JP2009148681A - Slurry composition - Google Patents
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- JP2009148681A JP2009148681A JP2007327879A JP2007327879A JP2009148681A JP 2009148681 A JP2009148681 A JP 2009148681A JP 2007327879 A JP2007327879 A JP 2007327879A JP 2007327879 A JP2007327879 A JP 2007327879A JP 2009148681 A JP2009148681 A JP 2009148681A
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- 239000002002 slurry Substances 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 109
- 239000002270 dispersing agent Substances 0.000 claims abstract description 62
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000011164 primary particle Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 28
- 239000011324 bead Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 19
- 238000003860 storage Methods 0.000 description 19
- 239000002131 composite material Substances 0.000 description 16
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 230000007774 longterm Effects 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 241000282341 Mustela putorius furo Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 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
- 125000002091 cationic group Chemical group 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
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- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、黒色無機酸化物を含むスラリー組成物の改良に関する。 The present invention relates to an improvement of a slurry composition containing a black inorganic oxide.
黒色無機酸化物を含むスラリー組成物は、塗料用、インキ用、トナー用、ゴム・プラスチック用、電子材料用等に広く使用されている。 Slurry compositions containing black inorganic oxides are widely used for paints, inks, toners, rubber / plastics, electronic materials and the like.
電子材料等の用途では、他の材料との混合が行われやすいように、微粒化された黒色無機酸化物を高濃度に含み、かつ低粘度のスラリーであることが特に要求されている（特許文献１，２）。 In applications such as electronic materials, it is particularly required to be a slurry having a high concentration of finely divided black inorganic oxide and a low viscosity so that it can be easily mixed with other materials (patent) References 1, 2).
また、近年、前記黒色無機酸化物を含むスラリーは、さらなる高濃度化の要求が強まっており、スラリーを長期保存しても、粘度の上昇、沈降分離が起こりにくく分散性の高い黒色無機酸化物スラリーの要求が強くなってきた。 In recent years, the slurry containing the black inorganic oxide has been increasingly demanded for higher concentration, and even when the slurry is stored for a long period of time, the viscosity is not increased and sedimentation separation hardly occurs. The demand for slurry has increased.
このような要求に対して、無機酸化物粉末の微粒子スラリーを作製しようとする場合、多量の有機溶剤を用いない限り、スラリー化は困難であり、高濃度の黒色無機酸化物スラリーを得ることは困難であるといった問題を有していた。 In order to produce a fine particle slurry of inorganic oxide powder in response to such demands, slurrying is difficult unless a large amount of organic solvent is used, and it is possible to obtain a high concentration black inorganic oxide slurry. It had the problem of being difficult.
また、無機酸化物を含有するスラリーを作製する際に、分散剤を添加することによりスラリーの粘度を下げ、機械的せん断力を加えることにより微粒子スラリーとする試みもある。しかしながら、このような試みでは、長期保存した場合、溶剤と無機酸化物粉末が分離したり、スラリーの粘度上昇が起きたりする問題があった。
本発明の課題は、微粒化された黒色無機酸化物を高濃度に含むスラリーであっても、長期間保存による粘度の上昇や、沈降分離が起こりにくい、分散性に優れた安価な黒色無機酸化物スラリーを提供することである。 An object of the present invention is to provide an inexpensive black inorganic oxide excellent in dispersibility, which is resistant to increase in viscosity and sedimentation due to long-term storage, even in a slurry containing a high concentration of atomized black inorganic oxide. Providing a product slurry.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、微粒化された黒色無機酸化物を分散したスラリー組成物の分散剤として、酸価、アミン価が共に３０ｍｇＫＯＨ／ｇ以上を有する水溶性の両性系分散剤を用いることにより上記課題を解決できることを見出し、本発明の完成に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors, as a dispersant for a slurry composition in which a finely divided black inorganic oxide is dispersed, have both an acid value and an amine value of 30 mgKOH / g or more. It has been found that the above-mentioned problems can be solved by using a water-soluble amphoteric dispersant having the present invention, and the present invention has been completed.
即ち、上記課題を解決することができる本発明のスラリー組成物は以下のとおりである。 That is, the slurry composition of this invention which can solve the said subject is as follows.
（１）黒色無機酸化物（Ａ）と、アミン価及び酸価を有する水溶性分散剤（Ｂ）と、有機溶剤（Ｃ）とを含み、前記水溶性分散剤（Ｂ）はアミン価が３０ｍｇＫＯＨ／ｇ以上かつ酸価が３０ｍｇＫＯＨ／ｇ以上であり、前記黒色無機酸化物（Ａ）は、その最大一次粒径が１μｍ以下であることを特徴とするスラリー組成物。 (1) A black inorganic oxide (A), a water-soluble dispersant (B) having an amine value and an acid value, and an organic solvent (C), wherein the water-soluble dispersant (B) has an amine value of 30 mgKOH / G or more and an acid value of 30 mgKOH / g or more, and the black primary oxide (A) has a maximum primary particle size of 1 μm or less.
（２）その配合割合は、質量％で、黒色無機酸化物（Ａ）５０〜９０％と、水溶性分散剤（Ｂ）０．１〜２５質量％と、有機溶剤（Ｃ）１〜４９．９質量％とを含むものが望ましい。 (2) The compounding ratio is mass%, black inorganic oxide (A) 50-90%, water-soluble dispersant (B) 0.1-25 mass%, and organic solvent (C) 1-49. What contains 9 mass% is desirable.
（３）黒色無機酸化物（Ａ）は、Ｎｉ，Ｃｏ及びＭｎからなる群から選択された１種類以上の金属を含むことが望ましい。 (3) The black inorganic oxide (A) preferably contains one or more metals selected from the group consisting of Ni, Co, and Mn.
（４）水溶性分散剤は、分散剤の１０質量％水溶液が、ｐＨ６．０〜１０．０であることが好ましい。 (4) As for a water-soluble dispersing agent, it is preferable that the 10 mass% aqueous solution of a dispersing agent is pH 6.0-10.0.
（５）有機溶剤は、アルコール系、エステル系、及びエーテル系から選択された溶剤の１種類以上であることが好ましい。 (5) The organic solvent is preferably one or more types of solvents selected from alcohols, esters, and ethers.
本発明では、上記のアミン価と酸価を有する水溶性分散剤を用いているので、微粒化された黒色無機酸化物を高濃度に含むスラリーであっても、長期間保存による粘度の上昇や、沈降分離が起こりにくい、分散性が高く安定した、しかも安価な黒色無機酸化物スラリーを提供することができる。 In the present invention, since the water-soluble dispersant having the amine value and acid value described above is used, even if the slurry contains a finely divided black inorganic oxide in a high concentration, the viscosity increases due to long-term storage. Thus, it is possible to provide a black inorganic oxide slurry that is less likely to cause sedimentation separation, is highly dispersible, stable, and inexpensive.
以下に本発明のスラリー組成物について詳細に説明する。 Below, the slurry composition of this invention is demonstrated in detail.
黒色無機酸化物（Ａ）
黒色無機酸化物は、その組成は限定されるものではないが、特にニッケル、コバルト、マンガンのうち少なくとも１種類以上からなる無機酸化物が好ましい。具体的には、四三酸化コバルトや、Ｎｉ１０〜４０重量％、Ｃｏ１０〜７０重量％、及びＭｎ１０〜７０重量％の範囲にあるニッケルコバルトマンガン複合酸化物などが挙げられる。
Black inorganic oxide (A)
The composition of the black inorganic oxide is not limited, but an inorganic oxide composed of at least one of nickel, cobalt, and manganese is particularly preferable. Specific examples include tribasic cobalt oxide, nickel cobalt manganese composite oxide in the range of Ni 10 to 40 wt%, Co 10 to 70 wt%, and Mn 10 to 70 wt%.
また、本発明では、この黒色無機酸化物は、スラリー化後の最大一次粒径で１μｍ以下とする必要がある。この理由は、前記黒色無機酸化物のスラリー化後の最大一次粒径が１μｍよりも大きくなると黒色無機酸化物含有スラリー中の黒色無機酸化物粉末が沈降分離しやすくなり、長期保存した場合、スラリー中の溶剤と黒色無機酸化物の分離が生じやすくなり、長期安定な分散性の高い黒色無機酸化物スラリーとなりにくいからである。 Moreover, in this invention, this black inorganic oxide needs to be 1 micrometer or less by the largest primary particle size after slurrying. The reason for this is that when the maximum primary particle size after slurrying the black inorganic oxide is larger than 1 μm, the black inorganic oxide powder in the black inorganic oxide-containing slurry tends to settle and separate, This is because the solvent and the black inorganic oxide are easily separated from each other, and it is difficult to obtain a black inorganic oxide slurry having a high long-term dispersibility.
黒色無機酸化物のうち、四三酸化コバルトは、常法に従ってコバルト水酸化物を６５０度程度で焼成し、焼成後粉砕することにより得られる。 Among the black inorganic oxides, tribasic cobalt tetroxide is obtained by firing a cobalt hydroxide at about 650 degrees according to a conventional method, and pulverizing after firing.
ニッケルコバルトマンガン複合酸化物は、ニッケルコバルトマンガンのオキシ水酸化物もしくは水酸化物を焼成することにより調製することができる。具体的には、原料として、ニッケル、コバルト、マンガンの水溶性塩を用いた金属塩混合水溶液に水酸化アルカリを加え、これを中和することにより得られるニッケルコバルトマンガン水酸化共沈体を用いる。この原料を用いれば任意の組成を原子レベルで均一に分散することができる。次いで、この水酸化共沈体を例えば５００℃〜８００℃で焼成することによって、このニッケルコバルトマンガン複合酸化物を得ることができる。この場合、焼成条件等を調節することによりニッケルコバルトマンガン複合酸化物の一次粒径を制御することができる。次いで、上記黒色無機酸化物を、ボールミル、ピンミル、ジェットミル等で粉砕して用いることが出来る。 The nickel cobalt manganese composite oxide can be prepared by firing an oxyhydroxide or hydroxide of nickel cobalt manganese. Specifically, a nickel-cobalt-manganese hydroxide coprecipitate obtained by adding an alkali hydroxide to a metal salt mixed aqueous solution using a water-soluble salt of nickel, cobalt, and manganese and neutralizing it as a raw material is used. . If this raw material is used, an arbitrary composition can be uniformly dispersed at the atomic level. Next, the nickel cobalt manganese composite oxide can be obtained by firing the hydroxide coprecipitate at, for example, 500 ° C. to 800 ° C. In this case, the primary particle size of the nickel cobalt manganese composite oxide can be controlled by adjusting the firing conditions and the like. Next, the black inorganic oxide can be used after being pulverized by a ball mill, a pin mill, a jet mill or the like.
水溶性分散剤（Ｂ）
本発明に使用される水溶性分散剤は、酸価、アミン価が共に３０ｍｇＫＯＨ／ｇ以上である。このような分散剤を用いることにより、分散性の高い長期に安定なスラリーを得ることができる。長期に安定な分散性のためには、共に３０ｍｇＫＯＨ／ｇ以上であることが必須である。また、酸価、アミン価の一方のみが３０ｍｇＫＯＨ／ｇ以上で、他方が３０ｍｇＫＯＨ／ｇ未満の場合、たとえ一方の数値のみを相当量高めても上記の本発明の目的を達成することができない。それらの理由は必ずしも明らかでないが、水溶性分散剤のアミン価或いは酸価の何れかが３０ｍｇＫＯＨ／ｇ未満であると、黒色無機酸化物スラリーの長期保存時に、スラリー中の溶剤と黒色無機酸化物との間で分離が生じやすくなる為、長期に安定な分散性の高い黒色無機酸化物スラリーとなりにくいと考えられる。
Water-soluble dispersant (B)
The water-soluble dispersant used in the present invention has an acid value and an amine value of 30 mgKOH / g or more. By using such a dispersant, a slurry having high dispersibility and a long-term stability can be obtained. Both must be 30 mgKOH / g or more for long-term stable dispersibility. When only one of the acid value and the amine value is 30 mgKOH / g or more and the other is less than 30 mgKOH / g, the object of the present invention cannot be achieved even if only one of the numerical values is increased by a considerable amount. The reason for this is not necessarily clear, but if either the amine value or the acid value of the water-soluble dispersant is less than 30 mg KOH / g, the solvent in the slurry and the black inorganic oxide during long-term storage of the black inorganic oxide slurry. Therefore, it is considered that a black inorganic oxide slurry that is stable for a long time and has high dispersibility is hardly obtained.
また、本発明に用いる分散剤（Ｂ）は水溶性のものを用いる。その理由は、分散剤が水溶性でないと、黒色無機酸化物スラリーの長期保存時に、スラリー中の溶剤と黒色無機酸化物との間で分離が生じやすくなり、長期に安定な分散性の高い黒色無機酸化物スラリーとなりにくいからである。 The dispersant (B) used in the present invention is water-soluble. The reason is that if the dispersant is not water-soluble, when the black inorganic oxide slurry is stored for a long period of time, separation between the solvent in the slurry and the black inorganic oxide tends to occur, and the long-term stable and highly dispersible black It is because it becomes difficult to become an inorganic oxide slurry.
また、上記水溶性分散剤（Ｂ）は、その１０質量％水溶液のｐＨが６．０〜１０．０であることが好ましい。分散剤の１０質量％水溶液ｐＨが６．０よりも小さくなると黒色無機酸化物スラリー中の無機酸化物と分散剤が反応することにより、長期保存した場合、スラリー中の無機酸化物の溶解を生ずる可能性がある。一方、分散剤の１０質量％水溶液ｐＨが１０．０よりも大きくなると黒色無機酸化物スラリーの長期保存時に、スラリー中の溶剤と黒色無機酸化物との間で分離が生じやすくなり、長期に安定な分散性の高い黒色無機酸化物スラリーとならない。 Moreover, it is preferable that the pH of the 10 mass% aqueous solution of the said water-soluble dispersing agent (B) is 6.0-10.0. When the pH of a 10% by weight aqueous solution of the dispersant is less than 6.0, the inorganic oxide in the black inorganic oxide slurry reacts with the dispersant, and when stored for a long time, the inorganic oxide in the slurry is dissolved. there is a possibility. On the other hand, if the pH of the 10% by weight aqueous solution of the dispersant is greater than 10.0, the black inorganic oxide slurry is likely to be separated between the solvent in the slurry and the black inorganic oxide during long-term storage, and stable for a long time. It is not a highly dispersible black inorganic oxide slurry.
このような水溶性分散剤（Ｂ）としては、上述した特性を有する両性系分散剤であれば周知のものを用いることが出来、具体的には、Disperbyk-180, Disperbyk-187（いずれもビックケミー社製製、商品名）等が挙げられる。 As such a water-soluble dispersant (B), known amphoteric dispersants having the above-described properties can be used. Specifically, Disperbyk-180, Disperbyk-187 (both are Big Chemie). And product names).
有機溶剤（Ｃ）
有機溶剤は、特に限定されるものではないが、アルコール系、エステル系、エーテル系、グリコール系溶剤が好ましく用いられる。例えば、市販のトリプロピレングリコールモノメチルエーテル（日本乳化剤社製）を使用することが可能である。
Organic solvent (C)
The organic solvent is not particularly limited, but alcohol-based, ester-based, ether-based and glycol-based solvents are preferably used. For example, commercially available tripropylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) can be used.
（Ａ）、（Ｂ）、（Ｃ）の配合割合
（Ａ）、（Ｂ）、（Ｃ）成分の配合割合は、スラリー全量を１００質量部とした場合、黒色無機酸化物（Ａ）を５０〜９０質量、水溶性分散剤（Ｂ）を０．１〜２５質量部、有機溶剤（Ｃ）を、１〜４９．９重量部、好ましくは、黒色無機酸化物（Ａ）を６０〜８５質量部、水溶性分散剤（Ｂ）を０．１〜１５質量部、有機溶剤（Ｃ）を、１０〜３９．９質量部である。
The blending ratios (A), (B), and (C) of (A), (B), and (C) are 50 blending ratios of the black inorganic oxide (A) when the total amount of slurry is 100 parts by mass. -90 mass, 0.1-25 mass parts of water-soluble dispersant (B), 1-49.9 parts by weight of organic solvent (C), preferably 60-85 mass of black inorganic oxide (A) Parts, 0.1 to 15 parts by mass of the water-soluble dispersant (B), and 10 to 39.9 parts by mass of the organic solvent (C).
他の配合成分
本発明の目的を損なわない限り、上記組成物に他の分散剤、添加剤、更には常套的に添加する成分等が含まれても良い。
Other ingredients
As long as the object of the present invention is not impaired, the above-mentioned composition may contain other dispersants, additives, components that are conventionally added, and the like.
スラリー組成物の製法
本発明の黒色無機酸化物スラリーを製造する方法は、特に限定されるものではないが、粉砕効率が高い湿式分散装置が推奨される。具体的には、ビーズミル、高圧ホモジナイザー、湿式ジェットミル等に代表される湿式粉砕機が挙げられるが、分散効率、粉砕効率、生産性から考えるとビーズミルがもっとも好ましい。
Manufacturing method of slurry composition
The method for producing the black inorganic oxide slurry of the present invention is not particularly limited, but a wet dispersion device having high grinding efficiency is recommended. Specific examples include wet pulverizers such as a bead mill, a high-pressure homogenizer, and a wet jet mill. A bead mill is most preferable in view of dispersion efficiency, pulverization efficiency, and productivity.
上記黒色無機酸化物スラリーを製造する装置の一例を図１に示す。図１の装置は、ビーズミル（１）、撹拌翼を備えた撹拌機（２）、スラリー槽（３）、スラリー輸送ポンプ（４）より構成された装置である。上記ビーズミルは、黒色無機酸化物スラリー作製時の粉砕により発熱を伴う為、冷却ジャケットを備えたビーズミルであることが好ましい。 An example of an apparatus for producing the black inorganic oxide slurry is shown in FIG. The apparatus of FIG. 1 is an apparatus comprised from the bead mill (1), the stirrer (2) provided with the stirring blade, the slurry tank (3), and the slurry transport pump (4). The bead mill is preferably a bead mill having a cooling jacket because it generates heat due to pulverization during the preparation of the black inorganic oxide slurry.
黒色無機酸化物粉末を、予めスラリー槽（３）で有機溶剤と分散剤を混合した混合溶剤に加え、撹拌することにより予備スラリーとすることが出来る。 The black inorganic oxide powder can be made into a preliminary slurry by adding the mixture to a mixed solvent obtained by mixing an organic solvent and a dispersant in a slurry tank (3) in advance.
上記予備スラリーをスラリー輸送ポンプ（４）により、直径０．０３〜１ｍｍのビーズを充填率５０％〜９５％で備え、ローター周速５〜２０ｍ／ｓのビーズミル（１）に輸送し、ビーズミル（１）の出口側からスラリーが排出され、スラリー槽（３）にスラリーが戻る。上記運転を繰り返すことにより循環運転を行い、黒色無機酸化物スラリーを得ることが可能である。 The preliminary slurry is transported to a bead mill (1) having a diameter of 0.03 to 1 mm with a filling rate of 50% to 95% by a slurry transport pump (4) and having a rotor peripheral speed of 5 to 20 m / s. The slurry is discharged from the outlet side of 1), and the slurry returns to the slurry tank (3). By repeating the above operation, it is possible to perform a circulation operation and obtain a black inorganic oxide slurry.
粉砕効率は、ビーズミルで使用されるビーズ径と黒色無機酸化物の一次粒径と凝集粒径に依存する。ビーズミルで使用されるビーズ径は、０．０３〜１ｍｍで使用可能であるが、より小さいビーズ径の使用が好ましく、０．３ｍｍ以下のビーズを使用することが好ましい。 The grinding efficiency depends on the bead diameter used in the bead mill, the primary particle diameter and the aggregate particle diameter of the black inorganic oxide. The bead diameter used in the bead mill can be 0.03 to 1 mm. However, it is preferable to use a smaller bead diameter, and it is preferable to use a bead having a diameter of 0.3 mm or less.
ビーズミルで使用されるビーズの材質は、特に限定されるものではなく、ジルコニアビーズ、アルミナビーズ、窒化ケイ素ビーズを使用できるが、粉砕効果、耐磨耗性の観点からジルコニアビーズを使用することが好ましい。 The material of the beads used in the bead mill is not particularly limited, and zirconia beads, alumina beads, and silicon nitride beads can be used, but zirconia beads are preferably used from the viewpoint of grinding effect and wear resistance. .
得られた黒色無機酸化物スラリーは、異物の除去の観点から、目開き１０μｍ以下、好ましくは、目開き５μｍ以下のフィルターで処理されることが好ましい。 The obtained black inorganic oxide slurry is preferably treated with a filter having an opening of 10 μm or less, preferably 5 μm or less, from the viewpoint of removing foreign substances.
以下、本発明の実施例を示す。以下に、本発明を具体的な実施例及び比較例について説明するが、本発明はこれら実施例に限定されるものではない。また、この実施例において、％は特に言及しない限り質量％を意味する。なお、実施例におけるスラリー化後の黒色無機酸化物の物性等は各々次のようにして測定した。 Examples of the present invention will be described below. Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited to these examples. In this example,% means mass% unless otherwise specified. In addition, the physical property etc. of the black inorganic oxide after slurrying in an Example were measured as follows, respectively.
（ａ）レーザー回折法によるスラリー中の黒色無機酸化物粉末の粒径
アルコール系溶剤（エタノールもしくは、トリプロピレングリコールモノメチルエーテル）で希釈した黒色無機酸化物スラリーを適量滴下分散後、マイクロトラック９３２０ＨＲＡ（×１００）（日機装社製）の試料室に希釈溶媒として０．２％ヘキサメタリン酸ナトリウム水溶液を用いて、１０〜２０分間超音波分散後、黒色無機酸化物スラリー中の黒色無機酸化物粉末の粒径を測定した。尚、得られる粒度分布曲線において、その累積頻度が５０％の粒径を意味する平均粒径を平均粒径Ｄ５０とした。また、累積頻度が１００％の粒径を意味する最大粒径を最大粒径Ｄ１００とした。
(A) Particle diameter of black inorganic oxide powder in slurry by laser diffraction method
An appropriate amount of black inorganic oxide slurry diluted with an alcohol solvent (ethanol or tripropylene glycol monomethyl ether) was dropped and dispersed, and then 0.2% as a dilution solvent in the sample chamber of Microtrac 9320HRA (× 100) (Nikkiso Co., Ltd.). The particle size of the black inorganic oxide powder in the black inorganic oxide slurry was measured after ultrasonic dispersion for 10 to 20 minutes using an aqueous sodium hexametaphosphate solution. In the obtained particle size distribution curve, the average particle size which means a particle size having a cumulative frequency of 50% was defined as an average particle size D50. The maximum particle size that means a particle size with a cumulative frequency of 100% was defined as the maximum particle size D100.
（ｂ）ＳＥＭ一次粒径
ＦＥ ＳＥＭ（電界放射型走査型電子顕微鏡）で２０，０００〜７０，０００倍の写真を撮影し、２００個の一次粒子のフェレー径を測定した。尚、測定した２００個の一次粒子のフェレー径の内、最大のものを最大一次粒径とする。また、得られる粒度分布曲線において、その累積頻度が５０％の粒径を意味する平均粒径を一次粒径Ｄ５０とした。
(B) SEM primary particle size
A 20,000 to 70,000-fold photograph was taken with an FE SEM (field emission scanning electron microscope), and the ferret diameter of 200 primary particles was measured. Of the measured ferret diameters of 200 primary particles, the largest one is defined as the maximum primary particle diameter. Further, in the obtained particle size distribution curve, the average particle size which means a particle size having a cumulative frequency of 50% was defined as a primary particle size D50.
（ｃ）黒色無機酸化物スラリーの長期保存後の分散性
黒色無機酸化物スラリー約４００ｇをサンプル容器（直径５５ｍｍ、高さ９５ｍｍ）に採取し、室温（２５℃）にて３０日間サンプル保存後、サンプル容器の上部（液面から１０ｍｍ）及び底部（底面から１０ｍｍ）のスラリーをそれぞれ約１０ｇルツボに採取後、６００℃で１時間熱処理し、溶剤及び分散剤を加熱除去することにより、サンプル容器の上部及び底部の固形分濃度を求めた。
(C) Dispersibility after long-term storage of black inorganic oxide slurry
About 400 g of the black inorganic oxide slurry is collected in a sample container (diameter 55 mm, height 95 mm) and stored at room temperature (25 ° C.) for 30 days, then the top (10 mm from the liquid level) and bottom (from the bottom) of the sample container. 10 mm) of each slurry was collected in about 10 g crucibles, then heat treated at 600 ° C. for 1 hour, and the solvent and dispersant were removed by heating to obtain the solid content concentrations at the top and bottom of the sample container.
また、黒色無機酸化物スラリーの長期保存後のスラリー濃度分布は（式１）で求めた。 The slurry concentration distribution after long-term storage of the black inorganic oxide slurry was determined by (Equation 1).
（底部固形分濃度−上部固形分濃度）×１００／底部固形分濃度 …（式１）
（ｄ）黒色無機酸化物スラリーの長期保存後の粘度安定性
黒色無機酸化物スラリー約４００ｇをサンプル容器（直径５５ｍｍ、高さ９５ｍｍ）に採取し、ＴＯＫＩＭＥＣ社製ＶＩＳＣＯＭＥＴＥＲ（型式：Ｂ８Ｈ）を用いてローター速度１００ｒｐｍ、ローターＮｏ．５の条件で粘度測定を行い、その値を初期粘度とした。
(Bottom solids concentration−top solids concentration) × 100 / bottom solids concentration (Formula 1)
(D) Viscosity stability after long-term storage of black inorganic oxide slurry
About 400 g of the black inorganic oxide slurry was collected in a sample container (diameter: 55 mm, height: 95 mm), and the rotor speed was set at 100 rpm with a rotor speed of 100 rpm using a VISCOMETER (model: B8H) manufactured by TOKIMEC. The viscosity was measured under the condition of 5, and the value was defined as the initial viscosity.
また、初期粘度測定後、室温（２５℃）にて３０日間サンプル保存後、初期粘度測定と同様な測定を行い、その値を保存後粘度とした。また、黒色無機酸化物スラリーの３０日保存後の粘度増加率は（式２）で求めた。 Further, after the initial viscosity measurement, the sample was stored at room temperature (25 ° C.) for 30 days, then the same measurement as the initial viscosity measurement was performed, and the value was defined as the viscosity after storage. Moreover, the viscosity increase rate after 30-day preservation | save of a black inorganic oxide slurry was calculated | required by (Formula 2).
（保存後粘度−初期粘度）×１００／初期粘度 …（式２）
（実施例１）
一次粒子が凝集して二次粒子を形成した球状のコバルト水酸化物を、焼成温度６５０℃で１０時間熱処理し、次いで粉砕することにより、平均粒径Ｄ５０が０．５０μｍ、最大粒径Ｄ１００が５．５μｍの四三酸化コバルトを得た。
(Viscosity after storage−initial viscosity) × 100 / initial viscosity (Formula 2)
Example 1
A spherical cobalt hydroxide in which primary particles are aggregated to form secondary particles is heat-treated at a firing temperature of 650 ° C. for 10 hours, and then pulverized to obtain an average particle size D50 of 0.50 μm and a maximum particle size D100 of 5.5 μm cobalt tetroxide was obtained.
得られた四三酸化コバルト１５ｋｇを、溶剤２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート５．０９ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１８７（ビックケミー社製）０．２１ｋｇの混合溶液に、四三酸化コバルト粉末の凝集した粉末塊が混合溶液中に残らないように撹拌機を用いて１時間撹拌し、予備スラリーを得た。尚、ビーズミルベッセル内及び配管等に溶剤２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレートが１．１２ｋｇ存在することを確認した。 15 kg of the obtained cobalt tetraoxide was added to a mixed solution of 5.09 kg of a solvent 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 0.21 kg of a dispersant DISPERBYK187 (manufactured by BYK Chemie). Stirring was carried out for 1 hour using a stirrer so that agglomerated powder lump of cobalt trioxide powder did not remain in the mixed solution to obtain a preliminary slurry. It was confirmed that 1.12 kg of the solvent 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was present in the bead mill vessel and piping.
このようにして得られた予備スラリーを、直径０．１ｍｍジルコニアビーズを体積換算で充填率８５％充填されたローターの回転周速１２ｍ／ｓビーズミル（アシザワ・ファインテック社製ＬＭＺ４型）ヘポンプにて導入して循環、湿式粉砕を行った。レーザー回折法による粒径測定でスラリー粒径が平衡に達したところを終点とした。 The pre-slurry thus obtained was pumped to a rotor rotating peripheral speed 12 m / s bead mill (LMZ4 type manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads having a diameter of 0.1 mm in a volume conversion rate of 85%. Introduced circulation and wet grinding. The end point was the point where the slurry particle size reached equilibrium in the particle size measurement by laser diffraction method.
なお、使用した分散剤の特性（酸価、アミン価、１０質量％水溶液ｐＨ，水溶性）は表１に示した。以下の実施例及び比較例も同様である。 The properties of the dispersant used (acid value, amine value, 10 mass% aqueous solution pH, water solubility) are shown in Table 1. The same applies to the following examples and comparative examples.
（実施例２）
有機溶剤としてトリプロピレングリコールモノメチルエーテル、分散剤としてＤＩＳＰＥＲＢＹＫ１８０（ビックケミー社製）を用いたこと以外は、（実施例１）と同様にして黒色無機酸化物スラリーを得た。
(Example 2)
A black inorganic oxide slurry was obtained in the same manner as in Example 1 except that tripropylene glycol monomethyl ether was used as the organic solvent and DISPERBYK180 (manufactured by Big Chemie) was used as the dispersant.
（実施例３）
ビーズミルのローター回転周速を９．０ｍ／ｓとしたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Example 3)
A black inorganic oxide slurry was obtained in the same manner as in (Example 2) except that the rotor rotation peripheral speed of the bead mill was 9.0 m / s.
（実施例４）
四三酸化コバルト１５ｋｇを有機溶剤トリプロピレングリコールモノメチルエーテル４．２４ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１８０（ビックケミー社製）１．０７ｋｇの混合溶液で予備スラリーとしたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
Example 4
Black as in Example 2 except that 15 kg of cobalt tetroxide was made into a pre-slurry with a mixed solution of 4.24 kg of organic solvent tripropylene glycol monomethyl ether and dispersant DISPERBYK180 (manufactured by Big Chemie) 1.07 kg. An inorganic oxide slurry was obtained.
（実施例５）
四三酸化コバルト１５ｋｇを有機溶剤トリプロピレングリコールモノメチルエーテル３．１７ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１８０（ビックケミー社製）２．１４ｋｇの混合溶液で予備スラリーとしたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Example 5)
Except that 15 kg of cobalt tetroxide was used as a pre-slurry with a mixed solution of 3.17 kg of organic solvent tripropylene glycol monomethyl ether and a dispersant DISPERBYK180 (manufactured by BYK Chemie) 2.14 kg, black as in Example 2 An inorganic oxide slurry was obtained.
（実施例６）
四三酸化コバルト１５ｋｇを有機溶剤トリプロピレングリコールモノメチルエーテル２，０９ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１８０（ビックケミー社製）３．２１ｋｇの混合溶液で予備スラリーとしたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Example 6)
Black as in Example 2 except that 15 kg of cobalt tetroxide was used as a pre-slurry with a mixed solution of 2,09 kg of organic solvent tripropylene glycol monomethyl ether and dispersant DISPERBYK180 (by Big Chemie) 3.21 kg. An inorganic oxide slurry was obtained.
（実施例７）
Ｎｉ：Ｃｏ：Ｍｎ＝１０：４５：４５である組成のニッケルコバルトマンガン複合水酸化物を焼成温度８００℃で１０時間熱処理し、次いで粉砕することにより得られた、平均粒径Ｄ５０が１．５３μｍ、最大粒径Ｄ１００が４．６μｍのニッケルコバルトマンガン複合酸化物を用いたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Example 7)
An average particle diameter D50 obtained by heat-treating nickel cobalt manganese composite hydroxide having a composition of Ni: Co: Mn = 10: 45: 45 at a firing temperature of 800 ° C. for 10 hours and then pulverizing is 1.53 μm. A black inorganic oxide slurry was obtained in the same manner as in Example 2 except that a nickel cobalt manganese composite oxide having a maximum particle size D100 of 4.6 μm was used.
（実施例８）
Ｎｉ：Ｃｏ：Ｍｎ＝２０：２０：６０である組成のニッケルコバルトマンガン複合水酸化物を焼成温度６５０℃で１０時間熱処理し、次いで粉砕することにより得られた、平均粒径Ｄ５０が０．６２μｍ、最大粒径Ｄ１００が３，８９μｍのニッケルコバルトマンガン複合酸化物を用いたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Example 8)
A nickel cobalt manganese composite hydroxide having a composition of Ni: Co: Mn = 20: 20: 60 was heat-treated at a firing temperature of 650 ° C. for 10 hours and then pulverized, and the average particle diameter D50 was 0.62 μm. A black inorganic oxide slurry was obtained in the same manner as in Example 2 except that a nickel cobalt manganese composite oxide having a maximum particle size D100 of 3,89 μm was used.
（実施例９）
Ｎｉ：Ｃｏ：Ｍｎ＝２０：６０：２０である組成のニッケルコバルトマンガン複合水酸化物を焼成温度６５０℃で１０時間熱処理し、次いで粉砕することにより得られた、平均粒径Ｄ５０が０．９５μｍ、最大粒径Ｄ１００が３．８９μｍのニッケルコバルトマンガン複合酸化物を用いたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
Example 9
A nickel cobalt manganese composite hydroxide having a composition of Ni: Co: Mn = 20: 60: 20 was heat-treated at a firing temperature of 650 ° C. for 10 hours and then pulverized, and the average particle diameter D50 was 0.95 μm. A black inorganic oxide slurry was obtained in the same manner as in (Example 2) except that a nickel cobalt manganese composite oxide having a maximum particle size D100 of 3.89 μm was used.
（実施例１０）
Ｃｏ：Ｍｎ＝１：１である組成のコバルトマンガン複合水酸化物を焼成温度７００℃で１０時間熱処理し、次いで粉砕することにより得られた、平均粒径Ｄ５０が０．９２μｍ、最大粒径Ｄ１００が４．６μｍのコバルトマンガン複合酸化物を用いたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Example 10)
An average particle diameter D50 of 0.92 μm and a maximum particle diameter D100 obtained by heat-treating a cobalt manganese composite hydroxide having a composition of Co: Mn = 1: 1 at a firing temperature of 700 ° C. for 10 hours and then grinding. A black inorganic oxide slurry was obtained in the same manner as in (Example 2) except that 4.6 μm of cobalt manganese composite oxide was used.
（比較例１）
四三酸化コバルト１５ｋｇを、有機溶剤２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート８．６３ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１８２（ビックケミー社製）０．２５ｋｇの混合溶液に、四三酸化コバルト粉末の凝集した粉末塊が混合溶液中に残らないように撹拌機を用いて１時間撹拌して作製した予備スラリーを使用したこと以外は、（実施例１）と同様にして黒色無機酸化物スラリーを得た。
(Comparative Example 1)
15 kg of cobalt trioxide is added to a mixed solution of organic solvent 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 8.63 kg and dispersant DISPERBYK182 (manufactured by BYK Chemie) 0.25 kg. A black inorganic oxide was used in the same manner as in Example 1 except that a preliminary slurry prepared by stirring for 1 hour using a stirrer was used so that agglomerated powder lump of cobalt powder did not remain in the mixed solution. A slurry was obtained.
（比較例２）
分散剤としてＤＩＳＰＥＲＢＹＫ１６３（ビックケミー社製）を用いたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Comparative Example 2)
A black inorganic oxide slurry was obtained in the same manner as in Example 2 except that DISPERBYK163 (manufactured by Big Chemie) was used as the dispersant.
（比較例３）
四三酸化コバルト１５ｋｇを、有機溶剤トリプロピレングリコールモノメチルエーテル４．６７ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１８５（ビックケミー社製）０．６４ｋｇの混合溶液で予備スラリーとしたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Comparative Example 3)
Except that 15 kg of cobalt tetroxide was used as a pre-slurry with a mixed solution of 4.67 kg of organic solvent tripropylene glycol monomethyl ether and dispersant DISPERBYK185 (manufactured by Big Chemie), the same procedure as in Example 2 was performed. A black inorganic oxide slurry was obtained.
（比較例４）
分散剤としてＤＩＳＰＥＲＢＹＫ１９１（ビックケミー社製）を用いたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Comparative Example 4)
A black inorganic oxide slurry was obtained in the same manner as in Example 2 except that DISPERBYK191 (manufactured by Big Chemie) was used as the dispersant.
（比較例５）
コバルト水酸化物を焼成温度８００℃で１０時間熱処理し、次いで粉砕することにより、平均粒径Ｄ５０を１．１６μｍ、最大粒径Ｄ１００を４．６３μｍとした四三酸化コバルトを用いたこと以外は、（実施例１）と同様にして黒色無機酸化物スラリーを得た。
(Comparative Example 5)
The cobalt hydroxide was heat-treated at a firing temperature of 800 ° C. for 10 hours and then pulverized to use cobalt tetroxide having an average particle diameter D50 of 1.16 μm and a maximum particle diameter D100 of 4.63 μm. In the same manner as in (Example 1), a black inorganic oxide slurry was obtained.
（比較例６）
四三酸化コバルト１５ｋｇを、有機溶剤トリプロピレングリコールモノメチルエーテル４．８８ｋｇと分散剤ＤＩＳＰＥＲＢＹＫ１４０（ビックケミー社製）０．４３ｋｇの混合溶液で予備スラリーとしたこと以外は、（実施例２）と同様にして黒色無機酸化物スラリーを得た。
(Comparative Example 6)
Except that 15 kg of cobalt tetroxide was used as a pre-slurry with a mixed solution of 4.88 kg of organic solvent tripropylene glycol monomethyl ether and dispersant DISPERBYK140 (manufactured by Big Chemie), the same procedure as in Example 2 was performed. A black inorganic oxide slurry was obtained.
実施例及び比較例の黒色無機酸化物スラリーの物性値及びスラリー保存特性を表１にまとめる。尚、本発明者は、本スラリー保存試験において、３０日間保存後のスラリー濃度分布が５０％以下、粘度増加率が２５０％以下の条件を満足することにより、長期保存特性に優れた黒色無機酸化物スラリーであることを確認している。 Table 1 summarizes the physical properties and slurry storage characteristics of the black inorganic oxide slurries of Examples and Comparative Examples. In addition, in the present slurry storage test, the present inventor has satisfied the conditions that the slurry concentration distribution after storage for 30 days is 50% or less and the viscosity increase rate is 250% or less. It is confirmed that the product slurry.
実施例１では、黒色無機酸化物粉末として四三酸化コバルトを用い、分散剤として酸価が３５ｍｇＫＯＨ／ｇ、アミン価が３５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤１質量％用いることにより得られた最大一次粒径０．４９μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーであってもスラリーの濃度分布幅は１０％であり、粘度増加率は１８９％であった。 Example 1 is obtained by using cobalt trioxide as a black inorganic oxide powder and using 1% by weight of an amphoteric water-soluble dispersant having an acid value of 35 mgKOH / g and an amine value of 35 mgKOH / g as a dispersant. The resulting black inorganic oxide slurry having a maximum primary particle size of 0.49 μm had a slurry concentration distribution width of 10% and a viscosity increase rate of 189% even after being stored for 30 days.
実施例２〜６では、黒色無機酸化物粉末として四三酸化コバルトを用い、分散剤として酸価が９５ｍｇＫＯＨ／ｇ、アミン価が９５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を１〜１５質量％用いることにより得られた最大一次粒径０．５３μｍ以下である黒色無機酸化物スラリーは、３０日保存後のスラリーであってもスラリーの濃度分布幅は３５％以下であり、粘度増加率は１７２％以下であった。 In Examples 2 to 6, 1 to 15 mass of an amphoteric water-soluble dispersant having an acid value of 95 mgKOH / g and an amine value of 95 mgKOH / g was used as the black inorganic oxide powder. The black inorganic oxide slurry having a maximum primary particle size of 0.53 μm or less obtained by using% is a slurry concentration distribution width of 35% or less even when the slurry is stored for 30 days, and the viscosity increase rate is It was 172% or less.
実施例７では、黒色無機酸化物粉末としてＮｉ：Ｃｏ：Ｍｎ：１０：４５：４５組成のニッケルコバルトマンガン複合酸化物を用い、分散剤として酸価が９５ｍｇＫＯＨ／ｇ、アミン価が９５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を１質量％用いることにより得られた最大一次粒径０．７５μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーであってもスラリーの濃度分布幅は２０％であり、粘度増加率は１２１％であった。 In Example 7, a nickel cobalt manganese composite oxide having a composition of Ni: Co: Mn: 10: 45: 45 was used as the black inorganic oxide powder, and the acid value was 95 mgKOH / g and the amine value was 95 mgKOH / g as the dispersant. The black inorganic oxide slurry having a maximum primary particle size of 0.75 μm obtained by using 1% by mass of a certain amphoteric water-soluble dispersant has a concentration distribution width of the slurry even after 30 days storage. The viscosity increase rate was 20% and the viscosity increase rate was 121%.
実施例８では、黒色無機酸化物粉末としてＮｉ：Ｃｏ：Ｍｎ＝２０：２０：６０組成のニッケルコバルトマンガン複合酸化物を用い、分散剤として酸価が９５ｍｇＫＯＨ／ｇ、アミン価が９５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を３質量％用いることにより得られた最大一次粒径０．６３μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーであってもスラリーの濃度分布幅は１２％であり、粘度増加率は４５％であった。 In Example 8, a nickel cobalt manganese composite oxide having a composition of Ni: Co: Mn = 20: 20: 60 was used as the black inorganic oxide powder, and the acid value was 95 mgKOH / g and the amine value was 95 mgKOH / g as the dispersant. The black inorganic oxide slurry having a maximum primary particle size of 0.63 μm obtained by using 3% by weight of a certain amphoteric water-soluble dispersant has a concentration distribution width of slurry of 30 days after storage. The viscosity increase rate was 12% and the viscosity increase rate was 45%.
実施例９では、黒色無機酸化物粉末としてＮｉ：Ｃｏ：Ｍｎ＝２０：６０：２０組成のニッケルコバルトマンガン複合酸化物を用い、分散剤として酸価が９５ｍｇＫＯＨ／ｇ、アミン価が９５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を３質量％用いることにより得られた最大一次粒径０．５８μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーであってもスラリーの濃度分布幅は１０％であり、粘度増加率は３９％であった。 In Example 9, a nickel cobalt manganese composite oxide having a composition of Ni: Co: Mn = 20: 60: 20 was used as the black inorganic oxide powder, and the acid value was 95 mgKOH / g and the amine value was 95 mgKOH / g as the dispersant. The black inorganic oxide slurry having a maximum primary particle size of 0.58 μm obtained by using 3% by mass of a certain amphoteric water-soluble dispersant has a concentration distribution range of slurry even after 30 days of storage. The viscosity increase rate was 39%.
実施例１０では、黒色無機酸化物粉末としてＣｏ：Ｍｎ＝１：１組成のコバルトマンガン複合酸化物を用い、分散剤として酸価が９５ｍｇＫＯＨ／ｇ、アミン価が９５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を１質量％用いることにより得られた最大一次粒径０．８２μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーであってもスラリーの濃度分布幅は２１％であり、粘度増加率は１３６％であった。 In Example 10, a cobalt-manganese composite oxide having a composition of Co: Mn = 1: 1 was used as the black inorganic oxide powder, and an amphoteric aqueous solution having an acid value of 95 mgKOH / g and an amine value of 95 mgKOH / g as the dispersant. The black inorganic oxide slurry having a maximum primary particle size of 0.82 μm obtained by using 1% by weight of the ionic dispersing agent has a slurry concentration distribution width of 21% even if it is a slurry after 30 days storage, The increase in viscosity was 136%.
比較例１〜３では、黒色無機酸化物粉末として四三酸化コバルトを用い、分散剤としてアミン価が１０〜１８ｍｇＫＯＨ／ｇであるカチオン系分散剤を１〜３％用いることにより得られた最大一次粒径０．４９μｍ以下である黒色無機酸化物スラリーは、３０日保存後のスラリーは溶剤と固形分が分離し、ハードケーキング（黒色無機酸化物が硬く沈殿した状態）を起した。 In Comparative Examples 1 to 3, the maximum primary obtained by using 1 to 3% of a cationic dispersant having an amine value of 10 to 18 mgKOH / g as a dispersant using black cobalt oxide as the black inorganic oxide powder. As for the black inorganic oxide slurry having a particle size of 0.49 μm or less, the slurry after storage for 30 days separated the solvent and the solid content, and caused hard caking (a state in which the black inorganic oxide was hardly precipitated).
比較例４では、黒色無機酸化物粉末として四三酸化コバルトを用い、分散剤として酸価が３０ｍｇＫＯＨ／ｇ、アミン価が２０ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を１質量％用いることにより得られた最大一次粒径０．５３μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーは溶剤と固形分が分離し、ソフトケーキング（黒色無機酸化物が柔らかく沈殿した状態）を起した。 In Comparative Example 4, tribasic cobalt tetraoxide was used as the black inorganic oxide powder, and 1% by weight of an amphoteric water-soluble dispersant having an acid value of 30 mgKOH / g and an amine value of 20 mgKOH / g was used as the dispersant. The obtained black inorganic oxide slurry having a maximum primary particle size of 0.53 μm was subjected to soft caking (a state in which the black inorganic oxide was softly precipitated) in the slurry after storage for 30 days, in which the solvent and the solid content were separated. .
比較例５では、黒色無機酸化物粉末として四三酸化コバルトを用い、分散剤として酸価が３５ｍｇＫＯＨ／ｇ、アミン価が３５ｍｇＫＯＨ／ｇである両性系の水溶性分散剤を１質量％用いることにより得られた最大一次粒径１．１６μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーは溶剤と固形分が分離し、ソフトケーキング（黒色無機酸化物が柔らかく沈殿した状態）を起した。 In Comparative Example 5, cobalt trioxide was used as the black inorganic oxide powder, and 1% by weight of an amphoteric water-soluble dispersant having an acid value of 35 mgKOH / g and an amine value of 35 mgKOH / g was used as the dispersant. The resulting black inorganic oxide slurry having a maximum primary particle size of 1.16 μm was subjected to soft caking (a state in which the black inorganic oxide was softly precipitated) in the slurry after storage for 30 days, in which the solvent and solid content were separated. .
比較例６では、黒色無機酸化物粉末として四三酸化コバルトを用い、分散剤として酸価が７２ｍｇＫＯＨ／ｇ、アミン価が７６ｍｇＫＯＨ／ｇである水溶性でない両性系分散剤を２％用いることにより得られた最大一次粒径０．４５μｍである黒色無機酸化物スラリーは、３０日保存後のスラリーは溶剤と固形分が分離し、ソフトケーキング（黒色無機酸化物が柔らかく沈殿した状態）を起した。 In Comparative Example 6, trivalent cobalt oxide was used as the black inorganic oxide powder, and 2% non-water-soluble amphoteric dispersant having an acid value of 72 mgKOH / g and an amine value of 76 mgKOH / g was used as the dispersant. The resulting black inorganic oxide slurry having a maximum primary particle size of 0.45 μm was subjected to soft caking (a state in which the black inorganic oxide was softly precipitated) in the slurry after storage for 30 days, in which the solvent and the solid content were separated.
以上の点を鑑み、本発明において得られる黒色無機酸化物スラリーは、微粒化された固形分の高い黒色無機酸化物からなるスラリーであって、長期間保存しても粘度の上昇、沈降分離の起こりにくい分散性の高い安価な黒色無機酸化物スラリーを提供できる。
１…冷却ジャケットを備えたビーズミル、２…撹拌翼を備えた撹拌機、３…反応槽、４…スラリー輸送ポンプ DESCRIPTION OF SYMBOLS 1 ... Bead mill provided with cooling jacket, 2 ... Stirrer provided with stirring blade, 3 ... Reaction tank, 4 ... Slurry transport pump
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