GB2167395A - Black pigment - Google Patents

Black pigment Download PDF

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Publication number
GB2167395A
GB2167395A GB08429695A GB8429695A GB2167395A GB 2167395 A GB2167395 A GB 2167395A GB 08429695 A GB08429695 A GB 08429695A GB 8429695 A GB8429695 A GB 8429695A GB 2167395 A GB2167395 A GB 2167395A
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United Kingdom
Prior art keywords
weight
nitrogen
titanium
oxygen
powder
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.)
Granted
Application number
GB08429695A
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GB8429695D0 (en
GB2167395B (en
Inventor
Motohiko Yoshizumi
Daisuke Shibuta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Metal Corp
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Mitsubishi Metal Corp
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Mitsubishi Metal Corp filed Critical Mitsubishi Metal Corp
Priority to GB8429695A priority Critical patent/GB2167395B/en
Publication of GB8429695D0 publication Critical patent/GB8429695D0/en
Publication of GB2167395A publication Critical patent/GB2167395A/en
Application granted granted Critical
Publication of GB2167395B publication Critical patent/GB2167395B/en
Expired legal-status Critical Current

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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
    • C09C1/36—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0821—Oxynitrides of metals, boron or silicon
    • 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
    • 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
    • C01P2006/40—Electric properties
    • 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
    • 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
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

A black titanium oxynitride powder is described, containing 4-35 weight % oxygen, 2-20 weight % nitrogen and 63-76 weight % titanium and having an O:N weight ratio of 15 to 0.2. The powder is obtained by reaction of titanium dioxide with nascent nitrogen. The material is useful as a non-toxic black pigment.

Description

SPECIFICATION Black pigment This invention relates to titanium oxynitride pigment powder having a black tint.
Background of the Invention Today carbon black powder and triiron tetraoxide powder are widely used as black pigments.
Carbon black is excellent as regards its black tint and tinting strength, but it is not easy to handle since it has poor affinity for resin materials and is very bulky. Also it is possibly toxic as it may contain carcinogenic 3,4-benzopyrene originating from raw materials, although in a very slight amount. Further, the specific surface area of carbon black is far greater than other pigment materials. Therefore, when it is mixed with another pigment, it is not easily dispersed uniformly.
Triion tetraoxide is inferior in dispersibility because of coagulation owing to magnetism. Also it is inferior in heat resistance, as it is oxidized to brown y-Fe203 when heated to about 150"C.
The lower oxide of titanium Ti,O,, 1(1 < nv10) is known as a black pigment. This is obtained by reducing titanium dioxide powder with titanium or hydrogen gas at a temperature not lower than 1 000"C. However, this material has a fundamental defect in that it easily sinters, causing grain growth and resulting in a coarse powder (1.0 m-6 or more in diameter) which is unsuitable for a pigment.
We have found that if titanium dioxide is reacted with a substance which liberates nascent nitrogen at the reaction temperature (such as ammonia, alkylamines, hydrazine, guanidine, urea, ammonium carbonate, etc.) titanium oxynitride is obtained. This material has colours which range from black through brownish black and purplish black to bluish black in accordance with variations in the composition, and has excellent affinity for resin materials, dispersibility, heat resistance and non-toxicity, in which respects known black pigment materials are unsatisfactory. Also this material can be obtained with varied specific surface areas by varying the conditions of the preparation.
Disclosure of the Invention This invention provides black titanium oxynitride pigment powder comprising or essentially consisting of 4-35 wt% oxygen, 2-20 wt% nitrogen and 63-76 wt% titanium, in which the weight ratio of oxygen to nitrogen is from 15 to 0.2.
In this composition range, the pigment powder of the invention has a distinct black colour.
Preferably, the titanium oxynitride pigment powder contains 6-32 wt% oxygen, 5-18 wt% nitrogen and 63-76 wt% titanium and the weight ratio of oxygen to nitrogen is 5-0.5.
More preferably, the titanium oxynitride pigment powder contains 10-27 wt% oxygen, 10-16 wt% nitrogen and 63-74 wt% titanium, and the weight ratio of oxygen to nitrogen is 2-1.0.
The pigment powder of this invention is excellent as regards colour and tinting strength. It can be obtained in varied black colours tinged with blue, purple, brown, etc. by varying the production conditions, as mention above.
Being free from toxic substances, this pigment powder is suitable for colouring plastics for food containers as well as for cosmetics.
The pigment powder has electric conductivity of 10-10 3 ohm cm in the compressed lump state, and therefore can be used for providing non-conductive materials with electric conductivity.
The contents of oxygen and nitrogen vary depending upon temperature and reaction time, the conditions of supply of the nascent-nitrogen-producing substance, etc.
The preferred reaction temperature is 550"C-950"C. At a temperature of below 500"C the reaction does not proceed easily and the product is less coloured, that is, becomes bluish grey.
On the contrary, at a temperature of above 950"C, sintering is promoted and coarse particles unsuitable for pigments are produced.
The preferred nitrogen source substance is ammonia gas. When ammonia gas is used, the reaction proceeds satisfactorily at atmospheric pressure and gives a black powder. However, if ammonia is pressurized to 2-3 kg/cm2 G, the reaction rate increases and the nitrogen content of the product increases and thus very black powder is obtained.
It is preferable to use titanium dioxide of smaller particle size (greater specific surface area), since a blacker powder is obtained with shorter reaction times.
The reaction product consists of NaCI type cubic lattice particles only or consists of composite particles of the NaCI type cubic lattice and rutile type tetragonal lattice. The latter may be partly mixed with anatase type crystal. The tetragonal lattice substance is residual titanium dioxide.
Example 1 In a tower reactor 30 cm in inside diameter and 130 cm in height equipped with agitations blades, 4 kg of titanium dioxide powder (availale from Tohoku Kagaku K.K. under the tradename TCA 555, specific surface area: 9.4m2/g, average particles size: 0.16 m-6) was placed. The reactor temperature was maintained at 800"C, ammonia gas was introduced from the bottom at the in-reactor velocity of 3 cm/sec, as the agitation blades are rotated at 15 rpm. The reaction was continued for 6 hours, and 3.1 kg of purplish black powder was recovered. There was some carry-over loss. The degree of blackness of the powder was measured with a Colorcomputer SM-3 by Suga Shikenki K.K. and the L value was 12. The specific surface area was 9.0 m2/g, the average particle size was 0.2 m-6. The oxygen content was 20 wt% and the nitrogen content was 13 wt%.The analysis was carried out by Inert Gas Fusion Chromatography using LECC TC-30 Nitrogen-Oxygen Determinator Model 750-200. The cubic lattice/tetragonal lattice intensity ratio in X-ray diffractrometry was 1/20.
Examples 2-4 Using the same apparatus and the same titanium dioxide powder as in Example 1, the reaction with ammonia was conducted under different conditions, and black powders were obtained. The results are shown in Table 1.
Examples 5-6 Using the same apparatus as in Example 1 and titanium dioxide powder available from Teikoku Kako K.K. under the tradename MT-500B (specific surface area 40 m2/g, average particle size: 0.04 m-6), the reaction with ammonia was conducted under different conditions and black powders were obtained. The results are shown in Table 1.
, - I WN X F. x. Reaction Conditions P:opcrti.s of I S xr 8 ? u n o Lp Charge o Time ou, tLcn ------------ N of ≈ I ~ ~ . ~r a X X' o o rpi ca/sec k/c.(; o L-valn o ,/g ç o o Cubic 'U I iH I o .;tY I cb yC1 n o o N p I ,PB. 8 1 2.5 black u k A L X arc 4 5/5 bL t 2 3.8 | as 9.4 0.2 z o 1/10 lack 5 ?(tsoon 3 750 5 15 t W 6 6 750 2 2.2 plisb 9 t o.G5 20 t lack C brown 3 300 4 20 2 1 2.0 ish 12 22 0.0? 5 20 0 black (cubic) I c , - un O o X uz o g w-JJ D .8 c w E eo o v ,8U W Y o O X X o S o . N. ç n - X X n J b l . ! I . In g o ] b O I En I c l u Fz I 1 IF j x I n + t t- I v . . l 1 1 L

Claims (2)

1. Black titanium oxynitride pigment powder essentially consisting of 4-35 weight % oxygen, 2-20 weight % nitrogen and 63-76 weight % titanium, having a weight ratio of oxygen to nitrogen of from 15 to 0.2.
2. A powder as claimed in Claim 1, which contains 6-32 weight % oxygen, 5-18 weight % nitrogen and 63-76 weight % titanium and has a weight ratio of oxygen to nitrogen of 5-0.5.
2. A powder as claimed in Claim 1, which contains 6-32 weight % oxygen, 5-18 weight % titanium and 63-76 weight % titanium and has a weight ratio of oxygen to nitrogen of 5-0.5.
3. A powder as claimed in Claim 2, which contains 10-27 weight % oxygen, 10-16 weight % nitrogen and 63-74 weight % titanium and has a weight ratio of oxygen to nitrogen of 2-1.0.
4. A titanium oxynitride powder substantially as described herein an any of the Examples herein.
5. A process for the preparation of titanium oxynitride as claimed in Claim 1 which comprises treating titanium dioxide with nascent nitrogen.
6. A process as claimed in Claim 5 in which the reaction temperature is 550 C-950 C and ammonia is used as the source of nascent nitrogen.
CLAIMS Amendments to the claims have been filed, and have the following effect: (b) New or textually amended claims have been filed as follows:
GB8429695A 1984-11-23 1984-11-23 Black pigment Expired GB2167395B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8429695A GB2167395B (en) 1984-11-23 1984-11-23 Black pigment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8429695A GB2167395B (en) 1984-11-23 1984-11-23 Black pigment

Publications (3)

Publication Number Publication Date
GB8429695D0 GB8429695D0 (en) 1985-01-03
GB2167395A true GB2167395A (en) 1986-05-29
GB2167395B GB2167395B (en) 1989-05-17

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217699A (en) * 1988-04-23 1989-11-01 Tioxide Group Plc Titanium nitrides containing oxygen
US7785501B2 (en) * 2004-12-28 2010-08-31 Dai Nippon Printing Co., Ltd. Black resin composition for display device, and member for display device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1126813A (en) * 1964-11-27 1968-09-11 Centre Nat Rech Scient Solid solutions of the transition metals nitrides and oxynitrides and methods of preparation thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1126813A (en) * 1964-11-27 1968-09-11 Centre Nat Rech Scient Solid solutions of the transition metals nitrides and oxynitrides and methods of preparation thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217699A (en) * 1988-04-23 1989-11-01 Tioxide Group Plc Titanium nitrides containing oxygen
US5002646A (en) * 1988-04-23 1991-03-26 Tioxide Group Plc Method for making titanium nitride
GB2217699B (en) * 1988-04-23 1991-11-20 Tioxide Group Plc Black titanium nitride and production thereof
US7785501B2 (en) * 2004-12-28 2010-08-31 Dai Nippon Printing Co., Ltd. Black resin composition for display device, and member for display device

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Publication number Publication date
GB8429695D0 (en) 1985-01-03
GB2167395B (en) 1989-05-17

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19981123