15 to 40 ° C.
[0049]
6. 5. The method according to 4 above, wherein the precipitating agent contains at least one substance selected from the group consisting of NaOH, Na 2 CO 3 , NH 3 , MgO and MgCO 3 .
[0050]
7. 5. The method according to 4 above, wherein the seed suspension is aged at a temperature of about 70 to 100 ° C. for 1 to 4 hours.
[0051]
8. The method of claim 3, wherein the seed concentration in the seed suspension is about 4 to 30 g / l.
[0052]
9. Metallic iron and iron (II) salt solution are added to the seed suspension, then the suspension is heated to a temperature of about 70-100 ° C., and then the suspension is added to the suspension per liter of suspension. 4. The process of claim 3 wherein the oxidation is carried out by aeration of about 0.2 to 50 l of air per hour until the desired color is obtained.
[0053]
Ten. The seed suspension is heated to a temperature of about 70 to 100 ° C., then the iron (II) salt solution and the alkaline solution are added, and then the suspension is added to the suspension at about every hour per liter of suspension. 4. The method according to 3 above, wherein the oxidation is carried out by aeration of 1 to 400 l of air until a desired color tone is obtained.
[0054]
11. The iron oxide direct red pigment according to 1 above, which has a color saturation exceeding 38.9 slabs in a lacquer test.
[0055]
12. 5. The method as described in 4 above, wherein the aqueous iron (II) sulfate solution has a concentration of about 20 to 40 g / l.
[0056]
13. The process of claim 4 wherein about 0.85 to 0.95 equivalents of said alkaline precipitant is added in step b).
[0057]
14. The process of claim 5 wherein the precipitation and oxidation steps are carried out at a temperature of about 20 to 35 ° C.
[0058]
15. 9. The method of claim 8, wherein the seed concentration in the seed suspension is about 7 to 20 g / l.
[0059]
16. The method of claim 9, wherein the suspension is heated to a temperature of about 75 to 90 ° C.
[0060]
17. The method of claim 10, wherein the suspension is heated to a temperature of about 75 to 90 ° C.
[0061]
18. 5. The method according to 4 above, wherein the oxygen-containing gas is air.
[0062]
19. 18. The process of claim 18, wherein the air is introduced into the iron hydroxide (II) or iron (II) carbonate suspension in an amount of about 20 to 300 liters per hour per liter of the suspension. the method of.
[Brief description of the drawings]
FIG. 1 is a particle structure electron micrograph of a seed of iron oxide (goethite) produced by the method of the present invention.
FIG. 2 is a particle structure electron micrograph of a normal yellow iron oxide (goethite) seed.
FIG. 3 is a chart of sealab data in a lacquer test in which the amounts of red component and yellow component are displayed on the horizontal axis and the vertical axis, respectively.
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4235947A DE4235947A1 (en) | 1992-10-23 | 1992-10-23 | Color-pure iron oxide direct red pigments, process for their preparation and their use |
DE4235947.3 | 1992-10-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06211524A JPH06211524A (en) | 1994-08-02 |
JP3651919B2 true JP3651919B2 (en) | 2005-05-25 |
Family
ID=6471262
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28212093A Expired - Fee Related JP3651919B2 (en) | 1992-10-23 | 1993-10-18 | Coloring of lacquers and plastics with iron oxide direct red pigment |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP3651919B2 (en) |
DE (1) | DE4235947A1 (en) |
GB (1) | GB2271767B (en) |
IT (1) | IT1270902B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2100612T3 (en) * | 1993-09-23 | 1997-06-16 | Bayer Ag | DIRECT RED PIGMENTS OF PURE IRON OXIDE, PROCEDURE FOR ITS OBTAINING AND USE. |
DE10232069A1 (en) * | 2002-07-16 | 2004-02-05 | Sachtleben Chemie Gmbh | Process for the production of iron hydroxide, iron oxide hydrate or iron oxide from filter salts of thin acid recovery |
CN101913656A (en) * | 2010-08-09 | 2010-12-15 | 铜陵瑞莱科技有限公司 | Method for preparing iron oxide yellow pigment by using titanium white by-product of ferrous sulfate |
IN2014DN01801A (en) * | 2011-09-30 | 2015-05-15 | Lanxess Deutschland Gmbh | |
PL3191409T3 (en) | 2014-09-11 | 2019-07-31 | Lanxess Deutschland Gmbh | Iron oxide red pigments with improved colour values |
ES2711339T3 (en) | 2016-03-16 | 2019-05-03 | Lanxess Deutschland Gmbh | Use of iron oxide red pigments in aqueous preparations |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2556406A1 (en) * | 1975-12-15 | 1977-06-16 | Bayer Ag | PROCESS FOR THE CONTINUOUS PRODUCTION OF IRON OXIDE HYDROXIDE |
DE3440911C2 (en) * | 1984-11-09 | 1997-08-21 | Bayer Ag | Process for the production of platelet-shaped iron oxide pigments |
DE3500470A1 (en) * | 1985-01-09 | 1986-07-10 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING LIGHT COLORED PURE IRON OXIDE RED PIGMENTS |
-
1992
- 1992-10-23 DE DE4235947A patent/DE4235947A1/en not_active Withdrawn
-
1993
- 1993-10-13 IT ITMI932170A patent/IT1270902B/en active IP Right Grant
- 1993-10-18 JP JP28212093A patent/JP3651919B2/en not_active Expired - Fee Related
- 1993-10-21 GB GB9321765A patent/GB2271767B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
GB9321765D0 (en) | 1993-12-15 |
ITMI932170A1 (en) | 1995-04-13 |
GB2271767A (en) | 1994-04-27 |
DE4235947A1 (en) | 1994-04-28 |
IT1270902B (en) | 1997-05-13 |
GB2271767B (en) | 1995-09-13 |
JPH06211524A (en) | 1994-08-02 |
ITMI932170A0 (en) | 1993-10-13 |
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